CN116598512A - Coating, preparation method thereof, electrochemical device and electronic equipment - Google Patents
Coating, preparation method thereof, electrochemical device and electronic equipment Download PDFInfo
- Publication number
- CN116598512A CN116598512A CN202310734204.7A CN202310734204A CN116598512A CN 116598512 A CN116598512 A CN 116598512A CN 202310734204 A CN202310734204 A CN 202310734204A CN 116598512 A CN116598512 A CN 116598512A
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- Prior art keywords
- coating
- gallium
- metal
- negative electrode
- electrochemical device
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- 238000000576 coating method Methods 0.000 title claims abstract description 169
- 239000011248 coating agent Substances 0.000 title claims abstract description 167
- 238000002360 preparation method Methods 0.000 title abstract description 8
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 83
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 82
- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- 239000002184 metal Substances 0.000 claims abstract description 47
- 229910001338 liquidmetal Inorganic materials 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims description 59
- 239000000203 mixture Substances 0.000 claims description 33
- -1 polysiloxane Polymers 0.000 claims description 30
- 238000002791 soaking Methods 0.000 claims description 29
- 238000005530 etching Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 20
- 238000004140 cleaning Methods 0.000 claims description 16
- 229910045601 alloy Inorganic materials 0.000 claims description 14
- 239000000956 alloy Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims 2
- 210000001787 dendrite Anatomy 0.000 abstract description 17
- 230000001351 cycling effect Effects 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 238000004132 cross linking Methods 0.000 abstract description 6
- 239000002149 hierarchical pore Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000001465 metallisation Methods 0.000 abstract description 4
- 230000001960 triggered effect Effects 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 description 44
- 239000000243 solution Substances 0.000 description 41
- 230000000052 comparative effect Effects 0.000 description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 27
- 239000011889 copper foil Substances 0.000 description 26
- 150000002641 lithium Chemical class 0.000 description 20
- 235000012431 wafers Nutrition 0.000 description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 18
- 239000007788 liquid Substances 0.000 description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 14
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
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- 238000005520 cutting process Methods 0.000 description 10
- 238000006073 displacement reaction Methods 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 239000011247 coating layer Substances 0.000 description 8
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 239000002033 PVDF binder Substances 0.000 description 7
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- 239000007774 positive electrode material Substances 0.000 description 7
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- 239000011230 binding agent Substances 0.000 description 6
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- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- ORMNPSYMZOGSSV-UHFFFAOYSA-N dinitrooxymercury Chemical compound [Hg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ORMNPSYMZOGSSV-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
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- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 4
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- 239000000463 material Substances 0.000 description 4
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- 229920001577 copolymer Polymers 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
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- 239000010954 inorganic particle Substances 0.000 description 3
- PQTLYDQECILMMB-UHFFFAOYSA-L platinum(2+);sulfate Chemical compound [Pt+2].[O-]S([O-])(=O)=O PQTLYDQECILMMB-UHFFFAOYSA-L 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OQMIRQSWHKCKNJ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2,3,3,3-hexafluoroprop-1-ene Chemical group FC(F)=C.FC(F)=C(F)C(F)(F)F OQMIRQSWHKCKNJ-UHFFFAOYSA-N 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
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- 150000001875 compounds Chemical class 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
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- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- QKBJDEGZZJWPJA-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound [CH2]COC(=O)OCCC QKBJDEGZZJWPJA-UHFFFAOYSA-N 0.000 description 2
- 229910000449 hafnium oxide Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
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- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
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- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
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- LEGITHRSIRNTQV-UHFFFAOYSA-N carbonic acid;3,3,3-trifluoroprop-1-ene Chemical compound OC(O)=O.FC(F)(F)C=C LEGITHRSIRNTQV-UHFFFAOYSA-N 0.000 description 1
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- SNQXJPARXFUULZ-UHFFFAOYSA-N dioxolane Chemical compound C1COOC1 SNQXJPARXFUULZ-UHFFFAOYSA-N 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- 229910001987 mercury nitrate Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- DRXYRSRECMWYAV-UHFFFAOYSA-N nitrooxymercury Chemical compound [Hg+].[O-][N+]([O-])=O DRXYRSRECMWYAV-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—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
- H01M4/64—Carriers or 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a coating, a preparation method thereof, an electrochemical device and electronic equipment, wherein the coating comprises a carrier and gallium-containing liquid metal dispersed in the carrier, surface holes and inner holes communicated with the surface holes are respectively distributed on the surface and the inside of the coating, and the surface holes and the inner holes form a hierarchical hole structure. According to the invention, after the coating is coated on the metal negative electrode, the unique hierarchical pore structure and the cross-linking structure can ensure that metal deposition occurs below the film, and after dendrites growing upwards are contacted with gallium-containing liquid metal in the coating, embrittlement reaction of the tips of the dendrites is triggered, so that chemical protection effect of the coating is exerted, and further, the cycling stability of an electrochemical device assembled by the negative electrode plate formed by the coating is improved.
Description
Technical Field
The invention relates to the technical field of electrochemical energy storage, in particular to a coating, a preparation method thereof, an electrochemical device and electronic equipment.
Background
In recent years, with rapid development of electric vehicles and mobile electronic devices, there is a demand for higher energy density of energy storage systems such as lithium ion secondary batteries. Among them, lithium metal, sodium metal, etc. have an ultra-high theoretical capacity (Li: 3860mAh/g, na:1166 mAh/g) and a proper electrode potential, and are becoming a research hot spot for metal secondary batteries. However, in the process that metal ions reach the surface of a metal negative electrode through an SEI film (i.e., a solid electrolyte interface film) to generate electrochemical precipitation, uneven precipitation forms are formed on the surface of the negative electrode, dendrite forms are gradually formed along with the progress of circulation, so that the reduction of coulomb efficiency is caused, safety problems such as battery short circuit and the like are caused, and commercialization of a metal secondary battery is restricted.
