CN115440989A - Negative current collector for lithium ion battery, pole piece and preparation method of negative current collector - Google Patents
Negative current collector for lithium ion battery, pole piece and preparation method of negative current collector Download PDFInfo
- Publication number
- CN115440989A CN115440989A CN202211207696.6A CN202211207696A CN115440989A CN 115440989 A CN115440989 A CN 115440989A CN 202211207696 A CN202211207696 A CN 202211207696A CN 115440989 A CN115440989 A CN 115440989A
- Authority
- CN
- China
- Prior art keywords
- current collector
- lithium ion
- ion battery
- copper plating
- negative
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000010949 copper Substances 0.000 claims abstract description 84
- 229910052802 copper Inorganic materials 0.000 claims abstract description 82
- 238000007747 plating Methods 0.000 claims abstract description 60
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000011888 foil Substances 0.000 claims abstract description 55
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 54
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000009713 electroplating Methods 0.000 claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 238000001035 drying Methods 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000004140 cleaning Methods 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 10
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 9
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 9
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 9
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 7
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 7
- 239000011975 tartaric acid Substances 0.000 claims description 7
- 235000002906 tartaric acid Nutrition 0.000 claims description 7
- 230000004913 activation Effects 0.000 claims description 5
- 239000006255 coating slurry Substances 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims 1
- 239000005030 aluminium foil Substances 0.000 claims 1
- 239000011247 coating layer Substances 0.000 claims 1
- 229960001484 edetic acid Drugs 0.000 claims 1
- 238000002161 passivation Methods 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- 238000007772 electroless plating Methods 0.000 abstract description 2
- 238000012983 electrochemical energy storage Methods 0.000 abstract 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 239000004115 Sodium Silicate Substances 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- 239000001509 sodium citrate Substances 0.000 description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 6
- 239000001488 sodium phosphate Substances 0.000 description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 6
- 229910052911 sodium silicate Inorganic materials 0.000 description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 6
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 6
- 235000019801 trisodium phosphate Nutrition 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 4
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- KRXFTOUYGXMRRU-UHFFFAOYSA-N 3h-1,3-benzothiazole-2-thione;sodium Chemical compound [Na].C1=CC=C2SC(=S)NC2=C1 KRXFTOUYGXMRRU-UHFFFAOYSA-N 0.000 description 3
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 3
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000467 phytic acid Substances 0.000 description 3
- 229940068041 phytic acid Drugs 0.000 description 3
- 235000002949 phytic acid Nutrition 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- BDOYKFSQFYNPKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BDOYKFSQFYNPKF-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 235000019253 formic acid Nutrition 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
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241000784732 Lycaena phlaeas Species 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1637—Composition of the substrate metallic substrate
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/52—Treatment of copper or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/22—Light metals
-
- 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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
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- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- 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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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
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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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Abstract
The invention provides a negative current collector, a pole piece and a preparation method for a lithium ion battery, belonging to the field of electrochemical energy storage.A compact copper can protect an inner layer aluminum foil at a low potential of a negative electrode by plating copper on the upper surface and the lower surface of the aluminum foil respectively, so that the weight of the negative current collector is reduced by the lighter aluminum material, the material cost is reduced, and the conductivity is also considered; the electroless copper plating has uniform thickness, simple process equipment, bright plating layer, fine and compact electroless plating crystal grains and low porosity, and can effectively improve the cycle performance of the battery; the small current electroplating is carried out to increase the thickness of the copper coating, and the surface defects of the coating can be reduced after the passivation treatment, so that the durability of the foil is improved.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a negative current collector and a pole piece for a lithium ion battery and a preparation method thereof.
Background
The lithium ion battery core is composed of a positive plate, a negative plate and a diaphragm, wherein the positive plate and the negative plate are formed by coating slurry containing active substances on a metal current collector, the positive current collector is aluminum foil, and the negative current collector is copper foil.
However, the current negative current collector made of pure copper also has the following defects: the price and density of copper are higher than those of aluminum. The cost of the negative current collector accounts for more than 10% of the cost of the lithium battery, and the surface density of the negative current collector is usually twice that of the positive current collector by adopting copper as the negative current collector.
