CN116072880A - Current collector, preparation method and application thereof, electrode and lithium ion battery - Google Patents
Current collector, preparation method and application thereof, electrode and lithium ion battery Download PDFInfo
- Publication number
- CN116072880A CN116072880A CN202310052601.6A CN202310052601A CN116072880A CN 116072880 A CN116072880 A CN 116072880A CN 202310052601 A CN202310052601 A CN 202310052601A CN 116072880 A CN116072880 A CN 116072880A
- Authority
- CN
- China
- Prior art keywords
- layer
- conductive
- current collector
- network
- thickness
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 81
- 239000002184 metal Substances 0.000 claims abstract description 81
- 239000002131 composite material Substances 0.000 claims abstract description 78
- 239000000758 substrate Substances 0.000 claims abstract description 57
- 239000004020 conductor Substances 0.000 claims abstract description 42
- 238000000576 coating method Methods 0.000 claims description 53
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 47
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 44
- -1 polyethylene Polymers 0.000 claims description 43
- 229910052782 aluminium Inorganic materials 0.000 claims description 40
- 239000011248 coating agent Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 38
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 37
- 229910052802 copper Inorganic materials 0.000 claims description 34
- 239000010949 copper Substances 0.000 claims description 34
- 239000002042 Silver nanowire Substances 0.000 claims description 33
- 239000002002 slurry Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000011148 porous material Substances 0.000 claims description 18
- 238000009713 electroplating Methods 0.000 claims description 16
- 239000002070 nanowire Substances 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 14
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 13
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 13
- 239000003063 flame retardant Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical group O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 13
- 229910001887 tin oxide Inorganic materials 0.000 claims description 13
- 239000004743 Polypropylene Substances 0.000 claims description 12
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 12
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 12
- 239000006258 conductive agent Substances 0.000 claims description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 12
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 12
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 12
- 229920001155 polypropylene Polymers 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- 239000003575 carbonaceous material Substances 0.000 claims description 10
- 239000007769 metal material Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000002562 thickening agent Substances 0.000 claims description 10
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 9
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 9
- 239000011149 active material Substances 0.000 claims description 9
- 239000004917 carbon fiber Substances 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 239000004642 Polyimide Substances 0.000 claims description 7
- 229920001721 polyimide Polymers 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 6
- 238000001771 vacuum deposition Methods 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 4
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 4
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 4
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 4
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- 239000002073 nanorod Substances 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920006324 polyoxymethylene Polymers 0.000 claims description 4
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 4
- 239000011118 polyvinyl acetate Substances 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229920002379 silicone rubber Polymers 0.000 claims description 4
- 239000004945 silicone rubber Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 238000007711 solidification Methods 0.000 claims description 4
- 230000008023 solidification Effects 0.000 claims description 4
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 claims description 4
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000001856 Ethyl cellulose Substances 0.000 claims description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229920001249 ethyl cellulose Polymers 0.000 claims description 2
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 2
- 229920000136 polysorbate Polymers 0.000 claims description 2
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 claims description 2
- 239000002135 nanosheet Substances 0.000 claims 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims 2
- 238000002791 soaking Methods 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052744 lithium Inorganic materials 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 8
- 210000001787 dendrite Anatomy 0.000 abstract description 5
- 239000012528 membrane Substances 0.000 description 44
- 239000000243 solution Substances 0.000 description 19
- 238000001035 drying Methods 0.000 description 14
- 238000007747 plating Methods 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 238000002156 mixing Methods 0.000 description 10
- 238000000465 moulding Methods 0.000 description 9
- 229920001169 thermoplastic Polymers 0.000 description 9
- 239000004416 thermosoftening plastic Substances 0.000 description 9
- 239000004594 Masterbatch (MB) Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000013077 target material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000011888 foil Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 4
- VFEKMAOUJHONFD-UHFFFAOYSA-N 5-[[[5-hydroxy-4-(hydroxymethyl)-6-methylpyridin-3-yl]methyldisulfanyl]methyl]-4-(hydroxymethyl)-2-methylpyridin-3-ol;hydrate;dihydrochloride Chemical compound O.Cl.Cl.OCC1=C(O)C(C)=NC=C1CSSCC1=CN=C(C)C(O)=C1CO VFEKMAOUJHONFD-UHFFFAOYSA-N 0.000 description 4
- AEMOLEFTQBMNLQ-AQKNRBDQSA-N D-glucopyranuronic acid Chemical compound OC1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O AEMOLEFTQBMNLQ-AQKNRBDQSA-N 0.000 description 4
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 description 4
- 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 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- 238000000149 argon plasma sintering Methods 0.000 description 4
- OHNSRYBTSVDDKA-BJMVGYQFSA-N chembl242112 Chemical compound NC(=S)N\N=C\C1=CC=CC=C1O OHNSRYBTSVDDKA-BJMVGYQFSA-N 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- OKGXJRGLYVRVNE-UHFFFAOYSA-N diaminomethylidenethiourea Chemical compound NC(N)=NC(N)=S OKGXJRGLYVRVNE-UHFFFAOYSA-N 0.000 description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 229940097043 glucuronic acid Drugs 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 description 4
- 235000011151 potassium sulphates Nutrition 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000005269 aluminizing Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229940093429 polyethylene glycol 6000 Drugs 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—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
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention belongs to the technical field of lithium batteries, and particularly relates to a current collector, a preparation method and application thereof, an electrode and a lithium ion battery. The current collector includes: the device comprises a substrate layer, composite conductive layers arranged on two surfaces of the substrate layer, and an oxide layer arranged on the composite conductive layers; wherein the composite conductive layer comprises a conductive network laid on the substrate layer, and a metal layer deposited on the conductive network and the substrate layer; the conductive network is provided with a grid structure formed by interlacing electric conductors, and the surface of the metal layer is provided with a concave-convex structure. The current collectorLarge surface area of 0.1-2m 2 And/g, the electrode has better electron conductivity when being used for preparing the lithium ion battery, the trend growth of lithium dendrites is effectively inhibited, and the safety and the cycle life of the lithium ion battery are improved. In addition, the current collector has the characteristic of light weight, and is beneficial to improving the weight energy density of the lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a current collector, a preparation method and application thereof, an electrode and a lithium ion battery.
Background
With promotion of new energy automobiles and promotion of competitiveness, higher requirements are put forward on lithium ion battery technology. At present, for the positive electrode and the negative electrode of a conventional lithium ion battery, a metal aluminum foil is generally adopted as a positive electrode current collector, a metal copper foil is generally adopted as a negative electrode current collector, the surface of the metal foil is simply roughened, the specific surface area is not large enough, the sufficient infiltration of electrolyte can be influenced, and the electronic conductivity is further influenced. In addition, once the battery is internally shorted, the current collector in the form of metal foil cannot cut off current, heat accumulation can cause thermal runaway, and further cause safety problems, resulting in reduced service life of the battery.
Therefore, the current collector with the micro-nano structure and the high specific surface area is provided, and has important significance for improving the electronic conductivity, the cycle life and the weight energy density of the lithium ion battery.
Disclosure of Invention
Aiming at the problem that the specific surface area of the current collector of the lithium ion battery is not large enough so as to influence the electronic conductivity, the invention provides a current collector, a preparation method and application thereof, an electrode and the lithium ion battery.
In order to achieve the above object, a first aspect of the present invention provides a current collector including: the device comprises a substrate layer, composite conductive layers arranged on two surfaces of the substrate layer, and an oxide layer arranged on the composite conductive layers;
Wherein the composite conductive layer comprises a conductive network disposed on the base layer, and a metal layer deposited and overlying the conductive network and the base layer;
the conductive network is provided with a grid structure formed by interlacing electric conductors, and the surface of the metal layer is provided with a concave-convex structure.
In a second aspect, the present invention provides a method for preparing a current collector, the method comprising:
(1) Forming a conductive network having a mesh structure formed by interleaving conductive bodies on both surfaces of the base layer;
(2) Depositing a copper layer or an aluminum layer on the conductive network and the substrate layer to form a metal layer;
(3) And forming an oxide layer on the metal layer to obtain the current collector.
A third aspect of the present invention provides a current collector prepared by the method of the second aspect described above.
A fourth aspect of the invention provides the use of a current collector as described in the first or third aspect in the preparation of a battery.
A fifth aspect of the present invention provides an electrode comprising a current collector, and an active material layer on a surface of the current collector; wherein,,
the current collector is the current collector described in the first aspect or the third aspect.
A sixth aspect of the present invention provides a lithium ion battery comprising the current collector of the fifth aspect.
