CN114551794A - Positive electrode active material, positive electrode, preparation method and lithium ion battery - Google Patents

Positive electrode active material, positive electrode, preparation method and lithium ion battery Download PDF

Info

Publication number
CN114551794A
CN114551794A CN202111554453.5A CN202111554453A CN114551794A CN 114551794 A CN114551794 A CN 114551794A CN 202111554453 A CN202111554453 A CN 202111554453A CN 114551794 A CN114551794 A CN 114551794A
Authority
CN
China
Prior art keywords
tungsten
positive electrode
cobalt
nickel
active material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202111554453.5A
Other languages
Chinese (zh)
Other versions
CN114551794B (en
Inventor
杨元婴
孙化雨
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Envision Power Technology Jiangsu Co Ltd
Envision Ruitai Power Technology Shanghai Co Ltd
Original Assignee
Envision Power Technology Jiangsu Co Ltd
Envision Ruitai Power Technology Shanghai Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Envision Power Technology Jiangsu Co Ltd, Envision Ruitai Power Technology Shanghai Co Ltd filed Critical Envision Power Technology Jiangsu Co Ltd
Priority to CN202111554453.5A priority Critical patent/CN114551794B/en
Publication of CN114551794A publication Critical patent/CN114551794A/en
Application granted granted Critical
Publication of CN114551794B publication Critical patent/CN114551794B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a positive active material, a positive electrode, a preparation method and a lithium ion battery, wherein the positive active material comprises nickel-cobalt-manganese ternary material powder and a tungsten-containing film layer coated on the surface of the nickel-cobalt-manganese ternary material powder, wherein the mass fraction of tungsten is 1000-4000 ppm; the positive electrode containing the positive active material has good ionic conductivity and electronic conductivity on the surface, improves the dynamic performance of the battery, and optimizes the direct-current impedance of the battery; meanwhile, the positive electrode can optimize lithium ion diffusion and obtain higher capacity.

