CN113991054A - Lithium-free negative plate for lithium battery and lithium battery - Google Patents
Lithium-free negative plate for lithium battery and lithium battery Download PDFInfo
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- CN113991054A CN113991054A CN202111275138.9A CN202111275138A CN113991054A CN 113991054 A CN113991054 A CN 113991054A CN 202111275138 A CN202111275138 A CN 202111275138A CN 113991054 A CN113991054 A CN 113991054A
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- lithium
- lithium battery
- fluoride
- current collector
- battery
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 197
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 190
- 239000007788 liquid Substances 0.000 claims abstract description 65
- 230000008021 deposition Effects 0.000 claims abstract description 51
- 230000001939 inductive effect Effects 0.000 claims abstract description 39
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 6
- 239000000956 alloy Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 239000007773 negative electrode material Substances 0.000 claims abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 43
- 239000011889 copper foil Substances 0.000 claims description 40
- 239000011230 binding agent Substances 0.000 claims description 22
- 239000003792 electrolyte Substances 0.000 claims description 19
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 14
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 14
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 14
- 239000011810 insulating material Substances 0.000 claims description 12
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 9
- 229910021389 graphene Inorganic materials 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052732 germanium Inorganic materials 0.000 claims description 7
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910001593 boehmite Inorganic materials 0.000 claims description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229940096017 silver fluoride Drugs 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 claims description 4
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 claims description 2
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910021569 Manganese fluoride Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 claims description 2
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 claims description 2
- 239000011244 liquid electrolyte Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 239000007784 solid electrolyte Substances 0.000 claims description 2
- 229910052713 technetium Inorganic materials 0.000 claims description 2
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 claims description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- NLPMQGKZYAYAFE-UHFFFAOYSA-K titanium(iii) fluoride Chemical compound F[Ti](F)F NLPMQGKZYAYAFE-UHFFFAOYSA-K 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 210000001787 dendrite Anatomy 0.000 abstract description 5
- 238000006056 electrooxidation reaction Methods 0.000 abstract description 3
- 230000006698 induction Effects 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 56
- 238000000576 coating method Methods 0.000 description 56
- 238000000151 deposition Methods 0.000 description 41
- 239000002033 PVDF binder Substances 0.000 description 38
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 32
- 238000000034 method Methods 0.000 description 25
- 238000001035 drying Methods 0.000 description 22
- 239000002904 solvent Substances 0.000 description 21
- 238000003756 stirring Methods 0.000 description 19
- 230000014759 maintenance of location Effects 0.000 description 16
- 238000002156 mixing Methods 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- BCNBMSZKALBQEF-UHFFFAOYSA-N 1,3-dimethylpyrrolidin-2-one Chemical compound CC1CCN(C)C1=O BCNBMSZKALBQEF-UHFFFAOYSA-N 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 229910001290 LiPF6 Inorganic materials 0.000 description 8
- 238000007599 discharging Methods 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 229910003002 lithium salt Inorganic materials 0.000 description 8
- 159000000002 lithium salts Chemical class 0.000 description 8
- 238000009517 secondary packaging Methods 0.000 description 8
- 239000006258 conductive agent Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 238000001755 magnetron sputter deposition Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000009516 primary packaging Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 125000005587 carbonate group Chemical group 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- OPHUWKNKFYBPDR-UHFFFAOYSA-N copper lithium Chemical compound [Li].[Cu] OPHUWKNKFYBPDR-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
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- 230000000977 initiatory effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- -1 polyoxyethylene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
-
- 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
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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)
- Secondary Cells (AREA)
Abstract
The invention relates to a lithium-free negative plate for a lithium battery and the lithium battery, and belongs to the technical field of lithium batteries. The lithium-free negative plate for the lithium battery comprises a negative current collector, wherein one or two surfaces of the negative current collector are sequentially provided with a lithium deposition induction layer and an inorganic electronic insulating layer in the direction away from the negative current collector; the lithium deposition inducing layer includes a negative active material capable of forming an alloy with lithium or a compound with lithium. According to the lithium-free negative plate, the lithium deposition inducing layer is arranged on one or two surfaces of the negative current collector in the direction away from the negative current collector, so that lithium can be induced to be uniformly deposited, the growth of lithium dendrites on the surface of the negative current collector is inhibited, the inorganic electronic insulating layer can prevent a lithium layer with a large specific surface area and a large porosity from being formed after lithium deposition, and further, a large amount of electrochemical corrosion is generated on a solid-liquid interface to reduce the coulomb efficiency, so that the safety and the cycle performance of a lithium battery are greatly improved.
Description
Technical Field
The invention relates to a lithium-free negative plate for a lithium battery and the lithium battery, and belongs to the technical field of lithium batteries.
Background
At present, lithium battery technology has been widely accepted and applied to power, energy storage and mobile power sources, but with the continuous progress of lithium battery research, human beings have a higher expectation on the energy density of lithium batteries, and a great deal of researchers have focused on improving the gram capacity of positive electrode materials to improve the energy density of lithium batteries, while the actual gram capacity of 811 high-nickel materials which are commercially and mature to be applied at present is 185mAh/g (1C), so that the energy density of batteries is improved to a certain extent, and in addition, the mass energy density of batteries reaches 240WH/kg by reducing the thicknesses of current collectors and diaphragms and reducing the mechanical structural members of batteries in battery design, so that the expected target cannot be met.
