CN114420896A - High-rate lithium battery negative electrode piece and preparation method and application thereof - Google Patents
High-rate lithium battery negative electrode piece and preparation method and application thereof Download PDFInfo
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- CN114420896A CN114420896A CN202011174016.6A CN202011174016A CN114420896A CN 114420896 A CN114420896 A CN 114420896A CN 202011174016 A CN202011174016 A CN 202011174016A CN 114420896 A CN114420896 A CN 114420896A
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- lithium
- negative electrode
- methylimidazolium
- lithium battery
- pole piece
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 80
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 49
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 48
- 239000002608 ionic liquid Substances 0.000 claims abstract description 44
- 238000005245 sintering Methods 0.000 claims abstract description 35
- 239000006185 dispersion Substances 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 24
- 239000003575 carbonaceous material Substances 0.000 claims description 15
- 229910021385 hard carbon Inorganic materials 0.000 claims description 11
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 8
- 229910021382 natural graphite Inorganic materials 0.000 claims description 7
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 6
- JOLFMOZUQSZTML-UHFFFAOYSA-M 1-methyl-3-propylimidazol-1-ium;chloride Chemical compound [Cl-].CCCN1C=C[N+](C)=C1 JOLFMOZUQSZTML-UHFFFAOYSA-M 0.000 claims description 5
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 5
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 4
- KYCQOKLOSUBEJK-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCN1C=C[N+](C)=C1 KYCQOKLOSUBEJK-UHFFFAOYSA-M 0.000 claims description 4
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 claims description 4
- JDOJFSVGXRJFLL-UHFFFAOYSA-N 1-ethyl-3-methylimidazol-3-ium;nitrate Chemical compound [O-][N+]([O-])=O.CCN1C=C[N+](C)=C1 JDOJFSVGXRJFLL-UHFFFAOYSA-N 0.000 claims description 4
- AJRFBXAXVLBZMP-UHFFFAOYSA-M 1-methyl-3-propylimidazol-1-ium;bromide Chemical compound [Br-].CCCN1C=C[N+](C)=C1 AJRFBXAXVLBZMP-UHFFFAOYSA-M 0.000 claims description 4
- INDFXCHYORWHLQ-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-butyl-3-methylimidazol-3-ium Chemical compound CCCCN1C=C[N+](C)=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F INDFXCHYORWHLQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 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
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 4
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 4
- BKGNDBUULDZRKY-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCN1C[NH+](C)C=C1 BKGNDBUULDZRKY-UHFFFAOYSA-N 0.000 claims description 3
- HZKDSQCZNUUQIF-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;hydrogen sulfate Chemical compound OS([O-])(=O)=O.CCN1C=C[N+](C)=C1 HZKDSQCZNUUQIF-UHFFFAOYSA-M 0.000 claims description 3
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021384 soft carbon Inorganic materials 0.000 claims description 3
- WXJHMNWFWIJJMN-UHFFFAOYSA-N 1-methyl-3-octyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCCCCCCN1C[NH+](C)C=C1 WXJHMNWFWIJJMN-UHFFFAOYSA-N 0.000 claims description 2
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 claims description 2
- 238000012986 modification Methods 0.000 description 30
- 230000004048 modification Effects 0.000 description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 26
- 239000000463 material Substances 0.000 description 18
- 230000008569 process Effects 0.000 description 16
- 238000005096 rolling process Methods 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 13
- 238000005056 compaction Methods 0.000 description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 12
- 239000012300 argon atmosphere Substances 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 229910002804 graphite Inorganic materials 0.000 description 10
- 239000010439 graphite Substances 0.000 description 10
- 239000012266 salt solution Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 238000010000 carbonizing Methods 0.000 description 9
- 239000006255 coating slurry Substances 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- WXMVWUBWIHZLMQ-UHFFFAOYSA-N 3-methyl-1-octylimidazolium Chemical compound CCCCCCCCN1C=C[N+](C)=C1 WXMVWUBWIHZLMQ-UHFFFAOYSA-N 0.000 description 3
- 229910013075 LiBF Inorganic materials 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910013188 LiBOB Inorganic materials 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 1
- QOHANVRCHGWPNG-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole;sulfuric acid Chemical compound OS(O)(=O)=O.CCN1CN(C)C=C1 QOHANVRCHGWPNG-UHFFFAOYSA-N 0.000 description 1
- OXFBEEDAZHXDHB-UHFFFAOYSA-M 3-methyl-1-octylimidazolium chloride Chemical class [Cl-].CCCCCCCCN1C=C[N+](C)=C1 OXFBEEDAZHXDHB-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 206010063385 Intellectualisation Diseases 0.000 description 1
