WO2022047737A1 - 锂金属负极复合集流体及其制备方法、锂离子电池 - Google Patents
锂金属负极复合集流体及其制备方法、锂离子电池 Download PDFInfo
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- WO2022047737A1 WO2022047737A1 PCT/CN2020/113535 CN2020113535W WO2022047737A1 WO 2022047737 A1 WO2022047737 A1 WO 2022047737A1 CN 2020113535 W CN2020113535 W CN 2020113535W WO 2022047737 A1 WO2022047737 A1 WO 2022047737A1
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- Prior art keywords
- diboride
- current collector
- lithium
- negative electrode
- layer
- Prior art date
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 148
- 239000002131 composite material Substances 0.000 title claims abstract description 81
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 14
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 14
- 238000002360 preparation method Methods 0.000 title description 15
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 107
- 150000003624 transition metals Chemical class 0.000 claims abstract description 107
- 229910052751 metal Inorganic materials 0.000 claims abstract description 69
- 239000002184 metal Substances 0.000 claims abstract description 69
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 36
- 229910033181 TiB2 Inorganic materials 0.000 claims description 27
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 claims description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 20
- 229910052742 iron Inorganic materials 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 239000010936 titanium Substances 0.000 claims description 13
- 238000005229 chemical vapour deposition Methods 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 238000005240 physical vapour deposition Methods 0.000 claims description 11
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 7
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 7
- 229910007948 ZrB2 Inorganic materials 0.000 claims description 7
- LMBUSUIQBONXAS-UHFFFAOYSA-N [Ti].[Fe].[Ni] Chemical compound [Ti].[Fe].[Ni] LMBUSUIQBONXAS-UHFFFAOYSA-N 0.000 claims description 7
- UHPOHYZTPBGPKO-UHFFFAOYSA-N bis(boranylidyne)chromium Chemical compound B#[Cr]#B UHPOHYZTPBGPKO-UHFFFAOYSA-N 0.000 claims description 7
- XSPFOMKWOOBHNA-UHFFFAOYSA-N bis(boranylidyne)tungsten Chemical compound B#[W]#B XSPFOMKWOOBHNA-UHFFFAOYSA-N 0.000 claims description 7
- OVYJWJFXGDOMSD-UHFFFAOYSA-N boron;manganese Chemical compound B#[Mn]#B OVYJWJFXGDOMSD-UHFFFAOYSA-N 0.000 claims description 7
- JEUVAEBWTRCMTB-UHFFFAOYSA-N boron;tantalum Chemical compound B#[Ta]#B JEUVAEBWTRCMTB-UHFFFAOYSA-N 0.000 claims description 7
- VWZIXVXBCBBRGP-UHFFFAOYSA-N boron;zirconium Chemical compound B#[Zr]#B VWZIXVXBCBBRGP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052793 cadmium Inorganic materials 0.000 claims description 7
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- MELCCCHYSRGEEL-UHFFFAOYSA-N hafnium diboride Chemical compound [Hf]1B=B1 MELCCCHYSRGEEL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052741 iridium Inorganic materials 0.000 claims description 7
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 239000010955 niobium Substances 0.000 claims description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052762 osmium Inorganic materials 0.000 claims description 7
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 7
- 229910052702 rhenium Inorganic materials 0.000 claims description 7
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052703 rhodium Inorganic materials 0.000 claims description 7
- 239000010948 rhodium Substances 0.000 claims description 7
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- 229910052713 technetium Inorganic materials 0.000 claims description 7
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000007769 metal material Substances 0.000 claims description 6
- 238000004544 sputter deposition Methods 0.000 claims description 6
- TWSYZNZIESDJPJ-UHFFFAOYSA-N boron;molybdenum Chemical compound B#[Mo]#B TWSYZNZIESDJPJ-UHFFFAOYSA-N 0.000 claims description 5
- 230000000737 periodic effect Effects 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 46
- 239000000758 substrate Substances 0.000 abstract 2
- 210000001787 dendrite Anatomy 0.000 description 30
- 238000000151 deposition Methods 0.000 description 18
- 238000012360 testing method Methods 0.000 description 15
- 230000008021 deposition Effects 0.000 description 12
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- 238000001764 infiltration Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000840 electrochemical analysis Methods 0.000 description 5
- 230000002401 inhibitory effect Effects 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NMJKIRUDPFBRHW-UHFFFAOYSA-N titanium Chemical compound [Ti].[Ti] NMJKIRUDPFBRHW-UHFFFAOYSA-N 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- IXQWNVPHFNLUGD-UHFFFAOYSA-N iron titanium Chemical compound [Ti].[Fe] IXQWNVPHFNLUGD-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 229910001000 nickel titanium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
-
- 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
Definitions
- the present application relates to the technical field of batteries, in particular to a lithium metal negative electrode composite current collector, a preparation method of a lithium metal negative electrode composite current collector, and a lithium ion battery.
