CN114551794B - 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 PDFInfo
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- CN114551794B CN114551794B CN202111554453.5A CN202111554453A CN114551794B CN 114551794 B CN114551794 B CN 114551794B CN 202111554453 A CN202111554453 A CN 202111554453A CN 114551794 B CN114551794 B CN 114551794B
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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 application provides an anode active material, an anode, a preparation method and a lithium ion battery, wherein the anode 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 surface of the positive electrode containing the positive electrode active material provides good ionic conductivity and electronic conductivity, improves the dynamic performance of the battery, and optimizes the direct current impedance of the battery; meanwhile, the anode can optimize lithium ion diffusion to obtain higher capacity.
Description
Technical Field
The application belongs to the field of lithium ion batteries, and particularly relates to an anode active material, an anode, a preparation method and a lithium ion battery.
Background
In order to solve the problems of material cost and limited cobalt ore resources, a low-cobalt ternary material LiNi is developed x Co y Mn 1-x-y O 2 (y is less than or equal to 0.13), however, the reduction of the Co content in the low-cobalt ternary material can reduce the overall conductivity of the material and influence the capacity exertion of the battery; according to researches, a small amount of tungsten compound is coated on the surface of the positive electrode, so that the surface of the material can be effectively improvedIon and electron conductivity, thereby reducing internal resistance of the battery and improving low temperature performance. The tungsten coating layer of the material obtained by the existing dry coating method is punctiform, 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 tungsten compounds and poor electrical conductivity.
Disclosure of Invention
Aiming at the problems of punctiform surface coating layers of positive electrode active materials, limited lithium ion diffusion and surface impedance improvement and the like in the prior art, the application provides a positive electrode active material, a positive electrode, a preparation method and a lithium ion battery, wherein the surface of the positive electrode active material is provided with a very uniform membranous coating, the ultrathin tungsten compound coating promotes the lithium ion diffusion in the charge and discharge process, the charge and discharge capacity of the material is effectively improved, the surface impedance and the circulation stability are effectively improved, and the preparation method is used for obtaining the positive electrode active material through wet mixing or spraying, so that the process is simple, the operation is convenient, and the sintering time is shortened.
To achieve the purpose, the application adopts the following technical scheme:
in a first aspect, the application provides a positive electrode active material, which 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.
In the application, 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 tungsten compound has more stable lithium ion diffusion in the charge and discharge process, the charge and discharge 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 the tungsten compound is not limited to the listed values, other non-listed values in the range of the values are also applicable, and the coating amount is lower than 1000ppm, the coating is uneven, and the improvement effect is limited; the coating amount is more than 4000ppm, and the surface agglomeration is easy, so that the coating amount of tungsten element is in the range of 1000 to 4000ppm by adopting the application, and the diffusion speed of lithium ions and the impedance of a battery can be simultaneously considered.
The particle diameter of the positive electrode active material is preferably 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 recited values, and other non-recited values within the range of values are equally applicable.
The particle size of the positive electrode active material is preferably 3-5 mu m, the size of the positive electrode 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 diffusion speed of lithium ions and the impedance of the battery are both considered.
Preferably, the molecular formula of the nickel-cobalt-manganese ternary material powder is LiNi x Co y Mn 1-x-y O 2 Where 0.5.ltoreq.x.ltoreq.0.9, 0.ltoreq.y.ltoreq.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, but not limited to the values recited, other non-recited values within this range of values being equally applicable.
The preferred molecular formula of the application is LiNi x Co y Mn 1-x-y O 2 The low cobalt-nickel-cobalt-manganese ternary material powder has the advantages that metal resources are saved due to low cobalt content, and the production cost of the positive electrode and the battery is effectively reduced.
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 the form of H 4 W、H 2 W 2 O 7 、WO 3 、WO 2 、BW、B 2 W、W 2 N 3 、WF 6 、WF 4 Or WOF 4 Any one or a combination of at least two or more of them;
(b) The tungsten in the tungsten-containing film layer exists in the form of H 2 W 2 O 7 And/or WF 6 The method comprises the steps of carrying out a first treatment on the surface of the Wherein a non-limiting exemplary combination may be H 4 W and H 2 W 2 O 7 Is combined with H 4 W and WO 3 Is combined with H 4 W and WO 2 Is a combination of (a)、WF 6 And H 2 W 2 O 7 Is combined with H 4 W and WF 6 Is a combination of BW and H 2 W 2 O 7 Is a combination of WF 4 And H 2 W 2 O 7 WOF of (a) 4 And H 2 W 2 O 7 Or W 2 N 3 And WF 6 But not limited to, the recited combinations, and other combinations not recited within this range are equally applicable.