- OBOXTJCIIVUZEN-UHFFFAOYSA-N [C].[O] Chemical group [C].[O] OBOXTJCIIVUZEN-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910021469 graphitizable carbon Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- IURDGNBWYHNACE-UHFFFAOYSA-N lithium;pyrrolidine Chemical compound [Li+].C1CCNC1 IURDGNBWYHNACE-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
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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
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
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Abstract
The invention relates to a high-rate lithium battery negative electrode piece and a preparation method and application thereof. The preparation method of the high-rate lithium battery negative pole piece comprises the following steps: (1) dispersing lithium salt in ionic liquid to obtain dispersion liquid; (2) and coating the obtained dispersion liquid on an unmodified negative electrode plate, then placing the negative electrode plate in a protective atmosphere at 100-300 ℃ for sintering, and finally cooling to room temperature to obtain the high-rate lithium battery negative electrode plate.
Description
Technical Field
The invention relates to a lithium battery negative electrode piece, a preparation method and application thereof, in particular to a high-rate lithium battery negative electrode piece, a preparation method and application thereof, and particularly relates to a high-rate lithium battery carbon negative electrode piece, a preparation method and application thereof, belonging to the technical field of lithium ion battery electrode piece materials.
Background
The carbon material is the most widely applied lithium ion battery cathode material at present, and lithium can be reversibly embedded into crystal lattices of the carbon material to effectively avoid the formation of lithium dendrites, so that the cycle stability and safety of the lithium ion battery are greatly improved. Carbon materials include primarily natural and synthetic graphite, graphitizable carbon, low temperature and non-graphitizable carbon, and doped carbon. Due to the development of electronic product intellectualization and the wide application of electric automobiles, the novel cathode material is obtained by graphitization treatment at 1900-2800 ℃. The cycling stability of the graphite is mainly related to the quality of a solid electrolyte membrane (SEI film) formed in the lithium intercalation process, so that when a large current is charged and discharged, the SEI film is damaged due to the impact of the current, the cycling stability is poor, the rapid capacity attenuation is caused, and the PC component of the electrolyte can be intercalated with lithium ions by the graphite layer, so that the capacity is too low, and the redundant SEI film is formed, so that the first efficiency of the battery is reduced, and the stability is poor. Therefore, the graphite-based electrode is considered to be unsuitable for the preparation of a power type battery, and thus is unsuitable for use in electric vehicles, electric tools, and the like, which require high-power discharge.
Many attempts have been made by many researchers to improve the high current charging and discharging characteristics of graphite. The main improvement methods include surface oxidation, carbon coating, surface deposition of metal or metal oxide, and the like. Some scientists partially oxidize the surface of the artificial graphite to form nano-scale micropores on the surface layer of the graphite and form a compact oxide layer on the surface of the graphite. It is possible to prevent co-intercalation of the electrolyte while increasing the path of lithium ion intercalation. Therefore, the first efficiency, reversible capacity and cycling stability of the graphite electrode can be improved to different degrees. The polythiophene is coated on the surface of the graphite to form a conductive network, so that the material has good conductivity and the irreversible capacity of the graphite can be effectively reduced.
Non-graphitizable carbon is also referred to as hard carbon, and refers to a carbon material that is difficult to graphitize even at high temperatures of 2500 ℃. Because the hard carbon has the characteristics of high specific capacity, stable cycle performance, excellent large-current charge and discharge performance and the like, researchers make a great deal of research on the hard carbon so as to prepare high-performance power batteries. However, the hard carbon material itself has a large surface area and surface functional groups formed during the preparation process may consume a large amount of lithium ions to form an SEI film when contacting an electrolyte, resulting in a large irreversible capacity loss. In addition, hard carbon materials also have the characteristic of voltage hysteresis.
