CN117476876A - Negative electrode, preparation method thereof, battery and power utilization device - Google Patents
Negative electrode, preparation method thereof, battery and power utilization device Download PDFInfo
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- CN117476876A CN117476876A CN202311554323.0A CN202311554323A CN117476876A CN 117476876 A CN117476876 A CN 117476876A CN 202311554323 A CN202311554323 A CN 202311554323A CN 117476876 A CN117476876 A CN 117476876A
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- lithium
- negative electrode
- substrate
- copper foil
- alloy layer
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- 238000002360 preparation method Methods 0.000 title abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 129
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 102
- 229910000733 Li alloy Inorganic materials 0.000 claims abstract description 67
- 239000001989 lithium alloy Substances 0.000 claims abstract description 67
- 238000000576 coating method Methods 0.000 claims abstract description 64
- 239000011248 coating agent Substances 0.000 claims abstract description 58
- 239000000126 substance Substances 0.000 claims abstract description 32
- 239000000758 substrate Substances 0.000 claims abstract description 31
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims abstract description 18
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052718 tin Inorganic materials 0.000 claims abstract description 13
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- 239000011701 zinc Substances 0.000 claims abstract description 10
- 229910052738 indium Inorganic materials 0.000 claims abstract description 9
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 7
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001947 lithium oxide Inorganic materials 0.000 claims abstract description 7
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052709 silver Inorganic materials 0.000 claims abstract description 7
- 239000004332 silver Substances 0.000 claims abstract description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 6
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000011068 loading method Methods 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 239000011777 magnesium Substances 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 5
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011135 tin Substances 0.000 claims abstract description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052788 barium Inorganic materials 0.000 claims abstract description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 239000011575 calcium Substances 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 239000010703 silicon Substances 0.000 claims abstract description 4
- 230000008018 melting Effects 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 8
- 238000009713 electroplating Methods 0.000 claims description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000004767 nitrides Chemical class 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000005229 chemical vapour deposition Methods 0.000 claims description 2
- 238000004544 sputter deposition Methods 0.000 claims description 2
- 210000001787 dendrite Anatomy 0.000 abstract description 13
- 230000008859 change Effects 0.000 abstract description 7
- 238000005336 cracking Methods 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- 238000010298 pulverizing process Methods 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 95
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 82
- 239000011889 copper foil Substances 0.000 description 82
- 239000002131 composite material Substances 0.000 description 32
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 description 27
- 229960002799 stannous fluoride Drugs 0.000 description 27
- 239000012300 argon atmosphere Substances 0.000 description 25
- 238000010438 heat treatment Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
- 239000000843 powder Substances 0.000 description 10
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 description 8
- RPJGYLSSECYURW-UHFFFAOYSA-K antimony(3+);tribromide Chemical compound Br[Sb](Br)Br RPJGYLSSECYURW-UHFFFAOYSA-K 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910001128 Sn alloy Inorganic materials 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 0.000 description 6
- 229910001923 silver oxide Inorganic materials 0.000 description 5
- 239000011592 zinc chloride Substances 0.000 description 5
- 235000005074 zinc chloride Nutrition 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229940096017 silver fluoride Drugs 0.000 description 4
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- WUALQPNAHOKFBR-UHFFFAOYSA-N lithium silver Chemical compound [Li].[Ag] WUALQPNAHOKFBR-UHFFFAOYSA-N 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- ZOMNDSJRWSNDFL-UHFFFAOYSA-N sulfanylidene(sulfanylideneindiganylsulfanyl)indigane Chemical compound S=[In]S[In]=S ZOMNDSJRWSNDFL-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000002140 antimony alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- LHJOPRPDWDXEIY-UHFFFAOYSA-N indium lithium Chemical compound [Li].[In] LHJOPRPDWDXEIY-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- KUJOABUXCGVGIY-UHFFFAOYSA-N lithium zinc Chemical compound [Li].[Zn] KUJOABUXCGVGIY-UHFFFAOYSA-N 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/0483—Processes of manufacture in general by methods including the handling of a melt
- H01M4/0488—Alloying
-
- 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
- H01M4/049—Manufacturing of an active layer by chemical means
- H01M4/0495—Chemical alloying
-
- 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
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a negative electrode, a preparation method thereof, a battery and an electric device. The negative electrode comprises a substrate, a lithium alloy layer covered on the surface of the substrate, and a solid electrolyte interface layer covered on the outer surface of the lithium alloy layer; the lithium alloy layer comprises lithium element and X element, wherein X comprises one or more of magnesium, calcium, barium, zinc, boron, aluminum, gallium, indium, carbon, silicon, tin, silver, germanium, lead, antimony and bismuth; the solid electrolyte interfacial layer comprises one or more of lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium sulfide, lithium oxide, or lithium nitride. The preparation method comprises the following steps: loading a compound Y on the surface of a substrate to obtain a pretreated substrate; coating molten lithium-containing substances on the surface of the pretreated substrate, and preserving heat to obtain the negative electrode. The invention relieves the problems of cracking, pulverization and falling off of the electrode caused by lithium dendrite growth and lithium metal volume change, and improves the stability and the cycle life when the lithium dendrite lithium ion battery is used for batteries.