The existence form of tungsten in the tungsten-containing film layer of the application preferably adopts H 4 W、H 2 W 2 O 7 、WO 3 、WO 2 、BW、B 2 W、W 2 N 3 、WF 6 、WF 4 Or WOF 4 Any one or a combination of at least two or more of them, further preferably H is used 2 W 2 O 7 And/or WF 6 The method is to select a low-cost and high-activity tungsten compound to carry out tungsten coating so as to obtain a positive electrode active material with more uniform coating effect.
In a second aspect, the present application provides a method for preparing the positive electrode active material according to the first aspect, the method comprising the steps of:
and mixing nickel-cobalt-manganese ternary material powder, tungsten-containing powder and an alcohol solvent by a wet method or spraying and calcining to obtain the positive electrode active material.
The wet mixing comprises dispersing nickel-cobalt-manganese ternary material powder and tungsten-containing powder in an alcohol solvent, stirring until the alcohol solvent volatilizes, and spraying comprises mixing and dispersing the tungsten-containing powder in the alcohol solvent and then spraying the tungsten-containing powder to the nickel-cobalt-manganese ternary material powder.
According to the preparation method of the positive electrode active material, a wet cladding or spraying mixing mode is adopted, so that tungsten compounds and low-cobalt ternary materials are uniformly distributed, the uniformity is improved, the subsequent sintering time is shortened, and the production efficiency is improved.
As a preferable technical scheme of the application, the molecular formula of the nickel-cobalt-manganese ternary material powder is LiNi x Co y Mn 1-x-y O 2 Where 0.5.ltoreq.x.ltoreq.0.9, 0.ltoreq.y.ltoreq.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, but not limited to the values recited, other non-recited values within this range of values being equally applicable.
The preferred molecular formula of the application is LiNi x Co y Mn 1-x-y O 2 The low cobalt-nickel-cobalt-manganese ternary material powder has the advantages that metal resources are saved due to low cobalt content, and the production cost of the positive electrode and the battery is effectively reduced.
Preferably, the tungsten-containing powder satisfies at least one of the following conditions (a) to (b):
(a) The tungsten-containing powder is H 4 W、H 2 W 2 O 7 、WO 3 、WO 2 、BW、B 2 W、W 2 N 3 、WF 6 、WF 4 Or WOF 4 Any one or a combination of at least two or more of them;
(b) The tungsten-containing powder is H 2 W 2 O 7 And/or WF 6 ；
Wherein a non-limiting exemplary combination may be H 4 W and H 2 W 2 O 7 Is combined with H 4 W and WO 3 Is combined with H 4 W and WO 2 Is a combination of WF 6 And H 2 W 2 O 7 Is combined with H 4 W and WF 6 Is a combination of BW and H 2 W 2 O 7 Is a combination of WF 4 And H 2 W 2 O 7 WOF of (a) 4 And H 2 W 2 O 7 Or W 2 N 3 And WF 6 But not limited to, the recited combinations, and other combinations not recited within this range are equally applicable.
Preferably, the alcoholic solvent comprises ethanol.
As a preferable technical scheme of the application, 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 to 99.99): (0.01 to 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 recited values, and other non-recited values within the range of values are equally applicable.
The application preferably adopts the mass ratio of the nickel-cobalt-manganese ternary material powder to the tungsten-containing powder of (98-99.99): (0.01-2), more preferably (98.9-99.1): (0.9-1.1), and the ratio of the nickel-cobalt-manganese ternary material powder to the tungsten-containing film layer is more reasonable, thereby being beneficial to the diffusion of lithium ions in positive electrodes and battery products.