The negative pole piece of the current lithium ion battery still has poor conductivity and poor high-rate performance: the negative electrode can form an SEI film in the formation process, when the charge-discharge current density is increased, a rapid transmission channel of ions and electrons cannot be formed, the electrochemical performance can be rapidly attenuated, and obviously the requirements of high capacity and high rate performance of modern lithium ion batteries cannot be met. Therefore, the development and research on the battery pole piece mainly focus on how to improve the SEI film of the negative electrode and inhibit the rate performance difference caused by the over-low conductivity, so as to expand the application range of the lithium battery to more fields of large-current application.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a high-rate lithium battery negative electrode sheet, and a preparation method and an application thereof, so as to improve electrochemical properties of a lithium battery, such as specific capacity, rate performance, cycling stability, and the like.
On the one hand, the preparation method of the high-rate lithium battery negative electrode piece comprises the following steps:
(1) dispersing lithium salt in ionic liquid to obtain dispersion liquid;
(2) and coating the obtained dispersion solution on an unmodified negative electrode plate (a negative electrode plate before modification), then placing in a protective atmosphere, sintering at 100-300 ℃, and finally cooling to room temperature to obtain the high-rate lithium battery negative electrode plate.
In the disclosure, the inventor prepares a layer of SEI film on the surface of an unmodified negative electrode sheet (negative electrode sheet before modification), which can effectively increase the conductivity between an electrolyte and a negative electrode, thereby making full use of active materials, reducing the consumption of the electrolyte and positive active lithium, and simultaneously shortening the migration path of lithium ions in the material to improve the rate capability of the material. Specifically, lithium salt is dispersed in ionic liquid, coated on an unmodified negative electrode plate, and then sintered at 100-300 ℃ in a protective atmosphere. During the pre-sintering period, the ionic liquid is carbonized and forms a stable SEI film with the surface of the negative electrode. And then continuously sintering to realize carbonization treatment, forming a stable conductive network structure in the process, removing unstable carbon-oxygen functional groups to form a stable high-conductivity system, and finally cooling to room temperature to obtain the pole piece with the structure, the appearance, the property, the lithium battery capacity and the like which are completely different from those of the conventional material.
Preferably, the lithium salt is selected from at least one of lithium fluoride, lithium acetylacetonate, lithium carbonate, lithium chloride, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium dioxalate borate, N-dialkylpyrrolidinium lithium salt, lithium difluorooxalato borate, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, and lithium N-ethylpyrrolidinium tetrafluoroborate.
Preferably, the concentration of the lithium salt in the dispersion is 0.01-10 wt%. Too low a concentration of the lithium salt may result in too low a lithium source, consuming lithium from the electrolyte and the positive electrode, and too high a concentration of the lithium salt may result in too many side reactions in the battery.
Preferably, the ionic liquid is selected from the group consisting of 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium nitrate, 1-ethyl-3-methylimidazolium hydrogen sulfate, 1-ethyl-3-methylimidazolium perchlorate, 1-propyl-3-methylimidazolium chloride, 1-propyl-3-methylimidazolium bromide, 1-propyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium bromide, 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) amide, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-octyl-3 methylimidazole tetrafluoroborate and 1-octyl-3 methylimidazole chloride salt.
Preferably, the mass ratio of the dispersion liquid to the unmodified negative electrode plate is 0.01wt% to 2wt%, and preferably 0.01wt% to 1 wt%. If the coating is too little, the surface of the pole piece cannot be completely covered, and the surface of the negative electrode cannot be completely modified. If the coating is excessive, the active material proportion of the negative electrode is too low, and the capacity exertion of the pole piece is influenced.
Preferably, the total time of sintering is 2-5 hours. The protective atmosphere may be an inert atmosphere, preferably an argon atmosphere.
Preferably, after sintering, the temperature is reduced to room temperature within 2-10 hours, so as to prevent the phenomena of pole piece surface fracture and surface crack caused by too fast temperature reduction.
Preferably, the material of the unmodified negative electrode plate is one of natural graphite, artificial graphite, a hard carbon material and a soft carbon material, and preferably at least one of natural graphite, artificial graphite and a hard carbon material.
And preferably, rolling the obtained high-rate lithium battery negative electrode plate under 10-80 MPa to ensure that the compaction density of the high-rate lithium battery negative electrode plate reaches 0.9-1.1 g/cm3。
In another aspect, the invention provides a high-rate lithium battery negative electrode plate prepared by the preparation method.