Description

Positive electrode active material, positive electrode, preparation method and lithium ion battery
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a positive active material, a positive electrode, a preparation method of the positive active material and a lithium ion battery.
Background
In order to solve the problems of material cost and cobalt ore resourceLimited problems to develop low cobalt ternary materials LiNixCoyMn1-x-yO2(y is less than or equal to 0.13), however, the decrease of the content of Co in the low-cobalt ternary material can reduce the overall conductivity of the material and influence the capacity exertion of the battery; according to research, a small amount of tungsten compound is coated on the surface of the positive electrode, so that the ionic and electronic conductivity of the surface of the material can be effectively improved, the internal resistance of the battery is reduced, and the low-temperature performance is improved. The tungsten coating layer of the material obtained by the existing dry coating is in a point shape, and the lithium ion diffusion and the surface impedance improvement are limited. Therefore, a new coating method is needed to solve the problems of uneven distribution of the tungsten compound and poor conductivity.
Disclosure of Invention
The invention provides a positive active material, a positive electrode, a preparation method and a lithium ion battery, aiming at the problems that the surface coating layer of the positive active material is in a point shape, the lithium ion diffusion and the surface impedance improvement are limited, and the like in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a positive electrode active material, including a nickel-cobalt-manganese ternary material powder and a tungsten-containing film layer coated on a surface of the nickel-cobalt-manganese ternary material powder, wherein a mass fraction of tungsten is 1000 to 4000 ppm.
In the invention, the tungsten compound coated on the positive electrode active material is distributed in a film shape, compared with the tungsten compound distributed in a dot shape on other ternary materials, the lithium ion diffusion is more stable in the charging and discharging process, the charging and discharging capacity of the material can be effectively improved, the surface impedance and the cycle stability are also effectively improved, wherein the mass fraction of tungsten is 1000 to 4000ppm, for example, 1000ppm, 1500ppm, 2000ppm, 2500ppm, 3000ppm, 3500ppm or 4000ppm, but not limited to the enumerated values, other unrecited values in the numerical range are also applicable, and the improvement effect is limited because the coating amount is less than 1000ppm, the coating is not uniform; the coating amount is more than 4000ppm and is easy to agglomerate on the surface, so that the coating amount of the tungsten element in the invention is in the range of 1000 to 4000ppm, and the lithium ion diffusion speed and the battery impedance can be considered at the same time.
Preferably, the particle size of the positive electrode active material is 3 to 5 μm, and may be, for example, 3 μm, 3.2 μm, 3.5 μm, 3.8 μm, 4 μm, 4.2 μm, 4.5 μm, 4.8 μm, or 5 μm, but is not limited to the enumerated values, and other unrecited values within this range of values are also applicable.
The particle size of the anode active material is preferably 3-5 μm, the anode active material in the particle size range is uniform, the proportion of the nickel-cobalt-manganese ternary material powder and the tungsten-containing film layer is more reasonable, and the lithium ion diffusion speed and the battery impedance are considered at the same time.
Preferably, the molecular formula of the nickel-cobalt-manganese ternary material powder is LiNixCoyMn1-x-yO2Where 0.5 ≦ x ≦ 0.9, 0 ≦ y ≦ 0.13, for example, x ≦ 0.5, y ≦ 0.13, x ≦ 0.5, y ≦ 0.1, x ≦ 0.6, y ≦ 0.13, x ≦ 0.6, y ≦ 0.1, x ≦ 0.7, y ≦ 0.1, x ≦ 0.8, y ≦ 0.1, or x ≦ 0.9, and y ≦ 0.1.
The preferred molecular formula of the invention is LiNixCoyMn1-x-yO2The low cobalt-nickel-cobalt-manganese ternary material powder has low cobalt content, saves metal resources and effectively reduces the production cost of the anode and the battery.
Preferably, the tungsten in the tungsten-containing film layer is present in a form satisfying at least one of the following conditions (a) to (b):
(a) the tungsten in the tungsten-containing film layer exists in a form of H4W、H2W2O7、WO3、WO2、BW、B2W、W2N3、WF6、WF4Or WOF4Any one or a combination of at least two of them;
(b) the tungsten in the tungsten-containing film layer exists in a form of H2W2O7And/or WF6(ii) a Wherein a non-limiting exemplary combination may be H4W and H2W2O7Combination of (1), H4W and WO3Combination of (1), H4W and WO2Combination of (5) and WF6And H2W2O7Combination of (1), H4W and WF6Combination of (a), BW and H2W2O7Combination of (5) and WF4And H2W2O7Combination of (1), WOF4And H2W2O7A combination of (A) and (B)2N3And WF6Combinations of (a) and (b) are not limited to the listed combinations, and other combinations not listed within the scope are equally applicable.
The tungsten in the tungsten-containing film layer is preferably in the form of H4W、H2W2O7、WO3、WO2、BW、B2W、W2N3、WF6、WF4Or WOF4Any one or a combination of at least two of them, further preferably H2W2O7And/or WF6The method is to select a low-cost and high-activity tungsten compound for tungsten coating so as to obtain a positive electrode active material with a more uniform coating effect.
In a second aspect, the present invention provides a method for producing a positive electrode active material according to the first aspect, the method comprising the steps of:
and mixing the nickel-cobalt-manganese ternary material powder, the tungsten-containing powder and the alcohol solvent by a wet method or spraying and then calcining to obtain the anode active material.
The wet mixing comprises the step of dispersing nickel-cobalt-manganese ternary material powder and tungsten-containing powder in an alcohol solvent, the stirring is carried out until the alcohol solvent is volatilized, and the spraying comprises the step of spraying the tungsten-containing powder to the nickel-cobalt-manganese ternary material powder after the tungsten-containing powder is mixed and dispersed in the alcohol solvent.
According to the preparation method of the cathode active material, a wet coating or spraying mixing mode is adopted, so that the tungsten compound and the low-cobalt ternary material are uniformly distributed, the homogeneity is improved, the subsequent sintering time is favorably shortened, and the production efficiency is improved.
As a preferable technical scheme of the invention, the molecular formula of the nickel-cobalt-manganese ternary material powder is LiNixCoyMn1-x-yO2Where 0.5 ≦ x ≦ 0.9, 0 ≦ y ≦ 0.13, for example, x ≦ 0.5, y ≦ 0.13, x ≦ 0.5, y ≦ 0.1, x ≦ 0.6, y ≦ 0.13, x ≦ 0.6, y ≦ 0.1, x ≦ 0.7, y ≦ 0.1, x ≦ 0.8, y ≦ 0.1, or x ≦ 0.9, and y ≦ 0.1.
The preferred molecular formula of the invention is LiNixCoyMn1-x-yO2The low cobalt-nickel-cobalt-manganese ternary material powder has low cobalt content, saves metal resources and effectively reduces the production cost of the anode and the battery.
Preferably, the tungsten-containing powder satisfies at least one of the following conditions (a) to (b):
(a) the tungsten-containing powder is H4W、H2W2O7、WO3、WO2、BW、B2W、W2N3、WF6、WF4Or WOF4Any one or a combination of at least two of them;
(b) the tungsten-containing powder is H2W2O7And/or WF6；
Wherein a non-limiting exemplary combination may be H4W and H2W2O7Combination of (1), H4W and WO3Combination of (1), H4W and WO2Combination of (5) and WF6And H2W2O7Combination of (1), H4W and WF6Combination of (a), BW and H2W2O7Combination of (5) and WF4And H2W2O7Combination of (2), WOF4And H2W2O7A combination of (A) and (B)2N3And WF6In combination with, but not exclusivelyOther combinations not listed within the scope are equally applicable, limited to the listed combinations.
Preferably, the alcoholic solvent comprises ethanol.
As a preferred embodiment of the present invention, in the wet mixing, the mass ratio of the nickel-cobalt-manganese ternary material powder to the tungsten-containing powder satisfies at least one of the following conditions (a) to (b):
(a) the mass ratio of the nickel-cobalt-manganese ternary material powder to the tungsten-containing powder is (98-99.99): 0.01-2;
(b) the mass ratio of the nickel-cobalt-manganese ternary material powder to the tungsten-containing powder is (98.9-99.1): (0.9-1.1); for example, it may be 98:2, 98.5:1.5, 98.9:1.1, 99:1, 99.1:0.9, 99.2:0.8, 99.5:0.5, 99.8:0.2, 99.9:0.1 or 99.99:0.01, but is not limited to the values listed, and other values not listed in the numerical range may be similarly applied.
The mass ratio of the nickel-cobalt-manganese ternary material powder to the tungsten-containing powder is preferably (98-99.99): (0.01-2), more preferably (98.9-99.1): (0.9-1.1), and the proportion of the nickel-cobalt-manganese ternary material powder to the tungsten-containing film layer is more reasonable, so that the lithium ion diffusion in the positive electrode and the battery product is facilitated.
Preferably, in the wet mixing, the liquid-solid ratio of the alcohol solvent to the nickel-cobalt-manganese ternary material powder is (1.8 to 2.2):1, and may be, for example, 1.8:1, 1.9:1, 2:1, 2.1:1 or 2.2:1, but is not limited to the enumerated values, and other non-enumerated values in the numerical range are also applicable.
The invention preferably adopts the liquid-solid ratio of the alcohol solvent to the nickel-cobalt-manganese ternary material powder of (1.8-2.2): 1, so that the nickel-cobalt-manganese ternary material and the tungsten-containing powder are more uniform in the mixing process, and the alcohol solvent is evaporated in the subsequent working procedure, thereby prolonging the sintering and combining time of the nickel-cobalt-manganese ternary material and the tungsten-containing powder.
Preferably, in the spraying, the mass ratio of the nickel-cobalt-manganese ternary material powder to the tungsten-containing powder satisfies at least one of the following conditions (a) to (b):
(a) the mass ratio of the nickel-cobalt-manganese ternary material powder to the tungsten-containing powder is (98-99.99): 0.01-2;
(b) the mass ratio of the nickel-cobalt-manganese ternary material powder to the tungsten-containing powder is (98.9-99.1): (0.9-1.1);
for example, it may be 98:2, 98.5:1.5, 98.9:1.1, 99:1, 99.1:0.9, 99.2:0.8, 99.5:0.5, 99.8:0.2, 99.9:0.1 or 99.99:0.01, but is not limited to the values listed, and other values not listed in the numerical range may be similarly applied.
Preferably, in the spraying, the liquid-solid ratio of the alcohol solvent to the nickel-cobalt-manganese ternary material powder is (1.8 to 2.2):1, and may be, for example, 1.8:1, 1.9:1, 2:1, 2.1:1 or 2.2:1, but is not limited to the enumerated values, and other non-enumerated values in the numerical range are also applicable.
Preferably, the calcination satisfies at least one of the following conditions (a) to (b):
(a) the temperature of the calcination is 200 to 600 ℃; for example, 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃ or 600 ℃, but is not limited to the recited values, and other unrecited values within the range of values are equally applicable;
(b) the calcination time is 8 to 20 hours; for example, the reaction time may be 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h or 20h, but the reaction time is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
The temperature of calcination in the present invention is preferably 200 to 600 c, and the time of calcination is preferably 8 to 20 hours, so that the coating effect, activity and powder strength of the positive electrode active material are better.
In a third aspect, the present invention provides a positive electrode comprising the positive electrode active material according to the first aspect.
As a preferred embodiment of the present invention, the positive electrode further includes a conductive material and a fluoropolymer.
Preferably, the mass ratio of the conductive material to the fluoropolymer is (0.2 to 7): (0.1 to 3), and may be, for example, 7:0.1, 6:0.2, 5:0.3, 4:0.4, 3:0.5, 2:0.6, 1:0.7, 0.8:1, 0.6:1.5, 0.5:2, 0.4:2.5, or 0.2:3, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the mass fraction of the positive electrode active material in the positive electrode is 90 to 99%, for example 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99%, but not limited to the recited values, and other values not recited in the range of values are also applicable.
In a fourth aspect, the present invention provides a method for producing the positive electrode according to the third aspect, the method comprising the steps of:
and pulping and tabletting the positive active material to obtain the positive electrode.
As a preferred embodiment of the present invention, the slurry includes a positive electrode active material, a conductive material, a fluoropolymer, and an organic solvent mixed to form a slurry.
Preferably, the mass ratio of the positive electrode active material, the conductive material and the fluoropolymer is (90 to 99): (0.2 to 7): (0.1 to 3), and may be, for example, 90:7:3, 92:5:3, 93:5:2, 94:4:2, 95:3.5:1.5, 98:1.8:0.2 or 99:0.7:0.3, but is not limited to the enumerated values, and other non-enumerated values within the numerical range are equally applicable.
Preferably, the conductive material includes conductive carbon black and conductive carbon tubes.
Preferably, the fluoropolymer includes any one or a combination of at least two of polyvinylidene fluoride, hexafluoropropylene, polyvinylidene fluoride-hexafluoropropylene copolymer, preferably polyvinylidene fluoride, wherein typical but non-limiting combinations are polyvinylidene fluoride and hexafluoropropylene, polyvinylidene fluoride and polyvinylidene fluoride-hexafluoropropylene copolymer, and hexafluoropropylene, but not limited to the listed combinations, and other combinations not listed in this range are also applicable.
Preferably, the mass ratio of the positive electrode active material, the conductive carbon black, the conductive carbon tube and the polyvinylidene fluoride is (90 to 99): (0.1 to 2): (0.1 to 5): (0.1 to 3), and may be, for example, 90:2:5:3, 92:1:4:3, 93:1:4:2, 94:1:3:2, 95:0.5:3:1.5, 98:0.5:1.3:0.2 or 99:0.2:0.5:0.3, but is not limited to the enumerated values, and other non-enumerated values within the numerical range may be equally applicable.
Preferably, the organic solvent comprises a nitrogen methyl pyrrolidone solvent.
Preferably, the mass ratio of the volume of the organic solvent to the positive electrode active material is (6 to 7) ml:1g, and may be, for example, 6ml:1g, 6.2ml:1g, 6.5ml:1g, 6.8ml:1g, or 7ml:1g, but is not limited to the enumerated values, and other unrecited values within this range are equally applicable.
In a preferred embodiment of the present invention, the tableting includes coating the slurry on a current collector, drying, and rolling to obtain the positive electrode.
Preferably, the current collector comprises a metal foil.
Preferably, the coated positive electrode has an areal density of 15 to 22g/cm2For example, it may be 15g/cm2、16g/cm2、17g/cm2、18g/cm2、19g/cm2、20g/cm2、21g/cm2Or 22g/cm2However, the numerical values recited are not intended to be limiting, and other numerical values not recited within the numerical range may be equally applicable.
Preferably, the compacted density of the rolled positive electrode is 3.3 to 3.8g/cm3For example, it may be 3.3g/cm3、3.4g/cm3、3.5g/cm3、3.6g/cm3、3.7g/cm3Or 3.8g/cm3However, the numerical values recited are not intended to be limiting, and other numerical values not recited within the numerical range may be equally applicable.
In a fifth aspect, the present invention provides a lithium ion battery, wherein the positive electrode comprises the positive electrode according to the third aspect, the separator comprises a polyethylene film and/or a polypropylene film, the negative electrode comprises a graphite-coated copper foil, and the electrolyte comprises a lithium hexafluorophosphate solution.
Preferably, the assembling steps of the lithium ion battery are as follows: sticking the positive electrode tab of aluminum material on the positive electrode, sticking the negative electrode tab of copper material on the negative electrode, cutting the sheet-shaped positive electrode, diaphragm and negative electrode into pieces with a thickness of (3-10) × (3-10) cm2The lithium ion battery is obtained by sequentially and tightly overlapping the positive electrode, the diaphragm and the negative electrode in sequence, injecting lithium hexafluorophosphate electrolyte into two sides of the diaphragm to form a battery cell, and overlapping the battery cell to the required number of layers.
The lithium ion battery provided by the invention adopts a nickel-cobalt-manganese ternary positive electrode with higher theoretical capacity and high reaction platform voltage as a raw material, and in order to save the consumption of Co element and ensure the material performance of the battery, a tungsten-coated low-cobalt ternary material LiNi is usedxCoyMn1-x-yO2(y is less than or equal to 0.13), on the basis, the coating form of the tungsten compound is optimized, so that the surface of the ternary material has an ultrathin tungsten compound layer, and the product battery has higher capacity and cycle stability.