Through the technical scheme, the invention has the following beneficial effects:
(1) The current collector provided by the invention is a composite current collector, which is sequentially arranged on a basal layerThe composite conductive layer and the oxide layer are arranged, the composite conductive layer contains a conductive network and a metal layer deposited and covered on the conductive network and the substrate layer, the surface of the metal layer is provided with an obvious micro-nano concave-convex structure, so that the current collector has a very large specific surface area which can reach 0.1-2m 2 The electrode can be fully contacted with the active material and bear more active materials, so that high-efficiency electron transmission is realized, and better electron conductivity is obtained;
(2) The micro-nano concave-convex structure of the current collector provided by the invention can effectively inhibit the trend growth of lithium dendrites, and improve the safety and the cycle life of the battery;
(3) The current collector has light weight, can bring the effect of reducing the weight of the lithium battery, and is beneficial to improving the weight energy density of the battery.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention. In the drawings:
Fig. 1 is a schematic side view of the layer structure of a current collector (without a template layer) according to one embodiment of the present invention.
Fig. 2 is a schematic side view of the layer structure of a current collector (provided with a template layer) according to another embodiment of the present invention.
Fig. 3 is a schematic top view of the surface of a current collector (without a template layer) according to one embodiment of the invention.
Fig. 4 is a schematic top view of the surface of a current collector (provided with a template layer) according to another embodiment of the present invention.
Description of the reference numerals
10-substrate layer 11-conductive network 12-metal layer
13-oxide layer 14-template layer
111-composite conductive layer (in case of no template layer in the current collector)
112-pores of conductive network (interweaving network)
211-composite conductive layer (in case of template layer in current collector)
212-holes of conductive network (interwoven mesh)
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
A first aspect of the present invention provides a current collector comprising: the device comprises a substrate layer, composite conductive layers arranged on two surfaces of the substrate layer, and an oxide layer arranged on the composite conductive layers;
wherein the composite conductive layer comprises a conductive network disposed on the base layer, and a metal layer deposited on the conductive network and the base layer;
the conductive network is provided with a grid structure formed by interlacing electric conductors, and the surface of the metal layer is provided with a concave-convex structure.
According to the present invention, the current collector has a multilayer structure, the composite conductive layer is provided on both surfaces of the base layer, and an oxide layer is provided on a surface of the composite conductive layer remote from the base layer. The composite conductive layer in the current collector provided by the invention contains a conductive network and a metal layer, wherein the conductive network is paved on the substrate layer, the metal layer is formed on the conductive network and the substrate layer through deposition, the surface of the metal layer is provided with bulges taking the conductive network as venation, and the oxide layer on the outermost layer is relatively thinner, so that the outer surface of the whole current collector presents a concave-convex structure with a plurality of mountains and valleys, and the specific surface area is extremely large, and the performance of the current collector is remarkably improved.
According to the invention, in the current collector, the thickness of the base layer is 1 to 15 μm, preferably 3 to 10 μm.
According to the present invention, in the current collector, the thickness of the composite conductive layer is 0.001 to 500 μm, preferably 1 to 100 μm. In the present invention, the thickness of the composite conductive layer as defined above refers to the respective thicknesses of the composite conductive layers distributed on both surfaces of the base layer, not the total thickness. In particular, the composite conductive layers distributed on both surfaces of the base layer may have the same thickness or may have different thicknesses, and the present invention is not particularly limited thereto, and preferably has the same thickness.
According to the invention, in the composite conductive layer, the thickness of the conductive network is 0.001-10 μm, preferably 0.01-0.5 μm.
According to the present invention, in the composite conductive layer, the thickness of the metal layer is 0.001 to 500 μm, preferably 1 to 100 μm.
According to the present invention, in the current collector, the oxide layer has a thickness of 0.001 to 10 μm, preferably 0.001 to 1 μm. The thickness of the oxide layer as defined above refers to the thickness of each of the oxide layers distributed on both surfaces of the current collector, not the total thickness. In particular, the oxide layers distributed on both surfaces of the current collector may have the same thickness or may have different thicknesses, and the present invention is not particularly limited thereto, and preferably has the same thickness.
According to the present invention, in the current collector, the metal layer has a concave-convex structure, so that the vertical distance between different positions on the outer surface of the metal layer (i.e., the surface away from the base layer) and the upper surface of the base layer is not exactly the same, specifically, the vertical distance between the outer surface of the metal layer above and near the conductor of the conductive network and the upper surface of the base layer is relatively large, representing a "mountain-like protrusion; the vertical distance between the outer surface of the metal layer above the mesh of the conductive network and the upper surface of the base layer is relatively small, representing a "valley" like depression, as compared to the aforementioned "mountain" like projections. In the present invention, the thickness of the metal layer refers to the maximum value of the vertical distance between each position of the outer surface of the metal layer and the upper surface of the base layer.
According to the present invention, in the current collector, the base layer contains a polymer. Preferably, the polymer is selected from at least one of polyethylene terephthalate, polyamide, polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, poly (paraphenylene terephthalamide), polypropylene, acrylonitrile-butadiene-styrene copolymer, polyvinyl formal, polyvinyl butyral, polyurethane, polyacrylonitrile, polyvinyl acetate, polyoxymethylene, phenolic resin, epoxy resin, polytetrafluoroethylene, polyvinylidene fluoride, silicone rubber, polycarbonate, polysulfone, polyethersulfone, and polyphenylene oxide.
According to the present invention, preferably, the base layer may contain functional particles, which may enable the base layer to have better flame retardant properties or interfacial conductive properties.
According to the invention, in the base layer, the polymer: the weight ratio of the functional particles can be (1-999): 1.
according to the invention, the functional particles are flame retardants and/or electrically conductive agents.
In the present invention, the flame retardant may be a flame retardant for polymers which is conventional in the art, and the present invention is not limited thereto. Preferably, the flame retardant is selected from at least one of magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, zinc borate, antimony trioxide, and layered silicate.
In the present invention, the conductive agent may be a conductive agent for a polymer which is conventional in the art, and the scope of the present invention is limited thereto. Preferably, the conductive agent is a conductive metal material and/or a conductive carbon material.
In the present invention, the conductive metal material is limited in a wide range, and various conductive metal materials, preferably at least one selected from the group consisting of metal nanowires, metal nanorods, and metal nanoplatelets, may be used; wherein the metal is selected from silver, copper or aluminum.
In the present invention, the conductive carbon material is limited in scope, and various conductive carbon materials, preferably at least one selected from the group consisting of conductive carbon black, carbon fiber and carbon nanotube, may be used.
According to the invention, in the current collector, the conductive network is an interweaved network formed by interweaving one-dimensional nano conductive materials; or the conductive network is an interlaced grid, wherein the interlaced grid is formed by connecting grid lines, and the grid lines are formed by interlacing and lapping one-dimensional nano conductive materials. The one-dimensional nano conductive material is the conductor. Preferably, the conductive network is an interweaved network formed by interweaving one-dimensional nano conductive materials.
According to the present invention, the one-dimensional nano conductive material is selected from at least one of metal nanowires, non-metal nanowires, and carbon fibers, preferably at least one selected from silver nanowires, copper nanowires, gold nanowires, nickel nanowires, silicon nanowires, carbon nanowires, and carbon fibers.
According to the invention, the one-dimensional nano conductive material has a thicker wire diameter, which is beneficial to forming a metal layer with higher mountain-like protrusions on the substrate layer and the conductive network, so as to further improve the surface area of the current collector. The wire diameter of the one-dimensional nano conductive material is 0.01-5 mu m, preferably 0.05-1 mu m; the line length of the one-dimensional nano conductive material is 5-500 mu m, preferably 50-500 mu m. The wire diameter refers to the diameter of the cross section of the one-dimensional nano conductive material.
According to the invention, in the case that the conductive network is an interlaced network formed by interlacing one-dimensional nano conductive materials, the pore diameter of the interlaced network is 1-80 μm, preferably 1-15 μm.
According to the invention, for the case where the conductive network is an interwoven mesh, the pore size of the interwoven mesh is 1-100 μm, preferably 20-40 μm. In the present invention, the pore diameter of the interlaced mesh refers to the size of pores surrounded by the grid lines forming the interlaced mesh.
According to the invention, the wire diameter of the grid lines of the interwoven mesh is 1-100 μm, preferably 1-10 μm. According to the invention, the number of layers of the conductive network (i.e. the interweaving network or interweaving grid) is 1-2, the mesh is sparse, and the current collector has larger pore diameter, which is beneficial to having high specific surface area and lighter weight.
According to one embodiment of the invention, when the conductive network is an interwoven mesh, a template layer is disposed between the base layer and the conductive network (interwoven mesh) is embedded in a surface of the template layer. In this case, the metal layer is deposited and overlaid on the conductive network (interwoven mesh) and template layer, and the thickness of the template layer does not account for the thickness of the composite conductive layer. In this case, the layer structure of the current collector provided by the invention is shown in fig. 2, and the surface top view effect of the current collector corresponding to the layer structure is shown in fig. 4.