In order to solve the technical problems, attempts are made to control the interfacial behavior of the metal negative electrode by coating a coating on the surface of the metal negative electrode. However, these coatings only provide physical barriers, the high active surface and infinite volume expansion characteristics of the metal electrode itself make it almost impossible to completely inhibit dendrite morphology deposition during long cycling. Gallium and gallium-based alloy atoms which are in liquid state at room temperature have weak binding force and have the functions of flowing, self-healing and the like, and are novel materials with the characteristics of fluid and metal. When in contact with ductile metals (Li, na, K, zn, al, etc.), gallium atoms can diffuse along the metal grain boundaries, inducing embrittlement of the contact region. Based on the embrittlement phenomenon, the gallium-containing metal is expected to provide a chemical barrier effect, so that dendrite behavior of a metal anode interface is regulated and controlled.
For example, in order to solve the dendrite problem of the metal negative electrode, CN114649502a makes the nucleation morphology of the metal lithium on the negative electrode current collector more orderly due to the influence of the gallium-based alloy coating by coating the gallium-based alloy layer with a thickness less than 500nm on the negative electrode current collector, promotes the metal lithium to grow more densely and uniformly on the negative electrode, reduces the contact area between the metal lithium negative electrode and the electrolyte, thereby reducing the amount of irreversible side reactions at the interface, reducing the loss amount of reversible lithium resources in each charge-discharge cycle, improving the cycle stability of the battery, and improving the energy density. However, gallium-based alloys are subject to aggregation during electrochemical processes, resulting in coating failure and poor cycling stability of the cell. CN109390585B utilizes the strong adhesion of liquid gallium and organic viscoelastic body to make composite film, effectively solves the problem of agglomeration, but the energy density of the lithium metal battery assembled from the pole pieces formed by it is lower, and the diffusion kinetics blocked causes the cycle life of the lithium metal battery assembled from the pole pieces formed by it to be shorter.
Disclosure of Invention
One of the purposes of the invention is to provide a coating to improve the cycling stability of an electrochemical device assembled by a negative electrode plate; a second object is to provide a method for preparing a coating as described above; a third object is to provide an electrochemical device; the fourth object is to provide an electronic device.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in some embodiments, the invention provides a coating, the coating comprises a carrier and gallium-containing liquid metal dispersed in the carrier, surface holes and internal holes communicated with the surface holes are respectively distributed on the surface and the inside of the coating, and the surface holes and the internal holes form a hierarchical hole structure.
In some embodiments, the surface pores have a pore size of 5-1000nm, preferably 10-100nm, more preferably 10-60nm.
In some embodiments, the surface pores have a pore size of 50% or more of the pores with a pore size of 60nm or less, preferably 90% or more.
In some embodiments, the carrier comprises a polysiloxane, a silicone, or a mixture of both.
In some embodiments, the gallium-containing metal comprises gallium or a gallium-based alloy.
In some embodiments, the gallium-based alloy contains gallium in an amount of 60wt% to 90wt%, preferably 65wt% to 90wt%.
In some embodiments, the mass percent of the carrier to gallium-containing metal is 90wt% to 20wt%:10wt% to 80wt%, preferably 70wt% to 30wt%: 30-70 wt%.
In some embodiments, the present invention also provides a method of preparing a coating as described above, the method comprising the steps of:
s1, adding gallium-containing liquid metal into a carrier, and uniformly mixing to obtain a mixture;
s2, coating the mixture on a metal substrate, and etching, cleaning, soaking and drying after drying.
In some embodiments, in step S1, the mixing is for a period of 0.5-2 hours.
In some embodiments, in step S2, the thickness of the coating is less than or equal to 50 μm, preferably less than or equal to 10 μm, more preferably less than or equal to 5 μm.
In some embodiments, in step S2, the concentration of the soaking solution used in the soaking process is 0.01-3mol, preferably 0.1-3mol/L.
In some embodiments, the present invention also provides an electrochemical device comprising a pole piece comprising a metal current collector and a coating as described above or made according to the preparation method described above on the metal current collector.
In some embodiments, the invention also provides an electronic device comprising an electrochemical apparatus as described in the claims.
The invention has the beneficial effects that:
in the invention, the surface holes are communicated with the inner holes to form a cross-linking structure, so that the flow and agglomeration of liquid metal in the coating are limited, the stability of the coating is improved, the cycling stability of an electrochemical device assembled by the anode pieces formed by the coating is further improved, the surface holes can promote the infiltration of electrolyte, the ion diffusion rate is improved, and the dynamic performance of the electrochemical device is not influenced; after the coating is coated on a metal negative electrode, the unique hierarchical pore structure and the cross-linking structure can ensure that metal deposition occurs below a film, dendrites growing upwards trigger embrittlement reaction of dendrite tips after contacting gallium-containing liquid metal in the coating, chemical protection effect of the coating is exerted, and the cycling stability of an electrochemical device assembled by a negative electrode plate formed by the coating is further improved.
Drawings
FIG. 1 is a schematic flow chart of the preparation process of the coating in example 1;
FIG. 2 is a schematic structural diagram of the coating prepared in example 1;
FIG. 3 is a graph showing the pore morphology of the surface nanopores and the pore size distribution of the coatings prepared in example 1 and comparative example 7, a is a graph showing the pore morphology of the surface of the coating prepared in example 1, b is a graph showing the pore size distribution of the surface of the coating prepared in example 1, and c is a graph showing the pore morphology of the surface of the coating prepared in comparative example 7;
FIG. 4 is an internal cross-linked pore morphology of the coating of example 1;
FIG. 5 is an assembled schematic view of a symmetrical battery;
FIG. 6 is an electron microscope scan of the surface of the coating produced in comparative example 6;
FIG. 7 shows the current density at 2mA/cm 2 Deposition amount is 1mAh/cm 2 After 50 cycles, the electron microscope scans (4 μm) of the surfaces of the negative electrode tabs of example 1 and comparative example 1, where a is the electron microscope scan of the surface of the negative electrode tab of example 1 and b is the electron microscope scan of the surface of the negative electrode tab of comparative example 1;
FIG. 8 shows the current density at 2mA/cm 2 Deposition amount is 1mAh/cm 2 After 50 cycles, the electron microscope scans (10 μm) of the negative electrode tab side of example 1 and comparative example 1, where a is the electron microscope scan of the negative electrode tab side of example 1 and b is the electron microscope scan of the negative electrode tab side of comparative example 1;
fig. 9 is a voltage curve of the symmetrical battery of example 1 and comparative example 1.
