CN117080456A - Negative electrode current collector, negative electrode sheet, lithium battery and manufacturing method thereof - Google Patents
Negative electrode current collector, negative electrode sheet, lithium battery and manufacturing method thereof Download PDFInfo
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- CN117080456A CN117080456A CN202311233369.2A CN202311233369A CN117080456A CN 117080456 A CN117080456 A CN 117080456A CN 202311233369 A CN202311233369 A CN 202311233369A CN 117080456 A CN117080456 A CN 117080456A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 238000002955 isolation Methods 0.000 claims abstract description 151
- 239000000758 substrate Substances 0.000 claims abstract description 120
- 239000004020 conductor Substances 0.000 claims abstract description 48
- 239000010410 layer Substances 0.000 claims description 284
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 65
- 239000010949 copper Substances 0.000 claims description 60
- 230000003647 oxidation Effects 0.000 claims description 50
- 238000007254 oxidation reaction Methods 0.000 claims description 50
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 47
- 229910052802 copper Inorganic materials 0.000 claims description 41
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 39
- 229910052782 aluminium Inorganic materials 0.000 claims description 38
- 229910045601 alloy Inorganic materials 0.000 claims description 35
- 239000000956 alloy Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 34
- 229910052759 nickel Inorganic materials 0.000 claims description 31
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 25
- 238000002161 passivation Methods 0.000 claims description 24
- 239000011888 foil Substances 0.000 claims description 21
- 239000011229 interlayer Substances 0.000 claims description 17
- 238000009792 diffusion process Methods 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 239000011651 chromium Substances 0.000 claims description 10
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical group [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 229910000838 Al alloy Inorganic materials 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical group [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 7
- 230000002265 prevention Effects 0.000 claims description 7
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 150000002736 metal compounds Chemical class 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 3
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 claims 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- 230000003064 anti-oxidating effect Effects 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 9
- 238000005240 physical vapour deposition Methods 0.000 description 9
- 230000002829 reductive effect Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 238000002845 discoloration Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005275 alloying Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000977 initiatory effect Effects 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 229910018565 CuAl Inorganic materials 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 229910018182 Al—Cu Inorganic materials 0.000 description 3
- 229910007857 Li-Al Inorganic materials 0.000 description 3
- 229910008447 Li—Al Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 229910002535 CuZn Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000007733 ion plating Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910001120 nichrome Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 229910010199 LiAl Inorganic materials 0.000 description 1
- -1 MBT compound Chemical class 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 description 1
- WPPDFTBPZNZZRP-UHFFFAOYSA-N aluminum copper Chemical compound [Al].[Cu] WPPDFTBPZNZZRP-UHFFFAOYSA-N 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical class [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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
-
- 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
- H01M10/04—Construction or manufacture in general
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
-
- 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
-
- 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)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The present disclosure provides a negative electrode current collector, a negative electrode sheet, a lithium battery, and a method of manufacturing the same, wherein the negative electrode current collector includes: a conductive substrate formed of a first conductive material; the first isolation layer is arranged on one side of the conductive substrate and is formed by a second conductive material; a second isolation layer disposed on a side of the conductive substrate remote from the first isolation layer, the second isolation layer being formed of the second conductive material; the first conductive material is different from the second conductive material, and the projection of the first isolation layer and the second isolation layer on the conductive substrate is overlapped with the conductive substrate.
Description
Cross Reference to Related Applications
The present disclosure claims chinese patent application No. submitted in china at 2023, 6 and 30.
202310802678.0, the entire contents of which are incorporated herein by reference.
Technical Field
The disclosure relates to the technical field of lithium batteries, in particular to a negative electrode current collector, a negative electrode plate, a lithium battery and a manufacturing method thereof.
Background
Lithium ion batteries, abbreviated as lithium batteries, are widely used in human daily life as a kind of efficient energy storage device. The traditional lithium ion battery cell internally comprises a pair of positive plate and negative plate, and the positive plate and the negative plate are stacked in multiple layers or wound to realize battery cells with different capacities. In the traditional lithium ion battery, aluminum foil is used as a positive current collector metal material, and copper foil is used as a negative current collector metal material, so that the volumes of the positive current collector in the positive plate and the negative current collector in the negative plate are larger, and the overall volume of the lithium ion battery is larger, and the effective energy volume is lower.
Disclosure of Invention
The application aims to provide a negative current collector, a negative plate, a lithium battery and a manufacturing method thereof, which can replace the traditional copper as the negative current collector, save copper resources and cost and improve safety.
The embodiment of the disclosure provides a negative electrode current collector for a lithium battery, comprising:
a conductive substrate formed of a first conductive material;
the first isolation layer is arranged on one side of the conductive substrate and is formed by a second conductive material;
a second isolation layer disposed on a side of the conductive substrate remote from the first isolation layer, the second isolation layer being formed of the second conductive material;
the first conductive material is different from the second conductive material, and the projection of the first isolation layer and the second isolation layer on the conductive substrate is overlapped with the conductive substrate.
In some embodiments, the negative electrode current collector further comprises:
the first interlayer is arranged on one side, close to the conductive substrate, of the first isolation layer, and two sides of the first interlayer are respectively combined with the first isolation layer and the conductive substrate and are configured to prevent diffusion between the first isolation layer and the conductive substrate; the method comprises the steps of,
the second interlayer is arranged on one side, close to the conductive substrate, of the second isolation layer, and two sides of the second interlayer are respectively combined with the second isolation layer and the conductive substrate and are configured to prevent diffusion between the second isolation layer and the conductive substrate.
In some embodiments, the negative electrode current collector further comprises:
a first oxidation preventing layer disposed on a side of the first isolation layer away from the conductive substrate, configured to prevent oxidation of the first isolation layer; the method comprises the steps of,
and the second oxidation prevention layer is arranged on one side of the second isolation layer, which is far away from the conductive substrate, and is configured to prevent the second isolation layer from being oxidized.