Description
Technical Field
The application relates to the field of battery materials, in particular to a negative electrode, a preparation method thereof, a battery and an electric device.
Background
With the rapid development of electric vehicles, portable electronic devices, and energy storage systems, there is an increasing demand for lithium ion batteries with high energy density, long cycle life, and higher safety performance. As one of the key components of lithium ion batteries, the performance of the negative electrode material is critical to the performance of the battery. The traditional lithium ion battery cathode material mainly adopts graphite, however, the lithium storage capacity is limited, and the requirement of high energy density cannot be met. In recent years, lithium metal has been attracting attention as an ideal negative electrode material because it has extremely high theoretical lithium storage capacity and low voltage plateau, and can significantly improve the energy density of the battery. However, lithium metal anodes are prone to dendrite growth, electrolyte decomposition, and safety problems during cycling.
For this purpose, the present invention is proposed.
Disclosure of Invention
The invention mainly aims to provide a negative electrode, a preparation method thereof, a battery and an electric device, so as to relieve the problems of cracking, pulverization, falling off and the like of the electrode caused by lithium dendrite growth and lithium metal volume change, and improve the stability and the cycle life when the negative electrode is used for the battery.
In order to achieve the above object, the present invention provides the following technical solutions.
A first aspect of the present invention provides a negative electrode comprising a substrate, and a lithium alloy layer covered on the surface of the substrate, and a solid electrolyte interface layer (Solid Electrolyte Interphase, SEI) covering the lithium alloy layer;
the lithium alloy layer comprises lithium element and X element, wherein X comprises one or more of magnesium, calcium, barium, zinc, boron, aluminum, gallium, indium, carbon, silicon, tin, silver, germanium, lead, antimony and bismuth;
the solid electrolyte interfacial layer includes one or more of lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium sulfide, lithium oxide, or lithium nitride.
Therefore, on one hand, the lithium element and the X element in the lithium alloy layer are uniformly distributed on the surface of the substrate, and the problems of cracking, pulverization, falling and the like of an electrode caused by the volume change of lithium metal are effectively relieved, so that the lithium alloy layer with a large range of thickness can be realized, and the lithium alloy layer can be ultrathin or super-thick.
On the other hand, the solid electrolyte interface layer is covered outside the lithium alloy layer to serve as a protective layer, so that the interface stability can be improved, the growth of lithium dendrites can be inhibited, and the stability and the cycle life of the lithium metal negative electrode can be improved.
The "cover" may be a direct cover or an indirect cover. Direct coverage refers to the two layers being in direct contact. Indirect coverage is that there may be other layer/film spacing between the two layers or at least a portion of the surface between the two layers. The "outer surface of the lithium alloy layer" refers to the side of the lithium alloy layer away from the substrate.
Further, the thickness of the lithium alloy layer is 1 to 200 μm, preferably 5 to 80 μm, more preferably 20 to 60 μm or 5 to 20 μm.
In general, the thinner the lithium alloy layer, the higher the first-turn coulombic efficiency, because the thinner lithium alloy layer can reduce the formation time of a natural SEI film and consumption of lithium resources, can alleviate the problem of growth of lithium dendrites, and reduces the short circuit and safety problems caused by dendrites, thereby improving the cycle stability. While thicker lithium alloy layers may increase the opportunity for dendrite growth, which may lead to degradation of cell performance during cycling. The present invention can provide a negative electrode having an ultrathin lithium alloy layer, wherein the thickness of the lithium alloy layer can preferably be 80 μm or less, even 60 μm or less, even 20 μm or less.
Further, the thickness of the solid electrolyte interface layer is 10nm to 1 μm. The solid electrolyte interface layer may not provide sufficient interface stability when too thin, lack sufficient mechanical strength, and cause interface problems between the electrolyte and the electrode; too thick increases the transport path of ions in the electrolyte layer, resulting in an increase in internal resistance of the battery and a decrease in power density of the battery. In general, the thickness is preferably 10nm to 1. Mu.m, for example, 10nm to 100nm,100nm to 500nm,500nm to 1. Mu.m, etc.
Further, the lithium alloy layer comprises a lithium alloy, wherein the lithium alloy is Li a X b ，0＜b/a≤72。
Further, the lithium alloy layer also comprises a lithium simple substance.
Further, the mass ratio of the lithium alloy in the lithium alloy layer is 1 to 100%, preferably 1 to 80%.
In the lithium alloy layer of the present invention, the lithium element and the X element may exist in the form of an alloy or in the form of a mixture of a simple substance of lithium and a lithium alloy. The lithium alloy in the lithium alloy layer can provide a framework for inducing uniform deposition of lithium ions, thereby reducing local current density and relieving damage to the electrode and interface due to volume change during cycling.
Further, the X comprises one or more of zinc, indium, tin, silver, magnesium, bismuth and lead, preferably tin.
Further, a film layer formed by one or more of fluoride, chloride, bromide, iodide, sulfide, oxide or nitride of X can be further included between the lithium alloy layer and the substrate; and/or one or more of fluoride, chloride, bromide, iodide, sulfide, oxide, or nitride of X may also be included in the lithium alloy layer.
Further, the substrate may be a foil such as copper foil, aluminum foil, stainless steel foil, or the like that functions as a current collector.
Further, X in the lithium alloy layer may be one or more, including but not limited to magnesium and calcium, barium and zinc, boron and aluminum, gallium and indium, carbon and silicon, germanium and tin, silver and germanium, lead and antimony, bismuth and zinc, zinc and indium, tin and silver, tin and indium, tin and zinc, or combinations of bismuth, zinc and indium, and the like.
Further, the lithium content in the lithium alloy layer and the solid electrolyte interface layer may be any value other than zero, for example, 99.9% or less, or 99% or less, or 80% or less, or between 40% and 80%, or 60% or less, or the like. The percentages herein refer to mass percentages.
A second aspect of the present invention provides a method for preparing the negative electrode of the first aspect, the method being carried out in an inert atmosphere or in a vacuum environment, comprising the steps of:
loading a compound Y on the surface of a substrate to obtain a pretreated substrate;
coating molten lithium-containing substances on the surface of the pretreated substrate, and preserving heat to prepare the negative electrode;
wherein the compound Y is one or more of fluoride, chloride, bromide, iodide, sulfide, oxide or nitride of X; the lithium-containing substance comprises a lithium simple substance, or a compound consisting of lithium and X and the lithium simple substance.
Because the molten compound Y has stronger wettability to the substrate than molten lithium, the invention does not load the molten lithium directly to the substrate, but loads the compound Y to the surface of the substrate in advance, thereby realizing the rapid wetting of the compound Y to the substrate, and loads the molten lithium to the Y coating, so that the molten lithium reacts with the compound Y, and the lithium element and the X element in the lithium alloy layer obtained by the reaction are uniformly distributed and have higher compactness.
Specifically, the compound Y coating is firstly loaded on a substrate, then a molten lithium-containing substance is coated on the surface of the compound Y, and chemical reactivity exists between lithium and fluorine, chlorine, bromine, iodine, sulfur, oxygen or nitrogen in the Y at the moment, so that lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium sulfide, lithium oxide or lithium nitride and lithium alloys can be generated, and the lithium alloys can induce uniform deposition of lithium ions, thereby reducing local current density and relieving the problems of electrode cracking, pulverization and shedding caused by volume change of lithium metal; the lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium sulfide, lithium oxide or lithium nitride which are generated together with the lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium sulfide, lithium oxide or lithium nitride can form a solid electrolyte interface layer, so that the interface stability can be improved, the growth of lithium dendrites can be inhibited, and the stability and the cycle life of the lithium metal cathode can be improved.
In the above method, the substrate may or may not be heated prior to application of the lithium-containing material in the molten state.
Further, prior to applying the molten lithium-containing material to the pretreated substrate surface, further comprising: the pretreated substrate is heated, preferably to below the melting point of compound Y. The effect of the heating is to promote the reaction of the lithium-containing material with compound Y.
Further, the melting point of the compound Y is higher than that of lithium.
When the melting point of the compound Y is higher than that of lithium, the following effects can be achieved: when molten lithium or a molten lithium alloy is applied, the compound Y does not melt due to the temperature of the molten lithium or the molten lithium alloy. If the melting point of the compound Y is lower than the melting point of lithium, the compound Y is melted when molten lithium or a molten lithium alloy is coated, and thus it cannot be ensured that it uniformly covers the surface of the substrate, thereby affecting the subsequent coating.
