CN117712386A - Composite copper foil, preparation method thereof and lithium ion secondary battery - Google Patents
Composite copper foil, preparation method thereof and lithium ion secondary battery Download PDFInfo
- Publication number
- CN117712386A CN117712386A CN202311442169.8A CN202311442169A CN117712386A CN 117712386 A CN117712386 A CN 117712386A CN 202311442169 A CN202311442169 A CN 202311442169A CN 117712386 A CN117712386 A CN 117712386A
- Authority
- CN
- China
- Prior art keywords
- layer
- copper
- plating layer
- copper foil
- copper plating
- 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 221
- 239000011889 copper foil Substances 0.000 title claims abstract description 120
- 239000002131 composite material Substances 0.000 title claims abstract description 81
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000010949 copper Substances 0.000 claims abstract description 102
- 229910052802 copper Inorganic materials 0.000 claims abstract description 101
- 238000007747 plating Methods 0.000 claims abstract description 92
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 32
- 238000004544 sputter deposition Methods 0.000 claims description 25
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 18
- 238000009713 electroplating Methods 0.000 claims description 16
- 239000000654 additive Substances 0.000 claims description 15
- 230000000996 additive effect Effects 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 12
- 229920000159 gelatin Polymers 0.000 claims description 12
- 239000008273 gelatin Substances 0.000 claims description 12
- 229920002799 BoPET Polymers 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 claims description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 9
- 108010010803 Gelatin Proteins 0.000 claims description 8
- 235000019322 gelatine Nutrition 0.000 claims description 8
- 235000011852 gelatine desserts Nutrition 0.000 claims description 8
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 5
- BQJTUDIVKSVBDU-UHFFFAOYSA-L copper;sulfuric acid;sulfate Chemical compound [Cu+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O BQJTUDIVKSVBDU-UHFFFAOYSA-L 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 150000003585 thioureas Chemical class 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 230000002401 inhibitory effect Effects 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 230000002265 prevention Effects 0.000 claims description 3
- 229920003169 water-soluble polymer Polymers 0.000 claims description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 150000003377 silicon compounds Chemical class 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims 1
- 239000011255 nonaqueous electrolyte Substances 0.000 abstract description 9
- 239000010410 layer Substances 0.000 description 128
- 230000000052 comparative effect Effects 0.000 description 38
- 239000011149 active material Substances 0.000 description 32
- 239000010408 film Substances 0.000 description 25
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 17
- 229910052744 lithium Inorganic materials 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 5
- -1 polyethylene terephthalate Polymers 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- 239000002210 silicon-based material Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 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
- 238000000151 deposition Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000006255 coating slurry Substances 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- 150000005676 cyclic carbonates Chemical class 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000002409 silicon-based active material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 150000005678 chain carbonates Chemical class 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- MGGGFDCMRADCEW-UHFFFAOYSA-N 1,3,5-trioxepane-2,4-dione Chemical compound O=C1OCCOC(=O)O1 MGGGFDCMRADCEW-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013595 LiCo0.5Ni0.5O2 Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910011669 LiNi0.7Co0.2Mn0.1O2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- MNOILHPDHOHILI-UHFFFAOYSA-N Tetramethylthiourea Chemical compound CN(C)C(=S)N(C)C MNOILHPDHOHILI-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000002194 amorphous carbon material Substances 0.000 description 1
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- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- 239000001273 butane Substances 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 description 1
- FTCLAXOKVVLHEG-UHFFFAOYSA-N sodium;3-sulfanylpropane-1-sulfonic acid Chemical compound [Na].OS(=O)(=O)CCCS FTCLAXOKVVLHEG-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
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- 239000011135 tin Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The present invention relates to a composite copper foil, comprising: a substrate layer; a copper layer formed on the surface of the base material layer; a first copper plating layer formed on a surface of the copper layer; a second copper plating layer formed on a surface of the first copper plating layer; and a carbon layer formed on the surface of the second copper plating layer. The thickness of the base material layer is 4-5 mu m, the thickness of the copper layer is 5-100nm, the thickness of the first copper plating layer is 100-400nm, and the thickness of the second copper plating layer is 500-1000nm. The invention also relates to a preparation method of the composite copper foil. The present invention also relates to a lithium ion secondary battery and a nonaqueous electrolyte, the composite copper foil constituting a current collector of an electrode of the lithium ion secondary battery.
Description
Technical Field
The present invention relates to the field of surface treatment, and more particularly, to a composite copper foil constituting a current collector of an electrode of a lithium ion secondary battery, a method of preparing the same, and a lithium ion secondary battery of a nonaqueous electrolyte.
Background
This section provides background information related to the present application, which does not necessarily constitute prior art.
The negative electrode current collector of the nonaqueous electrolyte lithium ion secondary battery generally employs a copper foil, the surface of which is coated with carbon particles as a negative electrode active material layer. The copper foil as the negative electrode current collector for lithium ion secondary batteries is produced by adding various water-soluble polymer substances, various surfactants, various organic sulfur compounds, chloride ions, and the like to a copper sulfate-sulfuric acid electrolyte solution as appropriate.