In view of the above, the research on lithium metal batteries has been pursued, but lithium metal batteries, on one hand, have a low volumetric energy density due to the use of excess lithium metal in the negative electrode, and on the other hand, the manufacturing process requires more strict environmental control on lithium metal, which increases the production cost, and lithium-free negative electrode batteries, which reduces the total mass of the batteries due to the absence of graphite or lithium metal in the negative electrode, are one of the development approaches of high energy density lithium batteries. The negative electrode of the lithium-free negative electrode battery is only a current collector in fact, the introduction of negative electrodes such as graphite or lithium metal is not needed, and the lithium of the full battery is completely sourced from the positive electrode lithium metal oxide; the design not only can greatly improve the theoretical specific capacity of the battery, but also can avoid the use of a Li sheet in the practical application and assembly process, thereby bringing great convenience; the copper foil is a heterogeneous substrate which is most widely adopted by the lithium ion battery without the negative electrode due to high conductivity and good mechanical property; the research core of the current non-negative electrode technology lies in how to ensure the uniform deposition of metal lithium on a copper current collector, and lithium copper cannot form an alloy, so that the lithium deposition on a copper foil is over-potential, the battery deposition efficiency is low, the deposition is not uniform, and irregular lithium dendrite can be formed in the deposition and removal processes of lithium. In the prior art, chinese patent application publication No. CN111969212A discloses a non-negative copper current collector for a lithium battery, in which an induced metal plating layer is plated on the surface of the current collector to form an alloy with lithium, the induced layer has a low overpotential for the lithium layer to induce uniform deposition of lithium, so that the growth of lithium dendrites is effectively inhibited, and the cycling stability and the service life of the battery are improved. Although the lithium deposition inducing layer for inducing lithium deposition is arranged on the copper current collector, the generation of lithium dendrites can be reduced, because a large amount of lithium deposition layers are directly exposed on a solid-liquid interface after charging, the exposed lithium has large specific surface area and unbalanced deposition state, but lithium is in a sub-equilibrium state, and irreversible electrochemical corrosion reaction is easy to occur with electrolyte, so that the cycle performance is reduced.
Disclosure of Invention
The invention aims to provide a lithium-free negative plate for a lithium battery, which can improve the cycle performance of the lithium-free negative battery.
The invention also provides a lithium battery adopting the lithium-free negative plate.
In order to achieve the above purpose, the lithium-free negative electrode sheet for the lithium battery adopts the following technical scheme:
a lithium-free negative electrode sheet for a lithium battery includes a negative electrode current collector; one or two surfaces of the negative current collector are sequentially provided with a lithium deposition inducing layer and an inorganic electronic insulating layer in the direction away from the current collector; the lithium deposition inducing layer includes a negative active material capable of forming an alloy with lithium or a compound with lithium.
According to the lithium-free negative plate for the lithium battery, the lithium deposition inducing layer is arranged on one or two surfaces of the negative current collector in the direction away from the negative current collector, and can induce lithium to be uniformly deposited, so that the growth of lithium dendrites on the surface of the negative current collector is inhibited, and the inorganic electronic insulating layer can prevent a lithium layer with a large specific surface area and a large porosity from being formed after lithium deposition, so that a large amount of electrochemical corrosion is generated on a solid-liquid interface to reduce the coulomb efficiency, and the safety and the cycle performance of the lithium battery are greatly improved.
Preferably, the lithium deposition inducing layer is easily alloyed with lithium metal, and the formation of the alloy facilitates uniform deposition of lithium on the surface of the negative electrode. Further preferably, the main component of the lithium deposition inducing layer is one or any combination of graphene, silicon carbide, aluminum, magnesium, indium, beryllium, calcium, barium, titanium, zirconium, vanadium, niobium, chromium, manganese, nickel, cobalt, technetium, rhenium, silver, gold, zinc, cadmium, boron and germanium. The lithium deposition inducing layer can be prepared by adopting a method of evaporation, electroplating, magnetron sputtering or coating. For example, the lithium deposition inducing layer is composed of silicon carbide, an aqueous binder of LA133 type, and carboxymethyl cellulose. The mass ratio of silicon carbide, the LA133 type aqueous binder, and carboxymethyl cellulose is preferably 96.2:0.8:3. And as another example, the lithium deposition inducing layer is formed by coating and drying the oily graphene dispersion liquid.
Preferably, the inorganic electronic insulating layer mainly comprises an inorganic electronic insulating material and a binder, and the mass ratio of the inorganic electronic insulating material to the binder is more than or equal to 70: 30. For example, the mass ratio of the inorganic electronic insulating material to the binder is 0.1:99.9 to 30: 70. Further preferably, the mass ratio of the inorganic electronic insulating material to the binder is 90-99: 1-10. The adhesive is one or more of water-soluble adhesive, hot-melt adhesive, organic solvent adhesive and emulsion adhesive. Preferably, the inorganic electronic insulating layer is formed by coating a coating mixture mainly composed of an inorganic electronic insulating material and a binder. The coating can be carried out by gravure, spray, extrusion, screen printing, and the like.
The coating mixture takes a liquid dispersant as a carrier, the liquid dispersant is water or an organic solvent, an inorganic electronic insulating material and a binder are uniformly dispersed in the liquid dispersant to form a coating mixture in a pasty or pasty state, then the coating mixture is coated on a current collector, finally the liquid dispersant is completely volatilized to form the inorganic electronic insulating layer, and the mass percentage of the liquid dispersant in the coating mixture is 50-99.9%. The mass ratio of the inorganic electronic insulating material and the binder in the coating mixture is 0.1-50%. Preferably, the solids content of the coating mixture is 8 to 35%, for example 12 to 35%.