According to the present invention, the template layer is preferably a resin layer. Preferably, the template layer has a thickness of 1-100 μm.
According to the present invention, when the conductive network is an interlaced network, the template layer is not provided between the base layer and the conductive network (interlaced network). In this case, the layer structure of the current collector provided by the invention is shown in fig. 1, and the surface top view effect of the current collector corresponding to the layer structure is shown in fig. 3.
According to the present invention, it is preferable that the template layer is not provided in the current collector, i.e., the conductive network in the current collector takes the form of an interlaced network, from the viewpoint that the current collector can have a larger specific surface area and better overall performance.
According to the present invention, in the current collector, the metal layer is a copper layer or an aluminum layer. Specifically, when the metal layer is a copper layer, the current collector may be used as a negative electrode current collector; when the metal layer is an aluminum layer, the current collector can be used as a positive current collector.
According to the invention, in the current collector, the oxide layer mainly plays a role in corrosion resistance and can be a tin oxide layer or an aluminum oxide layer; specifically, when the metal layer is a copper layer, the oxide layer corresponding to the metal layer is a tin oxide layer; when the metal layer is an aluminum layer, the corresponding oxide layer is an aluminum oxide layer.
The current collector provided by the invention has a very large specific surface area which can reach 0.1-2m 2 Preferably up to 1-2m per gram 2 And/g, which is mainly attributed to the fact that a micro-nano concave-convex structure is formed on the surface of the current collector, compared with the planar current collector in the prior art, the micro-nano concave-convex structure on the surface of the current collector can bring about a high specific surface area, so that the current collector can be fully contacted with an active material, the internal resistance is reduced, the carrying capacity of the current collector can be improved, more active materials can be carried, and the factors act together, so that an electrode with better performance can be prepared based on the current collector, the electrode has better electronic conductivity, the trend growth of lithium dendrites is effectively inhibited, and the safety and the cycle life of a lithium ion battery are improved. In addition, the polymer substrate is adopted, so that the current collector has the characteristic of light weight, and the weight energy density of the lithium ion battery is improved.
In the invention, the thicknesses of the substrate layer, the template layer, the composite conductive layer (comprising a conductive network and a metal layer) and the oxide layer can be measured by a micrometer.
In the present invention, the specific surface area of the current collector is measured by a nitrogen adsorption method.
In a second aspect, the present invention provides a method for preparing a current collector, the method comprising:
(1) Forming a conductive network having a mesh structure formed by interleaving conductive bodies on both surfaces of the base layer;
(2) Depositing a copper layer or an aluminum layer on the conductive network and the substrate layer to form a metal layer;
(3) And forming an oxide layer on the metal layer to obtain the current collector.
According to the preparation method of the current collector, firstly, a specific conductive network with a grid structure is paved on a substrate layer, then copper or aluminum is deposited on the conductive network and the substrate layer simultaneously, copper or aluminum tends to be deposited above and nearby the conductive body of the conductive network preferentially, in this way, the surface of a metal layer formed by final deposition is provided with protrusions taking the conductive network as venation, finally, a thinner oxide layer is formed on the surface of the metal layer through deposition or oxidation, and the current collector with a plurality of ' mountain and ' valley ' concave-convex structures is prepared on the surface, and has the characteristic of large specific surface area.
According to the present invention, in the step (1), the base layer contains a polymer selected from at least one of a polyethylene terephthalate, a polyamide, a polyimide, a polyethylene, a polypropylene, a polystyrene, a polyvinyl chloride, a polyethylene terephthalate, a polybutylene terephthalate, a poly-paraphenylene terephthalamide, a polypropylene, an acrylonitrile-butadiene-styrene copolymer, a polyvinyl formal, a polyvinyl butyral, a polyurethane, a polyacrylonitrile, a polyvinyl acetate, a polyoxymethylene, a phenol resin, an epoxy resin, a polytetrafluoroethylene, a polyvinylidene fluoride, a silicone rubber, a polycarbonate, a polysulfone, a polyethersulfone, and a polyphenylene oxide.
According to the present invention, preferably, the base layer may contain functional particles. In the base layer, the polymer: the weight ratio of the functional particles can be (1-999): 1.
according to the invention, the functional particles are flame retardants and/or electrically conductive agents.
In the present invention, the flame retardant may be a flame retardant for polymers which is conventional in the art, and the present invention is not limited thereto. Preferably, the flame retardant is selected from at least one of magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, zinc borate, antimony trioxide, and layered silicate.
In the present invention, the conductive agent may be a conductive agent for a polymer which is conventional in the art, and the scope of the present invention is limited thereto. Preferably, the conductive agent is a conductive metal material and/or a conductive carbon material.
In the present invention, the conductive metal material is limited in a wide range, and various conductive metal materials, preferably at least one selected from the group consisting of metal nanowires, metal nanorods, and metal nanoplatelets, may be used; wherein the metal is selected from silver, copper or aluminum.
In the present invention, the conductive carbon material is limited in scope, and various conductive carbon materials, preferably at least one selected from the group consisting of conductive carbon black, carbon fiber and carbon nanotube, may be used.
According to the present invention, the substrate layer can be obtained in a wide range of ways, and can be obtained commercially or by a conventional method for preparing a polymer film material, for example, the above-mentioned polymer master batch and functional particles can be mixed, and then the obtained mixture can be subjected to thermoplastic stretch molding to obtain the substrate layer.
According to the invention, the thickness of the base layer is 1-15 μm, preferably 3-10 μm.
According to the invention, in the step (1), the conductive network is an interweaved network formed by interweaving one-dimensional nano conductive materials; or the conductive network is an interlaced grid, wherein the interlaced grid is formed by connecting grid lines, and the grid lines are formed by interlacing and lapping one-dimensional nano conductive materials.
According to the present invention, the conductive network is preferably formed by a coating method. In the present invention, the coating method is understood according to the definition well known in the art, and the present invention is not described herein.
According to one embodiment of the present invention, in step (1), the forming of the interlaced network by a coating method includes: and coating first slurry containing one-dimensional nano conductive materials on two surfaces of the substrate layer to obtain a first wet film, and forming a conductive network after first solidification.
According to one embodiment of the present invention, the process of forming the interwoven mesh using a coating process comprises:
(i) Coating template layers on two surfaces of the substrate layer, and grooving the template layers to obtain a template layer with grid grooves;
(ii) Coating a second slurry containing one-dimensional nano conductive materials on the surface of the template layer with the grid grooves to obtain a second wet film, and obtaining a conductive film after second solidification;
(iii) And grinding the conductive film, wherein after the grinding, the conductive film remained in the grid groove forms an interweaved grid.
According to the invention, the first slurry and the second slurry also contain a solvent, a surfactant and a thickener.
According to the present invention, the solvent is contained in the first paste in an amount of 90 to 98wt%, the one-dimensional nano conductive material is contained in an amount of 0.1 to 5wt%, the surfactant is contained in an amount of 0.01 to 1wt%, and the thickener is contained in an amount of 0.01 to 10wt%, based on the total weight of the first paste.
According to the present invention, the solvent is contained in the second paste in an amount of 90 to 98wt%, the one-dimensional nano conductive material is contained in an amount of 0.1 to 5wt%, the surfactant is contained in an amount of 0.01 to 1wt%, and the thickener is contained in an amount of 0.01 to 10wt%, based on the total weight of the second paste.
According to the present invention, the solvent is limited in a wide range, and preferably at least one selected from the group consisting of water, N-methylpyrrolidone, ethanol and isopropanol.
According to the invention, the surfactant has the effect of wetting and reducing the surface tension. Preferably, the surfactant is at least one selected from polyvinylpyrrolidone, triton, tween, span, fatty amine and fluorocarbon.
According to the invention, the thickener has the functions of filling, leveling and adhesion. Preferably, the thickener is at least one selected from the group consisting of carboxymethyl cellulose, polyvinylpyrrolidone, polyvinyl butyral, hydroxypropyl methylcellulose, and ethyl cellulose.
According to the invention, the one-dimensional nano conductive material contained in the first slurry and the second slurry is at least one selected from silver nanowires, copper nanowires, gold nanowires, nickel nanowires, silicon nanowires, carbon nanowires and carbon fibers.
According to the invention, the one-dimensional nano conductive material has a thicker wire diameter, is beneficial to better lap joint formation of the conductive network on the substrate layer, and is beneficial to formation of a metal layer with higher mountain-like protrusions on the substrate layer and the conductive network, so as to further improve the surface area of the current collector. The wire diameter of the one-dimensional nano conductive material is 0.01-5 mu m, preferably 0.05-1 mu m; the line length of the one-dimensional nano conductive material is 5-500 mu m, preferably 50-500 mu m.