The surface of the electrolytic copper foil manufactured by the above-described manufacturing method is coated with carbon particles and dried, and then is pressed, to finally form a negative electrode. The tensile strength of the electrolytic copper foil is generally 300-350N/mm 2 When the copper foil is used as a copper foil for a negative electrode containing carbon particles as an active material, an appropriate elongation can be obtained, and the copper foil is a suitable material.
In order to further increase the capacity of a lithium ion secondary battery, a lithium ion secondary battery using silicon which is electrochemically alloyed with lithium at the time of charging as a negative electrode active material has been proposed, and conventionally, a powdered silicon or silicon compound is formed into a slurry with a binder by using an organic solvent, and then coated on an electrolytic copper foil, dried, and pressed. However, in such an electrode for a lithium ion secondary battery, the silicon active material absorbs lithium ions during charging and expands its volume about 4 times, and releases lithium ions during discharging and contracts. Therefore, there occurs a phenomenon in which the silicon active material is finely pulverized and peeled off from the surface of the electrolytic copper foil due to expansion and contraction of the volume of the active material layer caused by such charge and discharge, which causes a decrease in the cycle charge and discharge efficiency of the battery.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a composite copper foil which can be used as a current collector and can be applied to a lithium ion secondary battery instead of the existing electrolytic copper foil.
The present invention also provides a lithium ion secondary battery which can use a negative electrode in which an active material layer mainly composed of silicon is formed on a composite copper foil, and which is excellent in charge-discharge cycle performance.
In order to achieve the above purpose, the invention adopts the following technical scheme: a composite copper foil comprising:
a substrate layer;
a copper layer formed on the surface of the base material layer;
a first copper plating layer formed on a surface of the copper layer;
a second copper plating layer formed on a surface of the first copper plating layer;
and a carbon layer formed on the surface of the second copper plating layer.
The method for manufacturing the composite copper foil comprises the following steps:
a step of preparing a copper foil on the surface of the base material layer; and
a carbon layer is deposited on the surface of the copper foil.
Wherein the copper foil comprises a second copper plating layer, a first copper plating layer and a copper layer which are laminated in sequence. In such a way that the tensile strength of the composite copper foil is not less than 300N/mm 2 In the case of (a), the thickness of the base layer is preferably 4 to 5 μm, the thickness of the copper layer is preferably 5 to 100nm, the thickness of the first copper plating layer is preferably 100 to 400nm, and the thickness of the second copper plating layer is preferably 500 to 1000nm from the viewpoint of reducing the overall thickness of the composite copper foil. The thickness is a value measured by analyzing a layer cross section using an energy dispersive X-ray spectrometry (TEM-EDX) by a transmission electron microscope.
In one or more embodiments, the copper foil of the composite copper foil has a thickness of 0.8-1 μm.
The composite copper foil formed by a combination of wet film forming methods such as electroless copper plating and electrolytic copper plating, physical vapor film forming methods such as sputtering and vacuum deposition, and chemical vapor film forming, and particularly preferably the copper layer is a copper thin film layer produced by sputtering. The copper foil produced by a combination of the sputtering method and the electrolytic copper plating method is preferable in terms of in-plane uniformity of film thickness and productivity in a sheet-like or roll-like state.
In one or more embodiments, an anti-rust treatment is performed on the surface of the copper foil before the carbon layer is formed on the surface of the copper foil.
In addition, the negative electrode of the lithium ion secondary battery provided by the invention takes the composite copper foil as a current collector, and an active material layer is formed on the surface of the current collector. In one or more embodiments, the active material layer is deposited on the current collector by mixing the active material, binder, and solvent, making the mixture into a slurry, and then coating, drying, and extruding the slurry. The active material layer is preferably formed of an active material containing carbon, silicon, germanium, or tin as a main component. The carbon layer of the composite copper foil provides enhanced adhesion between the copper foil and the active material layer.
The substrate layer in the composite copper foil provided by the invention can be regarded as a carrier, and the composite copper foil is in the form of a copper foil with a carrier, and in the case of an ultrathin copper foil, the handling property can be improved by adopting the copper foil with the carrier. In particular, when the copper foil is produced by vacuum deposition such as sputtering, the carrier-containing copper foil is preferably used. Examples of the carrier include a resin film such as a PET film, a PEN film, an aramid film, a polyimide film, a nylon film, and a liquid crystal polymer, and a metal-coated resin film having a metal coating layer on the resin film.
In one or more embodiments, the active material layer of the lithium ion secondary battery is formed of an active material mainly composed of silicon, and the base material layer of the composite copper foil applied to the lithium ion secondary battery is preferably a PET film.
The composite copper foil provided by the invention can form an extremely thin copper foil with a thickness of not more than 1 μm on the surface of a base material layer, but the extremely thin copper foil formed in this way has an extremely flat copper foil surface, so that it is not expected to secure high adhesion strength between the extremely thin copper foil and an active material layer by utilizing the anchor effect of the surface roughness of the copper foil. Thus, by forming a carbon layer on the surface of the copper foil, a copper foil with a surface treatment layer formed by standard ion chemical vapor deposition (PECVD) or by sputtering can be obtained, so that the composite copper foil can achieve high adhesion strength with the active material layer and can reduce the contact resistance of the active material layer with the copper foil.