The organic solvent type binder is polyvinylidene fluoride.
Preferably, the inorganic electronic insulating material is selected from one or any combination of metal oxide, carbonate, sulfate, fluoride, molybdenum disulfide, diatomite, silica and boehmite.
Preferably, the metal oxide is selected from one or any combination of aluminum oxide, magnesium oxide, titanium dioxide, calcium oxide and zinc oxide. The carbonate is selected from one or any combination of magnesium carbonate, calcium carbonate and lithium carbonate. The fluoride is selected from one or any combination of aluminum fluoride, lithium fluoride, copper fluoride, zinc fluoride, magnesium fluoride, cobalt fluoride, iron fluoride, carbon fluoride, silver fluoride, titanium trifluoride and manganese fluoride.
Preferably, D of said inorganic electronically insulating material50Is 0.05-5 μm, preferably 0.05-1.5 μm.
The negative current collector is copper foil or copper-plated composite foil. The thickness of the negative electrode current collector is preferably 1 μm to 30 μm, more preferably 3 μm to 15 μm, for example, 8 μm.
Preferably, the lithium deposition inducing layer is disposed on the negative electrode current collector; the inorganic electronic insulating layer is disposed on the lithium deposition inducing layer.
The thickness of the lithium deposition inducing layer is preferably 0.005 to 10 μm, more preferably 5 to 50nm, and still more preferably 6 to 10 nm.
The thickness of the inorganic electron insulating layer is preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm, for example, 3 μm.
The lithium battery adopts the technical scheme that:
a lithium battery adopting the lithium-free negative plate for the lithium battery is provided.
The lithium battery adopts the lithium-free negative plate for the lithium battery, so that the lithium battery has higher safety and higher specific mass capacity.
Preferably, the lithium battery is a solid electrolyte lithium battery, a solid-liquid mixed electrolyte lithium battery, or a liquid electrolyte lithium battery.
Drawings
Fig. 1 is a schematic structural view of a lithium-free negative electrode sheet for a lithium battery of example 1;
fig. 2 is a graph showing the variation trend of the gram discharge capacity of the positive electrode of the lithium button cell obtained in the test of example 9 in the cycle process;
FIG. 3 is a graph showing the variation of the gram discharge capacity of the positive electrode of the single lithium battery tested in example 10 during the cycling process;
FIG. 4 is a graph showing the variation of the gram discharge capacity of the positive electrode of the single lithium battery tested in example 11 during cycling;
fig. 5 is a graph showing the variation of the gram discharge capacity of the positive electrode of the single lithium battery tested in example 12 during the cycling process.
Detailed Description
The technical solution of the present invention will be further described with reference to the following embodiments.
Example 1
The lithium-free negative electrode sheet for a lithium battery of the present embodiment, as shown in fig. 1, includes a negative electrode current collector 1, a lithium deposition inducing layer 2, and an inorganic electronic insulating layer 3, where the lithium deposition inducing layer 2 is disposed on one side of the negative electrode current collector 1, and the inorganic electronic insulating layer 3 is disposed on the lithium deposition inducing layer 2; the negative current collector 1 is a copper foil with the thickness of 8 mu m; the lithium deposition inducing layer is an aluminum metal layer with the thickness of 10 nm; the inorganic electronic insulating layer has a thickness of 3 μm and is made of nano SiO2And polyvinylidene fluoride, nano SiO2The mass ratio of the polyvinylidene fluoride to the polyvinylidene fluoride is 93:7, and the nano SiO is2The D50 particle size of (B) is 50 nm;
the preparation method of the lithium-free negative electrode sheet for the lithium battery comprises the following steps:
1) plating a 10nm aluminum metal layer on one surface of a copper foil by evaporation by taking the copper foil with the thickness of 8 microns as a negative electrode current collector;
2) N-N dimethyl pyrrolidone is used as a solvent, and nano SiO is added into the N-N dimethyl pyrrolidone firstly2Fully stirring for 30min, then adding a binder polyvinylidene fluoride, fully stirring and mixing for 30min, and slowly stirring for 30min for defoaming to obtain a coating liquid; in the coating liquid, nano SiO2The mass ratio of the polyvinylidene fluoride to the polyvinylidene fluoride is 93:7, and the solid content of the coating liquid is 12％；
3) Coating the coating solution obtained in the step 2) on an aluminum metal layer on a copper foil by using a wire rod, and after drying, forming an inorganic electronic insulating layer on the aluminum metal layer to obtain the lithium-free negative plate with the lithium deposition inducing layer and the inorganic electronic insulating layer.
Example 2
The lithium-free negative electrode sheet for a lithium battery of the present example is different from the lithium-free negative electrode sheet of example 1 only in that: the inorganic electronic insulating layer is composed of boehmite and polyvinylidene fluoride, and the mass ratio of the boehmite to the polyvinylidene fluoride is 96: 4.