According to the present invention, in forming the conductive network by a coating method, it is preferable that the thickness of the first wet film and the second wet film is each independently 1 to 500 μm.
In the present invention, the thickness of the wet film can be adjusted by changing the distance between the coating port of the coating apparatus and the film material (base layer).
According to the present invention, in forming the conductive network by a coating method, preferably, the conditions of the first curing and the second curing each independently include: the temperature is 100-160deg.C, and the time is 1-30min.
According to the present invention, in the process of forming the interlaced network by the coating method, the first paste may be coated on one surface of the substrate and first cured to form a conductive network (interlaced network), and then the first paste may be repeatedly coated on the other surface and first cured to form a conductive network (interlaced network), or the first paste may be coated on both surfaces of the substrate and first cured to form a conductive network (interlaced network), and the method may be flexibly selected according to the implementation conditions.
According to the present invention, in forming the interlaced grid by a coating method, the template layer is preferably a resin layer. Preferably, the template layer has a thickness of 1-100 μm.
According to the invention, in the process of forming the interweaving grids by a coating method, the depth of the grid grooves is 1-10 mu m, and the width is 1-10 mu m. In the invention, the grid groove is formed by intersecting and connecting a plurality of groove lines, and the width of the grid groove refers to the width of a single groove line.
According to the present invention, in the process of forming the interlaced grid by the coating method, the method of grooving the template layer is limited widely, and for example, a laser sintering method, an imprinting method, a photolithography method, or the like may be used, preferably a laser sintering method is used, the template layer is sintered by using a laser as a heat source, and grid grooves are formed on the surface of the template layer.
According to the present invention, in the process of forming the interlaced grid by a coating method, the depth of the grid grooves can be regarded as the thickness of the obtained conductive network (interlaced grid).
According to the present invention, in the process of forming the interlaced grids by the coating method, the definition range of the polishing process is wide, as long as polishing and removal of the conductive film on the outer surface of the template layer can be achieved, and only the remaining conductive film remains in the grid grooves and a conductive network (interlaced grid) is formed. For example, a nylon brush polishing method can be adopted.
According to the invention, in the step (1), the formed conductive network has a grid structure formed by interlacing the conductive bodies (the one-dimensional nano conductive material in the first slurry and the second slurry is the conductive body). The number of layers of the conductive network is 1-2, and meshes are distributed sparsely.
According to the invention, in step (1), the conductive network is formed to a thickness of 0.001 to 10. Mu.m, preferably 0.01 to 0.5. Mu.m.
According to the invention, in the step (1), for the case that the conductive network is an interlaced network formed by interlacing of one-dimensional nano conductive materials, the pore diameter of the interlaced network is 1-80 μm, preferably 1-15 μm.
According to the invention, in step (1), for the case where the conductive network is an interwoven mesh, the pore size of the interwoven mesh is 1-100 μm, preferably 20-40 μm. The wire diameter of the grid lines of the interlaced grid is 1-100 μm, preferably 1-10 μm.
According to the present invention, in the step (2), the deposition manner of the copper layer or the aluminum layer is defined widely, including but not limited to electroplating, vacuum plating, and the like.
Preferably, the copper layer is deposited by electroplating, and conventional electroplating copper process and parameters can be used, which is not particularly limited in the present invention.
Preferably, the aluminum layer is deposited by vacuum plating, and can be realized by adopting a conventional vacuum aluminizing process and parameters, which are not particularly limited in the invention.
According to the present invention, in the step (2), copper or aluminum is preferentially deposited over and around the conductor of the conductive network in the process of forming the metal layer, so that the vertical distance between the outer surface of the metal layer formed over and around the conductor of the conductive network and the upper surface of the base layer is relatively large, representing a "mountain-like protrusion; the vertical distance between the outer surface of the metal layer formed over the mesh of the conductive network and the upper surface of the base layer is relatively small, and the specific structure described above allows the deposited metal layer to have a very large specific surface area, compared to the aforementioned "mountain" shaped protrusions, which are represented by "valley" shaped depressions.
According to the invention, in step (2), the thickness of the metal layer is 0.001-500. Mu.m, preferably 1-100. Mu.m.
In the present invention, the thickness of the metal layer refers to the maximum value of the vertical distance between each position of the outer surface of the metal layer and the upper surface of the base layer.
According to the invention, in the step (3), the oxide layer is a tin oxide layer or an aluminum oxide layer. Preferably, the oxide layer has a thickness of 0.001-10 μm, preferably 0.001-1 μm.
According to the invention, in the step (3), specifically, when the metal layer is a copper layer, a tin oxide layer is deposited on the metal layer to obtain a negative electrode current collector; and when the metal layer is an aluminum layer, oxidizing the metal layer to form an aluminum oxide layer on the surface of the metal layer so as to obtain the positive current collector.
According to the present invention, in the step (3), the deposition manner of the tin oxide is limited to a wide range, including but not limited to a dipping method, magnetron sputtering, vacuum coating, etc., and preferably a dipping method is adopted.
According to the present invention, in the step (3), the range of the oxidation treatment is wide, and for example, the metal layer (aluminum layer) may be placed in an oxygen-containing atmosphere and heated until an aluminum oxide layer is formed on the surface.
A third aspect of the present invention provides a current collector prepared by the method of the second aspect described above.
According to the present invention, the current collector manufactured by the method according to the second aspect has the same structural composition, parameter index and performance as those of the current collector according to the first aspect of the present invention, and will not be described herein.
A fourth aspect of the invention provides the use of a current collector as described in the first or third aspect in the preparation of a battery.
According to the invention, the external surface of the current collector provided by the invention has a specific concave-convex structure, the specific surface area of the current collector is large, and the current collector can be used for preparing batteries, especially in the preparation of lithium ion batteries, can be more fully contacted with active materials and bear more active materials, so that the electrode has better electronic conductivity, the trend growth of lithium dendrites is effectively inhibited, and the safety and the cycle life of the lithium ion batteries are improved. In addition, the current collector has the characteristic of light weight, and is beneficial to improving the weight energy density of the lithium ion battery.
A fifth aspect of the present invention provides an electrode comprising a current collector, and an active material layer on a surface of the current collector; wherein,,
the current collector is the current collector described in the first aspect or the third aspect.
A sixth aspect of the present invention provides a lithium ion battery comprising the current collector of the fifth aspect.
The present invention will be described in detail by examples. In the following examples and comparative examples, common commercial products were used as the materials used unless otherwise specified.
Example 1
This example is used to illustrate the preparation of a current collector
(1-1) polyethylene terephthalate (PET) master batch was mixed with silver nanowires (wire diameter of 0.03 μm, wire length of 20 μm) to 99:1, and then carrying out thermoplastic biaxial stretching molding on the obtained mixture to obtain a sheet-shaped substrate layer with the thickness of 4.5 mu m;
(1-2) mixing water, silver nanowires (wire length 80 μm, wire diameter 0.1 μm), polyvinylpyrrolidone and carboxymethyl cellulose, stirring for 30min to obtain a paste containing silver nanowires (wherein the content of water is 97.15wt%, the content of silver nanowires is 0.45wt%, the content of polyvinylpyrrolidone is 0.8wt%, and the content of carboxymethyl cellulose is 1.6wt%, based on the total weight of the paste);
(1-3) uniformly coating the paste containing silver nanowires on one surface of the base layer using a small roll-to-roll coater, wherein the thickness of the wet film obtained by coating is 15 μm, and then drying and curing at 120 ℃ for 15min, thereby forming a conductive network (i.e., an interweaving network, thickness of 0.15 μm,2 layers) on the surface of the base layer; uniformly coating the slurry on the other surface of the substrate layer, wherein the thickness of a wet film obtained by coating is 15 mu m, drying and curing for 15min at 120 ℃, and forming a conductive network (i.e. an interweaving network, the thickness of which is 0.15 mu m and 2 layers) on the other surface of the substrate layer to obtain a first composite membrane; wherein the pore diameter of the conductive network (interweaving network) is 10 μm;
(2) Immersing the first composite membrane serving as a negative electrode in an industrial copper plating solution (1000 mL solution prepared by mixing 90g of copper sulfate, 60g of copper chloride, 55g of sodium sulfate, 80g of potassium sulfate, 15g of sodium polydithio-dipropyl sulfonate, 10g of sodium dodecyl sulfate, 35g of disodium hydrogen phosphate and deionized water), wherein a platinum electrode is used as a positive electrode, and forming a copper layer with a concave-convex structure on the surface of 1um on a conductive network and a substrate layer of the first composite membrane by electroplating (electroplating condition: constant current electroplating for 1min under the current density of 1A) to obtain a second composite membrane (wherein the thickness of the composite conductive layer is 1 um);
(3) The second composite membrane is placed in industrial tinning solution (the components are 10g of stannous sulfate, 20mL of concentrated sulfuric acid (98 wt%) and 0.1g of salicylaldehyde thiosemicarbazone, 0.02g of guanylthiourea, 60000.005g of polyethylene glycol, 0.01g of 4,4' - (2-pyridine methylene) diphenol, 0.2g of glucuronic acid and 0.01g of pyritinol hydrochloride are fully dissolved after deionized water is added to 1L of the solution), the solution is soaked for 0.5min, taken out and washed by deionized water, and then dried and cured for 15min at 80 ℃ to form a tin oxide layer with the thickness of 0.001um on the surface of a copper layer, so as to obtain a negative electrode current collector (marked as M1).