The following description is made with reference to specific embodiments.
Drawings
The invention is further illustrated by the accompanying drawings, which are not to be construed as limiting the invention in any way.
Fig. 1 is a schematic cross-sectional view of a composite copper foil according to an embodiment of the present invention.
Fig. 2 is a flowchart of a method for manufacturing a composite copper foil according to an embodiment of the present invention.
Wherein, the reference numerals are as follows: a composite copper foil 10, a PET film 11, a copper layer 12, a first copper plating layer 13, a second copper plating layer 14, and a carbon layer 15.
Detailed Description
It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
As shown in fig. 1, an embodiment of the present invention provides a composite copper foil 10, which composite copper foil 10 uses a PET (polyethylene terephthalate) film 11 as a base material layer, forms a copper layer 11 on the surface of the PET film 11 by an evaporation method such as sputtering, deposits a first copper plating layer 13 on the surface of the copper layer 11 by electroplating, and deposits a second copper plating layer 14 on the surface of the first copper plating layer 13 by electroplating. The laminated second copper plating layer 14, first copper plating layer 13 and copper layer 11 constitute copper foil, and a high surface energy copper foil is formed on the surface of the PET film 11 to increase wettability and improve tackiness so as to enhance the bonding ability of the carbon layer 15. The composite copper foil 10 has the above-described various layer structures in order so as to be vertically symmetrical on both surfaces of the base material layer 11.
The carbon layer 15 may be formed by amorphous carbon material deposited on the surface of the second copper plating layer 14 using existing deposition techniques, more specifically, the carbon layer 15 may be formed using existing polymer-form carbon material (PLC) and/or diamond-like carbon (DLC) material using Plasma Enhanced Chemical Vapor Deposition (PECVD) or by sputtering the carbon layer 15 deposited on the surface of the second copper plating layer 14. It should be appreciated that when deposited using Plasma Enhanced Chemical Vapor Deposition (PECVD) techniques, the carbon layer 15 may contain other elements such as hydrogen, nitrogen, or oxygen. The carbon layer 15 is formed from a thin layer of amorphous carbon. In this preferred embodiment, the thickness of the carbon layer 15 is preferably 10 to 100nm, and in this range, adhesion to the second copper plating layer 14 can be significantly improved and resistance can be reduced. The deposition of the carbon layer 15 enhances the adhesion durability of the subsequently applied active material layer to the copper foil.
The preparation method of the composite copper foil shown in fig. 1 is shown in fig. 2, and comprises the following steps:
s1, forming a copper layer on the surface of the PET film.
By the sputtering method, an extremely thin copper layer can be extremely well formed without impairing the flatness of the PET film surface. In the case of using the sputtering method, the sputtering method may be any of various known methods such as magnetron sputtering and bipolar sputtering, but magnetron sputtering is preferable in terms of high film forming speed and high productivity. The sputtering may be performed by either a DC (direct current) or RF (high frequency) power supply, and the reaching vacuum degree in the chamber before starting sputtering is preferably less than 1×10 -4 Pa. The gas used for sputtering is preferably an inert gas such as argon, and the most preferable gas is argon, and the flow rate of argon or the like is not particularly limited as long as it is appropriately determined according to the sputtering chamber size and the film forming conditions. In addition, from the viewpoint of maintaining continuous and stable film forming property without operation failure such as abnormal discharge or plasma irradiation failure, the pressure at the time of film forming is preferably in the range of 0.1 to 2.0 Pa. The pressure range may be set by adjusting the flow rate of the film forming power, argon gas, or the like according to the device configuration, capacity, exhaust capacity of the vacuum pump, rated capacity of the film forming power supply, or the like. In addition, the sputtering power is 0.05-10.0W/cm per unit area of the target in consideration of film thickness uniformity, productivity, etc 2 Is suitably set within the range of (2).
S2, electroplating is carried out on the surface of the copper layer to obtain a first copper plating layer.
The purpose of the deposition to form the first copper plating layer includes obtaining a surface excellent in flatness, and the plating solution used in this step is obtained by adding an additive a, an additive B, and chloride ions to a sulfuric acid-copper sulfate electrolyte. Wherein the additive A is more than one additive selected from thiourea or thiourea derivatives; the additive B is selected from one or more of thiourea or thiourea derivatives (such as thiourea, N '-dimethylthiourea, N' -diethylthiourea, tetramethylthiourea, thiosemicarbazide, N-allylthiourea, water-soluble thiourea such as ethylene thiourea, thiourea derivatives), polymer polysaccharides such as gelatin, polyethylene glycol, polypropylene glycol, starch, cellulose water-soluble polymers (such as carboxymethyl cellulose and hydroxyethyl cellulose), polyethyleneimine, and polyacrylamide.
S3, performing activation treatment on the surface of the first copper plating layer.
