Patent Application
20230352667
The present application relates to the technical field of secondary batteries, and in particular to a positive electrode plate, a secondary battery, a battery module, a battery pack and a power consuming device.
In recent years, with the increasing application range of secondary batteries, secondary batteries are widely used in energy storage power systems such as hydroelectric, thermal, wind and solar power stations, as well as electric tools, electric bicycles, electric motorcycles, electric vehicles, military equipment, aerospace and other fields. Due to the great development of secondary batteries, higher requirements have also been placed on the secondary batteries in terms of energy density, cycling performance, safety performance, etc. The existing lithium iron manganese phosphate makes the secondary battery have poor dynamic performance and cell rate performance, which can not meet the requirements of the power battery. The existing secondary battery made of lithium iron phosphate as positive electrode active material has excellent cycle stability and safety. However, the existence of one-dimensional lithium ion channels therein and the existence of two phases of LiFePO4 and FePO4 during the charge and discharge process make the internal phase change resistance of the material increase during charge and discharge process, resulting in poor dynamic performance and cell rate performance, short low-temperature cycle life and low low-temperature capacity retention rate.
The present application is made in view of the above-mentioned problems, and the object thereof is to provide a positive electrode plate, a secondary battery, a battery module, a battery pack, and a power consuming device, so as to solve the problems of low energy density, poor dynamic performance and low rate performance, short low-temperature cycle life and low low-temperature cycle capacity retention rate of the secondary battery made of the existing positive electrode active materials.
In order to achieve the above object, a first aspect of the present application provides a positive electrode plate, comprising 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 has a single-layer structure or a multi-layer structure; when the positive electrode film layer has a single-layer structure, at least one of the positive electrode film layers contains both a first positive electrode active material with a chemical formula of LiaAxMn1-yRyP1-zCzO4-nDn and a second positive electrode active material; and/or when the positive electrode film layer has a multi-layer structure, at least one of the positive electrode film layers contains both a first positive electrode active material with a chemical formula of LiaAxMn1-yRyP1-zCzO4-nDn and a second positive electrode active material; wherein A includes one or more elements selected from Zn, Al, Na, K, Mg, Nb, Mo and W; R includes one or more elements selected from Ti, V, Zr, Fe, Ni, Mg, Co, Ga, Sn, Sb, Nb and Ge; C includes one or more elements selected from B, S, Si and N; D includes one or more elements selected from S, F, Cl and Br; a is selected from the range of 0.9 to 1.1, x is selected from the range of 0.001 to 0.1, y is selected from the range of 0.001 to 0.5, z is selected from the range of 0.001 to 0.1, and n is selected from range of 0.001 to 0.1; the second positive electrode active material is selected from one or more of LiFePO4, carbon-coated LiFePO4, LiFebMcPO4 and carbon-coated LiFebMcPO4, wherein M independently includes one or more elements selected from Ti, Zn, Co, Mn, La, V, Mg, Al, Nb, W, Zr, Nb, Sm, Cr, Cu and B, b is independently selected from the range of 0.99 to 0.999 and b+c=1.
Thus, the applicant unexpectedly found that: by doping specific elements at the positions of Li, Mn, P and O of the compound LiMnPO4 in a specific amount at the same time to obtain a first positive electrode active material, the rate performance can be significantly improved, and meanwhile the dissolution of Mn and the doping elements at Mn position can be significantly reduced, such that the cycling performance and/or high-temperature stability can be significantly improved, and the gram capacity and compacted density of the material can also be improved, and the interfacial side reactions can be reduced.
In the present application, by the combination use of the first positive electrode active material and the second positive electrode active material, the advantages of the two materials are complementary, which improves the energy density of the secondary battery, and meanwhile allows the secondary battery to have excellent dynamic performance, rate performance, low-temperature cycle life and low-temperature cycle capacity retention rate.
A second aspect of the present application further provides a positive electrode plate, comprising a positive electrode current collector and a positive electrode film layer provided on at least one surface of the positive electrode current collector, wherein at least one of the positive electrode film layers has a multi-layer structure, and any one of the positive electrode film layers having a multi-layer structure respectively contains a first positive electrode active material with a chemical formula of LiaAxMn1-yRyP1-zCzO4-nDn and a second positive electrode active material in different layers; wherein A includes one or more elements selected from Zn, Al, Na, K, Mg, Nb, Mo and W; R includes one or more elements selected from Ti, V, Zr, Fe, Ni, Mg, Co, Ga, Sn, Sb, Nb and Ge; C includes one or more elements selected from B, S, Si and N; D includes one or more elements selected from S, F, Cl and Br; a is selected from the range of 0.9 to 1.1, x is selected from the range of 0.001 to 0.1, y is selected from the range of 0.001 to 0.5, z is selected from the range of 0.001 to 0.1, and n is selected from range of 0.001 to 0.1; the second positive electrode active material is selected from one or more of LiFePO4, carbon-coated LiFePO4, LiFebMcPO4 and carbon-coated LiFebMcPO4, wherein M independently includes one or more elements selected from Ti, Zn, Co, Mn, La, V, Mg, Al, Nb, W, Zr, Nb, Sm, Cr, Cu and B, b is independently selected from the range of 0.99 to 0.999 and b+c=1; optionally, any one of the positive electrode film layers having a multi-layer structure respectively contains the first positive electrode active material and the second positive electrode active material in adjacent layers.
Thus, the first positive electrode active material has significantly improved rate performance and meanwhile significantly reduces the dissolution of Mn and the doping elements at Mn position, such that the cycling performance and/or high-temperature stability can be significantly improved, and the gram capacity and compacted density of the material can also be improved, and the interfacial side reactions can be reduced.
In the present application, by the combination use of the first positive electrode active material and the second positive electrode active material, the advantages of the two materials are complementary, which improves the energy density of the secondary battery, and meanwhile allows the secondary battery to have excellent rate performance, dynamic performance, low-temperature cycle life and low-temperature cycle capacity retention rate.
A third aspect of the present application provides a positive electrode plate, comprising a positive electrode current collector and a positive electrode film layer A and a positive electrode film layer B respectively provided on both surfaces of the positive electrode current collector; wherein the positive electrode film layer A and the positive electrode film layer B independently have a single-layer structure or a multi-layer structure; at least one of the positive electrode film layers A contains a first positive electrode active material with a chemical formula of LiaAxMn1-yRyP1-zCzO4-nDn, and at least one of the positive electrode film layers B contains a second positive electrode active material; wherein A includes one or more elements selected from Zn, Al, Na, K, Mg, Nb, Mo and W; R includes one or more elements selected from Ti, V, Zr, Fe, Ni, Mg, Co, Ga, Sn, Sb, Nb and Ge; C includes one or more elements selected from B, S, Si and N; D includes one or more elements selected from S, F, Cl and Br; a is selected from the range of 0.9 to 1.1, x is selected from the range of 0.001 to 0.1, y is selected from the range of 0.001 to 0.5, z is selected from the range of 0.001 to 0.1, and n is selected from range of 0.001 to 0.1; the second positive electrode active material is selected from one or more of LiFePO4, carbon-coated LiFePO4, LiFebMcPO4 and carbon-coated LiFebMcPO4, wherein M independently includes one or more elements selected from Ti, Zn, Co, Mn, La, V, Mg, Al, Nb, W, Zr, Nb, Sm, Cr, Cu and B, b is independently selected from the range of 0.99 to 0.999 and b+c=1.
Thus, the first positive electrode active material has significantly improved rate performance and meanwhile significantly reduces the dissolution of Mn and the doping elements at Mn position, such that the cycling performance and/or high-temperature stability can be significantly improved, and the gram capacity and compacted density of the material can also be improved, and the interfacial side reactions can be reduced.
In the present application, by the combination use of the first positive electrode active material and the second positive electrode active material, the advantages of the two materials are complementary, which improves the energy density of the secondary battery, and meanwhile allows the secondary battery to have excellent rate performance, dynamic performance, low-temperature cycle life and low-temperature cycle capacity retention rate.