On the other hand, the invention also provides a lithium battery containing the high-rate lithium battery negative electrode piece.
Has the advantages that:
(1) in the invention, the obtained electrode plate of the lithium ion battery has high specific capacity, good rate performance and cycle stability, easily obtained raw materials and simple preparation process, and is expected to realize large-scale production;
(2) the prepared lithium battery negative pole piece (namely the lithium battery negative pole piece) has higher capacity (350 mAh/g). The specific capacity of the material is reserved, the first effect of the negative electrode is improved, meanwhile, the impedance of the electrode material is low, and the stability of the material in the circulating process is improved.
Drawings
Fig. 1 is a charge-discharge curve of the negative electrode plate of the lithium battery prepared in example 1 and a comparative sample (electrode plate before modification).
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the present disclosure, lithium fluoride, lithium acetylacetonate, lithium carbonate, lithium chloride, lithium hexafluorophosphate (LiPF) is used6) Lithium tetrafluoroborate (LiBF)4) The lithium ion battery negative electrode plate is prepared by physically mixing lithium perchlorate, lithium dioxalate borate (LiBOB), N-dialkyl pyrrolidinium lithium salt, lithium difluorooxalate borate (LiODFB), lithium bis (fluorosulfonyl) imide (LiFSI), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) and at least one lithium salt of N-ethyl pyrrolidinium tetrafluoroborate with ionic liquid and then sintering at high temperature.
Specifically, the lithium battery negative electrode plate is prepared by taking an ionic liquid containing lithium salt as a raw material, performing surface coating and high-temperature roasting, and performing heating, constant temperature and cooling processes according to the set curve to finish high temperature. The method for preparing the negative electrode sheet for a lithium battery is exemplarily described below.
And dispersing the lithium salt into the ionic liquid to prepare dispersions with different concentrations for later use. Wherein the concentration of lithium salt in the dispersion liquid is 0.01-10 wt% of ionic liquid. The ionic liquid can be 1-ethyl-3-methylimidazolium tetrafluoroborate [ EMIm][BF4]1-Ethyl-3-methylimidazolium hexafluorophosphate [ EMIm][PF6]1-Ethyl-3-methylimidazolium nitrate [ EMIm ]][NO3]1-Ethyl-3-methylimidazolium hydrogen sulfate [ EMIm][HSO3]1-Ethyl-3-methylimidazole perchlorate [ EMIm ]][ClO4]1-propyl-3-methylimidazolium chloride [ PMIm]Cl, 1-propyl-3-methylimidazolium bromide [ PMIm]Br, 1-propyl-3-methylimidazolium tetrafluoroborate [ PMIm][BF4]1-butyl-3 methylimidazolium chloride salt [ BMIm]Cl, 1-butyl-3 methylimidazolium bromide [ BMIm]Br, 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) amide [ C4mim][Tf2N]1-butyl-3-methylimidazolium hexafluorophosphate [ BMIm][PF6]1-octyl-3-methylimidazolium hexafluorophosphate [ C8mim [ ]][PF6]1-octyl-3-methylimidazolium tetrafluoroborate [ C8 mim)][BF4]1-octyl-3-methylimidazolium chloride salt [ C8mim ]]Cl, and the like.
The preparation of the negative pole piece before modification comprises the following steps: the negative electrode material, the conductive agent acetylene black and the binder polyvinylidene fluoride (PVDF) are fully stirred and uniformly mixed in an N-methyl pyrrolidone solvent system according to the mass ratio of (85-90%) (5-10%), and then coated on a negative electrode current collector Cu foil for drying, so as to obtain the negative electrode plate. Wherein, the negative electrode material can be selected from one of natural graphite, artificial graphite, hard carbon material and soft carbon material. And (3) performing compression molding to obtain the unmodified negative pole piece (namely the negative pole piece before modification). In addition, the negative pole piece before modification can also be sourced from the market.