The step uses an activating solution to activate the surface of the first copper plating layer, wherein the activating solution can comprise inorganic or organic acid, oxidant and additive. For example, the activating liquid includes sulfuric acid (the content of sulfuric acid is 5 to 7wt% relative to the total mass of the activating liquid), a corrosion inhibitor such as hydrogen peroxide, triazole, and a surfactant.
And S4, electroplating is carried out on the surface of the first copper plating layer to obtain a second copper plating layer.
The purpose of the deposition to form the second copper plating layer includes increasing the thickness of the copper foil by adding 3-thio-isothiouronium propylsulfonic acid, gelatin and chloride ions to the sulfuric acid-copper sulfate electrolyte. Gelatin can be regarded as a leveling agent, and during the electroplating process, gelatin can be adsorbed on the surface of a cathode (namely the second copper plating layer) to inhibit copper ions from reducing and refine grains, and the (220) crystal face of the second copper plating layer is preferential at room temperature; the 3-sulfur-isothiourea propyl sulfonic acid can be regarded as a brightening agent and a surfactant, and the 3-sulfur-isothiourea propyl sulfonic acid is adsorbed on the surface of a copper plating layer during electroplating and the sulfonic acid group is used for capturing Cu in an electrolyte 2+ And in Cl - Under the synergistic effect, the speed of obtaining electrons by copper ions is increased, the reduction efficiency is improved, and the 3-sulfur-isothiourea propyl sulfonic acid wets the cathode (namely the second copper plating layer), so that the mechanical property of the second copper plating layer is improved.
S5, performing rust prevention treatment on the surface of the second copper plating layer.
The adhesion strength to the carbon layer can be improved by subjecting the surface of the second copper plating layer to an anti-rust treatment, which may be an organic anti-rust treatment such as benzotriazole or a silane coupling agent treatment.
S6, forming a carbon layer with the thickness of 50nm on the surface of the second copper plating layer.
The amorphous carbon layer is formed by vapor phase film formation. The vapor deposition may be any of physical vapor deposition and chemical vapor deposition. By using the vapor phase film formation, the oxygen and/or carbon content can be easily controlled, and film formation can be performed at a desired extremely thin thickness (10 to 100 nm) on the surface of the second copper plating layer. Therefore, it is preferable to manufacture a carbon layer having a carbon concentration of not less than 80 at% and an oxygen concentration of not more than 20 at%, and the concentration of atoms in the carbon layer is measured by XPS (X-ray photoelectron spectroscopy). When the carbon concentration and the oxygen concentration are within the above ranges, the adhesion to the active material layer can be significantly improved, and the mechanism is not specified, and the presence of oxygen atoms in the carbon layer to some extent contributes to the improvement of the adhesion to the active material layer. For physical vapor deposition, preferably used is at least 1 gas selected from the group consisting of methane, ethane, propane, butane, acetylene and tetraethoxysilane, more preferably methane or carbon dioxide (CO) 2 )。
The steps also include cleaning and drying steps.
The active material layer described in the present invention is a material that absorbs and releases lithium, and preferably absorbs lithium by alloying, and examples of such active material materials include carbon, silicon, germanium, tin, lead, zinc, magnesium, sodium, aluminum, potassium, and indium. Among them, silicon is preferably used in view of its higher theoretical capacity. In particular, in the lithium ion secondary battery using the composite copper foil provided by the embodiment of the invention as a current collector, the active material layer is a layer using silicon as a main component. The active material layer in the embodiment of the present invention is preferably formed by a method in which an active material is made into a slurry together with a binder and a solvent, and then coated, dried, and pressed, and the active material layer may be formed on one or both sides of the current collector. Lithium may be previously stored or added to the active material layer in the embodiment of the present invention. Lithium may be added when forming the active material layer. That is, by forming an active material layer containing lithium, lithium is contained in the active material layer. Further, after the active material layer is formed, lithium may be stored in or added to the active material layer. As a method for absorbing or adding lithium to the active material layer, a method for electrochemically absorbing or adding lithium can be mentioned.
The nonaqueous electrolyte used in the lithium ion secondary battery of the embodiment of the invention is an electrolyte in which a solute is dissolved in a solvent. The solvent for the nonaqueous electrolyte is not particularly limited as long as it can be used for a lithium ion secondary battery, and examples thereof include cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and vinylene carbonate, and chain carbonates such as dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate. Preferably, a mixed solvent of a cyclic carbonate and a chain carbonate is used. In addition, a mixed solvent of the above cyclic carbonate and an ether solvent such as 1, 2-dimethoxyethane or 1, 2-diethoxyethane, and a chain ester such as γ -butyrolactone, sulfolane or methyl acetate may be used.
As the solute of the nonaqueous electrolyte, as long as it is a solute usable for a lithium ion secondary battery, liPF can be cited 6 、LiBF 4 、LiCF 3 SO 3 、LiN(CF 3 SO 2 ) 2 、LiN(C 2 F 5 SO 2 ) 2 、LiN(CF 3 SO 2 )(C 4 F 9 SO 2 )、LiC(CF 3 SO 2 ) 3 、LiC(C 2 F 5 SO 2 ) 3 、LiAsF 6 、LiClO 4 Etc. In particular, liXF is preferably used y (wherein X is P, as, sb, B, bi, al, ga, in, y is 6 when X is P, as or Sb, and y is 4 when X is B, bi, al, ga, in) and lithium perfluoroalkylsulfonate imide or lithium perfluoroalkylsulfonate methide. Wherein, specialLiPF is preferably used 6 With LiN (C) 2 F 5 SO 2 ) 2 Is a mixed solute of (a) and (b).
