Patent Application
20250171304
The present application relates to a technical field of lithium batteries, and in particular to a positive electrode composite material and a preparation method and application thereof.
In recent years, with the rapid development of new energy technologies, the research and development of power batteries has been in full swing, and the research and development of power batteries is gradually focused on the development of high-energy-density battery materials. Although ternary materials have excellent high specific capacity, there are certain concerns about the safety of ternary lithium batteries. However, although the material represented by lithium iron phosphate is structurally stable and the lithium iron phosphate battery has better safety, the lower specific energy of the material leads to a shorter driving range of the passenger vehicle using the lithium iron phosphate batteries, which cannot meet the travel requirements of people. Therefore, there is an urgent need to find a new type of lithium battery material which can take into account both high energy density and safety.
Both lithium manganese iron phosphate and lithium iron phosphate are of an olivine-type structure, and have excellent thermodynamic stability, so that the lithium manganese iron phosphate battery has a safety similar to that of the lithium iron phosphate battery, and the lithium manganese iron phosphate battery has an energy density similar to that of the ternary lithium battery. Therefore, the lithium manganese iron phosphate can be used as a material for the development of lithium batteries with both high energy density and high safety performance.
However, it should be noted that, compared with a transition energy gap of 0.3 eV in the lithium iron phosphate, the energy gap of electron transition in the lithium manganese iron phosphate is as high as 2 eV, and thus the lithium manganese iron phosphate is basically an insulator and has the disadvantages of low electron conductivity and low ion mobility. Moreover, the dissolution of the manganese element of the lithium manganese iron phosphate may appear during the cycle of the battery, resulting in a decrease in the structural stability of the lithium manganese iron phosphate, which directly limits the development and application of the lithium manganese iron phosphate battery.
In order to improve the electrical conductivity and structural stability of the lithium manganese iron phosphate material, the present application provides a positive electrode composite material and a preparation method and application thereof.
In a first aspect, the present disclosure provides a positive electrode composite material including a nano lithium manganese iron phosphate material, a first cladding layer coated on a surface of the nano lithium manganese iron phosphate material, and a second cladding layer coated on a surface of the first cladding layer;
the first cladding layer includes a nano ternary active material and the second cladding layer is a carbon cladding layer.
In a second aspect, the present disclosure provides a method of preparing a positive electrode composite material.
The method of preparing the positive electrode composite material including following steps.
In Step 1, an iron source, a first manganese source, and a first lithium source are added to a first aqueous solvent in a stirring state to form a first mixture, then a phosphorus source is added to the first mixture, after stirring and dissolving, a hydrothermal reaction is performed to obtain a nano lithium manganese iron phosphate material.
In Step 2, a nickel source, a second manganese source, a cobalt source, a second lithium source, and an ammonium salt are mixed with a second aqueous solvent, a second mixture is formed after stirring and dissolving, the nano lithium manganese iron phosphate material is mixed with the second mixture, an annealing process is performed after a hydrothermal reaction of the second mixture to form a first cladding layer on a surface of the nano lithium manganese iron phosphate material.
In Step 3, the nano lithium manganese iron phosphate material on the surface of which the first cladding layer are formed obtained in Step 2 is mixed with an organic carbon source solution, the nano lithium manganese iron phosphate material is taken out, an annealing treatment is performed after a drying treatment to obtain the positive electrode composite material.
In a third aspect, the present disclosure provides a positive electrode plate including a positive current collector and a positive electrode material layer disposed on a surface of the positive current collector, the positive electrode material layer includes a conductive agent, a binder, and the positive electrode composite material as described above.
In a fourth aspect, the present disclosure provides a lithium ion battery including a positive electrode plate as described above.
Unless otherwise indicated, all numbers used in the specification and claims to indicate quantities of components, reaction conditions, and the like are to be understood as being modified by the term “about. Thus, unless indicated to the contrary, the numerical parameters set forth herein are approximations that can vary depending on the desired properties that are obtained.
As used herein, the term “and/or” refers to one or all of the elements mentioned.
As used herein, the terms “comprise/comprising” and “include/including” cover a situation where only the elements mentioned are included and a situation where there are other elements that are not mentioned in addition to the elements mentioned.
All percentages used herein are percentages by weight, unless otherwise indicated.
As used in this specification, “a,” “an,” and “the” are intended to include “at least one” or “one or more” unless otherwise indicated. For example, “a component” refers to one or more components, and therefore more than one component may be contemplated and may be employed or used in the practice of the embodiments.