Further, the loading method comprises at least one of electroplating, sputtering, spraying, evaporating, coating and chemical vapor deposition.
These loading methods can uniformly load the compound Y in the substrate.
Further, the inert atmosphere includes any one of helium, neon or argon, preferably argon.
Further, the temperature of the heating may be appropriately adjusted depending on the melting point of the compound Y, for example, 180 to 1000℃or 200 to 800 ℃.
Further, the amount of the compound Y and the lithium-containing substance to be used depends on the thickness and chemical composition of the lithium alloy layer and the solid electrolyte interface layer on the final negative electrode, and the amount of the lithium-containing substance to be used is usually excessive, and the excessive amount is defined as an equivalent amount compared with the case where the compound Y is completely reacted. If the amount of the lithium-containing substance is low, the compound Y cannot be completely reacted, and a residual compound Y film layer exists between the lithium alloy layer and the base material on the finally obtained negative electrode, and/or the obtained lithium alloy layer contains the residual compound Y. If the lithium-containing material is excessive, the lithium alloy layer generally contains both a simple substance of lithium and a lithium alloy, and the lithium alloy refers to an alloy formed by a lithium element and an X element.
A third aspect of the invention provides a battery comprising the negative electrode of the first aspect or the negative electrode produced by the production method of the second aspect.
A fourth aspect of the invention provides an electrical device comprising the battery of the third aspect.
In conclusion, compared with the prior art, the invention achieves the following technical effects:
(1) A lithium alloy uniformly distributed anode is provided, which has better stability and longer cycle life.
(2) The method not only improves the wettability between the base material and lithium, but also prepares the interface layer of the lithium alloy and the solid electrolyte, thereby relieving the problems of electrode cracking and pulverization and falling caused by the volume change of lithium metal, and inhibiting the growth of lithium dendrite, so as to improve the stability and the cycle life of the lithium metal cathode.
The foregoing description is only an overview of the technical solutions of the present application, and may be implemented according to the content of the specification in order to make the technical means of the present application more clearly understood, and in order to make the above-mentioned and other objects, features and advantages of the present application more clearly understood, the following detailed description of the present application will be given.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the application. Also, like reference numerals are used to designate like parts throughout the accompanying drawings. In the drawings:
fig. 1 is a structural view of a composite lithium anode of the present invention;
FIG. 2 is a SEM image of a copper foil with a stannous fluoride layer prepared in example 1 of the present invention;
FIG. 3 is a cross-sectional element map of a copper foil with stannous fluoride layer prepared in example 1 of the present invention;
FIG. 4 is a mapping chart of surface elements of a copper foil with stannous fluoride layer prepared in example 1 of the present invention;
FIG. 5 is a SEM (scanning electron microscope) image of a composite lithium anode prepared in example 1 of the present invention;
FIG. 6 is a cross-sectional element map of a composite lithium anode prepared in example 1 of the present invention;
FIG. 7 is a surface element map of a composite lithium anode prepared in example 1 of the present invention;
FIG. 8 is a SEM (scanning electron microscope) image of a composite lithium anode prepared in example 2 of the present invention;
FIG. 9 is a SEM (scanning electron microscope) image of a composite lithium anode prepared in example 3 of the present invention;
fig. 10 is a state diagram of the copper foil with stannous fluoride layer prepared in example 1 of the present invention before, during and after physical contact with molten lithium metal, corresponding to the left, middle and right three diagrams, respectively;
fig. 11 is a graph showing the first-turn charge and discharge performance of the composite lithium anode in example 1 and comparative example 2 of the present invention;
fig. 12 is a cycle performance chart of the composite lithium anode in example 1 and comparative example 2 of the present invention.
Detailed Description
Embodiments of the technical solutions of the present application will be described in detail below with reference to the accompanying drawings. The following examples are only for more clearly illustrating the technical solutions of the present application, and thus are only examples, and are not intended to limit the scope of protection of the present application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application; the terms "comprising" and "having" and any variations thereof in the description and claims of the present application and in the description of the figures above are intended to cover non-exclusive inclusions.
In the description of the embodiments of the present application, the meaning of "plurality" is two or more unless explicitly defined otherwise.
Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment may be included in at least one embodiment of the present application. The appearances of such phrases in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. Those of skill in the art will explicitly and implicitly appreciate that the embodiments described herein may be combined with other embodiments.
In the description of the embodiments of the present application, the term "and/or" is merely an association relationship describing an association object, which means that three relationships may exist, for example, a and/or B may mean: a exists alone, A and B exist together, and B exists alone. In addition, the character "/" herein generally indicates that the front and rear associated objects are an "or" relationship.
In the description of the embodiments of the present application, the term "plurality" refers to more than two (including two).
Example 1
S1, in an argon atmosphere (O) 2 ,H 2 O<0.01 ppm), heating and melting stannous fluoride powder at 260 ℃, and coating the molten stannous fluoride on the surface of the copper foil by a coating mode, wherein the coating thickness is set to be 1 mu m, so as to obtain the copper foil with the stannous fluoride layer.
S2, in an argon atmosphere (O) 2 ,H 2 O<0.01 ppm), heating the copper foil with the stannous fluoride layer prepared in the step S1 to 200 ℃, then coating molten lithium metal on the surface of the copper foil, setting the coating thickness to be 30 mu m, preserving heat for 5 seconds, and cooling to obtain the copper foil/lithium simple substance+lithium tin alloy/lithium fluoride composite lithium anode, namely, sequentially laminating two layers of covers on the copper foil, wherein the covers close to the copper foil are layers containing lithium simple substance and lithium tin alloy, and the outer surface is covered with the lithium fluoride layer.
Example 2
S1, in an argon atmosphere (O) 2 ,H 2 O<0.01 ppm), heating and melting stannous fluoride powder at 260 ℃, and coating the molten stannous fluoride on the surface of the copper foil by a coating mode, wherein the coating thickness is set to be 1 mu m, so as to obtain the copper foil with the stannous fluoride layer.
S2, in an argon atmosphere (O) 2 ,H 2 O<0.01 ppm), heating the copper foil with the stannous fluoride layer prepared in the step S1 to 200 ℃, then coating molten lithium metal on the surface of the copper foil, setting the coating thickness to be 20 mu m, preserving heat for 4 seconds, and cooling to obtain the copper foil/lithium simple substance+lithium tin alloy/lithium fluoride composite lithium anode.
Example 3
S1, in an argon atmosphere (O) 2 ,H 2 O<0.01 ppm), heating and melting stannous fluoride powder at 260 ℃, and coating the molten stannous fluoride on the surface of the copper foil by a coating mode, wherein the coating thickness is set to be 1 mu m, so as to obtain the copper foil with the stannous fluoride layer.
S2, in an argon atmosphere (O) 2 ,H 2 O<0.01 ppm), heating the copper foil with the stannous fluoride layer prepared in the step S1 to 200 ℃, then coating molten lithium metal on the surface of the copper foil, setting the coating thickness to be 60 mu m, preserving heat for 7 seconds, and cooling to obtain the copper foil/lithium simple substance+lithium tin alloy/lithium fluoride composite lithium anode.
Example 4
S1, preparing a zinc chloride layer on the surface of a copper foil in an electroplating mode, wherein the electroplating solution is zinc chloride solution with the concentration of 0.5mol/L, the working electrode is the copper foil, the electroplating voltage is constant voltage of 2V, the electroplating time is 1min, after the electroplating is completed, the copper foil is washed three times by deionized water, and then the copper foil with the zinc chloride layer is prepared after drying, wherein the thickness of the zinc chloride layer is 2 mu m.
S2, in an argon atmosphere (O) 2 ,H 2 O<0.01 ppm), heating the copper foil with the zinc chloride layer prepared in the step S1 to 300 ℃, then coating molten lithium metal on the surface of the copper foil, setting the coating thickness to be 30 mu m, preserving heat for 17 seconds, and cooling to obtain the copper foil/lithium simple substance+lithium zinc alloy/lithium chloride composite lithium anode.
Example 5
S1, preparing an indium sulfide layer on the surface of a copper foil through an evaporation mode, heating indium sulfide in a vacuum evaporation device, heating to 850 ℃ at a heating rate of 5 ℃/min, keeping the temperature, converting indium sulfide powder into a liquid state, and finally volatilizing the indium sulfide powder into indium sulfide vapor. The distance between the indium sulfide and the copper foil is 25mm, the temperature of the copper foil is adjusted to 90 ℃, and the indium sulfide vapor is deposited on the surface of the copper foil, so that the copper foil with the indium sulfide layer is prepared, and the thickness of the indium sulfide layer is 550nm.
S2, in an argon atmosphere (O) 2 ,H 2 O<0.01 ppm), heating the copper foil with the indium sulfide layer prepared in the step S1 to 500 ℃, then coating molten lithium metal on the surface of the copper foil, setting the coating thickness to be 30 mu m, preserving heat for 7S, and cooling to obtain the copper foil/lithium simple substance+lithium indium alloy/lithium sulfide composite lithium anode.