The nonaqueous electrolyte may be a gel-like polymer electrolyte obtained by impregnating a polymer electrolyte such as polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, or the like with an electrolyte solution, liI, li 3 N, etc.
The electrolyte of the lithium ion secondary battery of the embodiment of the present invention can be used without limitation as long as the Li compound as a solute having ion conductivity and a solvent that dissolves and holds the Li compound do not decompose at the voltage at the time of charge and discharge of the battery or at the time of storage.
Examples of the positive electrode active material used for the positive electrode of the secondary battery include LiCoO 2 、LiNiO 2 、LiMn 2 O 4 、LiMnO 2 、LiCo 0.5 Ni 0.5 O 2 、LiNi 0.7 Co 0.2 Mn 0.1 O 2 Lithium-containing transition metal oxide and MnO 2 And metal oxides that do not contain lithium. Further, as long as it is a substance that can electrochemically intercalate and deintercalate lithium, it is possible to use without limitation.
According to the embodiment of the invention, the lithium ion secondary battery using the composite copper foil as the current collector can inhibit the reduction of the charge-discharge cycle efficiency, prevent the short circuit between the positive electrode and the negative electrode of the lithium ion secondary battery, and stably maintain the performance of the lithium ion secondary battery for a long time
The invention will be described more specifically with the following examples. The present invention is not limited to the following example groups, and can be modified and implemented as appropriate within a range where the gist thereof is not modified.
Example 1
Example 1 provides a composite copper foil, and the method of preparing the composite copper foil comprises the steps of:
s1, forming a copper layer with a thickness of 50nm on the surface of a PET (polyethylene terephthalate) film with a thickness of 4.5 mu m, and forming an extremely thin copper layer with a thickness of 50nm on the surface of the PET film with a thickness of 4.5 mu m by sputtering under the following device and conditions:
-means for: a winding type DC sputtering device;
-a target: a copper target;
reaching vacuum Pu: less than 1X 10 -4 Pa；
-gas: argon (flow: 100 sccm);
-sputtering pressure: 0.45Pa;
sputtering power: 1.0kW (3.1W/cm) 2 )；
S2, electroplating is carried out on the surface of the copper layer to obtain a first copper plating layer with the thickness of 300nm, and the composition of an electroplating solution and electroplating conditions are as follows:
-copper sulphate 200g/L;
-sulfuric acid 90g/L;
thiourea 5mg/L;
10mg/L polyacrylamide;
-40 mg/L chloride;
-current density 50A/dm 2 ；
-liquid temperature 50 ℃;
s3, performing activation treatment on the surface of the first copper plating layer, wherein the activation treatment is performed as follows: immersing in a dilute sulfuric acid solution with a sulfuric acid concentration of 150g/L and a liquid temperature of 30 ℃ for 5 seconds, thereby removing the surface oxide film, washing with water, and drying;
s4, electroplating on the surface of the first copper plating layer to obtain a 650nm second copper plating layer, wherein the composition of an electroplating solution and electroplating conditions are as follows:
-copper sulphate 200g/L;
-sulfuric acid 90g/L;
-6 mg/L of 3-thio-isothiourea propyl sulphonic acid;
-6 mg/L gelatin;
-40 mg/L chloride;
-current density 50A/dm 2 ；
-liquid temperature 50 ℃;
s5, performing rust prevention treatment on the surface of the second copper plating layer by using an aqueous solution containing 3g/L of 1,2, 3-benzotriazole;
s6, forming a carbon layer with the thickness of 50nm on the surface of the second copper plating layer by sputtering under the following device and conditions:
-means for: a winding type DC sputtering device;
-a target: a graphite target;
reaching vacuum Pu: less than 1X 10 -4 Pa；
-gas: argon (flow: 100 sccm) and methane gas (flow: 0-3.0 sccm);
-sputtering pressure: 0.45Pa;
sputtering power: 250W (0.8W/cm) 2 )。
In the case of forming the first copper plating layer and the second copper plating layer by electroplating, a titanium electrode covered with a noble metal oxide is used for the anode.
Example 2
Example 2 provides a composite copper foil, and the preparation method of the composite copper foil differs from the preparation method of the composite copper foil provided in example 1 only in that:
in step S2, the composition of the plating solution and the plating conditions are as follows:
-copper sulphate 300g/L;
130g/L sulfuric acid;
thiourea 10mg/L;
-polyacrylamide 20mg/L;
-40 mg/L chloride;
-current density 70A/dm 2 ；
-liquid temperature 50 ℃;
in step S4, the composition of the plating solution and the plating conditions are as follows:
-copper sulphate 300g/L;
130g/L sulfuric acid;
-10 mg/L of 3-thio-isothiourea propylsulfonic acid;
-gelatin 10mg/L;
-40 mg/L chloride;
-current density 70A/dm 2 ；
-liquid temperature 50 ℃;
in step S5, the second copper plating layer surface is subjected to rust inhibitive treatment using an aqueous solution containing 5g/L of 1,2, 3-benzotriazole.