Detailed Description
The invention will be further illustrated by the following specific examples, but it should be noted that embodiments of the invention
The specific material ratios, process conditions, results and the like described in the present application are only for illustration of the present invention, and are not intended to limit the scope of the present invention, and all equivalent changes or modifications made in accordance with the spirit of the present invention should be included in the scope of the present invention. Unless otherwise specified, "wt%" as shown in the description herein means "mass fraction".
In some embodiments, the present invention provides a coating comprising a carrier and a gallium-containing liquid metal dispersed in the carrier, the surface and the interior of the coating being respectively distributed with surface pores and interior pores communicating with the surface pores, the surface pores and the interior pores forming a hierarchical pore structure;
according to the electrochemical device, the surface holes are communicated with the inner holes to form a cross-linking structure, so that the flow and agglomeration of liquid metal in the coating are limited, the stability of the coating is improved, the circulation stability of the electrochemical device assembled by the anode piece formed by the coating is further improved, the surface holes can promote electrolyte infiltration, the ion diffusion rate is improved, the dynamic performance of the electrochemical device is not affected, after the coating is coated on a metal anode, the unique hierarchical hole structure and the cross-linking structure can ensure that metal deposition occurs below a film, and after dendrites growing upwards are contacted with gallium-containing liquid metal in the coating, the embrittlement reaction of the tip of the dendrites is triggered, the chemical protection effect of the coating is exerted, and the circulation stability of the electrochemical device assembled by the anode piece formed by the coating is further improved.
In some embodiments, the surface pores have a pore size of 5-1000nm;
according to the invention, the surface holes with the aperture of 5-1000nm can promote electrolyte infiltration, improve ion diffusion rate, not affect the dynamic performance of an electrochemical device assembled by the anode electrode plates formed by the coating, and simultaneously the nanoscale size can further prevent gallium-containing metal from flowing out, so that the cycling stability of the electrochemical device assembled by the anode electrode plates formed by the coating is improved.
In the invention, if the aperture of the surface hole is less than 5nm, ion transmission can be seriously hindered, and the electrochemical performance of an electrochemical device assembled by a negative electrode plate formed by a coating is affected; if the aperture of the surface hole is more than 1000nm, the gallium-containing metal in the coating is easy to be exposed and fall off, the chemical barrier effect of the coating on dendrites is reduced, and the cycling stability of the electrochemical device assembled by the negative electrode plate formed by the coating is further reduced.
It should be understood that in the present invention, surface pores and internal pores refer to pores distributed on the surface of the coating and within the coating, respectively.
In some embodiments, the pore size of the surface pores is 50% or more of the pores having a pore size of 250nm or less.
The ratio of pores having a pore diameter of 250nm or less means a percentage of the number of pores having a pore diameter of 250nm or less to the total number of surface pores.
In some embodiments, the mass percent of carrier to gallium-containing metal is 90wt% to 20wt%: 10-80 wt% of carrier comprising polysiloxane, silicone resin or mixture of the two, gallium-containing liquid metal comprising gallium or gallium-based alloy, gallium-based alloy comprising at least one of gallium-indium alloy, gallium-tin alloy and gallium-indium-tin alloy, gallium-based alloy containing gallium in 60-90 wt%.
According to the invention, the gallium-based alloy contains 60-90 wt% of gallium, so that the fluidity of the gallium-based alloy can be ensured, the coating can exert a chemical barrier effect on dendrites, and the cycling stability of an electrochemical device assembled by a negative electrode plate formed by the coating is ensured.
In the present invention, gallium-containing liquid metal means a metal substance which contains gallium and is liquid at room temperature.
In some embodiments, the present invention also provides a method of preparing a coating as described above, the method comprising the steps of:
s1, adding gallium-containing liquid metal into a carrier, and uniformly mixing to obtain a mixture;
s2, coating the mixture on a metal substrate, and etching, cleaning, soaking and drying after drying.
As shown in fig. 1, a large amount of bubbles can be introduced into a system formed by a carrier 12 (i.e., a carrier compound) and a gallium-containing liquid metal 11 in the stirring process to form a mixture 13 (i.e., a liquid mixture), so that the mixture can be cured at a high temperature to form a crosslinked porous structure; and then coating the mixture 13 on a metal substrate to form a film, drying to obtain a composite coating 14 with compact surface and porous inside, carrying out displacement treatment on the bottom metal substrate, soaking and etching the coating, and generating a large number of nanopores (i.e. surface holes) on the surface, and simultaneously generating a large number of holes (i.e. inner holes) communicated with the surface holes inside to form a self-supporting, ultrathin coating 15 (i.e. porous coating) with a hierarchical pore structure.
The structure of the obtained coating is shown in figure 2, the viscosity of the mixture is high, a large number of bubbles are introduced in the long-time mixing process, so that the cured coating has a crosslinked porous structure, the surface of the coating forms a large number of nano holes through soaking and etching, the interior of the coating forms a large number of inner holes communicated with the surface holes, the surface holes and the inner holes form a hierarchical hole structure, a large number of channels are provided for ion transmission, and metal deposition occurs below the coating; the physical confinement of the coating itself can provide a partial buffer for inhibiting dendrite growth; after dendrite formation is serious, dendrite growing upwards can penetrate into the coating layer and contact with the internal gallium-containing liquid metal to induce embrittlement reaction with the dendrite tip, so that the stress of the upward growth is relieved, and the ultra-long stable circulation of the electrochemical device formed by the coating layer is realized.
In some embodiments, the metal substrate comprises at least one of copper foil, aluminum foil, zinc foil, and tin foil.
In some embodiments, in step S2, the thickness of the coating is less than or equal to 50 μm.
In the invention, the thickness of the coating is less than or equal to 50 mu m, and the adverse effect of the excessive thickness on the energy density of the electrochemical device assembled by the anode piece formed by the coating can be avoided.
In some embodiments, the mixing time is 0.5-2 hours.
In the present invention, the cycle stability of the electrochemical device for coating formation can be further improved by controlling the mixing time of the support and the gallium-containing metal to 0.5 to 2 hours.
In some embodiments, in step S2, the etching solution used in the etching process includes at least one of an iron chloride solution, a mercury nitrate solution, a silver nitrate solution, a platinum sulfate solution, and a mixed acid, where the mixed acid includes hydrogen peroxide and a solution a, and the solution a includes at least one of hydrochloric acid, sulfuric acid, hydrofluoric acid, and nitric acid.
In the mixed acid, the volume content of the hydrogen peroxide is 60-90%.
In some embodiments, in step S2, the concentration of the etching solution used in the etching process is 0.1-4mol/L.
In some embodiments, in step S2, the etching time is 0.1-5h.
In the invention, the soaking liquid adopted in the soaking process comprises inorganic acid or inorganic alkali, wherein the inorganic acid can be at least one of hydrochloric acid, sulfuric acid and hydrofluoric acid, the inorganic alkali can be at least one of sodium hydroxide and potassium hydroxide, the concentration of the soaking liquid is 0.01-3mol/L, and the soaking time is 0.1-1.5h.
In the invention, the selection of the type, the concentration range and the etching time of the soaking liquid play a decisive role in the aperture, the number and the distribution of surface holes of the coating and the number of cross-linking hole channels, so that the ion transmission of the coating can be ensured.
In the invention, the drying temperature is 60-200 ℃, preferably 80-200 ℃; the drying time is 0.5-48h, preferably 0.5-20h.
In the invention, the drying temperature is 60-200 ℃, preferably 80-200 ℃; the drying time is 0.5-48h, preferably 0.5-20h.
In some embodiments, the present invention also provides an electrochemical device comprising a pole piece comprising a metal current collector and a coating as described above or made according to the preparation method described above on the metal current collector.
In some embodiments, the negative electrode includes at least one of lithium, sodium, potassium, zinc, and aluminum.
In the present invention, the electrode assembly of the electrochemical device includes a positive electrode sheet, a negative electrode sheet, and a separator (if necessary) interposed between the positive electrode sheet and the negative electrode sheet, and the electrochemical device is obtained by disposing the positive electrode sheet and the negative electrode sheet in opposition with the separator interposed therebetween (if necessary), and adding an electrolyte.
As for the positive electrode tab, the positive electrode tab may include a positive electrode current collector and a positive electrode active material layer on the positive electrode current collector.
The positive electrode current collector may be a foil, an open-cell foil, or a mesh-like strip material formed by processing a material such as aluminum, copper, nickel, or titanium, or may be a porous material such as a porous metal (e.g., a foamed metal).
As for the positive electrode active material layer, the positive electrode active material layer may be coated only on a partial region of the positive electrode current collector. The positive electrode active material layer may include a positive electrode active material, a conductive agent, and a binder.
As the conductive agent, for example, at least one of conductive carbon black, sheet graphite, graphene, and carbon nanotube can be cited as the conductive agent of the positive electrode sheet.
As the binder, for example, at least one of polyvinylidene fluoride, a copolymer of vinylidene fluoride-hexafluoropropylene, a styrene-acrylate copolymer, a styrene-butadiene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, sodium carboxymethyl cellulose, polyvinyl acetate, polyvinyl pyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene, and polyhexafluoropropylene may be cited as the binder in the positive electrode sheet.
The positive electrode active material may be at least one of lithium cobaltate, lithium nickelate, lithium manganate, lithium nickelate, lithium iron phosphate, lithium nickelate aluminate, and lithium nickelate manganate, and the above positive electrode active materials may be doped and coated.
The separator may be, for example, at least one of polyethylene, polypropylene, polyvinylidene fluoride, polyethylene terephthalate, polyimide, and aramid.
In some embodiments, the separator surface may further be provided with a porous layer disposed on at least one surface of the substrate of the separator, and the porous layer may include inorganic particles and a binder.
As the inorganic particles, the inorganic particles in the porous layer may be listed asFor example, alumina (Al) 2 O 3 ) Silicon oxide (SiO) 2 ) Magnesium oxide (MgO), titanium oxide (TiO) 2 ) Hafnium oxide (HfO) 2 ) Tin oxide (SnO) 2 ) Cerium oxide (CeO) 2 ) Nickel oxide (NiO), zinc oxide (ZnO), calcium oxide (CaO), zirconium oxide (ZrO) 2 ) Yttria (Y) 2 O 3 ) At least one of silicon carbide (SiC), boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide and barium sulfate.
As the binder, for example, at least one of polyvinylidene fluoride, a copolymer of vinylidene fluoride-hexafluoropropylene, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, sodium carboxymethyl cellulose, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene, and polyhexafluoropropylene may be cited as the binder in the porous layer.
It should be understood that in the present invention, the separator is not an essential component of the electrochemical device, for example, in some specific types of electrochemical devices (e.g., structures in which the positive electrode tab and the negative electrode tab are not in direct contact), the separator may not be necessary.
In some embodiments, the electrode assembly of the electrochemical device is a rolled electrode assembly or a stacked electrode assembly.
In some embodiments, the electrochemical device may further include an electrolyte. The electrolyte may be at least one of a gel electrolyte, a solid electrolyte, and an electrolyte solution.
Taking a lithium ion secondary battery as an example, the electrolyte includes a lithium salt and a solvent. Examples of the lithium salt include LiPF 6 、LiBF 4 、LiAsF 6 、LiClO 4 、LiB(C 6 H 5 ) 4 、LiCH 3 SO 3 、LiCF 3 SO 3 、LiN(SO 2 CF 3 ) 2 、LiC(SO 2 CF 3 ) 3 、LiSiF 6 At least one of LiBOB and lithium difluoroborate.