- lithium-based materials are generally used as anode materials for commercial lithium-ion batteries, and the theoretical capacity is limited (372 mAh/g), which is difficult to meet the needs of the development of high-performance lithium-ion batteries. Therefore, the development of new anode materials with high capacity has become an important research direction for lithium-ion batteries. Due to its ultra-high specific capacity (3860 mAh/g) and extremely low redox potential (-3.045 V vs SHE), lithium metal anode is very promising as a high-capacity anode material.
- lithium dendrites are easily formed, which not only leads to a rapid decrease in the performance of the battery, and shortens the battery life; , causing safety problems such as battery short circuit.
- a lithium layered composite material is disclosed. By distributing the composite additive evenly on the surface of the metal lithium sheet, and pressing the composite additive into the metal lithium sheet by a rolling method, the composite additive and the metal sheet are folded. The composite of lithium sheets is rolled to obtain an additive-metal lithium composite sheet with a layered structure.
- a double-layer structure composite negative electrode of lithium/modified graphene layer is disclosed, and the modified graphene is attached to the metal lithium sheet.
- One of the purposes of the embodiments of the present application is to provide a lithium metal negative electrode composite current collector and a preparation method thereof, aiming to solve the problem that the existing lithium metal negative electrode is easy to form lithium dendrites on the surface of the current collector, and the current collector material The problem of poor wettability and low binding force.
- a lithium metal negative electrode composite current collector comprising: a metal base layer and a transition metal boride layer disposed on at least one surface of the metal base layer.
- the transition metal boride in the transition metal boride layer, is selected from transition metal diborides.
- the transition metal boride includes: titanium diboride, zirconium diboride, hafnium diboride, vanadium diboride, niobium diboride, tantalum diboride, chromium diboride, diboride Molybdenum diboride, tungsten diboride, manganese diboride, technetium diboride, rhenium diboride, iron diboride, ruthenium diboride, osmium diboride, cobalt diboride, rhodium diboride, diboride At least one of iridium boride and cadmium diboride.
- the thickness of the transition metal boride layer is 0.2 ⁇ m ⁇ 10 ⁇ m.
- the metal material in the metal base layer, includes at least one of copper, iron, nickel, and titanium.
- the thickness of the transition metal boride layer is 1 ⁇ m ⁇ 4 ⁇ m.
- the metal base layer includes one of: copper, nickel, iron, titanium, iron-nickel alloy, iron-titanium-nickel alloy.
- a method for preparing a lithium metal negative electrode composite current collector comprising the steps of:
- a metal base layer is obtained, a transition metal boride layer is formed on at least one surface of the metal base layer, and a lithium metal negative electrode composite current collector is obtained.
- the step of forming a transition metal boride layer on a surface of the metal base layer includes: depositing a transition metal boride on a surface of the metal base layer by chemical vapor deposition and/or physical vapor deposition.