The preparation method of the lithium-free negative electrode sheet for the lithium battery comprises the following steps:
1) plating a 10nm aluminum metal layer on one surface of a copper foil by evaporation by taking the copper foil with the thickness of 8 microns as a negative electrode current collector;
2) adding boehmite (D) into N-N dimethyl pyrrolidone as solvent50125nm) for 30min, then adding a binder polyvinylidene fluoride, fully stirring and mixing for 30min, and slowly stirring for 30min to defoam to obtain a coating solution for later use; in the coating liquid, the mass ratio of the boehmite to the polyvinylidene fluoride is 96:4, and the solid content of the coating liquid is 35%;
3) and coating the prepared coating liquid on an aluminum metal layer on a copper foil by using a wire rod, and drying to form an inorganic electronic insulating layer on the aluminum metal layer, thereby obtaining the lithium-free negative plate with the lithium deposition inducing layer and the inorganic electronic insulating layer.
Example 3
The lithium-free negative electrode sheet for a lithium battery of the present example is different from the lithium-free negative electrode sheet of example 1 only in that: the lithium deposition inducing layer of the lithium-free negative plate of the present example was a silver metal layer with a thickness of 6nm, and the inorganic electronic insulating layer was made of Li2CO3(D501.5 μm) and polyvinylidene fluoride, Li2CO3And the mass ratio of polyvinylidene fluoride is 96: 4.
The preparation method of the lithium-free negative electrode sheet for the lithium battery comprises the following steps:
1) plating a 6nm silver metal layer on one surface of a copper foil by electroplating by taking the copper foil with the thickness of 8 microns as a negative current collector;
2) taking N-N dimethyl pyrrolidone as a solvent, firstly adding Li into the solvent2CO3Fully stirring the powder for 30min, then adding a binder polyvinylidene fluoride, fully stirring and mixing for 30min, and slowly stirring for 30min for defoaming to obtain a coating solution for later use; li in coating liquid2CO3The mass ratio of the coating liquid to the polyvinylidene fluoride is 96:4, and the solid content of the coating liquid is 30%;
3) and coating the coating liquid on the silver metal layer on the copper foil by using a wire rod, and drying to form an inorganic electronic insulating layer on the silver metal layer, thereby obtaining the lithium-free negative plate with the lithium deposition inducing layer and the inorganic electronic insulating layer.
Example 4
The lithium-free negative electrode sheet for a lithium battery of the present example differs from the lithium-free negative electrode sheet of example 1 only in that: in this embodiment, the lithium deposition inducing layer is a titanium metal layer with a thickness of 10nm, the inorganic electronic insulating layer is composed of lithium fluoride and polyvinylidene fluoride, and the mass ratio of the lithium fluoride to the polyvinylidene fluoride is 96: 4.
The preparation method of the lithium-free negative electrode sheet for the lithium battery comprises the following steps:
1) taking a copper foil with the thickness of 8 microns as a negative current collector, and compounding a 10nm titanium metal layer on one surface of the copper foil through magnetron sputtering;
2) using N-N dimethyl pyrrolidone as solvent, firstly adding lithium fluoride powder (D)50800nm) for 30min, then adding a binder polyvinylidene fluoride, fully stirring and mixing for 30min, and slowly stirring for 30min for defoaming to obtain a coating solution; in the coating liquid, the mass ratio of the lithium fluoride to the polyvinylidene fluoride is 96:4, and the solid content of the coating liquid is 20%;
3) and coating the coating liquid on the titanium metal layer on the copper foil by using a wire rod, and drying to form an inorganic electronic insulating layer on the titanium metal layer, thereby obtaining the lithium-free negative plate with the lithium deposition inducing layer and the inorganic electronic insulating layer.
Example 5
The lithium-free negative electrode sheet for a lithium battery of the present example differs from the lithium-free negative electrode sheet of example 1 only in that: the lithium deposition inducing layer of the lithium-free negative plate in the embodiment is a germanium metal layer with the thickness of 6nm, the inorganic electronic insulating layer is composed of magnesium oxide and polyvinylidene fluoride, and the mass ratio of the magnesium oxide to the polyvinylidene fluoride is 90: 10.
The preparation method of the lithium-free negative electrode sheet for the lithium battery comprises the following steps:
1) the copper foil with the thickness of 8 mu m is used as a negative current collector, and a germanium metal layer with the thickness of 6nm is compounded on one surface of the copper foil through magnetron sputtering;
2) adding magnesium oxide powder (D) into N-N dimethyl pyrrolidone as solvent50150nm) for 30min, then adding a binder polyvinylidene fluoride, fully stirring and mixing for 30min, and slowly stirring for 30min for defoaming to obtain a coating solution; in the coating liquid, the mass ratio of the magnesium oxide to the polyvinylidene fluoride is 90:10, and the solid content of the coating liquid is 25%;
3) and coating the coating liquid on the germanium metal layer on the copper foil by using a wire rod, and drying to form an inorganic electronic insulating layer on the germanium metal layer, thereby obtaining the lithium-free negative plate with the lithium deposition inducing layer and the inorganic electronic insulating layer.
Example 6
The lithium-free negative electrode sheet for a lithium battery of the present example differs from the lithium-free negative electrode sheet of example 1 only in that: the lithium deposition inducing layer of the lithium-free negative electrode sheet of the present example was a graphene layer having a thickness of 2 μm.
The preparation method of the lithium-free negative electrode sheet for the lithium battery comprises the following steps:
1) an 8-micron copper foil is used as a negative current collector, oil graphene with solid content of 5% is compounded on one surface of the copper foil through coating by using a wire rod, and after drying, a graphene layer is formed on the copper foil.
