CN112349905A - Double-coating modified lithium ion battery positive electrode material and preparation method thereof - Google Patents

Double-coating modified lithium ion battery positive electrode material and preparation method thereof Download PDF

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CN112349905A
CN112349905A CN201910720803.7A CN201910720803A CN112349905A CN 112349905 A CN112349905 A CN 112349905A CN 201910720803 A CN201910720803 A CN 201910720803A CN 112349905 A CN112349905 A CN 112349905A
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coating
positive electrode
electrode material
layer
lithium
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CN112349905B (en
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刘瑞福
郑斌
唐波
韩圭奭
石慧
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BASF Shanshan Battery Materials Co Ltd
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Hunan Shanshan New Energy Co ltd
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Abstract

The invention discloses a double-coating modified lithium ion battery anode material, which comprises an anode material substrate, a first coating coated on the surface of the substrate and a second coating coated on the surface of the first coating; wherein the first coating layer is a nano-sheet fast ion conductor layer; the second cladding layer is an Al compound layer. The double-layer surface-coated anode material is prepared by coating the nanosheet-shaped fast ion conductor layer firstly and then coating the aluminum-containing compound outer layer, and due to the barrier effect of the nanosheet-shaped fast ion conductor layer, the aluminum compound on the outer layer cannot diffuse into the transition metal layer in the material crystal lattice, so that the aluminum oxide coating layer which is favorable for the stability of the material interface is formed on the surface of the material; meanwhile, the dissolution of transition metal elements of the material and elements such as tungsten, molybdenum, vanadium and the like in the coating in the electrolyte is reduced, the surface structure of the material is effectively stabilized, and the interface side reaction of the material and the electrolyte is reduced.

Description

Double-coating modified lithium ion battery positive electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium ion battery anode material with a surface modified by a double coating layer and a preparation method thereof.
Background
Along with the increase of the nickel content, the surface of the high-nickel material becomes more fragile and easy to absorb moisture and carbon dioxide in the air to form Li2CO3And LiOH residual lithium exists on the surface of the material, the higher residual lithium can cause the processing performance of a battery pole piece to be poor, and the gas production behavior also exists in the recycling process of the lithium ion battery. Meanwhile, as long-cycle progress, the stability of the surface structure of the high-nickel material is also deteriorated, and structural transformation from a layered structure to spinel to a NiO rock-salt phase occurs on the surface of the material. When lithium ions are repeatedly deintercalated, intergranular and intragranular cracks are generated inside the material due to the anisotropy of crystals, and the electrolyte easily enters the inside of secondary particles of the material and erodes the surface of primary particles to generate various side reactions. These factors all deteriorate various performances of the lithium ion battery such as capacity, cycle and rate. Therefore, reduction of residual lithium on the surface of the material and improvement of the structural stability of the surface have been important research subjects for a high nickel layered positive electrode material. Surface coating of high nickel layered cathode materials is a common modification means, such as coating lithium transition metal oxide (Li)2ZrO3，LiAlO2And Li2WO4Etc.) and non-electrochemically active inorganic metal oxides or fluorides (Al)2O3MgO and AlF3Etc.).
Usually, Al2O3The coating is to improve the layered lithium transition metal oxide positive electrodeThe surface structure stability of the material and the effective method for reducing the interface side reaction between the material and the electrolyte. In the non-patent literature (Binghong Han, Baris Key, Saul H.Lapidus, Juan C.Garcia, Hakim Iddir, John T.Vaughey, and Fulya Dogan, Applied materials&Interfaces (47)2017:41291-41302) proves that the transition metal component composition of the layered cathode material can influence Al2O3Coating reaction on the surface of the material. The reduction of the content of transition metal Mn in the material can promote Al element to diffuse into the structure of the material, and for Al2O3The coated NMC532 material does not have any transition metal layer for Al element entering crystal lattice, but for Al2O3The NMC622 and NMC811 materials with lower Mn content are coated, Al element is found in a transition metal layer of crystal lattices after high-temperature sintering, and the Al content in the NMC811 material is higher. For high nickel layered cathode materials, Al2O3The coating can severely weaken its coating effect and even lead to poorer capacity and cycle performance. Therefore, for the high nickel layered lithium ion battery anode material, Al is directly carried out2O3Coating is not feasible.
For the layered cathode material coated with lithium transition metal oxide, tungsten coating can only realize low resistance of the material to improve the capacity and rate capability of the material, and a uniform and compact coating film cannot be formed on the surface of the material. Non-patent literature (XinheYang, Zicheng Zuo, Haiyan Wang, Quanbin Chen, Hui Zhang, Zhenlei Huang, Borng Wu, Henghui Zhuo, Electrochimica Acta (180)2015:604-609) proves that the tungsten element of the coating layer can be dissolved out in the electrolyte and enriched in the graphite negative electrode, so that the cycle performance is poor.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings in the background art and provide a double-coating modified lithium ion battery positive electrode material which simultaneously shows high capacity, long cycle and high rate characteristics and a preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a double-coating modified lithium ion battery anode material comprises an anode material substrate, a first coating coated on the surface of the substrate and a second coating coated on the surface of the first coating; wherein the first coating layer is a nano-sheet fast ion conductor layer; the second cladding layer is an Al compound layer.
Preferably, the fast ion conductor is at least one of lithium tungstate, lithium molybdate and lithium vanadate; the Al compound is LiAlO2And Al2O3At least one of (1).
In the above cathode material, preferably, the mass of the tungsten, molybdenum or vanadium element in the fast ion conductor layer accounts for 0.02-0.5% of the mass of the cathode material substrate, and the mass of the aluminum atom in the Al compound layer accounts for 0.02-0.2% of the mass of the cathode material substrate.
Preferably, the molecular formula of the matrix of the cathode material is LiuNi(1-x-y-z)CoxMnyMzO2Wherein u is more than or equal to 0.9 and less than or equal to 1.20 and 0<x≤0.20，0<y≤0.20，0<z is less than or equal to 0.05, M is a doping element, and M is at least one element of Al, Mg, Ti, Zr, V, B, La, Y, Cr, Mo, Ca, Fe, Hf, Zn, Si, W, Nb and Sm.
As a general inventive concept, the present invention also provides a method for preparing the above-mentioned cathode material, comprising the steps of:
(1) adding the positive electrode material matrix into water, and stirring to form uniform slurry A;
adding tungsten ammonium salt, molybdenum ammonium salt or vanadium ammonium salt into water (20-60 ℃) and stirring to form uniform solution B;
adding the solution B and the citric acid solution into the slurry A, uniformly stirring, and heating the mixture to evaporate water until viscous gel appears; drying and dehydrating the gel slurry to obtain a nano flaky fast ion conductor coated positive electrode material;
(2) and (2) mixing the nano flaky fast ion conductor coated positive electrode material prepared in the step (1) with an aluminum compound, sintering at a constant temperature of 500-700 ℃ for 3-10 h, crushing and screening to obtain the double coated layer modified lithium ion battery positive electrode material.
The effect of the aluminum oxide coating at low temperature (450 ℃) is not ideal, which causes the increase of the internal resistance and electrochemical polarization of the material, while the single aluminum oxide coating at high temperature (500-2、Al2O3The second coating layer is mainly used for stabilizing the surface structure of the material and further improving various properties of the material.
In the above preparation method, preferably, the positive electrode material matrix in step (1) is obtained by the following preparation method:
mixing Ni(1-x-y-z)CoxMny(OH)2Uniformly mixing the precursor with a lithium source and a compound containing M, sintering at a constant temperature of 600-900 ℃ for 5-20 h in an oxygen atmosphere, crushing, and screening to obtain a positive electrode material matrix; wherein the lithium source is at least one of lithium hydroxide, lithium carbonate and lithium nitrate; the M-containing compound is at least one of an oxide, an ammonium salt, a sulfate, a carbonate, a nitrate and an organic metal compound of M; M/(Ni + Co + Mn + M) is 0.1-2.0%.
In the above preparation method, preferably, in the slurry a, the mass ratio of water to the positive electrode material substrate is (0.4 to 1.0): 1. if the water amount is large, the surface state of the material is influenced, the electrochemical performance of the material is further deteriorated, the subsequent water evaporation time is too long, and the production efficiency is not facilitated; if the water content is low, the material and the water cannot form uniform slurry, the material and the water cannot be fully stirred to enable a gel layer to be uniformly dispersed on the surface of a core matrix material, and the wet coating process is difficult to carry out; therefore, controlling the amount of water within the scope of the present invention can optimally ensure the properties of the material.
In the above preparation method, the ratio of the molar weight of the citric acid to the molar weight of the fast ion conductor is preferably (1.0-4.0): 1. The generated coating is too fine, loose and dispersed due to the excessive consumption of the citric acid, and a uniform and compact coating layer cannot be formed on the surface of the material; if the consumption of the citric acid is too small, the citric acid does not have enough dispersion effect, stable gel is not easy to form on the surface of the core matrix material, and the formed coating material is easy to agglomerate and is not in a dispersed nano flake shape; therefore, the control of the dosage of the citric acid in the invention can not only ensure the uniform compactness of the coating layer, but also ensure that the coating layer is in a nano-flake shape.
In the above-mentioned preparation method, preferably, the aluminum compound is Al2O3、AlOOH、Al(OH)3And LiAlO2At least one of; the average particle size D50 is 0.1-20 microns.
In the preparation method, preferably, in the step (1), the heating temperature is 70-100 ℃; the drying temperature is 80-280 ℃, and the drying time is 2-10 h.
Compared with the prior art, the invention has the advantages that:
(1) the double-layer surface-coated anode material is prepared by coating the nanosheet-shaped fast ion conductor layer firstly and then coating the aluminum-containing compound outer layer, and due to the barrier effect of the nanosheet-shaped fast ion conductor layer, the aluminum compound on the outer layer cannot diffuse into the transition metal layer in the material crystal lattice, so that the aluminum oxide coating layer which is favorable for the stability of the material interface is formed on the surface of the material; meanwhile, the dissolution of transition metal elements of the material and elements such as tungsten, molybdenum, vanadium and the like in the coating in the electrolyte is reduced, the surface structure of the material is effectively stabilized, and the interface side reaction of the material and the electrolyte is reduced.
(2) In the preparation method, no extra lithium source (lithium hydroxide, lithium carbonate or other substances) is added in the wet coating stage or the dry aluminum coating stage, and the final double-layer coating substances mainly comprise lithium tungstate (lithium molybdate or lithium vanadate) and lithium metaaluminate, so that residual lithium on the surface (Li) is consumed while coating is performed in the method2CO3And LiOH and other compounds) to reduce the residual lithium on the surface of the material and the pH value, thereby improving the manufacturing and processing of the pole piecePerformance and reduced gas production behavior of lithium ion batteries.
(3) According to the invention, chelating agent citric acid is added in the preparation stage of the fast ion conductor coating layer, so that the coating particles are uniformly dispersed, and the agglomeration in the heating process is reduced, thereby forming uniform nano flaky coatings on the surface of primary particles of the anode material matrix and among the primary particles.
(4) According to the double-coating modified lithium ion battery anode material, the first coating has the functions of capacity and rate improvement, and the effect of weakening the diffusion dynamic behavior of Al element in the second coating; therefore, the fast ion conductor coating and the aluminum coating are combined together, so that the defect of a single fast ion conductor is overcome, and the fast ion conductor coating and the aluminum coating have a mutual synergistic effect, so that the high-capacity, long-cycle and high-rate characteristic performance of the anode material is further improved.
In conclusion, the lithium ion battery anode material is surface modified by the double coating layer, so that the excellent electrochemical properties of the anode material such as specific capacity, cycle and multiplying power are finally ensured.
Drawings
FIG. 1 is a FEI-SEM photograph of a material prepared in comparative example 1 of the present invention.
FIG. 2 is a FEI-SEM photograph of a material prepared in comparative example 2 of the present invention.
FIG. 3 is a FEI-SEM photograph of the material prepared in example 1 of the present invention.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
a double-layer coated modified lithium ion battery anode material comprises an anode material matrix Li1.02Ni0.87Co0.10Mn0.02Al0.01O2A first coating layer (nano flaky lithium tungstate) coated on the surface of the substrate and a second coating layer (aluminum compound layer, LiAlO)2Mainly contains partial Al2O3) (ii) a Wherein, the tungsten element accounts for 0.12 percent of the mass of the matrix of the anode material, and the aluminum element accounts for 0.12 percent of the mass of the matrix of the anode material. The preparation method of the double-coating modified lithium ion battery cathode material comprises the following steps:
(1) preparing a base material:
500g of Ni are weighed0.88Co0.10Mn0.02(OH)2Uniformly mixing the precursor, 230.8g of LiOH and 4.2g of nano aluminum hydroxide, sintering the mixed material at the constant temperature of 750 ℃ for 13h in an oxygen atmosphere (the oxygen flow is 40L/min), cooling, sieving by a 300-mesh sieve to obtain a lithium transition metal oxide matrix of the positive electrode material, and performing ICP (inductively coupled plasma) test to obtain the lithium transition metal oxide with the molecular formula of Li1.02Ni0.87Co0.10Mn0.02Al0.01O2。
(2) Nano-sheet-like fast ion conductor coating matrix material
Taking 400g of the anode material matrix prepared in the step (1), adding the matrix into 200g of deionized water, and stirring to disperse the matrix material in the water to form uniform slurry A;
3.35g of ammonium metatungstate ((NH) was weighed out4)6H2W12O40·xH2O) (the mass ratio of the tungsten element to the positive electrode material substrate is 0.12%) is added into 50mL of deionized water, and the mixture is stirred at 50 ℃ to fully dissolve ammonium metatungstate to form a solution B;
10mL of solution B and 20mL of citric acid solution (1.4g of citric acid monohydrate (C)6H8O7·H2O) 20mL of deionized water was addedThe solution formed in (1) was added to the slurry a and stirred continuously for 10 min; and heating the obtained slurry, keeping the temperature of the slurry at 80 ℃, slowly evaporating water until the slurry becomes viscous, then placing the viscous slurry in an oven for dehydration, keeping the drying process in a vacuum state, keeping the drying temperature at 130 ℃, and drying for 4 hours to obtain the nano flaky lithium tungstate coated base material.
(3) Double-coating modified lithium ion battery anode material
1.3g of nano-sized aluminum hydroxide (Al (OH)) having an average particle diameter of 2.0 μm3) And (3) uniformly mixing the reagent (the mass ratio of the aluminum element to the matrix of the positive electrode material is 0.12%) with 300g of the material coated in the step (2), sintering at the constant temperature of 650 ℃ for 8h in an oxygen atmosphere (the oxygen flow is 40L/min), and processing the sintered material by using a 300-mesh screen to obtain the final double-coating modified lithium ion battery positive electrode material.
Uniformly mixing the prepared double-coating modified lithium ion battery positive electrode material, conductive carbon black and a binder PVDF according to the mass ratio of 92:5:3, using NMP as a solvent, coating the mixture on an Al foil, drying the mixture at 120 ℃ for 12 hours, rolling and punching the mixture into 12mm round pieces, assembling the round pieces into a CR2032 type button battery in an argon-protected glove box (the oxygen content is less than 1ppm and the moisture is less than 1ppm) by using a metal lithium piece as a negative electrode, and carrying out electrochemical performance test at 25 ℃ under a voltage window of 3.0-4.3V. The specific test system is as follows: 0.1C (corresponding to a current density of 20.8mA/g) charge and 0.1C discharge in week 1; 0.2C charge, 0.2C discharge at week 2; 0.2C charge, 0.5C discharge at week 3; 0.2C charge, 1C discharge on week 4; 0.2C charge, 0.2C discharge at week 5; and 6 th to 55 th weeks, 1C charging and 1C discharging.
Example 2:
the present example differs from example 1 in step (2): 4.42g of ammonium molybdate tetrahydrate (H) are weighed24Mo7N6O24·4H2O) (the mass ratio of the molybdenum element to the positive electrode material substrate is 0.12%) is dissolved in 50mL of deionized water to prepare a solution B; the citric acid solution is prepared by weighing 2.6g citric acid monohydrate (C)6H8O7·H2O) was prepared by adding 20mL of deionized water, and the other process parameters were the same as in example 1.
Example 3
The present example differs from example 1 in step (2): 2.75g of ammonium metavanadate (NH) were weighed out4VO3) (the mass ratio of the vanadium element to the positive electrode material substrate is 0.06%) is dissolved in 50ml of deionized water to prepare a solution B; the citric acid solution is prepared by weighing 2.47g citric acid monohydrate (C)6H8O7·H2O) was added to 20ml of deionized water, and the other process parameters were the same as in example 1.
Comparative example 1:
this comparative example is a lithium transition metal oxide matrix Li of the positive electrode material prepared in the step (1) of example 11.02Ni0.8 7Co0.10Mn0.02Al0.01O2。
Comparative example 2:
the step (1) and the step (2) of the comparative example are completely consistent with the step (1), and the difference is that the step (3) is to sinter the dried matrix material coated with lithium tungstate at a constant temperature of 600 ℃ for 8 hours, and then to filter the sintered material through a 300-mesh sieve to obtain the final material product.
Comparative example 3:
step (1) of this comparative example is identical to example 1. Step (2) is to mix 300g of the base material prepared in step (1) with 1.3g of nanoscale Al (OH)3(the mass ratio of the aluminum element to the matrix of the anode material is 0.12 percent), uniformly mixing, sintering at constant temperature of 650 ℃ for 8 hours at the oxygen flow of 40L/min, and processing the sintered material by a 300-mesh screen to obtain the final finished product material.
Comparative example 4:
steps (1) and (3) of the comparative example are completely the same as example 1; the difference lies in that the preparation method of the step (2) comprises the following steps:
adding 400g of the base material prepared in the step (1) into 200g of deionized water, and stirring to disperse the base material in the water to prepare slurry A; 3.35g of ammonium metatungstate ((NH) was weighed out4)6H2W12O40·xH2O) (the mass ratio of the tungsten element to the matrix of the anode material is 0.12%) is added into 50mL of deionized water, and the mixture is stirred at 50 ℃ to fully dissolve the ammonium metatungstate, so that the anode material is preparedSolution B;
measuring 10mL of solution B, adding the solution B into the completely dispersed slurry A, heating and keeping the temperature of the slurry at 80 ℃ to slowly evaporate water until the slurry becomes viscous; and placing the obtained slurry in an oven for dehydration, wherein the drying process is kept in a vacuum state, the drying temperature is 130 ℃, and the drying time is 4 hours, so that the lithium tungstate coated high-nickel layered cathode material is obtained.
Comparative example 5:
steps (1) and (2) of this comparative example were completely the same as those of example 1 except that step (3):
1.3g of nano-sized aluminum hydroxide (Al (OH)3) Uniformly mixing a reagent (the mass ratio of the aluminum element to the matrix of the anode material is 0.12%) with 300g of the material coated in the step (2), sintering at the constant temperature of 450 ℃ for 8h at the oxygen flow of 40L/min, processing the sintered material by a 300-mesh screen to obtain the final finished anode material, and simultaneously carrying out residual lithium test and electrochemical performance evaluation on the material.
Electrochemical data of the button cell assembled by the materials obtained in the above examples and comparative examples, such as 0.1C specific discharge capacity, 0.2C specific discharge capacity, 0.5C specific discharge capacity, 1C specific discharge capacity, 50-cycle capacity retention rate (ratio of 55-cycle specific discharge capacity to 6-cycle specific discharge capacity), and the like, and surface residual lithium data of the materials are shown in table 1.
TABLE 1 electrochemical data of each example and comparative example and surface residual lithium data of materials
Figure BDA0002157126380000061
Figure BDA0002157126380000071
As can be seen from the data in Table 1, in comparison with the example 1 and the comparative example 4, after citric acid is added in the transition layer coating, the double-layer coating effect is better, and the material has better electrochemical performance; comparing example 1 with comparative example 5, it is shown that tungsten and aluminum cladding have desirable effects at high temperatures, which are otherwise undesirableThe Al is promoted to enter the crystal lattice of the material, and the advantages of the double-layer coating modification method are further illustrated. The coated material surface Li was compared with the primary sintered material of comparative example 12CO3And the LiOH content is obviously reduced, the manufacturing and processing performance of the pole piece can be improved, and the gas production behavior of the lithium ion battery can be reduced. The high nickel layered anode material has the advantages of a single coating material after double-layer coating modification, makes up for the defect of single coating, and the lithium ion battery formed by taking the material as an active substance has the characteristics of high capacity, high multiplying power and long cycle.
The FEI-SEM image of the material prepared in comparative example 1 of the invention is shown in FIG. 1, the FEI-SEM image of the material prepared in comparative example 2 is shown in FIG. 2, the FEI-SEM image of the material prepared in example 1 is shown in FIG. 3, FIG. 1 is an uncoated base material SEM, and the surface of the primary particles of the material is smooth and flat compared with FIGS. 2 and 3; FIG. 2 is an SEM image of a wet-process lithium tungstate-coated and dried material, wherein a fine coating layer is uniformly formed on the surface of the material, and the definition of an inserted picture is reduced relative to that of an original SEM image; fig. 3 shows the finished material with double coating layers after dry aluminum coating, wherein the coating is distributed on the surface of the material particles uniformly, and most of the coating is distributed in small particle island shape.
As can be seen from the FEI-SEM images of the above examples and comparative examples, the technical scheme of the invention can ensure that the transition layer and the shell layer cladding are uniformly coated on the surface of the material, so that the surface of the material can be well protected and the interface side reaction can be reduced.

Claims (10)

1. A double-coating modified lithium ion battery anode material is characterized by comprising an anode material substrate, a first coating coated on the surface of the substrate and a second coating coated on the surface of the first coating; wherein the first coating layer is a nano-sheet fast ion conductor layer; the second cladding layer is an Al compound layer.
2. The positive electrode material according to claim 1, wherein the fast ion conductor is at least one of lithium tungstate, lithium molybdate, and lithium vanadate; the Al compound is LiAlO2And Al2O3。
3. The positive electrode material according to claim 1, wherein the mass of the tungsten, molybdenum or vanadium element in the fast ion conductor layer accounts for 0.02-0.5% of the mass of the positive electrode material matrix, and the mass of the aluminum atom in the Al compound layer accounts for 0.02-0.2% of the mass of the positive electrode material matrix.
4. The positive electrode material according to any one of claims 1 to 3, wherein the matrix of the positive electrode material has a molecular formula of LiuNi(1-x-y-z)CoxMnyMzO2Wherein u is more than or equal to 0.9 and less than or equal to 1.20 and 0<x≤0.20，0<y≤0.20，0<z is less than or equal to 0.05, and M is at least one element of Al, Mg, Ti, Zr, V, B, La, Y, Cr, Mo, Ca, Fe, Hf, Zn, Si, W, Nb and Sm.
5. A method for producing the positive electrode material as claimed in any one of claims 1 to 4, comprising the steps of:
(1) adding the positive electrode material matrix into water, and stirring to form uniform slurry A;
adding tungsten ammonium salt, molybdenum ammonium salt or vanadium ammonium salt into water and stirring to form a uniform solution B;
adding the solution B and the citric acid solution into the slurry A, uniformly stirring, and heating the mixture to evaporate water until viscous gel appears; drying and dehydrating the gel slurry to obtain a nano flaky fast ion conductor coated positive electrode material;
(2) and (2) mixing the nano flaky fast ion conductor coated positive electrode material prepared in the step (1) with an aluminum compound, sintering at a constant temperature of 500-700 ℃ for 3-10 h, crushing and screening to obtain the double coated layer modified lithium ion battery positive electrode material.
6. The production method according to claim 5, wherein the positive electrode material matrix in the step (1) is obtained by the following production method:
mixing Ni(1-x-y-z)CoxMny(OH)2Uniformly mixing the precursor with a lithium source and a compound containing M, sintering at a constant temperature of 600-900 ℃ for 5-20 h in an oxygen atmosphere, crushing, and screening to obtain a positive electrode material matrix; wherein the lithium source is at least one of lithium hydroxide, lithium carbonate and lithium nitrate; the M-containing compound is at least one of an oxide, an ammonium salt, a sulfate, a carbonate, a nitrate and an organic metal compound of M; M/(Ni + Co + Mn + M) is 0.1-2.0%.
7. The method according to claim 5, wherein the mass ratio of water to the positive electrode material matrix in the slurry A is (0.4 to 1.0): 1.
8. the method according to claim 5, wherein the ratio of the molar amount of the citric acid to the molar amount of the fast ion conductor is (1.0-4.0): 1.
9. The method of claim 5, wherein the aluminum compound is Al2O3、AlOOH、Al(OH)3And LiAlO2At least one of; the average particle size D50 is 0.1-20 microns.
10. The method according to claim 5, wherein the heating temperature in step (1) is 70 to 100 ℃; the drying temperature is 80-280 ℃, and the drying time is 2-10 h.
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