CN114142033A - Modified graphite negative electrode material for lithium ion battery - Google Patents
Modified graphite negative electrode material for lithium ion battery Download PDFInfo
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- CN114142033A CN114142033A CN202111275162.2A CN202111275162A CN114142033A CN 114142033 A CN114142033 A CN 114142033A CN 202111275162 A CN202111275162 A CN 202111275162A CN 114142033 A CN114142033 A CN 114142033A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 49
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000007773 negative electrode material Substances 0.000 title claims description 13
- 239000010439 graphite Substances 0.000 claims abstract description 40
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 39
- 239000007787 solid Substances 0.000 claims abstract description 34
- 239000000843 powder Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 229910001868 water Inorganic materials 0.000 claims abstract description 13
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- 239000010416 ion conductor Substances 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 230000007935 neutral effect Effects 0.000 claims abstract description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- -1 zirconium ions Chemical class 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims 6
- 238000005253 cladding Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 239000010406 cathode material Substances 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 2
- 229910003002 lithium salt Inorganic materials 0.000 abstract 2
- 159000000002 lithium salts Chemical class 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 229910006213 ZrOCl2 Inorganic materials 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229910010631 Li6C Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/36—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 discloses a modified graphite cathode material for a lithium ion battery, which comprises the following process steps: dissolving a zirconium source and polyvinyl alcohol in deionized water to obtain a solution A; dispersing a certain amount of graphite in the solution A; filtering and collecting solid powder in the solution, and washing until the pH value is neutral; drying the solid powder to obtain the product with ZrO coated on the surface2The graphite solid powder of (4); coating the surface with ZrO2The graphite solid powder is uniformly mixed with a lithium source and sintered to form ZrO2Reacting with lithium salt to form a lithium ion conductor layer and ZrO2Lithium salt enters the graphite laminated structure to form doping; washing with water, and drying. The modified graphite cathode material for the lithium ion battery prepared by the invention has excellent performance, the electrolyte wettability on the surface of the material is high, the first effect of the battery is improved, and the preparation method is prolongedThe cycle life of the battery is prolonged.
Description
Technical Field
The invention relates to the field of new energy materials and lithium ion batteries, in particular to a modified graphite cathode material for a lithium ion battery.
Background
The lithium ion battery has the characteristics of long cycle life, strong cruising ability, high green environmental protection performance and the like, and is one of the most popular secondary batteries in portable electronic products. At present, graphite is the most widely used negative electrode material of lithium ion batteries, and has the advantages of rich resources, stable electrochemical performance, low price, high reversible capacity and the like. But it also has obvious defects, such as poor hydrophilicity of graphite cathode, incomplete wetting of electrolyte; the graphite layers are connected by weak van der waals force, so that the layer structure is easy to damage in the charging and discharging process, graphite is pulverized, falls off and the like, and the cycle performance of the battery is reduced; in the charging and discharging process, the graphite cathode reacts with the electrolyte to generate an SEI film, so that the first coulombic efficiency of the battery is reduced, and the like. Aiming at the problems, the graphite is mainly coated and modified at present.
At present, graphite is coated with metal oxide, and the main methods include atomic layer deposition, hydrolysis, and the like. Hydrolysis is preferred in view of the fact that atomic layer deposition is too costly and does not provide conditions for large scale production. The hydrolysis method has mild conditions, does not need any treatment equipment and has the condition of mass production.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a modified graphite lithium ion battery cathode material which has a remarkable effect of improving various performances of a lithium ion battery.
The invention provides a preparation method of a modified graphite cathode material for a lithium ion battery, which comprises the following steps:
s1, dissolving a certain amount of zirconium source and polyvinyl alcohol in deionized water to obtain a solution A;
s2, dispersing a certain amount of graphite in the solution A, heating at a certain temperature and continuously stirring for a period of time;
s3, filtering and collecting solid powder in the solution A, and washing with hot deionized water until the pH value is neutral;
s4, drying the washed solid powder at a certain temperature for a period of time to obtain the solid powder with the surface coated with ZrO2The graphite solid powder of (4);
s5 coating the surface with ZrO2The graphite solid powder and a lithium source are uniformly mixed according to a certain proportion and are put in an inert gas atmosphereSintering at 700 ℃ for 10 h;
and S6, washing and drying the sintered solid to finally obtain the modified graphite negative electrode material which is coated with the lithium ion conductor layer and is doped with zirconium ions and lithium ions.