2) N-N dimethyl pyrrolidone is used as a solvent, and nano SiO is added into the N-N dimethyl pyrrolidone firstly2Fully stirring for 30min, then adding a binder polyvinylidene fluoride, fully stirring and mixing for 30min, and slowly stirring for 30min for defoaming to obtain a coating liquid; in the coating liquid, nano SiO2(D5050nm) and polyvinylidene fluoride in a mass ratio of 93:7, wherein the solid content of the coating liquid is 12%;
3) coating the coating solution obtained in the step 2) on a graphene layer on a copper foil by using a wire rod, and forming an inorganic electronic insulating layer on the graphene layer after drying to obtain the lithium-free negative plate with the lithium deposition inducing layer and the inorganic electronic insulating layer.
Example 7
The lithium-free negative electrode sheet for a lithium battery of the present example differs from the lithium-free negative electrode sheet of example 1 only in that: the lithium deposition inducing layer of the lithium-free negative plate of the present example was a silicon carbide layer with a thickness of 3 μm, and the inorganic electron insulating layer was formed of MgSO4And polyvinylidene fluoride (MgSO)4And the mass ratio of the polyvinylidene fluoride is 90: 10.
The preparation method of the lithium-free negative electrode sheet for the lithium battery comprises the following steps:
1) the copper foil with the thickness of 8 mu m is used as a negative current collector, the silicon carbide mixed solution is compounded on one surface of the copper foil by coating with a wire rod, and then the copper foil is fully dried to form a silicon carbide layer on the surface of the copper foil; the silicon carbide mixed solution is formed by uniformly mixing water with silicon carbide, LA133 type aqueous binder and carboxymethyl cellulose (CMC), wherein the mass ratio of the silicon carbide to the LA133 type aqueous binder to the CMC is 96.2:0.8: 3.0; wherein water is used as solvent, and the silicon carbide mixed solution is slurry with solid content of 30%.
2) Taking N-N dimethyl pyrrolidone as a solvent, firstly adding MgSO (MgSO) into the solvent4Powder (D)50130nm), then adding a binder polyvinylidene fluoride, fully stirring and mixing for 30min, and then slowly stirring for 30min for defoaming to obtain a coating solution; in the coating solution, MgSO4The mass ratio of the polyvinylidene fluoride to the polyvinylidene fluoride is 90:10, and the solid content of the coating liquid is 25%;
3) and coating the coating liquid on the silicon carbide layer on the copper foil by using a wire rod, drying to form an inorganic electronic insulating layer on the silicon carbide layer, and drying to obtain the lithium-free negative plate with the lithium deposition inducing layer and the inorganic electronic insulating layer.
Example 8
The lithium battery of the embodiment is a liquid button lithium battery, and comprises a positive plate, a diaphragm and a negative plate, wherein the negative plate is the lithium-free negative plate for the lithium battery of the embodiment 1, and a wafer with the radius of 8mm is cut;the positive electrode is LiNi0.5Co0.2Mn0.3O2The active substance, the PVDF binder and the SP conductive agent are mixed into slurry according to the mass ratio of 94:3:3, and then the slurry is coated, dried, rolled and cut into pieces to obtain a circular piece with the radius of 7 mm.
The liquid button lithium battery of the embodiment is assembled: drying the cut positive plate and negative plate at 120 deg.C (positive) and 100 deg.C (negative) for 8h in vacuum environment, respectively, assembling the plate in dew point control environment, wherein the lithium salt of the selected electrolyte is LiPF6The solvent is carbonate conventional electrolyte, the diaphragm is a PP basal membrane with the thickness of 20 mu m, and the electricity-buckling assembly process is completed after the sealing.
After the liquid button lithium battery of the embodiment is kept stand for 24 hours, the battery is subjected to 0.1C charging/0.2C discharging circulation within the voltage range of 2.8-4.45V, the first effect of the obtained positive electrode is 90.1%, and the capacity retention ratio is 83.9% after 50 cycles.
Example 9
The lithium battery of this embodiment is a liquid button lithium battery, and includes a positive plate, a negative plate and a diaphragm, wherein the positive plate is the same as the positive plate employed in embodiment 8, and the negative plate is the lithium-free negative plate for the lithium battery of embodiment 2, and the negative plate with a radius of 8mm and the positive plate with a radius of 7mm are respectively cut.
The liquid button lithium battery of the embodiment is assembled: drying the cut positive plate and the cut negative plate respectively at 120 ℃ (positive) and 100 ℃ (negative) for 8h in a vacuum environment, and assembling the button cell by using the plates in a dew point control environment; the lithium salt of the selected electrolyte is LiPF6The solvent is carbonate conventional electrolyte, the diaphragm is a PP basal membrane with the thickness of 20 mu m, and the electricity-buckling assembly process is completed after the sealing.
After the liquid button lithium battery of the embodiment is kept stand for 24 hours, the battery is subjected to 0.1C charge/0.2C discharge cycle at 25 ℃ between 2.8 and 4.45V, the gram capacity of the anode obtained by testing changes in the cycle process, as shown in the figure 2, the initial effect of the anode in the group A data is 89.3%, and the capacity retention rate after 50 cycles is 75.7%.
For comparison, after a 10nm aluminum plating layer is formed on a copper foil with a thickness of 8 μm, the negative plate of the present embodiment is replaced, and the lithium button cell is assembled by the same assembling method, and the same test method in the present embodiment is used to test the change trend of the positive electrode discharge capacity of the lithium button cell in the cycle process, as shown in the data of B group in fig. 2, the first effect of the positive electrode is 91.3%, and the capacity retention rate after 50 cycles is 35.1%.