And coating the dispersion liquid on the surface of the negative plate before modification, and then putting the negative plate into a tube furnace containing a protective atmosphere for sintering. Wherein the protective atmosphere may be argon. The sintering temperature can be 100-300 ℃, the total time can be 2-5 hours, the raw materials can carbonize the ionic liquid at this stage, and the ionic liquid and lithium salt form a film with good conductivity, so that the formation of the conductive SEI is facilitated, and the structure is more stable. Preferably, the temperature rise rate of the sintering can be 5-10 ℃/min. As a detailed example, in an argon protection furnace, the sintering temperature curve is set to be heated to 100-300 ℃ from the room temperature at the speed of 5-10 ℃/min and the temperature is kept for 2-5 hours. After the sintering treatment, the temperature is reduced to room temperature for 2-10 hours, so as to prevent the phenomena of pole piece surface fracture, surface crack and the like caused by too fast temperature reduction. For example, the temperature is lowered from the treatment temperature (300 ℃) to room temperature over 5 hours in an argon atmosphere.
And (4) rolling the treated pole piece, and pressing the active substance to a preset compaction density. Wherein the rolling pressure can be 10-80 MPa. The predetermined compaction density may be 0.9 to 1.1g/cm3. The pole piece after rolling treatment is applied to the preparation of the lithium battery. The lithium battery further includes an electrolyte and a positive electrode, and preferably includes a separator and the like.
In the invention, the high-conductivity lithium battery negative electrode piece is prepared by coating the surface of a negative electrode piece with lithium salt-containing ionic liquid through a high-temperature sintering process. The SEI film is formed on the surface of the obtained negative pole piece and mainly consists of a lithium-doped carbon material, so that the negative pole piece has good conductivity. The obtained pole piece has good stability and higher conductivity within a proper voltage range (0.0-1.2V) by using a graphite pole piece. And after the lithium battery prepared by the obtained pole piece is cycled for 100 times, the capacity retention rate of the lithium battery is still higher than 98%.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
The preparation of the negative pole piece before modification comprises the following steps: fully stirring and uniformly mixing a negative electrode material, a conductive agent acetylene black and a binder polyvinylidene fluoride (PVDF) in an N-methyl pyrrolidone solvent system according to the mass ratio of (85-90%) (5-10%), and coating the mixture on a negative electrode current collector Cu foil for drying to obtain a negative electrode sheet, wherein the negative electrode material of the lithium ion battery can comprise artificial graphite, natural graphite, hard carbon and the like; the compacted density of the powder is 1g/cm3)；
Lithium fluoride is adopted as a raw material for forming an SEI film, and is dispersed in an ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate [ EMIm][BF4]Performing the following steps; weighing and preparing an ionic liquid solution with the lithium salt solution concentration of 0.1%, transferring and coating slurry of a lithium salt dispersion liquid (the mass ratio of the lithium salt dispersion liquid to the negative pole piece before modification is 1%) on the negative pole piece before modification, and placing the negative pole piece in an argon atmosphere, wherein the temperature rise rate of the pre-sintering is 5 ℃/min. Sintering at 300 deg.C for 2h, carbonizing the ionic liquid in the process and forming stable SEI film with the surface of the negative electrode, cooling to room temperature for 10 hr, and rolling the obtained pole piece (80Mpa) to the required compaction density (1 g/cm)3) And obtaining the high-rate lithium battery carbon negative pole piece. The pole piece with the structure, the appearance, the properties, the lithium battery capacity and the like completely different from the existing material is obtained.
And (3) testing electrical properties:
the prepared lithium battery electrode is used for measuring the capacity and the charge-discharge efficiency on an electrochemical workstation of Shanghai Chenghua CHI660D by using a constant current charging-discharging method. The voltage test range is 0.0V to 1.2V, and the constant current charging and discharging current is 0.7 mA;
preparing a lithium battery: placing an isolating membrane between the electrode plate and the lithium plate, stacking the electrode plate and the lithium plate in order, wherein the active substance content of the coated electrode plate is 2.1mg, the surface of the electrode plate coated with the active material is in contact with a diaphragm, sealing the isolating membrane and the electrode plate by adopting a packaging shell, and filling the prepared electrolyte to obtain an experimental button lithium battery containing the electrode;
and assembling the obtained product serving as an electrode material into an experimental button lithium battery in a glove box filled with argon. Then, the charge-discharge cycle is carried out at the multiplying power of 1C between 0.0 and 1.2V, and the first discharge capacity of the untreated pole piece is 330 mAh.g-1The first discharge capacity of the treated pole piece is 350 mAh.g-1The reversible capacity of 1C rate charge and discharge after 100 weeks of cycle (as shown in FIG. 1) still reaches 346mAh g-1Experimental lithium button cells showed excellent cycle life performance (as shown in table 1).