Preferably, the lithium ion battery is a button cell battery.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides a positive active material, wherein the surface of the positive active material contains a tungsten compound uniformly distributed in a film shape, and an ultrathin tungsten compound coating promotes lithium ion diffusion in the charge-discharge process, so that the charge-discharge capacity, surface pit formation and cycle stability of the material are effectively improved;
(2) the invention provides a preparation method of a positive active material, the positive active material is obtained by wet mixing or spraying, the sintering time is shortened and is reduced from 14-20 h of common sintering to 8-20 h, the process is simple, and the operation is convenient;
(3) the invention provides a lithium ion battery, which is prepared in an optimal range by adopting the positive active material and the preparation method provided by the invention, wherein the gram capacity of 2.8V to 4.3V is more than or equal to 184.9 mA.h/g, and the direct current impedance of 50 percent SOC is less than or equal to 96.2 omega at 25 ℃ and 50 percent SOC, so that the lithium ion battery has sufficient gram capacity and lower resistance, the direct current impedance of 50 percent SOC is less than or equal to 812 omega at-20 ℃, and the capacity retention rate of the lithium ion battery at-20 ℃ is more than or equal to 70.2 percent, so that the lithium ion battery has lower resistance and higher retention rate at low temperature, wide use environment and excellent performance.
Drawings
FIG. 1 is a graph comparing the gram capacities at 2.8 to 4.3V of example 1 of the present invention and comparative example 1.
FIG. 2 is a graph comparing DC impedances of example 1 of the present invention and comparative example 1.
FIG. 3 is a graph comparing the low temperature DC impedance of example 1 of the present invention and comparative example 1.
FIG. 4 is a graph comparing the low-temperature capacity retention rates of example 1 of the present invention and comparative example 1.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
In the prior art, a preparation method of a modified lithium nickel cobalt manganese oxide anode comprises the steps of mixing a lithium nickel cobalt manganese oxide with aluminum tungstate, and then sintering the mixture to obtain the modified lithium nickel cobalt manganese oxide anode, wherein the mixing mode is ball milling mixing. Lithium tungstate on the surface of the anode produced in the mixing mode is distributed in a dot shape, the improvement on the cycle performance, the rate performance and the conductivity performance of the anode is limited, and the direct current impedance is only between 10 and 25 omega.
The other technical scheme provides a preparation method of the ternary positive electrode coated with the lithium tungstate. The method comprises the steps of dissolving a tungsten-containing compound in an alcohol solvent or water to form a tungsten source solution, dispersing a porous nickel-cobalt-manganese oxide precursor in the tungsten source solution, and sintering to obtain the porous nickel-cobalt-lithium manganate with surfaces and inner walls of pores coated with lithium tungstate. The scheme provides an idea of wet coating of the tungsten layer, but does not provide a method for improving the point distribution of the tungsten compound.
The other technical scheme provides a tungsten-titanium co-coated lithium ion ternary anode and a preparation method thereof. The lithium ion ternary positive electrode is characterized in that the core of the lithium ion ternary positive electrode is a lithium ion ternary material, the outer layer of the lithium ion ternary positive electrode is a continuous and uniform tungsten-titanium composite film, a tungsten source compound, a titanium source compound and a stabilizer are dissolved in a solvent to form a blending liquid, a proper amount of lithium ion ternary material is added into the blending liquid to obtain slurry, high-pressure lithium source water mist is sprayed into the slurry, and the solvent is evaporated and calcined to obtain the lithium ion ternary positive electrode. The method respectively dissolves the core substance and the coating substance and mixes the core substance and the coating substance by spraying, and the operation is more complicated.
The embodiment of the application discloses a positive electrode active material, a positive electrode, a preparation method and a lithium ion battery. The surface of the positive active material is provided with very uniform film-shaped coating, the preparation method adopts a wet mixing or spraying and then calcining mode to obtain the positive active material, and the positive electrode is obtained through pulping and tabletting; the ultrathin tungsten compound coating promotes lithium ion diffusion in the charging and discharging processes, effectively improves the charging and discharging capacity of the material, and simultaneously effectively improves surface impedance and cycle stability.
In one embodiment, the present invention provides a positive electrode active material, wherein the content of tungsten is 1000 to 4000ppm and the particle size is 3 to 5 μm.
In another embodiment, the present invention provides a method for preparing a positive active material, the method comprising the steps of:
after the nickel-cobalt-manganese ternary material powder, the tungsten-containing powder and ethanol are mixed or sprayed by a wet method, calcining at 200-600 ℃ for 8-20 h to obtain the anode active material;
the wet mixing comprises dissolving nickel-cobalt-manganese ternary material powder and tungsten-containing powder in ethanol, stirring until the ethanol volatilizes, and the spraying comprises mixing tungsten-containing powder, dissolving in ethanol, and spraying to the nickel-cobalt-manganese ternary material powder;
the molecular formula of the nickel-cobalt-manganese ternary material powder is LiNixCoyMn1-x-yO2Wherein x is more than or equal to 0.5 and less than or equal to 0.9, y is more than or equal to 0 and less than or equal to 0.13, and the tungsten-containing powder comprises H4W、H2W2O7、WO3、WO2、BW、B2W、W2N3、WF6、WF4Or WOF4Any ofOne or a combination of at least two of them; in the wet mixing, the mass ratio of the nickel-cobalt-manganese ternary material powder to the tungsten-containing powder is (98-99.99): 0.01-2, and the liquid-solid ratio of the ethanol to the nickel-cobalt-manganese ternary material powder is (1.8-2.2): 1; in the spraying, the mass ratio of the nickel-cobalt-manganese ternary material powder to the tungsten-containing powder is (98-99.99): 0.01-2, and the liquid-solid ratio of the ethanol to the nickel-cobalt-manganese ternary material powder is (1.8-2.2): 1;
in another embodiment, the present invention provides a method for preparing a positive electrode comprising the above positive electrode active material, the method comprising the steps of:
mixing the positive active material, conductive carbon black, a conductive carbon tube, polyvinylidene fluoride and a nitrogen methyl pyrrolidone solvent to form slurry, coating the slurry on a metal foil, drying and rolling to obtain the positive electrode; wherein the mass ratio of the positive electrode active material, the conductive carbon black, the conductive carbon tube and the polyvinylidene fluoride is (90-99): (0.1-2): 0.1-5): 0.1-3, the mass ratio of the volume of the azomethidone solvent to the positive electrode active material is (6-7) ml:1g, the surface density of the coated positive electrode is 15-22 g/cm2The compacted density of the rolled positive electrode is 3.3 to 3.8g/cm3。
In another embodiment, the present invention provides a lithium ion battery, wherein a graphite-coated copper foil is used as a negative electrode, a polyethylene film and/or a polypropylene film is used as a separator, a lithium hexafluorophosphate solution is used as an electrolyte, an aluminum positive electrode tab is bonded to the positive electrode, a copper negative electrode tab is bonded to the negative electrode, and the sheet-shaped positive electrode, separator and negative electrode are cut into pieces of (3 to 10) × (3 to 10) cm2The size of the battery is determined, the battery is sequentially and tightly overlapped according to the sequence of the anode, the diaphragm and the cathode, lithium hexafluorophosphate electrolyte is injected into two sides of the diaphragm to form a battery core, and the 1Ah soft package battery is assembled.
It is understood that processes or substitutions and variations of conventional data provided by embodiments of the present invention are within the scope and disclosure of the present invention.
Examples 1 to 9
Each embodiment provides a lithium ion battery containing a positive electrode active material and a positive electrode, and each embodiment is prepared by the preparation method of the positive electrode active material, the positive electrode and the lithium ion battery, but the raw material types, the mixture ratios, the mixing modes and the process parameters of the embodiments are different.