- the chemical vapor deposition conditions include: in an inert atmosphere with a temperature of 1000°C to 1500°C, a pressure of 1.0 ⁇ 10 -3 Pa to 3.0 ⁇ 10 -3 Pa, and a pulse voltage of 3000V to 3300V , and chemical vapor deposition of the transition metal boride is performed.
- the conditions of the physical vapor deposition include: performing the physical vapor deposition of the transition metal boride under the conditions of a working pressure of 0.4Pa to 0.8Pa and a sputtering power of 1KW to 3KW.
- a lithium ion battery including a lithium metal negative electrode, the lithium metal negative electrode comprising: a lithium metal layer and a composite current collector disposed on a surface of the lithium metal layer, the composite current collector comprising a metal base layer and a transition metal boride layer disposed between the metal base layer and the lithium metal layer.
- the beneficial effects of the lithium metal negative electrode composite current collector are that: the transition metal boride layer can not only effectively improve the wettability and bonding force between the negative electrode lithium metal layer and the current collector, but also can form an atomic scale with lithium metal.
- the lattice matching can guide the uniform deposition of lithium metal atoms on the surface of the current collector, inhibit the growth of lithium dendrites, and effectively improve the safety and stability of the battery.
- the beneficial effect of the preparation method of the lithium metal negative electrode composite current collector provided by the embodiments of the present application is that: the transition metal boride is deposited on at least one surface of the metal base layer, and after the transition metal boride layer is formed, the lithium metal negative electrode composite current collector is obtained,
- the preparation method is simple and convenient, and is suitable for industrialized large-scale production and application.
- the beneficial effect of the lithium ion battery is that: since the negative electrode current collector adopts the above-mentioned composite current collector, a transition metal boride layer is arranged between the lithium metal layer and the metal base layer, so that the lithium metal layer and the composite current collector are formed.
- the layers are tightly combined, and the transition metal boride layer can form an atomic-scale lattice match with lithium, which can effectively inhibit the growth of lithium dendrites.
- FIG. 1 is a schematic structural diagram of a lithium metal negative electrode composite current collector provided in an embodiment of the present application
- Fig. 2 is the X-ray diffraction pattern of the composite current collector provided in Example 1 of the present application;
- FIG. 3 is a topography diagram of the current collector provided in Example 1 and Comparative Example 1 of the present application after depositing a lithium metal layer.
- Example 4 is a topography diagram of the current collectors provided in Example 1 and Comparative Example 1 of the present application after the deposition/stripping electrochemical test of lithium metal.
- first and second are only used for the convenience of description, and should not be understood as indicating or implying relative importance or implying indicating the number of technical features.
- At least one means one or more, and “plurality” means two or more.
- At least one item(s) below” or similar expressions refer to any combination of these items, including any combination of single item(s) or plural items(s).
- the term “and/or” describes the relationship between related objects, indicating that there can be three kinds of relationships, for example, A and/or B, which can mean that A exists alone, A and B exist at the same time, and B exists alone. where A and B can be singular or plural.
- the size of the sequence numbers of the above processes does not imply the sequence of execution, some or all of the steps may be executed in parallel or sequentially, and the execution sequence of each process should be determined by its function and inherent logic , and should not constitute any limitation on the implementation process of the embodiments of the present invention.
- a first aspect of an embodiment of the present application provides a lithium metal negative electrode composite current collector, comprising: a metal base layer and a transition metal boride layer disposed on at least one surface of the metal base layer.
- the transition metal boride layer disposed on one surface of the metal base layer itself has high conductivity and will not affect the current collector characteristics of the base layer itself.
- the transition metal boride layer introduced on the current collector metal base layer in this application not only has good interfacial wettability with lithium, but can effectively improve the wettability and bonding force between the negative electrode lithium metal layer and the current collector; and the transition metal boride layer It is a hexagonal structure, and its (001) crystal plane has a good lattice match with lithium metal, which can form an atomic-scale lattice match with lithium metal, thereby guiding the uniform deposition of lithium metal atoms on the surface of the current collector and inhibiting the growth of lithium dendrites. Effectively improve battery safety and stability.