Example 6
S1, preparing a silver oxide layer on the surface of a copper foil in a spraying mode, dispersing silver oxide in an acetone solution under the spraying pressure of 1MPa for 3S, respectively cleaning three times by using alcohol and deionized water, and then drying to obtain the copper foil with the silver oxide layer, wherein the thickness of the silver oxide layer is 3.2 mu m.
S2, in an argon atmosphere (O) 2 ,H 2 O<0.01 ppm), heating the copper foil with the silver oxide layer prepared in the step S1 to 250 ℃, then coating molten lithium metal on the surface of the copper foil, setting the coating thickness to be 30 mu m, preserving heat for 12 seconds, and cooling to obtain the copper foil/lithium simple substance+lithium silver alloy/lithium oxide composite lithium anode.
Example 7
The difference from example 1 is the method of forming the two-layer film, specifically as follows.
S1, in an argon atmosphere (O) 2 ,H 2 O<0.01 ppm), heating and melting stannous fluoride powder at 260 ℃, and coating the molten stannous fluoride on the surface of the copper foil by a coating mode, wherein the coating thickness is set to be 1 mu m, so as to obtain the copper foil with the stannous fluoride layer.
S2, in an argon atmosphere (O) 2 ,H 2 O<0.01 ppm), coating molten lithium metal on the surface of the copper foil, setting the coating thickness to be 30 mu m, preserving heat for 5s, and cooling to obtain the copper foil/lithium simple substance+lithium tin alloy/lithium fluoride composite lithium anode.
Example 8
The difference from example 1 is that the raw materials coated in step S1 are different, specifically as follows.
S1, in an argon atmosphere (O) 2 ,H 2 O<0.01 ppm), heating and melting the antimony tribromide powder at 260 ℃, and coating the melted antimony tribromide on the surface of the copper foil by a coating method, wherein the coating thickness is set to be 1 mu m, thereby obtaining the copper foil with the antimony tribromide layer.
S2, in an argon atmosphere (O) 2 ,H 2 O<0.01 ppm), heating the copper foil with the antimony tribromide layer prepared in the step S1 to 200 ℃, then coating molten lithium metal on the surface of the copper foil, setting the coating thickness to be 30 mu m, preserving heat for 5 seconds, and cooling to prepare the copper foil/lithium simple substance+lithium antimony alloy/lithium bromide composite lithium anode.
Example 9
S1, in an argon atmosphere (O) 2 ,H 2 O<0.01 ppm), and the magnesium chloride powder was heated to 760 c, and the molten magnesium chloride was coated on the surface of the copper foil by a coating method with a coating thickness set to 1 μm, to obtain a copper foil having a magnesium chloride layer.
S2, in an argon atmosphere (O) 2 ,H 2 O<0.01 ppm), heating the copper foil with the magnesium chloride layer prepared in the step S1 to 200 ℃, then coating molten lithium metal on the surface of the copper foil, setting the coating thickness to be 30 mu m, preserving heat for 5 seconds, and cooling to obtain the copper foil/lithium simple substance+lithium magnesium alloy/lithium chloride composite lithium anode.
Example 10
S1, in an argon atmosphere (O) 2 ,H 2 O<0.01 ppm), and the silver fluoride powder was heated to 500 c, and the molten silver fluoride was coated on the surface of the copper foil by a coating method with a coating thickness set to 1 μm, to obtain a copper foil having a silver fluoride layer.
S2, in an argon atmosphere (O) 2 ,H 2 O<0.01 ppm), heating the copper foil with the silver fluoride layer prepared in the step S1 to 200 ℃, then coating molten lithium metal on the surface of the copper foil, setting the coating thickness to be 30 mu m, preserving heat for 5 seconds, and cooling to obtain the copper foil/lithium simple substance+lithium silver alloy/lithium fluoride composite lithium anode.
Example 11
S1, in an argon atmosphere (O) 2 ,H 2 O<0.01 ppm), and the lead bromide powder was melted by heating at 400 c, and the melted lead bromide was coated on the surface of the copper foil by a coating method with a coating thickness set to 1 μm, to obtain a copper foil having a lead bromide layer.
S2, in an argon atmosphere (O) 2 ,H 2 O<0.01 ppm), heating the copper foil with the lead bromide layer prepared in the step S1 to 200 ℃, then coating molten lithium metal on the surface of the copper foil, setting the coating thickness to be 30 mu m, preserving heat for 5 seconds, and cooling to obtain the copper foil/lithium simple substance+lithium lead alloy/lithium bromide composite lithium anode.
Example 12
S1, in an argon atmosphere (O) 2 ,H 2 O<0.01 ppm), heating and melting bismuth trichloride powder at 260 ℃, and coating the melted bismuth trichloride on the surface of the copper foil by a coating method, wherein the coating thickness is set to be 1 μm, thereby obtaining the copper foil with a bismuth trichloride layer.
S2, in an argon atmosphere (O) 2 ,H 2 O<0.01 ppm), heating the copper foil with the bismuth trichloride layer prepared in the step S1 to 200 ℃, then coating molten lithium metal on the surface of the copper foil, setting the coating thickness to be 30 mu m, preserving heat for 5 seconds, and cooling to obtain the composite lithium anode of copper foil/lithium simple substance+lithium bismuth alloy/lithium chloride.
The negative electrode obtained in the above example has a structure as shown in fig. 1, and includes a substrate (i.e., copper foil), a lithium alloy layer, and an SEI layer, respectively, from bottom to top.
Comparative example 1
In an argon atmosphere (O) 2 ,H 2 O<0.01 ppm), heating and melting stannous fluoride powder at 260 ℃, and coating the molten stannous fluoride on the surface of the copper foil by a coating mode, wherein the coating thickness is set to be 1 mu m, so as to obtain the copper foil with the stannous fluoride layer.
Comparative example 2
In an argon atmosphere (O) 2 ,H 2 O<0.01 ppm), heating the copper foil to 200 ℃, then coating molten lithium metal on the surface of the copper foil, setting the coating thickness to be 30 mu m, preserving heat for 5s, and cooling to obtain the lithium metal foil.
Comparative example 3
The difference from example 1 is the method of forming the two-layer film, specifically as follows.
S1, in an argon atmosphere (O) 2 ,H 2 O<0.01 ppm) of molten lithium metal was coated on the surface of the copper foil, the coating thickness was set to 30 μm, and the copper foil was directly cooled.
S2, in an argon atmosphere (O) 2 ,H 2 O<0.01 ppm), and the molten lithium fluoride was coated on the surface of the foil obtained in S1 by a coating method, the coating thickness was set to 1 μm, thereby obtaining a negative electrode.
Performance testing
To verify the advancement of the inventive examples, the following performance tests were performed on all examples and comparative examples.
1. The composite lithium anode prepared in example 1 was characterized by scanning electron microscopy and a cross-sectional SEM image thereof (fig. 2) shows that the stannous fluoride layer has a thickness of about 1 μm. The cross-section element map (figure 3) and the surface element map (figure 4) show that the tin element and the fluorine element in the stannous fluoride layer are uniformly distributed. The SEM image (fig. 5) of the cross section thereof shows that the load thickness (including the sum of the thicknesses of the lithium alloy layer and the SEI film layer) of the composite lithium anode is about 30 μm. The cross-section element map (fig. 6) shows that the tin elements are uniformly distributed, which indicates that the lithium-tin alloy is uniformly distributed in the composite lithium anode. As can be seen from the surface element map (figure 7), fluorine elements are uniformly distributed on the surface, which means that stannous fluoride reacts with molten lithium to generate lithium fluoride, and the lithium fluoride is distributed on the surface of the composite lithium negative electrode, so that an SEI film is formed. The composite lithium negative electrodes prepared in example 2 and example 3 were characterized by scanning electron microscopy, and their cross-sectional SEM images (fig. 8 and 9) show that the thicknesses of the composite lithium negative electrodes were 20 μm and 60 μm, respectively.
2. The wettability of the stannous fluoride layer-supporting copper foil prepared in example 1 (i.e., the structure obtained in step S1) was characterized, and as shown in fig. 10, it can be seen that the stannous fluoride layer-supporting copper foil was instantaneously wettable with molten lithium.
3. The composite lithium negative electrodes prepared in examples and comparative examples were made into negative electrode sheets, and were combined with ternary positive electrode NCM523, separator and electrolyte (1.0M LiPF 6 Dissolution in EC: EMC: dec=1:1:1) CR2016 coin cells were assembled and cycled at 0.5C rate, with the data results shown in table 1.
Table 1 composite lithium anode of each example and comparative example and battery performance assembled thereof
From the above test results, it is shown that the composite lithium negative electrodes of examples 1 to 12 of the present invention exhibit higher initial coulombic efficiency and stable cycle performance, compared to the lithium negative electrode of comparative example 2 without lithium alloy and SEI film, indicating that the lithium alloy and SEI film of the composite lithium negative electrode can reduce lithium resource consumption, alleviate problems of cracking and powdering off of the electrode due to volume change, and improve interface stability, thereby improving stability and cycle life of the composite lithium negative electrode. Among them, the first-turn charge and discharge performance of example 1 and comparative example 2 is shown in fig. 11, and the cycle performance of example 1 and comparative example 2 is shown in fig. 12, and it can be seen that the first-turn charge and discharge performance and cycle performance of example 1 are significantly superior to those of comparative example 2.
As is apparent from examples 1 to 3, the thinner the lithium alloy layer in the composite lithium negative electrode, the higher the first-turn coulombic efficiency thereof, since the thinner lithium alloy layer can reduce the formation time of the natural SEI film and the consumption of lithium resources, can alleviate the problem of dendrite growth of lithium metal, and can reduce the short circuit and safety problems caused by dendrite, thereby improving the cycle stability of the battery. While thicker lithium alloy layers may increase the opportunity for dendrite growth, which may lead to degradation of cell performance during cycling.
As is clear from examples 1 and 7, since example 7 did not heat the pretreated substrate, the reaction rate was slower than example 1, resulting in a decrease in the lithium alloy content and the solid electrolyte interface layer thickness in the lithium alloy layer, resulting in poor performance.
As can be seen from examples 1 and 8, the composition was prepared from antimony tribromide (SbBr 3 ) The melting point of (2) is only 97 ℃, so that when the temperature is heated to 200 ℃ in the step S2, the antimony tribromide coated on the copper foil is melted, resulting in the melting point of the antimony tribromide on the copperThe distribution on the foil is uneven, so that when molten lithium is coated later, the lithium alloy and lithium bromide generated by the reaction are released unevenly, and the performance is poor.
As is apparent from example 1 and comparative example 3, since it is difficult to uniformly coat molten lithium on the surface of the copper foil current collector in comparative example 3, the problem of non-uniformity in thickness of the prepared negative electrode is more remarkable, resulting in poor performance.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the embodiments, and are intended to be included within the scope of the claims and description. In particular, the technical features mentioned in the respective embodiments may be combined in any manner as long as there is no structural conflict. The present application is not limited to the specific embodiments disclosed herein, but encompasses all technical solutions falling within the scope of the claims.
Claims (10)
1. A negative electrode, comprising a substrate, a lithium alloy layer covered on the surface of the substrate, and a solid electrolyte interface layer covered on the outer surface of the lithium alloy layer;
the lithium alloy layer comprises lithium element and X element, wherein X comprises one or more of magnesium, calcium, barium, zinc, boron, aluminum, gallium, indium, carbon, silicon, tin, silver, germanium, lead, antimony and bismuth;
the solid electrolyte interfacial layer includes one or more of lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium sulfide, lithium oxide, or lithium nitride.
2. The negative electrode according to claim 1, characterized in that the thickness of the lithium alloy layer is 1-200 μm, preferably 5-80 μm, more preferably 20-60 μm or 5-20 μm.
3. The anode according to claim 1, wherein the thickness of the solid electrolyte interface layer is 10nm to 1 μm.
4. The anode according to claim 1, wherein the lithium alloy layer comprises a lithium alloy, wherein the lithium alloy is Li a X b ，0＜b/a≤72；
Preferably, the lithium alloy layer comprises a lithium alloy and a lithium simple substance;
preferably, the mass ratio of the lithium alloy in the lithium alloy layer is 1 to 100%, preferably 1 to 80%.
5. The negative electrode according to claim 1, wherein X comprises one or more of zinc, indium, tin, silver, magnesium, bismuth, lead, preferably tin.
6. The method for producing a negative electrode according to any one of claims 1 to 5, characterized in that the production method is carried out in an inert atmosphere or a vacuum atmosphere, comprising the steps of:
loading a compound Y on the surface of a substrate to obtain a pretreated substrate;
coating molten lithium-containing substances on the surface of the pretreated substrate, and preserving heat to prepare the negative electrode;
wherein the compound Y is one or more of fluoride, chloride, bromide, iodide, sulfide, oxide or nitride of X; the lithium-containing substance comprises a lithium simple substance, or a compound consisting of lithium and X and the lithium simple substance.
7. The method according to claim 6, wherein the compound Y has a melting point higher than that of lithium.
8. The method of claim 6, wherein the loading comprises at least one of electroplating, sputtering, spraying, evaporating, coating, and chemical vapor deposition.
9. A battery comprising the negative electrode according to any one of claims 1 to 5 or the negative electrode produced by the production method according to any one of claims 6 to 8.
10. An electrical device comprising the battery of claim 9.
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