In an embodiment, a positive electrode composite material includes a nano lithium manganese iron phosphate material, a first cladding layer coated on a surface of the nano lithium manganese iron phosphate material, and a second cladding layer coated on a surface of the first cladding layer. Thickness of the first cladding layer ranges from 1/20 to 1/10 of a particle size D50 of the nano lithium manganese iron phosphate material. The term “D50” refers to a particle size corresponding to when a volume distribution percentage of a cumulative particle size of a sample reaches 50%. Its physical meaning is that 50% of the particles are larger than it, and 50% of the particles are smaller than it. D50 is also called the median diameter or median diameter.
In an embodiment, thickness of the second cladding layer ranges from 1/800 to 1/500 of the particle size D50 of the nano lithium manganese iron phosphate material.
By adjusting the thicknesses of the first cladding layer and the second cladding layer, the carbon cladding layer, the phase separation at the two-phase interfaces between the carbon cladding layer, the first cladding layer and the lithium manganese iron phosphate material will not occur while effectively cladding the nano lithium manganese iron phosphate material. The thickness enables the positive electrode composite material to have better structural stability, higher ionic conductivity, and higher electron conductivity, thereby improving the conductivity of the positive electrode composite material.
In an embodiment, the nano lithium manganese iron phosphate material has a particle size D50 of 600-1200 nm.
By controlling the particle size of the nano lithium manganese iron phosphate material, the thickness of the first cladding layer and the second cladding layer can be controlled within a reasonable range, so that the particle size of the final prepared positive electrode composite material is not too small or too large, and thus it has higher structural stability.
In an embodiment, the nano-ternary active material is a high nickel nano-ternary active material, a mole fraction of nickel in the high nickel nano-ternary active material ranges from 0.8 to 0.9.
By controlling the mole fraction of nickel in the high-nickel nano-ternary active material, the specific capacity of the positive electrode plate using the positive electrode composite material is increased, and the energy density of the lithium manganese iron phosphate battery is increased.
In an embodiment, the carbon cladding layer includes a carbon material selected from an organic carbon source, the organic carbon source is selected from at least one of glucose, sucrose, soluble starch, citric acid, β-cyclodextrin, or polyvinyl alcohol.
The positive electrode composite material has a specific surface area of 20-25 m2/g.
By controlling the specific surface area of the positive electrode composite material, the positive electrode composite material can have a better bonding property with the material such as a binder, a conductive agent, and the like, in the positive electrode plate, which is favorable for obtaining excellent conductive performance and cycling performance of the lithium battery.
In an embodiment, in a step one of a method of preparing the positive electrode composite material, a mass ratio of an iron source, a first manganese source, a first lithium source, and a phosphorus source is 25-29:16-18:6-10:10-15; and in the step one, a temperature for a hydrothermal synthesis ranges from 85° C. to 95° C., and time for the hydrothermal reaction ranges from 220 min to 260 min.
In an embodiment, in the step one, the iron source includes at least one of FeSO4, FeCl2, FeC2O4·2H2O, Fe(OH)3, or Fe(NO3)3; the first manganese source includes at least one of MnSO4, MnCO3, or MnCl2; the first lithium source includes at least one of Li2CO3, LiOH, or LiCl; the phosphorus source includes at least one of H3PO4, H3PO3, or LiH2PO4, the phosphoric acid refers to an aqueous solution of phosphoric acid with a mass concentration of 60%-85%; and the first aqueous solvent is water or an aqueous solution containing an ion or an organic solvent.
In an embodiment, in a step two, the mass ratio of the nickel source, the second manganese source, the cobalt source, the second lithium source, and the ammonium salt is 450-650:20-60:40-100:150-260:20-50; in step two, the temperature for the hydrothermal synthesis ranges from 110° C. to 130° C., and the time for the hydrothermal reaction ranges from 340 min to 380 min; and in the step two, a temperature for an annealing treatment ranges from 500° C. to 600° C., and annealing time ranges from 10 h to 14 h.
In an embodiment, in step two, the nickel source includes at least one of NiSO4, Ni(OH)2, or Ni(NO3)2; the second manganese source includes at least one of MnSO4, MnCO3, or MnCl2; the cobalt source includes at least one of Co(NO3)2, CoSO4, or CoCl2; the second lithium source includes at least one of Li2CO3, LiOH, or LiCl; the ammonium salt includes NH4F; and the second aqueous solvent is water or an aqueous solution containing an ion or an organic solvent.
In an embodiment, in a step three, a concentration of the organic carbon source solution ranges from 0.01 mol/L to 0.02 mol/L; and in step three, a temperature for the annealing treatment ranges from 700° C. to 800° C., and an annealing time ranges from 7 h to 9 h.
A highly dispersed nano lithium manganese iron phosphate material having a uniform precursor morphology is prepared by a hydrothermal reaction, so that a nucleation time window can be reduced, the synthesized nano lithium manganese iron phosphate material is uniformly suspended and dispersed in a solution, and nucleation sites are increased, thereby obtaining a positive electrode composite material having excellent cladding performance of the first cladding layer and the second cladding layer.
The positive electrode composite material, conductive carbon black (super pll, SP), polyvinylidene fluoride (PVDF), and carbon nanotube (CNT) were mixed and stirred at a mass ratio of 96.5:0.9:2:0.6 with N-methylpyrrolidone (NMP) as a solvent, so as to obtain a positive electrode slurry. The positive electrode slurry was uniformly coated on a carbon-coated aluminum foil with a thickness of 12 m, and then a drying process was performed at 90° C. to obtain a dried positive electrode plate.
Artificial graphite, SP, carboxymethyl cellulose (CMC) and styrene-butadiene rubber (SBR) were mixed and stirred at a mass ratio of 95.5:2:0.5:2 with deionized water as a solvent, so as to obtain a negative electrode slurry. The negative electrode slurry was then coated on a copper foil with a thickness of 8 m, and a vacuum drying process was performed on the electrode plate at 100° C.
The electrolyte solution was prepared in a glove box filled with argon gas, and in the glove box, the water content was less than 10 ppm and the oxygen content was less than 1 ppm. The electrolyte solution was prepared through following steps: ethylene carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC) with a volume ratio of 30:40:30 were used to prepare the electrolyte solution including LiPF6 and lithium bis(fluorosulfonyl)imide (LFSI) (LiPF6:LFSI=1.1:0.1 (molar ratio)) which have a concentration of 1.2 mol/L, and then additive vinylene carbonate (VC) of 0.5 wt %, fluoroethylene carbonate (FEC) of 1.5 wt %, 0.5 wt % of ethylene sulfate (DTD), and 0.5 wt % of LiPO2F2 were added and mixed homogeneously for later use.
The vacuum-dried positive and negative electrode plates and the separator were punched and then assembled into a CR2032 button cell in a glove box filled with argon gas.
DCIR data of the lithium battery in the example is shown in
The preparation of the positive electrode plate was the same as in Example 1.
The preparation of the negative electrode plate was the same as in Example 1.
The preparation of the lithium ion battery was the same as that of the lithium battery in Example 1.
The preparation of the positive electrode plate was the same as in Example 1.
The preparation of the negative electrode plate was the same as in Example 1.
The preparation of the lithium ion battery was the same as that of the lithium battery in Example 1.
This example differs from Example 1 in that: the thickness of the first cladding layer in the positive electrode composite material is 1/25 of the particle size of the nano lithium manganese iron phosphate material; the thickness of the second cladding layer is 1/300 of the particle size of the nano lithium manganese iron phosphate material; and specifically, in steps 2 and 3, steps of preparing the positive electrode composite material using the nano lithium manganese iron phosphate are as follows:
The rest of the example is consistent with Example 1.
This example differs from Example 1 in that: the thickness of the first cladding layer in the positive electrode composite material is ⅕ of the particle size of the nano lithium manganese iron phosphate material; the thickness of the second cladding layer is 1/1000 of the particle size of the 1 nano lithium manganese iron phosphate material; and specifically, in steps 2 and 3, steps of preparing the positive electrode composite material using the nano lithium manganese iron phosphate are as follows:
This example differs from Example 1 in that the nano lithium manganese iron phosphate material prepared in Step 1 has a particle size D50 of 400 nm, and specifically, the step of preparing the nano lithium manganese iron phosphate material in Step 1 is as follows:
Finally, a positive electrode composite material having a specific surface area of 13 m2/g was prepared; and the rest of the example is consistent with Example 1.
This example differs from Example 1 in that the nano lithium manganese iron phosphate material prepared in Step 1 has a particle size D50 of 1500 nm. Specifically, the step of preparing the nano lithium manganese iron phosphate material in Step 1 is as follows:
Finally, a positive electrode composite material having a specific surface area of 10 m2/g was prepared; and the rest of the example is consistent with Example 1.
This comparative example differs from Example 1 in the preparation of the positive electrode composite material, which was prepared by the following steps:
The rest of the comparative example is consistent with Example 1.
The DCIR data of the lithium battery in the comparative example is shown in
This comparative example differs from Example 1 in the preparation of the positive electrode composite material, the step 3 is omitted during the preparation of the positive electrode composite material, and the rest of the comparative example is consistent with Example 1.
The DCIR data of the lithium battery in the comparative example is shown in
This comparative example differs from Example 1 in the preparation of the positive electrode composite material, which was prepared by the following steps:
The rest of the comparative example is consistent with Example 1.