- the transition metal in the transition metal boride layer, is selected from: the first subgroup, the second subgroup, the third subgroup, the fourth subgroup, the fifth subgroup, the sixth subgroup of the periodic table of elements , at least one of the seventh subfamily and the eighth family. In further embodiments, in the transition metal boride layer, the transition metal boride is selected from transition metal diborides.
- transition metal borides include: titanium diboride, zirconium diboride, hafnium diboride, vanadium diboride, niobium diboride, tantalum diboride, chromium diboride, diboride Molybdenum diboride, tungsten diboride, manganese diboride, technetium diboride, rhenium diboride, iron diboride, ruthenium diboride, osmium diboride, cobalt diboride, rhodium diboride, diboride At least one of iridium and cadmium diboride.
- transition metal borides used in the examples of the present application all have high electrical conductivity, and will not affect the collecting effect of the current collector of the metal base layer on the current generated in the battery.
- transition metal borides have good interfacial wetting properties with lithium metal, which can effectively improve the bonding force between lithium metal and metal base layer.
- these transition metal borides can form atomic-scale lattice matching with lithium, guide the uniform deposition of lithium metal atoms on the surface of the current collector, and effectively inhibit the growth of lithium dendrites.
- the thickness of the transition metal boride layer is 0.2 ⁇ m ⁇ 10 ⁇ m, which can effectively ensure the improvement of the interface wetting/bonding performance and the lithium dendrite inhibition effect of the transition metal boride layer. If the thickness of the transition metal boride layer is too thin, it will cause too many defects, easily lead to uneven deposition of lithium, and it is difficult to improve the bonding stability between the metal base layer and the lithium metal anode layer, and at the same time, it will inhibit the effect of lithium dendrites. Also not good, the lithium dendrite surface density increases.
- the thickness of the transition metal boride layer is 1 ⁇ m to 4 ⁇ m, and the thickness of the transition metal boride layer can better improve the bonding stability between the metal base layer and the lithium metal negative electrode sheet, and at the same time, the lithium metal Dendrites have a better inhibitory effect.
- the thickness of the transition metal boride layer may be 0.2 ⁇ m, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, or 10 ⁇ m.
- the metal material includes: at least one of copper, iron, nickel, and titanium, these metal base layers can not only play a better supporting role for the negative electrode lithium metal; and these metal materials
- the prepared base layer does not react with lithium, has the functions of electronic conduction and ion insulation, has excellent collection effect on the current generated in the battery, and can collect the current generated in the battery and output it to the outside. In addition, it can prevent lithium ions from diffusing outward, make the negative electrode have better stability and safety performance, and improve the floating charge and stable cycling capabilities of high-energy density lithium metal negative electrode batteries.
- the metal base layer includes one of copper, nickel, iron, titanium, iron-nickel alloy, and iron-titanium-nickel alloy.
- the lithium metal negative electrode composite current collector includes: a metal base layer and a transition metal boride layer disposed on two opposite surfaces of the metal base layer.
- the transition metal boride layers By disposing the transition metal boride layers on both sides of the metal base layer at the same time, the The prepared composite current collector is suitable for winding batteries, laminated batteries and other systems, and has more practical value.
- the lithium metal negative electrode composite current collector provided in the embodiment of the present application can be prepared by the following method.
- a second aspect of the embodiments of the present application provides a method for preparing a lithium metal negative electrode composite current collector, comprising the steps of:
- a metal base layer is obtained, a transition metal boride layer is formed on at least one surface of the metal base layer, and a lithium metal negative electrode composite current collector is obtained.
- the lithium metal negative electrode composite current collector In the preparation method of the lithium metal negative electrode composite current collector provided in the second aspect of the present application, after the transition metal boride layer is formed on at least one surface of the metal base layer, the lithium metal negative electrode composite current collector is obtained, and the preparation method is simple and suitable for large-scale industrialization. production and application.