As the solvent, for example, at least one of a carbonate compound, a carboxylate compound, and an ether compound can be cited.
The carbonate compound includes, for example, at least one of a chain carbonate compound, a cyclic carbonate compound, a fluorinated carbonate compound, and other organic solvents.
The chain carbonate compound includes, for example, at least one of diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), and methylethyl carbonate (MEC). Examples of the cyclic carbonate compound include at least one of Ethylene Carbonate (EC), propylene Carbonate (PC), butylene Carbonate (BC) and Vinyl Ethylene Carbonate (VEC).
As the fluorocarbonate compound, at least one of fluoroethylene carbonate (FEC), 1, 2-difluoroethylene carbonate, 1, 2-trifluoroethylene carbonate, 1, 2-tetrafluoroethylene carbonate, 1-fluoro-2-methylethylene carbonate, 1-fluoro-1-methylethylene carbonate, 1, 2-difluoro-1-methylethylene carbonate, 1, 2-trifluoro-2-methylethylene carbonate, and trifluoromethyl ethylene carbonate can be cited.
Examples of the carboxylic acid ester compound include at least one of methyl acetate, ethyl acetate, n-propyl acetate, t-butyl acetate, methyl propionate, ethyl propionate, propyl propionate, γ -butyrolactone, decalactone, valerolactone, mevalonic acid lactone, caprolactone, and methyl formate.
Examples of the ether compound include at least one of dibutyl ether, tetraglyme, diglyme, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, ethoxymethoxyethane, 2-methyltetrahydrofuran, and tetrahydrofuran.
As the other organic solvent, at least one of dimethyl sulfoxide, 1, 2-dioxolane, sulfolane, methyl sulfolane, 1, 3-dimethyl-2-imidazolidone, N-methyl-2-pyrrolidone, formamide, dimethylformamide, acetonitrile, trimethyl phosphate, triethyl phosphate, trioctyl phosphate, and phosphoric acid ester may be cited, for example.
In some embodiments, taking lithium ion secondary battery as an example, the preparation method of the electrochemical device may be that the positive electrode plate, the separator and the negative electrode plate are sequentially wound or stacked to form an electrode piece, and then the electrode piece is packaged in an aluminum plastic film, and then the electrolyte is added to form and package the lithium ion secondary battery.
In the present invention, the electrochemical device is not particularly limited, and may be formed into a paper-type battery, a button-type battery, a coin-type battery, a laminate-type battery, a cylindrical battery, a square-type battery, or the like.
In the present invention, the electrochemical device may be a symmetrical battery.
In some embodiments, the invention also provides an electronic device comprising an electrochemical apparatus as described in the claims.
In the present invention, the electronic device is not particularly limited, and may be any electronic device known in the art.
In some embodiments, the electronic device may be exemplified by a notebook computer, a pen-input computer, a mobile computer, an electronic book player, a portable telephone, a portable facsimile machine, a portable copier, a portable printer, a headset, a video recorder, a liquid crystal television, a portable cleaner, a portable CD, a mini-compact disc, a transceiver, an electronic organizer, a calculator, a memory card, a portable audio recorder, a radio, a backup power supply, a motor, an automobile, a motorcycle, a power assisted bicycle, a lighting fixture, a toy, a game machine, a clock, an electric tool, a flash, a camera, a household large-sized battery, a capacitor, or the like.
The present invention will be described in detail with reference to specific exemplary examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, as many insubstantial modifications and variations are within the scope of the invention as would be apparent to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
It should be understood that in the following embodiments, only lithium and sodium are cited as the negative electrode current collector, copper foil is used as the metal substrate, ferric chloride solution, mercuric nitrate solution, silver nitrate solution, and platinum sulfate solution are used as the etching solution, gallium indium alloy, gallium indium tin alloy are used as the gallium-containing metal, hydrochloric acid, hydrofluoric acid, and potassium hydroxide are used as the soaking solution, and those skilled in the art may select other negative electrode current collectors except lithium and sodium, such as potassium, zinc, and aluminum, and other metal substrates except copper foil, such as aluminum foil, zinc foil, and tin foil, and other etching solutions except ferric chloride solution, mercuric nitrate solution, silver nitrate solution, and platinum sulfate solution, such as mixed acid, and other gallium-containing metals except gallium, gallium indium alloy, and gallium indium tin alloy, and other soaking solutions except hydrochloric acid, hydrofluoric acid, and potassium hydroxide, such as sulfuric acid and sodium hydroxide.
Example 1
(1) 8g of liquid gallium-indium alloy with gallium content of 68wt% and 2g of polydimethylsiloxane (CAS number 9016-00-6) are weighed and added into a mortar, and mechanically ground and mixed for 1h to obtain a uniform gray mixture;
(2) Spreading the uniform gray mixture on copper foil until the thickness of the coating film is 5 μm by using an automatic coater, and then drying for 12 hours at 100 ℃ to obtain a gallium-containing metal composite coating with smooth and compact surface;
(3) Placing the copper foil treated in the step (2) in FeCl with the concentration of 3mol/L 3 Soaking in the solution for 20min, performing displacement reaction, etching the copper foil, and leaving a self-supporting coating;
(4) After cleaning, transferring the self-supporting coating into hydrofluoric acid solution (the volume ratio of hydrogen fluoride to water is 5:100) to be fully soaked for 15min, forming a large number of nano holes on the surface of the coating, and drying for 12h at 100 ℃ after cleaning to obtain the coating with the thickness of 5 mu m.
The coating was scanned by electron microscopy and the results are shown in figure 3a and the pore size distribution of the pores at the surface of the coating was counted and the results are shown in figure 3 b.
As can be seen from fig. 3a, the surface of the coating prepared in this embodiment is distributed with a plurality of holes (i.e., surface holes), and the pore diameter of the surface holes is in the nanometer level.
As can be seen from FIG. 3b, the pore diameters of the surface pores are mainly distributed between 10 and 60nm, and the ratio of pores with the pore diameters of less than or equal to 30nm in the surface pores is 92%.
A cross-sectional sample was prepared using a focused ion beam and the internal morphology of the coating was examined and the results are shown in fig. 4.
As can be seen from fig. 4, the pores inside (i.e., the inner pores) of the coating layer prepared in this embodiment are communicated with the pores on the surface (i.e., the surface pores), i.e., the surface pores and the inner pores form a cross-linked structure, and the pore diameters of the surface pores and the inner pores are greatly different, i.e., the surface pores and the inner pores form a hierarchical pore structure.
(5) Cutting the coating into wafers with the diameter of 14cm by using a slicing machine, and transferring the wafers to lithium sheets with the diameter of 12cm to form modified lithium metal;
(6) As shown in fig. 5, a negative electrode case 51, a modified lithium metal 52, a separator 53, a modified lithium metal 52, and a positive electrode case 54 are sequentially placed, and assembled into a paired battery.
Example 2
(1) Weighing 5g of liquid gallium and 5g of polysiloxane (model I11413), adding into a centrifuge tube, adding ball-milling beads, and ball-milling and mixing for 1.5h to obtain a uniform gray mixture;
(2) Spreading the uniform gray mixture on copper foil until the thickness of the film is 5 μm, and then drying at 100deg.C for 12h to obtain a gallium-containing metal composite coating with smooth and compact surface;
(3) Placing the copper foil treated in the step (2) at 2mol/L AgNO 3 Soaking in the solution for 20min, performing displacement reaction, etching the copper foil, and leaving a self-supporting coating;
(4) After cleaning, transferring the self-supporting coating into hydrochloric acid solution (the volume ratio of hydrogen chloride to water is 20:100) to be fully soaked for 30min, forming a large number of nano holes on the surface of the coating, and drying the coating for 12h at the temperature of 100 ℃ after cleaning to obtain the coating with the thickness of 5 mu m.
(5) Cutting the coating into wafers with the diameter of 14cm by using a slicing machine, and transferring the wafers to lithium sheets with the diameter of 12cm to form modified lithium metal;
(6) As shown in fig. 5, a negative electrode case 51, a modified lithium metal 52, a separator 53, a modified lithium metal 52, and a positive electrode case 54 are sequentially placed, and assembled into a paired battery.
Example 3
(1) 2g of liquid gallium indium tin alloy with gallium content of 68wt% and 8g of methyl silicone resin (model S26897) are weighed and added into a mortar, and mechanically ground and mixed for 0.5h to obtain a uniform gray mixture;
(2) Spreading the uniform gray mixture on copper foil until the thickness of the film is 5 μm, and then drying for 12 hours at 100 ℃ to obtain a gallium-containing metal composite coating with smooth and compact surface;
(3) Placing the copper foil treated in the step (2) in PtSO with the concentration of 1mol/L 4 Soaking in the solution for 20min, performing displacement reaction, etching the copper foil, and leaving a self-supporting coating;
(4) After cleaning, the self-supporting coating is transferred into potassium hydroxide solution (the volume ratio of potassium hydroxide to water is 1:100) and is fully soaked for 60min, a large number of nano holes are formed on the surface of the coating, and the coating with the thickness of 5 mu m is obtained after cleaning and drying for 12h at the temperature of 100 ℃.
(5) Cutting the coating into wafers with the diameter of 14cm by using a slicing machine, and transferring the wafers to lithium sheets with the diameter of 12cm to form modified lithium metal;
(6) As shown in fig. 5, a negative electrode case 51, a modified lithium metal 52, a separator 53, a modified lithium metal 52, and a positive electrode case 54 are sequentially placed, and assembled into a paired battery.
Example 4
This embodiment differs from embodiment 1 in that:
(5) Cutting the coating into wafers with the diameter of 14cm by using a slicing machine, and transferring the wafers to sodium sheets with the diameter of 12cm to form modified sodium metal;
(6) And sequentially placing a negative electrode shell, modified sodium metal, a diaphragm, modified sodium metal and a positive electrode shell, and assembling the paired batteries.
Example 5
This embodiment differs from embodiment 2 in that:
(5) Cutting the coating into wafers with the diameter of 14cm by using a slicing machine, and transferring the wafers to sodium sheets with the diameter of 12cm to form modified sodium metal;
(6) And sequentially placing a negative electrode shell, modified sodium metal, a diaphragm, modified sodium metal and a positive electrode shell, and assembling the paired batteries.
Example 6
This embodiment differs from embodiment 3 in that:
(5) Cutting the coating into wafers with the diameter of 14cm by using a slicing machine, and transferring the wafers to sodium sheets with the diameter of 12cm to form modified sodium metal;
(6) And sequentially placing a negative electrode shell, modified sodium metal, a diaphragm, modified sodium metal and a positive electrode shell, and assembling the paired batteries.
Example 7
This embodiment differs from embodiment 1 in that:
(2) Spreading the uniform gray mixture on copper foil until the thickness of the coating film is 2 μm by using an automatic coater, and then drying for 12 hours at 100 ℃ to obtain a gallium-containing metal composite coating with smooth and compact surface;
(3) Placing the copper foil treated in the step (2) in FeCl with the concentration of 3mol/L 3 Soaking in the solution for 20min, performing displacement reaction, etching the copper foil, and leaving a self-supporting coating;
(4) After cleaning, transferring the self-supporting coating into hydrofluoric acid solution (the volume ratio of hydrogen fluoride to water is 5:100) and fully soaking for 15min, forming a large number of nano holes on the surface of the coating, and drying for 12h at 100 ℃ after cleaning to obtain a coating with the thickness of 2 mu m;
(5) Cutting the coating into wafers with the diameter of 14cm by using a slicing machine, and transferring the wafers to lithium sheets with the diameter of 12cm to form modified lithium metal;
(6) As shown in fig. 5, a negative electrode case 51, a modified lithium metal 52, a separator 53, a modified lithium metal 52, and a positive electrode case 54 are sequentially placed, and assembled into a paired battery.