In contrast, aluminum is second only to silver and copper, and although its conductivity is only 2/3 of that of copper, its density is only 1/3 of that of copper, so that the quality of aluminum wire is half that of copper wire for delivering the same amount of electricity. However, metallic aluminum cannot be used as a negative electrode current collector because of an alloying reaction with lithium ions at a low potential.
Based on the above background, the inventors considered plating copper on the surface of an aluminum current collector to use as a negative electrode current collector. However, the common copper plating technique is electrolytic copper, but because the metal potential of aluminum is low, the electrolytic copper on the surface of the aluminum foil can be quickly oxidized to form a layer of compact aluminum oxide protective film, which affects the binding force of the subsequent plating layer. In addition, the vacuum coating cost is too high, and large-scale mass production is difficult. Therefore, the inventor considers that a copper layer is generated on the surface of the aluminum foil by adopting an electroless copper plating mode, and the aluminum foil is protected by copper, so that the conductive requirement is met, the weight of the battery can be reduced, and the energy density of the battery can be improved.
Disclosure of Invention
In view of the above, the invention provides a negative current collector for a lithium ion battery, a pole piece and a preparation method thereof, which not only meet the conductive requirement, but also can reduce the weight of the battery and improve the energy density of the battery.
The technical scheme of the invention is realized as follows:
in one aspect, the invention provides a negative current collector for a lithium ion battery, which comprises an aluminum foil, wherein the upper surface and the lower surface of the aluminum foil are respectively provided with a copper plating layer, and the copper plating layer comprises a chemical copper plating layer attached to the surface of the aluminum foil.
On the basis of the above technical solution, preferably, the copper plating layer further includes an electroplated copper layer attached to a surface of the electroless copper plating layer.
On the basis of the technical scheme, preferably, the thickness of the aluminum foil is 6-13 μm, and the thickness of the copper plating layer is 1-2 μm.
In a second aspect, the present invention provides a method for preparing a negative electrode current collector for a lithium ion battery according to the first aspect, comprising the steps of,
s1, carrying out alkali washing and oil removal, ultrasonic cleaning, drying and plasma cleaning and activation on an aluminum foil;
and S2, carrying out chemical copper plating on two surfaces of the activated aluminum foil, and heating and drying to obtain the negative current collector for the lithium ion battery.
On the basis of the above technical scheme, preferably, the step S1 specifically includes placing the aluminum foil in an alkaline solution, ultrasonically cleaning the aluminum foil for 5-10min at 10-30 ℃, then placing the aluminum foil in a distilled water pool for ultrasonically cleaning, and drying the aluminum foil after cleaning.
Still further preferably, the alkaline solution comprises sodium hydroxide, sodium silicate, trisodium phosphate, sodium carbonate, sodium citrate and distilled water, and the 1L solution contains 10-14g of sodium hydroxide, 1-5g of sodium silicate, 10-14g of trisodium phosphate, 1-5g of sodium citrate and 4-8g of sodium carbonate, respectively.
More preferably, the step S1 specifically includes performing plasma cleaning and activation on the dried aluminum foil by using a roll-to-roll vacuum plasma cleaning machine, where the working gas is one or more of oxygen, nitrogen and methane, and the working pressure is 0.4-0.8MPa.
On the basis of the technical scheme, preferably, in the step S2, the chemical copper plating raw materials comprise copper sulfate, formaldehyde, tartaric acid, ethylene diamine tetraacetic acid disodium and sodium hydroxide, the pH value is adjusted to 12-13, the reaction temperature is 10-30 ℃, meanwhile, a low-frequency ultrasonic device is used in a chemical copper plating tank to remove bubbles when the aluminum foil enters water, and the increase speed of the thickness of a plating layer is controlled to be 1-3 mu m/h.
More preferably, the 1L of electroless copper plating raw material solution contains 13-17g of copper sulfate, 40-50g of formaldehyde, 15-17g of tartaric acid, 18-22g of disodium ethylene diamine tetraacetate and 10-14g of sodium hydroxide respectively.
On the basis of the above technical scheme, preferably, the method further comprises a step S3 of performing electro-coppering on two sides of the negative current collector subjected to electroless copper plating; and S4, passivating the copper-plated current collector.
More preferably, the copper electroplating in step S3 is carried out at a temperature of 20-30 ℃, the negative current collector obtained in step S2 is used as a cathode, and the current density is 1-2A/dm 2 And controlling the thickness of the coating by controlling the advancing speed of the coil stock, and meanwhile, installing a low-frequency ultrasonic device in the copper electroplating pool to remove bubbles on the surface of the negative current collector foil, and drying the negative current collector after the copper electroplating is finished after two times of water washing. Further preferably, when S1-S4 are performed continuously, intermediate drying and winding measures may not be required.
Still more preferably, the 1L of raw material solution for electrolytic copper plating in the step S3 includes 60 to 80g of anhydrous copper sulfate, 170 to 210g of sulfuric acid, 40 to 80mL of hydrochloric acid having a mass concentration of 37%, and 0.2 to 0.4mL of acid copper brightener.
Further preferably, the passivation in step S4 is performed at a temperature of 20-30 ℃, and the negative electrode current collector obtained in step S2 or S3 is immersed in a passivation bath and then dried.
Further preferably, 1L of the passivation solution raw material in step S4 comprises: 5-10ml of phytic acid with the mass concentration of 50%, 10-20g of citric acid, 15-25ml of polyethylene glycol, 15-30ml of hydrogen peroxide and 2-4g of 2-mercaptobenzothiazole sodium are subjected to passivation treatment for 5-10s.
In a third aspect, the invention provides a lithium ion battery negative electrode plate, which comprises a negative active coating, wherein the negative active coating is coated on the surface of the copper plating layer in the first aspect of the invention.
In a fourth aspect, the invention provides a method for preparing a negative electrode plate of a lithium ion battery in the third aspect, comprising the following steps,
a1, preparing anode active coating slurry;
a2, coating the negative active coating slurry on the surface of a copper coating of a negative current collector, and drying to obtain a negative plate;
and A3, rolling the negative pole piece, wherein the diameter of a roller of the double-roller machine is larger than that of the conventional roller, reducing the pressure of the double rollers by adopting a secondary rolling mode so as to reduce the extension of a copper-aluminum layer, and simultaneously avoiding microcracks from appearing on the surface of the foil to obtain the negative pole piece. Specifically, the diameter of the roller of the double-roller machine is 800mm.
Compared with the prior art, the negative current collector, the pole piece and the preparation method for the lithium ion battery have the following beneficial effects:
(1) The upper surface and the lower surface of the aluminum foil are plated with copper respectively, so that the compact copper can protect the inner aluminum foil under the low potential of the negative electrode, the lighter aluminum material also reduces the weight of the negative electrode current collector, reduces the material cost and also considers the conductivity;
(2) The electroless copper plating has uniform thickness, simple process equipment, bright plating layer, fine and compact electroless plating crystal grains and low porosity, and can effectively improve the cycle performance of the battery;
(3) The small current electroplating is carried out to increase the thickness of the copper coating, and the surface defects of the coating can be reduced after the passivation treatment, so that the durability of the foil is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a schematic front sectional view of a negative electrode current collector for a lithium ion battery of example 1;
fig. 2 is a schematic front sectional view of a negative electrode current collector for a lithium ion battery of example 2;
FIG. 3 is a process flow diagram of step S1 of the present invention;
FIG. 4 is a process flow diagram of step S2 of the present invention;
FIG. 5 is a process flow diagram of step S3 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
As shown in fig. 1, the negative electrode current collector for a lithium ion battery according to the present invention includes an aluminum foil 1, and electroless copper plating layers 21 are respectively disposed on upper and lower surfaces of the aluminum foil 1. Wherein the thickness of the aluminum foil 1 is 6 μm, and the thickness of the electroless copper plating layer 21 is 1 μm.
The preparation steps of the negative current collector are as follows:
s1, as shown in figure 3, placing a coil stock of aluminum foil 1 in an alkaline solution of an ultrasonic cleaning tank, keeping the coil stock in the ultrasonic cleaning tank for 5min at the temperature of 20 ℃, then performing ultrasonic cleaning in a distilled water tank, and then putting the coil stock into a drying workshop after cleaning; the alkaline solution consists of sodium hydroxide, sodium silicate, trisodium phosphate, sodium carbonate, sodium citrate and distilled water, wherein 10g of sodium hydroxide, 1g of sodium silicate, 10g of trisodium phosphate, 1g of sodium citrate and 4g of sodium carbonate are contained in 1L of solution respectively;
performing plasma cleaning and activation on the dried aluminum foil 1 by using a roll-to-roll vacuum plasma cleaning machine, wherein the working gas is oxygen, and the working pressure is 0.4MPa;
s2, after being activatedAnd carrying out chemical copper plating on two sides of the aluminum foil 1, and heating and drying to obtain the negative current collector for the lithium ion battery. Electroless copper plating to Cu 2+ +HCHO+2OH - ＝Cu+HCOOH+2Na + +H 2 And as shown in fig. 4, the step S2 is performed in a chemical aqueduct, the chemical copper plating raw material comprises copper sulfate, formaldehyde, tartaric acid, disodium ethylene diamine tetraacetate and sodium hydroxide, the pH value is adjusted to 12, the reaction temperature is 20 ℃, a low-frequency ultrasonic device is used in a chemical copper plating tank to remove bubbles when the aluminum foil 1 enters water, the coating thickness growth rate is 1.5 μm/h, and the cathode current collector after the electro-coppering is washed by two distilled water tanks and then sent to a drying chamber for drying. Wherein, 1L of the electroless copper plating raw material solution respectively contains 13g of copper sulfate, 40g of formaldehyde, 15g of tartaric acid, 18g of disodium ethylene diamine tetraacetate and 10g of sodium hydroxide.
And S4, passivating the copper-plated current collector. And S4, the passivation is carried out in a passivation tank, wherein 1L of passivation solution comprises the following raw materials: 5ml of phytic acid with the mass concentration of 50%, 10g of citric acid, 15ml of polyethylene glycol, 15ml of hydrogen peroxide and 2g of 2-mercaptobenzothiazole sodium are subjected to passivation treatment for 5s.
The negative electrode current collector obtained in step S4 was subjected to thickness and area density tests, and the results shown in table 1 were obtained.
The negative pole piece of the lithium ion battery also comprises a negative active coating, and the negative active coating is coated on the surface of the chemical copper plating layer 21. Specifically, the negative active coating may be prepared by the prior art, and generally includes graphite, a binder, a thickener, and a conductive agent. The preparation method comprises the following steps:
mixing artificial graphite, binder styrene butadiene rubber, thickener sodium carboxymethyl cellulose and conductive agent carbon black according to a mass ratio of 96.6:1.2:1.6:0.6 is dispersed in an organic solvent N-methyl pyrrolidone, then is evenly coated on an aluminum current collector of electroless copper plating, is dried, is secondarily rolled to the required compaction density by using a roll pair machine with the diameter of 800mm to obtain a negative pole piece, and is subjected to slitting and tab welding to obtain the negative pole piece for the lithium ion battery;
the prepared LiFePO is 4 With a binder of polyvinylidene fluoride and a conductive agent of carbonThe mass ratio of the black components to the black components is 97.0:1.5: dispersing the mixture in an organic solvent N-methyl pyrrolidone according to the proportion of 1.5, then uniformly coating the mixture on a current collector aluminum foil, drying the current collector aluminum foil, rolling the current collector aluminum foil to a required compaction density, splitting the strips and cutting the pieces, and welding tabs to obtain a positive pole piece for the lithium ion battery;
and winding the positive pole piece, the high-molecular porous diaphragm and the negative pole piece into a winding core, adding the lithium ion battery electrolyte, and then forming to obtain the lithium ion battery capable of being charged and discharged.
Example 2
As shown in fig. 1, the negative electrode current collector for a lithium ion battery according to the present invention includes an aluminum foil 1, copper plating layers 21 respectively disposed on upper and lower surfaces of the aluminum foil 1, and a copper plating layer 22 attached to a surface of the copper plating layer 21. Wherein the thickness of the aluminum foil 1 is 7 μm, and the thickness of the copper plating layer 2 is 2 μm.
The preparation steps of the negative current collector are as follows:
s1, as shown in figure 3, placing an aluminum foil 1 in an alkaline solution of an ultrasonic cleaning tank, ultrasonically cleaning for 7min at 25 ℃, then placing the aluminum foil in a distilled water tank for ultrasonic cleaning, and drying after cleaning; the alkaline solution consists of sodium hydroxide, sodium silicate, trisodium phosphate, sodium carbonate, sodium citrate and distilled water, and 1L of the solution contains 12g of sodium hydroxide, 3g of sodium silicate, 12g of trisodium phosphate, 3g of sodium citrate and 6g of sodium carbonate;
performing plasma cleaning and activation on the dried aluminum foil 1 by using a roll-to-roll vacuum plasma cleaning machine, wherein the working gas is one or more of oxygen, nitrogen and methane, and the working pressure is 0.6MPa;
and S2, carrying out chemical copper plating on two sides of the activated aluminum foil 1, and heating and drying to obtain the negative current collector for the lithium ion battery. Electroless copper plating to Cu 2+ +HCHO+2OH - ＝Cu+HCOOH+2Na + +H 2 Wherein, as shown in figure 4, the step S2 is carried out in a chemical aqueduct, the chemical copper plating raw materials comprise copper sulfate, formaldehyde, tartaric acid, ethylene diamine tetraacetic acid disodium and sodium hydroxide, the pH value is adjusted to 12.5, the reaction temperature is 25 ℃, simultaneously, a low-frequency ultrasonic device is used in a chemical copper plating tank to remove bubbles when the aluminum foil 1 enters water, and a plating layer is formedThe thickness growth speed is 2 mu m/h, and the cathode current collector after the electro-coppering is washed by two distilled water pools and then is sent into a drying chamber for drying. Wherein, 1L of the electroless copper plating raw material solution respectively contains 15g of copper sulfate, 45g of formaldehyde, 16g of tartaric acid, 20g of disodium ethylene diamine tetraacetate and 12g of sodium hydroxide.
S3, performing electro-coppering on two surfaces of the cathode current collector after electroless copper plating; specifically, as shown in FIG. 5, copper electroplating was carried out in an electrolytic cell at a temperature of 20 ℃ in a 1L volume of raw material solution for copper electroplating comprising 60g of anhydrous copper sulfate, 170g of sulfuric acid, 40mL of hydrochloric acid having a mass concentration of 37%, and 0.3mL of an acid copper brightener, using the negative current collector obtained in step S2 as a cathode, and using a current density of 1A/dm 2 And the coating thickness is controlled by controlling the advancing speed of the coil stock, and meanwhile, a low-frequency ultrasonic device is installed in the copper electroplating tank, so that bubbles on the surface of the negative current collector foil are removed, and the negative current collector after copper electroplating is finished is washed by two distilled water tanks and then is dried in a drying chamber.
And S4, passivating the copper-plated current collector. The 1L of passivation solution comprises the following raw materials: 5ml of phytic acid with the mass concentration of 50%, 10g of citric acid, 15ml of polyethylene glycol, 15ml of hydrogen peroxide and 3g of 2-mercaptobenzothiazole sodium are subjected to passivation treatment for 5 seconds.
The negative electrode current collector obtained in step S4 was subjected to thickness and area density tests, and the results shown in table 1 were obtained.
The lithium ion battery negative electrode piece and the lithium ion battery preparation method of the present embodiment are the same as those in embodiment 1, and are not described herein again.
Example 3
As shown in fig. 1, the negative electrode current collector for a lithium ion battery according to the present invention includes an aluminum foil 1, wherein electroless copper plating layers 21 are respectively disposed on upper and lower surfaces of the aluminum foil 1, and an electroplated copper layer 22 is attached to a surface of the electroless copper plating layer 21. Wherein the thickness of the aluminum foil 1 is 13 μm, and the thickness of the copper plating layer 2 is 2 μm.
The preparation steps of the negative current collector are as follows:
steps S1 to S4 are the same as those in embodiment 2, and are not described herein again.
The negative electrode current collector obtained in step S4 was subjected to thickness and area density tests, and the results shown in table 1 were obtained.
The lithium ion battery negative electrode piece and the lithium ion battery preparation method of the present embodiment are the same as those in embodiment 1, and are not described herein again.
Comparative example 1
As shown in fig. 1, the negative electrode current collector for lithium ion batteries according to the present invention employs a copper foil having a thickness of 6 μm.
Thickness and areal density tests were performed on the above negative electrode current collectors to obtain the results shown in table 1.
The preparation method of the negative electrode plate of the lithium ion battery and the lithium ion battery in the comparative example are the same as those in example 1, and are not repeated herein.
Comparative example 2
As shown in fig. 1, the negative electrode current collector for lithium ion batteries according to the present invention employs a copper foil having a thickness of 8 μm.
Thickness and areal density tests were performed on the above negative electrode current collectors, and the results shown in table 1 were obtained.
The preparation method of the negative pole piece of the lithium ion battery and the lithium ion battery of the comparative example are the same as the embodiment 1, and are not repeated herein.
TABLE 1 thickness and areal density of the current collector
From the graph, it can be seen that: compared with the common current collector with the same thickness, the weight energy density of the negative current collector prepared according to the invention is obviously improved;
the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The utility model provides a lithium ion battery is with negative current collector, it includes aluminium foil (1), its characterized in that: the upper surface and the lower surface of the aluminum foil (1) are respectively provided with a copper plating layer (2), and the copper plating layer (2) comprises a chemical copper plating layer (21) attached to the surface of the aluminum foil (1).
2. The negative electrode current collector for a lithium ion battery according to claim 1, wherein: the copper plating layer (2) further comprises a copper plating layer (22) attached to the surface of the electroless copper plating layer (21).
3. The negative electrode current collector for a lithium ion battery according to claim 1, wherein: the thickness of the aluminum foil (1) is 6-13 mu m, and the thickness of the copper plating layer (2) is 1-2 mu m.
4. The method for preparing a negative electrode current collector for a lithium ion battery according to claim 1, wherein: comprises the following steps of (a) preparing a solution,
s1, carrying out alkali washing oil removal, ultrasonic cleaning, drying and plasma cleaning activation on an aluminum foil (1);
and S2, carrying out chemical copper plating on two surfaces of the activated aluminum foil (1), and heating and drying to obtain the negative current collector for the lithium ion battery.
5. The method of preparing a negative electrode current collector for a lithium ion battery according to claim 4, wherein: the step S1 specifically comprises the steps of placing the aluminum foil (1) in an alkaline solution, carrying out ultrasonic cleaning for 5-10min at the temperature of 10-30 ℃, then placing the aluminum foil in a distilled water tank for ultrasonic cleaning, and drying after cleaning.
6. The method for preparing a negative electrode current collector for a lithium ion battery according to claim 4, wherein: in the step S2, the electroless copper plating raw materials comprise copper sulfate, formaldehyde, tartaric acid, ethylene diamine tetraacetic acid and sodium hydroxide, the pH value is adjusted to 12-13, the reaction temperature is 10-30 ℃, meanwhile, a low-frequency ultrasonic device is used in an electroless copper plating tank to remove bubbles when the aluminum foil (1) enters water, and the increase speed of the thickness of a plating layer is controlled to be 1-3 mu m/h.
7. The method for preparing a negative electrode current collector for a lithium ion battery according to claim 4, wherein: step S3, performing electro-coppering on two surfaces of the cathode current collector after electroless copper plating; and S4, passivating the copper-plated current collector.
8. The method for preparing a negative electrode current collector for a lithium ion battery according to claim 7, wherein: the step S3 is carried out at the temperature of 20-30 ℃, the negative current collector obtained in the step S2 is used as a cathode, and the current density is 1-2A/dm 2 And controlling the thickness of the coating by controlling the advancing speed of the coil stock, and meanwhile, installing a low-frequency ultrasonic device in the copper electroplating pool to remove bubbles on the surface of the negative current collector foil, and drying the negative current collector after the copper electroplating is finished after two times of water washing.
9. The utility model provides a lithium ion battery negative pole piece, includes negative pole active coating, its characterized in that: the negative active coating layer is coated on the surface of the copper plating layer (2) according to any one of claims 1 to 3.
10. The method for preparing the negative pole piece of the lithium ion battery as claimed in claim 9, characterized in that: comprises the following steps of (a) preparing a solution,
a1, preparing anode active coating slurry;
a2, coating the cathode active coating slurry on the surface of a copper plating layer (2) of a cathode current collector, and drying to obtain a cathode plate;
and A3, rolling the negative pole piece by using a roll-to-roll machine with the diameter of 800mm, and obtaining the negative pole piece by adopting a secondary rolling mode.
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