Example 10
The lithium battery of this embodiment is a liquid monolithic lithium battery, and includes a positive plate, a separator, and a negative plate, where the negative plate is the lithium-free negative plate (with tabs cut by a die) for the lithium battery of embodiment 3, and the positive plate is a lithium ion battery made of LiNi0.5Co0.2Mn0.3O2The active material, the PVDF binder and the SP conductive agent are mixed according to the mass ratio of 94:3:3, and then coated, dried, rolled and cut into pieces (pole pieces with pole lugs matched with the negative pole pieces).
Liquid monolithic cell assembly of the present embodiment: adopting a PE diaphragm with a single surface coated with ceramic, completing the assembly of a single-chip battery after lamination, tab welding, primary packaging, drying, liquid injection and secondary packaging, wherein the lithium salt of the selected electrolyte is LiPF6The solvent is a conventional electrolyte of carbonate, wherein the liquid injection and secondary packaging of the dried battery need to control the dew point of the operating environment.
After the single-chip battery of the embodiment is kept stand for 24 hours, pressure is applied to the single-chip battery by using a clamping plate, the battery is subjected to 0.1C charge/0.2C discharge circulation at 25 ℃ within the voltage range of 2.8-4.45V, the first positive electrode discharge gram capacity is 190.3mAh/g, the first charge and discharge efficiency is 90.5%, after 50 times of circulation, the capacity retention rate is 90.7%, and the gram capacity changes along with the circulation process as shown in C in figure 3.
For comparison, after the negative plate of this embodiment is replaced with a copper foil 8 μm thick, the single lithium battery is assembled by the same assembly method, and the same test method in this embodiment is used to test the variation trend of the positive electrode of the button lithium battery in the discharge capacity during the cycle, as shown in the data D in fig. 3, the first effect of the positive electrode is 90.8%, and the capacity retention rate after 50 cycles is 8.7%.
For comparison, after a 6nm thick silver metal layer is compounded on a copper foil with a thickness of 8 μm, the negative plate of the present embodiment is replaced, and then the single lithium battery is assembled by the same assembling method, and the same test method in the present embodiment is used to test the change trend of the positive electrode of the button lithium battery in the discharge capacity during the cycle, as shown in the data E in fig. 3, the first effect of the positive electrode is 89.9%, and the capacity retention rate after 50 cycles is 57.7%.
Example 11
The lithium battery of this example is a liquid monolithic lithium battery, comprising a positive plate, a separator and a negative plate, wherein the negative plate is the lithium-free negative plate for the lithium battery of example 4, and the positive plate is formed by mixing LiNi0.5Co0.2Mn0.3O2Mixing the active substance, the PVDF binder and the SP conductive agent according to the mass ratio of 94:3:3, coating on an aluminum foil, drying, rolling, and cutting into pieces (pole pieces with pole lugs matched with the negative pole pieces).
Assembly of the liquid monolithic lithium battery of the present embodiment: the diaphragm is a PE diaphragm with a single side coated with ceramic, the assembly of the single-chip battery is completed after lamination, tab welding, primary packaging, drying, liquid injection and secondary packaging, and the lithium salt of the selected electrolyte is LiPF6The solvent is a conventional electrolyte of carbonate, wherein the liquid injection and secondary packaging of the dried battery need to control the dew point of the operating environment.
After the liquid single-chip lithium battery of the embodiment is kept stand for 24 hours, pressure is applied to the single-chip lithium battery by using a clamping plate, the battery is subjected to 0.1C charging/0.2C discharging circulation at 25 ℃ in a voltage range of 2.8-4.45V, the first positive electrode discharging gram capacity is 189.9mAh/g, the first charging and discharging efficiency is 90.1%, after 50 times of circulation, the capacity retention rate is 95.1%, and the gram capacity changes along with the circulation process and is shown as F group data in fig. 4.
For comparison, after a 10nm titanium metal layer is compounded on a copper foil with a thickness of 8 μm and the negative electrode sheet of the embodiment is replaced, the single lithium battery is assembled by the same assembling method, and the change trend of the discharge gram capacity of the positive electrode of the single lithium battery in the cycle process is tested by the same testing method in the embodiment, as shown in the G group data of fig. 4, the first effect of the positive electrode is 90.5%, and the capacity retention rate after 50 cycles is 52.7%.
Example 12
The lithium battery of this example is a liquid monolithic battery comprising a positive plate, a separator and a negative plate, wherein the negative plate is the lithium-free negative plate for the lithium battery of example 5, and the positive plate is a lithium ion doped with the separator of example 50.5Co0.2Mn0.3O2The active material, the PVDF binder and the SP conductive agent are mixed according to the mass ratio of 94:3:3, and then coated, dried, rolled and cut into pieces (pole pieces with pole lugs matched with the negative pole pieces).
Assembly of the liquid monolithic lithium battery of the present embodiment: the diaphragm is a PE diaphragm with a single side coated with ceramic, the assembly of the single-chip battery is completed after lamination, tab welding, primary packaging, drying, liquid injection and secondary packaging, and the lithium salt of the selected electrolyte is LiPF6The solvent is a conventional electrolyte of carbonate, wherein the liquid injection and secondary packaging of the dried battery need to control the dew point of the operating environment.
After the single liquid single lithium battery in the embodiment is kept stand for 24 hours, a single pressure is applied by using a clamping plate, the battery is subjected to 0.1C charge/0.2C discharge circulation at 25 ℃ in a voltage range of 2.8-4.45V, the first positive electrode discharge gram capacity is 185.9mAh/g, the first charge-discharge efficiency is 86.5%, after 50 times of circulation, the capacity retention rate is 91%, and the gram capacity changes along with the circulation process as the H group data in fig. 5.
For comparison, after a 10nm germanium metal layer is compounded on a copper foil with a thickness of 8 μm and then the negative electrode sheet of the embodiment is replaced, the single lithium battery is assembled by the same assembling method, and the change trend of the discharge gram capacity of the positive electrode of the single lithium battery in the cycle process is tested by the same testing method in the embodiment, as shown in group I data of fig. 5, the first effect of the positive electrode is 90.3%, and the capacity retention rate after 50 cycles is 36.9%.
Example 13
The lithium battery of the embodiment is a liquid button lithium battery, and comprises a positive plate, a diaphragm and a negative plate, wherein the negative plate is the lithium-free negative plate for the lithium battery of the embodiment 6, and a wafer with the radius of 8mm is cut; the positive electrode is LiNi0.5Co0.2Mn0.3O2Active material and PVDF binderAnd mixing the SP conductive agent according to the mass ratio of 94:3:3, and then coating, drying, rolling and cutting into pieces to obtain a circular piece with the radius of 7 mm.
The liquid button lithium battery of the embodiment is assembled: drying the cut positive plate and negative plate at 120 deg.C (positive) and 100 deg.C (negative) respectively for 8h in vacuum environment, and assembling the button cell in dew point control environment, wherein the lithium salt of the selected electrolyte is LiPF6The solvent is carbonate conventional electrolyte, the diaphragm is a PP basal membrane with the thickness of 20 mu m, and the electricity-buckling assembly process is completed after the sealing.
After the liquid button lithium battery of the embodiment is kept stand for 24 hours, the battery is subjected to 0.1C charging/0.2C discharging circulation within the voltage range of 2.8-4.45V, the first effect of the obtained positive electrode is 89.1%, and the capacity retention ratio is 91.1% after 20-week circulation.
For comparison, the graphene-coated copper foil obtained in step 1) of the preparation method of the lithium-free negative electrode sheet for the lithium battery in example 6 is used as the lithium-free negative electrode sheet, the button lithium battery is assembled by using the assembly method of this embodiment (the adopted diaphragm and the adopted positive electrode sheet are the same as in this embodiment), the first effect of the positive electrode of the button lithium battery is only 85% by using the same test method in this embodiment, and the capacity retention rate after 20-week cycle is 50.1%.
Example 14
The lithium battery of the embodiment is a liquid button lithium battery, and comprises a positive plate, a diaphragm and a negative plate, wherein the negative plate is the lithium-free negative plate for the lithium battery of the embodiment 7, and a wafer with the radius of 8mm is cut; the positive electrode is LiNi0.5Co0.2Mn0.3O2The active substance, the PVDF binder and the SP conductive agent are mixed into slurry according to the mass ratio of 94:3:3, and then the slurry is coated, dried, rolled and cut into pieces to obtain a circular piece with the radius of 7 mm.
The liquid button lithium battery of the embodiment is assembled: drying the cut positive plate and negative plate at 120 deg.C (positive) and 100 deg.C (negative) respectively for 8 hr in vacuum environment, assembling the button cell in inert atmosphere, wherein the lithium salt of the selected electrolyte is LiPF6The solvent is a conventional electrolyte of carbonate, and the diaphragm isAnd (5) sealing the PP basal membrane with the thickness of 20 mu m, and then completing the electricity-fastening assembling process.
After the liquid button lithium battery of the embodiment is kept stand for 24 hours, the battery is subjected to 0.1C charging/0.2C discharging circulation within the voltage range of 2.8-4.45V, the first effect of the obtained positive electrode is 87.5 percent, and the capacity retention ratio is 81.1 percent after 50-week circulation.
For comparison, the silicon carbide layer-coated copper foil obtained in step 1) of the preparation method of the lithium-free negative electrode sheet for the lithium battery in example 7 is used as the lithium-free negative electrode sheet, the button lithium battery is assembled by using the assembly method of this embodiment (the diaphragm and the positive electrode sheet used in this embodiment are the same as in this embodiment), the first effect of the positive electrode of the button lithium battery is only 85% by using the same test method in this embodiment, and the capacity retention rate after 50-week cycle is 23.1%.
Example 15
The lithium-free negative electrode sheet for a lithium battery of the present example differs from the lithium-free negative electrode sheet of example 1 only in that: the lithium deposition inducing layer of the lithium-free negative electrode plate in the embodiment is a silver metal layer with the thickness of 2nm, the inorganic electronic insulating layer is composed of silver fluoride and polyethylene oxide, and the mass ratio of the nano silver fluoride to the polyethylene oxide is 70: 30.
The preparation method of the lithium-free negative electrode sheet for the lithium battery comprises the following steps:
1) the copper foil with the thickness of 8 mu m is used as a negative current collector, and a 2nm silver metal layer is compounded on one surface of the copper foil through magnetron sputtering;
2) N-N dimethyl pyrrolidone (NMP) is used as a solvent, and nano silver fluoride powder (D) is added into the solvent50210nm) for 30min, then adding a binder polyoxyethylene (solvent is NMP), fully stirring and mixing for 30min, and slowly stirring for 30min for defoaming to obtain a coating solution; in the coating liquid, the mass ratio of the silver fluoride to the polyvinylidene fluoride is 70:30, and the solid content of the coating liquid is 20%;
3) and coating the coating liquid on the silver metal layer on the copper foil by using a wire rod, drying to form an inorganic electronic insulating layer on the silver metal layer, and drying to obtain the lithium-free negative plate with the lithium deposition inducing layer and the inorganic electronic insulating layer.
Preparing the cathode plateThe liquid monolithic battery comprises a positive plate, a diaphragm and a negative plate, wherein the positive plate is prepared by mixing LiNi0.5Co0.2Mn0.3O2The active material, the PVDF binder and the SP conductive agent are mixed according to the mass ratio of 94:3:3, and then coated, dried, rolled and cut into pieces (pole pieces with pole lugs matched with the negative pole pieces).
Assembly of the liquid monolithic lithium battery of the present embodiment: the diaphragm is a PE diaphragm with a single side coated with ceramic, the assembly of the single-chip battery is completed after lamination, tab welding, primary packaging, drying, liquid injection and secondary packaging, and the lithium salt of the selected electrolyte is LiPF6The solvent is a conventional electrolyte of carbonate, wherein the liquid injection and secondary packaging of the dried battery need to control the dew point of the operating environment.
After the single cell of the embodiment is kept stand for 24 hours, the pressure is applied to the single cell by using the clamping plate, the cell is subjected to 0.1C charge/0.2C discharge circulation within the voltage range of 2.8-4.45V, the first positive electrode discharge gram capacity is 186.7mAh/g, the first charge-discharge efficiency is 89.9%, and the capacity retention rate is 91.3% after 50 times of circulation.
For comparison, after the copper foil with the thickness of 8 μm is plated with silver to replace the negative plate of the embodiment, the same assembly method is adopted to assemble the single lithium battery, the same test method is adopted in the embodiment, the first positive electrode discharging gram capacity is 185.7mAh/g, the first charging and discharging efficiency is 88.7%, and after 50 cycles, the capacity retention rate is 60.3%.
Claims (10)
1. A no lithium negative pole piece for lithium cell, including the negative pole current collector, characterized by: one or two surfaces of the negative current collector are sequentially provided with a lithium deposition inducing layer and an inorganic electronic insulating layer in the direction away from the negative current collector; the lithium deposition inducing layer includes a negative active material capable of forming an alloy with lithium or a compound with lithium.
2. The lithium-free negative electrode sheet for a lithium battery as claimed in claim 1, wherein: the main component of the lithium deposition inducing layer is one or any combination of graphene, silicon carbide, aluminum, magnesium, indium, beryllium, calcium, barium, titanium, zirconium, vanadium, niobium, chromium, manganese, nickel, cobalt, technetium, rhenium, silver, gold, zinc, cadmium, boron and germanium.
3. The lithium-free negative electrode sheet for a lithium battery as claimed in claim 1, wherein: the inorganic electronic insulating layer mainly comprises an inorganic electronic insulating material and a binder, and the mass ratio of the inorganic electronic insulating material to the binder is more than or equal to 70: 30.
4. The lithium-free negative electrode sheet for a lithium battery according to claim 3, characterized in that: the inorganic electronic insulating material is selected from one or any combination of metal oxide, carbonate, sulfate, fluoride, molybdenum disulfide, diatomite, silicon dioxide and boehmite.
5. The lithium-free negative electrode sheet for a lithium battery according to claim 4, wherein: the metal oxide is selected from one or any combination of aluminum oxide, magnesium oxide, titanium dioxide, calcium oxide and zinc oxide; the carbonate is selected from one or any combination of magnesium carbonate, calcium carbonate and lithium carbonate; the fluoride is selected from one or any combination of aluminum fluoride, lithium fluoride, copper fluoride, zinc fluoride, magnesium fluoride, cobalt fluoride, iron fluoride, carbon fluoride, silver fluoride, titanium trifluoride and manganese fluoride.
6. The lithium-free negative electrode sheet for a lithium battery as claimed in claim 1, wherein: the negative current collector is copper foil or copper-plated composite foil.
7. The lithium-free negative electrode sheet for a lithium battery as claimed in claim 1, wherein: the lithium deposition inducing layer is disposed on the negative current collector; the inorganic electronic insulating layer is disposed on the lithium deposition inducing layer.
8. The lithium-free negative electrode sheet for a lithium battery as claimed in claim 7, wherein: the thickness of the lithium deposition inducing layer is 0.005-10 μm, and the thickness of the inorganic electronic insulating layer is 0.1-20 μm.
9. A lithium battery using the lithium-free negative electrode sheet for a lithium battery as claimed in claim 1.
10. A lithium battery as claimed in claim 9, characterized in that: the lithium battery is a solid electrolyte lithium battery, a solid-liquid mixed electrolyte lithium battery or a liquid electrolyte lithium battery.
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| CN113991054B (en) | 2024-03-01 |
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Denomination of invention: A lithium free negative electrode sheet and lithium battery for lithium batteries Granted publication date: 20240301 Pledgee: Luoyang Chanrong Group Co.,Ltd. Pledgor: Luoyang storage and Transformation System Co.,Ltd. Registration number: Y2024980049121 |