- the composite current collector When the composite current collector is applied to a lithium ion battery, the negative electrode lithium metal layer is arranged on the surface of the transition metal boride layer in the composite current collector.
- the transition metal boride layer Through the intermediate transition metal boride layer, not only the wettability and bonding force between the lithium metal layer and the metal base current collector layer can be improved, but also the transition metal boride layer can form an atomic-scale lattice match with the lithium metal, making the lithium metal layer more Uniform deposition, thereby effectively inhibiting the growth of lithium dendrites.
- the step of forming a transition metal boride layer on a surface of the metal base layer includes: using chemical vapor deposition and/or physical vapor deposition, depositing a transition metal boride on a surface of the metal base layer to form a transition metal boride Floor.
- the method for depositing transition metal boride on the surface of the metal base layer in the embodiment of the present application can be flexibly selected according to the actual application situation, chemical vapor deposition or physical vapor deposition can be used, or a combination of the two deposition methods can be used to obtain the transition metal boride .
- the chemical vapor deposition conditions include: in an inert atmosphere with a temperature of 1000°C to 1500°C, a pressure of 1.0 ⁇ 10 -3 Pa to 3.0 ⁇ 10 -3 Pa and a pulse voltage of 3000V to 3300V.
- Chemical vapor deposition of transition metal borides The chemical vapor deposition conditions of the embodiments of the present application make the transition metal source and boron source and other raw materials react chemically on the metal base layer in gaseous form, and generate transition metal boride and deposit on the metal base layer to form a transition metal boride layer.
- the formed film layer is dense, uniform in thickness, smooth in surface, and tightly combined with the metal base layer.
- the conditions of the physical vapor deposition include: performing the physical vapor deposition of the transition metal boride under the conditions of a working pressure of 0.4Pa-0.8Pa and a sputtering power of 1KW-3KW.
- the transition metal boride is directly used as the target material, and a dense and uniform transition metal boride layer is formed on the metal base layer by sputtering deposition under the physical vapor deposition conditions, and is closely combined with the metal base layer.
- the preparation method of the lithium metal negative electrode composite current collector may also be as follows: depositing transition metal boride on two opposite surfaces of the metal base layer, forming transition metal boride layers on the two opposite surfaces of the metal base layer, and obtaining two opposite surfaces
- the lithium metal negative electrode composite current collector with the transition metal boride layer deposited on it makes it more suitable for winding, lamination and other battery systems, and is more widely used.
- the transition metal in the transition metal boride layer, is selected from: the first subgroup, the second subgroup, the third subgroup, the fourth subgroup, the fifth subgroup, the sixth subgroup of the periodic table of elements , at least one of the seventh subfamily and the eighth family. In some embodiments, in the transition metal boride layer, the transition metal boride is selected from transition metal diborides.
- transition metal borides include: titanium diboride, zirconium diboride, hafnium diboride, vanadium diboride, niobium diboride, tantalum diboride, chromium diboride, diboride Molybdenum, Tungsten Diboride, Manganese Diboride, Technetium Diboride, Rhenium Diboride, Iron Diboride, Ruthenium Diboride, Osmium Diboride, Cobalt Diboride, Rhodium Diboride, Diboride At least one of iridium and cadmium diboride.
- the thickness of the transition metal boride layer is 0.2 ⁇ m ⁇ 10 ⁇ m. In some embodiments, the thickness of the transition metal boride layer is 1 ⁇ m ⁇ 4 ⁇ m.
- the metal material in the metal base layer, includes at least one of copper, iron, nickel, and titanium.
- the metal base layer is selected from one of: copper, nickel, iron, titanium, iron-nickel alloy, iron-titanium-nickel alloy.
- a third aspect of the embodiments of the present application provides a lithium ion battery, including a lithium metal negative electrode, the lithium metal negative electrode includes: a lithium metal layer and a composite current collector disposed on a surface of the lithium metal layer, the composite current collector includes a metal base layer and a composite current collector disposed on a surface of the lithium metal layer.