Example 3
Example 2 provides a composite copper foil, and the preparation method of the composite copper foil differs from the preparation method of the composite copper foil provided in example 1 only in that:
in step S2, the composition of the plating solution and the plating conditions are as follows:
-copper sulphate 250g/L;
120g/L sulfuric acid;
thiourea 8mg/L;
15mg/L polyacrylamide;
-40 mg/L chloride;
-current density 60A/dm 2 ；
-liquid temperature 50 ℃;
in step S4, the composition of the plating solution and the plating conditions are as follows:
-copper sulphate 250g/L;
120g/L sulfuric acid;
-8 mg/L of 3-thio-isothiourea propyl sulphonic acid;
-gelatin 8mg/L;
-40 mg/L chloride;
-current density 60A/dm 2 ；
-liquid temperature 50 ℃.
In step S5, the second copper plating layer surface is subjected to rust inhibitive treatment using an aqueous solution containing 4g/L of 1,2, 3-benzotriazole.
In examples 1 to 3, the chloride ion concentration was adjusted to 40mg/L, but the chloride ion concentration was changed appropriately depending on the electrolysis conditions, and the concentration was not limited to this.
Comparative example 1
Comparative example 1 provided a double-sided photo-electrolytic copper foil for lithium batteries having a thickness of 4.5 μm, which was prepared by the following preparation method:
2000g of 3-mercapto 1-propanesulfonic acid sodium, 20g of polyethylene glycol and 1g of ethylene thiourea are taken and added into 1000L of deionized water for dissolution, so as to obtain a first additive solution;
adding 3000g of gelatin and 200g of hydroxyethyl cellulose into 1000L of deionized water for dissolution to obtain a second additive solution;
taking copper sulfate electrolyte, wherein the copper sulfate content is 250g/L, the sulfuric acid content is 120g/L, the chloride ion content is 40mg/L, the temperature of the copper sulfate electrolyte is 50 ℃, 100mL of first additive solution and 80mL of second additive solution are added into 1000L of copper sulfate electrolyte per hour, and the electrolyte formed by uniform stirring enters an electrolytic tank;
a noble metal oxide-covered titanium electrode was used at the anode and a titanium rotating roller was used at the cathode, the electrolyte having an electrolytic current density of 60A/dm in the electrolytic cell 2 After electrochemical reaction, a double-sided photo-electrolytic copper foil with a thickness of 4.5 μm was produced.
Comparative example 2
Comparative example 1 provides a rolled copper foil for lithium batteries having a thickness of 20. Mu.m, which is obtained by selecting an oxygen-free copper ingot having a brand TU2 as a raw material, and sequentially performing rough rolling, intermediate annealing, intermediate rolling, semi-finished product annealing, finished product rolling, anti-sticking agent application, finished product annealing, finished product cleaning and slitting
Comparative example 3
Comparative example 3 provides a composite copper foil, and the composite copper foil provided in comparative example 3 differs from the composite copper foil provided in example 3 only in that: the composite copper foil provided in comparative example 3 does not include a carbon layer, and the second copper plating layer of the composite copper foil provided in comparative example 3 has a thickness of 700nm.
Comparative example 4
Comparative example 4 provides a composite copper foil, and the composite copper foil provided in comparative example 4 differs from the composite copper foil provided in example 3 only in that: the composite copper foil provided in comparative example 4 did not include the second copper plating layer, and the first copper plating layer of the composite copper foil provided in comparative example 3 had a thickness of 950nm.
Comparative example 5
Comparative example 5 provides a composite copper foil, and the composite copper foil provided in comparative example 5 differs from the composite copper foil provided in example 3 only in that: the composite copper foil provided in comparative example 5 did not include the second copper plating layer and the carbon layer, and the first copper plating layer of the composite copper foil provided in comparative example 3 had a thickness of 1 μm.
Comparative example 6
Comparative example 6 provides a composite copper foil, and the composite copper foil provided in comparative example 6 differs from the composite copper foil provided in example 3 only in that: the composite copper foil provided in comparative example 6 uses a PP (polypropylene) film instead of a PET film, the PP film is a polymer obtained by addition polymerization of propylene, and the density is 0.89-0.91g/cm 3 Inflammable, melting point 189 deg.c, softening at 155 deg.c and use temperature range of-30-140 deg.c.
Comparative example 7
Comparative example 7 provides a composite copper foil, and the preparation method of the composite copper foil provided in comparative example 7 differs from the preparation method of the composite copper foil provided in example 3 only in that:
in step S4, the composition of the plating solution and the plating conditions are as follows:
-copper sulphate 300g/L;
130g/L sulfuric acid;
thiourea 10mg/L;
-polyacrylamide 20mg/L;
-40 mg/L chloride;
-current density 70A/dm 2 ；
-liquid temperature 50 ℃.
Comparative example 8
Comparative example 8 provides a composite copper foil, and the preparation method of the composite copper foil provided in comparative example 8 differs from the preparation method of the composite copper foil provided in example 3 only in that:
in step S2, the composition of the plating solution and the plating conditions are as follows:
-copper sulphate 250g/L;
120g/L sulfuric acid;
-8 mg/L of 3-thio-isothiourea propyl sulphonic acid;
-gelatin 8mg/L;
-40 mg/L chloride;
-current density 60A/dm 2 ；
-liquid temperature 50 ℃.
Comparative example 9
Comparative example 9 provides a composite copper foil, and the preparation method of the composite copper foil provided in comparative example 9 differs from the preparation method of the composite copper foil provided in example 3 only in that:
in step S4, the composition of the plating solution and the plating conditions are as follows:
-copper sulphate 250g/L;
120g/L sulfuric acid;
8mg/L of sodium 3-mercapto-1-propanesulfonate;
-gelatin 8mg/L;
-40 mg/L chloride;
-current density 60A/dm 2 ；
-liquid temperature 50 ℃.
Comparative example 10
Comparative example 10 provides a composite copper foil, and the preparation method of the composite copper foil provided in comparative example 10 differs from the preparation method of the composite copper foil provided in example 3 only in that:
in step S4, the composition of the plating solution and the plating conditions are as follows:
-copper sulphate 250g/L;
120g/L sulfuric acid;
-8 mg/L of 3-thio-isothiourea propyl sulphonic acid;
-hydroxyethylcellulose 8mg/L;
-40 mg/L chloride;
-current density 60A/dm 2 ；
-liquid temperature 50 ℃.
[ lithium ion Secondary Battery production ]
The composite copper foil provided in examples 1 to 3, the electrolytic copper foil provided in comparative example 1, the rolled copper foil provided in comparative example 2, and the composite copper foil provided in comparative examples 3 to 10 were used as negative electrode current collectors, respectively.
As the anode active material particles, silicon powder (purity 99.9%) having an average particle diameter of 15 μm was used, and the anode active material particles, a conductive agent (graphite SFG-6), a binder (polyimide), and an organic solvent (N-methyl-2-pyrrolidone) were mixed at a weight ratio of 15:3:1:1 to prepare an anode coating slurry. Next, the negative electrode coating paste was applied to the negative electrode current collector, and dried to form a negative electrode active layer on both sides of the negative electrode current collector, and the electrode thickness at this time was 85 μm. Then, the negative electrode was produced by rolling with a rolling roller to an electrode thickness of 60 μm and then drying under reduced pressure.
LiCoO having an average particle diameter of 20 μm was used as the positive electrode active material particles 2 And (3) powder. The positive electrode active material particles, a conductive agent (artificial graphite), a binder (polyvinylidene fluoride) and an organic solvent (N-methyl-2-pyrrolidone) are mixed in a weight ratio of 90:5:3:2 mixing them to prepare a positive electrode coating slurry. Next, the positive electrode coating slurry was applied to a positive electrode current collector made of 15 μm aluminum foil, and dried and then rolled to prepare a positive electrode having positive electrode active layers formed on both sides of the positive electrode current collector.
In the production of the nonaqueous electrolytic solution, liPF was caused to occur in a mixed solvent in which ethylene carbonate and ethylene dicarbonate were mixed at a volume ratio of 3:7 6 Dissolving to 1mol/L concentration, and blowing carbon dioxide at 25deg.C for 10min to dissolve carbon dioxide to saturation.
When a lithium ion secondary battery is produced by using the negative electrode, the positive electrode and the nonaqueous electrolyte, a positive electrode collector sheet made of aluminum is attached to the positive electrode, and a negative electrode collector sheet made of nickel is attached to the negative electrode and wound back, so that the positive electrode and the negative electrode face each other with a separator made of a polyethylene porous body interposed therebetween, thereby producing an electrode body. Then, the electrode body is inserted into an exterior body made of an aluminum composite film, the nonaqueous electrolyte is added to the exterior body, and the positive electrode collector tab and the negative electrode collector tab are taken out to the outside, and the opening of the exterior body is sealed.
The charge and discharge characteristics of the above lithium ion secondary batteries at a temperature of 25 ℃ were tested by the following method:
(1) First coulombic efficiency
The lithium ion secondary battery was charged to 4.2V at a current value of 1000mA and then discharged to 2.75V at a current value of 1000mA in an environment of 25 c, and the first coulombic efficiency was calculated.
First coulombic efficiency (%) = [ discharge capacity (mAh/g)/charge capacity (mAh/g) ] x 100
(2) Charge-discharge cycle
After the initial charge and discharge test was performed, the charge and discharge were repeated for 500 cycles at the same current of 1000mA, and the discharge capacity retention rate after the cycle was calculated according to the following formula:
(retention rate of discharge capacity after cycle) = [ discharge capacity after cycle)/(maximum discharge capacity) ] ×100
Test data of charge and discharge characteristics of the lithium ion secondary battery are shown in table 1.