The DCIR data of the lithium battery in the comparative example is shown in
The DCIR test was carried out on the lithium ion batteries of Examples 1 to 7 and Comparative Examples 1 to 3, and the testing method was as follows: a capacity calibration was carried out on the lithium battery at 25° C. under 1C, the state of charge capacity (SOC) was adjusted to 50%, then at SOC of 50%, all of the cells were discharged at 1C for 30 s (second), the discharging DCIR was calculated, and the test results are shown in
The lithium ion batteries of Examples 1 to 7 and Comparative Examples 1 to 3 were subjected to a discharging test at 25° C. under 5C rate, with a charge-discharge voltage in the range of 2.5 V-4.25 V, and specific test results are shown in
The lithium-ion batteries of Examples 1 to 7 and Comparative Examples 1 to 3 were subjected to a cycle performance test, and a specific test method was as follows: after the lithium battery was put on hold at 25° C. for 1 h, a cycle test was carried out with 3C step fast charge and 1C discharge, a charge-discharge voltage was in a range of 2.5 V-4.25 V, a capacity retention rate and a DCIR change rate were calculated, wherein DCIR increase rate=(DCIR for 500th cycle−initial DCIR)×100%/initial DCIR, and capacity retention rate=discharge capacity for 500th cycle×100%/initial discharge capacity; and the test results are shown in Table 1.
In combination with Examples 1-3, Comparative Examples 1-3,
With reference to Example 1, Examples 4 to 5, and Table 1, it can be seen that when the thicknesses of the first cladding layer and the second cladding layer are selected to be too large or too small, it is not conducive to the bonding stability between the carbon cladding layer, the first cladding layer, and the lithium manganese iron phosphate material, thereby negatively affecting the conductivity of the positive electrode composite material.
In combination with Example 1, Examples 6 to 7, and Table 1, it can be seen that when the particle size of the nano lithium manganese iron phosphate material is too high or too low, the specific surface area of the nano lithium manganese iron phosphate material is affected, which is not conducive to the formation of the first cladding layer with a suitable thickness on the surface of the lithium manganese iron phosphate material through the nano ternary active material, but also affects the further cladding of the second cladding layer, thereby not conducive to the formation of the positive electrode composite material with a suitable specific surface area. When the specific surface area of the positive electrode composite material is too small, the battery is high in battery internal resistance, low in discharge platform, low in capacity, poor in rate performance, and poor in cycle performance after the positive electrode composite material is applied in the positive electrode plate. When the specific surface area of the positive electrode composite material is too large, the positive electrode composite material is high in activity, easy to agglomerate, difficult to disperse, and difficult to process.
In an embodiment of the present disclosure, by nanocrystallizing the lithium manganese iron phosphate material, it is possible to provide more electrochemical reaction regions and shorter ion transport paths, improve the specific capacity of the material, reduce the degree of damage of the structure during charging and discharging so as to reduce the degree of attenuation of the specific capacity, overcome the problem of poor conductivity of the pure lithium manganese iron phosphate material, and improve the rate performance of the material.
In an embodiment of the present disclosure, it is possible to improve a degree of bonding of the lithium manganese iron phosphate material with the nano ternary active material during the coating process, and obtain a first cladding layer with excellent coating effect, so that the ternary active material forming the first cladding layer has a more complete layered structure, and the more complete the layered structure, the better the stability of the first cladding layer is, so as to improve cycle performance and safety performance of the positive electrode composite material.
In an embodiment of the present disclosure, the presence of the first cladding layer can increase the content of the deintercalable lithium ions in the positive electrode material and further increase the specific capacity of the positive electrode composite material, and the nano ternary active material in the first cladding layer and the lithium manganese iron phosphate material may complement each other in terms of performance and have a synergistic effect, thereby further improving the conductivity and the structural stability of the lithium manganese iron phosphate material.
In an embodiment of the present disclosure, a carbon material is introduced into the nano ternary active material of the first cladding layer to form a second cladding layer, so that the carbon material has good conductivity and stability, which is conducive to reducing the internal resistance, improving the charge transport capacity, and further improving the rate performance and the cycle stability of the lithium manganese iron phosphate material.
In an embodiment of the present disclosure, the presence of the second cladding layer and the first cladding layer can also effectively prevent the lithium manganese iron phosphate material from coming into direct contact with the electrolyte solution during the battery cycle, and avoid manganese dissolution of the lithium manganese iron phosphate material, so that the positive electrode composite material has high structural stability, thereby improving the cycle performance thereof.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202311581318.9 | Nov 2023 | CN | national |
| PCT/CN2024/070572 | Jan 2024 | WO | international |
This application claims priorities to Chinese Patent Application No. 202311581318.9, filed in the China National Intellectual Property Administration on Nov. 23, 2023, and to International Patent Application No. PCT/CN2024/070572 filed on Jan. 4, 2024, the disclosure of which is incorporated herein by reference in their entirety.