Unless otherwise specified, in the chemical formula of LiaAxMn1-yRyP1-zCzO4-n. Dn, when A is two or more elements, the above-mentioned limitation on the numerical range of x is not only a limitation on the stoichiometric number of each element as A, but also a limitation on the sum of the stoichiometric numbers of each element as A. For example, when A is two or more elements A1, A2 . . . An, the respective stoichiometric numbers x1, x2 . . . xn of A1, A2 . . . An 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, for the case where R, C and D is two or more elements, the limitations on the numerical ranges of the stoichiometric numbers of R, C and D in the present application also have the above meanings.
Unless otherwise specified, in the chemical formula of LiFebMcPO4, when M is two or more elements, the above-mentioned limitation on the numerical range of c is not only a limitation on the stoichiometric number of each element as M, but also a limitation on the sum of the stoichiometric numbers of each element as M. For example, when M is two or more elements M1, M2 . . . Mn, the respective stoichiometric numbers c1, c2 . . . cn of M1, M2 . . . Mn fall within the numerical range c defined in the present application, and the sum of c1, c2 . . . cn also falls within this numerical range.
In any embodiment of the first aspect to the third aspect, in the second positive electrode active material, the mass of carbon accounts for 0.1%-4% of the mass of carbon-coated LiFePO4; and/or the mass of carbon accounts for 0.1%-4% of the mass of the carbon-coated LiFebMcPO4. The use of the second positive electrode active material with the above carbon mass content can further ensure that the secondary battery has excellent rate performance, dynamic performance and low-temperature cycling performance, and has high energy density.
In any embodiment of the first aspect to the third aspect, the mass ratio of the first positive electrode active material to the second positive electrode active material is 1:7 to 7:1, and optionally 1:4 to 4:1. In this way, it is ensured that the secondary battery has high energy density, excellent dynamic performance, excellent rate performance, long low-temperature cycle life and high low-temperature cycle capacity retention rate, and the interface side reactions are reduced.
In any embodiment of the first aspect to the third aspect, in the first positive electrode active material, R is at least two elements selected from Ti, V, Zr, Fe, Ni, Mg, Co, Ga, Sn, Sb, Nb and Ge. Thus, the composition of the first positive electrode active material can be more accurately controlled.
In any embodiment of the first aspect to the third aspect, in the first positive electrode active material, A is any element selected from Mg and Nb; and/or R is at least two elements selected from Fe, Ti, V, Co and Mg, optionally is Fe and one or more elements selected from Ti, V, Co and Mg; and/or C is S; and/or D is F. By selecting the doping elements within the above range, the rate performance and electronic conductivity of the secondary battery can be further improved, so that the rate performance, gram capacity and high-temperature performance of the secondary battery can be improved and the interfacial side reactions can be alleviated.
In any embodiment of the first aspect to the third aspect, in the first positive electrode active material, x is selected from the range of 0.001 to 0.005. By selecting the value of x within this range, the dynamic performance of the first positive electrode active material can be further improved.
In any embodiment of the first aspect to the third aspect, in the first positive electrode active material, y is selected from the range of 0.01 to 0.5, and optionally selected from the range of 0.25 to 0.5. By selecting the value of y within this range, the gram capacity and rate performance of the first positive electrode active material can be further improved.
In any embodiment of the first aspect to the third aspect, in the first positive electrode active material, z is selected from the range of 0.001 to 0.005. By selecting the value of z within this range, the rate performance of the secondary battery can be further improved.
In any embodiment of the first aspect to the third aspect, in the first positive electrode active material, n is selected from the range of 0.001 to 0.005. By selecting the value of n within this range, the high-temperature performance of the secondary battery can be further improved.
In any embodiment of the first aspect to the third aspect, in the first positive electrode active material, the ratio of (1-y) to y is selected from 1 to 4, and optionally selected from 1.5 to 3. In this way, the energy density and cycling performance of the secondary battery can be further improved.
In any embodiment of the first aspect to the third aspect, in the first positive electrode active material, the ratio of a to x is selected from 9 to 1100, and optionally selected from 190 to 998. When this condition is satisfied, the energy density and cycling performance of the secondary battery can be further improved.
In any embodiment of the first aspect to the third aspect, the lattice change rate of the first positive electrode active material is less than 8%, and optionally less than 4%. By reducing the lattice change rate, it is beneficial to improve the rate performance of the secondary battery. The lattice change rate can be determined by a method known in the art, e.g., X-ray diffraction (XRD).
In any embodiment of the first aspect to the third aspect, the Li/Mn antisite defect concentration of the first positive electrode active material is less than 2%, and optionally less than 0.5%. 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 the percentage of Li+ exchanged with Mn2+ based on the total amount of Li+ in the positive electrode active material. By reducing the Li/Mn antisite defect concentration, it is beneficial to improve the gram capacity and rate performance of the first positive electrode active material. The Li/Mn antisite defect concentration can be determined by a method known in the art, e.g., XRD.
In any embodiment of the first aspect to the third aspect, the surface oxygen valence state of the first positive electrode active material is less than −1.82, and optionally −1.89 to −1.98. By reducing the surface oxygen valence state, the interfacial side reactions between the first positive electrode active material and the electrolyte solution can be alleviated, thereby improving the cycling performance and high-temperature stability of the secondary battery. The surface oxygen valence state can be determined by a method known in the art, e.g., electron energy loss spectroscopy (EELS).
In any embodiment of the first aspect to the third aspect, the compacted density of the first positive electrode active material at 3T is greater than 2.0 g/cm3, and optionally greater than 2.2 g/cm3. The higher the compacted density, the greater the weight of the first positive electrode active material per unit volume, thus increasing the compacted density is beneficial to improve the volumetric energy density of the cell. The compacted density can be determined in accordance with GB/T 24533-2009.
In any embodiment of the first aspect to the third aspect, the surface of the first positive electrode active material is further coated with carbon. Thus, the conductivity of the first positive electrode active material can be improved.
In any embodiment of the first aspect to the third aspect, 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. In this way, it is further ensured that the secondary battery has excellent rate performance, dynamic performance and low-temperature cycling performance, and has high energy density.
A fourth aspect of the present application provides a secondary battery, comprising the positive electrode plate according to the first aspect to 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, comprising at least one selected from the secondary battery of the fourth aspect of the present application, the battery module of the fifth aspect of the present application and the battery pack of the sixth aspect of the present application.
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, the embodiments of the positive electrode plate, secondary battery, battery module, battery pack and power consuming device of the present application are specifically disclosed in the detailed description 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 embodiments and optional embodiments 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, preferably 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 or closed-ended, unless otherwise stated. For example, “comprise” and “include” mean that other components not listed may further be comprised or included, or only the listed components may 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).
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 solution. During the 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 the positive and negative electrodes from short-circuiting and enables the active ions to pass through. The electrolyte solution mainly functions for conducting the active ions between the positive electrode plate and the negative electrode plate.
An embodiment of the first aspect of the present application provides a positive electrode plate, comprising 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 has a single-layer structure or a multi-layer structure; when the positive electrode film layer has a single-layer structure, at least one of the positive electrode film layers contains both a first positive electrode active material with a chemical formula of LiaAxMn1-yRyP1-zCzO4-nDn and a second positive electrode active material; and/or when the positive electrode film layer has a multi-layer structure, at least one of the positive electrode film layers contains both a first positive electrode active material with a chemical formula of LiaAxMn1-yRyP1-zCzO4-nDn and a second positive electrode active material; wherein A includes one or more elements selected from Zn, Al, Na, K, Mg, Nb, Mo and W; R includes one or more elements selected from Ti, V, Zr, Fe, Ni, Mg, Co, Ga, Sn, Sb, Nb and Ge; C includes one or more elements selected from B, S, Si and N; D includes one or more elements selected from S, F, Cl and Br; a is selected from the range of 0.9 to 1.1, x is selected from the range of 0.001 to 0.1, y is selected from the range of 0.001 to 0.5, z is selected from the range of 0.001 to 0.1, and n is selected from range of 0.001 to 0.1; the second positive electrode active material is selected from one or more of LiFePO4, carbon-coated LiFePO4, LiFebMcPO4 and carbon-coated LiFebMcPO4, wherein M independently includes one or more elements selected from Ti, Zn, Co, Mn, La, V, Mg, Al, Nb, W, Zr, Nb, Sm, Cr, Cu and B, b is independently selected from the range of 0.99 to 0.999 and b+c=1.