Preferably, in S1, the zirconium source is ZrOCl2.8(H2O), preferably ZrOCl in solution A2.8(H2O) concentration was 0.2 mol/L.
Preferably, in S2, the heating temperature is 100 ℃, the stirring speed is 300-500 rpm, and the stirring time is 24-48 h.
Preferably, in S2, the graphite powder has a mass of 4g to 16 g.
Preferably, in S4, the drying temperature is 120 ℃ and the drying time is 24 h.
Preferably, in S5, the lithium source is at least one of lithium hydroxide, lithium carbonate, lithium nitrate, lithium sulfate and lithium phosphate; the inert gas is at least one of nitrogen and argon; preferably, is coated with ZrO2The mixing mass ratio of the graphite solid powder to the lithium source is 1: 0.5-1.
The invention also provides the modified graphite cathode material for the lithium ion battery, which is prepared by the preparation method.
The invention also provides a lithium ion battery which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the negative electrode adopts the modified graphite negative electrode material for the lithium ion battery as a negative electrode active substance.
Has the advantages that: forming a layer of ZrO on the surface of graphite by hydrolysis2The operation is simple, and then the graphite is mixed with a lithium source and calcined at high temperature to form Li on the surface of the graphite2ZrO3Lithium ion conductor layer while Zr4+And Li+Doped into the graphite layer. Li as above2ZrO3The lithium ion conductor layer improves the wettability of the graphite surface to the electrolyte on one hand and improves the transmission efficiency of lithium ions on the other hand; in addition, zirconium ions are doped into the graphite laminated structure, so that the graphite layer spacing is increased, and the lithium ion transmission speed is favorably improved, so that the rate performance is improved; doping of lithium ions into graphite to form Li6C, additionally adding a lithium source to improveFirst-order and cycle life of the battery. The method is simple to operate, can be used for preparing a large amount of lithium ion batteries, and has a remarkable effect of improving the performance of the lithium ion batteries in all aspects.
Drawings
FIG. 1 is a photograph showing contact angles between graphite (a) before modification and graphite (b) after modification, which were prepared in example 1.
FIG. 2 is a graph showing the normal temperature cycle performance of examples 1, 2, 3 and 4.
Detailed Description
The present invention will be further illustrated with reference to the following specific embodiments, however, the scope of the present invention is not limited to the following examples.
Example 1
The invention provides a preparation method of a modified graphite cathode material for a lithium ion battery, which comprises the following steps:
s1: 0.02mol of ZrOCl28(H2O) in 100mL of deionized water to give solution A;
s2: dispersing 16g of graphite powder in the solution A, then heating at 100 ℃ and continuously stirring at a stirring speed of 400rpm for 24 h;
s3: the solid powder in solution a was collected by filtration and washed with hot deionized water until the pH was neutral;
s4: drying the washed solid powder at 120 deg.C for 24h to obtain the final product with ZrO coated surface2The graphite solid powder of (4);
s5: coating the surface with ZrO2Uniformly mixing the graphite solid powder with lithium carbonate according to the proportion of 1:1, and sintering for 10 hours at 700 ℃ in an argon atmosphere;
s6: and (3) after cooling, washing with water to remove redundant lithium carbonate, and drying to obtain the modified graphite cathode material which is coated with the lithium ion conductor layer and doped with zirconium ions and lithium ions.
The modified graphite negative electrode material prepared in the example 1 is mixed with conductive carbon black and sodium carboxymethylcellulose according to the mass ratio of 8:1:1, then a proper amount of N-methyl pyrrolidone is added, the mixture is uniformly mixed, coated on a copper foil, and dried in a vacuum oven at 80 ℃. Rolling and cutting to obtain electrode plate, using Li plate as counter electrode and electrolyteTo contain 1M LiPF6And (EC + DMC) (volume ratio of 1:1) mixed system, wherein the diaphragm is a microporous polyethylene film, and the button cell is assembled and formed in a glove box filled with argon gas, and then the performance of the button cell is tested.
Example 2
The invention provides a preparation method of a modified graphite cathode material for a lithium ion battery, which comprises the following steps:
s1: 0.02mol of ZrOCl28(H2O) in 100mL of deionized water to give solution A;
s2: dispersing 12g of graphite powder in the solution A, then heating at 100 ℃ and continuously stirring at a stirring speed of 400rpm for 24 h;
s3: the solid powder in solution a was collected by filtration and washed with hot deionized water until the pH was neutral;
s4: drying the washed solid powder at 120 deg.C for 24h to obtain the final product with ZrO coated surface2The graphite solid powder of (4);
s5: coating the surface with ZrO2Uniformly mixing the graphite solid powder with lithium hydroxide according to the proportion of 1:1, and sintering for 10 hours at 700 ℃ in an argon atmosphere;
s6: and (3) cooling, washing with water to remove redundant lithium hydroxide, and drying to obtain the modified graphite cathode material which is coated with the lithium ion conductor layer and is doped with zirconium ions and lithium ions.
The modified graphite negative electrode material prepared in the example 2 is mixed with conductive carbon black and polyvinylidene fluoride according to the mass ratio of 8:1:1, then a proper amount of N-methyl pyrrolidone is added, the mixture is uniformly mixed, coated on a copper foil, and dried in a vacuum oven at 80 ℃. Rolling and cutting to obtain electrode plate, using Li plate as counter electrode, and using electrolyte containing 1M LiPF6/And (EC + DMC) (volume ratio of 1:1) mixed system, wherein the diaphragm is a microporous polyethylene film, assembling and forming the button cell in an argon-filled glove box, and then testing the performance of the button cell.
Example 3
The invention provides a preparation method of a modified graphite cathode material for a lithium ion battery, which comprises the following steps:
s1: 0.02mol of ZrOCl28(H2O) in 100mL of deionized water to give solution A;
s2: dispersing 8g of graphite powder in the solution A, then heating at 100 ℃ and continuously stirring at a stirring speed of 400rpm for 24 h;
s3: the solid powder in solution a was collected by filtration and washed with hot deionized water until the pH was neutral;
s4: drying the washed solid powder at 120 deg.C for 24h to obtain the final product with ZrO coated surface2The graphite solid powder of (4);
s5: coating the surface with ZrO2Uniformly mixing the graphite solid powder with lithium hydroxide according to the proportion of 1:1, and sintering for 10 hours at 700 ℃ in an argon atmosphere;
s6: and (3) cooling, washing with water to remove redundant lithium hydroxide, and drying to obtain the modified graphite cathode material which is coated with the lithium ion conductor layer and is doped with zirconium ions and lithium ions.
The modified graphite negative electrode material prepared in example 3 was mixed with conductive graphite and polyvinylidene fluoride in a mass ratio of 8:1:1, and then an appropriate amount of N-methylpyrrolidone was added, mixed uniformly, coated on a copper foil, and dried in a vacuum oven at 80 ℃. Rolling and cutting to obtain electrode plate, using Li plate as counter electrode, and using electrolyte containing 1M LiPF6And (EC + DMC) (volume ratio of 1:1) mixed system, wherein the diaphragm is a microporous polypropylene film, assembling and forming the button cell in an argon-filled glove box, and then testing the performance of the button cell.
Example 4
The invention provides a preparation method of a modified graphite cathode material for a lithium ion battery, which comprises the following steps:
s1: 0.02mol of ZrOCl28(H2O) in 100mL of deionized water to give solution A;
s2: dispersing 4g of graphite powder in the solution A, then heating at 100 ℃ and continuously stirring at a stirring speed of 400rpm for 24 h;
s3: the solid powder in solution a was collected by filtration and washed with hot deionized water until the pH was neutral;
s4: drying the washed solid powder at 120 deg.C for 24h to obtain the final product with ZrO coated surface2The graphite solid powder of (4);
s5: coating the surface with ZrO2Uniformly mixing the graphite solid powder with lithium hydroxide according to the proportion of 1:1, and sintering for 10 hours at 700 ℃ in an argon atmosphere;
s6: and (3) cooling, washing with water to remove redundant lithium hydroxide, and drying to obtain the modified graphite cathode material which is coated with the lithium ion conductor layer and is doped with zirconium ions and lithium ions.
The modified graphite negative electrode material prepared in example 4 was mixed with carbon nanotubes and polyvinylidene fluoride in a mass ratio of 8:1:1, and then an appropriate amount of N-methylpyrrolidone was added, mixed uniformly, coated on a copper foil, and dried in a vacuum oven at 80 ℃. Rolling and cutting to obtain electrode plate, using Li plate as counter electrode, and using electrolyte containing 1M LiPF6And (EC + DMC) (volume ratio of 1:1) mixed system, wherein the diaphragm is a microporous polypropylene film, assembling and forming the button cell in an argon-filled glove box, and then testing the performance of the button cell.
Test examples
The modified graphite cathode material prepared by the method of the invention in the embodiment 1-4 and the common unmodified graphite cathode material are respectively assembled to form a button cell, and the performance of the button cell is tested. The specific experimental settings are as follows: the electrical property test data of the button cell assembled by the modified graphite cathode material prepared by the method of the embodiment 1-4 of the invention is recorded as an experimental group 1-4; the electrical performance test data of button cells assembled by common unmodified graphite cathode materials are recorded as a reference group, and the test results are shown in the following table:
| item | First effect of battery (%) | Capacity after 1000 cyclesRetention (%) |
| |
95.4 | 91.6 |
| |
96.8 | 92.2 |
| |
97.5 | 92.8 |
| |
98.2 | 94.1 |
| Reference group | 91.3 | 88.6 |
The data in the table show that the electrical performance data of the button cell batteries of the experimental groups 1 to 4 are superior to those of the reference group, which shows that the modified graphite cathode material prepared by the invention can obviously improve various electrical properties of the lithium ion battery, and the ratio of the zirconium source to the graphite is gradually increased along with the gradual reduction of the graphite dosage, so that the coating effect is better and better, and the electrical performance of the button cell batteries is also gradually improved.
Claims (8)
1. A preparation method of a modified graphite negative electrode material for a lithium ion battery is characterized by comprising the following steps:
s1, dissolving a certain amount of zirconium source and polyvinyl alcohol in deionized water to obtain a solution A;
s2, dispersing a certain amount of graphite in the solution A, heating at a certain temperature and continuously stirring for a period of time;
s3, filtering and collecting solid powder in the solution A, and washing with hot deionized water until the pH value is neutral;
s4, drying the washed solid powder at a certain temperature for a period of time to obtain the solid powder with the surface coated with ZrO2The graphite solid powder of (4);
s5 coating the surface with ZrO2Uniformly mixing the graphite solid powder with a lithium source according to a certain proportion, and sintering for 10 hours at 700 ℃ in an inert gas atmosphere;
and S6, washing and drying the sintered solid to finally obtain the modified graphite negative electrode material which is coated with the lithium ion conductor layer and is doped with zirconium ions and lithium ions.
2. The method for preparing the modified graphite anode material for the lithium ion battery as claimed in claim 1, wherein in S1, the zirconium source is ZrOCl2.8(H2O), ZrOCl in the liquid A2.8(H2O) concentration was 0.2 mol/L.
3. The preparation method of the modified graphite anode material for the lithium ion battery according to claim 1, wherein in S2, the heating temperature is 100 ℃, the stirring speed is 300-500 rpm, and the stirring time is 24-48 h.
4. The method for preparing a modified graphite anode material for a lithium ion battery according to claim 1, wherein the mass of the graphite powder in S2 is 4g to 16 g.
5. The method for preparing the modified graphite anode material for the lithium ion battery according to claim 1, wherein in S4, the drying temperature is 120 ℃ and the drying time is 24 h.
6. The method for preparing the modified graphite anode material for the lithium ion battery according to claim 1, wherein in S5, the lithium source is at least one of lithium hydroxide, lithium carbonate, lithium nitrate, lithium sulfate and lithium phosphate; inert gasIs one or more of nitrogen and argon; cladding with ZrO2The mixing mass ratio of the graphite solid powder to the lithium source is 1: 0.5-1.
7. The modified graphite anode material for the lithium ion battery, which is obtained by the preparation method of any one of claims 1 to 6.
8. The utility model provides a lithium ion battery, includes positive pole, negative pole, diaphragm and electrolyte, its characterized in that: the negative electrode uses the modified graphite negative electrode material for lithium ion batteries according to claim 7 as a negative electrode active material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114613963A (en) * | 2022-03-21 | 2022-06-10 | 惠州锂威新能源科技有限公司 | Negative electrode material, preparation method thereof, negative electrode plate and secondary battery |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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