Through testing, the specific surface area of M1 is 1.735M 2 /g。
Example 2
This example is used to illustrate the preparation of a current collector
(1-1) polypropylene (PP) master batch was mixed with silver nanowires (wire diameter 0.03 μm, wire length 20 μm) at 99:1, and then carrying out thermoplastic biaxial stretching molding on the obtained mixture to obtain a sheet-shaped substrate layer with the thickness of 4.5 mu m;
(1-2) mixing water, silver nanowires (wire length 80 μm, wire diameter 0.1 μm), polyvinylpyrrolidone and carboxymethyl cellulose, stirring for 30min to obtain a paste containing silver nanowires (wherein the content of water is 97wt%, the content of silver nanowires is 0.5wt%, the content of polyvinylpyrrolidone is 0.8wt%, and the content of carboxymethyl cellulose is 1.7wt%, based on the total weight of the paste);
(1-3) uniformly coating the paste containing silver nanowires on one surface of the base layer using a small roll-to-roll coater, wherein the thickness of the wet film obtained by coating is 20 μm, and then drying and curing at 120 ℃ for 10min, thereby forming a conductive network (i.e., an interweaving network, thickness of 0.17 μm,2 layers) on the surface of the base layer; uniformly coating the slurry on the other surface of the substrate layer, wherein the thickness of a wet film obtained by coating is 20 mu m, drying and curing for 10min at 120 ℃, and forming a conductive network (i.e. an interweaving network, the thickness of which is 0.17 mu m and 2 layers) on the other surface of the substrate layer to obtain a first composite membrane; wherein the pore diameter of the conductive network (interweaving network) is 15 μm;
(2) Immersing the first composite membrane serving as a negative electrode in an industrial copper plating solution (1000 mL solution prepared by mixing 90g of copper sulfate, 60g of copper chloride, 55g of sodium sulfate, 80g of potassium sulfate, 15g of sodium polydithio-dipropyl sulfonate, 10g of sodium dodecyl sulfate, 35g of disodium hydrogen phosphate and deionized water), wherein a platinum electrode is used as a positive electrode, and forming a copper layer with a concave-convex structure on the surface of 1um on a conductive network and a substrate layer of the first composite membrane by electroplating (electroplating condition: constant current electroplating for 1min under the current density of 1A) to obtain a second composite membrane (wherein the thickness of the composite conductive layer is 1 um);
(3) The second composite membrane is placed in industrial tinning solution (the components are 10g of stannous sulfate, 20mL of concentrated sulfuric acid (98 wt%) and 0.1g of salicylaldehyde thiosemicarbazone, 0.02g of guanylthiourea, 60000.005g of polyethylene glycol, 0.01g of 4,4' - (2-pyridine methylene) diphenol, 0.2g of glucuronic acid and 0.01g of pyritinol hydrochloride are fully dissolved after deionized water is added to 1L of the solution), the solution is soaked for 0.5min, taken out and washed by deionized water, and then dried and cured for 15min at 80 ℃ to form a tin oxide layer with the thickness of 0.001um on the surface of a copper layer, so as to obtain a negative electrode current collector (marked as M2).
Through test, the specific surface area of M2 is 1.605M 2 /g。
Example 3
This example is used to illustrate the preparation of a current collector
(1-1) polyimide master batch was mixed with silver nanowires (wire diameter of 0.03 μm, wire length of 20 μm) at 99:1, and then carrying out thermoplastic biaxial stretching molding on the obtained mixture to obtain a sheet-shaped substrate layer with the thickness of 4.5 mu m;
(1-2) mixing water, copper nanowires (wire length: 40 μm, wire diameter: 0.04 μm), polyoxyethylene-8-octylphenyl ether, and hydroxypropyl methylcellulose, and stirring for 30 minutes to obtain a slurry containing copper nanowires (wherein the content of water is 93wt%, the content of copper nanowires is 2wt%, the content of polyoxyethylene-8-octylphenyl ether is 1wt%, and the content of hydroxypropyl methylcellulose is 4wt%, based on the total weight of the slurry);
(1-3) uniformly coating the copper nanowire-containing slurry on one surface of the base layer using a small roll-to-roll coater, wherein the thickness of a wet film obtained by coating is 20 μm, and then drying and curing at 100 ℃ for 10min, thereby forming a conductive network (i.e., an interweaving network, thickness of 0.1 μm,2 layers) on the surface of the base layer; uniformly coating the slurry on the other surface of the substrate layer, wherein the thickness of a wet film obtained by coating is 20 mu m, drying and curing for 10min at 100 ℃, and forming a conductive network (the thickness is 0.1 mu m and 2 layers) on the other surface of the substrate layer to obtain a first composite membrane; wherein the pore size of the conductive network (i.e., the interweaving network) is 22 μm;
(2) Immersing the first composite membrane serving as a negative electrode in an industrial copper plating solution (1000 mL solution prepared by mixing 90g of copper sulfate, 60g of copper chloride, 55g of sodium sulfate, 80g of potassium sulfate, 15g of sodium polydithio-dipropyl sulfonate, 10g of sodium dodecyl sulfate, 35g of disodium hydrogen phosphate and deionized water), wherein a platinum electrode is used as a positive electrode, and forming a copper layer with a concave-convex structure on the surface of 1.5um on a conductive network and a substrate layer of the first composite membrane by electroplating (electroplating condition: constant current electroplating for 2min under the current density of 1A) to obtain a second composite membrane (wherein the thickness of the composite conductive layer is 1.5 mu m);
(3) The second composite membrane is placed in industrial tinning solution (the components are 10g of stannous sulfate, 20mL of concentrated sulfuric acid (content is 98%), 0.1g of salicylaldehyde thiosemicarbazone, 0.02g of guanylthiourea, 0.005g of polyethylene glycol 6000, 0.01g of 4,4' - (2-pyridine methylene) diphenol, 0.2g of glucuronic acid and 0.01g of pyritinol hydrochloride are fully dissolved after deionized water is added to 1L for 0.5min, taken out and washed by deionized water, and then dried and solidified for 15min at 80 ℃ to form a tin oxide layer with the thickness of 0.001um on the surface of a copper layer, thus obtaining a negative electrode current collector (marked as M3).
Through test, the specific surface area of M3 is 0.629M 2 /g。
Example 4
This example is used to illustrate the preparation of a current collector
(1-1) polyimide master batch was mixed with silver nanowires (wire diameter of 0.03 μm, wire length of 20 μm) at 99:1, and then carrying out thermoplastic biaxial stretching molding on the obtained mixture to obtain a sheet-shaped substrate layer with the thickness of 4.5 mu m;
(1-2) coating UV resin layers with a thickness of 5 μm on both sides of the base layer, and laser sintering grooving the UV resin layers to form a film sheet having grid grooves (depth of 3 μm and width of 4 μm);
uniformly coating the slurry containing silver nanowires used in the step (1-2) of the embodiment 1 on the surface of the membrane with the grid grooves by using a small roll-to-roll coater, wherein the thickness of a wet film obtained by coating is 10 mu m, drying and curing for 10min at 120 ℃ to obtain a conductive film, and polishing the conductive film on the surface of the membrane by using a nylon brush, wherein the rest of the conductive film is only remained in the grid grooves, namely conductive networks (i.e. interweaving grids, the thickness is 3 mu m and 1 layer) are respectively formed on two sides of the substrate layer, so as to obtain a first composite membrane; wherein the aperture of the conductive network (i.e. the interweaving grid) is 25 μm, and the wire diameter of the grid lines of the interweaving grid is 4 μm;
(2) Immersing the first composite membrane serving as a negative electrode in an industrial copper plating solution (1000 mL solution prepared by mixing 90g of copper sulfate, 60g of copper chloride, 55g of sodium sulfate, 80g of potassium sulfate, 15g of sodium polydithio-dipropyl sulfonate, 10g of sodium dodecyl sulfate, 35g of disodium hydrogen phosphate and deionized water), wherein a platinum electrode is used as a positive electrode, and forming a copper layer with a concave-convex structure on the surface of 1um on a conductive network and a UV resin layer of the first composite membrane by electroplating (electroplating condition: constant current electroplating for 1min under the current density of 1A) to obtain a second composite membrane (wherein the thickness of the composite conductive layer is 4 μm);
(3) The second composite membrane is placed in industrial tinning solution (the components are 10g of stannous sulfate, 20mL of concentrated sulfuric acid (98 wt%) and 0.1g of salicylaldehyde thiosemicarbazone, 0.02g of guanylthiourea, 60000.005g of polyethylene glycol, 0.01g of 4,4' - (2-pyridine methylene) diphenol, 0.2g of glucuronic acid and 0.01g of pyritinol hydrochloride are fully dissolved after deionized water is added to 1L of the solution), the solution is soaked for 0.5min, taken out and washed by deionized water, and then dried and cured for 15min at 80 ℃ to form a tin oxide layer with the thickness of 0.001um on the surface of a copper layer, so as to obtain a negative electrode current collector (marked as M4).