In some embodiments, the first intermediate layer and the second intermediate layer are formed from a third conductive material that is different from both the first conductive material and the second conductive material.
In some embodiments, orthographic projections of the first isolation layer, the first intermediate layer, and the first oxidation preventing layer on the conductive substrate overlap; and
orthographic projections of the second isolation layer, the second intermediate layer and the second oxidation prevention layer on the conductive substrate are overlapped.
In some embodiments, the material of the first intermediate layer and/or the second intermediate layer is selected from at least one of: from a single metal, metal oxide or conductive compound.
In some embodiments, the material of the first intermediate layer and/or the second intermediate layer is selected from at least one of:
the single metal is selected from one of Cu, cr, ta, zn, cd, in, ti, mn, co, mo, fe, sn, ge, bi, sb, re, tl, V, ni, nb and Tc;
the metal oxide is selected from Cu 2 O、ZnO、SnO 2 、Fe 2 O 3 、TiO 2 、ZrO 2 、Co 2 O 3 、WO 3 、In 2 O 3 、Al 2 O 3 And Fe (Fe) 3 O 4 At least one of (a) and (b);
the conductive compound is selected from TiB 2 、TiC、TiN、ZrB 2 、ZrC、ZrN、VB 2 、VC、VN、NbB 2 、NbC、NbN、TaB 2 、TaC、CrB 2 、Cr 3 C 2 、CrN、Mo 2 C、Mo 2 B 5 、W 2 B 5 WC and LaB 6 At least one of them.
In some embodiments, the material of the first intermediate layer and/or the second intermediate layer is selected from at least one of: nickel, nickel-based alloys, copper-based alloys, and titanium nitride.
In some embodiments, the nickel-based alloy is a nichrome having a mass ratio of nickel element to chromium element of (1:99) - (99:1);
the nickel-based alloy is nickel-aluminum alloy, and the mass ratio of nickel element to aluminum element in the nickel-aluminum alloy is (1:99) - (99:1);
the copper-based alloy is nickel-copper alloy, and the mass ratio of nickel element to copper element in the nickel-copper alloy is (1:99) - (99:1).
In some embodiments, the bonding force between the first release layer and the first intermediate layer is not less than 0.5N/15mm; the bonding force between the second isolation layer and the second intermediate layer is not less than 0.5N/15mm.
In some embodiments, the conductive substrate has a thickness D1, D1 satisfying: d1 is more than or equal to 2 mu m and less than or equal to 50 mu m;
the thicknesses of the first middle layer and the second middle layer are D2, and D2 meets the following conditions: d2 is more than or equal to 1nm and less than or equal to 1000nm;
the thickness of the first isolation layer and the second isolation layer is D3, and D3 meets the following conditions: d3 is less than or equal to 1nm and less than or equal to 1500nm.
In some embodiments, the material of the first and/or second oxidation preventing layer is selected from at least one of: a single metal or alloy or metal compound;
wherein the single metal is selected from at least one of Ti, V, cr, mn, fe, co, ni;
the alloy is at least one of nickel base alloy and copper base alloy;
the metal compound is TiB 2 、TiC、TiN、ZrB 2 、ZrC、ZrN、VB 2 、VC、VN、NbB 2 、NbC、NbN、TaB 2 、TaC、CrB 2 、Cr 3 C 2 、CrN、Mo 2 C、Mo 2 B 5 、W 2 B 5 WC and LaB 6 At least one of (a) and (b);
in some embodiments, the first and/or second oxidation preventing layer is selected from at least one of: the passivation solution is chromium-free passivation solution or organic passivation solution.
In some embodiments, the first and/or second oxidation preventing layer has a thickness of 1nm to 100nm.
In some embodiments, the conductive substrate is aluminum foil; the second conductive material is copper.
The present disclosure also provides a negative electrode sheet comprising a negative electrode current collector as set forth in any one of the above.
The present disclosure also provides a lithium battery including the negative electrode sheet as described above.
The present disclosure also provides a method of manufacturing a negative electrode current collector, the method comprising:
providing a conductive substrate formed of a first conductive material;
providing a first isolation layer on one side of the conductive substrate, wherein the first isolation layer is formed by a second conductive material;
disposing a second isolation layer on a side of the conductive substrate remote from the first isolation layer, the second isolation layer being formed of the second conductive material;
the first conductive material is different from the second conductive material, and the projection of the first isolation layer and the second isolation layer on the conductive substrate is overlapped with the conductive substrate.
In some embodiments, the method further comprises:
providing a first interlayer on one side of the first isolation layer, which is close to the conductive substrate, wherein two sides of the first interlayer are respectively combined with the first isolation layer and the conductive substrate and are configured to prevent diffusion between the first isolation layer and the conductive substrate; the method comprises the steps of,
and arranging a second intermediate layer on one side of the second isolation layer, which is close to the conductive substrate, wherein two sides of the second intermediate layer are respectively combined with the second isolation layer and the conductive substrate and are configured to prevent diffusion between the second isolation layer and the conductive substrate.
In some embodiments, the method of manufacturing further comprises:
providing a first oxidation preventing layer on one side of the first isolation layer away from the conductive substrate, configured to prevent oxidation of the first isolation layer; the method comprises the steps of,
and a second oxidation prevention layer is arranged on one side of the second isolation layer, which is far away from the conductive substrate, and is configured to prevent the second isolation layer from being oxidized.
The present disclosure also provides a method for manufacturing a negative electrode sheet, including the method for manufacturing a negative electrode current collector as described in any one of the above.
The present disclosure also provides a method of manufacturing a lithium battery, including a method of manufacturing a negative electrode sheet as described above.