Example 2
Lithium carbonate is used as a raw material for forming an SEI film, and is dispersed in ionic 1-ethyl-3-methylimidazolium hexafluorophosphate [ EMIm ]][PF6]Performing the following steps; weighing and preparing an ionic liquid solution with the lithium salt solution concentration of 0.2%, transferring and coating slurry of a lithium salt dispersion liquid (the mass ratio of the lithium salt dispersion liquid to the negative pole piece before modification is 1%) on the negative pole piece before modification, and placing the negative pole piece in an argon atmosphere, wherein the temperature rise rate of pre-sintering is 10 ℃/min. Sintering at 300 deg.C for 5h, carbonizing the ionic liquid in the process and forming stable SEI film with the surface of the negative electrode, cooling to room temperature for 10 hr, and rolling the obtained pole piece (80Mpa) to the required compaction density (1 g/cm)3) And obtaining the high-rate lithium battery carbon negative pole piece. The pole piece with the structure, the appearance, the properties, the lithium battery capacity and the like completely different from the existing material is obtained.
Example 3
Dispersing lithium acetylacetonate in ionic liquid 1-ethyl-3-methylimidazolium nitrate [ EMIm][NO3](ii) a Weighing and preparing an ionic liquid solution with the lithium salt solution concentration of 0.5%, transferring and coating slurry of a lithium salt dispersion liquid (the mass ratio of the lithium salt dispersion liquid to the negative pole piece before modification is 1%) on the negative pole piece before modification, and placing the negative pole piece in an argon atmosphere, wherein the pre-sintering heating rate is 8 ℃/min. Sintering at 200 deg.C for 3h, carbonizing the ionic liquid in the process and forming stable SEI film with the surface of the negative electrode, cooling to room temperature for 5 hr, and rolling the obtained pole piece (80Mpa) to required compaction density (1 g/cm)3) And obtaining the high-rate lithium battery carbon negative pole piece. The pole piece with the structure, the appearance, the properties, the lithium battery capacity and the like completely different from the existing material is obtained.
Example 4
Dispersing lithium chloride in ionic liquid 1-ethyl-3-methylimidazole hydrogen sulfate [ EMIm][HSO3](ii) a Weighing and preparing an ionic liquid solution with the lithium salt solution concentration of 0.1%, transferring and coating slurry of a lithium salt dispersion liquid (the mass ratio of the lithium salt dispersion liquid to the negative pole piece before modification is 1%) on the negative pole piece before modification, and placing the negative pole piece in an argon atmosphere, wherein the temperature rise rate of pre-sintering is 3 ℃/min. And sintering at 280 ℃ for 3h, carbonizing the ionic liquid in the process and forming a stable SEI film with the surface of the negative electrode, cooling to room temperature after 10 hours, and rolling the obtained pole piece to the required compaction density to obtain the high-magnification lithium battery carbon negative pole piece. The pole piece with the structure, the appearance, the properties, the lithium battery capacity and the like completely different from the existing material is obtained.
Example 5
Mixing lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Dispersed in ionic liquid 1-ethyl-3 methyl imidazole perchlorate [ EMIm][ClO4]Performing the following steps; weighing and preparing ionic liquid solutions with lithium salt solution concentrations of 0%, 0.1%, 0.2%, 0.5%, 1.0%, 2.0%, 5.0% and 10.0%, transferring and coating lithium salt dispersion liquid (the mass ratio of the lithium salt dispersion liquid to the negative pole piece before modification is 0.6%) slurry on the negative pole piece before modification, and placing the negative pole piece in an argon atmosphere, wherein the temperature rise rate of pre-sintering is 7 ℃/min. Firing at 250 ℃And (3) carbonizing the ionic liquid in the process to form a stable SEI film with the surface of the negative electrode, cooling to room temperature after 6 hours, and rolling the obtained pole piece (80Mpa) to the required compaction density (1 g/cm)3) And obtaining the high-rate lithium battery carbon negative pole piece. The pole piece with the structure, the appearance, the properties, the lithium battery capacity and the like completely different from the existing material is obtained.