Tested, the specific surface area of M4 is 0.347M 2 /g。
Example 5
This example is used to illustrate the preparation of a current collector
(1-1) polyimide master batch was mixed with silver nanowires (wire diameter of 0.03 μm, wire length of 20 μm) at 99:1, and then carrying out thermoplastic biaxial stretching molding on the obtained mixture to obtain a sheet-shaped substrate layer with the thickness of 4.5 mu m;
(1-2) mixing water, silver nanowires (wire length 80 μm, wire diameter 0.06 μm), polyoxyethylene-8-octylphenyl ether and carboxymethyl cellulose, stirring for 30min to obtain a slurry containing silver nanowires (wherein the content of water is 98wt%, the content of silver nanowires is 1wt%, the content of polyoxyethylene-8-octylphenyl ether is 0.3wt%, and the content of carboxymethyl cellulose is 0.7wt%, based on the total weight of the slurry);
(1-3) uniformly coating the paste containing silver nanowires on one surface of the base layer using a small roll-to-roll coater, coating the resultant wet film with a thickness of 15 μm, and then drying and curing at 120 ℃ for 15min to form a conductive network (i.e., an interweaving network, a thickness of 0.5 μm,2 layers) on the surface of the base layer; uniformly coating the slurry on the other surface of the substrate layer, wherein the thickness of a wet film obtained by coating is 15 mu m, drying and curing for 15min at 120 ℃, and forming a conductive network (i.e. an interweaving network, the thickness of which is 0.5 mu m and 2 layers) on the other surface of the substrate layer to obtain a first composite membrane; wherein the pore size of the conductive network (i.e., the interweaving network) is 10 μm;
(2) The first composite membrane is placed in a vacuum coating machine, and aluminum metal is used as a target material to carry out vacuum aluminum plating on a conductive network and a basal layer of the first composite membrane (the condition of vacuum aluminum plating is that the vacuum degree is 1 multiplied by 10) -3 Pa, the energy of an electron beam used for heating the aluminum target material is 12000 ev), forming an aluminum layer with a thickness of 1um and a concave-convex structure on the surface, and obtaining a second composite membrane (wherein the thickness of the composite conductive layer is 1 μm);
(3) And (3) oxidizing the second composite membrane in air at 50 ℃ for 10min to form an aluminum oxide layer with the thickness of 0.1um on the surface, thereby obtaining the positive electrode current collector (marked as M5).
Through testing, the specific surface area of M5 is 1.628M 2 /g。
Example 6
This example is used to illustrate the preparation of a current collector
(1-1) polyethylene terephthalate (PET) master batch was mixed with silver nanowires (wire diameter of 0.03 μm, wire length of 20 μm) to 99:1, and then carrying out thermoplastic biaxial stretching molding on the obtained mixture to obtain a sheet-shaped substrate layer with the thickness of 4.5 mu m;
(1-2) mixing water, silver nanowires (wire length 80 μm, wire diameter 0.1 μm), polyvinylpyrrolidone and carboxymethyl cellulose, stirring for 30min to obtain a paste containing silver nanowires (wherein the content of water is 98wt%, the content of silver nanowires is 0.5wt%, the content of polyvinylpyrrolidone is 0.5wt%, and the content of carboxymethyl cellulose is 1wt%, based on the total weight of the paste);
(1-3) uniformly coating the copper nanowire-containing slurry on one surface of the base layer using a small roll-to-roll coater, wherein the thickness of a wet film obtained by coating is 20 μm, and then drying and curing at 120 ℃ for 10min, thereby forming a conductive network (i.e., an interweaving network, thickness of 0.18 μm,2 layers) on the surface of the base layer; uniformly coating the slurry on the other surface of the substrate layer, wherein the thickness of a wet film obtained by coating is 20 mu m, drying and curing for 10min at 120 ℃, and forming a conductive network (i.e. an interweaving network, the thickness of which is 0.18 mu m and 2 layers) on the other surface of the substrate layer to obtain a first composite membrane; wherein the pore size of the conductive network (i.e., the interweaving network) is 15 μm;
(2) The first composite membrane is placed in a vacuum coating machine, and aluminum metal is used as a target material to carry out vacuum aluminum plating on a conductive network and a basal layer of the first composite membrane (the condition of vacuum aluminum plating is that the vacuum degree is 1 multiplied by 10) -3 Pa, the energy of an electron beam used for heating the aluminum target material is 12000 ev), forming an aluminum layer with a thickness of 1um and a concave-convex structure on the surface, and obtaining a second composite membrane (wherein the thickness of the composite conductive layer is 1 μm);
(3) And (3) oxidizing the second composite membrane in air at 50 ℃ for 10min to form an aluminum oxide layer with the thickness of 0.1um on the surface, thereby obtaining the positive electrode current collector (marked as M6).
Through testing, the specific surface area of M6 is 1.569M 2 /g。
Example 7
This example is used to illustrate the preparation of a current collector
(1-1) polyethylene terephthalate (PET) master batch was mixed with silver nanowires (wire diameter of 0.03 μm, wire length of 20 μm) to 99:1, and then carrying out thermoplastic biaxial stretching molding on the obtained mixture to obtain a sheet-shaped substrate layer with the thickness of 4.5 mu m;
(1-2) mixing water, silver nanowires (wire length: 40 μm, wire diameter: 0.03 μm), polyvinylpyrrolidone and carboxymethyl cellulose, and stirring for 30 minutes to obtain a paste containing silver nanowires (wherein the content of water is 97wt%, the content of silver nanowires is 2wt%, the content of polyvinylpyrrolidone is 0.3wt%, and the content of carboxymethyl cellulose is 0.7wt%, based on the total weight of the paste);
(1-3) uniformly coating the paste containing silver nanowires on one surface of the base layer using a small roll-to-roll coater, wherein the thickness of the wet film obtained by coating is 20 μm, and then drying and curing at 110 ℃ for 10min, thereby forming a conductive network (i.e., an interweaving network, thickness of 0.1 μm,2 layers) on the surface of the base layer; uniformly coating the slurry on the other surface of the substrate layer, wherein the thickness of a wet film obtained by coating is 20 mu m, drying and curing for 10min at 100 ℃, and forming a conductive network (i.e. an interweaving network, the thickness of which is 0.1 mu m and 2 layers) on the other surface of the substrate layer to obtain a first composite membrane; wherein the pore size of the conductive network (i.e., the interweaving network) is 22 μm;
(2) The first composite membrane is placed in a vacuum coating machine, and aluminum metal is used as a target material to carry out vacuum aluminum plating on a conductive network and a basal layer of the first composite membrane (the condition of vacuum aluminum plating is that the vacuum degree is 1 multiplied by 10) -3 Pa, the energy of an electron beam used for heating the aluminum target material is 12000 ev), forming an aluminum layer with a thickness of 1um and a concave-convex structure on the surface, and obtaining a second composite membrane (wherein the thickness of the composite conductive layer is 1 μm);
(3) And (3) oxidizing the second composite membrane in air at 50 ℃ for 10min to form an aluminum oxide layer with the thickness of 0.1um on the surface, thereby obtaining the positive electrode current collector (marked as M7).
