CN111254464A - Preparation method of ultrathin electrolytic copper foil for high-tensile-strength lithium ion battery - Google Patents
Preparation method of ultrathin electrolytic copper foil for high-tensile-strength lithium ion battery Download PDFInfo
- Publication number
- CN111254464A CN111254464A CN202010053840.XA CN202010053840A CN111254464A CN 111254464 A CN111254464 A CN 111254464A CN 202010053840 A CN202010053840 A CN 202010053840A CN 111254464 A CN111254464 A CN 111254464A
- Authority
- CN
- China
- Prior art keywords
- copper foil
- electrolyte
- compound
- electrolytic copper
- lithium ion
- Prior art date
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- Granted
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000011889 copper foil Substances 0.000 title claims abstract description 77
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- 239000003792 electrolyte Substances 0.000 claims abstract description 36
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 31
- 239000011593 sulfur Substances 0.000 claims abstract description 31
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 29
- 239000002000 Electrolyte additive Substances 0.000 claims abstract description 15
- 125000001309 chloro group Chemical class Cl* 0.000 claims abstract 2
- -1 disulfide compound Chemical class 0.000 claims description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 32
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 24
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 24
- 150000001412 amines Chemical group 0.000 claims description 19
- 239000004094 surface-active agent Substances 0.000 claims description 17
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 14
- 229920000570 polyether Polymers 0.000 claims description 14
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 12
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- FKHLBAOXRDYSRQ-UHFFFAOYSA-M sodium;4-(2-acetamidoethyldisulfanyl)butane-1-sulfinate Chemical compound [Na+].CC(=O)NCCSSCCCCS([O-])=O FKHLBAOXRDYSRQ-UHFFFAOYSA-M 0.000 claims description 11
- 150000003841 chloride salts Chemical class 0.000 claims description 9
- 238000003487 electrochemical reaction Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 6
- OCVLSHAVSIYKLI-UHFFFAOYSA-N 3h-1,3-thiazole-2-thione Chemical compound SC1=NC=CS1 OCVLSHAVSIYKLI-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229960001385 thiamine disulfide Drugs 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- ALYDDXONYRLFSU-UHFFFAOYSA-N ethene;thiourea Chemical compound C=C.NC(N)=S ALYDDXONYRLFSU-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 23
- 230000000694 effects Effects 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 238000007747 plating Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 230000002829 reductive effect Effects 0.000 description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical group [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 9
- 229910001431 copper ion Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- 150000001804 chlorine Chemical class 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- AXFZADXWLMXITO-UHFFFAOYSA-N N-acetylcysteamine Chemical compound CC(=O)NCCS AXFZADXWLMXITO-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000004070 electrodeposition Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- QGRBLDWNIGDYOW-UHFFFAOYSA-N dithiane 1,1-dioxide Chemical compound O=S1(=O)CCCCS1 QGRBLDWNIGDYOW-UHFFFAOYSA-N 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 239000003093 cationic surfactant Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000002563 ionic surfactant Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000009965 odorless effect Effects 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 150000002898 organic sulfur compounds Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000007794 irritation Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- WGJCBBASTRWVJL-UHFFFAOYSA-N 1,3-thiazolidine-2-thione Chemical compound SC1=NCCS1 WGJCBBASTRWVJL-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 206010012735 Diarrhoea Diseases 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 206010018910 Haemolysis Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229920002556 Polyethylene Glycol 300 Polymers 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019658 bitter taste Nutrition 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- WIYCQLLGDNXIBA-UHFFFAOYSA-L disodium;3-(3-sulfonatopropyldisulfanyl)propane-1-sulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)CCCSSCCCS([O-])(=O)=O WIYCQLLGDNXIBA-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000008588 hemolysis Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000028161 membrane depolarization Effects 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- GFEGEDUIIYDMOX-BMJUYKDLSA-N n-[(4-amino-2-methylpyrimidin-5-yl)methyl]-n-[(z)-3-[[(z)-2-[(4-amino-2-methylpyrimidin-5-yl)methyl-formylamino]-5-hydroxypent-2-en-3-yl]disulfanyl]-5-hydroxypent-2-en-2-yl]formamide Chemical compound C=1N=C(C)N=C(N)C=1CN(C=O)C(\C)=C(CCO)/SSC(/CCO)=C(/C)N(C=O)CC1=CN=C(C)N=C1N GFEGEDUIIYDMOX-BMJUYKDLSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000007785 strong electrolyte Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000626 sulfinic acid group Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- 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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Conductive Materials (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention relates to the field of copper foil, in particular to a preparation method of an ultrathin electrolytic copper foil for a high-tensile-strength lithium ion battery. The invention provides an electrolyte additive of an ultrathin electrolytic copper foil for a high-tensile-strength lithium ion battery, which comprises 0.15-0.9 g/L of sulfur-containing compound, 0.07-0.4 g/L of carrier, 0.01-0.27 g/L of nonionic surfactant and 0.07-0.4 g/L of chlorine salt. The extra-thin electrolytic copper foil for the high-tensile strength lithium ion battery has few electrolyte additives, so that the stability of the electrolyte is improved; meanwhile, the weight per unit area of the ultrathin copper foil prepared by using the electrolyte with the specific proportion obtained by the invention is 43.0-75.0 g/m2The unit area weight range is less than 1.0g/m2The thickness is uniform,has high tensile strength and high elongation.
Description
Technical Field
The invention relates to the field of copper foil, in particular to a preparation method of an ultrathin electrolytic copper foil for a high-tensile-strength lithium ion battery.
Background
The copper foil is used as a current collector of the negative electrode of the lithium ion battery, is a core raw material for manufacturing the lithium ion battery, accounts for about 5 percent of the total cost of the battery, and the development of the production technology and the quality of the performance directly influence the manufacturing process, the performance and the production cost of the lithium ion battery. With the rapid development of smart phones and new energy automobiles in recent years, the demand for lithium ion batteries is suddenly increased, and higher requirements are put forward on the performance and the quality of the lithium ion batteries. In the initial stage of production and development of lithium batteries, battery manufacturers all select rolled copper foil to manufacture a battery negative current collector. As the performance of the electrolytic copper foil is improved, the electrolytic copper foil is gradually used as a current collector of a lithium battery. Compared with the copper foil for the traditional Printed Circuit Board (PCB), the copper foil for the lithium battery has the advantages of thinner thickness, low roughness, higher tensile strength, high elongation, good conductivity, oxidation resistance, folding resistance, corrosion resistance and the like.
The general technical level of the electrolytic copper foil for lithium batteries produced by copper foil enterprises in China is still different from that of Japan and Korea, and although the total production amount of the copper foil is improved compared with the prior art, the grade of the electrolytic copper foil still needs to be improved, especially the product quality of high-grade electrolytic copper foil with high added value (such as the electrolytic copper foil for lithium batteries). Therefore, it is a trend in China to independently develop electrolytic copper foils for lithium ions.
At present, the development of the electrolytic copper foil has certain problems. When the electrolytic copper foil is used as a negative current collector of a lithium ion battery, on one hand, the electrolytic copper foil is required to have high tensile strength so as to be difficult to break when a negative active material is coated, and on the other hand, the electrolytic copper foil is required to have good extensibility so as to be fully contacted with the negative active material, reduce the internal resistance of the battery and improve the safety and the electric capacity of the battery; when the ultrathin copper foil is prepared, the requirement on the precision of a production process is very high, the ultrathin copper foil with excellent quality needs to be continuously prepared in high current density, high electrolysis temperature and short electrolysis time, and in the prior art, due to the fact that various additives are used, components influence each other under strict electrolysis conditions, the electrolyte performance is unstable, the ultrathin copper foil with uniform thickness cannot be prepared, or the quality of the copper foil cannot meet the use requirement of a lithium battery under the ultrathin thickness.
Disclosure of Invention
In view of some problems in the prior art, the invention provides an electrolyte additive of an extra-thin electrolytic copper foil for a high tensile strength lithium ion battery, which comprises 0.15-0.9 g/L of a sulfur-containing compound, 0.07-0.4 g/L of a carrier, 0.01-0.27 g/L of a non-ionic surfactant and 0.07-0.4 g/L of a chloride salt.
In a preferred embodiment of the present invention, the sulfur-containing compound is a disulfide compound and/or a trisulfide compound.
As a preferred embodiment of the present invention, the sulfur compound includes a disulfide compound; the disulfide compound comprises at least one of thiazolidinethione, sodium polydithio-dipropanesulfonate, sodium 4- [ [2- (acetamido) ethyl ] dithio ] -1-butanesulfinate, thiamine disulfide compound, 2-substituted hydrazono-1, 3-dithiolane, ethylene thiourea and 2-mercaptobenzimidazole.
In a preferred embodiment of the present invention, the nonionic surfactant is an amine-containing polyether surfactant.
In a preferred embodiment of the present invention, the amine-containing polyether surfactant is fatty amine polyoxyethylene ether.
According to a preferable technical scheme of the invention, the weight ratio of the sulfur-containing compound to the nonionic surfactant to the chloride salt is (3-4): 1: (1-2).
As a preferred technical solution of the present invention, the carrier is a polyether compound; the polyether compound comprises at least one of polyethylene glycol, an oxyethylene-oxypropyl copolymer and fatty alcohol-polyoxyethylene ether.
The invention provides an electrolyte of an ultrathin electrolytic copper foil for a high-tensile strength lithium ion battery.
As a preferable technical scheme of the invention, the electrolyte also comprises 180-250 g/L copper sulfate and 100-150 g/L sulfuric acid.
The third aspect of the invention provides a preparation method of an ultrathin electrolytic copper foil for a high-tensile strength lithium ion battery, which is characterized by comprising the following steps of:
(1) preparing an electrolyte: heating the electrolyte raw material to 45-60 ℃, uniformly mixing, and placing in an anode tank;
(2) electrochemical reaction: electrifying at a current density of 50-80A/dm2Under the condition, copper foil is separated out from the cathode and stripped to obtain the copper-clad laminate; the weight per unit area of the obtained electrolytic copper foil is 43.0 to 75.0g/m2The tensile strength is 400 to 480N/mm2Is extended byThe ratio is 3.5 to 8.5%.
Compared with the prior art, the invention has the following beneficial effects:
the extra-thin electrolytic copper foil for the high-tensile strength lithium ion battery has few electrolyte additives, so that the stability of the electrolyte is improved; meanwhile, the ultrathin copper foil prepared by using the electrolyte with the specific proportion obtained by the invention has uniform thickness, high tensile strength and high elongation.
Detailed Description
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
The invention provides an electrolyte additive of an ultrathin electrolytic copper foil for a high-tensile-strength lithium ion battery, which comprises 0.15-0.9 g/L of sulfur-containing compound, 0.07-0.4 g/L of carrier, 0.01-0.27 g/L of nonionic surfactant and 0.07-0.4 g/L of chlorine salt.
In one embodiment, the electrolyte additive comprises 0.3-0.8 g/L of sulfur-containing compound, 0.2g/L of carrier, 0.1-0.2 g/L of nonionic surfactant, and 0.2-0.3 g/L of chloride salt.
Preferably, the electrolyte additive comprises 0.5g/L of sulfur-containing compound, 0.2g/L of carrier, 0.15g/L of nonionic surfactant and 0.25g/L of chlorine salt.
Sulfur-containing compounds
The sulfur-containing compound is a substance containing sulfur, and includes an organic sulfur-containing compound and an inorganic sulfur-containing compound. The organic sulfur compound refers to an organic compound containing carbon-sulfur bonds, and exists in petroleum and animals and plants. Quantitatively, organic sulfur compounds are inferior to oxygen-or nitrogen-containing organic compounds. Organic sulfur compounds can be classified into organic compounds containing divalent sulfur and organic compounds containing higher (tetravalent or hexavalent) sulfur. The first class of compounds is mostly similar to their corresponding oxygen-containing compounds in terms of structure and chemical properties, as are the individual second class of compounds.
Preferably, the sulfur-containing compound is a disulfide compound and/or a trisulfide compound.
Examples of the trithio compound include diallyl trithio compound, dipropyl trithio compound, and diethyl trithio compound.
In one embodiment, the sulfur-containing compound is a disulfide compound; preferably, the disulfide compound comprises at least one of thiazolidinethione, sodium polydithio-dipropanesulfonate, sodium 4- [ [2- (acetylamino) ethyl ] dithio ] -1-butanesulfinate, thiamine disulfide, 2-substituted hydrazono-1, 3-dithiolane, ethylenethiourea, 2-mercaptobenzimidazole; further preferably, the disulfide compound comprises at least one of sodium 4- [ [2- (acetylamino) ethyl ] dithio ] -1-butanesulfinate, a thiamine disulfide compound, a 2-substituted hydrazono-1, 3-dithiolane; more preferably, the disulfide compound is sodium 4- [ [2- (acetylamino) ethyl ] dithio ] -1-butanesulfinate, the sodium 4- [ [2- (acetylamino) ethyl ] dithio ] -1-butanesulfinate has a CAS number of 19293-56-2, and the sodium 4- [ [2- (acetylamino) ethyl ] dithio ] -1-butanesulfinate has the following structure:
in one embodiment the process for the preparation of sodium 4- [ [2- (acetylamino) ethyl ] dithio ] -1-butanesulfinate comprises: 1, 1-dioxo-1, 2-dithiane and N-acetyl cysteamine are mixed in a molar ratio of 1: 1 in a ratio of 75mL of absolute ethyl alcohol, dropwise adding a methanol solution containing 33.3mmol of sodium methoxide into the ethanol solution, continuously stirring until the pH of the solution is neutral, adding excessive absolute ethyl ether until no white precipitate is generated, filtering, washing the precipitate with ethyl ether twice, and drying to obtain the product.
Preferably, the total amount of the 1, 1-dioxo-1, 2-dithiane and the N-acetylcysteamine accounts for 12-18 wt% of the absolute ethyl alcohol; more preferably, the total amount of 1, 1-dioxo-1, 2-dithiane and N-acetylcysteamine is 15 wt% of absolute ethanol.
The CAS number of the 1, 1-dioxo-1, 2-dithiane is 18321-15-8; the CAS number of the N-acetylcysteamine is 1190-73-4.
In the prior art, commonly used sulfur-containing compounds such as ethylene thiourea, 2-mercaptobenzimidazole, thiazolidinethione and the like have extremely strong adsorption capacity on a cathode, can effectively slow down electrodeposition of copper ions on the cathode and play a role in refining grains, but the substances can also form copper sulfide in a crystal structure, thereby greatly reducing the extensibility of the copper foil, and the disulfide compound with S-S bonds has smaller adsorption capacity on the cathode but is often required to be used together with a leveling agent, so that the types of additives are increased. As used in this application
Stable in air but reversibly disproportionated in water to form
The applicant has found that it is possible to obtain,
the instability of the copper foil has an unexpected effect on electrochemical reaction, the tensile strength and the extensibility of the extra-thin copper foil can be simultaneously improved, the extra-thin copper foil with uniform thickness can be obtained without using a leveling agent, and the extra-thin copper foil can not be burnt under high current density, and the possible reason is that the three compounds exist in the electrolyte at the same time through reversible disproportionation reaction, on one hand, the S-S bond enables the compound molecules to be attached to the cathode with proper adsorption force, the deposition rate of copper ions is regulated, the growth form of crystal grains is adjusted, but the crystal grains cannot be deposited in the copper foil along with the copper ions, and the copper foil is bright and the mechanical strength is increased due to the refined and compact crystal grain structure; on the other hand, the amine compound generated by disproportionation can play a role of a leveling agent, because the amine compound can carry positive charges in an acid environment, the amine compound can be adsorbed at a position with strong negative electric property of a cathode and competes with copper ions, so that the copper ions are not easy to deposit at a high current density position (such as a convex position, a pore opening and the like) and are transferred to a low current density position (such as a concave position, a pore bottom and the like), and the leveling effect is realized; furthermore, since the S-S bond is adsorbed facing the cathode, both ends of the molecule extend toward the electrolyte, at the cathodeA certain steric hindrance is formed on the surface of the electrode, and in addition, sulfinic acid groups on the compound can be complexed with copper ions, so that the deposition of the copper ions is further hindered, the number of crystal nuclei is increased, crystal grains are refined, and the tensile strength is improved; in addition, due to the existence of positive charges and the attachment of compounds on the surface of the cathode, the surface of the cathode and the copper foil are protected, and the scorching phenomenon caused by overlarge current is avoided.
Carrier agent
The carrier aids in the distribution of the brightener throughout the cathode recess, and is referred to as a carrier, but must be assisted by chloride ions. The carrier with lower molecular weight is easy to remain in water, and can form a diffusion layer with uniform thickness with an originally non-uniform water film, so that the originally non-uniform distribution of copper plating becomes more uniform, and the carrier has certain leveling capability. The carrier having a large molecular weight has a large electropositivity and is easily adsorbed on the negatively charged surface to be plated to form a monomolecular film, and the monomolecular film of the polymer can improve anodic polarization to suppress copper precipitation, alleviate current concentration caused by through-hole corners and the like, and have an effect of improving throwing power.
The carrier agent also enhances electrode polarization, increases overpotential, and enhances copper deposition inhibition in combination with chloride ions, and is also known as a Suppressor (Suppressor). When chlorine ions are contained, the effect of suppressing the copper electrodeposition reaction of the carrier depends on the molecular weight of the carrier, and the effect varies depending on the molecular weight of the carrier. In addition, the carrier can reduce the surface tension of the bath solution and increase the wetting effect.
Preferably, the carrier is a polyether compound, and the polyether compound comprises at least one of polyethylene glycol, an oxyethylene-oxypropyl copolymer and fatty alcohol-polyoxyethylene ether; further preferably, the carrier is polyethylene glycol.
The polyethylene glycol series products have no toxicity, no irritation, slightly bitter taste, good water solubility and good intermiscibility with a plurality of organic matter components. They have excellent lubricity, moisture retention, dispersibility, adhesives, antistatic agents, softeners and the like, and are widely applied in the industries of cosmetics, pharmacy, chemical fibers, rubber, plastics, papermaking, paint, electroplating, pesticides, metal processing, food processing and the like.
The properties vary depending on the relative molecular mass, from colorless, odorless, viscous liquids to waxy solids. The liquid has a molecular weight of 200-600, and gradually becomes semisolid when the molecular weight is above 600, and the properties of the liquid vary with the average molecular weight. Ranging from colorless odorless viscous liquids to waxy solids. As the molecular weight increases, its moisture absorption capacity decreases accordingly. The product is soluble in water, ethanol and many other organic solvents. Low vapor pressure and stability to heat, acid and alkali. Not as effective as many chemicals. Has good hygroscopicity, lubricity and cohesiveness. No toxicity and irritation. The average molecular weight is 300, n is 5-5.75, the melting point is-15-8 ℃, and the relative density is 1.124-1.130. The average molecular weight is 600, n is 12-13, the melting point is 20-25 ℃, the flash point is 246 ℃, and the relative density is 1.13(20 ℃). The average molecular weight is 4000, n is 70-85, and the melting point is 53-56 ℃.
Polyethylene glycol is very stable under normal conditions, but it reacts with oxygen in the air at temperatures of 120 ℃ or higher. In an inert atmosphere (such as nitrogen and carbon dioxide), the thermal cracking does not occur even when the temperature is increased to 200-240 ℃, and the thermal cracking occurs when the temperature is increased to 300 ℃. Adding antioxidant, such as phenothiazine with the mass fraction of 0.25-0.5%, can improve the chemical stability of the product. Any decomposition products thereof are volatile and do not form crusty or slimy deposits.
Polyethylene glycol is a polymer of ethylene oxide hydrolysate, is non-toxic and non-irritant, and is widely applied to various pharmaceutical preparations. The low molecular weight polyethylene glycols are relatively toxic and, taken together, the glycols are quite low in toxicity. Topical application of polyethylene glycol, particularly mucosal administration, can result in irritating pain. In external lotion, the product can increase skin flexibility and has moisturizing effect similar to glycerin. Diarrhea can occur with large doses given orally. In the case of injection, the maximum concentration of PEG 300 is about 30% (V/V), and hemolysis can occur at a concentration greater than 40% (V/V).
Addition polymers of polyethylene oxide and water. Those having a molecular weight of 700 or less are colorless, odorless, nonvolatile viscous liquids at 20 ℃ and have slight water-absorbing properties. The molecular weight is between 700 and 900, and the product is semisolid. The molecular weight of 1000 or more is light white waxy solid or flake paraffin or flowable powder. Miscible in water, soluble in many organic solvents such as alcohols, ketones, chloroform, glycerides, aromatic hydrocarbons, etc.; insoluble in most aliphatic hydrocarbons and diethyl ether.
As the molecular weight is increased, the water solubility, the vapor pressure, the water absorption, the solubility of the organic solvent and the like are correspondingly reduced, and the freezing point, the relative density, the flash point and the viscosity are correspondingly increased. Is thermally stable, does not work with many chemicals, and does not hydrolyze.
In one embodiment, the polyethylene glycol has a number average molecular weight of 1500 to 2500; preferably, the polyethylene glycol has a number average molecular weight of 2000.
Number average molecular weight: the polymer is composed of homologous mixture with same chemical composition and different polymerization degree, i.e. is composed of high polymer with different molecular chain length. The size of the molecules is usually characterized by the average molecular weight. The number average is called number average molecular weight and the symbol is Mn.
Nonionic surfactant
The surfactant is a substance which is added in a small amount and can cause the interface state of a solution system to change obviously. Has fixed hydrophilic and lipophilic groups and can be directionally arranged on the surface of the solution. The molecular structure of the surfactant has amphipathy: one end is a hydrophilic group, and the other end is a hydrophobic group; the hydrophilic group is often a polar group, such as carboxylic acid, sulfonic acid, sulfuric acid, amino or amino groups and salts thereof, hydroxyl, amide, ether linkages, and the like may also be used as the polar hydrophilic group; and the hydrophobic group is often a non-polar hydrocarbon chain, such as a hydrocarbon chain of 8 or more carbon atoms. The surfactant is divided into ionic surfactant (including cationic surfactant and anionic surfactant), nonionic surfactant, amphoteric surfactant, compound surfactant, other surfactants, etc.
Nonionic surfactants are those which do not ionize in aqueous solution and whose hydrophilic groups are composed mainly of a certain number of oxygen-containing groups (typically ether and hydroxyl groups). It is this which determines that nonionic surfactants are superior to ionic surfactants in some respects; because the ionic surfactant is not in an ionic state in the solution, the ionic surfactant has high stability, is not easily influenced by the existence of strong electrolyte inorganic salts, is not easily influenced by pH value, and has good compatibility with other types of surfactants.
Nonionic surfactants are mostly in liquid and slurry states, and their solubility in water decreases with increasing temperature. The nonionic surfactant has various good performances of washing, dispersing, emulsifying, foaming, wetting, solubilizing, antistatic, level dyeing, corrosion prevention, sterilization, protective colloid and the like, and is widely applied to various aspects of textile, paper making, food, plastic, leather, fur, glass, petroleum, chemical fiber, medicine, pesticide, coating, dye, fertilizer, film, photography, metal processing, mineral separation, building materials, environmental protection, cosmetics, fire protection, agriculture and the like.
Nonionic surfactants are classified by hydrophilic group and include both polyoxyethylene type and polyhydric alcohol type.
In one embodiment, the nonionic surfactant is an amine-containing polyether surfactant; preferably, the amine-containing polyether surfactant is fatty amine polyoxyethylene ether; more preferably, the tertiary amine value of the fatty amine polyoxyethylene ether is 75-85 mgKOH/g.
Examples of the fatty amine polyoxyethylene ether include laurylamine polyoxyethylene ether, stearylamine polyoxyethylene ether, laurylamine polyoxyethylene ether, and cocoamine polyoxyethylene ether.
Preferably, the fatty amine polyoxyethylene ether is octadecylamine polyoxyethylene ether, the octadecylamine polyoxyethylene ether is not particularly limited to the purchase manufacturer, and the octadecylamine polyoxyethylene ether is purchased from Heian petrochemical plants in Jiangsu province and has the model of AC-1810.
Octadecylamine polyoxyethylene ether is colorless to yellow solid, is insoluble to water, is soluble to organic solvents such as acetone and benzene, and has excellent emulsifying, dispersing, solubilizing, antistatic, lubricating and corrosion inhibiting capabilities.
The surface active agent is added into the electrolyte to reduce the surface tension of the cathode, so that the additive is easy to adsorb, and the dispersibility of the solution can be improved. The applicant finds that the leveling effect can be improved by using the fatty amine polyoxyethylene ether as the surfactant in the system, the leveling agent is not required to be added, the types of additives are reduced, and the stability and the electrolytic efficiency of the electrolyte are improved, and the possible reason is that although the fatty amine polyoxyethylene ether is a nonionic surfactant, the fatty amine polyoxyethylene ether can be converted into a cationic surfactant in an acid solution, so that the adsorption of the cationic surfactant on a cathode is increased, particularly the adhesion of the cationic surfactant on a convex part is increased, and the effects of grain refining and leveling are achieved; moreover, as the polyether surfactant, the polyether surfactant has certain defoaming and foam inhibiting effects, can reduce negative effects caused by bubbles and foams in the electrolyte, and improves the stability of electrochemical reaction; in addition, as the electrolyte carries positive charges in an acidic medium, the ion concentration in the solution is increased, the current efficiency is improved, and the electrolysis efficiency is further improved. The applicant finds through experiments that the best effect can be achieved only when the tertiary amine value of the fatty amine polyoxyethylene ether is within a certain range, and the possible reasons are that the ionic balance in an electrolyte system is broken through when the tertiary amine value is too high, the electrodeposition process of copper ions on a cathode is excessively inhibited, the electrolysis efficiency is reduced, the electrolysis effect is poor, the leveling effect is lost when the tertiary amine value is too low, and the ultrathin copper foil with uniform thickness cannot be obtained only by the effects of dispersion, wetting and the like of common surfactants.
Chlorine salt
The chlorine salt is sodium chloride, potassium chloride or hydrochloric acid; preferably, the chloride salt is sodium chloride, which is not particularly limited to the manufacturer.
The chloride salt is mainly used for providing chloride ions, the chloride ions are used as an anode activating agent and a stress relieving agent of the plating layer, can help the anode to be dissolved, and can be used for brightening and leveling the plating layer under the synergistic action of the chloride ions and the additive, and the tensile stress of the plating layer can be reduced. Proper amount of chloride ions can improve the brightness and leveling property of the coating and reduce the stress of the coating. The concentration of the chloride ions is too low, the coating loses luster, dendritic stripes are generated, and pinholes and scorching are easy to occur; too high concentration of chloride ions will lead to passivation of the anode, resulting in a white film on the anode and release of a large number of bubbles, and greatly reducing the efficiency of the electrode. Therefore, the concentration of chloride ions should be monitored in time, and it is impossible to prepare a plating solution or supplement the plating solution with tap water containing a large amount of chloride ions.
In one embodiment, the weight ratio of the sulfur-containing compound, the nonionic surfactant and the chloride salt is (3-4): 1: (1-2); preferably, the weight ratio of the sulfur-containing compound, the nonionic surfactant and the chloride salt is 3.3: 1: 1.7.
the applicant finds that when the sulfur-containing compound, the nonionic surfactant and the chlorine salt are added into the electrolyte together, a synergistic effect is generated between the sulfur-containing compound, the nonionic surfactant and the chlorine salt, the obtained ultrathin copper foil has excellent tensile and elongation properties while high electrolytic efficiency is ensured, and the possible reason is that the sulfur-containing compound and the nonionic surfactant actually achieve the effect of one agent for multiple purposes, namely the effect of a leveling agent, so that the types of the additives are reduced, the stability of the electrolyte is improved, when the sulfur-containing compound slows the electrodeposition, the nonionic surfactant increases the ion concentration in the solution, improves the current efficiency, accelerates the electrolytic rate to a certain extent, and in addition, the depolarization effect of the chlorine salt, the copper foil and the sulfur-containing compound are adsorbed on the cathode together, so that the overpotential of the electrochemical reaction is reduced, and the copper foil precipitation speed is further improved. Through a large number of experiments, the applicant finds that when a sulfur-containing compound, a nonionic surfactant and a chloride salt are added in a certain proportion, the effects of all components in a system are balanced, so that the grain refinement degree and the electrolytic efficiency are balanced, namely, the copper foil is quickly precipitated and the prepared copper foil has good performance, when the usage amount of the sulfur-containing compound is too small, the electrolytic copper foil has poor brightness, low tensile strength and easy scorching at a high current density position, otherwise, the extensibility is poor and the electrolytic efficiency is low; when the dosage of the nonionic surfactant is too small, the leveling effect is poor, the high-current density part is easy to be burnt, the reduction of the ion concentration causes the reduction of the electrolytic efficiency, and otherwise, the electrolytic efficiency is also reduced, because the nonionic surfactant molecules are greatly adsorbed on the cathode, the electrodeposition of copper is greatly hindered, and if the content is too large, micelles can be formed, so the performance of the electrolyte is greatly reduced; when the dosage of the chloride is too small, the ion concentration in the system is too low, so that the current density is low, the electrolysis efficiency is low, otherwise, the synergistic effect with the sulfur-containing compound is destroyed, the electrodeposition rate is too high, compact and fine crystals cannot be obtained, and the tensile property is seriously weakened.
The invention provides an electrolyte of an ultrathin electrolytic copper foil for a high-tensile strength lithium ion battery.
Preferably, the electrolyte also comprises 180-250 g/L of copper sulfate and 100-150 g/L of sulfuric acid; more preferably, the electrolyte also comprises 230g/L of copper sulfate and 140g/L of sulfuric acid.
In one embodiment, the solvent of the electrolyte is deionized water.
The sulfuric acid is dilute sulfuric acid, and the concentration of the sulfuric acid is 30 wt%.
Copper sulfate and sulfuric acid are main components of sulfate plating solution, and both of them participate in the electrode process and have interdependence relationship in the plating solution. The concentration of copper sulfate is too low, and the coating in the high current area is easy to be burnt; the copper sulfate concentration is too high, and the dispersing ability and leveling ability of the plating solution are lowered. The sulfuric acid is used for improving the conductivity of the solution, preventing the copper salt from hydrolyzing and enabling the plating layer to be fine in crystallization. The sulfuric acid concentration is too low, the conductivity of the solution is poor, and the dispersion capability of the plating solution is poor; too high a concentration of sulfuric acid reduces the mobility of copper ions, the plating efficiency, and the ductility of the copper plated layer, and the brightness of the plated layer. When the printed circuit board is electroplated, high dispersing capacity is required, the content of sulfuric acid can be increased, but at the same time, the content of copper sulfate must be reduced, otherwise, along with the increase of the content of sulfuric acid, the solubility of copper sulfate is reduced, so that the precipitation of copper sulfate is caused, and the quality of a plating layer is influenced. Therefore, copper sulfate and sulfuric acid need to be controlled within an appropriate concentration range.
The third aspect of the invention provides a preparation method of an ultrathin electrolytic copper foil for a high-tensile strength lithium ion battery, which is characterized by comprising the following steps of:
(1) preparing an electrolyte: heating the electrolyte raw material to 45-60 ℃, uniformly mixing, and placing in an anode tank;
(2) electrochemical reaction: electrifying at a current density of 50-80A/dm2And under the condition, separating out the copper foil from the cathode and stripping to obtain the copper-clad laminate.
Preferably, the method for preparing the extra thin electrolytic copper foil comprises the following steps:
(1) preparing an electrolyte: heating the electrolyte raw material to 57 ℃, uniformly mixing, and pouring into an anode tank;
(2) electrochemical reaction: passing electricity at a current density of 75A/dm2Under the condition, the copper foil is separated out at the cathode, and the copper foil is stripped from the cathode to obtain the ultrathin electrolytic copper foil for the high-tensile-strength lithium ion battery.
The weight per unit area of the electrolytic copper foil obtained by the present invention is 43.0 to 75.0g/m2The tensile strength is 400 to 480N/mm2The elongation is 3.5-8.5%.
Examples
Hereinafter, the present invention will be described in more detail by way of examples, but it should be understood that these examples are merely illustrative and not restrictive. The starting materials used in the examples which follow are all commercially available unless otherwise stated.
A: sulfur-containing compounds
A1: 4- [ [2- (acetylamino) ethyl ] dithio ] -1-butanesulfinic acid sodium salt
The preparation method of the sodium 4- [ [2- (acetylamino) ethyl ] dithio ] -1-butanesulfinate comprises the following steps: dissolving 5g of 1, 1-dioxo-1, 3.92g of 2-dithiane and N-acetylcysteamine in 75mL of absolute ethyl alcohol, dropwise adding a methanol solution containing 33.3mmol of sodium methoxide in the ethanol solution, continuously stirring until the pH value of the solution is neutral, adding excessive absolute ethyl ether until no white precipitate is generated, filtering, washing the precipitate twice with ethyl ether, and drying to obtain the product.
A2: thiazolidinethione, CAS: 96-53-7
A3: sodium polydithio dipropane sulfonate, CAS: 27206-35-5
B: carrier agent
B1: polyethylene glycol, available from Hipporo Biotech, Hangzhou, with a number average molecular weight of 2000
C: nonionic surfactant
C1: fatty amine polyoxyethylene ether purchased from Haian petrochemical plant of Jiangsu province and having a model number of AC-1810
C2: octyl phenol polyglycol ether, available from north lake, pharmaceutical chemicals ltd, CAS: 9002-93-1
C3: fatty amine polyoxyethylene ether available from Haian petrochemical plant of Jiangsu province, model number AC-1812
C4: fatty amine polyoxyethylene ether available from Haian petrochemical plant of Jiangsu province and with the model of AC-1802
D: chlorine salt
D1: sodium chloride, CAS: 7647-14-5
E: copper sulfate, CAS: 7758-99-8
F: sulfuric acid, available from Hangzhou Huafu chemical Co., Ltd, at a concentration of 30 wt%
Embodiments 1 to 14 provide an extra thin electrolytic copper foil for a high tensile strength lithium ion battery, and a preparation method of the extra thin electrolytic copper foil includes the following steps:
(1) preparing an electrolyte: heating the electrolyte raw materials to 57 ℃, uniformly mixing, and pouring into an anode tank, wherein the formula of the electrolyte is shown in table 1, the unit of the formula dosage is g/L, and the solvent is deionized water;
(2) electrochemical reaction: passing electricity at a current density of 75A/dm2Under the condition, the copper foil is separated out at the cathode, and the copper foil is stripped from the cathode to obtain the ultrathin electrolytic copper foil for the high-tensile-strength lithium ion battery.
Performance evaluation
1. Weight per unit area: the weight per unit area of the extra thin electrolytic copper foil for high tensile strength lithium ion batteries provided in examples 1 to 14 was measured in accordance with GB/T5230-1995.
2. Tensile strength: the tensile strength of the extra thin electrolytic copper foil for high tensile strength lithium ion batteries provided in examples 1 to 14 was tested according to GB/T5230-1995 standard.
3. Elongation percentage: the elongation of the extra thin electrolytic copper foil for high tensile strength lithium ion batteries provided in examples 1 to 14 was tested according to GB/T5230-1995.
TABLE 1
TABLE 2
| Weight per unit area (g/m)2) | Tensile strength (N/mm)2) | Elongation (%) | |
| Example 1 | 46.2 | 467 | 7.5 |
| Example 2 | 45.8 | 470 | 7.8 |
| Example 3 | 45.5 | 475 | 7.2 |
| Example 4 | 43.0 | 480 | 8.5 |
| Example 5 | 58.0 | 424 | 4.0 |
| Example 6 | 72.0 | 396 | 5.1 |
| Example 7 | 57.0 | 429 | 6.0 |
| Example 8 | 55.0 | 433 | 6.4 |
| Example 9 | 42.8 | 438 | 6.7 |
| Example 10 | 50.0 | 442 | 6.7 |
| Example 11 | 51.1 | 446 | 6.8 |
| Example 12 | 52.0 | 440 | 6.8 |
| Example 13 | 64 | 412 | 5.4 |
| Example 14 | 75 | 402 | 4.9 |
Table 2 shows performance test results of the extra thin electrolytic copper foil for high tensile strength lithium ion batteries provided in examples 1 to 14, and it can be seen from the test results in table 2 that the extra thin electrolytic copper foil for high tensile strength lithium ion batteries provided in the present invention has high tensile strength and high elongation; meanwhile, the weight per unit area of the extra thin electrolytic copper foil is 43.0 to 75.0g/m2Uniform thickness, and the unit area weight range is less than 1.0g/m2。
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. The electrolyte additive of the ultrathin electrolytic copper foil for the high-tensile-strength lithium ion battery is characterized by comprising 0.15-0.9 g/L of sulfur-containing compound, 0.07-0.4 g/L of carrier, 0.01-0.27 g/L of nonionic surfactant and 0.07-0.4 g/L of chlorine salt.
2. The electrolyte additive of claim 1 wherein the sulfur-containing compound is a disulfide compound and/or a trisulfide compound.
3. The electrolyte additive of claim 2 wherein the sulfur-containing compound is a disulfide compound; the disulfide compound comprises at least one of thiazolidinethione, sodium polydithio-dipropanesulfonate, sodium 4- [ [2- (acetamido) ethyl ] dithio ] -1-butanesulfinate, thiamine disulfide compound, 2-substituted hydrazono-1, 3-dithiolane, ethylene thiourea and 2-mercaptobenzimidazole.
4. The electrolyte additive of claim 1 wherein the non-ionic surfactant is an amine-containing polyether surfactant.
5. The electrolyte additive of claim 4 wherein the amine-containing polyether surfactant is a fatty amine polyoxyethylene ether.
6. The electrolyte additive according to claim 1, wherein the weight ratio of the sulfur-containing compound, the nonionic surfactant and the chloride salt is (3-4): 1: (1-2).
7. The electrolyte additive of claim 1 wherein the carrier is a polyether compound; the polyether compound comprises at least one of polyethylene glycol, an oxyethylene-oxypropyl copolymer and fatty alcohol-polyoxyethylene ether.
8. An electrolyte comprising the electrolyte additive according to any one of claims 1 to 7, which is an extra thin electrolytic copper foil for a high tensile strength lithium ion battery.
9. The electrolyte of claim 8, further comprising 180-250 g/L copper sulfate and 100-150 g/L sulfuric acid.
10. A preparation method of an ultrathin electrolytic copper foil for a high-tensile strength lithium ion battery is characterized by comprising the following steps of:
(1) preparing an electrolyte: heating the electrolyte raw material to 45-60 ℃, uniformly mixing, and placing in an anode tank; the electrolyte is the electrolyte according to claim 8 or 9;
(2) electrochemical reaction: electrifying at a current density of 50-80A/dm2Under the condition, copper foil is separated out from the cathode and stripped to obtain the copper-clad laminate; the weight per unit area of the obtained electrolytic copper foil is 43.0 to 75.0g/m2The tensile strength is 400 to 480N/mm2The elongation is 3.5-8.5%.
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| KR1020200126555A KR102442050B1 (en) | 2020-01-17 | 2020-09-29 | Preparation of extremely thin electrolytic copper foil for high tensile strength lithium ion battery |
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| CN112226790A (en) * | 2020-10-19 | 2021-01-15 | 九江德福科技股份有限公司 | Production method of ultrathin high-strength electronic copper foil |
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| CN113584537A (en) * | 2021-08-03 | 2021-11-02 | 东强（连州）铜箔有限公司 | Ultra-thin copper foil with resin layer and extremely low roughness and manufacturing method thereof |
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| CN112195487A (en) * | 2020-09-18 | 2021-01-08 | 九江德福科技股份有限公司 | Manufacturing method for improving tensile strength of light and thin copper foil |
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| CN112226790A (en) * | 2020-10-19 | 2021-01-15 | 九江德福科技股份有限公司 | Production method of ultrathin high-strength electronic copper foil |
| CN112469194A (en) * | 2020-11-27 | 2021-03-09 | 广东嘉元科技股份有限公司 | Low-profile electrolytic copper foil for high-density interconnected circuit board |
| CN112469194B (en) * | 2020-11-27 | 2022-08-05 | 广东嘉元科技股份有限公司 | Low-profile electrolytic copper foil for high-density interconnected circuit board |
| JP2023512132A (en) * | 2020-12-30 | 2023-03-24 | 広東嘉元科技股▲ふん▼有限公司 | Electrolytic copper foil for high frequency/high speed printed circuit board and its preparation method |
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| CN113046797A (en) * | 2021-03-10 | 2021-06-29 | 四川恒创博联科技有限责任公司 | Electrolytic copper foil additive |
| CN113584537A (en) * | 2021-08-03 | 2021-11-02 | 东强（连州）铜箔有限公司 | Ultra-thin copper foil with resin layer and extremely low roughness and manufacturing method thereof |
| CN113584537B (en) * | 2021-08-03 | 2023-01-06 | 东强（连州）铜箔有限公司 | Ultra-thin copper foil with resin layer and extremely low roughness and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111254464B (en) | 2021-06-18 |
| KR20210093729A (en) | 2021-07-28 |
| KR102442050B1 (en) | 2022-09-07 |
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Application publication date: 20200609 Assignee: Shandong Jiayuan new energy material Co.,Ltd. Assignor: GUANGDONG FINE YUAN SCIENCE TECHNOLOGY Co.,Ltd. Contract record no.: X2024980003955 Denomination of invention: Preparation method of ultra-thin electrolytic copper foil for high tensile strength lithium-ion batteries Granted publication date: 20210618 License type: Common License Record date: 20240407 Application publication date: 20200609 Assignee: Jiayuan Technology (Ningde) Co.,Ltd. Assignor: GUANGDONG FINE YUAN SCIENCE TECHNOLOGY Co.,Ltd. Contract record no.: X2024980003954 Denomination of invention: Preparation method of ultra-thin electrolytic copper foil for high tensile strength lithium-ion batteries Granted publication date: 20210618 License type: Common License Record date: 20240407 Application publication date: 20200609 Assignee: Meizhou District of Meixian City Jinxiang Copper Co.,Ltd. Assignor: GUANGDONG FINE YUAN SCIENCE TECHNOLOGY Co.,Ltd. Contract record no.: X2024980003953 Denomination of invention: Preparation method of ultra-thin electrolytic copper foil for high tensile strength lithium-ion batteries Granted publication date: 20210618 License type: Common License Record date: 20240407 |