Example 6
Mixing lithium tetrafluoroborate (LiBF)4) Dispersed in ionic liquid 1-propyl-3-methylimidazolium chloride [ PMIm]In Cl; weighing and preparing an ionic liquid solution with the lithium salt solution concentration of 0.2%, transferring and coating slurry of a lithium salt dispersion liquid (the mass ratio of the lithium salt dispersion liquid to the negative pole piece before modification is 1.5%) on the negative pole piece before modification, and placing the negative pole piece in an argon atmosphere, wherein the pre-sintering heating rate is 7 ℃/min. Sintering at 300 deg.C for 4h, carbonizing the ionic liquid in the process and forming stable SEI film with the surface of the negative electrode, cooling to room temperature for 10 hr, and rolling the obtained pole piece (80Mpa) to the required compaction density (1 g/cm)3) And obtaining the high-rate lithium battery carbon negative pole piece. The pole piece with the structure, the appearance, the properties, the lithium battery capacity and the like completely different from the existing material is obtained.
Example 7
Dispersing lithium perchlorate in ionic liquid 1-propyl-3 methylimidazolium bromide [ PMIm]In Br; weighing and preparing an ionic liquid solution with the lithium salt solution concentration of 0.1%, transferring and coating slurry of a lithium salt dispersion liquid (the mass ratio of the lithium salt dispersion liquid to the negative pole piece before modification is 1%) on the negative pole piece before modification, and placing the negative pole piece in an argon atmosphere, wherein the temperature rise rate of the pre-sintering is 5 ℃/min. Sintering at 300 deg.C for 2h, carbonizing the ionic liquid in the process and forming stable SEI film with the surface of the negative electrode, cooling to room temperature for 10 hr, and rolling the obtained pole piece (80Mpa) to the required compaction density (1.1 g/cm)3) And obtaining the high-rate lithium battery carbon negative pole piece. The pole piece with the structure, the appearance, the properties, the lithium battery capacity and the like completely different from the existing material is obtained.
Example 8
Lithium bis (oxalato) borate is used as a raw material for forming an SEI film, and boron bis (oxalato) borate is used as a raw material for forming an SEI filmLithium (LiBOB) is dispersed in ionic liquid 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) amide [ C4mim ]][Tf2N]Performing the following steps; weighing and preparing an ionic liquid solution with the lithium salt solution concentration of 0.2%, transferring and coating slurry of a lithium salt dispersion liquid (the mass ratio of the lithium salt dispersion liquid to the negative pole piece before modification is 1.9%) on the negative pole piece before modification, and placing the negative pole piece in an argon atmosphere, wherein the pre-sintering heating rate is 10 ℃/min. Sintering at 300 deg.C for 3h, carbonizing the ionic liquid in the process and forming stable SEI film with the surface of the negative electrode, cooling to room temperature for 10 hr, and rolling the obtained pole piece to required compaction density (0.9 g/cm)3) And obtaining the high-rate lithium battery carbon negative pole piece. The pole piece with the structure, the appearance, the properties, the lithium battery capacity and the like completely different from the existing material is obtained.
Example 9
Lithium difluoro (oxalato) borate (LiODFB) is dispersed in ionic liquid 1-butyl-3 methylimidazolium hexafluorophosphate [ BMIm][PF6]Performing the following steps; weighing and preparing an ionic liquid solution with the lithium salt solution concentration of 0.3%, transferring and coating slurry of a lithium salt dispersion liquid (the mass ratio of the lithium salt dispersion liquid to the negative pole piece before modification is 1%) on the negative pole piece before modification, and placing the negative pole piece in an argon atmosphere, wherein the temperature rise rate of the pre-sintering is 5 ℃/min. Sintering at 300 deg.C for 4h, carbonizing the ionic liquid in the process and forming stable SEI film with the surface of the negative electrode, cooling to room temperature for 2 hr, and rolling the obtained pole piece (80Mpa) to the required compaction density (1 g/cm)3) And obtaining the high-rate lithium battery carbon negative pole piece. The pole piece with the structure, the appearance, the properties, the lithium battery capacity and the like completely different from the existing material is obtained.
Example 10
Dispersing lithium bis (fluorosulfonyl) imide (LiFSI) in ionic liquid 1-octyl-3 methylimidazolium tetrafluoroborate [ C ]8mim][BF4]Performing the following steps; weighing and preparing an ionic liquid solution with the lithium salt solution concentration of 0.5%, transferring and coating slurry of a lithium salt dispersion liquid (the mass ratio of the lithium salt dispersion liquid to the negative pole piece before modification is 1%) on the negative pole piece before modification, and placing the negative pole piece in an argon atmosphere, wherein the temperature rise rate of the pre-sintering is 5 ℃/min. Sintering at 300 deg.C for 2hCarbonizing the ionic liquid and forming a stable SEI film with the surface of the negative electrode, cooling to room temperature after 10 hours, and rolling the obtained pole piece (80Mpa) to the required compaction density (1 g/cm)3) And obtaining the high-rate lithium battery carbon negative pole piece. The pole piece with the structure, the appearance, the properties, the lithium battery capacity and the like completely different from the existing material is obtained.
Example 11
In this embodiment, referring to example 5, the preparation process of the high-rate lithium battery negative electrode sheet is different in that: the mass ratio of the lithium salt dispersion liquid to the negative electrode plate before modification is 0.2%, 1.0%, 1.5% and 2.0%.
The performance test method of the high-conductivity lithium battery negative electrode piece obtained in the other examples and the comparative example is shown in example 1, and the performance test data is shown in table 1.
Table 1 shows the raw materials and performance parameters of the highly conductive lithium battery negative electrode sheet prepared in examples 1 to 10 of the present invention:
。
(Note: first Effect, means first coulombic efficiency)
Claims (10)
1. A preparation method of a high-rate lithium battery negative electrode piece is characterized by comprising the following steps:
(1) dispersing lithium salt in ionic liquid to obtain dispersion liquid;
(2) and coating the obtained dispersion liquid on an unmodified negative electrode plate, then placing the negative electrode plate in a protective atmosphere at 100-300 ℃ for sintering, and finally cooling to room temperature to obtain the high-rate lithium battery negative electrode plate.
2. The method according to claim 1, wherein the lithium salt is selected from at least one of lithium fluoride, lithium acetylacetonate, lithium carbonate, lithium chloride, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium dioxalate borate, N-dialkylpyrrolidinium lithium salt, lithium difluorooxalate borate, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, and lithium N-ethylpyrrolidinium tetrafluoroborate; the concentration of lithium salt in the dispersion liquid is 0.01-10 wt%.
3. The method according to claim 1 or 2, wherein the ionic liquid is selected from the group consisting of 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium nitrate, 1-ethyl-3-methylimidazolium hydrogen sulfate, 1-ethyl-3-methylimidazolium perchlorate, 1-propyl-3-methylimidazolium chloride, 1-propyl-3-methylimidazolium bromide, 1-propyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium bromide, 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) amide, 1-butyl-3-methylimidazolium hexafluorophosphate, At least one of 1-octyl-3-methylimidazole hexafluorophosphate, 1-octyl-3-methylimidazole tetrafluoroborate and 1-octyl-3-methylimidazole chloride salt.
4. The preparation method according to any one of claims 1 to 3, wherein the mass ratio of the dispersion to the unmodified negative electrode sheet is 0.01 to 2wt%, preferably 0.01 to 1 wt%.
5. The method according to any one of claims 1 to 4, wherein the total time of the sintering is 2 to 5 hours.
6. The method according to any one of claims 1 to 5, wherein the temperature is lowered to room temperature within 2 to 10 hours after completion of the sintering.
7. The preparation method according to any one of claims 1 to 6, wherein the unmodified negative electrode plate is made of one of natural graphite, artificial graphite, a hard carbon material and a soft carbon material, and preferably at least one of natural graphite, artificial graphite and a hard carbon material.
8. The preparation method of the high-rate lithium battery negative electrode plate according to claim 7, wherein the high-rate lithium battery negative electrode plate is rolled under 10-80 MPa to ensure that the compacted density of the high-rate lithium battery negative electrode plate is 0.9-1.1 g/cm3。
9. The high-rate lithium battery negative electrode piece prepared according to the preparation method of any one of claims 1 to 8.
10. A lithium battery comprising the high-rate lithium battery negative electrode sheet of claim 9.
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