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, for example, 1.8:1, 1.9:1, 2:1, 2.1:1 or 2.2:1, but the present application is not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
The application preferably adopts the alcohol solvent and the nickel cobalt manganese ternary material powder with the liquid-solid ratio of (1.8-2.2): 1, so that the nickel cobalt manganese ternary material and tungsten-containing powder can be more uniform in the mixing process, and the alcohol solvent is evaporated in the subsequent process, thereby prolonging the sintering and combining time of the nickel cobalt manganese ternary material and 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 to 99.99): (0.01 to 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 recited values, and other non-recited values within the range of values are equally applicable.
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, for example, it may be 1.8:1, 1.9:1, 2:1, 2.1:1 or 2.2:1, but not limited to the recited values, and other non-recited values within the range of values are equally 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, the temperature may be 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, or 600 ℃, but the temperature is not limited to the values listed, and other values not listed in the range are equally applicable;
(b) The calcination time is 8 to 20 hours; for example, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h or 20h may be used, but are not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The calcination temperature in the present application is preferably 200 to 600 c, and the calcination time is preferably 8 to 20 hours, so that the obtained positive electrode active material has better coating effect, activity and powder strength.
In a third aspect, the present application provides a positive electrode comprising the positive electrode active material as described in the first aspect.
As a preferred embodiment of the present application, 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), such as 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, as other non-recited values within the range of values are equally applicable.
Preferably, the positive electrode active material accounts for 90 to 99% of the positive electrode by mass, for example, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99%, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In a fourth aspect, the present application provides a method for preparing the positive electrode according to the third aspect, the method comprising the steps of:
and pulping and tabletting the positive electrode active material to obtain the positive electrode.
As a preferred embodiment of the present application, the pulping includes mixing a positive electrode active material, a conductive material, a fluoropolymer, and an organic solvent into a slurry.
Preferably, the mass ratio of the positive electrode active material, the conductive material and the fluorine-containing polymer 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 recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the conductive material includes conductive carbon black and conductive carbon tube.
Preferably, the fluoropolymer comprises any one or a combination of at least two of polyvinylidene fluoride, hexafluoropropylene, and polyvinylidene fluoride-hexafluoropropylene copolymer, preferably polyvinylidene fluoride, wherein typical but non-limiting combinations are combinations of polyvinylidene fluoride and hexafluoropropylene, combinations of polyvinylidene fluoride and polyvinylidene fluoride-hexafluoropropylene copolymer, combinations of polyvinylidene fluoride-hexafluoropropylene copolymer and hexafluoropropylene, and the like, but are not limited to the recited combinations, and other non-recited combinations within this range are equally 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, 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 not limited to the recited values, and other non-recited values within the range of values are 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 recited values, and other non-recited values within the range of values are equally applicable.
As a preferable technical scheme of the application, the tabletting comprises the steps of 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/cm 2 For example, 15g/cm 2 、16g/cm 2 、17g/cm 2 、18g/cm 2 、19g/cm 2 、20g/cm 2 、21g/cm 2 Or 22g/cm 2 But are not limited to, the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the positive electrode has a compacted density of 3.3 to 3.8g/cm 3 For example, it may be 3.3g/cm 3 、3.4g/cm 3 、3.5g/cm 3 、3.6g/cm 3 、3.7g/cm 3 Or 3.8g/cm 3 But are not limited to, the recited values, and other non-recited values within the range of values are equally applicable.
In a fifth aspect, the present application 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 copper foil coated with graphite, and the electrolyte comprises a lithium hexafluorophosphate solution.
Preferably, the assembling steps of the lithium ion battery are as follows: adhering an aluminum positive electrode lug to the positive electrode, adhering a copper negative electrode lug to the negative electrode, and cutting the sheet positive electrode, the sheet diaphragm and the sheet negative electrode into pieces of 3-10 x (3-10) cm 2 Sequentially and tightly stacking the lithium hexafluorophosphate electrolyte on two sides of the diaphragm according to the sequence of the positive electrode, the diaphragm and the negative electrode to form a battery core, and stacking the battery core to the required layer number to obtain the lithium ion battery.
The lithium ion battery provided by the application adopts the nickel-cobalt-manganese ternary anode with higher theoretical capacity and high reaction platform voltage as the primary electrodeIn 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 used x Co y Mn 1-x-y O 2 And (y is less than or equal to 0.13), the coating form of the tungsten compound is optimized on the basis, so that the surface of the ternary material is provided with 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 application has the beneficial effects that:
(1) The application provides a positive electrode active material, wherein the surface of the positive electrode active material contains membranous tungsten compounds which are uniformly distributed, and an ultrathin tungsten compound coating promotes lithium ion diffusion in the charge and discharge process, so that the charge and discharge capacity, surface impedance and cycle stability of the material are effectively improved;
(2) The application provides a preparation method of an anode active material, which is characterized in that the anode active material is obtained through wet mixing or spraying, the sintering time is shortened, the sintering time is reduced from 14 to 20 hours of common sintering to 8 to 20 hours, the process is simple, and the operation is convenient;
(3) The application provides a lithium ion battery, which adopts the positive electrode active material and the preparation method provided by the application, and adopts the lithium ion battery prepared in a preferable range, wherein the gram capacity of 2.8V to 4.3V is more than or equal to 184.9mA.h/g, the direct current impedance at 25 ℃ and 50% SOC is less than or equal to 96.2Ω, and the lithium ion battery has sufficient gram capacity and lower resistance, and the capacity retention rate at-20 ℃ and 50% SOC direct current impedance is less than or equal to 812 Ω and-20 ℃ is more than or equal to 70.2%, and the lithium ion battery provided by the application has lower resistance and higher retention rate at low temperature, and has wide use environment and excellent performance.
Drawings
FIG. 1 is a graph showing gram capacity at 2.8 to 4.3V for example 1 of the present application and comparative example 1.
Fig. 2 is a graph showing the dc impedance comparison between the example 1 of the present application and the comparative example 1.
Fig. 3 is a graph comparing the low Wen Zhiliu impedance of example 1 of the present application with that of comparative example 1.
FIG. 4 is a graph showing the low temperature capacity retention ratio of example 1 of the present application and comparative example 1.
Detailed Description
To facilitate understanding of the present application, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the application and are not to be construed as a specific limitation thereof.
The technical scheme of the application is further described below by the specific embodiments with reference to the accompanying drawings.
In the prior art, the preparation method of the modified lithium nickel cobalt manganese oxide anode comprises the steps of mixing the lithium nickel cobalt manganese oxide with aluminum tungstate, and then sintering to obtain the modified lithium nickel cobalt manganese oxide anode, wherein the mixing mode is ball milling mixing. The lithium tungstate on the surface of the positive electrode produced by the mixing mode is distributed in a dot shape, the improvement on the circulation, the multiplying power performance and the conductivity performance of the positive electrode is limited, and the direct current impedance is only between 10 and 25 omega.
Another technical proposal provides a preparation method of a ternary anode coated with lithium tungstate. And 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 the surface and the inner wall of the pore coated with lithium tungstate. This solution provides the idea of wet coating of the tungsten layer, but does not give a method for improving the punctiform distribution of the tungsten compound.
Another technical scheme provides a tungsten-titanium co-coated lithium ion ternary anode and a preparation method thereof. The inner core of the lithium ion ternary anode is a lithium battery ternary material, the outer layer 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 blend liquid, a proper amount of lithium battery ternary material is added into the blend 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 anode. The method is characterized in that the inner core material and the coating material are respectively dissolved and mixed by spraying, so that the operation is complex.
The embodiment of the application discloses an anode active material, an anode, a preparation method and a lithium ion battery. The surface of the positive electrode active material is provided with a very uniform membranous coating, the preparation method adopts a wet mixing or spraying and then calcining mode to obtain the positive electrode active material, and the positive electrode is obtained through pulping and tabletting; the ultrathin tungsten compound coating promotes lithium ion diffusion in the charge-discharge process, so that the charge-discharge capacity of the material is effectively improved, meanwhile, the surface impedance and the cycling stability are effectively improved, the preparation method is used for obtaining the anode active material through wet mixing or spraying, the process is simple, the operation is convenient, and the sintering time is shortened.
In one embodiment, the present application provides a positive electrode active material in which tungsten is contained in an amount of 1000 to 4000ppm and has a particle diameter of 3 to 5 μm.
In another embodiment, the present application provides a method for preparing a positive electrode active material, the method comprising the steps of:
mixing or spraying nickel-cobalt-manganese ternary material powder, tungsten-containing powder and ethanol by a wet method, and calcining at 200-600 ℃ for 8-20 hours to obtain the positive electrode active material;
the wet mixing comprises dissolving nickel-cobalt-manganese ternary material powder and tungsten-containing powder in ethanol, stirring until ethanol volatilizes, and spraying comprises dissolving tungsten-containing powder in ethanol, and then spraying to the nickel-cobalt-manganese ternary material powder;
the molecular formula of the nickel-cobalt-manganese ternary material powder is LiNi x Co y Mn 1-x-y O 2 Wherein 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 H 4 W、H 2 W 2 O 7 、WO 3 、WO 2 、BW、B 2 W、W 2 N 3 、WF 6 、WF 4 Or WOF 4 Any one or a combination of at least two or more 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 to 99.99): (0.01 to 2), and the ethanol and the nickel-cobalt-manganese areThe liquid-solid ratio of the ternary material powder is (1.8 to 2.2): 1;
in another embodiment, the present application provides a method for preparing a positive electrode including the above positive electrode active material, the method comprising the steps of:
the positive electrode active material, the conductive carbon black, the conductive carbon tube, the polyvinylidene fluoride and the azomethyl pyrrolidone solvent are mixed to form slurry, and the slurry is coated on a metal foil, dried and rolled 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 to 99), 0.1 to 2, 0.1 to 5, 0.1 to 3, the mass ratio of the volume of the azomethylpyrrolidone solvent to the positive electrode active material is (6 to 7) ml to 1g, and the surface density of the coated positive electrode is 15 to 22g/cm 2 The positive electrode has a compacted density of 3.3 to 3.8g/cm 3 。
In another embodiment, the application provides a lithium ion battery, wherein a copper foil coated with graphite is used as a negative electrode, a polyethylene film and/or a polypropylene film is used as a diaphragm, a lithium hexafluorophosphate solution is used as an electrolyte, a positive electrode tab made of aluminum is adhered to the positive electrode, a negative electrode tab made of copper is adhered to the negative electrode, and the sheet-shaped positive electrode, the diaphragm and the negative electrode are cut into pieces of (3 to 10) x (3 to 10) cm 2 Sequentially and tightly stacking the two electrodes according to the sequence of positive electrode, diaphragm and negative electrode, and injecting lithium hexafluorophosphate electrolyte into two sides of the diaphragm to form a battery core, thereby assembling the 1Ah soft-package battery.
It should be understood that the process provided by the embodiments of the present application or the replacement or variation of conventional data is within the scope of the present application and the disclosure.
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 adopting the preparation methods of the positive electrode active material, the positive electrode and the lithium ion battery respectively, but the raw material types, the proportion, the mixing mode and the technological parameters of each embodiment are different.
Comparative examples 1 to 2
Each comparative example provides a lithium ion battery containing a positive electrode active material and a positive electrode, and each comparative example is prepared by adopting the preparation methods of the positive electrode active material, the positive electrode and the lithium ion battery according to the comparative examples, but the raw material types, the proportion, the mixing mode and the technological parameters of the comparative examples are different.
The flexible pouch batteries prepared in examples 1 to 9 and comparative examples 1 to 2 were formed and aged. At room temperature, charging to 4.3V voltage at 0.33C rate, discharging to 2.8V at 0.33C rate to obtain capacity C 0 . Through C 0 And calculating the coating mass of the positive electrode to obtain the gram capacity of the positive electrode. The full charge of the batteries prepared in examples 1 to 9 and comparative examples 1 to 2 was then adjusted to 70% SOC (70% full charge), after which the batteries were discharged at a current density of 4C for 30s, the voltage difference before and after discharge divided by the current density being the direct current impedance of the batteries at that SOC (full charge). The direct current impedance values of 50% SOC and 20% SOC can be measured by the method; then the battery is placed in a constant temperature oven at-20 ℃ to be charged and discharged at a voltage window of 2.8V to 4.3V with a current density of 0.33C, and the DC impedance value of the battery at-20 ℃ is tested by the same method. At the same time, the discharge capacity C at-20℃was recorded 1 ，C 1 /C 0 I.e., the low-temperature capacity retention rate of the battery. Meanwhile, the DC impedance value of the battery at the temperature of-20 ℃ is tested.