Example 8
This comparative example differs from example 1 in that:
8g of liquid gallium and 2g of polydimethylsiloxane (CAS number 9016-00-6) were weighed into a mortar and mechanically milled and mixed for 1h to give a homogeneous gray mixture.
Example 9
This comparative example differs from example 3 in that:
(1) 8g of liquid gallium indium tin alloy with gallium content of 68wt% and 2g of methyl silicone resin (model S26897) are weighed and added into a mortar, and mechanically ground and mixed for 0.5h to obtain a uniform gray mixture;
(3) Placing the coating treated in the step (2) in PtSO with the concentration of 0.1mol/L 4 Soaking in the solution for 5 hours, carrying out displacement reaction, etching the copper foil, and leaving a self-supporting coating;
(4) After cleaning, transferring the self-supporting coating into 0.01mol/L potassium hydroxide solution, completely soaking for 1.5 hours, forming a large number of nano holes on the surface of the coating, and drying for 12 hours at the temperature of 100 ℃ after cleaning to obtain the coating with the thickness of 5 mu m.
Comparative example 1
This comparative example differs from example 1 in that:
and sequentially placing a cathode shell, lithium metal, a diaphragm, lithium metal and an anode shell, and assembling the paired batteries.
Comparative example 2
This comparative example differs from example 4 in that:
and sequentially placing a negative electrode shell, sodium metal, a diaphragm, sodium metal and a positive electrode shell, and assembling the paired batteries.
Comparative example 3
(1) 8g of liquid gallium-indium alloy with gallium content of 68wt% and 2g of polydimethylsiloxane (CAS number 9016-00-6) are weighed and added into a mortar, and mechanically ground and mixed for 10min to obtain a mixture;
(2) The mixture is scraped on a copper foil until the thickness of the coating film is 5 mu m by using an automatic coating machine, and then the coating film is dried for 12 hours at the temperature of 100 ℃ to obtain a gallium-containing metal composite coating with smooth and compact surface;
(3) Placing the copper foil treated in the step (2) in FeCl with the concentration of 3mol/L 3 Soaking in the solution for 20min, performing displacement reaction, etching copper foil, and leavingA self-supporting coating;
(4) After cleaning, the self-supporting coating was dried at 100℃for 12 hours to give a coating having a thickness of 5. Mu.m.
(5) Cutting the coating into wafers with the diameter of 14cm by using a slicing machine, and transferring the wafers to lithium sheets with the diameter of 12cm to form modified lithium metal;
(6) And sequentially placing a negative electrode shell, modified lithium metal, a diaphragm, modified lithium metal and a positive electrode shell, and assembling the paired batteries.
Comparative example 4
(1) 8g of liquid gallium-indium alloy with gallium content of 68wt% and 2g of polydimethylsiloxane (CAS number 9016-00-6) are weighed and added into a mortar, and mechanically ground and mixed for 10min to obtain a mixture;
(2) The mixture is scraped on a copper foil until the thickness of the coating film is 5 mu m by using an automatic coating machine, and then the coating film is dried for 12 hours at the temperature of 100 ℃ to obtain a gallium-containing metal composite coating with smooth and compact surface;
(3) Placing the copper foil treated in the step (2) in FeCl with the concentration of 3mol/L 3 Soaking in the solution for 20min, performing displacement reaction, etching the copper foil, and leaving a self-supporting coating;
(4) Cutting the coating into wafers with the diameter of 14cm by using a slicing machine, and transferring the wafers to sodium sheets with the diameter of 12cm to form modified sodium metal;
(5) And sequentially placing a negative electrode shell, modified lithium metal, a diaphragm, modified lithium metal and a positive electrode shell, and assembling the paired batteries.
Comparative example 5
The difference between this comparative example and example 1 is that:
(1) 8g of a liquid gallium indium alloy containing 30wt% gallium and 2g of polydimethylsiloxane (CAS number 9016-00-6) were weighed into a mortar, and mechanically ground and mixed for 1 hour to obtain a uniform gray mixture.
Comparative example 6
The difference between this comparative example and example 1 is that:
(1) 8g of a liquid gallium indium alloy containing 68wt% of gallium and 2g of a mixed glue solution (10 wt% of polyvinylidene fluoride in the mixed glue solution) formed by polyvinylidene fluoride (CAS No. 24937-79-9) and N-methylpyrrolidone are weighed, added into a mortar, mechanically ground and mixed for 1h, and a mixture is obtained.
(2) The mixture was knife coated on a copper foil until the thickness of the coating film was 5 μm by an automatic coater, followed by drying at 100℃for 12 hours, to obtain a gallium-containing metal composite coating having a smooth and dense surface.
As shown in fig. 6, after the mixed glue solution is cured, it is difficult to completely wrap the gallium-containing metal, and the exposed gallium-containing metal drops can cause contact between the positive electrode plate and the negative electrode plate, and the battery is short-circuited.
Comparative example 7
The difference between this comparative example and example 1 is that:
and (3) after the coating treated in the step (3) is cleaned, transferring the coating into 4mol/L hydrofluoric acid solution, and completely soaking the coating for 2 hours to prepare the over-etched coating.
The coating prepared in this comparative example was subjected to electron microscope scanning and the results are shown in fig. 3 c.
As can be seen from fig. 3c, the pore diameter of the pores of the surface of the coating obtained in this comparative example is in the micrometer scale.
Comparative example 8
The difference between this comparative example and example 1 is that:
(2) Spreading the uniform gray mixture on copper foil until the thickness of the coating film is 100 μm by using an automatic coater, and then drying for 12 hours at 100 ℃ to obtain a gallium-containing metal composite coating with smooth and compact surface;
(3) Placing the copper foil treated in the step (2) in FeCl with the concentration of 3mol/L 3 Soaking in the solution for 20min, performing displacement reaction, etching the copper foil, and leaving a self-supporting coating;
(4) After cleaning, transferring the self-supporting coating into hydrofluoric acid solution (the volume ratio of hydrogen fluoride to water is 5:100) to be fully soaked for 15min, forming a large number of nano holes on the surface of the coating, and drying for 12h at 100 ℃ after cleaning to obtain the coating with the thickness of 5 mu m.
(5) Cutting the coating into wafers with the diameter of 14cm by using a slicing machine, and transferring the wafers to lithium sheets with the diameter of 12cm to form modified lithium metal;
(6) As shown in fig. 5, a negative electrode case 51, a modified lithium metal 52, a separator 53, a modified lithium metal 52, and a positive electrode case 44 are sequentially placed, and assembled into a symmetrical battery.
Performance testing
After standing for 24 hours, the mixture was subjected to a current density of 2mA/cm 2 Deposition amount is 1mAh/cm 2 For 50 cycles. After the cycle was completed, the battery was disassembled in a glove box, and the electrode was washed 3 times with dimethyl carbonate and then subjected to electron microscope scanning, and the electron microscope scanning results of example 1 and comparative example 1 are shown in fig. 7 and 8; meanwhile, the cycle life of the symmetrical batteries assembled in examples 1 to 9 and comparative examples 1 to 8 was tested under the electrochemical parameters, and the results are shown in table 1; the voltage curves for the symmetrical cells in the cycle life test are shown in fig. 9 when the metal electrode interface is deposited uniformly.
Table 1 test results
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As can be seen from table 1, the cycle life of the battery assembled from the negative electrode tab formed by the coating layer of example 1 (subjected to the coating modification) was significantly improved as compared with that of comparative example 1 (not subjected to the coating modification). The result shows that the coating provided by the invention can obviously improve the cycle stability of an electrochemical device assembled by the formed negative electrode plate.
As can be seen from table 1, the cycle life of the battery assembled from the negative electrode tab formed by the coating layer of example 1 (etching) was significantly improved compared to that of comparative example 3 (etching was not performed). The results show that the etching treatment can significantly improve the cycle stability of the electrochemical device assembled by the anode piece formed by the coating.
As can be seen from table 1, the cycle life of the battery assembled from the anode tab formed by the coating layer of example 1 (in the liquid gallium indium alloy, the content of gallium is in the range of 60wt% to 90 wt%) is significantly improved as compared with comparative example 5 (in the liquid gallium indium alloy, the content of gallium is 30 wt%). The result shows that the control of the gallium content in the specific range (the gallium content is 60-90 wt%) in the gallium-based alloy can further improve the cycle stability of the electrochemical device assembled by the anode piece formed by the coating.
As can be seen from table 1, the cycle life of the battery assembled from the negative electrode tab formed by the coating layer of example 1 (the carrier was polydimethylsiloxane) was significantly improved compared with comparative example 6 (the carrier was a mixed dope of polyvinylidene fluoride PVDF and N-methylpyrrolidone in a mass ratio of 10:90). The results show that the invention can further improve the cycle stability of the electrochemical device assembled by the anode piece formed by the coating by selecting a specific carrier type (polysiloxane, silicone resin or a mixture of the two).
As can be seen from table 1, the cycle life of the battery assembled from the negative electrode tab formed by the coating layer of example 1 (the concentration of the soak solution is in the range of 0.01 to 3 mol/L) is significantly improved as compared with comparative example 7 (the concentration of the soak solution is 4 mol/L). The result shows that the invention can further improve the cycle stability of the electrochemical device assembled by the formed negative electrode plate by selecting the soaking solution with specific concentration (the concentration of the soaking solution is 0.01-3 mol/L).
As can be seen from table 1, the cycle life of the battery assembled from the negative electrode tab formed by the coating of example 1 (coated thickness < 10 μm) was significantly improved compared to comparative example 8 (coated thickness > 50 μm). The results show that the invention can further improve the cycle stability of an electrochemical device assembled from the formed negative electrode tab by setting the thickness of the coating within a specific range.
As can be seen from fig. 9a, example 1 shows a stable voltage curve with an overpotential lower than 50mV; as can be seen from fig. 9b, when a large amount of dendrite deposition occurs on the metal surface, the interfacial SEI film is repeatedly ruptured and reconstructed, resulting in a continuous increase in interfacial overpotential and a drastic fluctuation in the final voltage curve. The result shows that the coating provided by the invention can obviously improve the cycling stability of the electrochemical device assembled by the formed negative electrode plate, reduce the interface impedance of the negative electrode plate, and further reduce the overpotential of the electrochemical device assembled by the negative electrode plate formed by the coating.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (12)
1. The coating is characterized by comprising a carrier and gallium-containing liquid metal dispersed in the carrier, wherein surface holes and inner holes communicated with the surface holes are respectively distributed on the surface and the inside of the coating, and the surface holes and the inner holes form a hierarchical hole structure.
2. The coating of claim 1, wherein the surface pores have a pore size of 5-1000nm.
3. The coating of claim 1, wherein the surface pores have a pore size of 50% or more of pores having a pore size of 250nm or less.
4. The coating of claim 1, wherein the carrier comprises a polysiloxane, a silicone, or a mixture of both.
5. The coating of claim 1, wherein the gallium-containing liquid metal comprises gallium or a gallium-based alloy.
6. The coating of claim 5, wherein the gallium-based alloy comprises gallium in an amount of 60wt% to 90wt%.
7. A method for producing a coating according to any one of claims 1 to 6, characterized in that the method comprises the steps of:
s1, adding gallium-containing liquid metal into a carrier, and uniformly mixing to obtain a mixture;
s2, coating the mixture on a metal substrate, and etching, cleaning, soaking and drying after drying.
8. The method of claim 7, wherein the mixing time in step S1 is 0.5 to 2 hours.
9. The method according to claim 7, wherein the thickness of the coating in step S2 is 50 μm or less.
10. The method according to claim 7, wherein the concentration of the soaking solution used in the soaking process in step S2 is 0.01-3mol/L.
11. An electrochemical device comprising a pole piece comprising a metal current collector and the coating of any one of claims 1-6 or the coating produced according to the production method of any one of claims 7-10 on the metal current collector.
12. An electronic device, characterized in that the electronic device comprises the electrochemical apparatus according to claim 11.
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