Comparative examples 1 to 2
Each comparative example respectively provides a lithium ion battery containing a positive electrode active material and a positive electrode, each comparative example is respectively prepared by the preparation method of the positive electrode active material, the positive electrode and the lithium ion battery of the comparative example, but the raw material types, the mixture ratios, the mixing modes and the process parameters of the comparative examples are different.
The pouch cells prepared in examples 1 to 9 and comparative examples 1 to 2 were formed and aged. Charging to 4.3V voltage at 0.33C rate and discharging to 2.8V at 0.33C rate at room temperature to obtain capacity C0. Through C0And calculating the coating quality of the positive electrode to obtain the gram capacity of the positive electrode. The full charge state of the batteries prepared in examples 1 to 9 and comparative examples 1 to 2 was then adjusted to 70% SOC (70% full charge state), after which the batteries were discharged at a current density of 4C for 30s, and the difference in voltage between before and after discharge divided by the current density was the dc impedance of the batteries at that SOC (full charge state). The DC impedance values of 50% SOC and 20% SOC can be measured by the method; and then placing the battery in a constant-temperature oven at the temperature of 20 ℃ below zero, charging and discharging the battery at the voltage window of 2.8V to 4.3V with the current density of 0.33C, and testing the direct-current impedance value of the battery at the temperature of 20 ℃ below zero by using the same method. At the same time, the discharge capacity C at-20 ℃ is recorded1，C1/C0Namely the low-temperature capacity retention rate of the battery. Meanwhile, the direct current impedance value of the battery under the temperature condition of-20 ℃ is tested.
The gram capacity ratio of example 1 to comparative example 1 at 2.8 to 4.3V is shown in fig. 1, the wet coating gives better lithium ion diffusion path than the dry coating, and the gram capacity is increased from 184.2 to 185.7; direct current impedance pairing of example 1 and comparative example 1 as shown in fig. 2, wet coating optimized the contact surface of the material with the electrolyte, reduced side reactions, and reduced charge transfer impedance from 98m Ω to 93.7m Ω (50% SOC, 4C DC 30S, measured at room temperature, meaning 50% full chargeState, discharged at 4C constant current for 30 seconds), decreased from 863m Ω to 764m Ω at low temperature (50% SOC, measured under 1C DC 20S conditions, meaning 50% fully charged, discharged at 1C constant current for 20 seconds); the low-temperature DC impedance ratio of example 1 and comparative example 1 is shown in FIG. 3, the low-temperature capacity retention ratio of example 1 and comparative example 1 is shown in FIG. 4, and the wet coating reduces Li+The polarization passing through the interface process of the active substance/electrolyte improves the capacity retention rate at the temperature of-20 ℃ from 68% to 71%.
In the above different examples and comparative examples, different tungsten contents, mixing manners, types of raw materials, ratios, and process parameters of the positive electrode active material are shown in table 1, raw material ratios and process parameters of the positive electrode are shown in table 2, and parameters of the lithium ion battery are shown in table 3.
TABLE 1
Figure BDA0003418704210000131
TABLE 2
Figure BDA0003418704210000132
Figure BDA0003418704210000141
TABLE 3
Figure BDA0003418704210000142
From a summary of the data in tables 1 to 3 we can see that:
(1) the lithium ion battery containing the positive active material and the positive electrode obtained by the method of the embodiments 1 to 4 has the 2.8V to 4.3V gram capacity of more than or equal to 184.9 mA.h/g, and the 50% SOC direct current impedance of less than or equal to 96.2 omega at 25 ℃, so that the lithium ion battery has sufficient gram capacity and lower resistance value, and the 50% SOC direct current impedance of less than or equal to 812 omega at-20 ℃ and the capacity retention rate of more than or equal to 70.2 at-20 ℃, so that the lithium ion battery has lower resistance value and higher retention rate at low temperature, thereby showing that the lithium ion battery provided by the invention has good service performance at normal temperature, and particularly has higher retention rate at low temperature;
(2) it can be seen from the combination of examples 1 and 5 to 6 that, in examples 5 and 6, the calcination time is 6h and 24h, respectively, compared to example 1, the calcination time is 10h, the calcination time is too short, the crystallinity is low, and the side reactions are more significant in example 1, so that the 50% SOC DC impedance reaches 100.1 Ω at 25 ℃ and the 50% SOC DC impedance reaches 1035 Ω at 20 ℃ and the particle size is large due to too short sintering time in example 5, the gram capacity is reduced due to the growth of particles, the 2.8V-4.3V gram capacity is only 182.1mA · h/g, and the 2.8V-4.3V gram capacity 185.8mA · h/g and the 50% SOC DC impedance is 93.7 Ω at 25 ℃ and the capacity is 71% at-20 ℃ and the 50% SOC DC impedance is 764 Ω and the 20 ℃ in the lithium ion battery of example 1, thereby showing that the calcination time in the preferred range is used in the present invention, obtaining the lithium ion battery with more excellent performance;
(3) it can be seen from the combination of examples 1 and 7 to 8 that in examples 7 and 8, the calcination temperatures were 150 ℃ and 700 ℃ respectively, while in example 1, the calcination temperature was 300 ℃, the crystallinity was low, and the side reactions were more significant, and thus in example 7, the 50% SOC DC impedance reached 102.5 Ω at 25 ℃ and the 50% SOC DC impedance reached 990 Ω at 20 ℃ and the grain size was increased to 990 Ω in example 1, and the gram capacity was decreased due to the particle size increase caused by the sintering temperature being too high in example 8, and the 2.8V to 4.3V gram capacity was 183.2 mA.h/g, while in the lithium ion battery of example 1, the 2.8V to 4.3V gram capacity 185.8 mA.h/g, the 50% SOC DC impedance was 93.7 Ω at 25 ℃ and the 50% SOC DC impedance was 764 Ω at 20 ℃ and the capacity retention ratio was 71 ℃ and thus, indicating that the invention uses the calcination temperatures in the preferred ranges, obtaining the lithium ion battery with more excellent performance;
(4) combining example 1 and comparative example 1, it can be seen that comparative example 1 employs dry mixing, as compared to example 1, whereas example 1 employs wet mixing, comparative example 1 has a capacity of only 184.2mA · h/g from 2.8V to 4.3V g, 50% SOC DC impedance of 98 Ω at 25 ℃ and 863 Ω at 50% SOC DC impedance at 20 ℃ due to poor lithium ion diffusion by dry mixing, the lithium ion battery of example 1 had a 2.8V to 4.3V gram capacity of 185.8mA · h/g, a 50% SOC DC impedance of 93.7 Ω at 25 ℃, it has a 50% SOC DC impedance of 764 Ω at-20 deg.C and a capacity retention of 71% at 20 deg.C, therefore, the invention adopts the calcination temperature in the preferred range to obtain the lithium ion battery with sufficient gram capacity, lower resistance and superior performance at room temperature and low temperature;
(5) by combining example 1 and comparative example 2, it can be seen that the tungsten content of comparative example 2 is 4500ppm compared to example 1, while the tungsten content of example 1 is 3000ppm, comparative example 2, in which the tungsten content was too high to hinder lithium ion diffusion, had a capacity of only 184mA · h/g from 2.8V to 4.3V g, a 50% SOC DC resistance of 101.7 Ω at 25 ℃ and a 50% SOC DC resistance of 917 Ω at 20 ℃, the lithium ion battery of example 1 had a 2.8V to 4.3V gram capacity of 185.8mA · h/g, a 50% SOC DC impedance of 93.7 Ω at 25 ℃, it has a 50% SOC DC impedance of 764 Ω at-20 deg.C and a capacity retention of 71% at-20 deg.C, therefore, the invention adopts the calcination temperature in the preferred range to obtain the lithium ion battery with sufficient gram capacity, lower resistance and superior performance at room temperature and low temperature.
In summary, the lithium ion battery comprising the positive electrode active material and the positive electrode provided by the invention has sufficient gram capacity and lower resistance, and proves that the lithium ion battery provided by the invention has lower resistance and higher retention rate at low temperature, is wide in use environment, and is suitable for large-scale popularization and use.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (10)

1. The positive active material is characterized by comprising nickel-cobalt-manganese ternary material powder and a tungsten-containing film layer coated on the surface of the nickel-cobalt-manganese ternary material powder, wherein the mass fraction of tungsten is 1000-4000 ppm.
2. The positive electrode active material according to claim 1, wherein the particle diameter of the positive electrode active material is 3 to 5 μm.
3. The positive active material of claim 2, wherein the nickel-cobalt-manganese ternary material powder has a molecular formula of LiNixCoyMn1-x-yO2Wherein x is more than or equal to 0.5 and less than or equal to 0.9, and y is more than or equal to 0 and less than or equal to 0.13.
4. The positive electrode active material according to claim 2, wherein tungsten is present in the tungsten-containing film layer in a form satisfying at least one of the following conditions (a) to (b):
(a) the tungsten in the tungsten-containing film layer exists in a form of H4W、H2W2O7、WO3、WO2、BW、B2W、W2N3、WF6、WF4Or WOF4Any one or a combination of at least two of them;
(b) the tungsten in the tungsten-containing film layer exists in a form of H2W2O7And/or WF6。
5. A method for producing a positive electrode active material according to any one of claims 1 to 4, comprising the steps of:
mixing nickel-cobalt-manganese ternary material powder, tungsten-containing powder and an alcohol solvent by a wet method or spraying and then calcining to obtain the anode active material;
the wet mixing comprises the step of dispersing nickel-cobalt-manganese ternary material powder and tungsten-containing powder in an alcohol solvent, the stirring is carried out until the alcohol solvent is volatilized, and the spraying comprises the step of spraying the tungsten-containing powder to the nickel-cobalt-manganese ternary material powder after the tungsten-containing powder is mixed and dispersed in the alcohol solvent.
6. The method according to claim 5, wherein the molecular formula of the nickel-cobalt-manganese ternary material powder is LiNixCoyMn1-x-yO2Wherein x is more than or equal to 0.5 and less than or equal to 0.9, and y is more than or equal to 0 and less than or equal to 0.13.
7. The production method according to claim 5, wherein the mass ratio of the nickel-cobalt-manganese ternary material powder to the tungsten-containing powder satisfies at least one of the following conditions (c) to (d):
(c) the mass ratio of the nickel-cobalt-manganese ternary material powder to the tungsten-containing powder is (98-99.99): (0.01-2);
(d) the mass ratio of the nickel-cobalt-manganese ternary material powder to the tungsten-containing powder is (98.9-99.1): (0.9-1.1);
preferably, the liquid-solid ratio of the alcohol solvent to the nickel-cobalt-manganese ternary material powder is (1.8-2.2): 1.
8. The production method according to claim 4, wherein the calcination satisfies at least one of the following conditions (e) to (f):
(e) the temperature of the calcination is 200 to 600 ℃;
(f) the calcination time is 8 to 20 hours.
9. A positive electrode comprising the positive electrode active material according to any one of claims 1 to 4.
10. A lithium ion battery comprising the positive electrode according to claim 9.
CN202111554453.5A 2021-12-17 2021-12-17 Positive electrode active material, positive electrode, preparation method and lithium ion battery Active CN114551794B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111554453.5A CN114551794B (en) 2021-12-17 2021-12-17 Positive electrode active material, positive electrode, preparation method and lithium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111554453.5A CN114551794B (en) 2021-12-17 2021-12-17 Positive electrode active material, positive electrode, preparation method and lithium ion battery

Publications (2)

Publication Number Publication Date
CN114551794A true CN114551794A (en) 2022-05-27
CN114551794B CN114551794B (en) 2023-08-25

Family

ID=81668999

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111554453.5A Active CN114551794B (en) 2021-12-17 2021-12-17 Positive electrode active material, positive electrode, preparation method and lithium ion battery

Country Status (1)

Country Link
CN (1) CN114551794B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114914438A (en) * 2022-06-30 2022-08-16 远景动力技术(江苏)有限公司 Positive electrode active material, method for producing same, electrochemical device, and electronic device

Citations (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4115513A (en) * 1977-08-16 1978-09-19 Westinghouse Electric Corp. Processing of ammonium paratungstate from tungsten ores
KR20060109305A (en) * 2005-04-15 2006-10-19 대정화금주식회사 Cathode active material coated with fluorine compounds for lithium secondary batteries and method of producing thereof
JP2009051687A (en) * 2007-08-24 2009-03-12 Ishihara Sangyo Kaisha Ltd Flaky tungsten oxide, tungsten oxide film, their manufacturing methods and their use
CN103199233A (en) * 2012-01-06 2013-07-10 三星Sdi株式会社 Positive electrode material for lithium battery, positive electrode prepared from the positive material, and lithium battery including the positive electrode
US20160260962A1 (en) * 2015-03-05 2016-09-08 Uchicago Argonne, Llc METAL FLUORIDE PASSIVATION COATINGS PREPARED BY ATOMIC LAYER DEPOSITION ON LiCoO2 FOR LI-ION BATTERIES
CN106848252A (en) * 2017-03-16 2017-06-13 成都新柯力化工科技有限公司 One kind evaporation aluminum fluoride improves the durothermic method of ternary anode material of lithium battery
US20170203973A1 (en) * 2014-07-25 2017-07-20 Suzhou Hans Energy Storage Technology Co., Ltd. Applications of a tungsten-containing material
CN107112529A (en) * 2014-12-26 2017-08-29 住友金属矿山株式会社 Non-aqueous electrolyte secondary battery positive active material and its manufacture method and the non-aqueous electrolyte secondary battery for having used the positive active material
CN107408690A (en) * 2015-03-03 2017-11-28 住友金属矿山株式会社 Non-aqueous electrolyte secondary battery positive active material and its manufacture method
CN107658439A (en) * 2017-08-30 2018-02-02 格林美（无锡）能源材料有限公司 Lithium ion tertiary cathode material that a kind of tungsten titanium coats altogether and preparation method thereof
CN107910526A (en) * 2017-11-15 2018-04-13 何本科 A kind of preparation method of high magnification high security cobalt nickel lithium manganate ternary material
CN108400326A (en) * 2018-03-16 2018-08-14 博澳郢创（厦门）能源科技有限公司 A kind of nickelic tertiary cathode material and preparation method thereof through surface modification twice
CN108493429A (en) * 2018-05-03 2018-09-04 中南大学 The preparation method of anode composite material of lithium ion battery
CN108923032A (en) * 2018-07-16 2018-11-30 力信（江苏）能源科技有限责任公司 With the ternary cathode material of lithium ion battery and preparation method of modified metal oxide
CN110268561A (en) * 2017-02-28 2019-09-20 株式会社Lg化学 Cathode active material for lithium secondary battery, preparation method and the lithium secondary battery comprising the positive electrode active materials
CN111082026A (en) * 2019-12-31 2020-04-28 中南大学 Ternary cathode material coated with lithium tungstate and preparation method thereof
CN111384377A (en) * 2018-12-29 2020-07-07 宁德时代新能源科技股份有限公司 Positive electrode material and preparation method and application thereof
CN111916730A (en) * 2020-08-10 2020-11-10 贵州梅岭电源有限公司 Preparation method of WO3 modified nickel-rich ternary lithium ion battery positive electrode material
CN112909237A (en) * 2021-01-20 2021-06-04 厦门厦钨新能源材料股份有限公司 Modified lithium-nickel-cobalt-manganese oxide positive electrode material, and preparation method and application thereof
CN113644261A (en) * 2021-07-16 2021-11-12 万华化学(四川)有限公司 Method for modifying ternary cathode material through nano networking, cathode material and lithium ion battery

Patent Citations (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4115513A (en) * 1977-08-16 1978-09-19 Westinghouse Electric Corp. Processing of ammonium paratungstate from tungsten ores
KR20060109305A (en) * 2005-04-15 2006-10-19 대정화금주식회사 Cathode active material coated with fluorine compounds for lithium secondary batteries and method of producing thereof
JP2009051687A (en) * 2007-08-24 2009-03-12 Ishihara Sangyo Kaisha Ltd Flaky tungsten oxide, tungsten oxide film, their manufacturing methods and their use
CN103199233A (en) * 2012-01-06 2013-07-10 三星Sdi株式会社 Positive electrode material for lithium battery, positive electrode prepared from the positive material, and lithium battery including the positive electrode
US20170203973A1 (en) * 2014-07-25 2017-07-20 Suzhou Hans Energy Storage Technology Co., Ltd. Applications of a tungsten-containing material
CN107112529A (en) * 2014-12-26 2017-08-29 住友金属矿山株式会社 Non-aqueous electrolyte secondary battery positive active material and its manufacture method and the non-aqueous electrolyte secondary battery for having used the positive active material
CN107408690A (en) * 2015-03-03 2017-11-28 住友金属矿山株式会社 Non-aqueous electrolyte secondary battery positive active material and its manufacture method
US20160260962A1 (en) * 2015-03-05 2016-09-08 Uchicago Argonne, Llc METAL FLUORIDE PASSIVATION COATINGS PREPARED BY ATOMIC LAYER DEPOSITION ON LiCoO2 FOR LI-ION BATTERIES
CN110268561A (en) * 2017-02-28 2019-09-20 株式会社Lg化学 Cathode active material for lithium secondary battery, preparation method and the lithium secondary battery comprising the positive electrode active materials
CN106848252A (en) * 2017-03-16 2017-06-13 成都新柯力化工科技有限公司 One kind evaporation aluminum fluoride improves the durothermic method of ternary anode material of lithium battery
CN107658439A (en) * 2017-08-30 2018-02-02 格林美（无锡）能源材料有限公司 Lithium ion tertiary cathode material that a kind of tungsten titanium coats altogether and preparation method thereof
CN107910526A (en) * 2017-11-15 2018-04-13 何本科 A kind of preparation method of high magnification high security cobalt nickel lithium manganate ternary material
CN108400326A (en) * 2018-03-16 2018-08-14 博澳郢创（厦门）能源科技有限公司 A kind of nickelic tertiary cathode material and preparation method thereof through surface modification twice
CN108493429A (en) * 2018-05-03 2018-09-04 中南大学 The preparation method of anode composite material of lithium ion battery
CN108923032A (en) * 2018-07-16 2018-11-30 力信（江苏）能源科技有限责任公司 With the ternary cathode material of lithium ion battery and preparation method of modified metal oxide
CN111384377A (en) * 2018-12-29 2020-07-07 宁德时代新能源科技股份有限公司 Positive electrode material and preparation method and application thereof
CN111082026A (en) * 2019-12-31 2020-04-28 中南大学 Ternary cathode material coated with lithium tungstate and preparation method thereof
CN111916730A (en) * 2020-08-10 2020-11-10 贵州梅岭电源有限公司 Preparation method of WO3 modified nickel-rich ternary lithium ion battery positive electrode material
CN112909237A (en) * 2021-01-20 2021-06-04 厦门厦钨新能源材料股份有限公司 Modified lithium-nickel-cobalt-manganese oxide positive electrode material, and preparation method and application thereof
CN113644261A (en) * 2021-07-16 2021-11-12 万华化学(四川)有限公司 Method for modifying ternary cathode material through nano networking, cathode material and lithium ion battery

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
QIU-SHENG ZHOU等: ""Preparation and electrochromism of pyrochlore-type tungsten oxide film"", 《RARE MET.》, vol. 37, no. 7, pages 604 - 612, XP036520488, DOI: 10.1007/s12598-017-0886-9 *
李建圃等: ""焦绿石型氧化钨的研究现状和应用前景"", 《湖南有色金属》, vol. 26, pages 27 - 30 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114914438A (en) * 2022-06-30 2022-08-16 远景动力技术(江苏)有限公司 Positive electrode active material, method for producing same, electrochemical device, and electronic device

Also Published As

Publication number Publication date
CN114551794B (en) 2023-08-25

Similar Documents

Publication Publication Date Title
CN102479948B (en) Negative active core-shell material of a kind of lithium ion battery and preparation method thereof and a kind of lithium ion battery
EP2587571B1 (en) Positive-electrode composition for a nonaqueous-electrolyte secondary battery and method for manufacturing a positive-electrode slurry using said positive-electrode composition
CN109390563B (en) Modified lithium iron phosphate positive electrode material, preparation method thereof, positive plate and lithium secondary battery
Tang et al. Novel MnO/carbon composite anode material with multi-modal pore structure for high performance lithium-ion batteries
JP6575048B2 (en) The positive electrode composition for nonaqueous electrolyte secondary batteries, the nonaqueous electrolyte secondary battery, and the manufacturing method of the positive electrode composition for nonaqueous electrolyte secondary batteries.
CN110098383B (en) Cathode material, preparation method thereof, battery cathode and lithium ion battery
JP5842596B2 (en) Positive electrode composition for non-aqueous electrolyte secondary battery and method for producing positive electrode slurry for non-aqueous electrolyte secondary battery
CN114094068B (en) Cobalt-coated positive electrode material, preparation method thereof, positive electrode plate and lithium ion battery
CN112968165A (en) Modified sodium ion positive electrode material, modified sodium ion electrode and preparation method
CN107482182A (en) Carbon coating ion doping lithium manganese phosphate electrode material and preparation method thereof
CN108807928B (en) Synthesis of metal oxide and lithium ion battery
CN110335996A (en) A kind of high capacity lithium ion cells cathode and its application
CN111446429B (en) Poly-polyanion cathode material and preparation method and application thereof
CN106159225B (en) A method of producing carbon complex amorphous vanadium oxide powder
CN109167034B (en) Lithium-sulfur battery composite positive electrode material taking ternary material as carrier and preparation method thereof
CN114551794B (en) Positive electrode active material, positive electrode, preparation method and lithium ion battery
WO2017177960A1 (en) Electrolyte solution, battery, and battery pack
KR20160025893A (en) Composite positive electrode active material, positive electrode and lithium battery employing the same
CN114927667B (en) Positive electrode active material, preparation method thereof, positive electrode sheet and lithium ion secondary battery
CN114604896B (en) MXene composite modified binary manganese-based sodium electro-precursor and preparation method thereof
CN113206241B (en) Preparation method of single crystal nickel cobalt lithium manganate ternary material
JP4810729B2 (en) Lithium transition metal composite oxide and method for producing the same
CN113937279A (en) Positive electrode material, preparation method thereof and sodium ion battery
CN113764637A (en) Positive plate of high-energy-density lithium ion battery and preparation method thereof
EP3489198A1 (en) Cathode active material of lithium secondary battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant