CN115198319A - Electrolytic copper foil, electrode comprising electrolytic copper foil and lithium ion battery - Google Patents
Electrolytic copper foil, electrode comprising electrolytic copper foil and lithium ion battery Download PDFInfo
- Publication number
- CN115198319A CN115198319A CN202111533508.4A CN202111533508A CN115198319A CN 115198319 A CN115198319 A CN 115198319A CN 202111533508 A CN202111533508 A CN 202111533508A CN 115198319 A CN115198319 A CN 115198319A
- Authority
- CN
- China
- Prior art keywords
- copper foil
- electrolytic copper
- elongation
- lithium ion
- ion battery
- 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.)
- Granted
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 183
- 239000011889 copper foil Substances 0.000 title claims abstract description 166
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 57
- 238000005096 rolling process Methods 0.000 abstract description 28
- 238000010438 heat treatment Methods 0.000 abstract description 16
- 230000000052 comparative effect Effects 0.000 description 55
- 238000012360 testing method Methods 0.000 description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 17
- 239000010949 copper Substances 0.000 description 17
- 229910052802 copper Inorganic materials 0.000 description 16
- 239000011267 electrode slurry Substances 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 15
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 14
- 238000011282 treatment Methods 0.000 description 14
- 239000011888 foil Substances 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 12
- 230000037303 wrinkles Effects 0.000 description 12
- 238000000151 deposition Methods 0.000 description 10
- 230000008021 deposition Effects 0.000 description 10
- 230000002265 prevention Effects 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000006256 anode slurry Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- -1 polyoxyethylene Polymers 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000010439 graphite Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 239000011149 active material Substances 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000006257 cathode slurry Substances 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910001453 nickel ion Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000000600 sorbitol Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 239000002482 conductive additive Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 3
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 230000003449 preventive effect Effects 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007849 furan resin Substances 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 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
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 229920001197 polyacetylene Polymers 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910013292 LiNiO Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- GPUAPMRPNSQYIR-UHFFFAOYSA-N [Ir+3].[O-2].[O-2].[Ti+4] Chemical compound [Ir+3].[O-2].[O-2].[Ti+4] GPUAPMRPNSQYIR-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000005678 chain carbonates Chemical class 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- CDRCPXYWYPYVPY-UHFFFAOYSA-N iron(2+) oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+2].[Fe+2].[Fe+2] CDRCPXYWYPYVPY-UHFFFAOYSA-N 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- FXNGWBDIVIGISM-UHFFFAOYSA-N methylidynechromium Chemical group [Cr]#[C] FXNGWBDIVIGISM-UHFFFAOYSA-N 0.000 description 1
- 239000011331 needle coke Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 239000006253 pitch coke Substances 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004439 roughness measurement Methods 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
-
- 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
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention provides an electrolytic copper foil, an electrode containing the electrolytic copper foil and a lithium ion battery. The electrodeposited copper foil has opposing first and second surfaces, the maximum height of area (Sz) of each of the two surfaces is independently 1.1 to 3.0 micrometers, the electrodeposited copper foil has an initial elongation, a first elongation (measured after heat treatment at 100 ℃ for 15 minutes) and a second elongation (measured after heat treatment at 120 ℃ for 10 hours), the first elongation is less than the initial elongation, the second elongation is greater than the first elongation, and the second elongation is greater than or equal to 8%. By controlling the Sz of the two surfaces of the electrolytic copper foil, the relative relationship of the elongation rates after different heat treatments and the range of the second elongation rate, the rolling stability of the electrolytic copper foil can be improved, and the service life and the value of a lithium ion battery subsequently applied by the electrolytic copper foil are further improved.
Description
Technical Field
The present invention relates to an electrolytic copper foil, and more particularly, to an electrolytic copper foil for a lithium ion battery, an electrode including the electrolytic copper foil, and a lithium ion battery.
Background
The copper foil has good conductivity and has the advantage of low cost compared with noble metals such as silver and the like, so the copper foil is not only widely applied to basic industry, but also an important raw material of advanced technology industry; for example, copper foil is widely used as an electrode material for lithium ion batteries in the fields of Portable Electronic Devices (PED), electric Vehicles (EV), and the like.
With the demand for miniaturization and light weight of electronic and electric products, the copper foil used in the electronic and electric products is thinned, so that the performance and quality of the copper foil have more remarkable influence on the performance of the electronic and electric products.
For example, a typical lithium ion battery manufacturing process involves coating a copper foil with a negative electrode slurry, rolling the copper foil coated with an active material, and heat-treating the copper foil. If the copper foil cannot bear the influence of external force when being rolled to form a thin foil and has the defect of wrinkle (wrikle) or slurry falling, the copper foil cannot be suitable for the subsequent production and preparation process of the negative electrode; if the copper foil with the defects is still used for manufacturing the lithium ion battery, the active material of the lithium ion battery is easy to damage in the charging and discharging process, so that the service life of the lithium ion battery is greatly reduced.
Disclosure of Invention
In view of the disadvantages of the prior art, it is an object of the present invention to improve the conventional copper foil so that the copper foil has good stability after coating with a paste and rolling.
Another object of the present invention is to improve the conventional copper foil and to improve the product life of a lithium ion battery to be used subsequently.
In order to achieve the above object, the present invention provides an electrolytic copper foil having a first surface and a second surface opposite to each other, wherein the maximum surface height (Sz) of the first surface and the second surface is 1.1 micrometers to 3.0 micrometers; the electrolytic copper foil has an initial elongation measured before the electrolytic copper foil is not heat-treated, a first elongation measured after the electrolytic copper foil is heat-treated at 100 ℃ for 15 minutes, and a second elongation measured after the electrolytic copper foil is heat-treated at 120 ℃ for 10 hours, wherein the first elongation is less than the initial elongation, the second elongation is greater than the first elongation, and the second elongation is greater than or equal to 8%.
According to the invention, by controlling the Sz of the first surface and the second surface of the electrolytic copper foil, the initial elongation, the relationship between the first elongation and the second elongation and the range of the second elongation, the rolling stability of the electrolytic copper foil can be specifically improved, the problem that the electrolytic copper foil is wrinkled or the negative electrode slurry falls off after being rolled can be improved or even avoided, the cycle life of a lithium ion battery applied thereafter is prolonged, and the product value of the lithium ion battery is increased.
It is understood that the first elongation of the electrolytic copper foil measured by the heat treatment at 100 c for 15 minutes and the second elongation of the electrolytic copper foil measured by the heat treatment at 120 c for 10 hours correspond to a general two-stage heat treatment process for manufacturing an electrode for a lithium ion battery, and the ductility of the electrolytic copper foil after the heat treatment is critical to the quality of the electrode for a lithium ion battery to be subsequently applied.
Preferably, the Sz of the first surface and the second surface of the electrolytic copper foil can be 1.15 micrometers to 2.93 micrometers respectively and independently. More preferably, the Sz of the first surface of the electrolytic copper foil may be 1.15 to 2.93 micrometers, and the Sz of the second surface of the electrolytic copper foil may be 2.00 to 2.93 micrometers. Still more preferably, the Sz of the first surface of the electrolytic copper foil may be 1.15 to 2.93 micrometers, and the Sz of the second surface of the electrolytic copper foil may be 2.30 to 2.50 micrometers.
Preferably, the electrolytic copper foil may have an initial elongation of 2.0% to 6.5%. More preferably, the electrolytic copper foil may have an initial elongation of 2.1% to 6.4%. Still more preferably, the electrolytic copper foil may have an initial elongation of 2.1% to 6.2%.
Preferably, the first elongation of the electrolytic copper foil may be 1.5% to 6%. More preferably, the electrolytic copper foil may have a first elongation of 1.6% to 5.9%. Still more preferably, the electrolytic copper foil may have a first elongation of 1.7% to 5.8%.
Specifically, the electrolytic copper foil may have a second elongation of 8% to 15%. Preferably, the second elongation of the electrolytic copper foil may be 10% to 15%. In other embodiments, the electrolytic copper foil may have a second elongation of 8.3% to 14%.
Preferably, the electrolytic copper foil has a second elongation greater than the initial elongation, and a difference between the second elongation and the initial elongation may be 5.8% to 7.1%. More preferably, the difference between the second elongation and the initial elongation may be 5.9% to 7.1%.
According to the present invention, the thickness of the electrolytic copper foil may be 3 to 16 μm, but is not limited thereto. Specifically, the electrolytic copper foil may have a thickness of 4 to 12 micrometers or 6 to 12 micrometers.
The invention also provides an electrode for a lithium ion battery, which comprises the electrolytic copper foil.
The invention also provides a lithium ion battery which comprises the electrode.
According to the invention, the electrolytic copper foil can be used as a negative electrode of a lithium ion battery and can also be used as a positive electrode of the lithium ion battery. The electrolytic copper foil may be suitably used as a current collector (current collector), and at least one layer of active material is coated on one side or both sides of the electrolytic copper foil to manufacture an electrode of a lithium ion battery.
According to the present invention, the active materials may be classified into a positive electrode active material and a negative electrode active material. The negative active material contains a negative active material, and the negative active material can be a carbon-containing substance, a silicon-carbon composite, a metal oxide, a metal alloy or a polymer; carbon-containing substances or silicon-containing substances are preferred, but not limited thereto. Specifically, the carbonaceous material may be mesocarbon graphite Microspheres (MGP), non-graphite carbon (non-graphite carbon), coke (coke), graphite (graphite), glassy carbon (glass carbon), carbon fibers (carbon fiber), activated carbon (activated carbon), carbon black (carbon black), or high polymer calcine, but is not limited thereto; wherein the coke comprises pitch coke, needle coke or petroleum coke; the high polymer calcine is obtained by firing a high polymer such as phenol-formaldehyde resin (phenol-formaldehyde resin) or furan resin (furan resin) at an appropriate temperature so as to be carbonated. The silicon-containing substance has an excellent ability to form an alloy together with lithium ions and an excellent ability to extract lithium ions from the alloy lithium, and an advantage of having a large energy density can be achieved when the silicon-containing substance is used for a lithium ion secondary battery; the silicon-containing substance may be used In combination with cobalt (Co), iron (Fe), tin (Sn), nickel (Ni), copper (Cu), manganese (Mn), zinc (Zn), indium (In), silver (Ag), titanium (Ti), germanium (Ge), bismuth (Bi), antimony (Sb), chromium (Cr), ruthenium (Ru), molybdenum (Mo), or combinations thereof to form an alloy material. The elements of the metal or metal alloy may be selected from the group consisting of: cobalt, iron, tin, nickel, copper, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony, chromium, ruthenium and molybdenum, but are not limited thereto. Examples of the metal oxide are, but not limited to, iron sesquioxide, iron tetraoxide, ruthenium dioxide, molybdenum dioxide, and molybdenum trioxide. Examples of the polymer are polyacetylene (polyacetylene) and polypyrrole (polypyrole), but not limited thereto.
In one embodiment, the active material may be added with auxiliary additives according to the requirement, and the auxiliary additives may be a binder and/or a weak acid agent, but is not limited thereto. Preferably, the binder may be polyvinylidene fluoride (PVDF), styrene-butadiene rubber (SBR), carboxymethyl cellulose (CMC), polyacrylic acid (PAA), polyacrylonitrile (PAN), or polyacrylate (polyacrylate), and the weak acid agent may be oxalic acid, citric acid, lactic acid, acetic acid, or formic acid.