The specific surface area of M7 was tested to be 0.513M 2 /g。
Example 8
This example is used to illustrate the preparation of a current collector
(1-1) polypropylene (PP) was mixed with silver nanowires (wire diameter 0.03 μm, wire length 20 μm) at 99:1, and then carrying out thermoplastic biaxial stretching molding on the obtained mixture to obtain a sheet-shaped substrate layer with the thickness of 4.5 mu m;
(1-2) coating UV resin layers with a thickness of 5 μm on both sides of the base layer, and laser sintering grooving the UV resin layers to form a film sheet having grid grooves (depth of 3 μm and width of 4 μm);
Uniformly coating the slurry containing silver nanowires used in the step (1-2) of the embodiment 1 on the surface of the membrane with the grid grooves by using a small roll-to-roll coater, wherein the thickness of a wet film obtained by coating is 10 mu m, drying and curing for 10min at 120 ℃ to obtain a conductive film, and polishing the conductive film on the surface of the membrane by using a nylon brush, wherein the rest of the conductive film is only remained in the grid grooves, namely conductive networks (i.e. interweaving grids, the thickness is 3 mu m and 1 layer) are respectively formed on two sides of the substrate layer, so as to obtain a first composite membrane; wherein the aperture of the conductive network (i.e. the interweaving grid) is 25 μm, and the wire diameter of the grid lines of the interweaving grid is 4 μm;
(2) The first composite membrane is placed in a vacuum coating machine, and aluminum metal is used as a target material to carry out vacuum aluminum plating (the vacuum aluminum plating condition is that the vacuum degree is 1 multiplied by 10) on a conductive network and a UV resin layer of the first composite membrane -3 Pa, the energy of an electron beam used for heating the aluminum target material is 12000 ev), forming an aluminum layer with a thickness of 1um and a concave-convex structure on the surface, and obtaining a second composite membrane (wherein the thickness of the composite conductive layer is 4 μm);
(3) And (3) oxidizing the second composite membrane in air at 50 ℃ for 10min to form an aluminum oxide layer with the thickness of 0.1um on the surface, thereby obtaining the positive electrode current collector (marked as M8).
The specific surface area of M8 was tested to be 0.477m2/g.
Test case
(1-1) preparation of a negative electrode: the current collectors M1 to M4 prepared in examples 1 to 4 and a commercial planar negative electrode current collector copper foil D1 (prepared by electrolysis, thickness of 6um, specific surface area of 0.048M 2/g) were coated with negative electrode slurry (components of negative electrode slurry: 48wt% of natural graphite, 0.8wt% of super-P, 0.6wt% of thickener CMC, 0.6wt% of binder SBR and 50wt% of deionized water), respectively, to form a wet film having a thickness of 150um, and the negative electrode was obtained after vacuum drying at 150℃and designated as P1 to P4 and DP1, respectively.
(1-2) preparation of positive electrode: the surfaces of the current collectors M5 to M8 prepared in examples 5 to 8 and a commercial planar positive electrode current collector aluminum foil D2 (prepared by calendaring, thickness of 10um, specific surface area of 0.039M 2/g) were coated with positive electrode slurry (components of positive electrode slurry: 65wt% lithium cobaltate, super-P1.5 wt%, CNT 1wt%, PVDF 1.5wt%, and the balance water), respectively, to form a wet film having a thickness of 150um, and the positive electrode was obtained after vacuum drying at 150℃and designated as P5 to P8 and DP2, respectively.
(2-1) preparation of a battery: the cathodes P1-P4 and DP1 were connected to one another, and an electrolyte (1M LiPF 6 The solvent is EC and DEC according to the weight ratio of 1:1 mix), cellgard 2400 separator and battery case CR2032 were assembled into button cells, designated B1-B4 and DB1, respectively, in a glove box.
(2-2) preparation of a battery: the positive electrodes P5-P8 and DP2 were subjected to electrolytic solution (1M LiPF 6 The solvent is EC and DEC according to the weight ratio of 1:1 mix), cellgard 2400 separator and battery case CR2032 were assembled into button cells, designated B5-B8 and DB2, respectively, in a glove box.
Measuring the resistivity of the current collectors M1-M8 and D1-D2 by adopting a four-probe resistivity tester;
the batteries B1-B8 and DB1-DB2 are respectively tested on an electrochemical workstation by adopting a constant current charge-discharge method (test condition: at 25 ℃, current density is 50mA/g, voltage range is 0.01-3V);
the above test results are shown in tables 1 and 2, respectively.
TABLE 1
TABLE 2
As can be seen from tables 1 and 2, the current collectors B1-B4 and B5-B8 provided by the present invention have significantly higher specific surface areas and lower resistivity than the conventional copper foil (D1) and aluminum foil (D2) current collectors, respectively, due to the specific micro-nano concave-convex structure, which also indicates that the current collectors provided by the present invention can improve the electronic conductivity inside lithium ions.
In terms of safety, the current collector provided by the invention can effectively inhibit the formation of lithium dendrites due to the specific micro-nano concave-convex structure, and the middle plastic substrate layer can be melted during short circuit so as to effectively prevent further short circuit inside the battery, so that the safety performance of the battery is improved, and the current collector can be verified from the great improvement of the cycle life of the batteries B1-B4 compared with DB1 (and the cycle life of the batteries B5-B8 compared with DB 2).
In addition, the current collector provided by the invention is lighter than copper foil and aluminum foil, and higher weight energy density of the battery is brought.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (20)
1. A current collector, the current collector comprising: the device comprises a substrate layer, composite conductive layers arranged on two surfaces of the substrate layer, and an oxide layer arranged on the composite conductive layers;
wherein the composite conductive layer comprises a conductive network disposed on the base layer, and a metal layer deposited and overlying the conductive network and the base layer;
the conductive network is provided with a grid structure formed by interlacing electric conductors, and the surface of the metal layer is provided with a concave-convex structure.
2. A current collector according to claim 1, wherein the base layer has a thickness of 1-15 μm, preferably 3-10 μm;
Preferably, the thickness of the composite conductive layer is 0.001-500 μm, preferably 1-100 μm;
preferably, in the composite conductive layer, the thickness of the conductive network is 0.001-10 μm, preferably 0.01-0.5 μm; the thickness of the metal layer is 0.001-500 μm, preferably 1-100 μm;
preferably, the oxide layer has a thickness of 0.001-10 μm, preferably 0.001-1 μm.
3. The current collector according to claim 1 or 2, wherein the base layer contains a polymer selected from at least one of a poly (terephthalate), polyamide, polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, poly (paraphenylene terephthalamide), polypropylene, acrylonitrile-butadiene-styrene copolymer, polyvinyl formal, polyvinyl butyral, polyurethane, polyacrylonitrile, polyvinyl acetate, polyoxymethylene, phenolic resin, epoxy resin, polytetrafluoroethylene, polyvinylidene fluoride, silicone rubber, polycarbonate, polysulfone, polyethersulfone, and polyphenylene oxide;
preferably, the base layer contains functional particles;
preferably, in the base layer, the polymer: the weight ratio of the functional particles is (1-999): 1, a step of;
Preferably, the functional particles are flame retardants and/or conductive agents;
preferably, the flame retardant is selected from at least one of magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, zinc borate, antimony trioxide and layered silicate;
preferably, the conductive agent is a conductive metal material and/or a conductive carbon material;
preferably, the conductive metal material is selected from at least one of a metal nanowire, a metal nanorod, and a metal nanosheet; wherein the metal is selected from silver, copper or aluminum;
preferably, the conductive carbon material is selected from at least one of conductive carbon black, carbon fiber and carbon nanotube.
4. A current collector according to any one of claims 1-3, wherein the conductive network is an interwoven network of one-dimensional nano-conductive material interdigitate; or the conductive network is an interweaved grid, wherein the interweaved grid is formed by connecting grid lines, and the grid lines are formed by staggered lap joint of one-dimensional nano conductive materials;
preferably, the one-dimensional nano conductive material is selected from at least one of silver nanowires, copper nanowires, gold nanowires, nickel nanowires, silicon nanowires, carbon nanowires, and carbon fibers;
preferably, the wire diameter of the one-dimensional nano conductive material is 0.01-5 μm, preferably 0.05-1 μm; the wire length is 5-500 μm, preferably 50-500 μm;
Preferably, the pore size of the interweaving network is 1-80 μm, preferably 1-15 μm;
preferably, the pore size of the interwoven mesh is 1-100 μm, preferably 20-40 μm;
preferably, the wire diameter of the grid lines of the interlaced grid is 1-100 μm, preferably 1-10 μm;
preferably, when the conductive network is an interwoven mesh, a template layer is further disposed between the base layer and the conductive network, and the conductive network is embedded in a surface of the template layer; the metal layer is deposited and covers the conductive network and the template layer;
preferably, the template layer has a thickness of 1-100 μm.
5. The current collector according to any one of claims 1-4, wherein the metal layer is a copper layer or an aluminum layer;
preferably, the oxide layer is a tin oxide layer or an aluminum oxide layer;
preferably, the specific surface area of the current collector is 0.1-2m 2 Preferably 1-2m 2 /g。
6. A method of preparing a current collector, the method comprising:
(1) Forming a conductive network having a mesh structure formed by interleaving conductive bodies on both surfaces of the base layer;
(2) Depositing a copper layer or an aluminum layer on the conductive network and the substrate layer to form a metal layer;
(3) And forming an oxide layer on the metal layer to obtain the current collector.
7. The method of claim 6, wherein in step (1), the base layer comprises a polymer selected from at least one of a poly (terephthalate), a polyamide, a polyimide, a polyethylene, a polypropylene, a polystyrene, a polyvinyl chloride, a polyethylene terephthalate, a polybutylene terephthalate, a poly (paraphenylene terephthalamide), a polypropylene, an acrylonitrile-butadiene-styrene copolymer, a polyvinyl formal, a polyvinyl butyral, a polyurethane, a polyacrylonitrile, a polyvinyl acetate, a polyoxymethylene, a phenolic resin, an epoxy resin, a polytetrafluoroethylene, a polyvinylidene fluoride, a silicone rubber, a polycarbonate, a polysulfone, a polyethersulfone, and a polyphenylene oxide;
preferably, the base layer contains functional particles;
preferably, in the base layer, a polymer: the weight ratio of the functional particles is (1-999): 1, a step of;
preferably, the functional particles are flame retardants and/or conductive agents;
preferably, the flame retardant is selected from at least one of magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, zinc borate, antimony trioxide and layered silicate;
preferably, the conductive agent is a conductive metal material and/or a conductive carbon material;
Preferably, the conductive metal material is selected from at least one of a metal nanowire, a metal nanorod, and a metal nanosheet; wherein the metal is selected from silver, copper or aluminum;
preferably, the conductive carbon material is selected from at least one of conductive carbon black, carbon fiber and carbon nanotube;
preferably, the thickness of the base layer is 1-15 μm, preferably 3-10 μm.
8. The method of claim 6 or 7, wherein in step (1), the conductive network is an interlaced network formed by interlacing one-dimensional nano conductive materials; or the conductive network is an interweaved grid, wherein the interweaved grid is formed by connecting grid lines, and the grid lines are formed by staggered lap joint of one-dimensional nano conductive materials;
preferably, the conductive network is formed by a coating method.
9. The method of claim 8, wherein forming the interwoven network using a coating process comprises: and coating first slurry containing one-dimensional nano conductive materials on two surfaces of the substrate layer to obtain a first wet film, and forming an interweaving network after first solidification.
10. The method of claim 8, wherein forming the interwoven mesh using a coating process comprises:
(i) Coating template layers on two surfaces of the substrate layer, and grooving the template layers to obtain a template layer with grid grooves;
(ii) Coating a second slurry containing one-dimensional nano conductive materials on the surface of the template layer with the grid grooves to obtain a second wet film, and obtaining a conductive film after second solidification;
(iii) And grinding the conductive film, wherein after the grinding, the conductive film remained in the grid groove forms an interweaved grid.
11. The method of claim 10, wherein the one-dimensional nano-conductive material contained in the first and second slurries is selected from at least one of silver nanowires, copper nanowires, gold nanowires, nickel nanowires, silicon nanowires, carbon nanowires, and carbon fibers;
preferably, the wire diameter of the one-dimensional nano conductive material is 0.01-5 μm, preferably 0.05-1 μm; the wire length is 5-500 μm, preferably 50-500 μm;
preferably, the first slurry and the second slurry also contain a solvent, a surfactant and a thickener;
preferably, the solvent is selected from at least one of water, N-methylpyrrolidone, ethanol and isopropanol;
preferably, the surfactant is at least one selected from polyvinylpyrrolidone, triton, tween, span, fatty amine and fluorocarbon;
Preferably, the thickener is at least one selected from carboxymethyl cellulose, polyvinylpyrrolidone, polyvinyl butyral, hydroxypropyl methylcellulose, and ethyl cellulose;
preferably, the content of the solvent in the first slurry is 90-98wt%, the content of the one-dimensional nano conductive material is 0.1-5wt%, the content of the surfactant is 0.01-1wt%, and the content of the thickener is 0.01-10wt%, based on the total weight of the first slurry;
preferably, the solvent is contained in the second paste in an amount of 90 to 98wt%, the one-dimensional nano conductive material is contained in an amount of 0.1 to 5wt%, the surfactant is contained in an amount of 0.01 to 1wt%, and the thickener is contained in an amount of 0.01 to 10wt%, based on the total weight of the second paste.
12. The method of claim 10 or 11, wherein the first and second wet films each independently have a thickness of 1-500 μιη;
preferably, the conditions of the first curing and the second curing each independently include: the temperature is 100-160deg.C, and the time is 1-30min.
13. The method of any of claims 10-12, wherein the template layer is a resin layer, the template layer having a thickness of 1-100 μιη;
Preferably, the depth of the grid grooves is 1-10 μm and the width is 1-100 μm.
14. The method according to any one of claims 8-13, the thickness of the conductive network being 0.001-10 μm, preferably 0.01-0.5 μm;
the pore size of the interweaving network is 1-80 mu m, preferably 1-15 mu m;
the pore diameter of the interweaving grid is 1-100 mu m, preferably 20-40 mu m;
the wire diameter of the grid lines of the interlaced grid is 1-100 μm, preferably 1-10 μm.
15. The method according to any one of claims 6-14, wherein in step (2) the thickness of the metal layer is 0.001-500 μm, preferably 1-100 μm;
preferably, the copper layer is deposited by electroplating; and the aluminum layer is deposited in a vacuum coating mode.
16. The method of any one of claims 6-15, wherein in step (3), the oxide layer is a tin oxide layer or an aluminum oxide layer;
preferably, the thickness of the oxide layer is 0.001-10 μm, preferably 0.001-1 μm;
preferably, when the metal layer is a copper layer, depositing a tin oxide layer on the metal layer; when the metal layer is an aluminum layer, oxidizing the metal layer to form an aluminum oxide layer on the surface;
Preferably, the tin oxide layer is deposited by soaking.
17. A current collector made by the method of any one of claims 6-16.
18. Use of a current collector according to any one of claims 1-5 and 17 in the preparation of a battery.
19. An electrode comprising a current collector, and an active material layer supported on the surface of the current collector; wherein,,
the current collector is a current collector according to any one of claims 1 to 5 and 17.
20. A lithium ion battery comprising the electrode of claim 19.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310052601.6A CN116072880A (en) | 2023-02-02 | 2023-02-02 | Current collector, preparation method and application thereof, electrode and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310052601.6A CN116072880A (en) | 2023-02-02 | 2023-02-02 | Current collector, preparation method and application thereof, electrode and lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116072880A true CN116072880A (en) | 2023-05-05 |
Family
ID=86178151
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310052601.6A Pending CN116072880A (en) | 2023-02-02 | 2023-02-02 | Current collector, preparation method and application thereof, electrode and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116072880A (en) |
-
2023
- 2023-02-02 CN CN202310052601.6A patent/CN116072880A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11784298B2 (en) | Methods of reducing occurrences of short circuits and/or lithium plating in batteries | |
| US20220173372A1 (en) | Electrodes, electrochemical cells, and methods of forming electrodes and electrochemical cells | |
| JP6367390B2 (en) | Production of large capacity prism lithium ion alloy anode | |
| TWI616017B (en) | Multi-layer battery electrode design for enabling thicker electrode fabrication | |
| US20110070488A1 (en) | High performance electrodes | |
| KR101214727B1 (en) | Electrodes, method for preparing the same, and electrochemical capacitor comprising the same | |
| CN113594467B (en) | Composite current collector and lithium ion battery | |
| CN114361461A (en) | Flexible current collector core layer, current collector, pole piece, battery and preparation method of flexible current collector core layer, current collector, pole piece and battery | |
| EP3404746A1 (en) | Methods of reducing occurences of short circuits and/or lithium platings in batteries | |
| Yan et al. | Sandwich-structured cathodes with cross-stacked carbon nanotube films as conductive layers for high-performance lithium-ion batteries | |
| CN116072880A (en) | Current collector, preparation method and application thereof, electrode and lithium ion battery | |
| US11374228B2 (en) | Metallic textiles for flexible wearable lithium ion batteries | |
| CN116435523B (en) | Composite current collector, preparation method thereof, electrode plate and battery | |
| Kirchev | Alternative current-collectors | |
| US20240047640A1 (en) | Electrodes, electrochemical cells, and methods of forming electrodes and electrochemical cells | |
| CN118156514A (en) | Composite current collector with three-dimensional network structure, pole piece and electrochemical device | |
| CN114614075A (en) | Flexible lithium ion battery | |
| CN114447274A (en) | Pole piece and battery | |
| CN117542950A (en) | MXene self-growth process for metal foil surface, product and application thereof | |
| CN116960353A (en) | Flexible composite current collector and preparation method and application thereof | |
| CN118039921A (en) | Current collector with open structure, pole piece and electrochemical device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |