Patent Application
20230361296
The present application relates to the technical field of lithium batteries, in particular to a positive electrode active material and a preparation method therefor, a positive electrode plate containing the positive electrode active material, a secondary battery, a battery module, a battery pack, and a power consuming device.
With the rapid development in the new energy field, lithium ion batteries, due to their advantages of good electrochemical performance, no memory effect and little environmental pollution, are widely applied in various large power devices, energy storage systems and various consumable products, especially in the field of new energy vehicles such as pure electric vehicles and hybrid electric vehicles. Among the batteries, a lithium manganese phosphate positive electrode active material has the advantages of a high working voltage, a wide range of raw material sources and less environmental pollution, and is considered to be a positive electrode active material that is expected to replace lithium iron phosphate and become a power lithium ion battery.
However, in the related art, the cycling performance, high-temperature storage performance and safety performance of secondary batteries using lithium manganese phosphate positive electrode active materials have not been comprehensively improved, which greatly limits the wider application of lithium manganese phosphate batteries. Therefore, the industry is still looking forward to designing a lithium manganese phosphate positive electrode active material with a high gram capacity, good cycling performance and safety performance.
The present application is made in view of the above problems, and with an object to provide a positive electrode active material, a preparation method for the positive electrode active material, a positive electrode plate, a secondary battery, a battery module, a battery pack, and a power consuming device to solve existing problems, that the existing lithium manganese phosphate positive electrode active material is prone to Li/Mn antisite defects and serious manganese dissolution during the charging/discharging process, so as to solve the problems of a low capacity, poor safety performance and cycling performance of secondary batteries.
In order to achieve the above object, the first aspect of the present application provides a positive electrode active material, including a compound represented by formula (I),
LiaAxMn1-yByP1-zCzO4-nDn (I)
Therefore, in the present application, by doping a compound LiMnPO4 at Mn site and optionally Li, P and/or O sites with specific amounts of specific elements, a markedly improved rate performance can be obtained while the dissolution of Mn and Mn-site doping element is significantly reduced, thereby obtaining significantly improved cycling performance and/or high-temperature stability; and the gram capacity and compacted density of the material can also be enhanced.
In any embodiment, the A includes one or more elements selected from Rb, Cs, Be, Ca, Sr, Ba, Ga, In, Cd, V, Ta, Cr, Zn, Al, Na, K, Mg, Nb, Mo and W, optionally one or more elements selected from Zn, Al, Na, K, Mg, Nb, Mo and W; and/or
Therefore, the rate performance, gram capacity, compacted density, cycling performance and/or high temperature performance of the secondary battery can be further improved, and the dissolution of Mn and Mn-site doping elements can be further reduced.
In any embodiment, the A includes any element selected from Zn, Al, Na, K, Mg, Nb, Mo and W, and optionally any element selected from Mg and Nb; and/or
Therefore, the rate performance of the secondary battery can be further improved, the dissolution of Mn and Mn-site doping elements can be further reduced, the cycling performance and/or high temperature performance of the secondary battery can be improved, and the gram capacity and compacted density of the material can be further improved.
In any embodiment, the a is selected from a range of 0.9 to 1.1, optionally in a range of 0.97 to 1.01; and/or
Thus, the gram capacity of the material can be further improved, the rate performance and/or kinetic performance of the secondary battery can be further improved, and the cycling performance and/or high temperature performance of the battery can be further improved.
In any embodiment, the x is 0, the z is selected from a range of 0.001 to 0.5, and the n is selected from a range of 0.001 to 0.1; or,
Therefore, the present application, by doping the compound LiMnPO4 with specific elements in specific amounts at the Mn-site and optionally at the Li-site, P-site and/or O-site, especially at the Mn-site and the P-site of LiMnPO4 or doping LiMnPO4 with specific elements in specific amounts at the Li-site, Mn-site, P-site, and O-site, can significantly improve the rate performance, significantly reduce the dissolution of Mn and Mn-site doping elements, and significantly improve the cycling performance and/or high temperature stability and remarkably improve the gram capacity and the compaction density of the material.
In any embodiment, y:z is selected from a range of 0.002 to 999, optionally in a range of 0.025 to 999, more optionally in a range of 0.2 to 600. Therefore, the defects of the material can be reduced, and the integrity of the frame structure of the material can be improved, thereby effectively improving the structural stability of the material, and further improving the cycling stability of the secondary battery.
In any embodiment, z:n is selected from a range of 0.002 to 500, optionally in a range of 0.2 to 100, more optionally in a range of 0.2 to 50. Therefore, the defects of the material can be further reduced, and the integrity of the frame structure of the material can be further improved, thereby effectively improving the structural stability of the material, and further improving the cycling stability of the secondary battery.
In any embodiment,
Therefore, in the present application, by doping a compound LiMnPO4 at Li, Mn, P and O sites with specific amounts of specific elements, a markedly improved rate performance can be obtained while the dissolution of Mn and Mn-site doping element is significantly reduced, thereby obtaining significantly improved cycling performance and/or high-temperature stability; and the gram capacity and compacted density of the material can also be enhanced.
In any embodiment,
Thus, the present application, by doping the compound LiMnPO4 with specific elements in specific amounts at the Mn-site and P-site, can improve the rate performance, reduce the dissolution of Mn and Mn-site doping elements, improve the cycling performance and/or high temperature stability, increase the gram capacity and compaction density of the material.
In any embodiment, the positive electrode active material includes an inner core and a shell coating the inner core, and the inner core includes a compound as shown in the above formula I;
The present application, by doping the compound LiMnPO4 with specific elements in specific amounts at the Mn site and doping elements at Li-site, P-site and/or O-site to obtain a doped lithium manganese phosphate inner core and providing a coating on the surface of the core having ion conductivity and electron conductivity, provides a new positive electrode active material with a core-shell structure, and the use of the positive electrode active material in a secondary battery can significantly improve the high temperature cycling performance, cycling stability and high temperature storage performance of the secondary battery.
In any embodiment, the shell includes a coating layer;
Therefore, the present application can obtain a coating layer with ion conductivity or electron conductivity by using the above materials, thereby improving the high-temperature cycling performance, cycling stability and high-temperature storage performance of the secondary battery.
In any embodiment, the shell includes a first coating layer coating the inner core and a second coating layer coating the first coating layer;
Therefore, the present application using the above materials as the materials of the coating layers, and providing two layers of coating layers can further improve the high-temperature cycling performance, cycling stability and high-temperature storage performance of the secondary battery.
In any embodiment, the first coating layer includes one or more selected from pyrophosphate, phosphate, an oxide and a boride, and the second coating layer includes one or more selected from carbon and doped carbon.
Therefore, in the present application, the use of a first coating layer of a specific material and a second coating layer of a specific material can further improve the rate performance, further reduce the dissolution of Mn and Mn-site doping elements, thereby improving the cycling performance of the secondary battery and/or high temperature stability.
In any embodiment, the shell includes a first coating layer coating the inner core, a second coating layer coating the first coating layer, and a third coating layer coating the second coating layer;
Therefore, the present application, by using the above materials as the materials of the coating layers, and providing three coating layers, can further reduce the dissolution of Mn and Mn-site doping elements, and further improve the high-temperature cycling performance, cycling stability and high-temperature storage performance stability of the secondary battery.
In any embodiment, the first coating layer includes pyrophosphate, the second coating layer includes one or more selected from phosphate, an oxide and a boride, and the third coating layer includes one or more of carbon and doped carbon.
Therefore, in the present application, the use of the first coating layer of a specific material, the second coating layer of a specific material, and the third coating layer of a specific material further improves the rate performance and further reduces the dissolution of Mn and Mn-site doping elements, thereby improving the cycling performance and/or high-temperature stability of the secondary battery, and further increasing the gram capacity and compacted density of the material.
In any embodiment, each of the one or more coating layers independently includes one or more selected from pyrophosphate, phosphate, carbon, doped carbon, an oxide, a boride and a polymer.
In any embodiment, the pyrophosphate is Mb(P2O7)c; and/or
Therefore, the present application, by using the above materials as the coating layers, can further reduce the dissolution of Mn and Mn-site doping elements further increase the gram capacity and compaction density of the material, and further improve the rate performance and high-temperature cycling performance and high-temperature storage performance of the secondary battery.
In any embodiment, the M, X and Z each independently include one or more elements selected from Li, Fe, Ni, Mg, Co, Cu, Zn, Ti, Ag, Zr, Nb and Al; and/or
Therefore, the present application, by using the above specific materials as the coating layers, can further reduce the dissolution of Mn and Mn-site doping elements and further improve the high-temperature cycling performance and high-temperature storage performance of the secondary battery.
In any embodiment, the positive electrode active material includes an inner core and a shell coating the inner core;
Thus, the positive electrode active material of the present application can improve the gram capacity, cycling performance and safety performance of the secondary battery. Although the mechanism is not yet clear, it is speculated that the lithium manganese phosphate positive electrode active material of the present application has a core-shell structure, wherein doping the lithium manganese phosphate inner core at the manganese and phosphorus sites with elements, not only can effectively reduce the dissolution of manganese, and then reduce the migration of manganese ions to the negative electrode, reduce the consumption of electrolyte due to the decomposition of the SEI film, improve the cycling performance and safety performance of the secondary battery, and also promote the adjustment of Mn—O bonds, reduce the migration barrier of lithium ions, and promote the migration of lithium ions, and improve the rate performance of the secondary battery. Coating the inner core with a first coating layer including pyrophosphate and phosphate can further increase the migration resistance of manganese, and reduce the dissolution thereof, the content of lithium impurity on the surface, and the contact between the inner core and the electrolyte, thereby reducing the interface side reactions, reducing gas production, improving the high-temperature storage performance, cycling performance and safety performance of secondary batteries. By further coating the carbon-containing layer as the second coating layer, the safety performance and kinetic performance of the secondary battery can be further improved.
In any embodiment, the positive electrode active material includes an inner core and a shell coating the inner core;
The present application, by doping elements at the manganese site of lithium manganese phosphate and doping elements at the phosphorus site to obtain a doped lithium manganese phosphate inner core and sequentially coating the surface of the core with three layers, provides a new lithium manganese phosphate positive electrode active material with a core-shell structure, and the use of the positive electrode active material in a secondary battery can significantly improve the high temperature cycling performance, cycling stability and high temperature storage performance of the secondary battery.
In any embodiment, the one or more coating layers in the shell which are farthest from the inner core each independently comprise one or more of polysiloxanes, polysaccharides and polysaccharide derivatives.
As a result, the uniformity of coating can be improved, and the interface side reactions caused by a high voltage can be effectively prevented, thereby improving the high-temperature cycling performance and high-temperature storage performance of the material. Moreover, the coating layer has good electron conductivity and ion conductivity, which helps to increase the gram capacity of the material while reducing the heat generation of the battery cell.
In any embodiment, the polysiloxane comprises a structural unit represented by formula (i),
In any embodiment, the polysiloxane includes a blocking group including at least one selected from the group consisting of the following functional groups: a polyether, a C1-C8 alkyl, a C1-C8 haloalkyl, a C1-C8 heteroalkyl, a C1-C8 halogenated heteroalkyl, a C2-C8 alkenyl, a C2-C8 haloalkenyl, a C6-C20 aromatic hydrocarbon group, a C1-C8 alkoxy, a C2-C8 epoxy group, a hydroxyl, a C1-C8 hydroxyalkyl, an amino, a C1-C8 aminoalkyl, a carboxyl, a C1-C8 carboxyalkyl.
In any embodiment, the polysiloxane includes one or more selected from polydimethylsiloxane, polydiethylsiloxane, polymethylethylsiloxane, polymethylvinylsiloxane, polyphenylmethylsiloxane, polymethylhydrogensiloxane, carboxy-functionalized polysiloxane, epoxy-terminated polysiloxane, methoxy-terminated polydimethylsiloxane, hydroxypropyl-terminated polydimethylsiloxane, polymethylchloropropylsiloxane, hydroxyl-terminated polydimethylsiloxane, polymethyltrifluoropropylsiloxane, perfluorooctylmethylpolysiloxane, aminoethylaminopropyl polydimethylsiloxane, polyether-terminated polydimethylsiloxane, side-chain aminopropyl polysiloxane, aminopropyl-terminated polydimethylsiloxane, side-chain phosphate-grafted polydimethylsiloxane, side-chain polyether-grafted polydimethylsiloxane, 1,3,5,7-octamethylcyclotetrasiloxane, 1,3,5,7-tetrahydro-1,3,5,7-tetramethylcyclotetrasiloxane, cyclopentasiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, cyclic polymethylvinylsiloxane, hexadecylmethylcyclooctasiloxane, tetradecamethylcycloheptasiloxane, and cyclopolydimethylsiloxane.
In any embodiment, the number average molecular weights of the polysiloxane, the polysaccharide and the polysaccharide derivative are each independently 300000 or less, optionally 10000 to 200000, more optionally 20000 to 120000, further optionally 400 to 80000.
In any embodiment, the polysiloxane has a polar functional group mass content percentage of α, with 0≤α<50%, optionally 5%≤α≤30%.
In any embodiment, the substituents attached to the sugar units in the polysaccharide and the polysaccharide derivative each independently include at least one of the following functional groups: —OH, —COOH and a salt thereof, —R—OH, —SO3H and a salt thereof, a sulfate ester group, an alkoxy group, where R represents an alkylene, optionally a C1-C5 alkylene;
optionally, the substituents attached to the sugar units in the polysaccharide and the polysaccharide derivative each independently include at least one of the following functional groups: —OH, —COOH, —COOLi, —COONa, —COOK, —SO3H, —SO3Li, —SO3Na, —SO3K, —CH2—SO3H, —CH2—SO3Li, —CH2—SO3Na, —CH2—SO3K, a methoxy, and an ethoxy.
In any embodiment, the polysaccharide includes one or more selected from pectin, carboxymethyl starch, hydroxypropyl starch, dextrin, cellulose ether, carboxymethyl chitosan, hydroxyethyl cellulose, carboxymethyl cellulose, carboxypropyl methyl cellulose, guar gum, sesbania gum, acacia gum, lithium alginate, sodium alginate, potassium alginate, fucoidan, agar, carrageenan, xanthan gum and fenugreek gum.
In any embodiment, the mass percentages of the substituents attached to the sugar units in the polysaccharide and the polysaccharide derivative are each independently 20% to 85%, optionally 30% to 78%.
In any embodiment, the degree of lattice mismatch between the material of the inner core and the material of the shell is less than 10%. Therefore, the contact between the inner core and the shell (or coating layer) can be improved to prevent the shell (or coating layer) from detachment.
In any embodiment, based on the weight of the positive electrode active material,
When the content of the manganese element in the present application is within the above range, the problems of poor material structure stability and density decreasing can be effectively reduced, thereby improving the performance of the secondary battery such as cycling, storage and compaction density. Moreover, the problem of a too low voltage can be reduced, thereby improving the energy density of the secondary battery.
In any embodiment, the surface of the positive electrode active material is coated with one or more of carbon and doped carbon; optionally, the surface of the positive electrode active material is coated with carbon. Therefore, the electrical conductivity of the positive electrode active material can be improved.
In any embodiment, the doping elements in the doped carbon include one or more selected from nitrogen, phosphorus, sulfur, boron and fluorine. It facilitates to control the properties of the doped carbon layer.
In any implementation, in the inner core,
Therefore, the energy density and cycling performance of the positive electrode active material can be further improved.
In any implementation, in the inner core, the ratio of z to 1-z is 1:9 to 1:999, optionally 1:499 to 1:249. Thus, the cycling performance and rate performance of the secondary battery are further improved.
In any embodiment, the coating amount of the shell is 0.1% to 6%, based on the weight of the inner core. The coating amount of the coating layer in the present application is in some embodiments within the above range, which can enable the full coating of the inner core, while further improving the kinetic performance and safety performance of the secondary battery without sacrificing the gram capacity of the positive electrode active material.
In any embodiment, the coating amount of the first coating layer is greater than 0 wt % and less than or equal to 7 wt %, optionally greater than 0 and less than or equal to 6 wt %, more optionally greater than 0 and less than or equal to 5.5 wt % or 4-5.6 wt %, further optionally greater than 0 and less than or equal to 2 wt %, based on the weight of the inner core; and/or
In any embodiment, the shell further includes a fourth coating layer coating the third coating layer and a fifth coating layer coating the fourth coating layer; wherein
In the positive electrode active material with a core-shell structure of the present application, the coating amount of the each coating layer in the present application is in some embodiments within the above range, which thus can enable the full coating of the inner core, while further improving the kinetic performance and safety performance of the secondary battery without sacrificing the gram capacity of the positive electrode active material.
In any embodiment, the shell is located on 40% to 90% of the surface of the inner core, optionally 60% to 80% of the surface. Thus, the inner core can be fully coated, thereby improving the kinetic performance and safety performance of the secondary battery.
In any embodiment, the thickness of the shell is 1-15 nm.
In any embodiment, the thickness of the first coating layer is 1-10 nm, optionally 2-10 nm; and/or
In the present application, when the first coating layer has a thickness within the above range, the adverse effect on the dynamic performance of the material can be further reduced, and problem that the migration of transition metal ions cannot be effectively prevented can be reduced.
The second coating layer has a thickness within the above range, such that the surface structure of the second coating layer is stable, and the side reaction with the electrolyte is small, so the interface side reaction can be effectively reduced, thereby improving the high temperature performance of the secondary battery.
The third coating layer has a thickness within above range, such that the electrical conductivity of the material can be improved and the compaction density performance of the battery electrode plate prepared by using the positive electrode active material can be improved.
In any embodiment, the one or more coating layers each independently include one or more selected from pyrophosphate, phosphate and an oxide, and from one or more of pyrophosphate, phosphate and an oxide in a crystalline state;
Herein, the crystalline state means that the crystallinity is 50% or more, that is, 50%-100%. A crystalline state with a crystallinity less than 50% is referred to as a glassy state. The crystallinity of the crystalline pyrophosphate and crystalline phosphate of the present application is 50% to 100%.
The pyrophosphate and phosphate with a certain crystallinity enable not only the full achievement of the ability of the pyrophosphate coating layer to prevent the dissolution of manganese and the excellent ability of the phosphate coating layer to conduct lithium ions, as well as the reduction of the interface side reactions, but also the better lattice matching between the phosphate coating layer and the phosphate coating layer, such that a close combination between the coating layer and the coating layer can be achieved.
In any embodiment, in the shell, a weight ratio of the pyrophosphate to the phosphate and a weight ratio of the pyrophosphate to the oxide are each independently 1:3 to 3:1, optionally 1:3 to 1:1. Therefore, using pyrophosphate and phosphate in a suitable weight ratio range or pyrophosphate and oxide in a suitable weight ratio range, can not only effectively prevent the dissolution of manganese, but also effectively reduce the content of lithium impurities on the surface and reduce interface side reactions, thereby improving the high-temperature storage performance, safety performance and cycling performance of the secondary battery.
In any embodiment, the one or more coating layers each independently includes carbon, and the carbon is a mixture of SP2-form carbon and SP3-form carbon; optionally, in the carbon, a molar ratio of the SP2-form carbon to the SP3-form carbon is any value within a range of 0.07-13, more optionally any value within a range of 0.1-10, further optionally any value within a range of 2.0-3.0.
In the present application, the overall performance of the secondary battery is improved by limiting the molar ratio of the SP2-form carbon to the SP3-form carbon within the above range.
In any embodiment, the one or more coating layers each independently include doped carbon, and, in the doped carbon, a mass content of the doping element is no more than 30%; and optionally, in the doped carbon, the mass content of the doping element is 20% or less. Doping elements within the above content range can not only fully improve the conductivity of the pure carbon layer, but also effectively avoid the excessive surface activity due to excessive doping of doping elements, thereby effectively controlling the interface side reactions resulting from the overdoping of the coating layer.
In any embodiment, the one or more coating layers each independently includes doped carbon, and in the doped carbon,
Since the nitrogen atoms and sulfur atoms have an atomic radius closer to that of carbon atoms and the carbon skeleton does not tend to damage, when the doping amounts of nitrogen atoms and sulfur atoms are within the above relatively wide range, the conductivity of the doped carbon layer can be fully utilized, and the lithium ion transport and lithium ion desolvation ability can also be promoted.
Due to the difference in atomic radius between the phosphorus atoms, boron atoms and/or fluorine atoms and the carbon atoms, excessive doping may tend to the damage of the carbon skeleton, so when the phosphorus atoms, boron atoms and/or fluorine atoms are in relatively small doping amounts in the above range, the conductivity of the doped carbon layer can be fully utilized, and the lithium ion transport and lithium ion desolvation ability can also be promoted.
In any embodiment, the one or more coating layers each independently include pyrophosphate, and the pyrophosphate has an interplanar distance in a range of 0.293-0.470 nm, optionally 0.297-0.462 nm or 0.293-0.326 nm, more optionally 0.300-0.310 nm, and the crystal direction (111) has an angle in a range of 18.00°-32.57°, optionally 18.00°-32.00° or 26.41°-32.57°, more optionally 19.211°-30.846°, further optionally 29.00°-30.00°; and/or
Both the first coating layer and the second coating layer in the positive electrode active material of the present application are crystalline substances, and the interplanar spacing and angle ranges thereof are within the above ranges. Thus, the impurity phase in the coating layer can be effectively reduced, thereby improving the gram capacity, cycling performance and rate performance of the material.
In any embodiment, the positive electrode active material has a lattice change rate of, before and after complete lithium intercalation-deintercalation, 50% or less, optionally 9.8% or less, more optionally 8.1% or less, further optionally 7.5% or less, further optionally 6% or less, further optionally 4% or less, further optionally 3.8% or less, and further optionally 2.0-3.8% or less.
Therefore, the use of positive electrode active material can improve the gram capacity and rate performance of the secondary battery.
In any embodiment, the positive electrode active material has an Li/Mn antisite defect concentration of 5.3% or less, optionally 5.1% or less, more optionally 4% or less, further optionally 2.2% or less, more further optionally 2% or less, more further optionally 1.5%-2.2% or 0.5% or less.
The Li/Mn antisite defect concentration within the above range avoids the prevention of transport of Li+ by Mn2+, while increasing the gram capacity and rate performance of the positive electrode active material.
In any embodiment, the positive electrode active material has a compacted density at 3 T of 1.89 g/cm3 or more, optionally 1.95 g/cm3 or more, more optionally 1.98 g/cm3 or more, further optionally 2.0 g/cm3 or more, more further optionally 2.2 g/cm3 or more, more further optionally 2.2 g/cm3 or more and 2.8 g/cm3 or less, or 2.2 g/cm3 or more and 2.65 g/cm3 or less.
Thus, increasing the compaction density increases the weight of the active material per unit volume, which is more conducive to increasing the volumetric energy density of the secondary battery.
In any embodiment, the positive electrode active material has a surface oxygen valence state of −1.55 or less, optionally −1.82 or less, more optionally −1.88 or less, further optionally −1.90 or less or −1.98 to −1.88, more further optionally −1.98 to −1.89, more further optionally −1.98 to −1.90.
Therefore, by limiting the surface oxygen valence state of the positive electrode active material within the above range, the interface side reactions between the positive electrode active material and the electrolyte can be reduced, thereby improving the performance, such as cycling, high temperature storage and gas production, of the battery cell.
The second aspect of the present application also provides a method for preparing a positive electrode active material, including the steps of:
Therefore, in the present application, by doping a compound LiMnPO4 with specific elements in specific amounts at Mn-site and optionally Li, P and/or O-sites, a markedly improved rate performance can be obtained while the dissolution of Mn and Mn-site doping element is significantly reduced, thereby obtaining significantly improved cycling performance and/or high-temperature stability; and the gram capacity and compacted density of the material can also be enhanced.
In any embodiment, the method specifically includes the steps of:
In any embodiment, in the step of preparing the slurry, a lithium source, a phosphorus source, optionally an element A source, optionally an element C source, optionally an element D source, a carbon source, a source of a doping element for a carbon layer, a solvent, and the manganese salt doped with element B are added to a reaction container for grinding and mixing to obtain a slurry; the other steps are the same as above; to obtain the positive electrode active material;
In any embodiment, the method includes the steps of:
In any embodiment, the method includes the steps of:
In any embodiment, the method includes the steps of:
In any embodiment, the method includes the steps of:
In any embodiment, the method includes the steps of:
In any embodiment, the method includes the steps of:
In any embodiment, the method includes the steps of:
In any embodiment, the method includes the steps of:
In any embodiment, the element A source is selected from at least one of the elementary substances, oxides, phosphates, oxalates, carbonates, and sulfates of element A; and/or
In any embodiment, in the step of preparing the manganese salt doped with element B,
In any embodiment, in the step of preparing the slurry, grinding and mixing are carried out for 1-15 hours, optionally 8-15 hours; optionally, the mixing is carried out at a temperature of 20-120° C., more optionally 40-120° C., for 1-10 h.
In any embodiment, in the step of preparing the inner core, the sintering is carried out at a temperature in a range of 600-900° C. for 6-14 hours.
In any embodiment, the step of preparing the slurry also includes: a carbon source is added into the reaction container for grinding and mixing.
In any embodiment, the MP2O7 powder is prepared by the following procedure:
In any embodiment, in the method for preparing an MP2O7 powder,
The drying step involves drying at 100-300° C., optionally 150-200° C., for 4-8 hours.
In any embodiment, in the method for preparing an MP2O7 powder,
the sintering step involves sintering at 500-800° C., optionally 650-800° C., in an inert gas atmosphere for 4-10 hours.
In any embodiment, the sintering temperature in the coating step is 500-800° C., and the sintering time is 4-10 hours.
In any embodiment, in the first coating step,
In any embodiment, in the second coating step,
In any embodiment, the sintering in the third coating step is carried out at 700-800° C. for 6-10 hours.
A third aspect of the present application provides a positive electrode plate, including a positive electrode current collector and a positive electrode film layer provided on at least one surface of the positive electrode current collector, wherein the positive electrode film layer includes a first positive electrode active material, and the first positive electrode active material is a positive electrode active material of the first aspect of the present application, or a positive electrode active material prepared by the method of the second aspect of the present application; optionally, the content of the positive electrode active material in the positive electrode film layer is 90-99.5 wt %, more optionally 95-99.5 wt %, based on the total weight of the positive electrode film layer.
In any embodiment, the positive electrode plate further includes a second positive electrode active material, and the second positive electrode active material is different from the first positive electrode active material.
In any embodiment, the second positive electrode active material includes one or more of LiEtCosF(1-t-s)O2, spinel-type lithium manganate and spinel-type of lithium titanate, wherein E includes one or more elements selected from group VIII, F includes one or more elements selected from groups IIIA and VIIB, t is selected from a range of 0 to 0.9, the sum of t and s is selected from a range of 0.3 to 1.
In any embodiment, E includes one or more elements selected from Ni, Fe, Ru, and Rh, and F includes one or more elements selected from Mn, Al, Ga, and In.
In any embodiment, the second positive electrode active material is selected from one or more of LiNitCosMn(1-t-s)O2, LiNitCosAl(1-t-s)O2, LiCoO2, spinel-type lithium manganate and spinel-type lithium titanate; wherein t is independently selected from 0.3-0.9, optionally 0.33-0.8, and the sum oft and s is independently selected from 0.3-0.9, optionally 0.66-0.9.
In any embodiment, the mass ratio of the first active material to the second active material is 1:7-7:1, optionally 1: 4-4:1.
In any embodiment, in the second positive electrode active material,
In any embodiment, the sum of the mass of the first positive electrode active material and the second positive electrode active material accounts for 88%-98.7% of the mass of the positive electrode plate.
A fourth aspect of the present application provides a secondary battery, including the positive electrode active material of the first aspect of the present application or the positive electrode active material prepared by the method of the second aspect of the present application or the positive electrode plate of the third aspect of the present application.
A fifth aspect of the present application provides a battery module comprising the secondary battery of the fourth aspect of the present application.
A sixth aspect of the present application provides a battery pack comprising the battery module of the fifth aspect of the present application.
A seventh aspect of the present application provides a power consuming device, including at least one selected from a secondary battery of the fourth aspect of the present application, a battery module of the fifth aspect of the present application and a battery pack of the sixth aspect of the present application.
1. A positive electrode active material having a chemical formula of LiaAxMn1-yByP1-zCzO4-nDn
2. The positive electrode active material of item 1, wherein the A, C and D are each independently any element in the respective ranges, and the B is at least two elements in the range thereof;
3. The positive electrode active material according to 1 or 2, wherein the x is selected from a range of 0.001 to 0.005; and/or, the y is selected from a range of 0.01 to 0.5, and optionally in a range of 0.25 to 0.5; and/or, the z is selected from a range of 0.001 to 0.005; and/or, the n is selected from a range of 0.001 to 0.005.
4. The positive electrode active material of any one of items 1 to 3, wherein (1-y):y is in a range of 1 to 4, and optionally in a range of 1.5 to 3, and a:x is in a range of 9 to 1100, and optionally in a range of 190 to 998.
5. The positive electrode active material of any one of items 1 to 4, wherein it has a lattice change rate of 8% or less, and optionally 4% or less.
6. The positive electrode active material of any one of items 1 to 5, wherein it has an Li/Mn antisite defect concentration of 2% or less, and optionally 0.5% or less.
7. The positive electrode active material of any one of items 1 to 6, wherein it has a surface oxygen valence state of no more than −1.82, and optionally −1.89 to −1.98.
8. The positive electrode active material of any one of items 1 to 7, wherein it has a compacted density under 3 T of 2.0 g/cm3 or more, and optionally 2.2 g/cm3 or more.
9. The positive electrode active material of any one of items 1 to 8, wherein it has a surface coated with carbon.
10. A method for preparing a positive electrode active material, comprising the steps of:
11. The method of item 10, wherein the element A source is selected from at least one of the elementary substance, oxide, phosphate, oxalate, carbonate and sulfate of the element A, the element B source is selected from at least one of the elementary substance, oxide, phosphate, oxalate, carbonate and sulfate of the element B, the element C source is selected from at least one of the sulfate, borate, nitrate and silicate of the element C, and the element D source is selected from at least one of the elementary substance and ammonium salt of the element D.
12. The method of item 10 or 11, wherein the stirring of step (1) is carried out at a temperature in a range of 60° C. to 120° C., and/or
13. The method of any one of items 10 to 12, wherein the grinding and mixing of step (2) are carried out for 8 to 15 h.
14. The method of any one of items 10 to 13, wherein the sintering in step (4) is carried out at a temperature in a range of 600-900° C. for 6-14 hours.
15. The method of any one of items 10 to 14, wherein step (2) also includes: a carbon source is added into the reaction container for grinding and mixing.
16. A positive electrode plate, including a positive electrode current collector and a positive electrode film layer provided on at least one surface of the positive electrode current collector, the positive electrode film layer including a positive electrode active material of any one of items 1 to 9 or a positive electrode active material prepared by the method of any one of items to 15, and the content of the positive electrode active material in the positive electrode film layer being 10 wt % or more, and optionally 95 to 99.5 wt %, based on the total weight of the positive electrode film layer.
17. A secondary battery, including a positive electrode active material of any one of items 1 to 8 or a positive electrode active material prepared by the method of any one of items 10 to 15 or a positive electrode plate of item 16.
18. A battery module, wherein it includes a secondary battery of item 17.
19. A battery pack, wherein it includes a battery module of item 18.
20. A power consuming device, including at least one selected from a secondary battery of item 17, a battery module of item 18, and a battery pack of item 19.
1) a positive electrode active material with a core-shell structure, which includes an inner core and a shell coating the inner core,
2) The positive electrode active material of item 1), wherein
3) The positive electrode active material of item 1) or 2), wherein
4) The positive electrode active material of items 1)-3), wherein
5) The positive electrode active material of items 1)-4), wherein
6) The positive electrode active material of items 1)-5), wherein
7) The positive electrode active material of items 1)-6), wherein
8) The positive electrode active material of items 1)-7), wherein
The coating amount of the second coating layer is greater than 0 wt % and less than or equal to 6 wt %, optionally 3-5 wt %, based on the weight of the inner core.
9) The positive electrode active material of items 1)-8), wherein
10) The positive electrode active material of items 1)-9), wherein
11) The positive electrode active material of items 1)-10), wherein
12) The positive electrode active material of items 1)-11), wherein
13) The positive electrode active material of items 1)-12), wherein
14) A method for preparing a positive electrode active material, including the following steps:
15) The preparation method for the positive electrode active material of item 14), wherein the step to provide the inner core material includes the steps of:
16) The method of item 15), wherein
17) The method of any one of items 15) to 16), wherein
18) The method of any one of items 14) to 17), wherein
19) The method of item 18), wherein
20) The method of any one of items 18) to 19), wherein
21) The method of any one of items 14) to 20), wherein
22) A positive electrode plate, including a positive electrode current collector and a positive electrode film layer provided on at least one surface of the positive electrode current collector, the positive electrode film layer including a positive electrode active material of any one of items 1) to 13) or a positive electrode active material prepared by the method of any one of items 14) to 21), and the content of the positive electrode active material in the positive electrode film layer being 10 wt % or more, based on the total weight of the positive electrode film layer.
23) The positive electrode plate of item 22), wherein the content of the positive electrode active material in the positive electrode film layer is 90-99.5 wt %, based on the total weight of the positive electrode film layer.
24) A secondary battery, including a positive electrode active material of any one of items 1) to 13) or a positive electrode active material prepared by the method of any one of items 14) to 21) or a positive electrode plate of item 22) or 23).
25) A battery module, characterized by including a secondary battery of item 24).
26) A battery pack, characterized by including a battery module of item 25).
27) A power consuming device, characterized by including at least one selected from a secondary battery of item 24), a battery module of item 25), and a battery pack of item 26).
(1). A positive electrode active material with a core-shell structure, which includes an inner core and a shell coating the inner core,
the inner core has a chemical formula of Li1+xMn1-yAyP1-zRzO4, where x is any value in a range of −0.100 to 0.100, y is any value in a range of 0.001 to 0.500, z is any value in a range of 0.001 to 0.100, and A is one or more elements selected from Zn, Al, Na, K, Mg, Mo, W, Ti, V, Zr, Fe, Ni, Co, Ga, Sn, Sb, Nb and Ge, optionally one or more elements of Fe, Ti, V, Ni, Co and Mg, R is one or more elements selected from B, Si, N and S, optionally, R is an element selected from B, Si, N and S;
(2) The positive electrode active material with a core-shell structure of item (1), wherein
(3) The positive electrode active material with a core-shell structure of item (1) or (2), wherein in the inner core, the ratio of y to 1-y is 1:10 to 1:1, optionally 1:4 to 1:1.
(4) The positive electrode active material with a core-shell structure of items (1) to (3), wherein in the inner core, the ratio of z to 1-z is 1:9 to 1:999, optionally 1:499 to 1:249.
(5) The positive electrode active material with a core-shell structure of (1)-(4), wherein the carbon in the third coating layer is a mixture of SP2-form carbon and SP3-form carbon, optionally, the molar ratio of the SP2-form carbon to the SP3-form carbon is any value within a range of 0.1-10, optionally any value within a range of 2.0-3.0.
(6) The positive electrode active material with a core-shell structure of any one of items (1) to (5), wherein
(7) The positive electrode active material with a core-shell structure of any one of (1)-(6), wherein the first coating layer has a thickness of 1-10 nm; and/or
(8) The positive electrode active material with a core-shell structure of any one of items (1) to (7), wherein
(9) The positive electrode active material with a core-shell structure of any one of items (1)-(8), wherein the positive electrode active material with a core-shell structure has a lattice change rate, before and after complete intercalation-deintercalation, of lithium of 4% or less, optionally 3.8% or less, more optionally 2.0-3.8% or less.
(10) The positive electrode active material with a core-shell structure of any one of items (1)-(9), wherein the positive electrode active material with a core-shell structure has an Li/Mn antisite defect concentration of is 4% or less, optionally 2.2% or less, more optionally 1.5-2.2%.
(11) The positive electrode active material with a core-shell structure of any one of items (1)-(10), wherein the positive electrode active material with a core-shell structure has a compacted density under 3 T of 2.2 g/cm3 or more, optionally 2.2 g/cm3 or more and 2.8 g/cm3 or less.
(12) The positive electrode active material with a core-shell structure of any one of items (1)-(11), wherein the positive electrode active material with a core-shell structure has a surface oxygen valence state of −1.90 or less, optionally −1.90 to −1.98.
(13) A method for preparing a positive electrode active material, including the following steps:
(14) The preparation method for the positive electrode active material of item (13), wherein the step to provide the inner core material includes the steps of:
(15) The preparation method for a positive electrode active material of item (14), wherein
(16) The preparation method for a positive electrode active material of item (14), wherein in step (2), the mixing is carried out at a temperature of 20-120° C., optionally 40-120° C., for 1-10 hours.
(17) The preparation method for a positive electrode active material of any one of items (14)-(16), wherein
(18) The preparation method for a positive electrode active material of any one of items (13)-(17), wherein the coating step includes:
(19) The preparation method for a positive electrode active material of item (18), wherein
(20) The preparation method for a positive electrode active material of any one of items (18)-(19), wherein
(21) The preparation method for a positive electrode active material of any one of items (18)-(20), wherein the sintering in the third coating step is carried out at 700-800° C. for 6-10 hours.
(22) A positive electrode plate, including a positive electrode current collector and a positive electrode film layer provided on at least one surface of the positive electrode current collector, the positive electrode film layer including a positive electrode active material with a core-shell structure of any one of items (1) to (12) or a positive electrode active material prepared by the preparation method for a positive electrode active material of any one of items (13) to (21), and the content of the positive electrode active material in the positive electrode film layer being no less than 90-99.5 wt %, optionally 95 to 99.5 wt %, based on the total weight of the positive electrode film layer.
(23) A secondary battery, including a positive electrode active material of any one of items (1) to (12) or a positive electrode active material prepared by the preparation method for a positive electrode active material of any one of items (13) to (21) or a positive electrode plate of item (22).
(24) A battery module, including a secondary battery of item (23).
(25) A battery pack, including a battery module of item (24).
(26) A power consuming device, including at least one selected from a secondary battery of item (23), a battery module of item (24), and a battery pack of item (25).
1 battery pack; 2 upper box body; 3 lower box body; 4 battery module; 5 secondary battery; 51 housing; 52 electrode assembly; 53 top cover assembly.
Hereinafter, embodiments of the positive electrode active material and the preparation method therefor, the negative electrode plate, the secondary battery, the battery module, the battery pack, and the power consuming device of the present application are described in detail and specifically disclosed with reference to the accompanying drawings as appropriate. However, unnecessary detailed illustrations may be omitted in some instances. For example, there are situations where detailed description of well known items and repeated description of actually identical structures are omitted. This is to prevent the following description from being unnecessarily verbose, and facilitates understanding by those skilled in the art. Moreover, the accompanying drawings and the descriptions below are provided for enabling those skilled in the art to fully understand the present application, rather than limiting the subject matter disclosed in claims.
“Ranges” disclosed in the present application are defined in the form of lower and upper limits, and a given range is defined by selection of a lower limit and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive, and may be arbitrarily combined, that is, any lower limit may be combined with any upper limit to form a range. For example, if the ranges of 60-120 and 80-110 are listed for a particular parameter, it should be understood that the ranges of 60-110 and 80-120 are also contemplated. Additionally, if minimum range values 1 and 2 are listed, and maximum range values 3, 4, and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In the present application, unless stated otherwise, the numerical range “a-b” denotes an abbreviated representation of any combination of real numbers between a and b, where both a and b are real numbers. For example, the numerical range “0-5” means that all real numbers between “0-5” have been listed herein, and “0-5” is just an abbreviated representation of combinations of these numerical values. In addition, when a parameter is expressed as an integer of ≥2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, and the like.
All the implementations and optional implementations of the present application can be combined with one another to form new technical solutions, unless otherwise stated.
All technical features and optional technical features of the present application can be combined with one another to form a new technical solution, unless otherwise stated.
Unless otherwise stated, all the steps of the present application can be carried out sequentially or randomly, in some embodiments sequentially. For example, the method including steps (a) and (b) indicates that the method may include steps (a) and (b) carried out sequentially, and may also include steps (b) and (a) carried out sequentially. For example, reference to “the method may further include step (c)” indicates that step (c) may be added to the method in any order, e.g., the method may include steps (a), (b) and (c), steps (a), (c) and (b), or steps (c), (a) and (b).
The terms “comprise” and “include” mentioned in the present application are open-ended, unless otherwise stated. For example, “comprise” and “include” may mean that other components not listed may or may not further be comprised or included.
In the present application, the term “or” is inclusive unless otherwise specified. For example, the phrase “A or B” means “A, B, or both A and B”. More specifically, a condition “A or B” is satisfied by any one of the following: A is true (or present) and B is false (or not present); A is false (or not present) and B is true (or present); or both A and B are true (or present). In this disclosure, the phrases “at least one of A, B, and C” and “at least one of A, B, or C” both mean only A, only B, only C, or any combination of A, B, and C.
[Secondary Battery]
A secondary battery, also known as a rechargeable battery or an accumulator, refers to a battery of which active materials can be activated by means of charging for reuse of the battery after the battery is discharged.
Generally, the secondary battery comprises a positive electrode plate, a negative electrode plate, a separator and an electrolyte. During a charge/discharge process of the battery, active ions (e.g., lithium ions) are intercalated and de-intercalated back and forth between the positive electrode plate and the negative electrode plate. The separator is provided between the positive electrode plate and the negative electrode plate, and mainly prevents positive and negative electrodes from short-circuiting and enables the active ions to pass through. The electrolyte is provided between the positive electrode plate and the negative electrode plate and mainly functions for active ion conduction.
[Positive Electrode Active Material]
One embodiment of the present application provides a positive electrode active material, including a compound represented by formula (I),
LiaAxMn1-yByP1-zCzO4-nDn (I)
Unless otherwise stated, in the above chemical formula, when the A is a combination of at least two elements, the above definition of the numerical range of x not only represents a definition of the stoichiometric number of each element as A, but also represents a definition of the sum of the stoichiometric numbers of the elements as A. For example, when the A is a combination of at least two elements A1, A2 . . . An, the stoichiometric numbers x1, x2 . . . xn of A1, A2 . . . An each fall within the numerical range of x defined in the present application, and the sum of x1, x2 . . . xn also falls within this numerical range. Similarly, when B, C and D are each a combination of at least two elements, the definitions of the numerical ranges of the stoichiometric numbers of B, C and D in the present application also have the above meanings.
The positive electrode active material of the present application is obtained by doping a compound LiMnPO4 with elements, wherein A, B, C and D are respectively the elements for doping at Li, Mn, P and O sites of the compound LiMnPO4. Without wishing to be bound by theory, it is now believed that a performance improvement of lithium manganese phosphate is associated with a reduction in the lattice change rate of lithium manganese phosphate in a lithium intercalation/de-intercalation process and a decrease in surface activity. A reduction in the lattice change rate can reduce the difference of lattice constants between two phases at a grain boundary, lower the interface stress and enhance the Li+ transport ability at an interface, thereby improving the rate performance of the positive electrode active material. A high surface activity can easily lead to severe interfacial side reactions, and exacerbates gas production, electrolyte solution consumption and interface damage, thereby affecting the cycling performance and the like of the battery. In the present application, the lattice change rate can be reduced by doping at the Li and/or Mn sites. The Mn-site doping also effectively decreases the surface activity, thereby inhibiting the Mn dissolution and the interfacial side reactions between the positive electrode active material and the electrolyte solution. The P-site doping increases the change rate of the Mn—O bond length and reduces the small-polaron migration barrier of the material, which is beneficial for electronic conductivity. The O-site doping plays a good role in reducing the interfacial side reactions. The P-site and O-site doping also has an effect on the dissolution of Mn of antisite defects and the dynamic performance. Therefore, the doping reduces the antisite effect concentration in the material, improves the dynamic performance and gram capacity of the material, and can also change the particle morphology, thereby increasing the compacted density. The applicant has unexpectedly found that: By doping a compound LiMnPO4 at Mn site and optionally Li, P and/or O sites with specific amounts of specific elements, a markedly improved rate performance can be obtained while the dissolution of Mn and Mn-site doping element is significantly reduced, thereby obtaining significantly improved cycling performance and/or high-temperature stability; and the gram capacity and compacted density of the material can also be enhanced.
In some embodiments, the A includes one or more elements selected from Rb, Cs, Be, Ca, Sr, Ba, Ga, In, Cd, V, Ta, Cr, Zn, Al, Na, K, Mg, Nb, Mo and W, optionally one or more elements selected from Zn, Al, Na, K, Mg, Nb, Mo and W; and/or
In some embodiments, the A includes any element selected from Zn, Al, Na, K, Mg, Nb, Mo and W, and optionally any element selected from Mg and Nb; and/or
By selecting the Li-site doping element in the above ranges, the lattice change rate in a lithium de-intercalation process can be further reduced, thereby further improving the rate performance of the battery. By selecting the Mn-site doping element in the above ranges, the electronic conductivity can be further increased while the lattice change rate is further reduced, thereby improving the rate performance and gram capacity of the battery. By selecting the P-site doping element in the above ranges, the rate performance of the battery can be further improved. By selecting the O-site doping element in the above ranges, interfacial side reactions can be further alleviated, thereby improving the high-temperature performance of the battery.
In some embodiments, the a is selected from a range of 0.9 to 1.1, optionally in a range of 0.97 to 1.01; and/or
By selecting the y value in the above ranges, the gram capacity and rate performance of the material can be further improved. By selecting the x value in the above ranges, the dynamic performance of the material can be further improved. By selecting the z value in the above ranges, the rate performance of the secondary battery can be further improved. By selecting the n value in the above ranges, the high-temperature performance of the secondary battery can be further improved.
In some embodiments, the x is 0, z is selected from a range of 0.001 to 0.5, and n is selected from a range of 0.001 to 0.1; or,
Therefore, the present application, by doping the compound LiMnPO4 with specific elements in specific amounts at the Mn-site and optionally at the Li-site, P-site and/or O-site, especially at the Mn-site and the P-site of LiMnPO4 or doping LiMnPO4 with specific elements in specific amounts at the Li-site, Mn-site, P-site, and O-site, can significantly improve the rate performance, significantly reduce the dissolution of Mn and Mn-site doping elements, and significantly improve the cycling performance and/or high temperature stability and remarkably improve the gram capacity and the compaction density of the material.
In some embodiments, y:z is selected from a range of 0.002 to 999, optionally in a range of 0.025 to 999 or 0.002 to 500, more optionally in a range of 0.2 to 600, such as 0.2, 0.25, 1, 2, 3, 4, 5, 6, 8, 10, 12, 13, 15, 17, 20, 70, 80, 84, 67, 91, 100, 134, 150, 182, 200, 250, 300, 320, 350, 400, 420, 450, 500, 600, 999 or a range composed of any two of the above values. Therefore, the defects of the material can be reduced, and the integrity of the frame structure of the material can be improved, thereby effectively improving the structural stability of the material, and further improving the cycling stability of the secondary battery.
In some embodiments, z:n is selected from a range of 0.002 to 500, optionally in a range of 0.2 to 100, more optionally in a range of 0.2 to 50, such as 0.2, 0.8, 1, 1.25, 4, 5, 50 or a range composed of any two of the above values. Therefore, the defects of the material can be further reduced, and the integrity of the frame structure of the material can be further improved, thereby effectively improving the structural stability of the material, and further improving the cycling stability of the secondary battery.
In some embodiments,
Therefore, in the present application, by doping a compound LiMnPO4 at Li, Mn, P and O sites with specific amounts of specific elements, a markedly improved rate performance can be obtained while the dissolution of Mn and Mn-site doping element is significantly reduced, thereby obtaining significantly improved cycling performance and/or high-temperature stability; and the gram capacity and compacted density of the material can also be enhanced.
In some embodiments,
Thus, the present application, by doping the compound LiMnPO4 with specific elements in specific amounts at the Mn-site and P-site, can improve the rate performance, reduce the dissolution of Mn and Mn-site doping elements, improve the cycling performance and/or high temperature stability, increase the gram capacity and compaction density of the material.
The average particle size range of the inner core prepared in the present application is 50-500 nm, and the Dv50 is 200-300 nm. The primary particle size of the inner core is in a range of 50-500 nm, and the Dv50 is 200-300 nm. Thus, the gram capacity of the secondary battery is increased, and the uniformity of the coating layer coating the inner core is improved.
In this application, the median particle size DV50 represents a particle size corresponding to a cumulative volume distribution percentage of the material reaching 50%. In the present application, the median particle size Dv50 of the material may be determined using a laser diffraction particle size analysis method. For example, the determination may be carried out with reference to the standard GB/T 19077-2016 using a laser particle size analyzer (e.g., Malvern Master Size 3000).
It is possible to ensure that each element is uniformly distributed in the crystal lattice without aggregation by means of process control (for example, sufficient mixing and grinding of various source materials). The positions of the main characteristic peaks in the XRD pattern of the lithium manganese phosphate doped with B and C elements are consistent with those of the undoped LiMnPO4, indicating that no impurity phase is introduced in the doping process, and an improvement in performance of the inner core is mainly attributed to the doping with elements, rather than an impurity phase. After preparing the positive electrode active material of the present application, the inventors of the present application cut out an middle area of the prepared positive electrode active material particles by a focusing ion beam (abbreviated as FIB), and tested through transmission electron microscope (abbreviated as TEM) and X-ray energy dispersive spectrum (abbreviated as EDS) analysis and found that the elements are uniformly distributed with no aggregation.
In some embodiments, the positive electrode active material includes an inner core and a shell coating the inner core, and the inner core includes a compound as shown in the above formula (I);
The present application, by doping the compound LiMnPO4 with specific elements in specific amounts at the Mn site and doping elements at Li-site, P-site and/or O-site to obtain a doped lithium manganese phosphate inner core and providing a coating on the surface of the core having ion conductivity and electron conductivity, provides a new positive electrode active material with a core-shell structure, and the use of the positive electrode active material in a secondary battery can significantly improve the high temperature cycling performance, cycling stability and high temperature storage performance of the secondary battery.
In some embodiments, the shell includes a coating layer;
Therefore, the present application can obtain a coating layer with ion conductivity or electron conductivity by using the above materials, thereby improving the high-temperature cycling performance, cycling stability and high-temperature storage performance of the secondary battery.
In some embodiments, the shell includes a first coating layer coating the inner core and a second coating layer coating the first coating layer;
Therefore, the present application using the above materials as the materials of the coating layers, and providing two layers of coating layers can further improve the high-temperature cycling performance, cycling stability and high-temperature storage performance of the secondary battery.
In some embodiments, the first coating layer includes one or more selected from pyrophosphate, phosphate, an oxide and a boride, and the second coating layer includes one or more selected from carbon and doped carbon.
Therefore, in the present application, the use of a first coating layer of a specific material and a second coating layer of a specific material can further improve the rate performance, further reduce the dissolution of Mn and Mn-site doping elements, thereby improving the cycling performance of the secondary battery and/or high temperature stability.
In some embodiments, the shell includes a first coating layer coating the inner core, a second coating layer coating the first coating layer, and a third coating layer coating the second coating layer;
Therefore, the present application, by using the above materials as the materials of the coating layers, and providing three coating layers, can further reduce the dissolution of Mn and Mn-site doping elements, and further improve the high-temperature cycling performance, cycling stability and high-temperature storage performance stability of the secondary battery.
In some embodiments, the first coating layer includes pyrophosphate, the second coating layer includes one or more selected from phosphate, an oxide and a boride, and the third coating layer includes one or more of carbon and doped carbon.
Therefore, in the present application, the use of the first coating layer of a specific material, the second coating layer of a specific material, and the third coating layer of a specific material further improves the rate performance and further reduces the dissolution of Mn and Mn-site doping elements, thereby improving the cycling performance and/or high-temperature stability of the secondary battery, and further increasing the gram capacity and compacted density of the material.
In some embodiments, each of the one or more coating layers independently includes one or more selected from pyrophosphate, phosphate, carbon, doped carbon, an oxide, a boride and a polymer.
In some embodiments, the pyrophosphate is Mb(P2O7)c; and/or
Therefore, the present application, by using the above materials as the coating layers, can further reduce the dissolution of Mn and Mn-site doping elements further increase the gram capacity and compaction density of the material, and further improve the rate performance and high-temperature cycling performance and high-temperature storage performance of the secondary battery.
In some embodiments, the M, X and Z each independently include one or more elements selected from Li, Fe, Ni, Mg, Co, Cu, Zn, Ti, Ag, Zr, Nb and Al; and/or
Therefore, the present application, by using the above specific materials as the coating layers, can further reduce the dissolution of Mn and Mn-site doping elements and further improve the high-temperature cycling performance and high-temperature storage performance of the secondary battery.
In some embodiments, the positive electrode active material includes an inner core and a shell coating the inner core;
As shown in
It should be pointed out that, as shown in
In some embodiments, the positive electrode active material includes an inner core and a shell coating the inner core;
The positive electrode active material of the present application can improve the gram capacity, cycling performance and safety performance of the secondary battery. Although the mechanism is not yet clear, it is speculated that the lithium manganese phosphate positive electrode active material of the present application has a core-shell structure, wherein doping the lithium manganese phosphate inner core at the manganese and phosphorus sites with element B and element C, not only can effectively reduce the dissolution of manganese, and then reduce the migration of manganese ions to the negative electrode, reduce the consumption of electrolyte due to the decomposition of the SEI film, improve the cycling performance and safety performance of the secondary battery, and also promote the adjustment of Mn—O bonds, reduce the migration barrier of lithium ions, and promote the migration of lithium ions, and improve the rate performance of the secondary battery. Coating the inner core with a first coating layer including pyrophosphate can further increase the migration resistance of manganese, and reduce the dissolution thereof, the content of lithium impurity on the surface, and the contact between the inner core and the electrolyte, thereby reducing the interface side reactions, reducing gas production, improving the high-temperature storage performance, cycling performance and safety performance of secondary batteries. Further coating with a phosphate coating layer with excellent lithium ion conductivity, the interface side reactions on the surface of the positive electrode active material can be effectively reduced, thereby improving the high-temperature cycling and storage performance of the secondary battery. Further coating with a carbon layer as the third coating layer, can further improve the safety performance and kinetic performance of the secondary battery. In addition, in the inner core, the element B doped at the manganese site of lithium manganese phosphate also facilitates to reduce the lattice change rate of the lithium manganese phosphate during the process of lithium intercalation-deintercalation, and improves the structural stability of the lithium manganese phosphate positive electrode active material, greatly reducing the dissolution of manganese and reducing the oxygen activity on the particle surface. The element C doped at the phosphorus site also facilitates to change the difficulty of the change of the Mn—O bond length, thereby improving the electron conductivity and reducing the migration barrier of lithium ions, promoting the migration of lithium ions, and improving the rate performance of the secondary battery.
In addition, the entire inner core system keeps electrical neutrality, which can ensure that the defects and impurity phases in the positive electrode active material are as small as possible. If there is an excess of a transition metal (such as manganese) in the positive electrode active material, since the structure of the material system itself is relatively stable, the excess transition metal is likely prone to be precipitated in the form of an elementary substance, or form impurity phases inside the lattice to keep the electrical neutrality, so that such an impurity can be as little as possible. In addition, ensuring the electrical neutrality of the system can also result in lithium vacancies in the material in some cases, so that the kinetic performance of the material is more excellent.
In some embodiments, the one or more coating layers in the shell which are farthest from the inner core each independently comprise one or more of polysiloxanes, polysaccharides and polysaccharide derivatives.
As a result, the uniformity of coating can be improved, and the interface side reactions caused by a high voltage can be effectively prevented, thereby improving the high-temperature cycling performance and high-temperature storage performance of the material. Moreover, the coating layer has good electron conductivity and ion conductivity, which helps to increase the gram capacity of the material while reducing the heat generation of the battery cell.
In some embodiments, the polysiloxane comprises a structural unit represented by formula (i),
In some embodiments, the polysiloxane includes a blocking group including at least one selected from the group consisting of the following functional groups: a polyether, a C1-C8 alkyl, a C1-C8 haloalkyl, a C1-C8 heteroalkyl, a C1-C8 halogenated heteroalkyl, a C2-C8 alkenyl, a C2-C8 haloalkenyl, a C6-C20 aromatic hydrocarbon group, a C1-C8 alkoxy, a C2-C8 epoxy group, a hydroxyl, a C1-C8 hydroxyalkyl, an amino, a C1-C8 aminoalkyl, a carboxyl, a C1-C8 carboxyalkyl.
In some embodiments, the polysiloxane includes one or more selected from polydimethylsiloxane, polydiethylsiloxane, polymethylethylsiloxane, polymethylvinylsiloxane, polyphenylmethylsiloxane, polymethylhydrogensiloxane, carboxy-functionalized polysiloxane, epoxy-terminated polysiloxane, methoxy-terminated polydimethylsiloxane, hydroxypropyl-terminated polydimethylsiloxane, polymethylchloropropylsiloxane, hydroxyl-terminated polydimethylsiloxane, polymethyltrifluoropropylsiloxane, perfluorooctylmethylpolysiloxane, aminoethylaminopropyl polydimethylsiloxane, polyether-terminated polydimethylsiloxane, side-chain aminopropyl polysiloxane, aminopropyl-terminated polydimethylsiloxane, side-chain phosphate-grafted polydimethylsiloxane, side-chain polyether-grafted polydimethylsiloxane, 1,3,5,7-octamethylcyclotetrasiloxane, 1,3,5,7-tetrahydro-1,3,5,7-tetramethylcyclotetrasiloxane, cyclopentasiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, cyclic polymethylvinylsiloxane, hexadecylmethylcyclooctasiloxane, tetradecamethylcycloheptasiloxane, and cyclopolydimethylsiloxane.
In some embodiments, the number average molecular weights of the polysiloxane, the polysaccharide and the polysaccharide derivative are each independently 300000 or less, optionally 10000 to 200000, more optionally 20000 to 120000, further optionally 400 to 80000.
In some embodiments, the polysiloxane has a polar functional group mass content percentage of α, with 0≤α<50%, optionally 5%≤α≤30%.
In some embodiments, the substituents attached to the sugar units in the polysaccharide and the polysaccharide derivative each independently include at least one of the following functional groups: —OH, —COOH and a salt thereof, —R—OH, —SO3H and a salt thereof, a sulfate ester group, an alkoxy group, where R represents an alkylene, optionally a C1-C5 alkylene;
In some embodiments, the polysaccharide includes one or more selected from pectin, carboxymethyl starch, hydroxypropyl starch, dextrin, cellulose ether, carboxymethyl chitosan, hydroxyethyl cellulose, carboxymethyl cellulose, carboxypropyl methyl cellulose, guar gum, sesbania gum, acacia gum, lithium alginate, sodium alginate, potassium alginate, fucoidan, agar, carrageenan, xanthan gum and fenugreek gum.
In some embodiments, the mass percentages of the substituents attached to the sugar units in the polysaccharide and the polysaccharide derivative are each independently 20% to 85%, optionally 30% to 78%.
In some embodiments, the degree of lattice mismatch between the material of the inner core and the material of the shell is less than 10%. Therefore, the contact between the inner core and the shell (or coating layer) can be improved to prevent the shell (or coating layer) from detachment.
In some embodiments, based on the weight of the positive electrode active material,
In the present application, in the case where manganese is contained only in the inner core of the positive electrode active material, the content of manganese may correspond to that of the inner core.
In the present application, limiting the manganese element content within the above range can further improve the stability and density of the material, thereby improving the performance of the secondary battery such as cycling, storage and compaction density. Moreover, a relatively high voltage can be maintained, thereby improving the energy density of the secondary battery.
In the present application, limiting the phosphorus element content within the above range can effectively reduce the influence of small polaron conduction on the electrical conductivity of the material, and can further improve the stability of the lattice structure, thereby affecting the overall stability of the material.
The weight ratio of manganese to phosphorus content has the following effects on the performance of secondary battery: it can further reduce the dissolution of manganese, further improve the stability and gram capacity of the positive electrode active material, and then affect the cycling performance and storage performance of the secondary battery; it can reduce the impurity phase and further reduce the discharge voltage platform of the material, thereby reducing the energy density of the secondary battery.
The determination of manganese and phosphorus elements can be carried out by conventional technical means in the art. In particular, the following methods are used to determine the manganese and phosphorus contents: dissolving the material in dilute hydrochloric acid (concentration 10-30%), measuring the content of each element in the solution using ICP, and then determining and converting the manganese content to obtain the weight percentage thereof.
In some embodiments, the surface of the positive electrode active material is coated with one or more of carbon and doped carbon; optionally, the surface of the positive electrode active material is coated with carbon. Therefore, the electrical conductivity of the positive electrode active material can be improved.
In some embodiments, the doping elements in the doped carbon include one or more selected from nitrogen, phosphorus, sulfur, boron and fluorine. It facilitates to control the properties of the doped carbon layer.
In some embodiments, in the inner core,
Here, y denotes the sum of the stoichiometric numbers of the Mn-site doping elements. When the above conditions are satisfied, the energy density and cycling performance of the positive electrode active material can be further improved.
In some embodiments, in the inner core, the ratio of z to 1-z is 1:9 to 1:999, optionally 1:499 to 1:249. When the above conditions are satisfied, the energy density and cycling performance of the positive electrode active material can be further improved.
In some embodiments, the coating amount of the shell is 0.1% to 6%, based on the weight of the inner core. The coating amount of the coating layer in the present application is in some embodiments within the above range, which can enable the full coating of the inner core, while further improving the kinetic performance and safety performance of the secondary battery without sacrificing the gram capacity of the positive electrode active material.
In some embodiments, the coating amount of the first coating layer is greater than 0 wt % and less than or equal to 7 wt %, optionally greater than 0 and less than or equal to 6 wt %, more optionally greater than 0 and less than or equal to 5.5 wt % or 4-5.6 wt %, further optionally greater than 0 and less than or equal to 2 wt %, based on the weight of the inner core; and/or
In some embodiments, the shell further includes a fourth coating layer coating the third coating layer and a fifth coating layer coating the fourth coating layer; wherein
In the positive electrode active material with a core-shell structure of the present application, the coating amount of the each coating layer in the present application is in some embodiments within the above range, which thus can enable the full coating of the inner core, while further improving the kinetic performance and safety performance of the secondary battery without sacrificing the gram capacity of the positive electrode active material.
In some embodiments, the shell is located on 40% to 90% of the surface of the inner core, optionally 60% to 80% of the surface. Thus, the inner core can be fully coated, thereby improving the kinetic performance and safety performance of the secondary battery.
In some embodiments, the thickness of the shell is 1-15 nm.
In some embodiments, the thickness of the first coating layer is 1-10 nm, optionally 2-10 nm; and/or
In some embodiments, the thickness of the first coating layer can be about 2 nm, about 3 nm, about 4 nm, about 5 nm, about 6 nm, about 7 nm, about 8 nm, about 9 nm, or about 10 nm, or within any range of any of the above values.
In some embodiments, the thickness of the second coating layer can be about 2 nm, about 3 nm, about 4 nm, about 5 nm, about 6 nm, about 7 nm, about 8 nm, about 9 nm, about 10 nm, about 11 nm, about 12 nm, about 13 nm, about 14 nm, about 15 nm, or within any range of any of the above numerical values.
In some embodiments, the thickness of the third coating layer can be about 2 nm, about 3 nm, about 4 nm, about 5 nm, about 6 nm, about 7 nm, about 8 nm, about 9 nm, about 10 nm, about 11 nm, about 12 nm, about 13 nm, about 14 nm, about 15 nm, about 16 nm, about 17 nm, about 18 nm, about 19 nm, about 20 nm, about 21 nm, about 22 nm, about 23 nm, about 24 nm or about nm, or within any range of any of the above numerical values.
In the present application, when the first coating layer has a thickness within the above range, the adverse effect on the dynamic performance of the material can be further reduced, and problem that the migration of transition metal ions cannot be effectively prevented can be reduced.
The second coating layer has a thickness within the above range, such that the surface structure of the second coating layer is stable, and the side reaction with the electrolyte is small, so the interface side reaction can be effectively reduced, thereby improving the high temperature performance of the secondary battery.
The third coating layer has a thickness within above range, such that the electrical conductivity of the material can be improved and the compaction density performance of the battery electrode plate prepared by using the positive electrode active material can be improved.
The thickness determination of the coating layer is mainly carried out by FIB, and the specific method may include the following steps: randomly selecting a single particle from the positive electrode active material powder to be tested, cut out a thin slice with a thickness of about 100 nm from the middle position or near the middle position of the selected particle, and then conducting a TEM test on the slice, measuring the thickness of the coating layer, with 3-5 positions being measured and the average value taken.
In some embodiments, the one or more coating layers each independently include one or more selected from pyrophosphate, phosphate and an oxide, and from one or more of pyrophosphate, phosphate and an oxide in a crystalline state;
Herein, the crystalline state means that the crystallinity is 50% or more, that is, 50%-100%. A crystalline state with a crystallinity less than 50% is referred to as a glassy state. The crystallinity of the crystalline pyrophosphate and crystalline phosphate of the present application is 50% to 100%.
The pyrophosphate and phosphate with a certain crystallinity enable not only the full achievement of the ability of the pyrophosphate coating layer to prevent the dissolution of manganese and the excellent ability of the phosphate coating layer to conduct lithium ions, as well as the reduction of the interface side reactions, but also the better lattice matching between the phosphate coating layer and the phosphate coating layer, such that a close combination between the coating layer and the coating layer can be achieved.
It should be noted that, in the present application, the crystallinity can be adjusted, for example, by adjusting the process conditions of the sintering process, such as the sintering temperature, and sintering time. The crystallinity can be measured by methods known in the art, such as by X-ray diffraction, density, infrared spectroscopy, differential scanning calorimetry, and nuclear magnetic resonance absorption methods. In particular, the method for measuring the crystallinity of the positive electrode active material by the X-ray diffraction method may include the following steps:
In some embodiments, in the shell, a weight ratio of the pyrophosphate to the phosphate and a weight ratio of the pyrophosphate to the oxide are each independently 1:3 to 3:1, optionally 1:3 to 1:1. Therefore, using pyrophosphate and phosphate in a suitable weight ratio range or pyrophosphate and oxide in a suitable weight ratio range, can not only effectively prevent the dissolution of manganese, but also effectively reduce the content of lithium impurities on the surface and reduce interface side reactions, thereby improving the high-temperature storage performance, safety performance and cycling performance of the secondary battery.
In some embodiments, the one or more coating layers each independently includes carbon, and the carbon is a mixture of SP2-form carbon and SP3-form carbon; optionally, in the carbon, a molar ratio of the SP2-form carbon to the SP3-form carbon is any value within a range of 0.07-13, more optionally any value within a range of 0.1-10, further optionally any value within a range of 2.0-3.0.
In some embodiments, the molar ratio of the SP2-form carbon to SP3-form carbon can be about 0.1, about 0.2, about 03, about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, about 1, about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, or about 10, or within any range of any of the above values.
In the present application, “about” a numerical value means a range, i.e., a range of ±10% of the numerical value.
The comprehensive electrical performance of the secondary battery is improved by selecting the form of carbon in the carbon coating layer. Specifically, by using a mixed form of SP2-form and SP3-form carbon and limiting the ratio of SP2-form to SP3-form carbon within a certain range, the following can be avoided: if the carbon in the coating layer is in the form of amorphous SP3, the conductivity is poor; if all the carbon is in a graphitized SP2-form, although the conductivity is good, there are few lithium ion paths, which is not conducive to the deintercalation of lithium. In addition, limiting the molar ratio of SP2-form carbon to SP3-form carbon within the above range can not only achieve good electrical conductivity, but also ensure the paths of lithium ions, which is beneficial to the realization of the function of the secondary battery and the cycling performance thereof. The mixing ratio of the SP2-form and the SP3-form carbon can be controlled by sintering conditions such as the sintering temperature and sintering time. The molar ratio of the SP2-form carbon to SP3-form carbon can be determined by Raman spectroscopy, and the specific measuring method is as follows: splitting the energy spectrum of the Raman measurement, to obtain Id/Ig (where Id is the peak intensity of SP3-form carbon, and Ig is the peak intensity of SP2-form carbon) and thus to confirm the molar ratio of the two forms.
In some embodiments, the one or more coating layers each independently include doped carbon, and, in the doped carbon, a mass content of the doping element is 30% or less; and optionally, in the doped carbon, the mass content of the doping element is 20% or less. Doping elements within the above content range can not only fully improve the conductivity of the pure carbon layer, but also effectively avoid the excessive surface activity due to excessive doping of doping elements, thereby effectively controlling the interface side reactions resulting from the overdoping of the coating layer.
In some embodiments, the one or more coating layers each independently includes doped carbon, and in the doped carbon,
Since the nitrogen atoms and sulfur atoms have an atomic radius closer to that of carbon atoms and the carbon skeleton does not tend to damage, when the doping amounts of nitrogen atoms and sulfur atoms are within the above relatively wide range, the conductivity of the doped carbon layer can be fully utilized, and the lithium ion transport and lithium ion desolvation ability can also be promoted.
Due to the difference in atomic radius between the phosphorus atoms, boron atoms and/or fluorine atoms and the carbon atoms, excessive doping may tend to the damage of the carbon skeleton, so when the phosphorus atoms, boron atoms and/or fluorine atoms are in relatively small doping amounts in the above range, the conductivity of the doped carbon layer can be fully utilized, and the lithium ion transport and lithium ion desolvation ability can also be promoted.
In some embodiments, the one or more coating layers each independently include pyrophosphate, and the pyrophosphate has an interplanar distance in a range of 0.293-0.470 nm, optionally 0.297-0.462 nm or 0.293-0.326 nm, more optionally 0.300-0.310 nm, and the crystal direction (111) has an angle in a range of 18.00°-32.57°, optionally 18.00°-32.00° or 26.41°-32.57°, more optionally 19.211°-30.846°, further optionally 29.00°-30.00°; and/or
Both the first coating layer and the second coating layer in the positive electrode active material of the present application are crystalline substances, and the interplanar spacing and angle ranges thereof are within the above ranges. Thus, the impurity phase in the coating layer can be effectively reduced, thereby improving the gram capacity, cycling performance and rate performance of the material.
In some embodiments, the positive electrode active material has a lattice change rate of, before and after complete lithium intercalation-deintercalation, 50% or less, optionally 9.8% or less, more optionally 8.1% or less, further optionally 7.5% or less, further optionally 6% or less, further optionally 4% or less, further optionally 3.8% or less, and further optionally 2.0-3.8% or less.
By lowering the lattice change rate, the Li ion transport can be made easier, that is, the Li ions have a stronger migration ability in the material, which is beneficial in improving the rate performance of the secondary battery. The lattice change rate may be measured with a method known in the art, e.g., X-ray diffraction (XRD).
In some embodiments, the positive electrode active material has an Li/Mn antisite defect concentration of 5.3% or less, optionally 5.1% or less, more optionally 4% or less, further optionally 2.2% or less, more further optionally 2% or less, more further optionally 1.5%-2.2% or 0.5% or less.
The so-called Li/Mn antisite defect means that the positions of Li+ and Mn2+ have been exchanged in the LiMnPO4 lattices. The Li/Mn antisite defect concentration refers to a percentage of the Li+ exchanged with Mn2+ based on the total amount of Li+ in the positive electrode active material. The Mn2+ of antisite defects can hinder the transport of Li+, and a reduction in the Li/Mn antisite defect concentration is beneficial in improving the gram capacity and rate performance of the positive electrode active material. The Li/Mn antisite defect concentration may be measured with a method known in the art, e.g., XRD.
In some embodiments, the positive electrode active material has a compacted density at 3 T of 1.89 g/cm3 or more, optionally 1.95 g/cm3 or more, more optionally 1.98 g/cm3 or more, further optionally 2.0 g/cm3 or more, more further optionally 2.2 g/cm3 or more, more further optionally 2.2 g/cm3 or more and 2.8 g/cm3 or less, or 2.2 g/cm3 or more and 2.65 g/cm3 or less.
A higher compacted density indicates a greater weight of the active material per unit volume, and thus, increasing the compacted density is beneficial in increasing the volumetric energy density of a cell. The compacted density may be measured in accordance with GB/T 24533-2009.
In some embodiments, the surface oxygen valence state of the positive electrode active material is −1.55 or less, optionally −1.82 or less, in some embodiments −1.88 or less, further optionally −1.90 or less or −1.98 to −1.88, more further optionally −1.98 to −1.89, and more further optionally −1.98 to −1.90.
By lowering the surface oxygen valence state, the interfacial side reactions between the positive electrode active material and an electrolyte solution can be alleviated, thereby improving the cycling performance and high-temperature stability of the secondary battery. The surface oxygen valence state may be measured with a method known in the art, e.g., electron energy loss spectroscopy (EELS).
[Method for Producing Positive Electrode Active Material]
The present application provides a method for preparing a positive electrode active material, includes the steps of:
Therefore, in the present application, by doping a compound LiMnPO4 with specific elements in specific amounts at Mn-site and optionally Li, P and/or O-sites, a markedly improved rate performance can be obtained while the dissolution of Mn and Mn-site doping element is significantly reduced, thereby obtaining significantly improved cycling performance and/or high-temperature stability; and the gram capacity and compacted density of the material can also be enhanced.
In some embodiments, the method specifically includes the steps of:
In some embodiments, in the step of preparing the slurry, a lithium source, a phosphorus source, optionally an element A source, optionally an element C source, optionally an element D source, a carbon source, a source of a doping element for a carbon layer, a solvent, and the manganese salt doped with element B are added to a reaction container for grinding and mixing to obtain a slurry; the other steps are the same as above; to obtain the positive electrode active material;
In some embodiments, the solvents in the step of preparing the manganese salt doped with element B and the step of preparing the slurry can each independently be a solvent conventionally used by those skilled in the art for the preparation of a manganese salt and lithium manganese phosphate, for example they can be each independently selected from at least one of ethanol, water (such as deionized water), etc.
In some embodiments, the method also includes the steps of:
In some embodiments, the method also includes the steps of:
In some embodiments, the method also includes the steps of:
In some embodiments, the method also includes the steps of:
In some embodiments, the method also includes the steps of:
The positive electrode active material includes an inner core and a shell coating the inner core, the inner core includes LiaAxMn1-yByP1-zCzO4-nDn, the shell includes a first coating layer coating the inner core, a second coating layer coating the first coating layer and a third coating layer coating the second coating layer, the first coating layer including pyrophosphate LifQP2O7 and/or Qg(P2O7)h, the second coating layer includes phosphate XPO4, and the third coating layer includes carbon, wherein A, B, C, D, a, x, y, z and n are defined as in [Positive electrode active material], and Q, X, f, g and h are defined as in [positive electrode active material].
In some embodiments, the method also includes the steps of:
In some embodiments, the method also includes the steps of:
In some embodiments, the method also includes the steps of:
The positive electrode active material and the polymer are coated by dry-coating or wet-coating, and the obtained material includes an inner core and a shell coating the inner core;
In any embodiment, the element A source is selected from at least one of the elementary substances, oxides, phosphates, oxalates, carbonates, and sulfates of element A; and/or
In some embodiments, the acid is selected from one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, an organic acid like oxalic acid, etc., and may be, for example, oxalic acid. In some embodiments, the acid is a dilute acid with a concentration of 60 wt % or less.
In some embodiments, the manganese source may be a manganese-containing substance useful for preparing lithium manganese phosphate that is known in the art. For example, the manganese source may be selected from one or a combination of elemental manganese, manganese dioxide, manganese phosphate, manganese oxalate and manganese carbonate.
In some embodiments, the lithium source may be a lithium-containing substance useful for preparing lithium manganese phosphate that is known in the art. For example, the lithium source may be selected from one or a combination of lithium carbonate, lithium hydroxide, lithium phosphate and lithium dihydrogen phosphate.
In some embodiments, the phosphorus source may be a phosphorus-containing substance useful for preparing lithium manganese phosphate that is known in the art. For example, the phosphorus source may be selected from one or a combination of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate and phosphoric acid.
The addition amounts of respective sources of the elements A, B, C and D depend on a target doping amount, and a ratio of the amounts of the lithium source, the manganese source and the phosphorus source conforms to a stoichiometric ratio.
In any embodiment, in the step of preparing the manganese salt doped with element B,
In some embodiments, in the step of preparing the slurry, grinding and mixing are carried out for 1-15 hours, optionally 8-15 hours; optionally, the mixing is carried out at a temperature of 20-120° C., more optionally 40-120° C., for 1-10 h.
By controlling the reaction temperature, the stirring speed and the mixing time during the doping, the doping elements can be uniformly distributed, and the sintered material has a higher degree of crystallinity, thereby improving the gram capacity, rate performance and the like of the material.
In some embodiments, the filter cake can be washed before drying same in the step of preparing the manganese salt doped with element B.
In some embodiments, the drying in the step of preparing the manganese salt doped with element B can be carried out by means and conditions known to those skilled in the art. For example, the drying temperature can be in a range of 120° C. to 300° C. Optionally, the dried filter cake may be ground into particles, for example, to a median particle size Dv50 of the particles in a range of 50 to 200 nm. Herein, the median particle size Dv50 refers to a particle size corresponding to a cumulative volume distribution percentage of the positive electrode active material reaching 50%. In the present application, the median diameter Dv50 of the inner core can be determined by laser diffraction particle size analysis method. For example, the determination may be carried out with reference to the standard GB/T 19077-2016 using a laser particle size analyzer (e.g., Malvern Master Size 3000).
In some embodiments, in the step of preparing the slurry, a carbon source is also added to the reaction container for grinding and mixing. Therefore, the method can result in a positive electrode active material having a surface coated with carbon. Optionally, the carbon source includes one or a combination of starch, sucrose, glucose, polyvinyl alcohol, polyethylene glycol and citric acid. The molar ratio of the amount of the carbon source to the amount of the lithium source is usually in a range of 0.1% to 5%. The grinding may be carried out by suitable grinding means known in the art, e.g., sanding.
The temperature and time of the spray drying can be conventional temperature and time for spray drying in the art, e.g., at 100° C. to 300° C. for 1 to 6 hours.
In some embodiments, in the step of preparing the inner core, the sintering is carried out at a temperature in a range of 600-900° C. for 6-14 hours.
In some embodiments, the sintering is carried in a protective atmosphere, and the protective atmosphere can be nitrogen, an inert gas, hydrogen or a mixture thereof.
In any embodiment, the MP2O7 powder is a commercially available product, or the MP2O7 powder is prepared by the following procedure:
In some embodiments, in the method for preparing an MP2O7 powder,
In some embodiments, in the method for preparing an MP2O7 powder,
In some embodiments, the sintering temperature in the coating step is 500-800° C., and the sintering time is 4-10 h.
In some embodiments, optionally, the XPO4 suspension comprising a carbon source is commercially available, or optionally, prepared by: uniformly mixing a lithium source, a X source, a phosphorus source and a carbon source in a solvent, then increasing the temperature of the reaction mixture to 60-120° C. and keep same for 2-8 hours to obtain an XPO4 suspension containing a carbon source. Optionally, during the preparation of the XPO4 suspension containing a carbon source, the pH of the mixture is adjusted to 4-6.
In some embodiments, in the step of preparing the positive electrode active material, the mass ratio of the inner core, MP2O7 powder to the XPO4 suspension containing a carbon source is: 1:(0.001-0.05):(0.001-0.05).
In some embodiments, in the first coating step,
In some embodiments, in the second coating step,
In some embodiments, the sintering in the third coating step is carried out at 700-800° C. for 6-10 hours.
[Positive Electrode Plate]
The positive electrode plate includes a positive electrode current collector and a positive electrode film layer provided on at least one surface of the positive electrode current collector, the positive electrode film layer includes a first positive electrode active material, and the first positive electrode active material is the positive electrode active material as described above or the positive electrode active material prepared by method as described above; optionally, the content of the positive electrode active material in the positive electrode film layer is 90-99.5 wt %, more optionally 95-99.5 wt %, based on the total weight of the positive electrode film layer.
In some embodiments, the positive electrode plate further includes a second positive electrode active material, and the second positive electrode active material is different from the first positive electrode active material.
In some embodiments, the second positive electrode active material includes one or more of LiEtCosF(1-t-s)O2, spinel-type lithium manganate and spinel-type of lithium titanate, wherein E includes one or more elements selected from group VIII, F includes one or more elements selected from groups IIIA and VIIB, t is selected from a range of 0 to 0.9, the sum of t and s is selected from a range of 0.3 to 1.
In some embodiments, E includes one or more elements selected from Ni, Fe, Ru, and Rh, and F includes one or more elements selected from Mn, Al, Ga, and In.
In some embodiments, the second positive electrode active material is selected from one or more of LiNitCosMn(1-t-s)O2, LiNitCosAl(1-t-s)O2, LiCoO2, spinel-type lithium manganate and spinel-type lithium titanate; wherein t is independently selected from 0.3-0.9, optionally 0.33-0.8, and the sum oft and s is independently selected from 0.3-0.9, optionally 0.66-0.9.
In some embodiments, the mass ratio of the first active material to the second active material is 1:7-7:1, optionally 1: 4-4:1.
In some embodiments, in the second positive electrode active material,
In some embodiments, the sum of the mass of the first positive electrode active material and the second positive electrode active material accounts for 88%-98.7% of the mass of the positive electrode plate.
As an example, the positive electrode current collector has two surfaces opposite in its own thickness direction, and the positive electrode film layer is provided on either or both of opposite surfaces of the positive electrode current collector.
In some embodiments, the positive current collector can be a metal foil or a composite current collector. For example, as a metal foil, an aluminum foil can be used. The composite current collector may comprise a polymer material substrate and a metal layer formed on at least one surface of the polymer material substrate. The composite current collector can be formed by forming a metal material (aluminum, an aluminum alloy, nickel, a nickel alloy, titanium, a titanium alloy, silver and a silver alloy, etc.) on a polymer material substrate (such as polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some implementations, the positive electrode active material may also be a positive electrode active material known in the art for batteries. As an example, the positive electrode active material may include at least one of the following materials: lithium-containing phosphates of an olivine structure, lithium transition metal oxides, and their respective modified compounds.
However, the present application is not limited to these materials, and other conventional materials that can be used as positive electrode active materials for batteries may also be used. These positive electrode active materials may be used alone or in combination of two or more.
In some embodiments, the positive electrode film layer may optionally comprise a binder. As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and fluorine-containing acrylate resin.
In some embodiments, the positive electrode film layer also optionally comprises a conductive agent. As an example, the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the positive electrode plate can be prepared as follows: dispersing the above-mentioned components for preparing the positive electrode plate, such as a positive electrode active material, a conductive agent, a binder and any other components, in a solvent (e.g., N-methyl pyrrolidone) to form a positive electrode slurry; and coating the positive electrode current collector with the positive electrode slurry, followed by the procedures such as drying and cold pressing, so as to obtain the positive electrode plate.
[Negative Electrode Plate]
The negative electrode plate comprises a negative electrode current collector and a negative electrode film layer provided on at least one surface of the negative electrode current collector, wherein the negative electrode film layer comprises a negative electrode active material.
As an example, the negative electrode current collector has two surfaces opposite in its own thickness direction, and the negative electrode film layer is provided on either or both of the two opposite surfaces of the negative electrode current collector.
In some embodiments, the negative current collector may be a metal foil or a composite current collector. For example, as a metal foil, a copper foil can be used. The composite current collector may comprise a polymer material substrate and a metal layer formed on at least one surface of the polymer material substrate. The composite current collector can be formed by forming a metal material (copper, a copper alloy, nickel, a nickel alloy, titanium, a titanium alloy, silver and a silver alloy, etc.) on a polymer material substrate (e.g., polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the negative electrode active material can be a negative electrode active material known in the art for batteries. As an example, the negative electrode active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, a silicon-based material, a tin-based material and lithium titanate, etc. The silicon-based material may be selected from at least one of elemental silicon, silicon oxides, silicon carbon composites, silicon nitrogen composites and silicon alloys. The tin-based material may be selected from at least one of elemental tin, tin oxides, and tin alloys. However, the present application is not limited to these materials, and other conventional materials that can be used as negative electrode active materials for batteries can also be used. These negative electrode active materials may be used alone or in combination of two or more.
In some embodiments, the negative electrode film layer may optionally comprise a binder. As an example, the binder may be selected from at least one of a styrene butadiene rubber (SBR), polyacrylic acid (PAA), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS).
In some embodiments, the negative electrode film layer may optionally comprise a conductive agent. As an example, the conductive agent may be selected from at least one of superconductive carbon, acetylene black, carbon black, ketjenblack, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the negative electrode film layer may optionally comprise other auxiliary agents, such as thickener (e.g. sodium carboxymethyl cellulose (CMC-Na)) and the like.
In some embodiments, the negative electrode plate can be prepared as follows: dispersing the above-mentioned components for preparing the negative electrode plate, such as negative electrode active material, conductive agent, binder and any other components, in a solvent (e.g. deionized water) to form a negative electrode slurry; and coating a negative electrode current collector with the negative electrode slurry, followed by procedures such as drying and cold pressing, so as to obtain the negative electrode plate.
[Electrolyte]
The electrolyte functions to conduct ions between the positive electrode plate and the negative electrode plate. The type of the electrolyte is not specifically limited in the present application, and can be selected according to actual requirements. For example, the electrolyte may be in a liquid state, a gel state or an all-solid state.
In some embodiments, the electrolyte is liquid and includes an electrolyte salt and a solvent.
In some embodiments, the electrolyte salt may be selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bisfluorosulfonimide, lithium bistrifluoromethanesulfonimide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalate borate, lithium dioxalate borate, lithium difluorodioxalate phosphate and lithium tetrafluorooxalate phosphate.
In some embodiments, the solvent may be selected from at least one of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, 1,4-butyrolactone, sulfolane, dimethyl sulfone, ethyl methyl sulfone, and diethyl sulfone.
In some embodiments, the electrolyte solution further optionally comprises an additive. As an example, the additive may include a negative electrode film-forming additive and a positive electrode film-forming additive, and may further include an additive that can improve some performance of the battery, such as an additive that improves overcharge performance of the battery, or an additive that improves high-temperature performance or low-temperature performance of the battery.
[Separator]
In some embodiments, the secondary battery further comprises a separator. The type of the separator is not particularly limited in the present application, and any well known porous-structure separator with good chemical stability and mechanical stability may be selected.
In some embodiments, the material of the separator may be selected from at least one of glass fibers, non-woven fabrics, polyethylene, polypropylene and polyvinylidene fluoride. The separator may be either a single-layer film or a multi-layer composite film, and is not limited particularly. When the separator is a multi-layer composite film, the materials in the respective layers may be same or different, which is not limited particularly.
In some embodiments, an electrode assembly may be formed by a positive electrode plate, a negative electrode plate and a separator by a winding process or a stacking process.
In some embodiments, the secondary battery may comprise an outer package. The outer package can be used to encapsulate the above-mentioned electrode assembly and electrolyte.
In some embodiments, the outer package of the secondary battery can be a hard shell, for example, a hard plastic shell, an aluminum shell, a steel shell, etc. The outer package of the secondary battery may also be a soft bag, such as a pouch-type soft bag. The material of the soft bag may be plastics, and the examples of plastics may include polypropylene, polybutylene terephthalate, polybutylene succinate, etc.
The shape of the secondary battery is not particularly limited in the present application, and may be cylindrical, square or of any other shape. For example,
In some embodiments, with reference to
In some embodiments, the secondary battery can be assembled into a battery module, and the number of the secondary batteries contained in the battery module may be one or more, and the specific number can be selected by those skilled in the art according to the application and capacity of the battery module.
Optionally, the battery module 4 may also comprise a housing with an accommodating space, and a plurality of secondary batteries 5 are accommodated in the accommodating space.
In some embodiments, the above battery module may also be assembled into a battery pack, the number of the battery modules contained in the battery pack may be one or more, and the specific number can be selected by those skilled in the art according to the application and capacity of the battery pack.
In addition, the present application further provides a power consuming device. The power consuming device comprises at least one of the secondary battery, battery module, or battery pack provided by the present application. The secondary battery, the battery module or the battery pack may be used as a power supply or an energy storage unit of the power consuming device. The power consuming device may include a mobile device (e.g., a mobile phone, a laptop computer, etc.), an electric vehicle (e.g., a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf cart, an electric truck), an electric train, ship, and satellite, an energy storage system, and the like, but is not limited thereto.
As a power consuming device, the secondary battery, battery module or battery pack can be selected according to the usage requirements thereof.
Hereinafter, the examples of the present application will be explained. The examples described below are exemplary and are merely for explaining the present application, and should not be construed as limiting the present application. The examples in which techniques or conditions are not specified are based on the techniques or conditions described in documents in the art or according to the product introduction. The reagents or instruments used therein for which manufacturers are not specified are all conventional products that are commercially available.
The sources of the raw materials involved in the examples of the present application are as follows:
[Positive Electrode Active Material Including Inner Core and Preparation of Battery]
1) Preparation of a Positive Electrode Active Material
Preparation of doped manganese oxalate: 1.3 mol of MnSO4·H2O and 0.7 mol of FeSO4·H2O are mixed thoroughly for 6 hours in a mixer. The mixture is transferred into a reaction kettle, and 10 L of deionized water and 2 mol of oxalic acid dihydrate (in oxalic acid) are added. The reaction kettle is heated to 80° C., stirring is performed for 6 hours at a rotation speed of 600 rpm, and the reaction is completed (no bubbles are generated), so as to obtain an Fe-doped manganese oxalate suspension. Then, the suspension is filtered, and the resulting filter cake is dried at 120° C. and then ground to obtain Fe-doped manganese oxalate particles with a median particle size Dv50 of about 100 nm.
Preparation of doped lithium manganese phosphate: 1 mol of the above manganese oxalate particles, 0.497 mol of lithium carbonate, 0.001 mol of Mo(SO4)3, an 85% aqueous phosphoric acid solution containing 0.999 mol of phosphoric acid, 0.001 mol of H4SiO4, 0.0005 mol of NH4HF2 and 0.005 mol of sucrose are added into 20 L of deionized water. The mixture is transferred into a sander and thoroughly ground and stirred for 10 hours to obtain a slurry. The slurry is transferred into a spray drying apparatus for spray-drying granulation, where the drying temperature is set at 250° C. and the drying time is 4 hours, so as to obtain particles. The above powder is sintered at 700° C. for 10 hours in a protective atmosphere of nitrogen (90% by volume) hydrogen (10% by volume), so as to obtain carbon-coated Li0.994Mo0.001Mn0.65Fe0.35P0.999Si0.001O3.999F0.001. The positive electrode active material may be tested for element content using inductively coupled plasma (ICP) emission spectroscopy.
2) Preparation of Button Battery
The above positive electrode active material, polyvinylidene fluoride (PVDF) and acetylene black in a weight ratio of 90:5:5 are added into N-methylpyrrolidone (NMP), and stirred in a drying room to make a slurry. An aluminum foil is coated with the above slurry, followed by drying and cold pressing, so as to obtain a positive electrode plate. The coating amount is 0.2 g/cm2, and the compacted density is 2.0 g/cm3.
A lithium plate is used as a negative electrode, a solution of 1 mol/L LiPF6 in ethylene carbonate (EC), diethyl carbonate (DEC) and dimethyl carbonate (DMC) in a volume ratio of 1:1:1 is used as an electrolyte solution, and the lithium plate and the electrolyte solution are assembled, together with the positive electrode plate prepared above, into a button battery in a button battery box.
(3) Preparation of Full Battery
The above positive electrode active material is uniformly mixed with a conductive agent acetylene black and a binder polyvinylidene fluoride (PVDF) in a weight ratio of 92:2.5:5.5 in an N-methylpyrrolidone solvent system, and the mixture is applied to an aluminum foil, followed by drying and cold pressing, so as to obtain a positive electrode plate. The coating amount is 0.4 g/cm2, and the compacted density is 2.4 g/cm3.
Negative electrode active materials artificial graphite and hard carbon, a conductive agent acetylene black, a binder styrene butadiene rubber (SBR) and a thickening agent sodium carboxymethylcellulose (CMC) are uniformly mixed in deionized water in a weight ratio of 90:5:2:2:1, and the mixture is applied to a copper foil, followed by drying and cold pressing, so as to obtain a negative electrode plate. The coating amount is 0.2 g/cm2, and the compacted density is 1.7 g/cm3.
With a polyethylene (PE) porous polymer film as a separator, the positive electrode plate, the separator and the negative electrode plate are stacked in sequence, such that the separator is located between the positive electrode and the negative electrode to play a role of isolation, and then winding is performed to obtain a bare cell. The bare cell is placed in an outer package, and the same electrolyte solution as that for the preparation of the button battery is injected, followed by encapsulation, so as to obtain a full battery.
Except that in “1) Preparation of positive electrode active material”, the amount of high-purity Li2CO3 is changed into 0.4885 mol, Mo(SO4)3 is replaced by MgSO4, the amount of FeSO4·H2O is changed into 0.68 mol, 0.02 mol of Ti(SO4)2 is also added in the preparation of doped manganese oxalate, and H4SiO4 is replaced by HNO3, the rest are the same as in Example I-1.
Except that in “1) Preparation of positive electrode active material”, the amount of high-purity Li2CO3 is changed into 0.496 mol, Mo(SO4)3 is replaced by W(SO4)3, and H4SiO4 is replaced by H2SO4, the rest are the same as in Example I-1.
Except that in “1) Preparation of positive electrode active material”, the amount of high-purity Li2CO3 is changed into 0.4985 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.0005 mol of Al2(SO4)3, and NH4HF2 is replaced by NH4HCl2, the rest are the same as in Example I-1.
Except that in “1) Preparation of positive electrode active material”, 0.7 mol of FeSO4·H2O is changed into 0.69 mol, 0.01 mol of VCl2 is also added in the preparation of doped manganese oxalate, the amount of Li2CO3 is changed into 0.4965 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.0005 mol of Nb2(SO4)5, and H4SiO4 is replaced by H2SO4, the rest are the same as in Example I-1.
Except that in “1) Preparation of positive electrode active material”, the amount of FeSO4·H2O is changed into 0.68 mol, 0.01 mol of VCl2 and 0.01 mol of MgSO4 are also added in the preparation of doped manganese oxalate, the amount of Li2CO3 is changed into 0.4965 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.0005 mol of Nb2(SO4)5, and H4SiO4 is replaced by H2SO4, the rest are the same as in Example I-1.
Except that in “1) Preparation of positive electrode active material”, MgSO4 is replaced by CoSO4, the rest are the same as in Example I-6.
Except that in “1) Preparation of positive electrode active material”, MgSO4 is replaced by NiSO4, the rest are the same as in Example I-6.
Except that in “1) Preparation of positive electrode active material”, the amount of FeSO4·H2O is changed into 0.698 mol, 0.002 mol of Ti(SO4)2 is also added in the preparation of doped manganese oxalate, the amount of Li2CO3 is changed into 0.4955 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.0005 mol of Nb2(SO4)5, H4SiO4 is replaced by H2SO4, and NH4HF2 is replaced by NH4HCl2, the rest are the same as in Example I-1.
Except that in “1) Preparation of positive electrode active material”, the amount of FeSO4·H2O is changed into 0.68 mol, 0.01 mol of VCl2 and 0.01 mol of MgSO4 are also added in the preparation of doped manganese oxalate, the amount of Li2CO3 is changed into 0.4975 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.0005 mol of Nb2(SO4)5, and NH4HF2 is replaced by NH4HBr2, the rest are the same as in Example I-1.
Except that in “1) Preparation of positive electrode active material”, the amount of FeSO4·H2O is changed into 0.69 mol, 0.01 mol of VCl2 is also added in the preparation of doped manganese oxalate, the amount of Li2CO3 is changed into 0.499 mol, Mo(SO4)3 is replaced by MgSO4, and NH4HF2 is replaced by NH4HBr2, the rest are the same as in Example I-1.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.36 mol, the amount of FeSO4·H2O is changed into 0.6 mol, 0.04 mol of VCl2 is also added in the preparation of doped manganese oxalate, the amount of Li2CO3 is changed into 0.4985 mol, Mo(SO4)3 is replaced by MgSO4, and H4SiO4 is replaced by HNO3, the rest are the same as in Example I-1, and Li0.997Mg0.001Mn0.68Fe0.3V0.02P0.999N0.001O3.999F0.001 is obtained.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.16 mol, and the amount of FeSO4·H2O is changed into 0.8 mol, the rest are the same as in Example I-12.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.3 mol, and the amount of VCl2 is changed into 0.1 mol, the rest are the same as in Example I-12.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.2 mol, 0.1 mol of VCl2 is also added in the preparation of doped manganese oxalate, the amount of Li2CO3 is changed into 0.494 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.005 mol of MgSO4, and H4SiO4 is replaced by H2SO4, the rest are the same as in Example I-1.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.2 mol, 0.1 mol of VCl2 is also added in the preparation of doped manganese oxalate, the amount of Li2CO3 is changed into 0.467 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.005 mol of MgSO4, 0.001 mol of H4SiO4 is replaced by 0.005 mol of H2SO4, and 1.175 mol of 85% phosphoric acid is replaced by 1.171 mol of 85% phosphoric acid, the rest are the same as in Example I-1.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.2 mol, 0.1 mol of VCl2 is also added in the preparation of doped manganese oxalate, the amount of Li2CO3 is changed into 0.492 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.005 mol of MgSO4, H4SiO4 is replaced by H2SO4, and 0.0005 mol of NH4HF2 is changed into 0.0025 mol, the rest are the same as in Example I-1.
Except that in “1) Preparation of positive electrode active material”, the amount of FeSO4·H2O is changed into 0.5 mol, 0.1 mol of VCl2 and 0.1 mol of CoSO4 are also added in the preparation of doped manganese oxalate, the amount of Li2CO3 is changed into 0.492 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.005 mol of MgSO4, H4SiO4 is replaced by H2SO4, and 0.0005 mol of NH4HF2 is changed into 0.0025 mol, the rest are the same as in Example I-1.
Except that in “1) Preparation of positive electrode active material”, the amount of FeSO4·H2O is changed into 0.4 mol, and 0.1 mol of CoSO4 is changed into 0.2 mol, the rest are the same as in Example I-18.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.5 mol, the amount of FeSO4·H2O is changed into 0.1 mol, and the amount of CoSO4 is changed into 0.3 mol, the rest are the same as in Example I-18.
Except that in “1) Preparation of positive electrode active material”, 0.1 mol of CoSO4 is replaced by 0.1 mol of NiSO4, the rest are the same as in Example I-18.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.5 mol, the amount of FeSO4·H2O is changed into 0.2 mol, and 0.1 mol of CoSO4 is replaced by 0.2 mol of NiSO4, the rest are the same as in Example I-18.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.4 mol, the amount of FeSO4·H2O is changed into 0.3 mol, and the amount of CoSO4 is changed into 0.2 mol, the rest are the same as in Example I-18.
Except that in “1) Preparation of positive electrode active material”, 1.3 mol of MnSO4·H2O is changed into 1.2 mol, 0.7 mol of FeSO4·H2O is changed into 0.5 mol, 0.1 mol of VCl2 and 0.2 mol of CoSO4 are also added in the preparation of doped manganese oxalate, the amount of Li2CO3 is changed into 0.497 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.005 mol of MgSO4, H4SiO4 is replaced by H2SO4, and 0.0005 mol of NH4HF2 is changed into 0.0025 mol, the rest are the same as in Example I-1.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.0 mol, the amount of FeSO4·H2O is changed into 0.7 mol, and the amount of CoSO4 is changed into 0.2 mol, the rest are the same as in Example I-18.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.4 mol, the amount of FeSO4·H2O is changed into 0.3 mol, 0.1 mol of VCl2 and 0.2 mol of CoSO4 are also added in the preparation of doped manganese oxalate, the amount of Li2CO3 is changed into 0.4825 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.005 mol of MgSO4, the amount of H4SiO4 is changed into 0.1 mol, the amount of phosphoric acid is changed into 0.9 mol, and the amount of NH4HF2 is changed into 0.04 mol, the rest are the same as in Example I-1.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.4 mol, the amount of FeSO4·H2O is changed into 0.3 mol, 0.1 mol of VCl2 and 0.2 mol of CoSO4 are also added in the preparation of doped manganese oxalate, the amount of Li2CO3 is changed into 0.485 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.005 mol of MgSO4, the amount of H4SiO4 is changed into 0.08 mol, the amount of phosphoric acid is changed into 0.92 mol, and the amount of NH4HF2 is changed into 0.05 mol, the rest are the same as in Example I-1.
The stirring rotation speed and temperature in the preparation of doped manganese oxalate, time of grinding and stirring in a sander, and sintering temperature and sintering time are changed, see Table 13 for details.
The lithium source, manganese source, phosphorus source and sources of doping elements A, B, C and D are changed, see Table 14 for details.
(1) Preparation of Doped Manganese Oxalate
1.2 mol of MnSO4·H2O and 0.79 mol of FeSO4·H2O are mixed thoroughly for 6 hours in a mixer; the mixture is transferred into a reaction kettle, 10 L of deionized water, 2 mol of oxalic acid dihydrate and 0.01 mol of VCl2 are added thereto, heated to 80° C., and then stirred for 6 hours at a rotation speed of 600 rpm, the reaction is completed (no bubbles are generated), so as to obtain an Fe-doped manganese oxalate suspension; the suspension is filtered, and the resulting filter cake is dried at 120° C. and then ground to obtain Fe-doped manganese oxalate particles with a particle size Dv50 of about 100 nm.
(2) Preparation of Doped Lithium Manganese Phosphate
1 mol of the Fe-doped manganese oxalate particles, 0.45 mol of lithium carbonate, 0.05 mol of MgSO4, an 85% aqueous phosphoric acid solution containing 0.9 mol of phosphoric acid, 0.1 mol of H4SiO4, 0.05 mol of NH4HF2 and 0.005 mol of sucrose are added into 20 L of deionized water, and the mixture is transferred into a sander and thoroughly ground and stirred for 10 hours to obtain a slurry. The slurry is transferred into a spray drying apparatus for spray-drying granulation, where the drying temperature is set at 250° C. and the drying time is 4 h, so as to obtain particles; the particles are sintered at 700° C. for 10 hours in a protective atmosphere of nitrogen (90% v/v)+hydrogen (10% v/v) to obtain a positive electrode active material. The element content is detected using inductively coupled plasma (ICP) emission spectrometry, and the chemical formula Li0.9Mg0.05Mn0.6Fe0.395V0.005P0.9Si0.1O3.9F0.1 is obtained.
Except that in step (2), lithium carbonate is 0.55 mol, MgSO4 is 0.001 mol, and NH4HF2 is 0.001 mol, the rest are the same as in Preparation example B55; and a positive electrode active material Li1.1Mg0.001Mn0.6Fe0.395V0.005P0.9Si0.1O3.998F0.002 is obtained.
Except that in step (2), MgSO4 is 0.1 mol, 85% aqueous phosphoric acid solution contains 0.95 mol of phosphoric acid, H4SiO4 is 0.05 mol, and NH4HF2 is 0.025 mol, the rest are the same as in Preparation example B55; and a positive electrode active material Li0.9Mg0.001Mn0.6Fe0.395V0.005P0.95Si0.05O3.95F0.05 is obtained.
Except that in step (1), MnSO4·H2O is 1.998 mol, FeSO4·H2O is 0.002 mol and VCl2 is not used; and except that in step (2), lithium carbonate is 0.475 mol, 85% aqueous phosphoric acid solution contains 0.96 mol of phosphoric acid, H4SiO4 is 0.04 mol, and NH4HF2 is 0.01 mol; the rest are the same as in Preparation example B55; a positive electrode active material Li0.95Mg0.05Mn0.999Fe0.001P0.96Si0.04O3.99F0.01 is obtained.
Except that in step (1), MnSO4·H2O is 1.98 mol, FeSO4·H2O is 0.02 mol and VCl2 is not used; and except that in step (2), lithium carbonate is 0.475 mol, 85% aqueous phosphoric acid solution contains 0.96 mol of phosphoric acid, H4SiO4 is 0.04 mol, and NH4HF2 is 0.01 mol; the rest are the same as in Preparation example B55; a positive electrode active material Li0.95Mg0.05Mn0.99Fe0.001P0.96Si0.04O3.99F0.01 is obtained.
Except that in step (1), MnSO4·H2O is 1.6 mol, FeSO4·H2O is 0.4 mol and VCl2 is not used; and except that in step (2), lithium carbonate is 0.475 mol, 85% aqueous phosphoric acid solution contains 0.96 mol of phosphoric acid, H4SiO4 is 0.04 mol, and NH4HF2 is 0.01 mol; the rest are the same as in Preparation example B55; a positive electrode active material Li0.95Mg0.05Mn0.8Fe0.2P0.96Si0.04O3.99F0.01 is obtained.
Preparation of Fe, Co and V co-doped manganese oxalate: 689.5 g of manganese carbonate (in MnCO3, the same below), 455.2 g of ferrous carbonate (in FeCO3, the same below), 4.6 g of cobalt sulfate (in CoSO4, the same below) and 4.9 g of vanadium dichloride (in VCl2, the same below) are mixed thoroughly for 6 hours in a mixer. The mixture is transferred into a reaction kettle, and 5 L of deionized water and 1260.6 g of oxalic acid dihydrate (in C2H2O4·2H2O, the same below) are added. The reaction kettle is heated to 80° C., stirring is performed for 6 hours at a rotation speed of 600 rpm until the reaction is completed (no bubbles are generated), so as to obtain an Fe, Co, V and S co-doped manganese oxalate suspension. Then, the suspension is filtered, and the resulting filter cake is dried at 120° C. and then ground, so as to obtain Fe, Co, and V co-doped manganese oxalate dihydrate particles with a median particle size Dv50 of 100 nm.
Preparation of Fe, Co, V and S co-doped lithium manganese phosphate: Manganese oxalate dihydrate particles (1793.4 g) obtained in the previous step, 314 g of lithium carbonate (in Li2CO3, the same below), 89.8 g of MgSO4, 1.6 g of 60% dilute sulfuric acid (in 60% H2SO4, the same below) and 1148.9 g of ammonium dihydrogen phosphate (in NH4H2PO4, the same below) are added to 20 L of deionized water, and the mixture is stirred for 10 hours for mixing uniformly, so as to obtain a slurry. The slurry is transferred into a spray drying apparatus for spray-drying granulation, where the drying temperature is set at 250° C. and the drying time is 4 hours, so as to obtain a powder. The above powder is sintered at 700° C. for 4 hours in a protective atmosphere of nitrogen (90% by volume)+hydrogen (10% by volume), so as to Li0.85Mg0.075Mn0.60Fe0.393V0.004Co0.003P0.999S0.001O4.
Except that MgSO4 is not added and the mass of lithium carbonate is 425 g, the rest are the same as in Example I-61, so as to obtain Li1.15Mn0.60Fe0.393V0.004Co0.003P0.999S0.001O4.
Except that cobalt sulfate, vanadium dichloride and MgSO4 are not added, the mass of manganese carbonate is 1.149 g, the mass of ferrous carbonate is 1157 g, and the mass of lithium carbonate is 425 g, the rest are the same as in Example I-61, so as to obtain Li1.15Mn0.001Fe0.999P0.999S0.001O4.
Except that Mo(SO4)3 is not added, lithium carbonate is adjusted to 0.575 mol, MnSO4·H2O is adjusted to 0.002 mol, FeSO4·H2O is adjusted to 1.998 mol, the aqueous phosphoric acid solution with a phosphoric acid concentration of 85% is adjusted to 0.5 mol, 0.001 mol of H4SiO4 is replaced by 0.5 mol of H2SO4, manganese oxalate particles are adjusted to 0.875 mol, and NH4HF2 is adjust to 0.25 mol, the rest are the same as in Example I-1, so as to obtain Li1.15Mn0.001Fe0.999P0.5S0.5O3.5F0.5.
Except that MgSO4 is not added and the amount of Li2CO3 is changed to 0.499 mol, the rest are the same as in Example I-12, so as to obtain Li0.998Mn0.68Fe0.3V0.02P0.999N0.001O3.999F0.001.
Except that HNO3 is not added and the aqueous phosphoric acid solution with a phosphoric acid concentration of 85% is adjusted to 1 mol, the rest are the same as in Example I-12, so as to obtain Li0.997Mg0.001Mn0.68Fe0.3V0.02PO3.999F0.001.
Except that NH4HF2 is not added, the rest are the same as in Example I-12, so as to obtain Li0.997Mg0.001Mn0.68Fe0.3V0.02P0.999N0.001O4.
Except that MgSO4 and HNO3 are not added, the amount of Li2CO3 is changed to 0.499 mol, and the aqueous phosphoric acid solution with a phosphoric acid concentration of 85% is adjusted to 1 mol, the rest are the same as in Example I-12, so as to obtain Li0.998Mn0.68Fe0.3V0.02PO3.999F0.001.
1) Preparation of a Positive Electrode Active Material
Preparation of doped manganese oxalate: 1.3 mol of MnSO4·H2O and 0.7 mol of FeSO4·H2O are mixed thoroughly for 6 hours in a mixer. The mixture is transferred into a reaction kettle, and 10 L of deionized water and 2 mol of oxalic acid dihydrate (in oxalic acid) are added. The reaction kettle is heated to 80° C., stirring is performed for 6 hours at a rotation speed of 600 rpm, and the reaction is completed (no bubbles are generated), so as to obtain an Fe-doped manganese oxalate suspension. Then, the suspension is filtered, and the resulting filter cake is dried at 120° C. and then ground to obtain Fe-doped manganese oxalate particles with a median particle size Dv50 of about 100 nm.
Preparation of doped lithium manganese phosphate: 1 mol of the above manganese oxalate particles, 0.497 mol of lithium carbonate, 0.001 mol of Mo(SO4)3, an 85% aqueous phosphoric acid solution containing 0.999 mol of phosphoric acid, 0.001 mol of H4SiO4, 0.0005 mol of NH4HF2, 0.05 mol of sucrose and 0.025 mol of ethanediamine are added into 20 L of deionized water. The mixture is transferred into a sander and thoroughly ground and stirred for 10 hours to obtain a slurry. The slurry is transferred into a spray drying apparatus for spray-drying granulation, where the drying temperature is set at 250° C. and the drying time is 4 hours, so as to obtain particles. The above powder is sintered at 700° C. for 10 hours in a protective atmosphere of nitrogen (90% by volume)+hydrogen (10% by volume), so as to obtain Li0.994Mo0.001Mn0.65Fe0.35P0.999Si0.001O3.999F0.001 coated with a doped carbon layer.
2) Preparation of Button Battery
The above positive electrode active material, polyvinylidene fluoride (PVDF) and acetylene black in a weight ratio of 90:5:5 are added into N-methylpyrrolidone (NMP), and stirred in a drying room to make a slurry. An aluminum foil is coated with the above slurry, followed by drying and cold pressing, so as to obtain a positive electrode plate. The coating amount is 0.2 g/cm2, and the compacted density is 2.0 g/cm3.
A lithium plate is used as a negative electrode, a solution of 1 mol/L LiPF6 in ethylene carbonate (EC), diethyl carbonate (DEC) and dimethyl carbonate (DMC) in a volume ratio of 1:1:1 is used as an electrolyte solution, and the lithium plate and the electrolyte solution are assembled, together with the positive electrode plate prepared above, into a button battery in a button battery box.
(3) Preparation of Full Battery
The above positive electrode active material is uniformly mixed with a conductive agent acetylene black and a binder polyvinylidene fluoride (PVDF) in a weight ratio of 92:2.5:5.5 in an N-methylpyrrolidone solvent system, and the mixture is applied to an aluminum foil, followed by drying and cold pressing, so as to obtain a positive electrode plate. The coating amount is 0.4 g/cm2, and the compacted density is 2.4 g/cm3.
Negative electrode active materials artificial graphite and hard carbon, a conductive agent acetylene black, a binder styrene butadiene rubber (SBR) and a thickening agent sodium carboxymethylcellulose (CMC) are uniformly mixed in deionized water in a weight ratio of 90:5:2:2:1, and the mixture is applied to a copper foil, followed by drying and cold pressing, so as to obtain a negative electrode plate. The coating amount is 0.2 g/cm2, and the compacted density is 1.7 g/cm3.
With a polyethylene (PE) porous polymer film as a separator, the positive electrode plate, the separator and the negative electrode plate are stacked in sequence, such that the separator is located between the positive electrode and the negative electrode to play a role of isolation, and then winding is performed to obtain a bare cell. The bare cell is placed in an outer package, and the same electrolyte solution as that for the preparation of the button battery is injected, followed by encapsulation, so as to obtain a full battery.
Except that in “1) Preparation of positive electrode active material”, the amount of high-purity Li2CO3 is changed into 0.4885 mol, Mo(SO4)3 is replaced by MgSO4, the amount of FeSO4·H2O is changed into 0.68 mol, 0.02 mol of Ti(SO4)2 is also added in the preparation of doped manganese oxalate, and H4SiO4 is replaced by HNO3, the rest are the same as in Example 1.
Preparation of manganese oxalate: 1 mol of MnSO4·H2O is added into a reaction kettle, and 10 L of deionized water and 1 mol of oxalic acid dihydrate (in oxalic acid) are added. The reaction kettle is heated to 80° C., stirring is performed for 6 hours at a rotation speed of 600 rpm, and the reaction is completed (no bubbles are generated), so as to obtain a manganese oxalate suspension. Then, the suspension is filtered, and the resultant filter cake is dried at 120° C. and then ground, so as to obtain manganese oxalate particles with a median particle size Dv50 of about 50 to 200 nm.
Preparation of lithium manganese phosphate: 1 mol of the above manganese oxalate particles, 0.5 mol of lithium carbonate, an 85% aqueous phosphoric acid solution containing 1 mol of phosphoric acid and 0.005 mol of sucrose are added into 20 L of deionized water. The mixture is transferred into a sander and thoroughly ground and stirred for 10 hours to obtain a slurry. The slurry is transferred into a spray drying apparatus for spray-drying granulation, where the drying temperature is set at 250° C. and the drying time is 4 hours, so as to obtain particles. The above powder is sintered at 700° C. for 10 hours in a protective atmosphere of nitrogen (90% by volume)+hydrogen (10% by volume), so as to obtain carbon-coated LiMnPO4.
Except that in Comparative example I-1, 1 mol of MnSO4·H2O is replaced by 0.85 mol of MnSO4·H2O and 0.15 mol of FeSO4·H2O, which are added into a mixer and thoroughly mixed for 6 hours before adding into a reaction kettle, the rest are the same as in Comparative example I-1.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.9 mol, 0.7 mol of FeSO4·H2O is replaced by 0.1 mol of ZnSO4, the amount of Li2CO3 is changed into 0.495 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.005 mol of MgSO4, the amount of phosphoric acid is changed into −1 mol, and no H4SiO4 and NH4HF2 is added, the rest are the same as in Example I-1.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.2 mol, the amount of FeSO4·H2O is changed into 0.8 mol, the amount of Li2CO3 is changed into 0.45 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.005 mol of Nb2(SO4)5, 0.999 mol of phosphoric acid is changed into −1 mol, 0.0005 mol of NH4HF2 is changed into 0.025 mol, and no H4SiO4 is added, the rest are the same as in Example I-1.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.4 mol, the amount of FeSO4·H2O is changed into 0.6 mol, the amount of Li2CO3 is changed into 0.38 mol, and 0.001 mol of Mo(SO4)3 is replaced by 0.12 mol of MgSO4, the rest are the same as in Example I-1.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 0.8 mol, 0.7 mol of FeSO4·H2O is changed into 1.2 mol of ZnSO4, the amount of Li2CO3 is changed into 0.499 mol, and 0.001 mol of Mo(SO4)3 is replaced by 0.001 mol of MgSO4, the rest are the same as in Example I-1.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.4 mol, the amount of FeSO4·H2O is changed into 0.6 mol, the amount of Li2CO3 is changed into 0.534 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.001 mol of MgSO4, the amount of phosphoric acid is changed into 0.88 mol, the amount of H4SiO4 is changed into 0.12 mol, and the amount of NH4HF2 is changed into 0.025 mol, the rest are the same as in Example I-1.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.2 mol, the amount of FeSO4·H2O is changed into 0.8 mol, the amount of Li2CO3 is changed into 0.474 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.001 mol of MgSO4, the amount of phosphoric acid is changed into 0.93 mol, the amount of H4SiO4 is changed into 0.07 mol, and the amount of NH4HF2 is changed into 0.06 mol, the rest are the same as in Example I-1.
[Preparation of Double-Coated Positive Electrode Active Material and Battery]
(1) Preparation of a Positive Electrode Active Material
Preparation of Co-Doped Lithium Manganese Phosphate Inner Core
Preparation of Fe, Co and V co-doped manganese oxalate: 689.5 g of manganese carbonate (in MnCO3, the same below), 455.2 g of ferrous carbonate (in FeCO3, the same below), 4.6 g of cobalt sulfate (in CoSO4, the same below) and 4.9 g of vanadium dichloride (in VCl2, the same below) are mixed thoroughly for 6 hours in a mixer. The mixture is transferred into a reaction kettle, and 5 L of deionized water and 1260.6 g of oxalic acid dihydrate (in C2H2O4·2H2O, the same below) are added. The reaction kettle is heated to 80° C., stirring is performed for 6 hours at a rotation speed of 600 rpm until the reaction is completed (no bubbles are generated), so as to obtain an Fe, Co, V and S co-doped manganese oxalate suspension. Then, the suspension is filtered, and the resulting filter cake is dried at 120° C. and then ground, so as to obtain Fe, Co, and V co-doped manganese oxalate dihydrate particles with a median particle size Dv50 of 100 nm.
Preparation of Fe, Co, V and S co-doped lithium manganese phosphate: Manganese oxalate dihydrate particles (1793.4 g) obtained in the previous step, 369.0 g of lithium carbonate (in Li2CO3, the same below), 1.6 g of 60% dilute sulfuric acid (in 60% H2SO4, the same below) and 1148.9 g of ammonium dihydrogen phosphate (in NH4H2PO4, the same below) are added to 20 L of deionized water, and the mixture is stirred for 10 hours for mixing uniformly, so as to obtain a slurry. The slurry is transferred into a spray drying apparatus for spray-drying granulation, where the drying temperature is set at 250° C. and the drying time is 4 hours, so as to obtain a powder. The above powder is sintered at 700° C. for 4 hours in a protective atmosphere of nitrogen (90% by volume)+hydrogen (10% by volume), so as to obtain 1572.1 g of Fe, Co, V and S co-doped lithium manganese phosphate.
Preparation of Lithium Iron Pyrophosphate and Lithium Iron Phosphate
Preparation of lithium iron pyrophosphate powder: 4.77 g of lithium carbonate, 7.47 g of ferrous carbonate, 14.84 g of ammonium dihydrogen phosphate and 1.3 g of oxalic acid dihydrate are dissolved in 50 ml of deionized water. The pH of the mixture is 5, and stirring is performed for 2 hours such that the reaction mixture is fully reacted. Then, the reacted solution is heated to 80° C. and kept at this temperature for 4 hours to obtain a suspension of Li2FeP2O7, which is filtered, washed with deionized water, and dried at 120° C. for 4 hours to obtain a powder. The powder is sintered at 650° C. under a nitrogen atmosphere for 8 h, cooled naturally to room temperature and then ground to obtain a Li2FeP2O7 powder.
Preparation of lithium iron phosphate suspension: 11.1 g of lithium carbonate, 34.8 g of ferrous carbonate, 34.5 g of ammonium dihydrogen phosphate, 1.3 g of oxalic acid dihydrate and 74.6 g of sucrose (in C12H22O11, the same below) are dissolved in 150 ml of deionized water to obtain a mixture, and then stirring is performed for 6 hours such that the mixture is fully reacted. Then, the reacted solution is heated to 120° C. and kept at this temperature for 6 hours to obtain a suspension of LiFePO4.
Coating
1572.1 g of the above Fe, Co, V and S co-doped lithium manganese phosphate and 15.72 g of the above lithium iron pyrophosphate (Li2FeP2O7) powder are added into the suspension of lithium iron phosphate (LiFePO4) prepared in the previous step, stirred and mixed uniformly, then transferred to a vacuum oven and dried at 150° C. for 6 h. The resulting product is then dispersed by sanding. After dispersion, the obtained product is sintered at 700° C. under a nitrogen atmosphere for 6 hours to obtain the target product of double-coated lithium manganese phosphate.
(2) Preparation of Positive Electrode Plate
The double-coated lithium manganese phosphate positive electrode active material prepared above, a conductive agent acetylene black and a binder polyvinylidene fluoride (PVDF) are added to N-methylpyrrolidone (NMP) in a weight ratio of 92:2.5:5.5, followed by stirring and uniformly mixing to obtain a positive electrode slurry. The positive electrode slurry is uniformly coated onto an aluminum foil in 0.280 g/1540.25 mm2, followed by drying, cold pressing, and slitting to obtain the positive electrode plate.
(3) Preparation of Negative Electrode Plate
Negative electrode active materials artificial graphite and hard carbon, a conductive agent acetylene black, a binder styrene butadiene rubber (SBR) and a thickening agent sodium carboxymethylcellulose (CMC) are dissolved in deionized water in a weight ratio of 90:5:2:2:1, followed by stirring and uniformly mixing to prepare a negative electrode slurry. The negative electrode slurry is uniformly coated onto a negative electrode current collector copper foil in 0.117 g/1540.25 mm2, followed by drying, cold pressing, and slitting to obtain the negative electrode plate.
(4) Preparation of Electrolyte Solution
In an argon atmosphere glove box (H2O<0.1 ppm, and O2<0.1 ppm), the organic solvent ethylene carbonate (EC)/ethyl methyl carbonate (EMC) is mixed uniformly by a volume ratio of 3/7, and 12.5% by weight (on the basis of the weight of the organic solvent) of LiPF6 is dissolved in the above organic solvent and stirred uniformly to obtain the electrolyte solution.
(5) Separator
A commercially available PP-PE copolymer microporous film having a thickness of 20 μm and an average pore size of 80 nm (Model 20, from Zhuogao Electronic Technology Co. Ltd.) is used.
(6) Preparation of Full Battery
The above obtained positive electrode plate, separator and negative electrode plate are stacked in sequence, such that the separator is located between the positive electrode plate and the negative electrode plate to function for isolation, and are then wound to obtain a bare cell. The bare cell is placed in an outer package, injected with the above electrolyte solution and packaged to obtain a full battery.
(7) Preparation of Button Battery
The double-coated lithium manganese phosphate positive electrode active material prepared above, PVDF and acetylene black are added into NMP in the weight ratio of 90:5:5, and stirred in a drying room to make a slurry. An aluminum foil is coated with the above slurry, followed by drying and cold pressing, so as to obtain a positive electrode plate. The coating amount is 0.2 g/cm2, and the compacted density is 2.0 g/cm3.
A lithium plate is used as a negative electrode, a solution of 1 mol/L LiPF6 in ethylene carbonate (EC)+diethyl carbonate (DEC)+dimethyl carbonate (DMC) in a volume ratio of 1:1:1 is used as an electrolyte solution, and the lithium plate and the electrolyte solution are assembled, together with the positive electrode plate prepared above, into a button battery in a button battery box.
In the preparation process of the co-doped lithium manganese phosphate inner core, except that vanadium dichloride and cobalt sulfate are not used, and 463.4 g of ferrous carbonate, 1.6 g of 60% dilute sulfuric acid, 1148.9 g of ammonium dihydrogen phosphate and 369.0 g of lithium carbonate are used, the preparation conditions of the lithium manganese phosphate inner core in Examples II-1-2 to II-1-6 are the same as in Example II-1-1.
In addition, in the preparation process of lithium iron pyrophosphate and lithium iron phosphate and in the process of coating the first coating layer and the second coating layer, except that the raw materials used are adjusted correspondingly according to the ratio of the coating amount shown in Table 1 to the coating amount corresponding to Example II-1-1, such that the amount of Li2FeP2O7/LiFePO4 in Examples II-1-2 to II-1-6 is 12.6 g/37.7 g, 15.7 g/47.1 g, 18.8 g/56.5 g, 22.0 g/66.0 g and 25.1 g/75.4 g, respectively, the amount of sucrose in the Examples II-1-2 to II-1-6 is 37.3 g, other conditions are the same as in Example II-1-1.
Except that the amounts of sucrose are 74.6 g, 149.1 g, 186.4 g and 223.7 g, respectively, such that the corresponding coating amounts of the carbon layer as the second coating layer are 31.4 g, 62.9 g, 78.6 g and 94.3 g, respectively, the conditions of Examples II-1-7 to II-1-10 are the same as in Example II-1-3.
In the preparation process of lithium iron pyrophosphate and lithium iron phosphate, except that the amounts of various raw materials are adjusted correspondingly according to the coating amount shown in Table 1, such that the amount of Li2FeP2O7/LiFePO4 is 23.6 g/39.3 g, 31.4 g/31.4 g, 39.3 g/23.6 g and 47.2 g/15.7 g, respectively, the conditions of Examples II-1-11 to II-1-14 are the same as in Example II-1-7.
In the preparation process of co-doped lithium manganese phosphate inner core, except that iron ferrous carbonate is replaced by 492.80 g of ZnCO3, the conditions of Example II-1-15 are the same as in Example II-1-14.
Except that in the preparation process of co-doped lithium manganese phosphate inner core of Example II-1-16, ferrous carbonate is replaced by 466.4 g of NiCO3, 5.0 g of zinc carbonate and 7.2 g of titanium sulfate; except that in the preparation process of co-doped lithium manganese phosphate inner core of Example II-1-17, 455.2 g of ferrous carbonate and 8.5 g of vanadium dichloride are used; and except that in the preparation process of co-doped lithium manganese phosphate inner core of Example II-1-18, 455.2 g of ferrous carbonate, 4.9 g of vanadium dichloride and 2.5 g of magnesium carbonate are used, the conditions of Examples II-1-17 to I-19 are the same as in Example II-1-7.
Except that in the preparation process of co-doped lithium manganese phosphate inner core of Example II-1-19, 369.4 g of lithium carbonate is used, and dilute sulphuric acid is replaced by 1.05 g of 60% dilute nitric acid; and except that in the preparation process of co-doped lithium manganese phosphate inner core of Example II-1-20, 369.7 g of lithium carbonate is used, and dilute sulphuric acid is replaced by 0.78 g of siliceous acid, the conditions of Examples II-1-19 to II-1-20 are the same as in Example II-1-18.
Except that in the preparation process of co-doped lithium manganese phosphate inner core of Example II-1-21, 632.0 g of manganese carbonate, 463.30 g of ferrous carbonate, 30.5 g of vanadium dichloride, 21.0 g of magnesium carbonate and 0.78 g of siliceous acid are used; and except that in the preparation process of co-doped lithium manganese phosphate inner core of Example II-1-22, 746.9 g of manganese carbonate, 289.6 g of ferrous carbonate, 60.9 g of vanadium dichloride, 42.1 g of magnesium carbonate and 0.78 g of siliceous acid are used, the conditions of Examples II-1-21 to II-1-22 are the same as in Example II-1-20.
Except that in the preparation process of co-doped lithium manganese phosphate inner core of Example II-1-23, 804.6 g of manganese carbonate, 231.7 g of ferrous carbonate, 1156.2 g of ammonium dihydrogen phosphate, 1.2 g of boric acid (with a mass fraction of 99.5%) and 370.8 g of lithium carbonate are used; and except that in the preparation process of co-doped lithium manganese phosphate inner core of Example II-1-24, 862.1 g of manganese carbonate, 173.8 g of ferrous carbonate, 1155.1 g of ammonium dihydrogen phosphate, 1.86 g of boric acid (with a mass fraction of 99.5%) and 371.6 g of lithium carbonate are used, the conditions of Examples II-1-23 to II-1-24 are the same as in Example II-1-22.
Except that in the preparation process of co-doped lithium manganese phosphate inner core of Example II-1-25, 370.1 g of manganese carbonate, 1.56 g of siliceous acid and 1147.7 g of ammonium dihydrogen phosphate are used, the conditions of Example II-1-25 are the same as in Example II-1-20.
Except that in the preparation process of co-doped lithium manganese phosphate inner core of Example II-1-26, 368.3 g of lithium carbonate, 4.9 g of 60% dilute sulfuric acid, 919.6 g of manganese carbonate, 224.8 g of ferrous carbonate, 3.7 g of vanadium dichloride, 2.5 g of magnesium carbonate and 1146.8 g of ammonium dihydrogen phosphate are used, the conditions of Example II-1-26 are the same as in Example II-1-20.
Except that in the preparation process of co-doped lithium manganese phosphate inner core of Example II-1-27, 367.9 g of manganese carbonate, 6.5 g of 60% dilute sulfuric acid and 1145.4 g of ammonium dihydrogen phosphate are used, the conditions of Example II-1-27 are the same as in Example II-1-20.
Except that in the preparation process of co-doped lithium manganese phosphate inner core of Examples II-1-28 to II-1-33, 1034.5 g of manganese carbonate, 108.9 g of ferrous carbonate, 3.7 g of vanadium dichloride and 2.5 g of magnesium carbonate are used; the amounts of lithium carbonate are respectively: 367.6 g, 367.2 g, 366.8 g, 366.4 g, 366.0 g and 332.4 g; the amounts of ammonium dihydrogen phosphate are respectively: 1144.5 g, 1143.4 g, 1142.2 g, 1141.1 g, 1139.9 g and 1138.8 g; and the amounts of 60% dilute sulfuric acid are respectively: 8.2 g, 9.8 g, 11.4 g, 13.1 g, 14.7 g and 16.3 g, the conditions of Examples II-1-28 to II-1-33 are the same as in Example II-1-20.
Preparation of the Inner Core Li1.1Mn0.6Fe0.393Mg0.007P0.9Si0.1O4:
Preparation of Fe and Mg co-doped manganese oxalate: 689.5 g of manganese carbonate (in MnCO3, the same below), 455.2 g of ferrous carbonate (in FeCO3, the same below) and 5.90 g of magnesium carbonate (in MgCO3, the same below) are mixed thoroughly for 6 hours in a mixer. The mixture is transferred into a reaction kettle, and 5 L of deionized water and 1260.6 g of oxalic acid dihydrate (in C2H2O4·2H2O, the same below) are added. The reaction kettle is heated to 80° C., stirring is performed for 6 hours at a rotation speed of 600 rpm until the reaction is completed (no bubbles are generated), so as to obtain an Fe and Mg co-doped manganese oxalate suspension. Then, the suspension is filtered, and the resulting filter cake is dried at 120° C. and then ground, so as to obtain Fe and Mg co-doped manganese oxalate dihydrate particles with a median particle size Dv50 of 100 nm.
Preparation of Fe, Mg and Si co-doped lithium manganese phosphate: Manganese oxalate dihydrate particles (1791.3 g) obtained in the previous step, 406.3 g of lithium carbonate (in Li2CO3, the same below), 7.8 g of siliceous acid (in H2SiO3, the same below) and 1035.0 g of ammonium dihydrogen phosphate (in NH4H2PO4, the same below) are added to 20 L of deionized water, and the mixture is stirred for 10 hours for mixing uniformly, so as to obtain a slurry. The slurry is transferred into a spray drying apparatus for spray-drying granulation, where the drying temperature is set at 250° C. and the drying time is 4 h, so as to obtain a powder. The above powder is sintered at 700° C. for 4 hours in a protective atmosphere of nitrogen (90% by volume)+hydrogen (10% by volume), so as to obtain 1574.0 g of Fe, Mg and Si co-doped lithium manganese phosphate.
Other conditions refer to Example II-1-1.
Preparation of the Inner Core LiMn0.50Fe0.50P0.995N0.005O4.
Preparation of Fe-doped manganese oxalate: 574.7 g of manganese carbonate (in MnCO3, the same below) and 579.27 g of ferrous carbonate (in FeCO3, the same below) are mixed thoroughly for 6 hours in a mixer. The mixture is transferred into a reaction kettle, and 5 L of deionized water and 1260.6 g of oxalic acid dihydrate (in C2H2O4·2H2O, the same below) are added. The reaction kettle is heated to 80° C., stirring is performed for 6 hours at a rotation speed of 600 rpm until the reaction is completed (no bubbles are generated), so as to obtain an Fe-doped manganese oxalate suspension. Then, the suspension is filtered, and the resulting filter cake is dried at 120° C. and then ground, so as to obtain Fe-doped manganese oxalate dihydrate particles with a median particle size Dv50 of 100 nm.
Preparation of Fe and N co-doped lithium manganese phosphate: Manganese oxalate dihydrate particles (1794.4 g) obtained in the previous step, 369.4 g of lithium carbonate (in Li2CO3, the same below), 5.25 g of dilute nitric acid (in 60% HNO3, the same below) and 1144.3 g of ammonium dihydrogen phosphate (in NH4H2PO4, the same below) are added to 20 L of deionized water, and the mixture is stirred for 10 hours for mixing uniformly, so as to obtain a slurry. The slurry is transferred into a spray drying apparatus for spray-drying granulation, where the drying temperature is set at 250° C. and the drying time is 4 h, so as to obtain a powder. The above powder is sintered at 700° C. for 4 hours in a protective atmosphere of nitrogen (90% by volume)+hydrogen (10% by volume), so as to obtain 1572.2 g of Fe and N co-doped lithium manganese phosphate.
Other conditions refer to Example II-1-1.
Except that in the preparation of inner core LiMn0.909Fe0.091P10.99N0.01O4, 1044.6 g of manganese carbonate, 1138.5 g of ammonium dihydrogen phosphate and 369.4 g of lithium carbonate are used, and 105.4 g of ferrous carbonate and 10.5 g of dilute nitric acid (in 60% HNO3, the same below) are additionally added, the rest are the same as in Example II-1-1.
Except that in the preparation of inner core LiMn0.091Fe0.909P0.995N0.005O4, 104.5 g of manganese carbonate, 1138.5 g of ammonium dihydrogen phosphate and 371.3 g of lithium carbonate are used, and 1052.8 g of ferrous carbonate and 5.25 g of dilute nitric acid (in 60% HNO3, the same below) are additionally added, the rest are the same as in Example II-1-1.
In the preparation process of lithium iron pyrophosphate and lithium iron phosphate and in the process of coating the first coating layer and the second coating layer, except that the raw materials used are adjusted correspondingly according to the ratio of the coating amount shown in Table 4 to the coating amount corresponding to Example II-1-1, such that the amount of Li2FeP2O7/LiFePO4 is 62.9 g/47.1 g, respectively, other conditions are the same as in Example II-1-1.
In the preparation process of silver pyrophosphate, 463.4 of silver oxide (in Ag2O, the same below) and 230.6 phosphoric acid (in 85% H3PO4, the same below) are mixed thoroughly. It is heated to 450° C. while stirring continuously for 2 hours such that the reaction mixture is fully reacted. Then the reacted solution is kept at 450° C. for 4 hours to obtain a viscous paste containing Ag4P2O7, which finally becomes a solid; the solid is washed with deionized water, and the resulting product is ground in a ball mill containing ethanol for 4 h, and the resulting product is dried under an infrared lamp to obtain a Ag4P2O7 powder. The rest are the same as in Example II-1-1.
Except in the process of preparing Fe, Co, V and S co-doped lithium manganese phosphate, the powder is sintered at 650° C. for 43.5 hours in the protective atmosphere of nitrogen (90% by volume)+hydrogen (10% by volume), the rest are the same as in Example II-1-21.
Preparation of the Inner Core LiMn0.999Fe0.001P0.995N0.005O4
Preparation of Fe-doped manganese oxalate: 1148.0 g of manganese carbonate (in MnCO3, the same below) and 11.58 g of ferrous carbonate (in FeCO3, the same below) are mixed thoroughly for 6 hours in a mixer. The mixture is transferred into a reaction kettle, and 5 L of deionized water and 1260.6 g of oxalic acid dihydrate (in C2H2O4·2H2O, the same below) are added. The reaction kettle is heated to 80° C., stirring is performed for 6 hours at a rotation speed of 600 rpm until the reaction is completed (no bubbles are generated), so as to obtain an Fe-doped manganese oxalate suspension. Then, the suspension is filtered, and the resulting filter cake is dried at 120° C. and then ground, so as to obtain Fe-doped manganese oxalate dihydrate particles with a median particle size Dv50 of 100 nm.
Preparation of Fe and N co-doped lithium manganese phosphate: Manganese oxalate dihydrate particles (1789.9 g) obtained in the previous step, 369.4 g of lithium carbonate (in Li2CO3, the same below), 5.25 g of dilute nitric acid (in 60% HNO3, the same below) and 1144.3 g of ammonium dihydrogen phosphate (in NH4H2PO4, the same below) are added to 20 L of deionized water, and the mixture is stirred for 10 hours for mixing uniformly, so as to obtain a slurry. The slurry is transferred into a spray drying apparatus for spray-drying granulation, where the drying temperature is set at 250° C. and the drying time is 4 h, so as to obtain a powder. The above powder is sintered at 700° C. for 4 hours in a protective atmosphere of nitrogen (90% by volume)+hydrogen (10% by volume), so as to obtain 1567.7 g of Fe and N co-doped lithium manganese phosphate.
Other conditions of Example II-1-41 refer to Example II-1-1.
Except that in the preparation process of lithium iron pyrophosphate (Li2FeP2O7), in the powder sintering step, the sintering temperature is 550° C. and the sintering time is 1 h to control the crystallinity of Li2FeP2O7 to be 30%; and except in the preparation process of lithium iron phosphate (LiFePO4), in the coating sintering step, the sintering temperature is 650° C. and the sintering time is 2 h to control the crystallinity of LiFePO4 to be 30%, other conditions are the same as in Example II-1-1.
Except that in the preparation process of lithium iron pyrophosphate (Li2FeP2O7), in the powder sintering step, the sintering temperature is 550° C. and the sintering time is 2 h to control the crystallinity of Li2FeP2O7 to be 50%; and except in the preparation process of lithium iron phosphate (LiFePO4), in the coating sintering step, the sintering temperature is 650° C. and the sintering time is 3 h to control the crystallinity of LiFePO4 to be 50%, other conditions are the same as in Example II-1-1.
Except that in the preparation process of lithium iron pyrophosphate (Li2FeP2O7), in the powder sintering step, the sintering temperature is 600° C. and the sintering time is 3 h to control the crystallinity of Li2FeP2O7 to be 70%; and except in the preparation process of lithium iron phosphate (LiFePO4), in the coating sintering step, the sintering temperature is 650° C. and the sintering time is 4 h to control the crystallinity of LiFePO4 to be 70%, other conditions are the same as in Example II-1-1.
Except that in the preparation process of lithium iron pyrophosphate (Li2FeP2O7), in the powder sintering step, the sintering temperature is 650° C. and the sintering time is 4 h to control the crystallinity of Li2FeP2O7 to be 100%; and except in the preparation process of lithium iron phosphate (LiFePO4), in the coating sintering step, the sintering temperature is 700° C. and the sintering time is 6 h to control the crystallinity of LiFePO4 to be 100%, other conditions are the same as in Example II-1-1.
Except that in the preparation process of Fe, Co, and V co-doped manganese oxalate particles, the heating temperature/stirring time in the reaction kettle of Example II-3-1 is respectively 60° C./120 min; The heating temperature/stirring time in the reaction kettle of Example II-3-2 is respectively 70° C./120 min; The heating temperature/stirring time in the reaction kettle of Example II-3-3 is respectively 80° C./120 min; The heating temperature/stirring time in the reaction kettle of Example II-3-4 is respectively 90° C./120 min; The heating temperature/stirring time in the reaction kettle of Example II-3-5 is respectively 100° C./120 min; The heating temperature/stirring time in the reaction kettle of Example II-3-6 is respectively 110° C./120 min; The heating temperature/stirring time in the reaction kettle of Example II-3-7 is respectively 120° C./120 min; The heating temperature/stirring time in the reaction kettle of Example II-3-8 is respectively 130° C./120 min; The heating temperature/stirring time in the reaction kettle of Example II-3-9 is respectively 100° C./60 min; The heating temperature/stirring time in the reaction kettle of Example II-3-10 is respectively 100° C./90 min; The heating temperature/stirring time in the reaction kettle of Example II-3-11 is respectively 100° C./150 min; Except that the heating temperature/stirring time in the reaction kettle of Example II-3-12 is respectively 100° C./180 min, other conditions of Examples II-3-1 to II-3-12 are the same as in Example II-1-1.
Examples II-4-1 to II-4-4: Except that in the preparation process of lithium iron pyrophosphate (Li2FeP2O7), in the drying step, the drying temperature/drying time is 100° C./4 h, 150° C./6 h, 200° C./6 h and 200° C./6 h, respectively; and except that in the preparation process of lithium iron pyrophosphate (Li2FeP2O7), in the sintering step, the sintering temperature and sintering time are 700° C./6 h, 700° C./6 h, 700° C./6 h and 600° C./6 h, respectively, other conditions are the same as in Example II-1-7.
Examples II-4-5 to II-4-7: Except that in the coating process, the drying temperature/drying time in the drying step is 150° C./6 h, 150° C./6 h and 150° C./6 h, respectively; and except that in the coating process, the sintering temperature and sintering time in the sintering step are 600° C./4 h, 600° C./6 h and 800° C./8 h, respectively, other conditions are the same as in Example II-1-12.
(1) Preparation of co-doped lithium manganese phosphate inner core: It is the same as “Preparation of co-doped lithium manganese phosphate inner core” in Example II-1-1.
(2) Preparation of lithium iron pyrophosphate and suspension containing aluminum oxide and sucrose:
Preparation of lithium iron pyrophosphate powder: 4.77 g of lithium carbonate, 7.47 g of ferrous carbonate, 14.84 g of ammonium dihydrogen phosphate and 1.3 g of oxalic acid dihydrate are dissolved in 50 ml of deionized water. The pH of the mixture is 5, and stirring is performed for 2 hours such that the reaction mixture is fully reacted. Then, the reacted solution is heated to 80° C. and kept at this temperature for 4 hours to obtain a suspension of Li2FeP2O7, which is filtered, washed with deionized water, and dried at 120° C. for 4 hours to obtain a powder. The powder is sintered at 650° C. under a nitrogen atmosphere for 8 h, cooled naturally to room temperature and then ground to obtain a Li2FeP2O7 powder.
Preparation of the suspension containing aluminum oxide and sucrose: 47.1 g of nano-Al2O3 (with a particle size of 20 nm) and 74.6 g of sucrose (in C12H22O11, the same below) are dissolved in 1500 ml of deionized water, and then stirred for 6 hours such that the mixture is fully reacted. Then, the resulting solution is heated to 120° C. and kept at this temperature for 6 hours to obtain a suspension containing aluminum oxide and sucrose.
(3) Coating
1572.1 g of the above Fe, Co, V and S co-doped lithium manganese phosphate and 15.72 g of the above lithium iron pyrophosphate (Li2FeP2O7) powder are added into the suspension containing aluminum oxide and sucrose prepared in the previous step, stirred and mixed uniformly, then transferred to a vacuum oven and dried at 150° C. for 6 h. The resulting product is then dispersed by sanding. After dispersion, the obtained product is sintered at 700° C. under a nitrogen atmosphere for 6 hours to obtain the target product of double-coated lithium manganese phosphate.
In the preparation process of the co-doped lithium manganese phosphate inner core, except that vanadium dichloride and cobalt sulfate are not used, and 463.4 g of ferrous carbonate, 1.6 g of 60% dilute sulfuric acid, 1148.9 g of ammonium dihydrogen phosphate and 369.0 g of lithium carbonate are used, the preparation conditions of the lithium manganese phosphate inner core in Example II-5-2 are the same as in Example II-5-1.
In addition, in the preparation process of lithium iron pyrophosphate and the suspension containing aluminum oxide and sucrose and in the process of coating the first coating layer and the second coating layer, except that the raw materials used are adjusted correspondingly according to the ratio of the coating amount shown in Table 24 to the coating amount corresponding to Example II-5-1, such that the amount of Li2FeP2O7/Al2O3 in Example II-5-2 is 12.6 g/37.68 g, respectively, the amount of sucrose in the Example II-5-2 is 37.3 g, other conditions are the same as in Example II-5-1.
Step S1: Preparation of Doped Manganese Oxalate
1.3 mol of MnSO4·H2O and 0.7 mol of FeSO4·H2O are mixed thoroughly for 6 hours in a mixer; the mixture is transferred into a reaction kettle, 10 L of deionized water and 2 mol of oxalic acid dihydrate are added thereto, heated to 80° C., and then stirred for 6 hours at a rotation speed of 600 rpm, the reaction is completed (no bubbles are generated), so as to obtain an Fe-doped manganese oxalate suspension; the suspension is filtered, and the resulting filter cake is dried at 120° C. and then ground to obtain Fe-doped manganese oxalate particles with a particle size Dv50 of about 100 nm.
Step S2: Preparation of Inner Core Containing Li0.994Mo0.001Mn0.65Fe0.35P0.999Si0.001O3.999F0.001
1 mol of the Fe-doped manganese oxalate particles, 0.497 mol of lithium carbonate, 0.001 mol of Mo(SO4)3, an 85% aqueous phosphoric acid solution containing 0.999 mol of phosphoric acid, 0.001 mol of H4SiO4, 0.0005 mol of NH4HF2 and 0.005 mol of sucrose are added into 20 L of deionized water, and the mixture is transferred into a sander and thoroughly ground and stirred for 10 hours to obtain a slurry. The slurry is transferred into a spray drying apparatus for spray-drying granulation, where the drying temperature is set at 250° C. and the drying time is 4 h, so as to obtain particles; the particles are sintered at 700° C. for 10 hours in a protective atmosphere of nitrogen (90% v/v)+hydrogen (10% v/v) to obtain a inner core material. The element content of the inner core material is detected using inductively coupled plasma (ICP) emission spectrometry, and the chemical formula of the inner core is obtained as shown above.
Step S3: Preparation of Lithium Iron Pyrophosphate Powder
4.77 g of lithium carbonate, 7.47 g of ferrous carbonate, 14.84 g of ammonium dihydrogen phosphate and 1.3 g of oxalic acid dihydrate are dissolved in 50 ml of deionized water. The pH of the mixture is 5, and stirring is performed for 2 hours such that the reaction mixture is fully reacted. Then, the reacted solution is heated to 80° C. and kept at this temperature for 4 hours to obtain a suspension of Li2FeP2O7, which is filtered, washed with deionized water, and dried at 120° C. for 4 hours to obtain a powder. The powder is sintered at 650° C. under a nitrogen atmosphere for 8 h, cooled naturally to room temperature and then ground to obtain a Li2FeP2O7 powder.
Step S4: Preparation of the Suspension Containing Aluminum Oxide and Sucrose
4.71 g of nano-Al2O3 (with a particle size of 20 nm) and 3.73 g of sucrose (in C12H22O11, the same below) are dissolved in 150 ml of deionized water, and then stirred for 6 hours such that the mixture is fully reacted. The mixture is then heated to 120° C. and kept at this temperature for 6 hours to obtain a suspension containing aluminum oxide and sucrose.
Step S5: Preparation of Two-Layer Coating
157.21 g of the above inner core and 1.57 g of the above lithium iron pyrophosphate (Li2FeP2O7) powder are added into the suspension containing aluminum oxide and sucrose prepared in the previous step, stirred and mixed uniformly, then transferred to a vacuum oven and dried at 150° C. for 6 h, then the resulting product is dispersed by sanding; after dispersion, the product is sintered at 700° C. for 6 hours under a nitrogen atmosphere to obtain double-coated lithium manganese phosphate.
Except that in the preparation of lithium iron pyrophosphate (Li2FeP2O7) powder of step S3, in the powder sintering step, the sintering temperature is 550° C. and the sintering time is 1 h to control the crystallinity of Li2FeP2O7 to be 30%, other conditions are the same as in Example II-5-3.
Preparation of doped manganese oxalate: 1.3 mol of MnSO4·H2O and 0.7 mol of FeSO4·H2O are mixed thoroughly for 6 hours in a mixer. The mixture is transferred into a reaction kettle, and 10 L of deionized water and 2 mol of oxalic acid dihydrate (in oxalic acid) are added. The reaction kettle is heated to 80° C., stirring is performed for 6 hours at a rotation speed of 600 rpm, and the reaction is completed (no bubbles are generated), so as to obtain an Fe-doped manganese oxalate suspension. Then, the suspension is filtered, and the resultant filter cake is dried at 120° C. and then ground, so as to obtain Fe-doped manganese oxalate particles with a median particle size Dv50 of about 100 nm.
Preparation of inner core: 1 mol of the above manganese oxalate particles, 0.497 mol of lithium carbonate, 0.001 mol of Mo(SO4)3, an 85% aqueous phosphoric acid solution containing 0.999 mol of phosphoric acid, 0.001 mol of H4SiO4, 0.0005 mol of NH4HF2 and 0.005 mol of sucrose are added into 20 L of deionized water. The mixture is transferred into a sander and thoroughly ground and stirred for 10 hours to obtain a slurry. The slurry is transferred into a spray drying apparatus for spray-drying granulation, where the drying temperature is set at 250° C. and the drying time is 4 h, so as to obtain particles. The above powder is sintered at 700° C. for 10 hours in a protective atmosphere of nitrogen (90% by volume)+hydrogen (10% by volume), so as to obtain carbon-coated Li0.994Mo0.001Mn0.65Fe0.35P0.999Si0.001O3.999F0.001, i.e., inner core. The element content may be tested using inductively coupled plasma (ICP) emission spectroscopy.
Coating of the coating layer: Aminoethylaminopropyl polydimethylsiloxane is dissolved in xylene to form a coating solution, then the prepared inner core is added thereto and stirred evenly to form a mixed slurry, then the mixed slurry is placed in a wet coating machine, and dried under a nitrogen atmosphere at 120° C. for 4 h, so as to obtain a positive electrode active material. The mass content percentage of the polar functional groups (i.e., —CH2NH2 and —CH2—) of aminoethylaminopropyl polydimethylsiloxane is 12%, the number average molecular weight is 3700, and the coating amount is 1% by weight, based on the weight of the prepared inner core.
See Example II-1-1 for the preparation of button battery and full battery.
Step S1: Preparation of Fe, Co, V and S Co-Doped Manganese Oxalate
689.6 g of manganese carbonate, 455.27 g of ferrous carbonate, 4.65 g of cobalt sulfate and 4.87 g of vanadium dichloride are mixed thoroughly for 6 hours in a mixer. The resulting mixture is then transferred into a reaction kettle, 5 L of deionized water and 1260.6 g of oxalic acid dihydrate are added, heated to 80° C., then stirred thoroughly for 6 hours at a rotation speed of 500 rpm and mixed uniformly until the reaction is completed (no bubbles are generated), so as to obtain an Fe, Co, and V co-doped manganese oxalate suspension. Then, the suspension is filtered, dried at 120° C. and then sanded, so as to obtain manganese oxalate particles with a particle size of 100 nm.
Step S2: Preparation of inner core Li0.997Mn0.60Fe0.393V0.004Co0.003P0.997S0.003O4
1793.1 g of manganese oxalate prepared in (1), 368.3 g of lithium carbonate, 1146.6 g of ammonium dihydrogen phosphate and 4.9 g of dilute sulfuric acid are added to 20 L of deionized water, fully stirred, and mixed uniformly and reacted at 80° C. for 10 hours to obtain a slurry. The slurry is transferred into a spray drying apparatus for spray-drying granulation, and dried at a temperature of at 250° C. to obtain a powder. In a protective atmosphere (90% of nitrogen and 10% of hydrogen), the powder is sintered in a roller kiln at 700° C. for 4 hours to obtain the above inner core material.
Step S3: Preparation of the First Coating Layer Suspension
Preparation of a Li2FeP2O7 solution: 7.4 g of lithium carbonate, 11.6 g of ferrous carbonate, 23.0 g of ammonium dihydrogen phosphate and 12.6 g of oxalic acid dihydrate are dissolved in 500 mL of deionized water, the pH is controlled to be 5, then same is stirred and reacted at room temperature for 2 hours to obtain a solution, and then the solution is heated to 80° C. and kept at this temperature for 4 hours to obtain a first coating layer suspension.
Step S4: Coating of the First Coating Layer
1571.9 g of doped lithium manganese phosphate inner core material obtained in step S2 is added to the first coating layer suspension (the content of the coating material is 15.7 g) obtained in step S3, fully stirred and mixed for 6 h; after uniformly mixing, same is transferred in an oven at 120° C. and dried for 6 h, and then sintered at 650° C. for 6 hours to obtain a pyrophosphate coated material.
Step S5: Preparation of the Second Coating Layer Suspension
3.7 g of lithium carbonate, 11.6 g of ferrous carbonate, 11.5 g of ammonium dihydrogen phosphate and 12.6 g of oxalic acid dihydrate are dissolved in 1500 mL of deionized water, then same is stirred and reacted for 6 hours to obtain a solution, and then the solution is heated to 120° C. and kept at this temperature for 6 hours to obtain a second coating layer suspension.
Step S6: Coating of the Second Coating Layer
1586.8 g of the pyrophosphate coated material obtained in step S4 is added to the second coating layer suspension (the content of the coating material is 47.1 g) obtained in step S5, fully stirred and mixed for 6 h; after uniformly mixing, same is transferred in an oven at 120° C. and dried for 6 h, and then sintered at 700° C. for 8 hours to obtain a two-layer coated material.
Step S7: Preparation of Aqueous Solution of the Third Coating Layer
37.3 g of sucrose is dissolved in 500 g of deionized water, then stirred and fully dissolved to obtain an aqueous solution of sucrose.
Step S8: Coating of the Third Coating Layer
1633.9 g of the two-layer coated material obtained in step S6 is added to the sucrose solution obtained in step S7, stirred together and mixed for 6 h; after uniformly mixing, same is transferred in an oven at 150° C. and dried for 6 h, and then sintered at 700° C. for 10 hours to obtain a third-layer coated material.
Step S9: Coating of the Fourth Coating Layer
Hydroxy-terminated polydimethylsiloxane is dissolved in xylene to form a fourth coating solution, then the three-layer coated material obtained in step S8 is added thereto and stirred evenly to form a mixed slurry, then the mixed slurry is placed in a wet coating machine, and dried under a nitrogen atmosphere at 120° C. for 4 h, so as to obtain a four-layer coated positive electrode active material. The mass content percentage of the polar functional groups (i.e., —OH—) of hydroxy-terminated polydimethylsiloxane is 3.4%, the number average molecular weight is 1000, and the coating amount is 1% by weight, based on the weight of the three-layer coated material obtained in step S8.
See Example II-1-1 for the preparation of button battery and full battery.
Preparation of doped manganese oxalate: 1.3 mol of MnSO4·H2O and 0.7 mol of FeSO4·H2O are mixed thoroughly for 6 hours in a mixer. The mixture is transferred into a reaction kettle, and 10 L of deionized water and 2 mol of oxalic acid dihydrate (in oxalic acid) are added. The reaction kettle is heated to 80° C., stirring is performed for 6 hours at a rotation speed of 600 rpm, and the reaction is completed (no bubbles are generated), so as to obtain an Fe-doped manganese oxalate suspension. Then, the suspension is filtered, and the resultant filter cake is dried at 120° C. and then ground, so as to obtain Fe-doped manganese oxalate particles with a median particle size Dv50 of about 100 nm.
Preparation of inner core: 1 mol of the above manganese oxalate particles, 0.497 mol of lithium carbonate, 0.001 mol of Mo(SO4)3, an 85% aqueous phosphoric acid solution containing 0.999 mol of phosphoric acid, 0.001 mol of H4SiO4, 0.0005 mol of NH4HF2 and 0.005 mol of sucrose are added into 20 L of deionized water. The mixture is transferred into a sander and thoroughly ground and stirred for 10 hours to obtain a slurry. The slurry is transferred into a spray drying apparatus for spray-drying granulation, where the drying temperature is set at 250° C. and the drying time is 4 h, so as to obtain particles. The above powder is sintered at 700° C. for 10 hours in a protective atmosphere of nitrogen (90% by volume)+hydrogen (10% by volume), so as to obtain carbon-coated Li0.994Mo0.001Mn0.65Fe0.35P0.999Si0.001O3.999F0.001, i.e., inner core. The element content may be tested using inductively coupled plasma (ICP) emission spectroscopy.
Coating of the coating layer: Carboxymethyl chitosan is dissolved in deionized water to form a coating solution, then the inner core material is added thereto and stirred evenly to form a mixed slurry, then the mixed slurry is placed in a wet coating machine, and dried under a nitrogen atmosphere at 120° C. for 4 h, so as to obtain a positive electrode active material. The mass content percentage of substituents connected to sugar units in carboxymethyl chitosan is 60.2%, the number average molecular weight is 26000, and the coating amount is 1% by weight, based on the weight of the inner core.
See Example II-1-1 for the preparation of button battery and full battery.
Preparation of manganese oxalate: 1149.3 g of manganese carbonate is added into a reaction kettle, and 5 L of deionized water and 1260.6 g of oxalic acid dihydrate (in C2H2O4·2H2O, the same below) are added. The reaction kettle is heated to 80° C., stirring is performed for 6 hours at a rotation speed of 600 rpm until the reaction is completed (no bubbles are generated), so as to obtain a manganese oxalate suspension. Then, the suspension is filtered, and the resulting filter cake is dried at 120° C. and then ground to obtain manganese oxalate dihydrate particles with a median particle size Dv50 of 100 nm.
Preparation of carbon-coated lithium manganese phosphate: 1789.6 g of manganese oxalate dihydrate particles obtained above, 369.4 g of lithium carbonate (in Li2CO3, the same below), 1150.1 g of ammonium dihydrogen phosphate (in NH4H2PO4, the same below) and 31 g of sucrose (in C12H22O11, the same below) are added to 20 L of deionized water, and the mixture is stirred for 10 hours to be uniformly mixed, so as to obtain a slurry. The slurry is transferred into a spray drying apparatus for spray-drying granulation, where the drying temperature is set at 250° C. and the drying time is 4 h, so as to obtain a powder. The above powder is sintered at 700° C. for 4 hours in a protective atmosphere of nitrogen (90% by volume)+hydrogen (10% by volume), so as to obtain carbon doped lithium manganese phosphate.
Except that 689.5 g of manganese carbonate is used and 463.3 g of ferrous carbonate is additionally added, other conditions of Comparative example II-2 are the same as in Comparative example II-1.
Except that 1148.9 g of ammonium dihydrogen phosphate and 369.0 g of lithium carbonate are used, and 1.6 g of 60% dilute sulfuric acid is additionally added, other conditions of Comparative example II-3 are the same as in Comparative example II-1.
Except that 689.5 g of manganese carbonate, 1148.9 g of ammonium dihydrogen phosphate and 369.0 g of lithium carbonate are used, and 463.3 g of ferrous carbonate and 1.6 g of 60% dilute sulfuric acid are additionally added, other conditions of Comparative example II-4 are the same as in Comparative example II-1.
Except for the following additional steps: Preparation of lithium iron pyrophosphate powder: 9.52 g of lithium carbonate, 29.9 g of ferrous carbonate, 29.6 g of ammonium dihydrogen phosphate and 32.5 g of oxalic acid dihydrate are dissolved in 50 ml of deionized water. The pH of the mixture is 5, and stirring is performed for 2 hours such that the reaction mixture is fully reacted. Then, the reacted solution is heated to 80° C. and kept at this temperature for 4 hours to obtain a suspension of Li2FeP2O7, which is filtered, washed with deionized water, and dried at 120° C. for 4 hours to obtain a powder. The powder is sintered at 500° C. under a nitrogen atmosphere for 4 h, and then ground after cooling to room temperature naturally to control the crystallinity of Li2FeP2O7 to be 5%; when preparing a carbon-coated material, the amount of Li2FeP2O7 is 62.8 g, other conditions of Comparative example II-5 are the same as Comparative example II-4.
Except for the following additional steps: Preparation of lithium iron phosphate suspension: 14.7 g of lithium carbonate, 46.1 g of ferrous carbonate, 45.8 g of ammonium dihydrogen phosphate and 50.2 g of oxalic acid dihydrate are dissolved in 500 ml of deionized water, and then stirred for 6 hours such that the mixture is fully reacted. Then, the reacted solution is heated to 120° C. and kept at this temperature for 6 hours to obtain a LiFePO4 suspension; in the preparation process of lithium iron phosphate (LiFePO4), the sintering temperature is 600° C. and the sintering time is 4 hours in the coating sintering step to control the crystallinity of LiFePO4 to be 8%; and when preparing a carbon-coated material, the amount of LiFePO4 is 62.8 g, other conditions of Comparative example II-6 are the same as Comparative example II-4.
Preparation of lithium iron pyrophosphate powder: 2.38 g of lithium carbonate, 7.5 g of ferrous carbonate, 7.4 g of ammonium dihydrogen phosphate and 8.1 g of oxalic acid dihydrate are dissolved in 50 ml of deionized water. The pH of the mixture is 5, and stirring is performed for 2 hours such that the reaction mixture is fully reacted. Then, the reacted solution is heated to 80° C. and kept at this temperature for 4 hours to obtain a suspension of Li2FeP2O7, which is filtered, washed with deionized water, and dried at 120° C. for 4 hours to obtain a powder. The powder is sintered at 500° C. under a nitrogen atmosphere for 4 h, cooled naturally to room temperature and then ground to control the crystallinity of Li2FeP2O7 to be 5%.
Preparation of lithium iron phosphate suspension: Except that 11.1 g of lithium carbonate, 34.7 g of ferrous carbonate, 34.4 g of ammonium dihydrogen phosphate, 37.7 g of oxalic acid dihydrate and 37.3 g of sucrose (in C12H22O11, the same below) are dissolved in 1500 ml of deionized water, and then stirred for 6 hours such that the mixture is fully reacted. Then, the reacted solution is heated to 120° C. and kept at this temperature for 6 hours to obtain a suspension of LiFePO4.
15.7 g of the obtained lithium iron pyrophosphate powder is added to the above lithium iron phosphate (LiFePO4) and sucrose suspension; in the preparation process, the sintering temperature is 600° C. and the sintering time is 4 h in the coating sintering step to control the crystallinity of LiFePO4 to be 8%, other conditions of Comparative example II-7 are the same as in Comparative example II-4, and amorphous lithium iron pyrophosphate, amorphous lithium iron phosphate, and the carbon-coated positive electrode active material are obtained.
Except that in the preparation process of lithium iron pyrophosphate (Li2FeP2O7), in Comparative examples II-8 to II-10, the drying temperature/drying time in the drying step is 80° C./3 h, 80° C./3 h and 80° C./3 h, respectively; in the preparation process of lithium iron pyrophosphate (Li2FeP2O7), in Comparative examples II-8 to II-10, the sintering temperature/sintering time in the sintering step is 400° C./3 h, 400° C./3 h and 350° C./2 h, respectively; in Comparative example II-11, in the preparation process of lithium iron phosphate (LiFePO4), the drying temperature/drying time in the drying step is 80° C./3 h; and in Comparative examples II-8 to II-11, the amount of Li2FeP2O7/LiFePO4 is 47.2 g/15.7 g, 15.7 g/47.2 g, 62.8 g/0 g, and 0 g/62.8 g, respectively, other conditions are the same as in Example II-1-7.
The preparation of the positive electrode plate, the negative electrode plate, the electrolyte solution, the separator and the battery of the above Examples and Comparative examples are all the same as in Example II-1-1.
[Preparation of Three-Layer Coated Positive Electrode Active Material and Battery]
Step 1: Preparation of a Positive Electrode Active Material
Step S1: Preparation of Fe, Co, V and S Co-Doped Manganese Oxalate
689.6 g of manganese carbonate, 455.27 g of ferrous carbonate, 4.65 g of cobalt sulfate and 4.87 g of vanadium dichloride are mixed thoroughly for 6 h in a mixer. The resulting mixture is then transferred into a reaction kettle, 5 L of deionized water and 1260.6 g of oxalic acid dihydrate are added, heated to 80° C., then stirred thoroughly for 6 h at a rotation speed of 500 rpm and mixed uniformly until the reaction is completed (no bubbles are generated), so as to obtain an Fe, Co, and V co-doped manganese oxalate suspension. Then, the suspension is filtered, dried at 120° C. and then sanded, so as to obtain manganese oxalate particles with a particle size of 100 nm.
Step S2: Preparation of Inner Core Li0.997Mn0.60Fe0.393V0.004Co0.003P0.997S0.003O4
1793.1 g of manganese oxalate prepared in (1), 368.3 g of lithium carbonate, 1146.6 g of ammonium dihydrogen phosphate and 4.9 g of dilute sulfuric acid are added to 20 L of deionized water, fully stirred, and mixed uniformly and reacted at 80° C. for 10 h to obtain a slurry. The slurry is transferred into a spray drying apparatus for spray-drying granulation, and dried at a temperature of at 250° C. to obtain a powder. In a protective atmosphere (90% of nitrogen and 10% of hydrogen), the powder is sintered in a roller kiln at 700° C. for 4 h to obtain the above inner core material.
Step S3: Preparation of the First Coating Layer Suspension
Preparation of a Li2FeP2O7 solution: 7.4 g of lithium carbonate, 11.6 g of ferrous carbonate, 23.0 g of ammonium dihydrogen phosphate and 12.6 g of oxalic acid dihydrate are dissolved in 500 mL of deionized water, the pH is controlled to be 5, then same is stirred and reacted at room temperature for 2 h to obtain a solution, and then the solution is heated to 80° C. and kept at this temperature for 4 h to obtain a first coating layer suspension.
Step S4: Coating of the First Coating Layer
1571.9 g of doped lithium manganese phosphate inner core material obtained in step S2 is added to the first coating layer suspension (the content of the coating material is 15.7 g) obtained in step S3, fully stirred and mixed for 6 h; after uniformly mixing, same is transferred in an oven at 120° C. and dried for 6 h, and then sintered at 650° C. for 6 h to obtain a pyrophosphate coated material.
Step S5: Preparation of the Second Coating Layer Suspension
3.7 g of lithium carbonate, 11.6 g of ferrous carbonate, 11.5 g of ammonium dihydrogen phosphate and 12.6 g of oxalic acid dihydrate are dissolved in 1500 mL of deionized water, then same is stirred and reacted for 6 h to obtain a solution, and then the solution is heated to 120° C. and kept at this temperature for 6 h to obtain a second coating layer suspension.
Step S6: Coating of the Second Coating Layer
1586.8 g of the pyrophosphate coated material obtained in step S4 is added to the second coating layer suspension (the content of the coating material is 47.1 g) obtained in step S5, fully stirred and mixed for 6 h; after uniformly mixing, same is transferred in an oven at 120° C. and dried for 6 h, and then sintered at 700° C. for 8 h to obtain a two-layer coated material.
Step S7: Preparation of Aqueous Solution of the Third Coating Layer
37.3 g of sucrose is dissolved in 500 g of deionized water, then stirred and fully dissolved to obtain an aqueous solution of sucrose.
Step S8: Coating of the Third Coating Layer
1633.9 g of the two-layer coated material obtained in step S6 is added to the sucrose solution obtained in step S7, stirred together and mixed for 6 h; after uniformly mixing, same is transferred in an oven at 150° C. and dried for 6 h, and then sintered at 700° C. for 10 h to obtain a third-layer coated material.
Step 2: Preparation of Positive Electrode Plate
The three-layer coated positive electrode active material prepared above, a conductive agent acetylene black and a binder polyvinylidene fluoride (PVDF) are added to N-methylpyrrolidone (NMP) in a weight ratio of 97.0:1.2:1.8, followed by stirring and uniformly mixing to obtain a positive electrode slurry. The positive electrode slurry is uniformly coated onto an aluminum foil in 0.280 g/1540.25 mm2, followed by drying, cold pressing, and slitting to obtain the positive electrode plate.
Step 3: Preparation of Negative Electrode Plate
Negative electrode active materials artificial graphite and hard carbon, a conductive agent acetylene black, a binder styrene butadiene rubber (SBR) and a thickening agent sodium carboxymethylcellulose (CMC) are dissolved in deionized water as a solvent in a weight ratio of 90:5:2:2:1, followed by stirring and uniformly mixing to prepare a negative electrode slurry. The negative electrode slurry is uniformly coated onto a negative electrode current collector copper foil in 0.117 g/1540.25 mm2, followed by drying, cold pressing, and slitting to obtain the negative electrode plate.
Step 4: Preparation of Electrolyte Solution
In an argon atmosphere glove box (H2O<0.1 ppm, and O2<0.1 ppm), the organic solvent ethylene carbonate (EC)/ethyl methyl carbonate (EMC) is mixed uniformly by a volume ratio of 3/7, and 12.5% (on the basis of the weight of the ethylene carbonate/ethyl methyl carbonate solvent) by weight of LiPF6 is dissolved in the above organic solvent and stirred uniformly to obtain the electrolyte solution.
Step 5: Preparation of Separator
A commercially available PP-PE copolymer microporous film having a thickness of 20 μm and an average pore size of 80 nm (Model 20, from Zhuogao Electronic Technology Co. Ltd.) is used.
Step 6: Preparation of Full Battery
The above obtained positive electrode plate, separator and negative electrode plate are stacked in sequence, such that the separator is located between the positive electrode plate and the negative electrode plate to function for isolation, and are then wound to obtain a bare cell. The bare cell is placed in an outer package, injected with the above electrolyte solution and packaged to obtain a full battery.
(Preparation of Button Battery)
The positive electrode active material prepared above, polyvinylidene fluoride (PVDF) and acetylene black in a weight ratio of 90:5:5 are added into N-methylpyrrolidone (NMP), and stirred in a drying room to make a slurry. An aluminum foil is coated with the above slurry, followed by drying and cold pressing, so as to obtain a positive electrode plate. The coating amount is 0.2 g/cm2, and the compacted density is 2.0 g/cm3.
A lithium plate is used as a negative electrode, a solution of 1 mol/L LiPF6 in ethylene carbonate (EC), diethyl carbonate (DEC) and dimethyl carbonate (DMC) in a volume ratio of 1:1:1 is used as an electrolyte solution, and the lithium plate and the electrolyte solution are assembled, together with the positive electrode plate prepared above, into a button battery in a button battery box.
The positive electrode active materials and batteries in Examples III-2 to III-53 and Comparative examples III-1 to III-17 are prepared in a manner similar to Example III-1, and the differences in the preparation of positive electrode active materials are shown in the Tables 1-6, wherein in Comparative examples III-1 to III-2, Comparative examples III-4 to III-10 and Comparative example III-12, the first layers are not coated, so there are no steps S3 and S4; and in comparative examples III-1 to III-11, the second layers are not coated, so there are no steps S5-S6.
Note: In all Examples and Comparative examples of the present application, if not indicated, the first coating layer material and/or the second coating layer material used are crystalline by default.
Examples III-30 to III-42 are carried out in a manner similar to that in Example III-1, and the differences are shown in Tables 7-8 below.
The sintering temperature and sintering time in steps S4, S6 and S8 are changed, and the rest are the same as in Example III-1, see Table 30 for details.
The reaction temperature and reaction time in the preparation of the inner core are changed, and the rest are the same as in Example III-1, see Table 31 for details.
Step S1: Preparation of Fe, Co, V and S Co-Doped Manganese Oxalate
689.6 g of manganese carbonate, 455.27 g of ferrous carbonate, 4.65 g of cobalt sulfate and 4.87 g of vanadium dichloride are mixed thoroughly for 6 h in a mixer. The resulting mixture is then transferred into a reaction kettle, 5 L of deionized water and 1260.6 g of oxalic acid dihydrate are added, heated to 80° C., then stirred thoroughly for 6 h at a rotation speed of 500 rpm and mixed uniformly until the reaction is completed (no bubbles are generated), so as to obtain an Fe, Co, and V co-doped manganese oxalate suspension. Then, the suspension is filtered, dried at 120° C. and then sanded, so as to obtain manganese oxalate particles with a particle size of 100 nm.
Step S2: Preparation of Inner Core Li0.997Mn0.60Fe0.393V0.004Co0.003P0.997S0.003O4
1793.1 g of manganese oxalate prepared in (1), 368.3 g of lithium carbonate, 1146.6 g of ammonium dihydrogen phosphate and 4.9 g of dilute sulfuric acid are added to 20 L of deionized water, fully stirred, and mixed uniformly and reacted at 80° C. for 10 h to obtain a slurry. The slurry is transferred into a spray drying apparatus for spray-drying granulation, and dried at a temperature of at 250° C. to obtain a powder. In a protective atmosphere (90% of nitrogen and 10% of hydrogen), the powder is sintered in a roller kiln at 700° C. for 4 h to obtain a inner core material. The element content of the inner core material is detected using inductively coupled plasma (ICP) emission spectrometry, and the chemical formula of the inner core is obtained as shown above.
Step S3: Preparation of the First Coating Layer Suspension
Preparation of Li2FeP2O7 solution: 7.4 g of lithium carbonate, 11.6 g of ferrous carbonate, 23.0 g of ammonium dihydrogen phosphate and 12.6 g of oxalic acid dihydrate are dissolved in 500 mL of deionized water, the pH is controlled to be 5, then same is stirred and reacted at room temperature for 2 h to obtain a solution, and then the solution is heated to 80° C. and kept at this temperature for 4 h to obtain a first coating layer suspension.
Step S4: Coating of the First Coating Layer
1571.9 g of doped lithium manganese phosphate inner core material obtained in step S2 is added to the first coating layer suspension (the content of the coating material is 15.7 g) obtained in step S3, fully stirred and mixed for 6 h; after uniformly mixing, same is transferred in an oven at 120° C. and dried for 6 h, and then sintered at 650° C. for 6 h to obtain a pyrophosphate coated material.
Step S5: Preparation of the Second Coating Layer Suspension
47.1 g of nanoscale Al2O3 (with a particle size of about 20 nm) is dissolved in 1500 mL of deionized water, and stirred for 2 h to obtain a second coating layer suspension.
Step S6: Coating of the Second Coating Layer
1586.8 g of the pyrophosphate coated material obtained in step S4 is added to the second coating layer suspension (the content of the coating material is 47.1 g) obtained in step S5, fully stirred and mixed for 6 h; after uniformly mixing, same is transferred in an oven at 120° C. and dried for 6 h, and then sintered at 700° C. for 8 h to obtain a two-layer coated material.
Step S7: Preparation of Aqueous Solution of the Third Coating Layer
37.3 g of sucrose is dissolved in 500 g of deionized water, then stirred and fully dissolved to obtain an aqueous solution of sucrose.
Step S8: Coating of the Third Coating Layer
1633.9 g of the two-layer coated material obtained in step S6 is added to the sucrose solution obtained in step S7, stirred together and mixed for 6 h; after uniformly mixing, same is transferred in an oven at 150° C. and dried for 6 h, and then sintered at 700° C. for 10 h to obtain a third-layer coated material.
Inner core: Li0.997Mn0.60Fe0.393V0.004Co0.003P0.997S0.003O4; the first coating layer contains 1% of crystalline Li2FeP2O7; the second coating layer contains 3% of crystalline Al2O3; and the third coating layer contains 1% of carbon, in which the molar ratio of SP2 to SP3 is 2.2.
Except that in step S8, the amount of sucrose is 111.9 g and sintering is carried out at 600° C. for 9 h, the rest are the same as in Example III-4-1.
Inner core, the first coating layer and the second coating layer are the same as in Example III-4-1; the third coating layer contains 3% of carbon, in which the molar ratio of SP2 to SP3 is 2.3.
Step S1: Preparation of Doped Manganese Oxalate
1.3 mol of MnSO4·H2O and 0.7 mol of FeSO4·H2O are mixed thoroughly for 6 hours in a mixer; the mixture is transferred into a reaction kettle, 10 L of deionized water and 2 mol of oxalic acid dihydrate are added thereto, heated to 80° C., and then stirred for 6 hours at a rotation speed of 600 rpm, the reaction is completed (no bubbles are generated), so as to obtain an Fe-doped manganese oxalate suspension; the suspension is filtered, and the resulting filter cake is dried at 120° C. and then ground to obtain Fe-doped manganese oxalate particles with a particle size Dv50 of about 100 nm.
Step S2: Preparation of inner core containing Li0.994Mo0.001Mn0.65Fe0.35P0.999Si0.001O3.999F0.001
1 mol of the Fe-doped manganese oxalate particles, 0.497 mol of lithium carbonate, 0.001 mol of Mo(SO4)3, an 85% aqueous phosphoric acid solution containing 0.999 mol of phosphoric acid, 0.001 mol of H4SiO4, 0.0005 mol of NH4HF2 and 0.005 mol of sucrose are added into 20 L of deionized water, and the mixture is transferred into a sander and thoroughly ground and stirred for 10 hours to obtain a slurry. The slurry is transferred into a spray drying apparatus for spray-drying granulation, where the drying temperature is set at 250° C. and the drying time is 4 h, so as to obtain particles; the particles are sintered at 700° C. for 10 hours in a protective atmosphere of nitrogen (90% v/v)+hydrogen (10% v/v) to obtain a inner core material. The element content of the inner core material is detected using inductively coupled plasma (ICP) emission spectrometry, and the chemical formula of the inner core is obtained as shown above.
Step S3: Preparation of the First Coating Layer Suspension
Preparation of Li2FeP2O7 solution: 7.4 g of lithium carbonate, 11.6 g of ferrous carbonate, 23.0 g of ammonium dihydrogen phosphate and 12.6 g of oxalic acid dihydrate are dissolved in 500 mL of deionized water, the pH is controlled to be 5, then same is stirred and reacted at room temperature for 2 h to obtain a solution, and then the solution is heated to 80° C. and kept at this temperature for 4 h to obtain a first coating layer suspension.
Step S4: Coating of the First Coating Layer
157.2 g of doped lithium manganese phosphate inner core material obtained in step S2 is added to the first coating layer suspension (the content of the coating material is 1.572 g) obtained in step S3, fully stirred and mixed for 6 h; after uniformly mixing, same is transferred in an oven at 120° C. and dried for 6 h, and then sintered at 650° C. for 6 h to obtain a pyrophosphate coated material.
Step S5: Preparation of the Second Coating Layer Suspension
4.71 g of nano-Al2O3 (with a particle size of about 20 nm) is dissolved in 1500 mL of deionized water, and stirred for 2 h to obtain a second coating layer suspension.
Step S6: Coating of the Second Coating Layer
158.772 g of the pyrophosphate coated material obtained in step S4 is added to the second coating layer suspension (the content of the coating material is 4.71 g) obtained in step S5, fully stirred and mixed for 6 h; after uniformly mixing, same is transferred in an oven at 120° C. and dried for 6 h, and then sintered at 700° C. for 8 h to obtain a two-layer coated material.
Step S7: Preparation of Aqueous Solution of the Third Coating Layer
37.3 g of sucrose is dissolved in 500 g of deionized water, then stirred and fully dissolved to obtain an aqueous solution of sucrose.
Step S8: Coating of the Third Coating Layer
1633.9 g of the two-layer coated material obtained in step S6 is added to the sucrose solution obtained in step S7, stirred together and mixed for 6 h; after uniformly mixing, same is transferred in an oven at 150° C. and dried for 6 h, and then sintered at 700° C. for 10 h to obtain a third-layer coated material.
Inner core: Li0.994Mo0.001Mn0.65Fe0.35P0.999Si0.001O3.999F0.001; the first coating layer contains 1% of crystalline Li2FeP2O7; the second coating layer contains 3% of crystalline Al2O3; and the third coating layer contains 1% of carbon, in which the molar ratio of SP2 to SP3 is 2.2.
Except for the following differences, the rest are the same as in Example III-4-3:
Step S3: 53.3 g of aluminum chloride, 34.5 g of ammonium dihydrogen phosphate and 18.9 g of oxalic acid dihydrate are dissolved in 500 mL of deionized water, the pH is controlled to be 4, then same is stirred and reacted at room temperature for 2 h to obtain a solution, and then the solution is heated to 80° C. and kept at this temperature for 4 h to obtain a first coating layer suspension.
Step S4: Except that sintering is carried out at 680° C. for 8 h, the rest are the same as step S4 of Example III-4-3.
Inner core, the second coating layer and the third coating layer are the same as in Example III-4-3; the first coating layer contains 1% of crystalline Al4(P2O7)3.
[Mixed Use of Two Positive Electrode Active Materials and Preparation of Battery]
The inner core material of Example I-1 is mixed with lithium nickel cobalt manganate LiNi0.5Co0.2Mn0.3O2 in a mass ratio of 1:1 as the positive electrode active material.
Preparation of positive electrode plate: The slurry of positive electrode active material is evenly coated on both sides of the aluminum foil of the current collector in a coating amount of 0.019 g/cm2, vacuum-dried at a high temperature of 100-120° C. for 14 h, and compacted by a roller press to obtain the positive electrode plate P4.
Preparation of negative electrode plate: A negative electrode active material artificial graphite, a conductive agent superconducting carbon black (Super-P), a binder styrene butadiene rubber (SBR) and a thickening agent sodium carboxymethylcellulose (CMC-Na) are dissolved in deionized water in a mass ratio of 95%:1.5%:1.8%:1.7, followed by fully stirring and uniformly mixing to obtain a negative electrode slurry with a viscosity of 3000 mPa s and a solid content of 52%; the negative electrode slurry is coated on a negative electrode current collector copper foil with a thickness of 6 μm, and then baked at 100° C. for 4 hours for drying, followed by roll pressing to obtain the negative electrode plate with a compacted density of 1.75 g/cm3.
Separator: A Polypropylene Film is Used.
Preparation of electrolyte solution: ethylene carbonate, dimethyl carbonate and 1,2-propylene glycol carbonate are mixed in a volume ratio of 1:1:1, and then LiPF6 is evenly dissolved in the above solution to obtain an electrolyte solution. In the electrolyte solution, the concentration of LiPF6 is 1 mol/L.
Preparation of full battery: the above positive electrode plate is used, and a bare cell is formed by a winding method according to the sequence of a negative electrode plate, a separator, and a positive electrode plate, and aluminum tabs and copper tabs are respectively punched out to obtain the bare cell; Copper and copper tabs, and aluminum and aluminum tabs of two bare cells are welded together to the top cover of the battery via an adapter. After the bare cells are wrapped and insulated, the bare cells are put into an aluminum shell, and the top cover and the aluminum shell are welded to form a dry cell. The day cell is baked to remove water and then injected with an electrolyte solution, and the battery is formed and aged to obtain a whole battery accordingly.
Preparation of button battery: The above positive electrode plate, negative electrode and electrolyte solution are assembled together into a button battery in a button battery box.
The inner core material of Example I-1 is mixed with nickel cobalt lithium aluminate LiNi0.33Co0.33Al0.34O2 in a mass ratio of 1:1 as the positive electrode active material.
The rest are the same as in Example IV-1.
Test of Battery
1. Testing Method of Lattice Change Rate:
In a constant-temperature environment at 25° C., a positive electrode active material sample is placed in XRD (model: Bruker D8 Discover) and tested at 1°/min, and the test data are organized and analyzed; and with reference to the standard PDF card, lattice constants a0, b0, c0 and v0 at this moment are calculated (a0, b0 and c0 represent the lengths of a unit cell on all sides, and v0 represents the volume of the unit cell, which may be obtained directly from XRD refinement results).
By using the method for preparing a button battery in the above examples, the positive electrode active material sample is made into a button battery, and the button battery is charged at a small rate of 0.05 C until the current is reduced to 0.01 C. Then a positive electrode plate in the button battery is taken out and soaked in dimethyl carbonate (DMC) for 8 h. Then the positive electrode plate is dried, powder is scraped off, and particles with a particle size of less than 500 nm are screened out. Sampling is performed, and a cell volume v1 is calculated in the same way as that for testing the fresh sample as described above. (v0−v1)/v0×100% is shown in a table as a lattice change rate (cell volume change rate) of the sample before and after complete lithium intercalation and de-intercalation.
2. Li/Mn Antisite Defect Concentration:
The XRD results determined in the “Method for measuring lattice change rate” are compared with the PDF (Powder Diffraction File) card of a standard crystal, so as to obtain a Li/Mn antisite defect concentration. Specifically, the XRD results determined in the “Method for measuring lattice change rate” are imported into a general structure analysis system (GSAS) software, and refinement results are obtained automatically, including the occupancies of different atoms; and a Li/Mn antisite defect concentration is obtained by reading the refinement results.
3. Compacted Density:
5 g of positive electrode active material powder prepared above is put into a compaction dedicated mold (U.S. CARVER mold, model: 13 mm), and then the mold is placed on a compacted density instrument. A pressure of 3 T is applied, the thickness of the powder under pressure (thickness after pressure relief) is read on the device, and the compacted density is calculated with ρ=m/v, where the area value used is the standard small picture area of 1540.25 mm2.
4. 3 C Charge Constant Current Rate:
Under a constant temperature environment of 25° C., the fresh full batteries prepared in each of the above Examples and Comparative examples are left to stand for 5 m, and discharged at ⅓C to 2.5 V. The full battery is allowed to stand for 5 min, charged at ⅓C to 4.3 V, and then charged at a constant voltage of 4.3 V until the current is less than or equal to 0.05 mA. The full battery is allowed to stand for 5 min, and the charge capacity at this moment is recorded as CO. The full battery is discharged at ⅓C to 2.5 V, allowed to stand for 5 min, then charged at 3 C to 4.3 V, and allowed to stand for 5 min, and the charge capacity at this moment is recorded as C1. The 3 C charge constant current rate is C1/C0×100%.
A higher 3 C charge constant current rate indicates a better rate performance of the second battery.
5. Dissolution Test of Transition Metal Mn (and Fe Doping Mn Position):
After cycling at 45° C. until the capacity is fading to 80%, the full batteries prepared in each of the above Examples and Comparative examples are discharged to a cut-off voltage of 2.0 V at a rate of 0.1 C. Then the battery is disassembled, a negative electrode plate is taken out, a round piece of 30 unit areas (1540.25 mm2) is randomly taken from the negative electrode plate, and inductively coupled plasma (ICP) emission spectroscopy is performed with Agilent ICP-OES730. The amounts of Fe (if the Mn position of the positive electrode active material is doped with Fe) and Mn therein are calculated according to the ICP results, and then the dissolution of Mn (and Fe doping the Mn position) after cycling is calculated. The testing standard is in accordance with EPA-6010D-2014.
6. Surface Oxygen Valence State:
5 g of a positive electrode active material prepared above is made into a button battery according to the method for preparing a button battery in the above examples. The button battery is charged at a small rate of 0.05 C until the current is reduced to 0.01 C. Then a positive electrode plate in the button battery is taken out and soaked in DMC for 8 h. Then the positive electrode plate is dried, powder is scraped off, and particles with a particle size of less than 500 nm are screened out. The obtained particles are measured with electron energy loss spectroscopy (EELS, instrument model used: Tabs F200S), so as to obtain an energy loss near-edge structure (ELNES) which reflects the density of states and energy level distribution of an element. According to the density of states and energy level distribution, the number of occupied electrons is calculated by integrating the data of valence-band density of states, and then a valence state of surface oxygen after the charging is extrapolated.
7. Measurement of Manganese and Phosphorus Elements in Positive Electrode Active Material:
5 g of the positive electrode active material prepared above is dissolved in 100 ml of inverse aqua regia (concentrated hydrochloric acid:concentrated nitric acid=1:3) (concentrated hydrochloric acid concentration is about 37%, concentrated nitric acid concentration is about 65%). The content of each element in the solution is measured by ICP, and then the content of manganese or phosphorus element is measured and converted (100% x the amount of manganese or phosphorus element/the amount of the positive electrode active material) to obtain its weight ratio.
8. Method for Measuring Initial Gram Capacity of Button Battery:
At 2.5 to 4.3 V, the button batteries prepared in each of the above Examples III- and Comparative examples III- are charged at 0.1 C to 4.3 V, then charged at a constant voltage of 4.3 V until the current is less than or equal to 0.05 mA, allowed to stand for 5 min, and then discharged at 0.1 C to 2.0 V; and the discharge capacity at this moment is the initial gram capacity, which is recorded as DO.
9. Cell Expansion Test of Full Battery Stored at 60° C. for 30 Days:
The full batteries prepared in each of the above Examples III- and Comparative examples III- are stored at 60° C. with 100% state of charge (SOC). Before and after and during the storage, the open-circuit voltage (OCV) and AC internal impedance (IMP) of a cell are measured for monitoring the SOC, and the volume of the cell is measured. Herein, the full battery is taken out after every 48 h of storage, and allowed to stand for 1 h, then the OCV and internal IMP are measured, and the cell volume is measured with the displacement method after the full battery is cooled to room temperature. The displacement method means that the gravity F1 of the cell is measured separately using a balance of which the on-board data is subjected to automatic unit conversion, then the cell is completely placed in deionized water (with a density known as 1 g/cm3), the gravity F2 of the cell at this moment is measured, the buoyancy Fbuoyancy on the cell is F1−F2, and then the cell volume V=(F1−F2)/(ρ×g) is calculated according to the Archimedes principle Fbuoyancy=ρ×g×Vdisplacement.
From the test results of OCV and IMP, the battery of all the example always maintains a SOC of no less than 99% in the experimental process till the end of the storage.
After 30 days of storage, the cell volume is measured, and a percentage increase in cell volume after the storage relative to the cell volume before the storage is calculated.
In addition, residual capacity of the cell is measured. At 2.5 to 4.3 V, the full battery is charged at 1 C to 4.3 V, and then charged at a constant voltage of 4.3 V until the current is less than or equal to 0.05 mA. The full battery is allowed to stand for 5 min, and the charge capacity at this moment is recorded as the residual capacity of the cell.
10. Test of Cycling Performance of Full Battery at 45° C.:
In a constant-temperature environment at 45° C., at 2.5 to 4.3 V, a full battery is charged at 1 C to 4.3 V, and then charged at a constant voltage of 4.3 V until the current is ≤0.05 mA, allowed to stand for 5 min, then discharged at 1 C to 2.5 V, and the capacity is recorded as Dr, (n=0, 1, 2, . . . ). The above-mentioned process is repeated until the capacity is fading to 80%, and the number of repetitions at this moment is recorded, which is the number of cycles corresponding to the 80% capacity retention rate at 45° C.
11. Test of Interplanar Distance and Angle:
1 g of each positive electrode active material powder prepared above is placed in a 50 mL test tube, and 10 mL of alcohol with a mass fraction of 75% is injected into the test tube, then fully stirred and dispersed for 30 min, and then a clean disposable plastic straw is used to take an appropriate amount of the solution, which is dripped on a 300-mesh copper mesh, at this moment, part of the powder will remain on the copper mesh. The copper mesh and the sample are transferred to TEM (Talos F200s G2) sample chamber for testing, the original picture of the TEM test is obtained and the original picture format (xx.dm3) is saved.
The original picture obtained from the above TEM test is opened in Digital Micrograph software, and Fourier transform (automatically completed by the software after the clicking operation) is performed to obtain a diffraction pattern, and the distance from the diffraction spot to the center position in the diffraction pattern is measured to obtain the interplanar distance, and the angle is calculated according to the Bragg equation.
By comparing the obtained interplanar distance and corresponding angle data with their standard values, different materials in the coating layer can be identified.
12. Test of the Coating Layer Thickness:
The test of the coating layer thickness mainly comprises cutting a thin slice with a thickness of about 100 nm from the middle of the single particle of the positive electrode active material prepared above by FIB, and then performing a TEM test on the thin slice to obtain the original picture of the TEM test, and saving the original picture format (xx.dm3).
The original picture obtained from the above TEM test is opened in Digital Micrograph software, the coating layer is be identified with the lattice spacing and angle information, and the thickness of the coating layer is measured.
The thickness is measured at three locations on the selected particle and the average value is taken.
13. Determination of the Molar Ratio of SP2 Form to SP3 Form of the Carbon in the Third Coating Layer
This test is performed by Raman spectroscopy. By splitting the energy spectrum of the Raman test, Id/Ig is obtained, where Id is the peak intensity of SP3-form carbon, and Ig is the peak intensity of SP2-form carbon, thereby determining the molar ratio of the two.
14. Average Discharge Voltage (V) Test of Button Battery:
The button battery prepared above is allowed to stand for 5 min at a constant temperature of 25° C., discharged at 0.1 C to 2.5 V, allowed to stand for 5 min, charged at 0.1 C to 4.3 V, and then charged at a constant voltage of 4.3 V until the current is less than or equal to 0.05 mA, and allowed to stand for 5 min; then discharged at 0.1 C to 2.5 V, the discharge capacity at this moment is the initial gram capacity, which is recorded as D0; the discharge energy is the initial energy, which is recorded as E0; so the average discharge voltage V of the button battery is E0/D0.
15. Test of the Crystallinity of Pyrophosphate and Phosphate by X-Ray Diffraction:
5 g of the positive electrode active material powder prepared above is taken and measured for total scattering intensity by X-rays, which is the sum of the scattering intensity of the entire space material, and is only related to the intensity of the primary ray, the chemical structure, and the total number of electrons participating in the diffraction, that is, the mass, but has nothing to do with the order of the sample; then the crystalline scattering and non-crystalline scattering are separated from the diffraction pattern, and the degree of crystallinity is the ratio of the scattering of the crystalline part to the total intensity of the scattering.
16. A Secondary Battery is Tested as Follows:
The performance test results of all Examples and Comparative examples are shown in the Table below.
[Determination Results of Positive Electrode Active Material Including Inner Core and Battery]
The compositions of the positive electrode active materials of Examples I-1 to I-11 and Comparative examples I-1 to I-8 are shown in Table 9. The performance data of the positive electrode active materials or button batteries or full batteries of Examples I-1 to I-11 and
Comparative examples I-1 to I-8 obtained according to the above performance testing methods are shown in Table 10. The compositions of the positive electrode active materials of Examples I-12 to I-27 are shown in Table 11. The performance data of positive electrode active materials or button batteries or full batteries of Examples I-12 to I-27 obtained according to the above performance testing methods are shown in Table 12.
A positive electrode active material, a button battery and a full battery are prepared in the same way as in Example I-1, except that the stirring rotation speed and temperature in the preparation of doped manganese oxalate, the time of grinding and stirring in a sander, and the sintering temperature and sintering time are changed, specifically as shown in Table 13 below.
And, the performance data of the positive electrode active materials or button batteries or full batteries of Examples I-28 to I-41 obtained according to the above performance testing methods are shown in Table 14.
A positive electrode active material, a button battery and a full battery are prepared in the same way as in Example I-1, except that the lithium source, the manganese source, the phosphorus source and the sources of doping elements A, B, C and D are changed, specifically as shown in Table 15 below. The prepared positive electrode active materials all had the same composition as in Example I-1, namely, Li0.994Mo0.001Mn0.65Fe0.35P0.999Si0.001O3.999F0.001.
And, the performance data of the positive electrode active materials or button batteries or full batteries of Examples I-42 to I-54 obtained according to the above performance testing methods are shown in Table 16.
It can be seen from Tables 9-18 above that, the positive electrode active materials of the examples of the present application all achieve a better effect than the comparative examples in one or even all terms of cycling performance, high-temperature stability, gram capacity and compacted density.
Through comparison between Examples I-18 to I-20 and I-23 to I-25, it can be seen that in the case of the same rest elements, when (1-y):y is in a range of 1 to 4, the energy density and cycling performance of the secondary battery can be further improved.
It can be seen from the above table that the specific capacity and rate performance of the positive electrode active material are also improved correspondingly when the doped carbon layer is compared with the undoped carbon layer.
[Determination Results of Two-Layer Coated Positive Electrode Active Material and Battery]
From the combination of Examples II-1-1 to II-1-41 and Comparative examples II-1 to II-4, it can be seen that the existence of the first coating layer is beneficial to reduce the Li/Mn antisite defect concentration of the obtained material and the dissolution of Fe and Mn after cycling, increase the gram capacity of button battery of the battery, and improve the safety performance and cycling performance of the battery. When other elements are doped on the Mn site and phosphorus site respectively, the lattice change rate, antisite defect concentration and Fe and Mn dissolution of the obtained material can be significantly reduced, the gram capacity of the battery can be increased, and the safety performance and cycling performance of the battery can be improved.
From the combination of Examples II-1-1 to II-1-6, it can be seen that with the increase of the amount of the first coating layer from 3.2% to 6.4%, the Li/Mn antisite defect concentration of the obtained material gradually decreases, and the Fe and Mn dissolution gradually decreases after cycling, and the safety performance and cycling performance at 45° C. of the corresponding battery are also improved, but the gram capacity of the button battery decreases slightly. Optionally, when the total amount of the first coating layer is 4-5.6% by weight, the overall performance of the corresponding battery is the best.
From the combination of Example II-1-3 and Examples II-1-7 to II-1-10, it can be seen that with the increase of the amount of the second coating layer from 1% to 6%, the Li/Mn antisite defect concentration of the obtained material gradually decreases, and the Fe and Mn dissolution gradually decreases after cycling, and the safety performance and cycling performance at 45° C. of the corresponding battery are also improved, but the gram capacity of the button battery decreases slightly. Optionally, when the total amount of the second coating layer is 3-5% by weight, the overall performance of the corresponding battery is the best.
From the combination of Examples II-1-11 to II-1-15 and Comparative examples II-5 to II-6, it can be seen that when Li2FeP2O7 and LiFePO4 exist simultaneously in the first coating layer, especially the weight ratio of Li2FeP2O7 and LiFePO4 is 1:3 to 3:1, and especially 1:3 to 1:1, the improvement of battery performance is more obvious.
1refers to the crystallinity of Li2FeP2O7 and LiFePO4 are 30%, 50%, 70%, and 100%, respectively.
It can be seen from Table 21 that as the crystallinity of pyrophosphate and phosphate in the first coating layer gradually increases, the lattice change rate of the corresponding material, the Li/Mn antisite defect concentration, and the dissolution of Fe and Mn gradually decrease, the button battery capacity of the battery is gradually increased, and the safety performance and cycling performance are also gradually improved.
It can be seen from Table 22 that by adjusting the reaction temperature and reaction time in the reaction kettle during the preparation of manganese oxalate particles, various performances of the positive electrode active material of the present application can be further improved. For example, when the reaction temperature gradually increases from 60° C. to 130° C., the lattice change rate and Li/Mn antisite defect concentration first decreases and then increases, and the corresponding metal dissolution and safety performance after cycling also show similar rules, while the button battery capacity and cycling performance first increase and then decrease with the increase of temperature. Keeping the reaction temperature constant and adjusting the reaction time can also show a similar rule.
It can be seen from Table 23 that when preparing lithium iron pyrophosphate by the method of the present application, by adjusting the drying temperature/time and sintering temperature/time during the preparation process, the performance of the obtained material can be improved, thereby improving the battery performance. From Comparative examples II-8 to II-11, it can be seen that when the drying temperature in the preparation process of lithium iron pyrophosphate is lower than 100° C. or the temperature in the sintering step is lower than 400° C., Li2FeP2O7, which is expected to be prepared in the present application, will not be obtained, thereby failing to improve the material properties as well as the performance of the battery comprising the resulting material.
[Determination Results of Three-Layer Coated Positive Electrode Active Material and Battery]
It can be seen from Table 26 that, compared with Comparative examples, these Examples achieve a smaller lattice change rate, a smaller Li/Mn antisite defect concentration, a larger compacted density, and a surface oxygen valence state more closer to −2 valence, less Mn and Fe dissolution after cycling, and better battery performance, such as better high-temperature storage performance and high-temperature cycling performance.
It can be seen from Table 27 that by doping the manganese and phosphorus sites of lithium manganese iron phosphate (containing 35% of manganese and about 20% of phosphorus) and three-layer coating, the manganese element content in the positive electrode active material and the weight content ratio of manganese element to phosphorus element is obviously reduced; in addition, comparing Examples III-1 to III-14 with Comparative examples III-3, III-4 and III-12, combined with Table 26, it can be known that the decrease of manganese and phosphorus elements in the positive electrode active material will lead to the decrease of manganese and iron dissolution and the improvement of the battery performance of the secondary battery prepared therefrom.
It can be seen from Table 28 that the use of the first coating layer and the second coating layer containing other elements within the scope of the present application can also obtain a positive electrode active material with good performance and achieve good battery performance results.
It can be seen from Table 29 that the interplanar distance and angle between the first coating layer and the second coating layer in the present application are both within the scope of the present application.
III. Investigation of the Influence of Coating Layer Sintering Method on the Performances of Positive Electrode Active Material and Secondary Battery
The batteries of the Examples and Comparative examples in the Table below are prepared similarly to Example III-1, except that the method parameters in the Table below are used. The results are shown in Table 13 below.
It can be seen from the above that when the sintering temperature range in step S4 is 650-800° C. and the sintering time is 2-6 h, the sintering temperature in step S6 is 500-700° C. and the sintering time is 6-10 h, and the sintering temperature in step S8 is 700-800° C. and the sintering time is 6-10 h, smaller lattice change rate, smaller Li/Mn antisite defect concentration, less dissolution of manganese and iron elements, better 3 C charge constant current rate, larger battery capacity, better battery cycling performance, and better high temperature storage stability can be achieved.
In addition, compared with Example III-2-16 (the sintering temperature in step S4 is 750° C. and the sintering time is 4.5 h), Example III-2-1 (the sintering temperature in step S4 is 750° C. and the sintering time is 4 h) achieves better positive electrode active material performance and battery performance, which indicates that when the sintering temperature of step S4 is 750° C. or greater than 750° C., it is needed to control the sintering time to less than 4.5 h.
IV. Investigation of the Influence of Reaction Temperature and Reaction Time in Inner Core Preparation on the Performances of Positive Electrode Active Material and Battery
The positive electrode active materials and batteries of Examples III-3-1 to III-3-20 in the Table below are prepared similarly to Example III-1, and for the differences in the preparation of positive electrode active materials, please refer to the method parameters in the Table below. The results are also shown in the Table below.
It can be seen from Table 31 that when the reaction temperature range in step S1 is 60-120° C. and the reaction time is 2-9 h; and the reaction temperature range in step S2 is 40-120° C. and the reaction time is 1-10 h, the powder properties of the positive electrode active material (lattice change rate, Li/Mn antisite defect concentration, surface oxygen valence state, compacted density) and the performances of the prepared battery (electric capacity, high-temperature cycling performance, high-temperature storage performance) are all excellent.
[Test Results of Battery Using a Mixture of Two Positive Electrode Active Materials]
The secondary battery using two positive electrode active materials has higher energy density, higher cell rate performance, better kinetic performance and low temperature performance, longer cycle life, and higher safety.
It should be noted that the present application is not limited to the above embodiments. The above embodiments are exemplary only, and any embodiment that has substantially same constitutions as the technical ideas and has the same effects within the scope of the technical solution of the present application falls within the technical scope of the present application. In addition, without departing from the gist of the present application, various modifications that can be conceived by those skilled in the art to the embodiments, and other modes constructed by combining some of the constituent elements of the embodiments also fall within the scope of the present application.
| Number | Date | Country | Kind |
|---|---|---|---|
| PCT/CN2021/125898 | Oct 2021 | WO | international |
| PCT/CN2021/130350 | Nov 2021 | WO | international |
| PCT/CN2021/140462 | Dec 2021 | WO | international |
This application is a continuation of International Application No. PCT/CN2022/126778, filed on Oct. 21, 2022, which claims priority to International Application No. PCT/CN2021/125898, filed on Oct. 22, 2021, International Application No. PCT/CN2021/130350, filed on Nov. 12, 2021, and International Application No. PCT/CN2021/140462, filed on Dec. 22, 2021, the entire contents of all of which are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/CN2022/126778 | Oct 2022 | US |
| Child | 18351925 | US |