- the lithium ion battery provided by the third aspect of the present application since the negative electrode current collector adopts the above-mentioned composite current collector, a transition metal boride layer is arranged between the lithium metal layer and the metal base layer, so that the lithium metal layer and the composite current collector layer are closely combined At the same time, the transition metal boride layer can form an atomic-scale lattice match with lithium, which can effectively inhibit the growth of lithium dendrites. Therefore, the lithium-ion battery provided by the embodiments of the present application has good safety and stability, and has a long service life, and has a broader application prospect.
- the transition metal in the transition metal boride layer, is selected from: the first subgroup, the second subgroup, the third subgroup, the fourth subgroup, the fifth subgroup, the sixth subgroup of the periodic table of elements , at least one of the seventh subfamily and the eighth family. In some embodiments, in the transition metal boride layer, the transition metal boride is selected from transition metal diborides.
- transition metal borides include: titanium diboride, zirconium diboride, hafnium diboride, vanadium diboride, niobium diboride, tantalum diboride, chromium diboride, diboride Molybdenum, Tungsten Diboride, Manganese Diboride, Technetium Diboride, Rhenium Diboride, Iron Diboride, Ruthenium Diboride, Osmium Diboride, Cobalt Diboride, Rhodium Diboride, Diboride At least one of iridium and cadmium diboride.
- the thickness of the transition metal boride layer is 0.2 ⁇ m ⁇ 10 ⁇ m. In some embodiments, the thickness of the transition metal boride layer is 1 ⁇ m ⁇ 4 ⁇ m.
- the metal material includes at least one of copper, iron, nickel, and titanium. In some embodiments, the metal base layer includes one of: copper, nickel, iron, titanium, iron-nickel alloy, iron-titanium-nickel alloy.
- a lithium metal negative electrode composite current collector adopts titanium as a base metal substance, and uses titanium diboride as an infiltration layer, wherein the thickness of the titanium diboride infiltration layer is 3 ⁇ m.
- the specific preparation process is as follows:
- step 2 After step 2, turn off the titanium diboride target and take out the sample from the vacuum coating chamber to obtain the composite current collector.
- a lithium metal negative electrode composite current collector using titanium as a base metal substance and titanium diboride as an infiltration layer, wherein the thickness of the titanium diboride infiltration layer is 3 ⁇ m, and the chemical vapor deposition method is used to prepare the titanium diboride infiltration layer. .
- the specific preparation process is as follows:
- the selected chemical reaction precursor system is TiCl 4 -BCl 3 -H 2 -Ar, in which the Ti source is to heat the TiCl 4 liquid in a 65 °C water bath to form TiCl 4 vapor, with argon as the carrier gas and together with other gases. It was transported into the CVD reaction chamber, and a titanium diboride film was deposited on the surface of the titanium foil for 5 h to obtain a composite current collector.
- Embodiments 3-7 respectively provide a lithium metal negative electrode composite current collector based on a titanium diboride wetting layer. Except for the base layer materials used in Examples 3-7 and Example 1, the wetting layer, preparation steps and testing methods are different. All are the same; the base layers used are: copper, nickel, iron, iron-nickel alloy, iron-titanium-nickel alloy.
- Embodiments 8-16 respectively provide a lithium metal negative electrode composite current collector based on titanium diboride infiltration layers of different thicknesses. , preparation steps and testing methods are the same; the thickness of titanium diboride infiltration layer are: 0.2 ⁇ m, 0.5 ⁇ m, 1 ⁇ m, 2 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 8 ⁇ m, 10 ⁇ m.
- Embodiments 17-34 respectively provide a lithium metal negative electrode composite current collector based on different transition metal boride infiltration layers.
- the difference between Embodiments 17-34 and Embodiment 1 is the type of transition metal infiltration layer, wherein the thickness of the infiltration layer, the base layer , preparation steps and testing methods are the same; the transition metal infiltration layers are respectively zirconium diboride, hafnium diboride, vanadium diboride, niobium diboride, tantalum diboride, chromium diboride, molybdenum diboride, Tungsten Diboride, Manganese Diboride, Technetium Diboride, Rhenium Diboride, Iron Diboride, Ruthenium Diboride, Osmium Diboride, Cobalt Diboride, Rhodium Diboride, Iridium Diboride, Cadmium diboride.
- the present application has carried out the following performance tests on the lithium metal negative electrode composite current collectors prepared in Examples 1 to 34:
- This application has carried out an X-ray diffraction test on the lithium metal negative electrode composite current collector prepared in Example 1.
- the XRD pattern is shown in Figure 2 (the ordinate is the intensity), and 2 diffraction peaks appear, which are calibrated by the PDF card.
- the deposited transition metal boride layer was determined to be titanium diboride.
- the composite current collector with double-layer structure prepared in Example 1 and the ordinary titanium foil current collector without transition metal boride modification in Comparative Example 1 were immersed in molten lithium metal respectively, and formed on the surface of the current collector after drying. Lithium metal layer.
- the test results are shown in Figure 3: Li metal formed a uniform Li metal layer on the surface of the composite current collector prepared in Example 1, showing good wettability and bonding strength (left a in Figure 3); In Comparative Example 1, the lithium metal layer formed on the surface of ordinary titanium foil has bubbling phenomenon, and the distribution of lithium metal is uneven, with poor wettability and low bonding strength (right b in Figure 3).
- the composite current collectors prepared in Examples 1 and 2 and the titanium foil without transition metal boride in Comparative Example 1 were respectively subjected to the deposition/stripping electrochemical test of lithium metal.
- an in-situ optical test device was used to assemble a half-cell with a lithium metal sheet as the counter electrode and ethylene carbonate (EC) and diethyl carbonate (DEC) with a volume ratio of 1:1 as the electrolyte.
- EC ethylene carbonate
- DEC diethyl carbonate
- Example base layer material Wetting layer material Lithium Dendritic Surface Density Percentage 1 titanium Titanium Diboride 1% 2 titanium Titanium Diboride 1.2% 3 copper Titanium Diboride 8% 4 nickel Titanium Diboride 9% 5 iron Titanium Diboride 3% 6 Iron-nickel alloy Titanium Diboride 4% 7 Iron-titanium-nickel alloy Titanium Diboride 6%
- Example Titanium diboride layer thickness ( ⁇ m) Lithium Dendritic Surface Density Percentage 8 0.2 7% 9 0.5 5% 10 1 3% 11 2 1% 12 4 2% 13 5 4% 14 6 6% 15 8 8% 16 10 10%
- the composite current collectors with different thicknesses of titanium diboride layers prepared in Examples 8 to 16 of the present application have a good effect of suppressing lithium dendrites with a thickness between 0.2 and 10 microns.
- the areal density is less than 10%.
- the thickness of the titanium diboride layer is 1-4 ⁇ m, there is a better effect of inhibiting lithium dendrites, and the density of lithium dendrites is lower than 3%.
Abstract
Description
实施例 | 基底层材料 | 浸润层材料 | 锂枝晶面密度百分比 |
1 | 钛 | 二硼化钛 | 1% |
2 | 钛 | 二硼化钛 | 1.2% |
3 | 铜 | 二硼化钛 | 8% |
4 | 镍 | 二硼化钛 | 9% |
5 | 铁 | 二硼化钛 | 3% |
6 | 铁-镍合金 | 二硼化钛 | 4% |
7 | 铁-钛-镍合金 | 二硼化钛 | 6% |
实施例 | 二硼化钛层厚度(μm) | 锂枝晶面密度百分比 |
8 | 0.2 | 7% |
9 | 0.5 | 5% |
10 | 1 | 3% |
11 | 2 | 1% |
12 | 4 | 2% |
13 | 5 | 4% |
14 | 6 | 6% |
15 | 8 | 8% |
16 | 10 | 10% |
实施例 | 过渡金属化合物 | 锂枝晶面密度百分比 |
17 | 二硼化锆 | 1% |
18 | 二硼化铪 | 3% |
19 | 二硼化钒 | 10% |
20 | 二硼化铌 | 5% |
21 | 二硼化钽 | 3% |
22 | 二硼化铬 | 8% |
23 | 二硼化钼 | 7% |
24 | 二硼化钨 | 4% |
25 | 二硼化锰 | 2% |
26 | 二硼化锝 | 9% |
27 | 二硼化铼 | 3% |
28 | 二硼化铁 | 5% |
29 | 二硼化钌 | 9% |
30 | 二硼化锇 | 4% |
31 | 二硼化钴 | 7% |
32 | 二硼化铑 | 3% |
33 | 二硼化铱 | 6% |
34 | 二硼化镉 | 4% |
Claims (13)
- 一种锂金属负极复合集流体,其特征在于,包括:金属基底层和至少设置在所述金属基底层一表面的过渡金属硼化物层。
- 如权利要求1所述的锂金属负极复合集流体,其特征在于,过渡金属硼化物层中,过渡金属选自:元素周期表第一副族、第二副族、第三副族、第四副族、第五副族、第六副族、第七副族、第八族中的至少一种。
- 如权利要求2所述的锂金属负极复合集流体,其特征在于,所述过渡金属硼化物层中,过渡金属硼化物选自过渡金属二硼化物。
- 如权利要求3所述的锂金属负极复合集流体,其特征在于,所述过渡金属硼化物包括:二硼化钛、二硼化锆、二硼化铪、二硼化钒、二硼化铌、二硼化钽、二硼化铬、二硼化钼、二硼化钨、二硼化锰、二硼化锝、二硼化铼、二硼化铁、二硼化钌、二硼化锇、二硼化钴、二硼化铑、二硼化铱、二硼化镉中的至少一种。
- 如权利要求1、3或4所述的锂金属负极复合集流体,其特征在于,所述过渡金属硼化物层的厚度为0.2μm~10μm。
- 如权利要求5所述的锂金属负极复合集流体,其特征在于,所述过渡金属硼化物层的厚度为1μm~4μm。
- 如权利要求1所述的锂金属负极复合集流体,其特征在于,所述金属基底层中,金属材料包括:铜、铁、镍、钛中的至少一种。
- 如权利要求7所述的锂金属负极复合集流体,其特征在于,所述金属基底层包括:铜、镍、铁、钛、铁-镍合金、铁-钛-镍合金中的一种。
- 一种锂金属负极复合集流体的制备方法,其特征在于,包括步骤:获取金属基底层,至少在所述金属基底层一表面形成过渡金属硼化物层,得到锂金属负极复合集流体。
- 如权利要求9所述的锂金属负极复合集流体的制备方法,其特征在于,在所述金属基底层一表面形成过渡金属硼化物层的步骤包括:采用化学气相沉积和/或物理气相沉积,在所述金属基底层一表面沉积过渡金属硼化物,形成所述过渡金属硼化物层。
- 如权利要求10所述的锂金属负极复合集流体的制备方法,其特征在于,所述化学气相沉积的条件包括:在温度为1000℃~1500℃,压强为1.0×10 -3Pa ~3.0×10 -3Pa,脉冲电压为3000V~3300V的惰性气氛下,进行所述过渡金属硼化物的化学气相沉积。
- 如权利要求10所述的锂金属负极复合集流体的制备方法,其特征在于,所述物理气相沉积的条件包括:在工作气压为0.4Pa~0.8Pa,溅射功率为1KW~3KW的条件下,进行所述过渡金属硼化物的物理气相沉积。
- 一种锂离子电池,其特征在于,包括锂金属负极,所述锂金属负极包括:锂金属层和设置在所述锂金属层一表面的复合集流体,所述复合集流体包括金属基底层和设置在所述金属基底层与所述锂金属层之间的过渡金属硼化物层。
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