It should be noted that: when the positive electrode plate comprises two positive electrode film layers, the expression “positive electrode film layer has a single-layer structure or multi-layer structure” means that each of the two positive electrode film layers independently has a single-layer structure or multi-layer structure; “when the positive electrode film layer has a single-layer structure” means that one or two positive electrode film layers have a single-layer structure; “when the positive electrode film layer has a multi-layer structure” means that one or two positive electrode film layers have a multi-layer structure.
The first positive electrode active material of the present application is obtained by doping elements in the compound LiMnPO4, wherein A, R, C and D are elements doped at the positions of Li, Mn, P and O of the compound LiMnPO4, respectively. Without wishing to be bound by theory, the inventors of the present application found that the performance improvement of lithium manganese phosphate is related to the decrease of the lattice change rate of lithium manganese phosphate during lithium de-intercalation and the decrease of the surface activity. A reduction in the lattice change rate can reduce the difference of lattice constants between the two phases at the grain boundary, lower the interface stress and enhance the Li+ transport ability at the interface, thereby improving the rate performance of the positive electrode active material. However, high surface activity can easily lead to serious interface side reactions, aggravate gas production, electrolyte solution consumption and interface damage, thereby affecting the cycling performance of the secondary battery. In the present application, the lattice change rate is reduced by doping at the positions of Li and Mn. The Mn-position doping also effectively decreases the surface activity, thereby inhibiting the dissolution of Mn 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-position doping plays a good role in reducing the interfacial side reactions. The P-position and O-position doping also has an effect on the dissolution of Mn of antisite defects and the dynamic performance. Therefore, the doping reduces the antisite defect concentration in the material, improves the dynamic performance and gram capacity of the material, and can also change the morphology of the particles, thereby increasing the compacted density. The applicant has unexpectedly found that: by doping specific elements at the positions of Li, Mn, P and O of the compound LiMnPO4 in a specific amount at the same time, the rate performance can be significantly improved, and meanwhile the dissolution of Mn and the doping elements at Mn position can be significantly reduced, such that the cycling performance and/or high-temperature stability can be significantly improved, and the gram capacity and compacted density of the material can also be improved. In addition, in the present application, by the combination use of the first positive electrode active material and the second positive electrode active material, the advantages of the two materials are complementary, which improves the energy density of the secondary battery; and the first positive electrode active material is uniformly dispersed around the second positive electrode active material, and the doping on the positions of Li, P, and Mn of the first positive electrode active material can further reduce the lattice change rate during lithium de-intercalation process and improve the electronic conductivity, so that the conductivity and the rate of lithium de-intercalation of the materials used in combination can be thoroughly improved, thereby improving the energy density of the secondary battery and allowing the materials used in combination have excellent power performance and low-temperature performance. Moreover, due to the O-position doping of the first positive electrode active material, the interfacial side reactions are reduced, which allows to achieve good cycle stability and will not deteriorate the cycling performance. The stable skeleton structure of the second material is beneficial to improve the stability of the first positive electrode material in the materials used in combination, thereby allowing the secondary battery to have excellent cycling performance.
In some embodiments of the first aspect, a positive electrode film layer C and a positive electrode film layer D are respectively provided on both surfaces of the positive electrode current collector, wherein the positive electrode film layer C has a multi-layer structure, and the positive electrode film layer D has a single-layer structure, at least one of the positive electrode film layers C contains both a first positive electrode active material and a second positive electrode active material; optionally, the positive electrode film layer D contains either or both of the first positive electrode active material and the second positive electrode active material; and optionally, the remaining layers of the positive electrode film layer C contain the first positive electrode active material or the second positive electrode active material.
In some embodiments of the first aspect, a positive electrode film layer C and a positive electrode film layer D are respectively provided on both surfaces of the positive electrode current collector, wherein the positive electrode film layer C has a multi-layer structure, and the positive electrode film layer D has a single-layer structure, the positive electrode film layer D contains both a first positive electrode active material and a second positive electrode active material; optionally, any one of the positive electrode film layers C contains the first positive electrode active material or the second positive electrode active material.
In some embodiments of the first aspect, a positive electrode film layer is respectively provided on both surfaces of the positive electrode current collector, each of the positive electrode film layers has a multi-layer structure, and at least one of the positive electrode film layers contains both a first positive electrode active material and a second positive electrode active material; and optionally, the remaining layers of the positive electrode film layer contain the first positive electrode active material or the second positive electrode active material.
An embodiment of the second aspect of the present application provides a positive electrode plate, comprising a positive electrode current collector and a positive electrode film layer provided on at least one surface of the positive electrode current collector, wherein at least one of the positive electrode film layers has a multi-layer structure, and any one of the positive electrode film layers having a multi-layer structure respectively contains a first positive electrode active material with a chemical formula of LiaAxMn1-yRyP1-zCzO4-nDn and a second positive electrode active material in different layers; wherein A includes one or more elements selected from Zn, Al, Na, K, Mg, Nb, Mo and W; R includes one or more elements selected from Ti, V, Zr, Fe, Ni, Mg, Co, Ga, Sn, Sb, Nb and Ge; C includes one or more elements selected from B, S, Si and N; D includes one or more elements selected from S, F, Cl and Br; a is selected from the range of 0.9 to 1.1, x is selected from the range of 0.001 to 0.1, y is selected from the range of 0.001 to 0.5, z is selected from the range of 0.001 to 0.1, and n is selected from range of 0.001 to 0.1; the second positive electrode active material is selected from one or more of LiFePO4, carbon-coated LiFePO4, LiFebMcPO4 and carbon-coated LiFebMcPO4, wherein M independently includes one or more elements selected from Ti, Zn, Co, Mn, La, V, Mg, Al, Nb, W, Zr, Nb, Sm, Cr, Cu and B, b is independently selected from the range of 0.99 to 0.999 and b+c=1; optionally, any one of the positive electrode film layers having a multi-layer structure respectively contains the first positive electrode active material and the second positive electrode active material in adjacent layers.
In some embodiments of the second aspect, a positive electrode film layer is respectively provided on both surfaces of the positive electrode current collector, each of the positive electrode film layers has a multi-layer structure, and the adjacent two layers of the positive electrode film layer respectively contain the first positive electrode active material and the second positive electrode active material.
In some embodiments of the second aspect, a positive electrode film layer E and a positive electrode film layer F are respectively provided on both surfaces of the positive electrode current collector, wherein the positive electrode film layer E has a multi-layer structure, and the positive electrode film layer F has a single-layer structure, and the adjacent two layers of the positive electrode film layer E respectively contain a first positive electrode active material and a second positive electrode active material; and optionally, the remaining layers of the positive electrode film layer E and the positive electrode film layer F contain the first positive electrode active material or the second positive electrode active material.
An embodiment of the third aspect of the present application provides a positive electrode plate, comprising a positive electrode current collector and a positive electrode film layer A and a positive electrode film layer B respectively provided on both surfaces of the positive electrode current collector; wherein the positive electrode film layer A and the positive electrode film layer B independently has a single-layer structure or a multi-layer structure; at least one of the positive electrode film layers A contains a first positive electrode active material with a chemical formula of LiaAxMn1-yRyP1-zCzO4-nDn, and at least one of the positive electrode film layers B contains a second positive electrode active material; wherein A includes one or more elements selected from Zn, Al, Na, K, Mg, Nb, Mo and W; R includes one or more elements selected from Ti, V, Zr, Fe, Ni, Mg, Co, Ga, Sn, Sb, Nb and Ge; C includes one or more elements selected from B, S, Si and N; D includes one or more elements selected from S, F, Cl and Br; a is selected from the range of 0.9 to 1.1, x is selected from the range of 0.001 to 0.1, y is selected from the range of 0.001 to 0.5, z is selected from the range of 0.001 to 0.1, and n is selected from range of 0.001 to 0.1; the second positive electrode active material is selected from one or more of LiFePO4, carbon-coated LiFePO4, LiFebMcPO4 and carbon-coated LiFebMcPO4, wherein M independently includes one or more elements selected from Ti, Zn, Co, Mn, La, V, Mg, Al, Nb, W, Zr, Nb, Sm, Cr, Cu and B, b is independently selected from the range of 0.99 to 0.999 and b+c=1.