Compared with the related art, the method has the following technical effects:
1. the negative electrode current collector disclosed by the disclosure adopts the aluminum foil as the conductive substrate, and a multi-layer metal film structure is deposited on the aluminum foil substrate to form a multi-layer metal structure, so that the defect that aluminum cannot be used as a negative electrode in a traditional lithium battery is overcome, the traditional copper foil is replaced to be used as the negative electrode current collector, and copper resources and cost are saved;
2. the isolating layer is of a continuous and compact film structure, the aluminum foil is isolated from the electrolyte, the alloying of the negative electrode Li-Al material can be prevented, and the conductivity of the negative electrode current collector can be improved;
3. the PVD and the reagent are adopted to perform anti-oxidation treatment on the PVD copper surface, so that oxidative discoloration of the Cu surface in the pole piece coating and baking process is prevented, interface resistance between the current collector and the active substance can be reduced, the internal resistance of the lithium ion battery prepared by utilizing the negative current collector is further reduced, and the rate capability and the cycle performance of the lithium ion battery are improved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the disclosure and together with the description, serve to explain the principles of the disclosure. It will be apparent to those of ordinary skill in the art that the drawings in the following description are merely examples of the disclosure and that other drawings may be derived from them without undue effort. In the drawings:
fig. 1 is a schematic cross-sectional structure of a negative electrode current collector provided in some embodiments of the present disclosure;
fig. 2 is a flow chart of a method of manufacturing a negative electrode current collector provided in some embodiments of the present disclosure;
FIG. 3 is a flow chart of a method of manufacturing a negative electrode current collector according to further embodiments of the present disclosure; and
fig. 4 is a flowchart illustrating a method for manufacturing a negative electrode current collector according to other embodiments of the present disclosure.
Detailed Description
For the purpose of promoting an understanding of the principles and advantages of the disclosure, reference will now be made in detail to the drawings, in which it is apparent that the embodiments described are only some, but not all embodiments of the disclosure. Based on the embodiments in this disclosure, all other embodiments that a person of ordinary skill in the art would obtain without making any inventive effort are within the scope of protection of this disclosure.
The terminology used in the embodiments of the disclosure is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. As used in this disclosure of embodiments and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise, the "plurality" generally includes at least two.
It should be understood that the term "and/or" as used herein is merely one relationship describing the association of the associated objects, meaning that there may be three relationships, e.g., a and/or B, may represent: a exists alone, A and B exist together, and B exists alone. In addition, the character "/" herein generally indicates that the front and rear associated objects are an "or" relationship.
It should be understood that although the terms first, second, third, etc. may be used in embodiments of the present disclosure, these should not be limited to these terms. These terms are only used to distinguish one from another. For example, a first may also be referred to as a second, and similarly, a second may also be referred to as a first, without departing from the scope of embodiments of the present disclosure.
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a product or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such product or apparatus. Without further limitation, an element defined by the phrase "comprising" does not exclude the presence of other like elements in a commodity or device comprising such element.
In the related art, a lithium battery generally comprises a positive electrode plate and a negative electrode plate, and the positive electrode plate and the negative electrode plate realize battery cells with different capacities through multilayer superposition or positive electrode winding. The positive electrode sheet generally includes a positive electrode current collector and positive electrode active materials coated on both sides of the positive electrode current collector. The positive current collector typically employs aluminum foil, which is typically 10 to 15 microns thick. The negative electrode sheet generally includes a negative electrode current collector and a negative electrode active material coated on both sides of the negative electrode current collector. The negative current collector typically employs copper foil, which is typically 4.5 to 9 microns thick. The lithium ion battery generally adopts aluminum as a positive electrode current collector metal material and copper as a negative electrode current collector metal material. This is because the oxidation potential of the metal aluminum is high, and the size of the lattice octahedral voids of the metal aluminum is similar to that of lithium, so that the metal aluminum is extremely easy to react with lithium to form LiAl and Li 3 Al 2 、Li 4 Al 3 Such alloys consume not only a large amount of li+ but also destroy the structure and morphology of the metallic aluminum itself, so that aluminum can serve as a current collector for the positive electrode of a lithium ion battery, but cannot serve as a current collector for the negative electrode of a lithium ion battery. Cu has little lithium intercalation capacity in the charge and discharge process of the battery, and keeps stable structure and electrochemical performance, so the Cu can be used as a current collector of the negative electrode of the ion battery. The copper foil is thicker and the price is higher, so that the negative current collector occupies a considerable volume, the effective energy volume ratio of the lithium battery is low, the miniaturization of the lithium battery is not facilitated, and the cost of the lithium battery is higher.
The embodiment of the disclosure provides a negative electrode current collector for a lithium battery, comprising: a conductive substrate formed of a first conductive material; the first isolation layer is arranged on one side of the conductive substrate and is formed by a second conductive material; a second isolation layer disposed on a side of the conductive substrate remote from the first isolation layer, the second isolation layer being formed of the second conductive material; the first conductive material is different from the second conductive material, and the projection of the first isolation layer and the second isolation layer on the conductive substrate is overlapped with the conductive substrate.
Alternative embodiments of the present disclosure are described in detail below with reference to the drawings.
Fig. 1 is a schematic cross-sectional structure of a negative electrode current collector provided in some embodiments of the present disclosure; specifically, the disclosed embodiments provide a negative electrode current collector 100 for a lithium battery, including: a conductive substrate 1 formed of a first conductive material; a first isolation layer 4 disposed on one side of the conductive substrate 1, the first isolation layer 4 being formed of a second conductive material; a second isolation layer 5 provided on a side of the conductive substrate 1 remote from the first isolation layer 4, the second isolation layer 5 being formed of the second conductive material; wherein the first conductive material is different from the second conductive material, and the projection of the first isolation layer 4 and the second isolation layer 5 on the conductive substrate 1 is overlapped with the conductive substrate. The aluminum foil is adopted as the conductive substrate 1, and the multi-layer metal film structure formed by different materials is symmetrically deposited on the two sides of the aluminum foil substrate to form a multi-layer metal structure, so that the conductivity of the negative electrode current collector is enhanced, the aluminum foil is adopted as the conductive substrate, the weight of the negative electrode current collector is reduced, the cost is reduced, the defect that aluminum cannot be used as a negative electrode in a traditional lithium battery is overcome, the traditional copper foil which is expensive and thick is used as the negative electrode current collector is replaced, copper resources and cost are saved, and the safety is improved; the isolating layer in the present disclosure is a continuous and compact copper film layer structure, which can completely isolate the aluminum foil from the electrolyte, can prevent alloying of the negative electrode Li-Al material, and can improve the conductivity of the negative electrode current collector.
In some embodiments, the conductive substrate has a thickness D1, D1 satisfying: d1 is more than or equal to 2 mu m and less than or equal to 50 mu m; preferably, 2 μm.ltoreq.D1.ltoreq.5 μm, for example, 2 μm, 3 μm, 4 μm, etc., so that the thickness of the negative electrode current collector can be greatly reduced, which is advantageous for miniaturization of the lithium battery.
In some embodiments, the material of the first isolation layer 4 and/or the second isolation layer 5 is selected from at least one of the following: a single metal with purity of more than or equal to 98 wt%: aluminum, copper, nickel, iron, titanium, silver, gold, cobalt, chromium, molybdenum, or tungsten; preferably, one of aluminum, copper, nickel, iron, titanium, silver, gold, cobalt, chromium, molybdenum and tungsten with a purity of 99-100 wt%; or alternatively; at least one selected from copper-aluminum alloy, copper-nickel alloy and copper-tin alloy.
In some embodiments, the thickness D3 of the first isolation layer 4 and the second isolation layer 5 is 1-1500nm, preferably 30-1000nm, respectively; compared with the traditional copper foil cathode, the first isolation layer 4 and the second isolation layer 5 can deposit thinner copper layers in a PVD mode, so that copper materials are saved, and the overall thickness of the cathode plate is reduced.
In some embodiments, the bonding force between the first isolation layer 4 and the first intermediate layer 2 and/or the bonding force between the second isolation layer 5 and the second intermediate layer 3 is greater than or equal to 0.5N/15mm, and the stronger bonding force avoids the first isolation layer 4 and the first intermediate layer 2 or the second isolation layer 5 from being peeled off from the second intermediate layer 3 during the curling or application process, thereby affecting the conductivity.
The function of the isolation layer is to prevent the exposure of the conductive substrate Al, and the operation can be realized if the isolation layer is a continuous compact film (for example, the thickness is more than or equal to 30 nm); another function of the isolation layer is to conduct electricity, but if the isolation layer is too thin (several tens of nanometers), it will interdiffuse with the conductive substrate in a short time (several days or several weeks), so that Al is exposed, the original function of the isolation layer is lost, and if the isolation layer is too thick, the process cost, the material use efficiency and the like are increased, so that the isolation layer may be set between 1 and 1500nm, preferably 30 to 1000nm.
The phenomenon of infirm interface bonding between the conductive substrate and the isolation layer can occur, because only van der Waals force exists between the conductive substrate and the isolation layer, a layer of aluminum oxide film is naturally formed on the aluminum surface of the conductive substrate, so that the bonding strength between Cu and Al is not high, and if CuAl is layered due to the not high bonding strength in the use process of the battery, the conductive effect is lost, so that the bonding force of the conductive substrate and the isolation layer is hoped to be more than or equal to 0.5N/15mm.
Because aluminum is used as the conductive substrate, and the aluminum negative electrode current collector is used as the negative electrode, alloying reaction can occur with metal lithium, so that the conductivity is invalid, therefore, an isolating layer (Cu) is arranged on the aluminum conductive substrate, an aluminum copper coating layer is formed, the alloying reaction between Li and Al can be blocked while the conductivity is not reduced, and the stability of the lithium battery is improved.
In some embodiments, the AI serving as the conductive layer and the Cu serving as the isolation layer are both positioned at the negative electrode, under the action of the electrolyte, mutual diffusion and galvanic corrosion of Al-Cu can possibly occur, and the interlayer is designed between the Al-Cu layers, so that the mutual diffusion and corrosion of the Al-Cu layers can be prevented or slowed down, the conductive effect can be achieved, and the binding force between the aluminum and the copper can be enhanced.
In some embodiments, as shown in fig. 1, the negative electrode current collector 100 further includes: a first intermediate layer 2, the first intermediate layer 2 being disposed on a side of the first isolation layer 4 close to the conductive substrate 1, both sides of the first intermediate layer 2 being bonded to the first isolation layer 4 and the conductive substrate 1, respectively, configured to prevent diffusion between the first isolation layer 4 and the conductive substrate 1; and a second intermediate layer 3, the second intermediate layer 3 is disposed on one side of the second isolation layer 5 near the conductive substrate 1, and two sides of the second intermediate layer 3 are respectively combined with the second isolation layer 5 and the conductive substrate 1, and are configured to prevent diffusion between the second isolation layer 5 and the conductive substrate 1.
Specifically, in some embodiments, the material of the first intermediate layer 2 and/or the second intermediate layer 3 is selected from at least one of the following:
the single metal is selected from one of Cu, cr, ta, zn, cd, in, ti, mn, co, mo, fe, sn, ge, bi, sb, re, tl, V, ni, nb and Tc;
the metal oxide is selected from Cu 2 O、ZnO、SnO 2 、Fe 2 O 3 、TiO 2 、ZrO 2 、Co 2 O 3 、WO 3 、In 2 O 3 、Al 2 O 3 And Fe (Fe) 3 O 4 At least one of (a) and (b);
the conductive compound is selected from TiB 2 、TiC、TiN、ZrB 2 、ZrC、ZrN、VB 2 、VC、VN、NbB 2 、NbC、NbN、TaB 2 、TaC、CrB 2 、Cr 3 C 2 、CrN、Mo 2 C、Mo 2 B 5 、W 2 B 5 WC and LaB 6 At least one of them.
In some embodiments, the material of the first intermediate layer 2 and/or the second intermediate layer 3 is selected from at least one of the following: nickel, nickel-based alloys, copper-based alloys, and titanium nitride.
In some embodiments, the nickel-based alloy is a nichrome having a mass ratio of nickel element to chromium element of (1:99) - (99:1); the nickel-based alloy is nickel-aluminum alloy, and the mass ratio of nickel element to aluminum element in the nickel-aluminum alloy is (1:99) - (99:1); the copper-based alloy is nickel-copper alloy, and the mass ratio of nickel element to copper element in the nickel-copper alloy is (1:99) - (99:1). The metal nickel can be used for the negative electrode of the lithium ion battery, the electrode potential of the nickel is between copper and aluminum, the galvanic corrosion of the aluminum can be inhibited, and the mutual diffusion between copper and aluminum is prevented, so that the material of the intermediate layer is selected from nickel or nickel-based alloy, the other element of the nickel-based alloy is preferentially selected from copper or aluminum from the lattice matching degree of metal atoms, the lattice matching degree of nickel copper or nickel aluminum and copper or aluminum is higher, and the respective content in the alloy is fully within the protection range.
In some embodiments, the thickness D2 of the first intermediate layer 6 and/or the second intermediate layer 7 is 1-1000nm, preferably 5-500nm. The intermediate layer has the functions of conducting electricity and enhancing the bonding strength between CuAl, prevents mutual diffusion of the CuAl and the CuAl, is generally thinner, and can be made as thin as possible as long as the intermediate layer has the functions, so that raw materials and cost are saved, and the film can be formed generally by 1-1000nm, preferably 5-100 nm or 5-500nm.
In some embodiments, the negative electrode current collector 100 further includes a first oxidation preventing layer 6, the first oxidation preventing layer 6 being disposed on a side of the first separator 4 remote from the conductive substrate 1; and a second oxidation preventing layer 7, the second oxidation preventing layer 7 being disposed on a side of the second isolation layer 5 remote from the conductive substrate 1. For example, the isolating layer such as Cu can generate oxidative discoloration in the process of pole piece coating and baking, and the oxidation discoloration can be prevented by the reasonably designed oxidation-resistant protective layer above Cu.
In some embodiments, the orthographic projections of the first oxidation preventing layer 6, the first isolating layer 4 and the first intermediate layer 2 on the conductive substrate 1 coincide; and the second oxidation preventing layer 7, the second isolating layer 5 and the second intermediate layer 3 are overlapped on the front projection of the conductive substrate 1. Therefore, the anti-oxidation layer can completely cover the isolation layer and the middle layer, and the anti-oxidation performance of the negative electrode current collector is improved.
In some embodiments, the first oxidation preventing layer 6 and/or the second oxidation preventing layer 7 may be PVD metal oxidation preventing layers, and the material of the metal oxidation preventing layers is selected from at least one of the following: a single metal or alloy or metal compound; wherein the single metal is selected from at least one of Ti, V, cr, mn, fe, co, ni; the alloy is at least one of nickel base alloy and copper base alloy; the metal compound is TiB 2 、TiC、TiN、ZrB 2 、ZrC、ZrN、VB 2 、VC、VN、NbB 2 、NbC、NbN、TaB 2 、TaC、CrB 2 、Cr 3 C 2 、CrN、Mo 2 C、Mo 2 B 5 、W 2 B 5 WC and LaB 6 At least one of them.
The PVD oxidation-preventing layer is a metal or alloy layer formed by vacuum depositing a layer of the material on the surface of the first isolation layer 4 and/or the second isolation layer 5, wherein the deposition mode can be at least one of vacuum deposition such as magnetron sputtering, ion plating, vacuum evaporation and the like, the deposition thickness is 1nm-100nm, the oxidation-preventing layer is used for inhibiting oxidative discoloration of the rich high-temperature environment, and if the PVD oxidation-preventing layer is obtained in a PVD mode, the minimum thickness which needs to be deposited in the rich high-temperature environment and does not discolor is generally set to be 1nm-100nm, preferably 3nm-50nm. The oxidation preventing layer is required to meet the requirement of a vacuum oven at 100-150 ℃ for 5-30min, oxidation discoloration of the current collector does not occur in the process, and the oxidation preventing layer does not additionally reduce the conductivity of the negative current collector compared with the negative current collector without the oxidation preventing layer.
In some embodiments, the first oxidation preventing layer 6 and/or the second oxidation preventing layer 7 may be a passivation layer selected from a passivation solution of at least one of: the passivation solution is chromium-free passivation solution or organic passivation solution.
The method for forming the passivation layer comprises the steps of selecting the passivation solution for spraying and/or soaking, and then rolling and drying the passivation layer. Wherein the spraying or soaking time is 1-60s, and the drying temperature is 50-120 ℃ until no solvent remains on the surface. The anti-oxidation layer of the passivation solution is not required to be in thickness, the anti-oxidation layer of the passivation solution is required to be dried to obtain a uniform and compact anti-oxidation layer, the reaction film forming time is slightly different due to the difference of reagent types, for example, the time period of 1-60s can cover the reaction film forming time of the passivation solution, and the drying is determined according to the curing temperature of the reaction film forming of different passivation solutions.
The organic passivating agent can be modified benzotriazole, and the preparation method comprises the following steps: preparing a 0.5mmol/LBTA and 0.5mmol/L MBT compound solution, magnetically stirring until the compound solution is completely dissolved, coating a copper current collector base film by a coating machine, drying for 30min in a drying box at 50-80 ℃, and taking out.
Examples:
in the first embodiment, cu with a thickness of 300nm was vapor deposited on the upper and lower surfaces of an Al foil with a thickness of 12 μm. The battery is prepared, the first effect and the cycle performance of the battery are represented, and the corrosiveness of the battery after the battery pole piece is disassembled is compared.
In the second embodiment, cu with the thickness of 800nm is evaporated on the upper surface and the lower surface of an Al foil with the thickness of 12um to prepare a battery, the first effect, the cycle performance and the corrosiveness of the battery after the disassembly of a battery pole piece are represented.
In the third embodiment, ni layers with the thickness of 10nm are sputtered on the upper surface and the lower surface of an Al foil with the thickness of 12um, cu with the thickness of 300nm is vacuum evaporated on the upper surface and the lower surface of the Ni layer, and the battery is prepared, so that the initial effect, the cycle performance and the corrosiveness of the battery after the battery pole piece is disassembled are represented.
In the fourth embodiment, ni layers with the thickness of 10nm are deposited on the upper and lower surfaces of Al foil with the thickness of 12um, cu with the thickness of 300nm is deposited on the upper and lower surfaces of the Ni layers in a vacuum manner, and CuZn alloy with the thickness of 10nm is magnetron sputtered on the upper and lower surfaces of Cu. The battery is prepared, the first effect and the cycle performance of the battery are represented, and the corrosiveness of the battery after the battery pole piece is disassembled is compared.
In the fifth embodiment, ni layers with the thickness of 10nm are deposited on the upper and lower surfaces of Al foil with the thickness of 12um, cu with the thickness of 300nm is deposited on the upper and lower surfaces of the Ni layers in a vacuum manner, a chromium-free passivating agent is coated on the upper and lower surfaces of Cu, and the Cu is rolled and dried. The negative current collector material is used for preparing a battery, which characterizes the initial effect and the cycle performance of the battery and compares the corrosiveness of the battery after the battery pole piece is disassembled.
In the sixth embodiment, cu with the thickness of 300nm is vacuum evaporated on the upper and lower surfaces of an Al foil with the thickness of 12um, a chromium-free passivating agent is coated on the upper and lower surfaces of Cu, and the Cu is rolled and dried. The negative current collector material is used for preparing a battery, which characterizes the initial effect and the cycle performance of the battery and compares the corrosiveness of the battery after the battery pole piece is disassembled.
In the seventh embodiment, cu with a thickness of 300nm is vacuum deposited on the upper and lower surfaces of an Al foil with a thickness of 12um, and a CuZn alloy with a thickness of 10nm is magnetron sputtered on the upper and lower surfaces of Cu. The negative current collector material is used for preparing a battery, which characterizes the initial effect and the cycle performance of the battery and compares the corrosiveness of the battery after the battery pole piece is disassembled.
The pure Cu foil of the first comparative example and the pure Cu foil of the second comparative example are used as a negative current collector to prepare a battery cell, and the battery cell is characterized in material performance, initial effect of the battery cell, cycle performance and corrosiveness after disassembling the battery pole piece.
Table 1 negative electrode current collector material performance comparison
As can be seen from the comparison result of the negative electrode current collector performance of the multilayer structure and the negative electrode current collector of the pure copper foil in Table 1, firstly, the thickness of copper in the composite structure of examples 1-7 of the application is very small, thus greatly reducing the use amount of copper, greatly saving Cu raw material resources and reducing cost while the electrical performance is comparable to that of the pure copper foil.
The sheet resistances of examples 1 to 7 of the present application are all relatively low, and although slightly higher than those of the comparative examples, they still have substantially equivalent sheet resistances, indicating that the multilayer negative electrode current collector formed by the examples of the present application still has good conductivity.
In the embodiment 3 to the embodiment 5, the interlayer is added between the aluminum and the copper, so that the bonding force between Cu and Al can be increased, and the bonding force is obviously better than that of the embodiment without the interlayer. And the tensile strengths of examples 1-7 are close to those of the comparative examples, demonstrating the better tensile properties of the present application.
According to the application, the anti-oxidation layers are added in the embodiments 4 to 7, so that the roughness is higher, the surface energy of the composite current collector is enhanced, the bonding performance of the composite current collector and the active substances can be improved, and the anti-oxidation layers are not added in the embodiments 1 to 3 and the comparative examples, so that the roughness is lower, the surface energy of the composite current collector is lower, and the bonding force with the active substances is weaker.
According to the application, the oxidation resistance of the composite current collector is obviously improved because the oxidation resistance layer is added in the embodiment 4 to the embodiment 7, and the composite current collector does not change color in a high-temperature oxygen-enriched environment.
Table 2 negative electrode current collector cell performance comparison
As can be seen from the comparison results of the performances of the negative current collector cells in Table 2, the internal resistance values of the embodiments 1 to 7 of the present application are low and close to those of the comparative examples, which indicates that the negative current collector cells with the multi-layer structure formed in the embodiments of the present application still have good conductivity.
The first coulomb efficiency and the cycle number of the capacity retention rate of the embodiment 1 to the embodiment 7 of the application are close to those of the comparative example, which shows that the negative current collector cell formed by each embodiment of the application has better discharge performance.
As can be seen from the cell results in table 2, examples 1 to 7 of the present application can be used as negative electrode current collectors, and the cell performance is good, and no pulverization of the barrier Cu occurs after the cell is disassembled.
The negative electrode current collector with the structure can be used for the negative electrode end of a battery. The present disclosure also provides a negative electrode sheet including the negative electrode current collector 100 as described in the above embodiments.
The present disclosure also provides a lithium battery including the negative electrode sheet described in the above embodiment.
The present disclosure also provides a method for manufacturing the negative electrode current collector 100, as shown in fig. 2, including the steps of:
step S102: providing a conductive substrate formed of a first conductive material;
step S104: providing a first isolation layer on one side of the conductive substrate, wherein the first isolation layer is formed by a second conductive material;
step S106: disposing a second isolation layer on a side of the conductive substrate remote from the first isolation layer, the second isolation layer being formed of the second conductive material;
the first conductive material is different from the second conductive material, and the projection of the first isolation layer and the second isolation layer on the conductive substrate is overlapped with the conductive substrate.
In some embodiments, as shown in fig. 3, the method further comprises:
step S108: providing a first interlayer on one side of the first isolation layer, which is close to the conductive substrate, wherein two sides of the first interlayer are respectively combined with the first isolation layer and the conductive substrate and are configured to prevent diffusion between the first isolation layer and the conductive substrate; the method comprises the steps of,
step S110: and arranging a second intermediate layer on one side of the second isolation layer, which is close to the conductive substrate, wherein two sides of the second intermediate layer are respectively combined with the second isolation layer and the conductive substrate and are configured to prevent diffusion between the second isolation layer and the conductive substrate.
In some embodiments, as shown in fig. 4, the manufacturing method further comprises:
step S112: providing a first oxidation preventing layer on one side of the first isolation layer away from the conductive substrate, configured to prevent oxidation of the first isolation layer; the method comprises the steps of,
step S114: and a second oxidation prevention layer is arranged on one side of the second isolation layer, which is far away from the conductive substrate, and is configured to prevent the second isolation layer from being oxidized.
In some embodiments, the method of providing a first oxidation preventing layer on a side of the first isolation layer remote from the substrate and/or providing a second oxidation preventing layer on a side of the second isolation layer remote from the substrate comprises at least one of: knife coating, roll coating, spray coating, chemical vapor deposition, plasma vapor deposition, atomic layer deposition, pulsed laser deposition, vacuum evaporation, ion plating, radio frequency sputtering, magnetron sputtering, or reactive sputtering.
In some embodiments, the method of providing a first oxidation preventing layer on a side of the first isolation layer remote from the substrate and/or providing a second oxidation preventing layer on a side of the second isolation layer remote from the substrate comprises: forming a first isolation layer oxide layer on one side of the first isolation layer far away from the substrate through spraying or soaking chromium passivation solution, chromium-free passivation solution or organic passivation solution; and forming the second isolation layer oxide layer on one side of the second isolation layer far away from the substrate through spraying or soaking chromium passivation solution, chromium-free passivation solution or organic passivation solution.
The present disclosure also provides a method for manufacturing a negative electrode sheet, including the method for manufacturing a negative electrode current collector as described in any one of the above.
The present disclosure also provides a method of manufacturing a lithium battery, including a method of manufacturing a negative electrode sheet as described above.
The negative electrode current collector disclosed by the disclosure adopts the aluminum foil as the conductive substrate, and a multi-layer metal film structure is deposited on the aluminum foil substrate to form a multi-layer metal structure, so that the defect that aluminum cannot be used as a negative electrode in a traditional lithium battery is overcome, the traditional copper foil is replaced to be used as the negative electrode current collector, copper resources and cost are saved, and safety is improved; the isolating layer is of a continuous and compact film structure, the aluminum foil is isolated from the electrolyte, the alloying of the negative electrode Li-Al material can be prevented, and the conductivity of the negative electrode current collector can be improved; in addition, PVD and a reagent are adopted to perform anti-oxidation treatment on the PVD copper surface, so that oxidative discoloration of the Cu surface in the pole piece coating and baking process is prevented, interface resistance between a current collector and an active substance can be reduced, further internal resistance of the lithium ion battery prepared by utilizing the negative current collector is reduced, and rate performance and cycle performance of the lithium ion battery are improved.
Finally, it should be noted that: in the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other.
The above embodiments are merely for illustrating the technical solution of the present disclosure, and are not limiting thereof; although the present disclosure has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present disclosure.
Claims (22)
1. A negative electrode current collector for a lithium battery, comprising:
a conductive substrate formed of a first conductive material;
the first isolation layer is arranged on one side of the conductive substrate and is formed by a second conductive material;
a second isolation layer disposed on a side of the conductive substrate remote from the first isolation layer, the second isolation layer being formed of the second conductive material;
the first conductive material is different from the second conductive material, and the projection of the first isolation layer and the second isolation layer on the conductive substrate is overlapped with the conductive substrate.
2. The negative current collector of claim 1, further comprising:
the first interlayer is arranged on one side, close to the conductive substrate, of the first isolation layer, and two sides of the first interlayer are respectively combined with the first isolation layer and the conductive substrate and are configured to prevent diffusion between the first isolation layer and the conductive substrate; the method comprises the steps of,
the second interlayer is arranged on one side, close to the conductive substrate, of the second isolation layer, and two sides of the second interlayer are respectively combined with the second isolation layer and the conductive substrate and are configured to prevent diffusion between the second isolation layer and the conductive substrate.
3. The anode current collector of claim 2, wherein the anode current collector further comprises:
a first oxidation preventing layer disposed on a side of the first isolation layer away from the conductive substrate, configured to prevent oxidation of the first isolation layer; the method comprises the steps of,
and the second oxidation prevention layer is arranged on one side of the second isolation layer, which is far away from the conductive substrate, and is configured to prevent the second isolation layer from being oxidized.
4. The anode current collector of claim 2, wherein the first intermediate layer and the second intermediate layer are formed of a third conductive material that is different from both the first conductive material and the second conductive material.
5. The negative electrode current collector according to claim 3, wherein,
orthographic projections of the first isolation layer, the first intermediate layer and the first oxidation preventing layer on the conductive substrate are overlapped; and
orthographic projections of the second isolation layer, the second intermediate layer and the second oxidation prevention layer on the conductive substrate are overlapped.
6. The anode current collector according to claim 2, wherein the material of the first intermediate layer and/or the second intermediate layer is selected from at least one of: from a single metal, metal oxide or conductive compound.
7. The anode current collector according to claim 6, wherein the material of the first intermediate layer and/or the second intermediate layer is selected from at least one of:
the single metal is selected from one of Cu, cr, ta, zn, cd, in, ti, mn, co, mo, fe, sn, ge, bi, sb, re, tl, V, ni, nb and Tc;
the metal oxide is selected from Cu 2 O、ZnO、SnO 2 、Fe 2 O 3 、TiO 2 、ZrO 2 、Co 2 O 3 、WO 3 、In 2 O 3 、Al 2 O 3 And Fe (Fe) 3 O 4 At least one of (a) and (b);
the conductive compound is selected from TiB 2 、TiC、TiN、ZrB 2 、ZrC、ZrN、VB 2 、VC、VN、NbB 2 、NbC、NbN、TaB 2 、TaC、CrB 2 、Cr 3 C 2 、CrN、Mo 2 C、Mo 2 B 5 、W 2 B 5 WC and LaB 6 At least one of them.
8. The anode current collector according to claim 7, wherein the material of the first intermediate layer and/or the second intermediate layer is selected from at least one of: nickel, nickel-based alloys, copper-based alloys, and titanium nitride.
9. The negative electrode current collector according to claim 8, wherein,
the nickel-based alloy is nickel-chromium alloy, and the mass ratio of nickel element to chromium element in the nickel-chromium alloy is (1:99) - (99:1);
the nickel-based alloy is nickel-aluminum alloy, and the mass ratio of nickel element to aluminum element in the nickel-aluminum alloy is (1:99) - (99:1);
the copper-based alloy is nickel-copper alloy, and the mass ratio of nickel element to copper element in the nickel-copper alloy is (1:99) - (99:1).
10. The negative electrode current collector according to claim 2, wherein a binding force between the first separator and the first intermediate layer is not less than 0.5N/15mm; the bonding force between the second isolation layer and the second intermediate layer is not less than 0.5N/15mm.
11. The negative electrode current collector according to claim 2, wherein,
the thickness of the conductive substrate is D1, and D1 meets the following conditions: d1 is more than or equal to 2 mu m and less than or equal to 50 mu m;
the thicknesses of the first middle layer and the second middle layer are D2, and D2 meets the following conditions: d2 is more than or equal to 1nm and less than or equal to 1000nm;
the thickness of the first isolation layer and the second isolation layer is D3, and D3 meets the following conditions: d3 is less than or equal to 1nm and less than or equal to 1500nm.
12. A negative electrode current collector according to claim 3, wherein the material of the first and/or second oxidation preventing layer is selected from at least one of: a single metal or alloy or metal compound;
wherein the single metal is selected from at least one of Ti, V, cr, mn, fe, co, ni;
the alloy is at least one of nickel base alloy and copper base alloy;
the metal compound is TiB 2 、TiC、TiN、ZrB 2 、ZrC、ZrN、VB 2 、VC、VN、NbB 2 、NbC、NbN、TaB 2 、TaC、CrB 2 、Cr 3 C 2 、CrN、Mo 2 C、Mo 2 B 5 、W 2 B 5 WC and LaB 6 At least one of them.
13. A negative electrode current collector according to claim 3, wherein the first and/or second oxidation preventing layer is selected from at least one of: the passivation solution is chromium-free passivation solution or organic passivation solution.
14. The negative electrode current collector according to claim 3, wherein the thickness of the first and/or second oxidation preventing layer is 1nm to 100nm.
15. The negative current collector of claim 1, wherein the conductive substrate is aluminum foil; the second conductive material is copper.
16. A negative electrode sheet, characterized in that the negative electrode sheet comprises the negative electrode current collector according to any one of claims 1 to 15.
17. A lithium battery comprising the negative electrode sheet of claim 16.
18. A method of manufacturing a negative electrode current collector, the method comprising:
providing a conductive substrate formed of a first conductive material;
providing a first isolation layer on one side of the conductive substrate, wherein the first isolation layer is formed by a second conductive material;
disposing a second isolation layer on a side of the conductive substrate remote from the first isolation layer, the second isolation layer being formed of the second conductive material;
the first conductive material is different from the second conductive material, and the projection of the first isolation layer and the second isolation layer on the conductive substrate is overlapped with the conductive substrate.
19. The method of manufacturing of claim 18, further comprising:
providing a first interlayer on one side of the first isolation layer, which is close to the conductive substrate, wherein two sides of the first interlayer are respectively combined with the first isolation layer and the conductive substrate and are configured to prevent diffusion between the first isolation layer and the conductive substrate; the method comprises the steps of,
and arranging a second intermediate layer on one side of the second isolation layer, which is close to the conductive substrate, wherein two sides of the second intermediate layer are respectively combined with the second isolation layer and the conductive substrate and are configured to prevent diffusion between the second isolation layer and the conductive substrate.
20. The method of manufacturing according to claim 19, wherein the method of manufacturing further comprises:
providing a first oxidation preventing layer on one side of the first isolation layer away from the conductive substrate, configured to prevent oxidation of the first isolation layer; the method comprises the steps of,
and a second oxidation prevention layer is arranged on one side of the second isolation layer, which is far away from the conductive substrate, and is configured to prevent the second isolation layer from being oxidized.
21. A method for manufacturing a negative electrode sheet, characterized by comprising the method for manufacturing a negative electrode current collector according to any one of claims 18 to 20.
22. A method of manufacturing a lithium battery comprising the method of manufacturing a negative electrode sheet of claim 210.
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