The gram capacity pair at 2.8 to 4.3V of example 1 and comparative example 1 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; the direct current impedance pairs of example 1 and comparative example 1 are as shown in fig. 2, the wet coating optimizes the contact surface of the material and the electrolyte, the side reaction is reduced, the charge transfer impedance is reduced, the temperature is reduced from 98mΩ to 93.7mΩ (50% soc,4C DC 30s, meaning 50% full charge, 30 seconds of constant current discharge at 4C), the temperature is reduced from 863mΩ to 764mΩ (50% soc,1C DC 20s, meaning 50% full charge, 20 seconds of constant current discharge at 1C) at low temperature; low temperature dc impedance pair for example 1 and comparative example 1 as shown in fig. 3, low temperature capacity retention for example 1 and comparative example 1 as shown in fig. 4, wet coating reduced Li + Through activityPolarization during the material/electrolyte interface process increased the capacity retention from 68% to 71% at-20 ℃.
The above examples and comparative examples show different tungsten contents, mixing modes, raw material types, ratios and process parameters in the positive electrode active materials, the raw material ratios and process parameters of the positive electrode are shown in table 1, and the parameters of the lithium ion battery are shown in table 2.
TABLE 1
TABLE 2
TABLE 3 Table 3
From a review of the data in tables 1 to 3 we can see:
(1) The lithium ion battery containing the positive electrode active material and the positive electrode obtained by the method of the examples 1 to 4 has the gram capacity of 2.8V to 4.3V of more than or equal to 184.9mA.h/g, the direct current impedance of 50% SOC at 25 ℃ of less than or equal to 96.2Ω, and the lithium ion battery has sufficient gram capacity and lower resistance value, the direct current impedance of 50% SOC at-20 ℃ of less than or equal to 812 Ω, and the capacity retention rate at-20 ℃ of more than or equal to 70.2%, and the lithium ion battery also has lower resistance value and higher retention rate at low temperature, so that the lithium ion battery provided by the application 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, 5 to 6 that, in example 5 and example 6, the calcination time is 6h and 24h, respectively, compared with example 1, but the calcination time of example 1 is 10h, the example 5 has much side reaction due to the too short calcination time, the 50% soc direct current impedance reaches 100.1Ω, -20 ℃ and the 50% soc direct current impedance reaches 1035Ω, the example 6 has a particle size larger due to the too long calcination time, resulting in a gram capacity drop, the capacity of 2.8V to 4.3V is only 182.1ma·h/g, and the lithium ion battery of example 1 has a capacity of 2.8V to 4.3V is 185.8ma·h/g, the 50% soc direct current impedance is 93.7Ω, the 50% soc direct current impedance is 764 Ω, and the capacity retention rate is 71% at-20 ℃, thereby obtaining a lithium ion battery with superior performance by adopting the calcination time within the preferred range;
(3) It can be seen from the combination of examples 1, 7 to 8 that, in examples 7 and 8, the calcination temperature was 150 ℃ and 700 ℃ respectively, whereas in example 1 the calcination temperature was 300 ℃, and in example 7 the crystallization degree was too short, and the side reactions were much, so that the 50% soc direct current resistance at 25 ℃ reached 102.5 Ω, -20 ℃ and the 50% soc direct current resistance reached 990 Ω, and in example 8 the particle size was increased due to the too high sintering temperature, resulting in a decrease in gram capacity, and in example 2.8V to 4.3V gram capacity was only 183.2ma·h/g, whereas in example 1 the lithium ion battery 2.8V to 4.3V gram capacity 185.8ma·h/g, and in example 25 ℃, the 50% soc direct current resistance was 93.7 Ω, and in-20 ℃ the 50% soc direct current resistance was 764 Ω, and the capacity retention rate at 20 ℃ was 71%, thus indicating that the present application employs a calcination temperature within the preferred range to obtain a lithium ion battery having superior performance;
(4) As can be seen from the comprehensive examples 1 and 1, the comparative example 1 uses dry mixing compared with the example 1, but the example 1 uses wet mixing, and the comparative example 1 uses dry mixing, so that the lithium ion diffusion is poor, and therefore, the capacity of 2.8V to 4.3V g is only 184.2mA.h/g, the 50% SOC direct current impedance reaches 98 Ω at 25 ℃, the 50% SOC direct current impedance reaches 863 Ω at 20 ℃, and the capacity of 2.8V to 4.3V g of the lithium ion battery of the example 1 is 185.8 mA.h/g, the 50% SOC direct current impedance at 25 ℃ is 93.7Ω, and the capacity retention rate at-20 ℃ is 764 Ω, and therefore, the application adopts the calcination temperature in the preferred range, and the lithium ion battery with sufficient gram capacity and low resistance and superior performance at room temperature and low temperature is obtained;
(5) As can be seen from the comprehensive examples 1 and 2, the tungsten content of comparative example 2 is 4500ppm compared with that of example 1, but the tungsten content of example 1 is 3000ppm, and the tungsten content of comparative example 2 is too high, which hinders the diffusion of lithium ions, so that the capacity of 2.8V to 4.3V g is only 184 mA.h/g, the DC impedance of 50% SOC is 101.7 Ω at 25 ℃, the DC impedance of 50% SOC is up to 917 Ω at-20 ℃, and the DC impedance of 2.8V to 4.3V g is 185.8 mA.h/g, the DC impedance of 50% SOC is 93.7 Ω at 25 ℃, and the DC impedance of 50% SOC is 764Ω at-20 ℃, thus indicating that the lithium ion battery with sufficient capacity and low resistance and superior performance at room temperature and low temperature is obtained by adopting the calcination temperature in the preferred range.
In summary, the lithium ion battery containing the positive electrode active material and the positive electrode provided by the application has sufficient gram capacity and lower resistance, and the lithium ion battery provided by the application has lower resistance and higher retention rate at low temperature, and is wide in use environment and suitable for being popularized and used in a large range.
The applicant declares that the above is only a specific embodiment of the present application, but the scope of the present application is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present application disclosed by the present application fall within the scope of the present application and the disclosure.
Claims (8)
1. The positive electrode active material is characterized by comprising nickel-cobalt-manganese ternary material powder and a tungsten-containing film layer which is coated on the surface of the nickel-cobalt-manganese ternary material powder and distributed in a film shape, wherein the mass fraction of tungsten is 1000-4000 ppm;
the tungsten in the tungsten-containing film layer exists in the form of H 2 W 2 O 7 ；
The particle diameter of the positive electrode active material is 3 to 5 μm.
2. The positive electrode active material according to claim 1, wherein the nickel-cobalt-manganese ternary material powder has a molecular formula of LiNi x Co y Mn 1-x-y O 2 Wherein 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 x+y is less than 1.
3. A method for producing the positive electrode active material according to claim 1 or 2, characterized in that the method comprises the steps of:
the nickel-cobalt-manganese ternary material powder, tungsten-containing powder and alcohol solvent are subjected to wet mixing or spraying and then are calcined to obtain the positive electrode active material;
the wet mixing comprises dispersing nickel-cobalt-manganese ternary material powder and tungsten-containing powder in an alcohol solvent, stirring until the alcohol solvent volatilizes, spraying comprises dispersing tungsten-containing powder in the alcohol solvent, and then spraying to the nickel-cobalt-manganese ternary material powder, wherein the calcining temperature is 200-600 ℃, and the calcining time is 8-20 h.
4. The method according to claim 3, wherein the mass ratio of the nickel cobalt manganese ternary material powder to the tungsten-containing powder is (98 to 99.99): (0.01 to 2).
5. The method according to claim 4, wherein the mass ratio of the nickel cobalt manganese ternary material powder to the tungsten-containing powder is (98.9 to 99.1): 0.9 to 1.1.
6. The method according to claim 3, wherein the ratio of the alcohol solvent to the Ni-Co-Mn ternary material powder is (1.8 to 2.2): 1.
7. A positive electrode comprising the positive electrode active material according to claim 1 or 2.
8. A lithium ion battery, comprising the positive electrode of claim 7.
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