Further, the discharge capacity retention after 100 cycles was calculated according to the following formula.
(retention rate of discharge capacity after cycle) = [ discharge capacity after cycle)/(maximum discharge capacity) ] ×100
The lithium ion secondary batteries after the disassembly cycle were examined for the absence of wrinkles in the negative electrode current collector of each negative electrode, and the results are shown in table 1.
TABLE 1
When the anode active material particles are silicon, the silicon active material absorbs lithium ions during charging and expands its volume about 4 times, and releases lithium ions during discharging and contracts it. Because the volume expansion of the silicon material in the charge and discharge process is larger than that of the carbon material in the charge and discharge process, the phenomenon that the silicon material is peeled off from the negative electrode current collector due to the expansion and contraction of the silicon material volume caused by charge and discharge needs to be avoided, and meanwhile, the phenomenon that the negative electrode current collector generates larger stress and wrinkles due to the expansion and contraction of the silicon material volume caused by charge and discharge needs to be avoided. When the silicon material is peeled off from the negative electrode current collector, a decrease in the discharge capacity retention rate of the lithium ion secondary battery occurs. When the negative electrode current collector is deformed such as creased, a problem that the positive electrode and the negative electrode are easily short-circuited occurs. As can be seen from the results of table 1, the use of the composite copper foil of the example of the present invention as a negative electrode current collector can provide a lithium ion secondary battery which can suppress the occurrence of deformation such as wrinkling due to charge and discharge, prevent the occurrence of short circuit between the positive electrode and the negative electrode of the lithium ion secondary battery, and can maintain a high discharge capacity retention rate even 500 repeated charge and discharge cycles even with the use of the composite copper foil of the example of the present invention as a negative electrode current collector, and has a long life.
In addition, although the example of the present invention describes the case where the active material is silicon, even when an active material containing silicon oxide, carbon, or tin as a main component is used, it is possible to provide a lithium ion secondary battery which can suppress deformation of the negative electrode current collector due to charge and discharge, prevent the occurrence of short circuit between the positive electrode and the negative electrode of the lithium ion secondary battery, does not reduce the capacity even when charge and discharge cycles are repeated, has a long life, and can be miniaturized.
The composite copper foil of the examples of the present invention may also be laminated with a rigid or flexible insulating substrate for use as a printed circuit substrate.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. A composite copper foil is characterized in that,
the composite copper foil includes:
a substrate layer;
a copper layer formed on the surface of the base material layer;
a first copper plating layer formed on a surface of the copper layer;
a second copper plating layer formed on a surface of the first copper plating layer;
a carbon layer formed on the surface of the second copper plating layer;
the thickness of the base material layer is 4-5 mu m, the thickness of the copper layer is 5-100nm, the thickness of the first copper plating layer is 100-400nm, and the thickness of the second copper plating layer is 500-1000nm.
2. The composite copper foil according to claim 1, wherein the total thickness of the second copper plating layer, the first copper plating layer and the copper layer, which are sequentially laminated, is 0.8 to 1 μm.
3. The composite copper foil according to claim 2, wherein the base material layer is a PET film.
4. The method for preparing a composite copper foil according to claim 3, comprising the steps of:
s1, forming the copper layer on the surface of the PET film by a sputtering method;
s2, electroplating is carried out on the surface of the copper layer to obtain the first copper plating layer;
s3, performing activation treatment on the surface of the first copper plating layer;
s4, electroplating is carried out on the surface of the first copper plating layer to obtain the second copper plating layer;
s5, performing rust prevention treatment on the surface of the second copper plating layer;
s6, forming a carbon layer on the surface of the second copper plating layer through gas phase film formation.
5. The method according to claim 4, wherein the plating solution used in the step S2 is obtained by adding an additive a, an additive B and chloride ions to a sulfuric acid-copper sulfate electrolyte; the additive A is more than one additive selected from thiourea or thiourea derivatives; the additive B is selected from thiourea or thiourea derivatives, animal glue, gelatin, polyethylene glycol, polypropylene glycol, starch, cellulose water-soluble polymer, polyethylenimine and polyacrylamide or a combination of more than one of the above.
6. The method according to claim 4, wherein in the step S3, the surface of the first copper plating layer is subjected to an activation treatment using a dilute sulfuric acid solution having a sulfuric acid concentration of 150g/L and a liquid temperature of 30 ℃.
7. The method according to claim 4, wherein the electroplating solution used in the step S4 is prepared by adding 3-sulfur-isothiouronium propyl sulfonic acid, gelatin and chloride ions to a sulfuric acid-copper sulfate electrolyte.
8. The method according to claim 4, wherein in the step S5, the surface of the second copper plating layer is subjected to rust inhibitive treatment using an aqueous solution containing 1,2, 3-benzotriazole.
9. A lithium ion secondary battery comprising a positive electrode and a negative electrode, the negative electrode comprising a negative current collector and negative active layers formed on both sides of the negative current collector, characterized in that the negative current collector comprises the composite copper foil of claim 3.
10. The lithium ion secondary battery according to claim 9, wherein the anode active layer comprises silicon or a silicon compound.
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