In an embodiment of the second or third aspect of the present application, the first positive electrode active material has significantly improved rate performance and meanwhile significantly reduces the dissolution of Mn and the doping elements at Mn position, such that the cycling performance and/or high-temperature stability can be significantly improved, and the gram capacity and compacted density of the material can also be improved, and the interfacial side reactions can be reduced, and the specific principle is the same as that in the first embodiment of the present application. Although the mechanism is not very clear, in the present application, by the combination use of the first positive electrode active material and the second positive electrode active material, the advantages of the two materials are complementary, which improves the energy density of the secondary battery, and meanwhile allows the secondary battery to have excellent rate performance, dynamic performance, low-temperature cycle life and low-temperature cycle capacity retention rate. Specifically, the first positive electrode active material is uniformly dispersed around the second positive electrode active material, and the doping on the positions of Li, P, and Mn of the first positive electrode active material can further reduce the lattice change rate during lithium de-intercalation process and improve the electronic conductivity, so that the conductivity and the rate of lithium de-intercalation of the materials used in combination can be thoroughly improved, thereby improving the energy density of the secondary battery and allowing the materials used in combination have excellent power performance and low-temperature performance. Moreover, due to the 0-position doping of the first positive electrode active material, the interfacial side reactions are reduced, which allows to achieve good cycle stability and will not deteriorate the cycling performance. The stable skeleton structure of the second material is beneficial to improve the stability of the first positive electrode material in the materials used in combination, thereby allowing the secondary battery to have excellent cycling performance.
Unless otherwise specified, in the chemical formula of LiaAxMn1-yRyP1-zCzO4-nDn, when A is two or more elements, the above-mentioned limitation on the numerical range of x is not only a limitation on the stoichiometric number of each element as A, but also a limitation on the sum of the stoichiometric numbers of each element as A. For example, when A is two or more elements A1, A2 . . . An, the respective stoichiometric numbers x1, x2 . . . xn of A1, A2 . . . An 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, for the case where R, C and D is two or more elements, the limitations on the numerical ranges of the stoichiometric numbers of R, C and D in the present application also have the above meanings.
Unless otherwise specified, in the chemical formula of LiFebMcPO4, when M is two or more elements, the above-mentioned limitation on the numerical range of c is not only a limitation on the stoichiometric number of each element as M, but also a limitation on the sum of the stoichiometric numbers of each element as M. For example, when M is two or more elements M1, M2 . . . Mn, the respective stoichiometric numbers c1, c2 . . . cn of M1, M2 . . . Mn fall within the numerical range c defined in the present application, and the sum of c1, c2 . . . cn also falls within this numerical range.
In some embodiments of the first to third aspects, the first positive electrode active material of LiaAxMn1-yRyP1-zCzO4-nDn thoroughly keeps electrically neutral.
In some embodiments of the first to third aspects, LiFebMcPO4 thoroughly keeps electrically neutral.
In some embodiments of the first aspect to the third aspect, in the second positive electrode active material, the mass of carbon accounts for 0.1%-4% of the mass of carbon-coated LiFePO4; and/or the mass of carbon accounts for 0.1%-4% of the mass of the carbon-coated LiFebMcPO4. The use of the second positive electrode active material with the above carbon mass content can further ensure that the secondary battery has excellent rate performance, dynamic performance and low-temperature cycling performance, and has high energy density.
In some embodiments of the first to third aspects, the mass ratio of the first active material to the second active material is 1:7 to 7:1, optionally 1:4 to 4:1, and further optionally 1:3 to 3:1, such as 1:7, 1:5, 1:3, 1:2, 3:5, 1:1, 5:3, 2:1, 3:1, 5:1, or 7:1. In this way, it is ensured that the secondary battery has high energy density, excellent dynamic performance, excellent rate performance, long low-temperature cycle life and high low-temperature cycle capacity retention rate, and the interface side reaction is reduced.
In some embodiments of the first to third aspects, in the first positive electrode active material, R is at least two elements selected from Ti, V, Zr, Fe, Ni, Mg, Co, Ga, Sn, Sb, Nb and Ge. Thus, the composition of the first positive electrode active material can be more easily and accurately controlled.
In some embodiments of the first to third aspects, in the first positive electrode active material, A is any element selected from Mg and Nb. and/or R is at least two elements selected from Fe, Ti, V, Co and Mg, optionally is Fe and one or more elements selected from Ti, V, Co and Mg; and/or C is S; and/or D is F. By selecting Li-position doping elements within the above range, the lattice change rate during lithium de-intercalation process can be further reduced, thereby further improving the rate performance of the secondary battery. By selecting Mn-position doping elements within the above range, the electronic conductivity can be further improved and the lattice change rate can be further reduced, thereby improving the rate performance and gram capacity of the secondary battery. By selecting P-position doping elements within the above range, the rate performance of the secondary battery can be further improved. By selecting O-position doping elements within the above range, the interfacial side reactions can be further alleviated, thereby improving the high-temperature performance of the secondary battery.
In some embodiments of the first to third aspects, in the first positive electrode active material, x is selected from the range of 0.001 to 0.005. By selecting the value of x within this range, the dynamic performance of the first positive electrode active material can be further improved.
In some embodiments of the first to third aspects, in the first positive electrode active material, y is selected from the range of 0.01 to 0.5, and optionally selected from the range of 0.25 to 0.5. By selecting the value of y within this range, the gram capacity and rate performance of the first positive electrode active material can be further improved.
In some embodiments of the first to third aspects, in the first positive electrode active material, z is selected from the range of 0.001 to 0.005. By selecting the value of z within this range, the rate performance of the secondary battery can be further improved.
In some embodiments of the first to third aspects, in the first positive electrode active material, n is selected from the range of 0.001 to 0.005. By selecting the value of n within this range, the high-temperature performance of the secondary battery can be further improved.
In some embodiments of the first to third aspects, in the first positive electrode active material, the ratio of (1-y) to y is selected from 1 to 4, and optionally selected from 1.5 to 3, and the ratio of a to x is selected from 9 to 1100, and optionally selected from 190 to 998. When this condition is satisfied, the energy density and cycling performance of the secondary battery can be further improved.
In some embodiments of the first to third aspects, the lattice change rate of the first positive electrode active material is less than 8%, and optionally less than 4%. 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 to improve the rate performance of the secondary battery. The lattice change rate can be determined by a method known in the art, e.g., X-ray diffraction (XRD).
In some embodiments of the first to third aspects, the Li/Mn antisite defect concentration of the first positive electrode active material is less than 2%, and optionally less than 0.5%. 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 the percentage of Li+ exchanged with Mn2+ based on the total amount of Li+ in the positive electrode active material. By reducing the Li/Mn antisite defect concentration, it is beneficial to improve the gram capacity and rate performance of the first positive electrode active material. The Li/Mn antisite defect concentration can be determined by a method known in the art, e.g., XRD.
In some embodiments of the first to third aspects, the surface oxygen valence state of the first positive electrode active material is less than −1.82, and optionally −1.89 to −1.98. By reducing the surface oxygen valence state, the interfacial side reactions between the first positive electrode active material and the electrolyte solution can be alleviated, thereby improving the cycling performance and high-temperature stability of the secondary battery. The surface oxygen valence state can be determined by a method known in the art, e.g., electron energy loss spectroscopy (EELS).
In some embodiments of the first to third aspects, the compacted density of the first positive electrode active material at 3T is greater than 2.0 g/cm3, and optionally greater than 2.2 g/cm3. The higher the compacted density, the greater the weight of the first positive electrode active material per unit volume, thus increasing the compacted density is beneficial to improve the volumetric energy density of the cell. The compacted density can be determined in accordance with GB/T 24533-2009.
In some embodiments of the first to third aspects, the surface of the first positive electrode active material is further coated with carbon. Thus, the conductivity of the first positive electrode active material can be improved.
In some embodiments of the first to third aspects, 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. In this way, it is further ensured that the secondary battery has excellent rate performance, dynamic performance and low-temperature cycling performance, and has high energy density.
In some embodiments of the first to third aspects, 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 the two opposite surfaces of the positive electrode current collector.
In some embodiments of the first to third aspects, the positive electrode current collector may 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 substrate and a metal layer formed on at least one surface of the polymer 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 substrate (such as polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments of the first to third aspects, the positive electrode film layer may further comprise other positive electrode active materials known in the art for secondary 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 secondary batteries can also be used. These positive electrode active materials may be used alone or in combination of two or more. Herein, examples of lithium transition metal oxides may include, but are not limited to, at least one of lithium nickel oxide (e.g. LiNiO2), lithium manganese oxide (e.g. LiMnO2 and LiMn2O4), lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide and modified compounds thereof, etc. Examples of lithium-containing phosphate with olivine structure may include, but are not limited to, at least one of lithium manganese phosphate (e.g. LiMnPO4), composite material of lithium manganese phosphate and carbon, lithium iron manganese phosphate, and composite material of lithium iron manganese phosphate and carbon.
In some embodiments of the first to third aspects, the positive electrode film layer further 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 of the first to third aspects, the positive electrode film layer further optionally comprise 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 of the first to third aspects, the first positive electrode active material with a chemical formula of LiaAxMn1-yRyP1-zCzO4-nDn is prepared by the following steps:
In some embodiments of the first to third aspects, in step (1), the mixing is carried out at 60° C.-120° C.; and/or, in step (1), the mixing is carried out by stirring at 200-800 rpm.
In some embodiments of the first to third aspects, in step (2), the mixing is carried out for 8-15 h.
In some embodiments of the first to third aspects, in step (2), the sintering is carried out at 600° C.-900° C. for 6-14 h.
In some embodiments of the first to third aspects, the source of element A is selected from one or more of the elemental form, oxides, phosphates, oxalates, carbonates and sulfates of element A; and/or
In the present application, the source of manganese may be a manganese-containing substance known in the art that can be used to prepare lithium manganese phosphate. As an example, the source of manganese can be selected from one or more of elemental manganese, manganese dioxide, manganese phosphate, manganese oxalate and manganese carbonate.
In the present application, the acid can be selected from one or more of organic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, silicic acid, and siliceous acid, and organic acids such as oxalic acid. In some embodiments, the acid is a dilute organic acid having a concentration of 60% by weight or less.
In the present application, the source of lithium may be a lithium-containing substance known in the art that can be used to prepare lithium manganese phosphate. As an example, the source of lithium is selected from one or more of lithium carbonate, lithium hydroxide, lithium phosphate and lithium dihydrogen phosphate.
In the present application, the source of phosphorus may be a phosphorus-containing substance known in the art that can be used to prepare lithium manganese phosphate. As an example, the source of phosphorus is selected from one or more of diammonium phosphate, ammonium dihydrogen phosphate, ammonium phosphate and phosphoric acid.
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 electrode 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 substrate and a metal layer formed on at least one surface of the polymer 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 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 secondary 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 can be selected from at least one of elemental silicon, silicon oxides, silicon carbon composites, silicon nitrogen composites and silicon alloys. The tin-based material can 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 can be used alone or in combination of two or more.
In some embodiments, the negative electrode film layer further optionally comprise a binder. As an example, the binder can be selected from at least one of 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 further optionally comprise a conductive agent. As an example, the conductive agent can be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the negative electrode film layer further optionally comprise other auxiliary agents, such as thickener (e.g. sodium carboxymethyl cellulose (CMC-Na)), etc.
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.
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 comprises an electrolyte salt and a solvent.
In some embodiments, the electrolyte salt can 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 can 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, a positive electrode film-forming additive, and also an additive that can improve certain performances of the battery, such as an additive that improve the overcharge performance of the battery, or an additive that improve the high-temperature performance or low-temperature performance of the battery.
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 and used.
In some embodiments, the material of the separator can 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 the positive electrode plate, the negative electrode plate and the separator by means of a winding process or a laminating 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, such as 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, and 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-mentioned 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.
For the 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 techniques or conditions that are not specified in examples are according to the techniques or conditions described in documents in the art or the product introduction. The reagents or instruments used, if they are not marked with the manufacturer, are common products that are commercially available.
Preparation of doped manganese oxalate: 1.3 mol of MnSO4·H2O and 0.7 mol of FeSO4·H2O are mixed thoroughly for 6 h 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 h at a stirring 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.
Preparation of doped lithium manganese phosphate: 1 mol of the Fe-doped manganese oxalate particles, 0.497 mol of lithium carbonate, 0.001 mol of Mo(SO4)3, an 85% of 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 h to obtain a slurry. The slurry is transferred into a spray drying apparatus for spray-drying granulation, wherein 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 h in a protective atmosphere of nitrogen (90% v/v)+hydrogen (10% v/v), so as to obtain the positive electrode active material 1, that is, carbon-coated Li0.994Mo0.001Mn0.65Fe0.35P0.999Si0.001O3.999F0.001. The element content of the positive electrode active material can be determined by inductively coupled plasma (ICP) emission spectroscopy.
Except that the amount of high-purity Li2CO3 is changed into 0.4885 mol, Mo(SO4)3 is replaced by equimolar amount of MgSO4, the amount of FeSO4·H2O is changed into 0.68 mol, 0.02 mol of Ti(SO4)2 is further added in the preparation of doped manganese oxalate, and H4SiO4 is replaced by equimolar amount of HNO3, the others are the same as those in preparation example 1.
Except that the amount of high-purity Li2CO3 is changed into 0.496 mol, Mo(SO4)3 is replaced by equimolar amount of W(SO4)3, and H4SiO4 is replaced by equimolar amount of H2SO4, the others are the same as those in preparation example 1.
Except that 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 equimolar amount of NH4HCl2, the others are the same as those in preparation example 1.
Except that 0.7 mol of FeSO4·H2O is changed into 0.69 mol, 0.01 mol of VCl2 is further 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 equimolar amount of H2SO4, the others are the same as those in preparation example 1.
Except that the amount of FeSO4·H2O is changed into 0.68 mol, 0.01 mol of VCl2 and 0.01 mol of MgSO4 are further 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 equimolar amount of H2SO4, the others are the same as those in preparation example 1.
Except that MgSO4 is replaced by equimolar amount of CoSO4, the others are the same as those in preparation example 6.
Except that MgSO4 is replaced by equimolar amount of NiSO4, the others are the same as those in preparation example 6.
Except that the amount of FeSO4·H2O is changed into 0.698 mol, 0.002 mol of Ti(SO4)2 is further 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 equimolar amount of H2SO4, and NH4HF2 is replaced by equimolar amount of NH4HCl2, the others are the same as those in preparation example 1.
Except that the amount of FeSO4·H2O is changed into 0.68 mol, 0.01 mol of VCl2 and 0.01 mol of MgSO4 are further 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 equimolar amount of NH4HBr2, the others are the same as those in preparation example 1.
Except that the amount of FeSO4·H2O is changed into 0.69 mol, 0.01 mol of VCl2 is further added in the preparation of doped manganese oxalate, the amount of Li2CO3 is changed into 0.499 mol, Mo(SO4)3 is replaced by equimolar amount of MgSO4, and NH4HF2 is replaced by equimolar amount of NH4HBr2, the others are the same as those in preparation example 1.
Except that 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 further added in the preparation of doped manganese oxalate, the amount of Li2CO3 is changed into 0.4985 mol, Mo(SO4)3 is replaced by equimolar amount of MgSO4, and H4SiO4 is replaced by equimolar amount of HNO3, the others are the same as those in preparation example 1.
Except that the amount of MnSO4·H2O is changed into 1.16 mol, the amount of FeSO4·H2O is changed into 0.8 mol, the others are the same as those in preparation example 12.
Except that the amount of MnSO4·H2O is changed into 1.3 mol, the amount of VCl2 is changed into 0.1 mol, the others are the same as those in preparation example 12.
Except that the amount of MnSO4·H2O is changed into 1.2 mol, 0.1 mol of VCl2 is further 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 equimolar amount of H2SO4, the others are the same as those in preparation example 1.
Except that the amount of MnSO4·H2O is changed into 1.2 mol, 0.1 mol of VCl2 is further 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% of phosphoric acid is replaced by 1.171 mol of 85% of phosphoric acid, the others are the same as those in preparation example 1.
Except that the amount of MnSO4·H2O is changed into 1.2 mol, 0.1 mol of VCl2 is further 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 equimolar amount of H2SO4, and 0.0005 mol of NH4HF2 is changed into 0.0025 mol, the others are the same as those in preparation example 1.
Except that the amount of FeSO4·H2O is changed into 0.5 mol, 0.1 mol of VCl2 and 0.1 mol of CoSO4 are further 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 equimolar amount of H2SO4, and 0.0005 mol of NH4HF2 is changed into 0.0025 mol, the others are the same as those in preparation example 1.
Except that the amount of FeSO4·H2O is changed into 0.4 mol, and 0.1 mol of CoSO4 is changed into 0.2 mol, the others are the same as those in preparation example 18.
Except that 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 others are the same as those in preparation example 18.
Except that 0.1 mol of CoSO4 is replaced by 0.1 mol of NiSO4, the others are the same as those in preparation example 18.
Except that 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 others are the same as those in preparation example 18.
Except that the amount of MnSO4·H2O is changed into 1.4 mol, the amount of FeSO4·H2O is changed into 0.3 mol, the amount of CoSO4 is changed into 0.2 mol, the others are the same as those in preparation example 18.
Except that 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 further 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 equimolar amount of H2SO4, and 0.0005 mol of NH4HF2 is changed into 0.0025 mol, the others are the same as those in preparation example 1.
Except that 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 others are the same as those in preparation example 18.
Except that 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 further 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 others are the same as those in preparation example 1.
Except that 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 further 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 others are the same as those in preparation example 1.
The positive electrode active material is prepared in the same way as in preparation example 1, except changing the stirring speed and temperature, grinding and stirring time in a sander, sintering temperature and time during the preparation of doped manganese oxalate, as shown in Table 1 below.
The positive electrode active material is prepared in the same manner as in preparation example 1, except changing the sources of lithium, manganese, phosphorus and doping elements A, B, C, and D, as shown in Table 2 below. The prepared positive electrode active materials have the same composition as that in example 1, that is, Li0.994Mo0.001Mn0.65Fe0.35P0.999Si0.001O3.999F0.001.
The positive electrode active materials of preparation examples 55-74 are as shown in Table 3.
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 (based on oxalic acid) are added thereto. The reaction kettle is heated to 80° C., stirring is performed for 6 h at a stirring 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 resulting filter cake is dried at 120° C. and then ground to obtain manganese oxalate particles with a median particle size Dv50 of 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% of 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 h to obtain a slurry. The slurry is transferred into a spray drying apparatus for spray-drying granulation, wherein 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 h 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 1, 1 mol of MnSO4·H2O is replaced by 0.85 mol of MnSO4·H2O and 0.15 mol of FeSO4·H2O, and the mixture is added into a mixer for mixing for 6 h before being added into the reaction kettle, and the others are the same as those in comparative example 1.
Except that 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, without the addition of H4SiO4 and NH4HF2, the others are the same as those in preparation example 1.
Except that 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, and 0.0005 mol of NH4HF2 is changed into 0.025 mol, without the addition of H4SiO4, the others are the same as those in preparation example 1.
Except that 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, 0.001 mol of Mo(SO4)3 is replaced by 0.12 mol of MgSO4, the others are the same as those in preparation example 1.
Except that the amount of MnSO4·H2O is changed into 0.8 mol, 0.7 mol of FeSO4·H2O is replaced by 1.2 mol of ZnSO4, the amount of Li2CO3 is changed into 0.499 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.001 mol of MgSO4, the others are the same as those in preparation example 1.
Except that 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 others are the same as those in preparation example 1.
Except that 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 others are the same as those in preparation example 1.
A positive electrode active material, a binder of PVDF and a conductive agent of superconducting carbon black (Super-P) are mixed in a mass ratio of 97%:1.5%:1.5%, and then dispersed in a solvent of N-methylpyrrolidone, so as to obtain a slurry of the positive electrode active material with a solid content of 60% w/w.
The slurry of the positive electrode active material of preparation example 1 is uniformly coated on both sides of the current collector of aluminum foil 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 P1.
The slurry of the positive electrode active material of preparation example 55 is uniformly coated on both sides of the current collector of aluminum foil 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 P2.
The slurry of the positive electrode active material of preparation example 1 is uniformly coated on one side of the aluminum foil in a coating amount of 0.019 g/cm2, and the slurry of the positive electrode active material of preparation example 55 is uniformly coated on the other side of the aluminum foil 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 P3.
The slurry of the positive electrode active material of preparation example 56 is uniformly coated on both sides of the current collector of aluminum foil in a coating amount of 0.019 g/cm2, the others are the same as those in example 3, to obtain the positive electrode plate P4.
The slurry of the positive electrode active material of preparation example 1 is uniformly coated on one side of the aluminum foil in a coating amount of 0.019 g/cm2, and the slurry of the positive electrode active material of preparation example 56 is uniformly coated on the other side of the aluminum foil in a coating amount of 0.019 g/cm2, the others are the same as those in example 3, to obtain the positive electrode plate P5.
The slurry of the positive electrode active material of preparation example 55 is uniformly coated on one side of the aluminum foil in a coating amount of 0.019 g/cm2, and the slurry of the positive electrode active material of preparation example 56 is uniformly coated on the other side of the aluminum foil in a coating amount of 0.019 g/cm2, the others are the same as those in example 3, to obtain the positive electrode plate P6.
The slurry of the positive electrode active material of preparation example 1 and the slurry of the positive electrode active material of preparation example 55 are sequentially coated on both sides of the aluminum foil with a coating amount of each slurry being 0.010 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 P7.
The slurry of the positive electrode active material of preparation example 1 and the slurry of the positive electrode active material of preparation example 55 are sequentially coated on both sides of the aluminum foil with a coating amount of each slurry being 0.010 g/cm2, the others are the same as those in example 7, to obtain the positive electrode plate P8.
The slurry of the positive electrode active material of preparation example 56 and the slurry of the positive electrode active material of preparation example 1 are sequentially coated on both sides of the aluminum foil with a coating amount of each slurry being 0.010 g/cm2, the others are the same as those in example 7, to obtain the positive electrode plate P9.
The slurry of the positive electrode active material of preparation example 1 and the slurry of the positive electrode active material of preparation example 56 are sequentially coated on both sides of the aluminum foil with a coating amount of each slurry being 0.010 g/cm2, the others are the same as those in example 7, to obtain the positive electrode plate P10.
The slurry of the positive electrode active material of preparation example 56 and the slurry of the positive electrode active material of preparation example 55 are sequentially coated on both sides of the aluminum foil with a coating amount of each slurry being 0.010 g/cm2, the others are the same as those in example 7, to obtain the positive electrode plate P11.
The slurry of the positive electrode active material of preparation example 55 and the slurry of the positive electrode active material of preparation example 56 are sequentially coated on both sides of the aluminum foil with a coating amount of each slurry being 0.010 g/cm2, the others are the same as those in example 7, to obtain the positive electrode plate P12.
The slurry of the positive electrode active material of preparation example 1 and the slurry of the positive electrode active material of preparation example 55 are sequentially coated on the A side of the aluminum foil with a coating amount of each slurry being 0.010 g/cm2, and the slurry of the positive electrode active material of preparation example 1 is uniformly coated on the B side of the aluminum foil with a coating amount of slurry being 0.020 g/cm2, then 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 P13.
The slurry of the positive electrode active material of preparation example 1 and the slurry of the positive electrode active material of preparation example 55 are sequentially coated on the A side of the aluminum foil with a coating amount of each slurry being 0.010 g/cm2, and the slurry of the positive electrode active material of preparation example 55 is uniformly coated on the B side of the aluminum foil with a coating amount of slurry being 0.020 g/cm2, the others are the same as those in example 13, to obtain the positive electrode plate P14.
The slurry of the positive electrode active material of preparation example 1 and the slurry of the positive electrode active material of preparation example 55 are sequentially coated on the A side of the aluminum foil with a coating amount of each slurry being 0.010 g/cm2, and the slurry of the positive electrode active material of preparation example 56 is uniformly coated on the B side of the aluminum foil with a coating amount of slurry being 0.020 g/cm2, the others are the same as those in example 13, to obtain the positive electrode plate P15.
The slurry of the positive electrode active material of preparation example 55 and the slurry of the positive electrode active material of preparation example 1 are sequentially coated on the A side of the aluminum foil with a coating amount of each slurry being 0.010 g/cm2, and the slurry of the positive electrode active material of preparation example 1 is uniformly coated on the B side of the aluminum foil with a coating amount of slurry being 0.020 g/cm2, the others are the same as those in example 13, to obtain the positive electrode plate P16.
The slurry of the positive electrode active material of preparation example 55 and the slurry of the positive electrode active material of preparation example 1 are sequentially coated on the A side of the aluminum foil with a coating amount of each slurry being 0.010 g/cm2, and the slurry of the positive electrode active material of preparation example 55 is uniformly coated on the B side of the aluminum foil with a coating amount of slurry being 0.020 g/cm2, the others are the same as those in example 13, to obtain the positive electrode plate P17.
The slurry of the positive electrode active material of preparation example 55 and the slurry of the positive electrode active material of preparation example 1 are sequentially coated on the A side of the aluminum foil with a coating amount of each slurry being 0.010 g/cm2, and the slurry of the positive electrode active material of preparation example 56 is uniformly coated on the B side of the aluminum foil with a coating amount of slurry being 0.020 g/cm2, the others are the same as those in example 13, to obtain the positive electrode plate P18.
The slurry of the positive electrode active material of preparation example 1 and the slurry of the positive electrode active material of preparation example 56 are sequentially coated on the A side of the aluminum foil with a coating amount of each slurry being 0.010 g/cm2, and the slurry of the positive electrode active material of preparation example 1 is uniformly coated on the B side of the aluminum foil with a coating amount of slurry being 0.020 g/cm2, the others are the same as those in example 13, to obtain the positive electrode plate P19.
The slurry of the positive electrode active material of preparation example 1 and the slurry of the positive electrode active material of preparation example 56 are sequentially coated on the A side of the aluminum foil with a coating amount of each slurry being 0.010 g/cm2, and the slurry of the positive electrode active material of preparation example 55 is uniformly coated on the B side of the aluminum foil with a coating amount of slurry being 0.020 g/cm2, the others are the same as those in example 13, to obtain the positive electrode plate P20.
The slurry of the positive electrode active material of preparation example 1 and the slurry of the positive electrode active material of preparation example 56 are sequentially coated on the A side of the aluminum foil with a coating amount of each slurry being 0.010 g/cm2, and the slurry of the positive electrode active material of preparation example 56 is uniformly coated on the B side of the aluminum foil with a coating amount of slurry being 0.020 g/cm2, the others are the same as those in example 13, to obtain the positive electrode plate P21.
The slurry of the positive electrode active material of preparation example 56 and the slurry of the positive electrode active material of preparation example 1 are sequentially coated on the A side of the aluminum foil with a coating amount of each slurry being 0.010 g/cm2, and the slurry of the positive electrode active material of preparation example 1 is uniformly coated on the B side of the aluminum foil with a coating amount of slurry being 0.020 g/cm2, the others are the same as those in example 13, to obtain the positive electrode plate P22.
The slurry of the positive electrode active material of preparation example 56 and the slurry of the positive electrode active material of preparation example 1 are sequentially coated on the A side of the aluminum foil with a coating amount of each slurry being 0.010 g/cm2, and the slurry of the positive electrode active material of preparation example 55 is uniformly coated on the B side of the aluminum foil with a coating amount of slurry being 0.020 g/cm2, the others are the same as those in example 13, to obtain the positive electrode plate P23.
The slurry of the positive electrode active material of preparation example 56 and the slurry of the positive electrode active material of preparation example 1 are sequentially coated on the A side of the aluminum foil with a coating amount of each slurry being 0.010 g/cm2, and the slurry of the positive electrode active material of preparation example 56 is uniformly coated on the B side of the aluminum foil with a coating amount of slurry being 0.020 g/cm2, the others are the same as those in example 13, to obtain the positive electrode plate P24.
The slurry of the positive electrode active material of preparation example 55 and the slurry of the positive electrode active material of preparation example 56 are sequentially coated on the A side of the aluminum foil with a coating amount of each slurry being 0.010 g/cm2, and the slurry of the positive electrode active material of preparation example 1 is uniformly coated on the B side of the aluminum foil with a coating amount of slurry being 0.020 g/cm2, the others are the same as those in example 13, to obtain the positive electrode plate P25.
The slurry of the positive electrode active material of preparation example 55 and the slurry of the positive electrode active material of preparation example 56 are sequentially coated on the A side of the aluminum foil with a coating amount of each slurry being 0.010 g/cm2, and the slurry of the positive electrode active material of preparation example 55 is uniformly coated on the B side of the aluminum foil with a coating amount of slurry being 0.020 g/cm2, the others are the same as those in example 13, to obtain the positive electrode plate P26.
The slurry of the positive electrode active material of preparation example 55 and the slurry of the positive electrode active material of preparation example 56 are sequentially coated on the A side of the aluminum foil with a coating amount of each slurry being 0.010 g/cm2, and the slurry of the positive electrode active material of preparation example 56 is uniformly coated on the B side of the aluminum foil with a coating amount of slurry being 0.020 g/cm2, the others are the same as those in example 13, to obtain the positive electrode plate P27.
The slurry of the positive electrode active material of preparation example 56 and the slurry of the positive electrode active material of preparation example 55 are sequentially coated on the A side of the aluminum foil with a coating amount of each slurry being 0.010 g/cm2, and the slurry of the positive electrode active material of preparation example 1 is uniformly coated on the B side of the aluminum foil with a coating amount of slurry being 0.020 g/cm2, the others are the same as those in example 13, to obtain the positive electrode plate P28.
The slurry of the positive electrode active material of preparation example 56 and the slurry of the positive electrode active material of preparation example 55 are sequentially coated on the A side of the aluminum foil with a coating amount of each slurry being 0.010 g/cm2, and the slurry of the positive electrode active material of preparation example 55 is uniformly coated on the B side of the aluminum foil with a coating amount of slurry being 0.020 g/cm2, the others are the same as those in example 13, to obtain the positive electrode plate P29.
The slurry of the positive electrode active material of preparation example 56 and the slurry of the positive electrode active material of preparation example 55 are sequentially coated on the A side of the aluminum foil with a coating amount of each slurry being 0.010 g/cm2, and the slurry of the positive electrode active material of preparation example 56 is uniformly coated on the B side of the aluminum foil with a coating amount of slurry being 0.020 g/cm2, the others are the same as those in example 13, to obtain the positive electrode plate P30.
The slurry of the positive electrode active material of preparation example 57 is uniformly coated on both sides of the current collector of aluminum foil 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 P31.
The slurry of the positive electrode active material of preparation example 58 is uniformly coated on both sides of the current collector of aluminum foil 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 P32.
The slurry of the positive electrode active material of preparation example 59 is uniformly coated on both sides of the current collector of aluminum foil 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 P33.
The slurry of the positive electrode active material of preparation example 60 is uniformly coated on both sides of the current collector of aluminum foil 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 P34.
The slurry of the positive electrode active material of preparation example 61 is uniformly coated on both sides of the current collector of aluminum foil 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 P35.
The slurry of the positive electrode active material of preparation example 62 is uniformly coated on both sides of the current collector of aluminum foil 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 P36.
The slurry of the positive electrode active material of preparation example 63 is uniformly coated on both sides of the current collector of aluminum foil 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 P37.
The slurry of the positive electrode active material of preparation example 64 is uniformed coated on both sides of the current collector of aluminum foil in a coating amount of 0.019 g/cm2, the others are the same as those in example 37, to obtain the positive electrode plate P38.
The slurry of the positive electrode active material of preparation example 65 is uniformed coated on both sides of the current collector of aluminum foil in a coating amount of 0.019 g/cm2, the others are the same as those in example 37, to obtain the positive electrode plate P39.
The slurry of the positive electrode active material of preparation example 66 is uniformed coated on both sides of the current collector of aluminum foil in a coating amount of 0.019 g/cm2, the others are the same as those in example 37, to obtain the positive electrode plate P40.
The slurry of the positive electrode active material of preparation example 67 is uniformed coated on both sides of the current collector of aluminum foil in a coating amount of 0.019 g/cm2, the others are the same as those in example 37, to obtain the positive electrode plate P41.
The slurry of the positive electrode active material of preparation example 68 is uniformed coated on both sides of the current collector of aluminum foil in a coating amount of 0.019 g/cm2, the others are the same as those in example 37, to obtain the positive electrode plate P42.
The slurry of the positive electrode active material of preparation example 69 is uniformed coated on both sides of the current collector of aluminum foil in a coating amount of 0.019 g/cm2, the others are the same as those in example 37, to obtain the positive electrode plate P3.
The slurry of the positive electrode active material of preparation example 70 is uniformed coated on both sides of the current collector of aluminum foil in a coating amount of 0.019 g/cm2, the others are the same as those in example 37, to obtain the positive electrode plate P44.
The slurry of the positive electrode active material of preparation example 71 is uniformed coated on both sides of the current collector of aluminum foil in a coating amount of 0.019 g/cm2, the others are the same as those in example 37, to obtain the positive electrode plate P45.
The slurry of the positive electrode active material of preparation example 72 is uniformed coated on both sides of the current collector of aluminum foil in a coating amount of 0.019 g/cm2, the others are the same as those in example 37, to obtain the positive electrode plate P46.
The slurry of the positive electrode active material of preparation example 73 is uniformed coated on both sides of the current collector of aluminum foil in a coating amount of 0.019 g/cm2, the others are the same as those in example 37, to obtain the positive electrode plate P47.
The slurry of the positive electrode active material of preparation example 74 is uniformed coated on both sides of the current collector of aluminum foil in a coating amount of 0.019 g/cm2, the others are the same as those in example 37, to obtain the positive electrode plate P48.
The parameters of the above positive electrode plate are shown in Table 4.
A negative electrode active material of artificial graphite, a conductive agent of superconducting carbon black (Super-P), a binder of styrene butadiene rubber (SBR) and a thickening agent of 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 of copper foil with a thickness of 6 m, and then baked at 100° C. for 4 h for drying, followed by roll pressing to obtain the negative electrode plate with a compacted density of 1.75 g/cm3.
A polypropylene film is used.
Ethylene carbonate, dimethyl carbonate and 1,2-propylene glycol carbonate are mixed in a volume ratio of 1:1:1, and then LiPF6 is uniformly dissolved in the above solution to obtain an electrolyte solution. In the electrolyte solution, the concentration of LiPF6 is 1 mol/L.
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 full battery accordingly. Herein, the structure of the batteries made of the positive electrode plates P1, P2, P3, P8, P10, P11, P12, P17, P18, P23, P24, P26, and P27 is shown in
The above positive electrode plate, negative electrode plate and electrolyte solution are assembled together into a button battery in a button battery box.
A spherical aberration electron microscope (ACSTEM) is used to characterize the internal microstructure and surface structure of the positive electrode active material with high spatial resolution, combined with three-dimensional reconstruction technology to obtain the chemical formula of the positive electrode active material.
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 can be obtained directly from XRD refinement results).
The positive electrode active material sample is made into a positive electrode plate according to the method for preparing the positive electrode plate P1, and then same is made into a button battery according to the above “Preparation of button battery”, and the button battery is charged at a small rate of 0.05C until the current is reduced to 0.01C. 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. Sampling was performed, and a lattice constant 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 of the sample before and after complete lithium de-intercalation.
The XRD results determined in the “Method for determining 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 determining 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.
5 g of positive electrode active material sample is made into a positive electrode plate according to the method for preparing the positive electrode plate P1, and then same is made into a button battery according to the above “Preparation of button battery”. The button battery is charged at a small rate of 0.05C until the current is reduced to 0.01C. 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 determined by electron energy loss spectroscopy (EELS, instrument model used: Talos 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.
5 g of positive electrode active material powder 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 3T is exerted, the thickness (after pressure relief) of the powder under pressure is read from the instrument, and a compacted density is calculated through ρ=m/v.
6. Method for Measuring Dissolution of Mn (and Fe Doping on Mn Position) after Cycling
The positive electrode active material sample is made into a positive electrode plate according to the method for preparing the positive electrode plate P1, and then same is made into a full battery according to the above “Preparation of full battery”.
A full battery after cycling to 80% attenuated capacity at 45° C. is discharged to a cut-off voltage of 2.0 V at a rate of 0.1C. 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 on the Mn position) after cycling is calculated. The testing standard is in accordance with EPA-6010D-2014.
At 2.5 to 4.3 V, a button battery is charged at 0.1C 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 0.1C to 2.0 V; and the discharge capacity at this moment is the initial gram capacity, marked as DO.
In a constant-temperature environment at 25° C., a fresh full battery is allowed to stand for 5 min, and discharged at 1/3C 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 C0. The full battery is discharged at ⅓C to 2.5 V, allowed to stand for 5 min, then charged at 3C to 4.3 V, and allowed to stand for 5 min, and the charge capacity at this moment is recorded as C1. The 3C charge constant current rate is C1/C0×100%.
A higher 3C charge constant current rate indicates a better rate performance of the battery.
In a constant-temperature environment at 45° C., at 2.5 to 4.3 V, a full battery is charged at 1C 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 then discharged at 1C to 2.5V, and the discharge capacity at this moment is recorded as DO. The above-mentioned charge/discharge cycle is repeated until the discharge capacity is reduced to 80% of D0. The number of cycles experienced by the battery at this moment is recorded.
A full battery with 100% SOC (State of Charge) is stored at 60° C. 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×V displacement).
From the test results of OCV and IMP, the battery of 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 1C 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.
Table 5 shows the compositions of the positive electrode active materials of preparation examples 1-11 and comparative examples 1-8. Table 6 shows the performance data of the positive electrode active materials or button batteries or full batteries of preparation examples 1-11 and comparative examples 1-8 obtained according to the above-mentioned performance testing methods. Table 7 shows the compositions of the positive electrode active materials of preparation examples 12-27. Table 8 shows the performance data of the positive electrode active materials or button batteries or full batteries of preparation examples 12-27 obtained according to the above-mentioned performance testing methods. Table 9 shows the performance data of the positive electrode active materials or button batteries or full batteries of preparation examples 28-41 obtained according to the above-mentioned performance testing methods. Table 10 shows the performance data of the positive electrode active materials or button batteries or full batteries of preparation examples 42-54 obtained according to the above-mentioned performance testing methods.
It can be seen from Tables 6, 8, 9 and 10 above that, the positive electrode active materials of the preparation 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 preparation examples 18-20 and 23-25, 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.
The following tests are carried out on the secondary batteries made of positive electrode plates P2-P48:
The results are shown in Table 11.
It can be seen from the above results that:
The above shows that the secondary battery made of the positive electrode plate of the present application has higher energy density, better dynamic performance, better cell rate performance, longer low-temperature cycle life, higher low-temperature cycle capacity retention rate 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.
This application is a continuation of International Application PCT/CN2022/084258, filed Mar. 31, 2022 and entitled “POSITIVE ELECTRODE PLATE, SECONDARY BATTERY, BATTERY MODULE, BATTERY PACK, AND POWER CONSUMING DEVICE”, which is incorporated herein by reference in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/CN2022/084258 | Mar 2022 | US |
| Child | 18350756 | US |