According to the present invention, the lithium ion battery of the present invention may be a lithium cobalt battery (LiCoO) according to the composition of the cathode slurry 2 battery), lithium nickel battery (LiNiO) 2 battery), lithium manganese battery (LiMn) 2 O 4 battery), lithium cobalt nickel battery (LiCo) X Ni 1-X O 2 battery) or lithium iron phosphate battery (LiFePO) 4 battery), and the like, but are not limited thereto.
According to the present invention, the electrolyte may include a solvent, an electrolyte, or an additive added as the case may be. The solvent in the electrolyte includes a non-aqueous solvent such as: cyclic carbonates such as Ethylene Carbonate (EC) and Propylene Carbonate (PC); chain carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC); or sultone, but is not limited thereto; the aforementioned solvents may be used alone or in combination of two or more.
According to the present invention, the lithium ion battery may be a stack type lithium ion battery including a negative electrode and a positive electrode stacked through a separator, or a spiral wound stack type lithium ion battery including a continuous electrode and a separator spirally wound together, but is not limited thereto. The lithium ion battery of the present invention can be applied to notebook personal computers, mobile phones, electric vehicles, energy storage systems, and can be manufactured as, for example, a cylindrical type secondary battery, a square type secondary battery, a pouch type secondary battery, or a button type secondary battery, according to various application products, but is not limited thereto.
Drawings
FIG. 1 is a schematic view showing the production flow of electrolytic copper foils of examples 1 to 16 and comparative examples 1 to 12.
FIG. 2 is a side view of the electrolytic copper foils of examples 1 to 16 and comparative examples 1 to 12.
Detailed Description
Hereinafter, embodiments of electrolytic copper foil will be described with reference to several examples, and several comparative examples will be provided as a control, so that those skilled in the art can easily understand the advantages and effects of the present invention through the contents of the following examples and comparative examples. It is to be understood that the examples set forth herein are presented by way of illustration only of embodiments of the invention and are not intended to limit the scope of the invention, which can be modified or adapted by persons skilled in the art in light of the common general knowledge in order to make or use the teachings of the invention without departing from its spirit.
Electrolytic copper foil
Examples 1 to 16
Examples 1 to 16 were electrolytic copper foils obtained by using the production apparatus shown in FIG. 1 and successively passing through substantially the same electrodeposition step and rust-preventive treatment step.
As shown in FIG. 1, the apparatus for producing an electrolytic copper foil comprises an electrolytic deposition device 10, a rust preventive treatment device 20 and a series of guide rolls. The electrowinning apparatus 10 comprises a cathode drum 11, an insoluble anode plate 12, a copper electrolyte 13 and a feed pipe 14. The cathode roller 11 is a rotatable titanium cathode roller. The insoluble anode plate 12 is an iridium titanium dioxide plate (IrO) 2 coated titanium plate) disposed below cathode drum 11 and substantially surrounding the lower half of cathode drum 11, said insoluble anode plates 12 having an anode surface 121 facing cathode drum 11. Cathode roll 11 and insoluble anode plates 12 are spaced from each other to receive copper electrolyte 13 fed from feed tube 14. The rust preventive treatment device 20 includes a rust preventive treatment tank 21 and two sets of electrode plates 211a and 211b provided therein. The series of guide rollers includes a first guide roller 31, a second guide roller 32, a third guide roller 33, a fourth guide roller 34, a fifth guide roller 35 and a sixth guide roller 36, which can convey the electrodeposited original foil to the rust-proofing device 20 for rust-proofing treatment, remove the excess rust-proofing substance on the surface of the original foil by an air knife 40 after the rust-proofing treatment, and finally wind the original foil on the sixth guide roller 36 to obtain the electrolytic copper foil 50.
The method for producing the electrolytic copper foil 50 of examples 1 to 16 by using the apparatus for producing an electrolytic copper foil shown in FIG. 1 will be collectively described below.
First, a copper electrolytic solution 13 for an electrolytic deposition step is prepared, and in the electrolytic deposition step, a cathode roller 11 is rotated at a constant speed and fixed axis, and a current is applied to the cathode roller 11 and an insoluble anode plate 12, so that copper ions in the copper electrolytic solution 13 are deposited on the surface of the cathode roller 11 to form a raw foil, and then the raw foil is peeled from the cathode roller 11 and guided to a first guide roller 31.
Here, the formulation of the copper electrolyte 13 and the preparation process conditions of the electrolytic deposition are as follows:
I. formulation of copper electrolyte 13:
copper sulfate (CuSO) 4 ·5H 2 O): about 320 grams per liter (g/L) made from copper wire dissolved in 50wt% sulfuric acid;
sulfuric acid: about 110g/L;
chloride ion: about 25ppm;
small molecular weight glue (SV, available from Nippi inc.): about 5.5ppm, molecular weight between 4000 and 7000Da;
sodium 3-mercapto-1-propanesulfonate (sodium 3-mercapto-1-propanesulfonate, MPS, available from HOPAX): about 3ppm;
thiourea (thiourea, available from Panreac quiimica Sau): about 0.01ppm;
polyoxyethylene sorbitol fatty acid ester (polyoxyyethylene sorbent acid ester, tween 20): the contents are shown in the following table 1; and
nickel ion (Ni) 2+ ): the contents are shown in table 1 below.
Preparation process conditions of electrolytic deposition:
temperature of copper electrolyte 13: about 55 ℃; and
current density: about 50 amperes per square decimeter (A/dm) 2 )。
Subsequently, the original foil is transported to the rust prevention device 20 through the first guide roller 31 and the second guide roller 32 for rust prevention treatment, so that the original foil is immersed into the rust prevention treatment tank 21 filled with the chromium rust prevention solution, and then the two sets of pole plates 211a and 211b are transported by the third guide roller 33 for rust prevention treatment, so that the first rust prevention layer and the second rust prevention layer are formed on the two opposite surfaces of the original foil through electrolytic deposition.
The formula of the chromium antirust liquid and the preparation process conditions of the antirust treatment are as follows:
I. the formula of the chromium antirust liquid comprises the following components:
chromic acid (CrO) 3 ): about 1.5g/L.
II, preparation process conditions of rust prevention treatment:
liquid temperature: 25 ℃;
current density: about 0.5A/dm 2 (ii) a And
treatment time: about 2 seconds.
After the above-mentioned conditions are completed, the copper foil subjected to the rust prevention treatment is guided to the fourth guide roller 34, and the excess rust prevention substance on the surface is removed and dried by the air knife 40, and then transferred to the sixth guide roller 36 by the fifth guide roller 35, and wound on the sixth guide roller 36 to obtain the electrolytic copper foil 50.
Examples 1 to 16 differ mainly in the thickness of the obtained electrolytic copper foil, the content of polyoxyethylene sorbitol fatty acid ester in the copper electrolyte, the content of nickel ions, and the roughness of the anode surface; the roughness of the anode surface is the maximum height (Rz) measured according to JIS B0601-1994, and the parameters are shown in Table 1.
Here, the apparatus and conditions selected for measuring Rz of the anode surface are as follows:
I. the measuring instrument is as follows:
portable surface roughness measurement instrument (contact): SJ-410, available from Mitutoyo.
Measurement conditions:
radius of the needle tip: 2 microns;
the needle point angle: 60 degrees;
cutoff length (cut off length, λ c): 0.8 mm; and
evaluation length (evaluation length): 4 mm.
According to the above-mentioned manufacturing method, the electrolytic copper foils of examples 1 to 8 having a thickness of about 6 μm and examples 9 to 16 having a thickness of about 12 μm can be manufactured, respectively. As shown in fig. 2, the electrolytic copper foil 50 of each example comprises a copper layer 51 (corresponding to the original foil not subjected to the rust-preventive treatment step described above), a first rust-preventive layer 52 and a second rust-preventive layer 53, the copper layer 51 comprising a deposition side (deposited side) 511 and a roll side (dry side) 512 on opposite sides, the deposition side 511 being a surface of the original foil facing the insoluble anode plate and the roll side 512 being a surface of the original foil contacting the cathode roll during the electrolytic deposition; a first antirust layer 52 is formed on the deposition surface 511 of the copper layer 51, the first antirust layer 52 has a first surface 521 located on the outermost side, a second antirust layer 53 is formed on the roll surface 512 of the copper layer 51, the second antirust layer 53 has a second surface 531 located on the outermost side, and the first surface 521 and the second surface 531 are both outermost surfaces of the electrolytic copper foil 50 located on opposite sides.
Comparative examples 1 to 12
Comparative examples 1 to 6 as a control of examples 1 to 8 and comparative examples 7 to 12 as a control of examples 9 to 16, which were prepared substantially as in examples 1 to 16, were prepared by varying the thickness of the electrolytic copper foil obtained in each comparative example, the polyoxyethylene sorbitol fatty acid ester content of the copper electrolyte used, the nickel ion content and the Rz of the anode surface, which are shown in Table 1; in addition, the electrolytic copper foils of comparative examples 1 to 6 also had the structure shown in FIG. 2, and the thicknesses thereof were all 6 μm; the electrolytic copper foils of comparative examples 7 to 12 also had the structure shown in FIG. 2, and all had a thickness of 12 μm.
Table 1: thickness of electrolytic copper foils of examples 1 to 16 (E1 to E16) and comparative examples 1 to 12 (C1 to C12), content of polyoxyethylene sorbitol fatty acid ester in copper electrolyte used in preparation process, content of nickel ion, and Rz of anode surface
Test example 1: elongation percentage
This test example used the electrodeposited copper foils of examples 1 to 16 and comparative examples 1 to 12 as test samples, and each of the test samples was analyzed for elongation without heat treatment and after different heat treatments according to the IPC-TM-650 standard method.
Herein, the following instruments and conditions were used to measure the elongation of the sample after the following heat treatment conditions, respectively:
I. and (3) heat treatment conditions:
(i) The initial elongation (EL 0) of the sample to be tested is measured under the analysis conditions without heat treatment at room temperature of 25 ℃;
(ii) Heating the sample to be tested at 100 ℃ for 15 minutes and then returning the temperature to about 25 ℃, and then measuring a first elongation (EL 1) under the analysis conditions;
(iii) The sample to be tested was heated at 100 ℃ for 15 minutes, warmed to about 25 ℃ and then at 120 ℃ for 10 hours, and after warming to about 25 ℃, the second elongation (EL 2) was determined under the analysis conditions described above.
II, a measuring instrument:
AG-I Universal tensile machine, available from Shimadzu Corp.
Measurement conditions:
sample size: a length of about 100 mm and a width of about 12.7 mm;
chuck distance (chuck distance): 50 mm; and
beam speed (crosscut speed): 50 mm/min.
The results of measuring EL0, EL1, EL2 of the electrodeposited copper foils of examples 1 to 8 and comparative examples 1 to 6 are shown in Table 2, and the results of measuring EL0, EL1, EL2 of the electrodeposited copper foils of examples 9 to 16 and comparative examples 7 to 12 are shown in Table 3, depending on the thickness difference of the electrodeposited copper foils. In addition, the present test example separately analyzes the difference (Δ EL) between EL2 and EL0 2-0 ) Relative relationship between EL1 and EL0 (Δ EL) 1-0 ) If EL1 is larger than EL0, it is indicated by "+", and if EL1 is smaller than EL0, it is indicated by "-", and the results are also shown in tables 2 and 3 below.
It was observed in the experiment that the second elongation of the electrodeposited copper foil measured after the heat treatment at 100 ℃ for 15 minutes and then at 120 ℃ for 10 hours was substantially the same as or similar to the elongation of the electrodeposited copper foil measured after the heat treatment at 120 ℃ for 10 hours.
Test example 2: maximum height of face
In this test example, the electrolytic copper foils of examples 1 to 16 and comparative examples 1 to 12 were used as samples to be tested, and the maximum surface heights (Sz) of the first surface and the second surface of each sample to be tested were measured according to the standard method of ISO 25178-2.
Herein, the apparatus and the measurement conditions selected for measuring the Sz of the electrolytic copper foil are as follows:
I. the measuring instrument is as follows:
laser scanning confocal microscope: LEXT OLS5000-SAF, available from Olympus; and
an objective lens: MPLAPON-100xLEXT.
Measurement conditions:
wavelength of light source: 405 nanometers;
magnification of objective lens: 100 times of the total weight of the powder;
optical zooming: 1.0 time;
observation area: 129 microns by 129 microns;
resolution ratio: 1024 pixels × 1024 pixels;
mode (2): removing auto tilt (auto tilt remove);
a filter lens: no filter;
temperature: 24 +/-3 ℃; and
relative humidity: 63 +/-3 percent.
Electrodes
Examples 1A to 16A, comparative examples 1A to 12A
The first and second surfaces of the electrodeposited copper foils of the foregoing examples 1 to 16 and comparative examples 1 to 12 may be coated with negative electrode slurry containing a negative electrode active material, respectively, to prepare negative electrodes for lithium ion batteries. Specifically, the negative electrode can be substantially prepared by the steps described below.
First, a negative electrode slurry was prepared, the composition of which is as follows:
mesogenic graphite carbon Microspheres (MGP): 93.9 parts by weight as a negative electrode active material;
conductive carbon black (Super P): 1 part by weight as a conductive additive;
polyvinylidene fluoride (PVDF 6020): 5 parts by weight of a solvent binder;
oxalic acid: 0.1 part by weight; and
n-methylpyrrolidone (NMP): 60 parts by weight.
Then, respectively coating the negative electrode slurry on the first surface and the second surface of the electrolytic copper foil, wherein the coating thickness of the negative electrode slurry is about 200 microns, and heating the negative electrode slurry in an oven at 100 ℃ for 15 minutes to remove water preliminarily; rolling with a roller to obtain rolled electrolytic copper foil (density up to 1.5 g/cubic centimeter (g/cm) 3 ) ); the rolled electrolytic copper foil was then heated at 120 ℃ for 10 hours to completely remove water, to obtain examples 1A to 16A and comparative example 1A and 12A.
Here, the coating conditions and rolling conditions set when the negative electrode was manufactured were as follows:
I. coating conditions are as follows:
coating rate: 5m/min; and
coating thickness: each side is about 200 μm.
II, rolling conditions:
rolling speed: 1m/min;
rolling pressure: 3000 pounds per square inch (psi);
roll size of the roll mill: 250mm (the outer diameter,
) X 250mm (width);
hardness of the roller: 62 to 65HRC; and
roller material: high carbon chromium bearing steel (SUJ 2).
Test example 3: stability of rolling
In order to evaluate whether the electrolytic copper foil has expected rolling stability when used for manufacturing a negative electrode, the test uses the negative electrodes of examples 1A to 16A and comparative examples 1A to 12A as samples to be tested, and the samples to be tested are visually observed to see whether wrinkles or the negative electrode slurry falls off on the surface of the samples to be tested (the rolled electrolytic copper foil). If the sample to be detected is observed to be wrinkled or the cathode slurry falls off, evaluating as X, and displaying that the rolling stability of the sample to be detected is poor; if the sample to be tested has no wrinkles or no cathode slurry falls off, the sample to be tested is evaluated as "O", and the result shows that the sample to be tested can have the expected rolling stability, and the results are shown in tables 2 and 3.
As can be seen from the test results of the electrodeposited copper foils with the thickness of 6 μm in table 2 below, the electrodeposited copper foils of comparative examples 2 to 6 were observed to have wrinkles or a negative electrode slurry falling off after the rolling test, and the rolling stability was poor, indicating that the electrodeposited copper foils of comparative examples 2 to 6 could not be manufactured into negative electrodes for lithium ion batteries (comparative examples 2A to 6A). As can be seen from the test results of the electrodeposited copper foils with a thickness of 12 μm in table 3 below, the electrodeposited copper foils of comparative examples 8 to 12 were also observed to have wrinkles or fall off of the negative electrode slurry after the roll press test, and the roll press stability was poor, indicating that the electrodeposited copper foils of comparative examples 8 to 12 are also not suitable for use in the manufacture of negative electrodes for lithium ion batteries (comparative examples 8A to 12A).
Lithium ion battery
The cathode can be further matched with an anode to prepare a lithium ion battery. As described above, since the electrodeposited copper foils of comparative examples 2 to 6 and 8 to 12 cannot have desired roll stability and cannot be applied to the negative electrode for the lithium ion battery, only examples 1A to 16A and comparative examples 1A and 7A were combined with the same type of positive electrode to fabricate lithium ion batteries of examples 1B to 16B and comparative examples 1B and 7B. For convenience of explanation, the manufacturing process of the lithium ion battery using the negative electrode is described in the following.
First, a positive electrode slurry was prepared, the composition of which is as follows:
lithium cobalt oxide (LiCoO) 2 ): 89 parts by weight of a positive electrode active material;
flake graphite (KS 6): 5 parts by weight of a conductive additive;
conductive carbon black (Super P): 1 part by weight as a conductive additive;
polyvinylidene fluoride (PVDF 1300): 5 parts by weight of a solvent binder; and
n-methylpyrrolidone (NMP): 195 parts by weight.
Then, the positive electrode slurry was coated on both surfaces of an aluminum foil, after the solvent was volatilized, the positive electrodes and the negative electrodes of the examples and comparative examples were cut to a specific size, and a microporous separator (model: celgard 2400, manufactured by Celgard corporation) was alternately stacked between the positive electrodes and the negative electrodes, and placed in a pressing mold (model: LBC322-01H, available from new aegaku technologies ltd) filled with an electrolyte, and sealed to obtain a laminated lithium ion battery (size 41 mm × 34 mm × 53 mm).
Test example 4: charge and discharge cycle life
In this test example, the lithium ion batteries of examples 1B to 16B and comparative examples 1B and 7B were used as samples to be tested, and the number of charge and discharge cycles until the capacitance was reduced to 80% of the initial capacitance was recorded through a series of charge and discharge cycles under the following test conditions, and the charge and discharge cycles were defined as the charge and discharge cycle life of the samples to be tested, and the results are shown in tables 2 and 3.
Here, the conditions of the charge-discharge cycle test were as follows:
a charging mode: constant current-constant voltage (CCCV);
a discharging mode: a Constant Current (CC);
charging voltage: 4.2 volts (V);
charging current: 5C;
discharge voltage: 2.8V:
discharge current: 5C;
measuring the temperature: about 55 deg.c.
As can be seen from the above description, the lithium ion batteries of examples 1B to 16B and comparative examples 1B and 7B differ only in the electrolytic copper foil used for the negative electrode thereof, and thus the charge and discharge cycle life of the lithium ion battery is mainly attributed to the characteristics of the electrolytic copper foil.
Table 2: EL0, EL1, EL2,. DELTA.EL of examples 1 to 8 (E1 to E8) and comparative examples 1 to 6 (C1 to C6) 1-0 、ΔEL 2-0 Sz of the first surface, sz of the second surface, rolling stability, and the number of charge and discharge cycles of the lithium ion battery manufactured by using the electrolytic copper foil
As shown in table 2 above, the first surface and the second surface of the electrolytic copper foil of examples 1 to 8 both have a proper Sz (both falling within the range of 1.1 micron to 3.0 microns), and the first elongation of the electrolytic copper foil is smaller than the initial elongation, the second elongation is greater than the first elongation, and the second elongation of the electrolytic copper foil is greater than or equal to 8%, so that the electrolytic copper foil can obtain good roll stability, and particularly, the problem that the electrolytic copper foil is wrinkled or the negative electrode slurry falls off after roll pressing is avoided, and thus, the lithium ion battery manufactured by using the electrolytic copper foil has an excellent cycle life, and the number of charge and discharge cycles can reach more than 800.
In a contrary view of the electrodeposited copper foils of comparative examples 1 to 6, since the electrodeposited copper foils fail to simultaneously have three characteristics of (1) the Sz of the first surface and the Sz of the second surface being in an appropriate range, (2) the first elongation being less than the initial elongation, the second elongation being greater than the first elongation, and (3) the second elongation being greater than or equal to 8%, the electrodeposited copper foils of comparative examples 2 to 6 have a problem of wrinkles or falling of the negative electrode slurry after rolling, which is not favorable for subsequent application to a lithium ion battery, while comparative example 1 can be made into a lithium ion battery, but the number of charge and discharge cycles thereof is only 756 times, which still needs to be improved.
Further elaboration of the test results of the electrolytic copper foils of comparative examples 1 to 6 revealed that the electrolytic copper foil of comparative example 1 had a second elongation of less than 8%, and that the number of charge and discharge cycles of the electrolytic copper foil applied to a lithium ion battery was only 756 times; the first elongation of the electrolytic copper foil of comparative example 2 is greater than the initial elongation, so the electrolytic copper foil is likely to wrinkle after rolling, which causes the anode slurry to easily fall off when coated on the electrolytic copper foil, the Sz of the first surface of the electrolytic copper foil of comparative examples 3 and 5 exceeds 3.0 micrometers, which causes the electrolytic copper foil of comparative examples 3 and 5 to also easily wrinkle after rolling, and the anode slurry is likely to fall off when coated on the electrolytic copper foil, while the Sz of the first surface of the electrolytic copper foil of comparative examples 4 and 6 is less than 1.1 micrometers, which causes the problem that the adhesion between the electrolytic copper foil of comparative examples 4 and 6 and the anode slurry is not good and the anode slurry falls off, so the electrolysis of comparative examples 2 to 6 cannot have the desired rolling stability, and is difficult to be applied to the manufacture of lithium ion batteries.
As shown in table 2 above, the electrolytic copper foils of examples 3 and 4 both had a second elongation of more than 10%, and the number of charge and discharge cycles of the lithium ion battery was more than 1000, which resulted in a more excellent cycle life.
Table 3: EL0, EL1, EL2,. DELTA.EL- 1-0 、ΔEL 2-0 Sz of the first surface, sz of the second surface, rolling stability, and the number of charge and discharge cycles of the lithium ion battery manufactured by using the electrolytic copper foil
As shown in table 3 above, the first surface and the second surface of the electrolytic copper foil in examples 9 to 16 both have a proper Sz (both falling within the range of 1.1 micron to 3.0 microns), and the first elongation of the electrolytic copper foil is smaller than the initial elongation, and the second elongation of the electrolytic copper foil is greater than or equal to 8%, so that the electrolytic copper foil can obtain good rolling stability, and specifically, the problem that the electrolytic copper foil is wrinkled after rolling or the negative electrode slurry falls off is avoided, and thus, the lithium ion battery prepared by using the electrolytic copper foil can have an excellent cycle life, and the number of charge and discharge cycles can reach more than 800.
In contrast to the electrolytic copper foils of comparative examples 7 to 12, the electrolytic copper foils of comparative examples 8 to 12 have no characteristics of (1) the Sz of the first surface and the Sz of the second surface being in a proper range, (2) the first elongation being less than the initial elongation, and (3) the second elongation being greater than or equal to 8%, so that the electrolytic copper foils of comparative examples 8 to 12 have wrinkles or a problem of falling-off of the negative paste after rolling, which is not favorable for subsequent application to a lithium ion battery, while comparative example 7 can be used to manufacture a lithium ion battery, but the number of charge and discharge cycles is 766, and still needs to be improved.
As can be seen from further detailed test results of the electrolytic copper foils of comparative examples 7 to 12, the electrolytic copper foil of comparative example 7 has a second elongation of less than 8%, and the number of charge and discharge cycles of the electrolytic copper foil applied to a lithium ion battery is 766 times; the first elongation of the electrolytic copper foil of comparative example 8 is greater than the initial elongation, so the electrolytic copper foil is likely to wrinkle after rolling, which causes the anode slurry to easily fall off when coated on the electrolytic copper foil, the Sz of the first surface of the electrolytic copper foil of comparative examples 9 and 11 exceeds 3.0 μm, which causes the electrolytic copper foil of comparative examples 9 and 11 to easily wrinkle after rolling, and the anode slurry is likely to fall off when coated on the electrolytic copper foil, while the Sz of the first surface of the electrolytic copper foil of comparative examples 10 and 12 is less than 1.1 μm, which causes the problem that the adhesion between the electrolytic copper foil of comparative examples 10 and 12 and the anode slurry is not good and the anode slurry falls off, so that the electrolysis of comparative examples 8 to 12 cannot have the desired rolling stability, and is difficult to be applied to the manufacture of lithium ion batteries.
As shown in table 3 above, the electrolytic copper foils of examples 9 to 16 all had a second elongation of more than 10%, so that the lithium ion batteries had more than 1000 charge/discharge cycles and more excellent cycle life.
In summary, the invention can specifically avoid the phenomenon of wrinkle or cathode slurry shedding of the electrolytic copper foil in the rolling process by regulating the Sz, the initial elongation, the relationship between the first elongation and the second elongation, and the range of the second elongation of the first surface and the second surface of the electrolytic copper foil, and improve the cycle life of the lithium ion battery applied thereafter.
Claims (10)
1. An electrolytic copper foil having opposing first and second surfaces, wherein the first and second surfaces have a face maximum height Sz each independently of the other of from 1.1 to 3.0 microns; the electrolytic copper foil has an initial elongation measured before the electrolytic copper foil is not heat-treated, a first elongation measured after the electrolytic copper foil is heat-treated at 100 ℃ for 15 minutes, and a second elongation measured after the electrolytic copper foil is heat-treated at 120 ℃ for 10 hours, wherein the first elongation is less than the initial elongation, the second elongation is greater than the first elongation, and the second elongation is greater than or equal to 8%.
2. The electrolytic copper foil of claim 1, wherein the Sz of the first surface and the second surface are each independently 1.15 to 2.93 microns.
3. The electrolytic copper foil of claim 2, wherein the first surface has an Sz of 1.15 to 2.93 micrometers and the second surface has an Sz of 2.00 to 2.93 micrometers.
4. The electrolytic copper foil of claim 1, wherein the electrolytic copper foil has an initial elongation of 2 to 6.5%.
5. The electrolytic copper foil of claim 1, wherein the first elongation of the electrolytic copper foil is 1.5% to 6%.
6. The electrolytic copper foil of any one of claims 1 to 5, wherein the second elongation of the electrolytic copper foil is 8% to 15%.
7. The electrolytic copper foil of claim 6, wherein the second elongation of the electrolytic copper foil is 10% to 15%.
8. The electrolytic copper foil of any one of claims 1 to 5, wherein the second elongation of the electrolytic copper foil is greater than the initial elongation, and a difference between the second elongation and the initial elongation is 5.8% to 7.1%.
9. An electrode for a lithium ion battery, characterized in that the electrode comprises the electrolytic copper foil according to any one of claims 1 to 8.
10. A lithium ion battery comprising the electrode of claim 9.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111533508.4A CN115198319B (en) | 2021-12-15 | 2021-12-15 | Electrolytic copper foil, electrode comprising same and lithium ion battery |
| KR1020210189354A KR102435606B1 (en) | 2021-12-15 | 2021-12-28 | Electrolytic copper foil, electrode and lithium ion battery comprising the same |
| JP2022001084A JP7153148B1 (en) | 2021-12-15 | 2022-01-06 | Electrolytic copper foil, electrode, and lithium ion battery comprising the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111533508.4A CN115198319B (en) | 2021-12-15 | 2021-12-15 | Electrolytic copper foil, electrode comprising same and lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115198319A true CN115198319A (en) | 2022-10-18 |
| CN115198319B CN115198319B (en) | 2023-11-17 |
Family
ID=83574295
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111533508.4A Active CN115198319B (en) | 2021-12-15 | 2021-12-15 | Electrolytic copper foil, electrode comprising same and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115198319B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106086945A (en) * | 2016-06-22 | 2016-11-09 | 安徽铜冠铜箔有限公司 | The preparation method of a kind of ultra-thin type double face photoelectron Copper Foil and prepared Copper Foil |
| CN106340668A (en) * | 2015-07-06 | 2017-01-18 | 古河电气工业株式会社 | Electrolytic copper foil, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
| CN108505076A (en) * | 2017-02-24 | 2018-09-07 | 南亚塑胶工业股份有限公司 | Electrolytic solution, electrolytic copper foil and method for producing same |
| US20180288884A1 (en) * | 2017-03-31 | 2018-10-04 | Jx Nippon Mining & Metals Corporation | Surface Treated Copper Foil, Surface Treated Copper Foil With Resin Layer, Copper Foil With Carrier, Laminate, Method For Manufacturing Printed Wiring Board, Heat Dissipation Substrate, And Method For Manufacturing Electronic Device |
| WO2018207786A1 (en) * | 2017-05-09 | 2018-11-15 | Ｊｘ金属株式会社 | Electrolytic copper foil, copper-clad laminate, printed wiring board, production method therefor, electronic device, and production method therefor |
| JP2020026563A (en) * | 2018-08-16 | 2020-02-20 | ケイシーエフ テクノロジース カンパニー リミテッド | Copper foil having minimized sag, wrinkle, and tear, electrode comprising the same, secondary battery comprising the same, and manufacturing method therefor |
| KR102132695B1 (en) * | 2019-03-21 | 2020-07-10 | 케이씨에프테크놀로지스 주식회사 | Electrolytic Copper Foil Capable of Improving Capacity Retention Rate of Secondary Battery, Electrode Comprising The Same, Secondary Battery Comprising The Same, and Method for Manufacturing The Same |
| CN112447980A (en) * | 2019-08-27 | 2021-03-05 | 长春石油化学股份有限公司 | Electrolytic copper foil, electrode comprising same and lithium ion battery |
| CN112864397A (en) * | 2019-11-27 | 2021-05-28 | 长春石油化学股份有限公司 | Electrolytic copper foil, electrode and lithium ion battery comprising same |
| CN113161554A (en) * | 2020-01-22 | 2021-07-23 | 长春石油化学股份有限公司 | Electrolytic copper foil, electrode and lithium ion battery comprising same |
-
2021
- 2021-12-15 CN CN202111533508.4A patent/CN115198319B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106340668A (en) * | 2015-07-06 | 2017-01-18 | 古河电气工业株式会社 | Electrolytic copper foil, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
| CN106086945A (en) * | 2016-06-22 | 2016-11-09 | 安徽铜冠铜箔有限公司 | The preparation method of a kind of ultra-thin type double face photoelectron Copper Foil and prepared Copper Foil |
| CN108505076A (en) * | 2017-02-24 | 2018-09-07 | 南亚塑胶工业股份有限公司 | Electrolytic solution, electrolytic copper foil and method for producing same |
| US20180288884A1 (en) * | 2017-03-31 | 2018-10-04 | Jx Nippon Mining & Metals Corporation | Surface Treated Copper Foil, Surface Treated Copper Foil With Resin Layer, Copper Foil With Carrier, Laminate, Method For Manufacturing Printed Wiring Board, Heat Dissipation Substrate, And Method For Manufacturing Electronic Device |
| WO2018207786A1 (en) * | 2017-05-09 | 2018-11-15 | Ｊｘ金属株式会社 | Electrolytic copper foil, copper-clad laminate, printed wiring board, production method therefor, electronic device, and production method therefor |
| JP2020026563A (en) * | 2018-08-16 | 2020-02-20 | ケイシーエフ テクノロジース カンパニー リミテッド | Copper foil having minimized sag, wrinkle, and tear, electrode comprising the same, secondary battery comprising the same, and manufacturing method therefor |
| KR102132695B1 (en) * | 2019-03-21 | 2020-07-10 | 케이씨에프테크놀로지스 주식회사 | Electrolytic Copper Foil Capable of Improving Capacity Retention Rate of Secondary Battery, Electrode Comprising The Same, Secondary Battery Comprising The Same, and Method for Manufacturing The Same |
| CN112447980A (en) * | 2019-08-27 | 2021-03-05 | 长春石油化学股份有限公司 | Electrolytic copper foil, electrode comprising same and lithium ion battery |
| CN112864397A (en) * | 2019-11-27 | 2021-05-28 | 长春石油化学股份有限公司 | Electrolytic copper foil, electrode and lithium ion battery comprising same |
| CN113161554A (en) * | 2020-01-22 | 2021-07-23 | 长春石油化学股份有限公司 | Electrolytic copper foil, electrode and lithium ion battery comprising same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115198319B (en) | 2023-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111801444B (en) | Electrolytic copper foil, electrode and lithium ion secondary battery comprising same | |
| TWI466367B (en) | A lithium ion secondary battery, an electrode for the secondary battery, an electrode for an electrolytic copper foil | |
| TWI532235B (en) | Copper covered steel foil, negative electrode, method for manufacturing negative electrode power collection body, and battery | |
| CN112864397B (en) | Electrolytic copper foil, electrode and lithium ion battery comprising same | |
| US10122021B2 (en) | Electrolytic copper foil, and collector, negative electrode, and lithium battery comprising same | |
| US11962014B2 (en) | Copper foil for current collector of lithium secondary battery | |
| US20170141404A1 (en) | Electrolytic copper foil, and collector, negative electrode, and lithium battery comprising same | |
| CN112447980B (en) | Electrolytic copper foil, electrode comprising same and lithium ion battery | |
| KR102244477B1 (en) | Electrolytic copper foil and electrode and lithium-ion cell comprising the same | |
| US10418636B2 (en) | Current-collector metal foil, current collector, and current-collector-metal-foil manufacturing method | |
| KR102435606B1 (en) | Electrolytic copper foil, electrode and lithium ion battery comprising the same | |
| CN111279019B (en) | Electrolytic copper foil, method for producing the electrolytic copper foil, and anode for high-capacity lithium secondary battery comprising the electrolytic copper foil | |
| CN115198319B (en) | Electrolytic copper foil, electrode comprising same and lithium ion battery | |
| TWI773613B (en) | Electrolytic copper foil, electrode and lithium ion battery comprising the same | |
| TWI830347B (en) | Electrolytic copper foil, electrode and lithium ion battery comprising the same | |
| EP4299795A1 (en) | Electrolytic copper foil and electrode and lithium-ion cell comprising the same | |
| JP7377326B1 (en) | Electrolytic copper foil and electrodes and lithium-ion batteries using them | |
| US20230420640A1 (en) | Electrolytic copper foil and electrode and lithium-ion cell comprising the same | |
| CN117344357A (en) | Electrolytic copper foil, electrode comprising same and lithium ion battery | |
| CN117344356A (en) | Electrolytic copper foil, electrode comprising same and lithium ion battery | |
| TW202400846A (en) | Electrolytic copper foil, electrode and lithium ion battery comprising the same |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |