CN111785964B - Artificial two-dimensional solid electrolyte interface material of lithium metal battery, anode precursor material, anode, preparation and application thereof - Google Patents
Artificial two-dimensional solid electrolyte interface material of lithium metal battery, anode precursor material, anode, preparation and application thereof Download PDFInfo
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- CN111785964B CN111785964B CN201910643764.5A CN201910643764A CN111785964B CN 111785964 B CN111785964 B CN 111785964B CN 201910643764 A CN201910643764 A CN 201910643764A CN 111785964 B CN111785964 B CN 111785964B
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 134
- 239000000463 material Substances 0.000 title claims abstract description 97
- 239000002243 precursor Substances 0.000 title claims abstract description 39
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 49
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 239000011669 selenium Substances 0.000 claims description 59
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 47
- 239000007789 gas Substances 0.000 claims description 47
- 238000004544 sputter deposition Methods 0.000 claims description 46
- 239000000758 substrate Substances 0.000 claims description 42
- 229910052711 selenium Inorganic materials 0.000 claims description 37
- 239000013077 target material Substances 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 32
- 239000002184 metal Substances 0.000 claims description 32
- 239000003792 electrolyte Substances 0.000 claims description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 13
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 13
- 238000004070 electrodeposition Methods 0.000 claims description 12
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052721 tungsten Inorganic materials 0.000 claims description 12
- 239000010937 tungsten Substances 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 9
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 239000011889 copper foil Substances 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- ALCDAWARCQFJBA-UHFFFAOYSA-N ethylselanylethane Chemical compound CC[Se]CC ALCDAWARCQFJBA-UHFFFAOYSA-N 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 229910000058 selane Inorganic materials 0.000 claims description 3
- YFXWODPYUNGUEE-UHFFFAOYSA-N [I].[Li] Chemical compound [I].[Li] YFXWODPYUNGUEE-UHFFFAOYSA-N 0.000 claims description 2
- WFLRGOXPLOZUMC-UHFFFAOYSA-N [Li].O=C=O Chemical compound [Li].O=C=O WFLRGOXPLOZUMC-UHFFFAOYSA-N 0.000 claims description 2
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- ZVSWQJGHNTUXDX-UHFFFAOYSA-N lambda1-selanyllithium Chemical compound [Se].[Li] ZVSWQJGHNTUXDX-UHFFFAOYSA-N 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 229910021384 soft carbon Inorganic materials 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002905 metal composite material Substances 0.000 claims 1
- 210000001787 dendrite Anatomy 0.000 abstract description 12
- KMIIKDGPMVFXKU-UHFFFAOYSA-N selanylidene(sulfanylidene)tungsten Chemical compound [W](=S)=[Se] KMIIKDGPMVFXKU-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005546 reactive sputtering Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 62
- 210000004027 cell Anatomy 0.000 description 34
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 30
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 26
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 16
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 16
- 229910052786 argon Inorganic materials 0.000 description 15
- 239000006260 foam Substances 0.000 description 14
- 238000000151 deposition Methods 0.000 description 13
- 238000001816 cooling Methods 0.000 description 11
- 229910052717 sulfur Inorganic materials 0.000 description 11
- 239000004743 Polypropylene Substances 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- -1 polypropylene Polymers 0.000 description 10
- 229920001155 polypropylene Polymers 0.000 description 10
- 238000004321 preservation Methods 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003365 glass fiber Substances 0.000 description 7
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 230000008021 deposition Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000009417 prefabrication Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004073 vulcanization 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- 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
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention belongs to the technical field of lithium battery materials, and particularly discloses a two-dimensional structure solid electrolyte interface material, wherein the chemical formula of the interface material is W (S) x Se 1‑x ) 2 Wherein x is more than 0 and less than 1. The invention also provides a cathode precursor material compounded with the two-dimensional solid electrolyte interface material, a composite lithium cathode prepared by filling lithium by the cathode precursor material, and a lithium metal battery loaded with the cathode. The invention relates to and proposes the use of tungsten selenide sulfide as an artificial solid electrolyte interface film for the first time, and adopts a selenizing method after reactive sputtering, so that the obtained film has high density and good flatness, can effectively inhibit lithium dendrite, realizes long cyclicity and high safety of a lithium metal battery, has low requirements on equipment, is easy to realize large-area industrialization, and can be applied in large scale in production.
Description
Technical Field
The invention relates to an artificial solid electrolyte interface film and a preparation method thereof, in particular to a selenium-tungsten sulfide film and a preparation method thereof, belonging to the technical fields of new energy materials and energy storage devices.
Background
Since the advent of lithium ion batteries, the lithium ion batteries have been developed in recent years, and have been widely used in various 3C products, and along with the rapid development of society, the palm-top of electrical equipment and the large-scale development and application of electric bicycles, electric automobiles and smart grids, the development of secondary batteries with higher specific energy to meet the requirement of the rapid development of society is a great challenge facing the current world.
The metal lithium anode has ultrahigh mass specific energy (3865 mAh/g), ultralow electrochemical potential (-3.045 vs SHE) and higher electrochemical reaction reversibility, and is the most ideal anode material. Although lithium negative electrodes possess many advantages, the existence of lithium dendrite growth, low coulombic efficiency, poor cycling and serious safety problems have hampered the commercialization of various lithium metal batteries (e.g., lithium sulfur batteries, lithium air batteries, etc.).
Unlike the conventional lithium ion battery, the electrochemical working principle of the lithium metal negative electrode is different from the conventional lithium ion battery in that the lithium metal negative electrode is dissolved and deposited in the process of charging and discharging, and side reactions are easy to occur in the process of charging and discharging due to high reactivity of the lithium metal, so that lithium and electrolyte are consumed, irreversible loss of the lithium and the electrolyte is caused, and the coulomb efficiency is reduced and the cycle performance is deteriorated. The metallic lithium is deposited without host, and there is infinite volume expansion during the dissolution/deposition process; meanwhile, lithium dendrites are generated in the charge and discharge process, if the lithium dendrites which grow linearly break from the root part in the dissolution process, the lithium is wrapped by electrolyte to form dead lithium, and the dead lithium is embedded into a bulk phase, so that not only can the coulomb efficiency be reduced, but also the bulk phase impedance can be increased, the electrode reaction is not facilitated in the next step, and the lithium dendrites can possibly puncture a solid electrolyte interface film (SEI film) between a lithium metal negative electrode and the electrolyte, so that a diaphragm is punctured, the battery is short-circuited, and serious safety problems are caused.
To address these problems, researchers have proposed various research methods and solutions, mainly focused on: (1) The current collector or the lithium cathode with the 3D structure can relieve volume expansion, and reduce local actual current density to inhibit lithium dendrite generation, but the method increases the contact area of electrolyte and lithium, so that more metal lithium and electrolyte are lost; (2) By adopting organic or inorganic solid electrolyte as a lithium surface modification layer or adopting high-concentration electrolyte, the generation of lithium dendrite is inhibited, but the existing solid electrolyte still has the problems of poor ionic conductivity and the like, and the high-concentration electrolyte has the problems of higher cost and the like; (3) By constructing a layer of artificial SEI film on the surface of a lithium negative electrode through a physical, chemical or electrochemical method, the contact between the lithium negative electrode and an organic electrolyte is reduced, the growth of lithium dendrites is inhibited, the serious safety problem caused by short circuits is avoided, the artificial SEI film can effectively play a role only by needing rigidity to inhibit the generation of the lithium dendrites and flexibility to relieve the volume expansion of the lithium anode.
Disclosure of Invention
In order to solve the problems of poor mechanical property and low coulombic efficiency of the existing lithium metal cathode SEI film, the invention provides an artificial two-dimensional solid electrolyte interface material (artificial SEI film or solid electrolyte interface material) which aims to improve and improve the cycle performance and the safety performance of a lithium metal battery.
The second object of the present invention is to provide a negative electrode precursor material for a lithium metal battery compounded with the artificial SEI film.
The third object of the invention is to provide a preparation method of the lithium metal battery anode precursor material.
The fourth object of the present invention is to provide a lithium metal battery negative electrode coated with the artificial SEI film.
The fifth object of the present invention is to provide a method for preparing the negative electrode of the lithium metal battery.
A sixth object of the present invention is to provide a lithium metal battery comprising the negative electrode of the lithium metal battery.
An artificial two-dimensional solid electrolyte interface material with a chemical formula of W (S) x Se 1-x ) 2 Wherein x is more than 0 and less than 1.
The invention provides a solid electrolyte interface material with an all-new structure, and finds that the solid electrolyte interface material is used as an artificial SEI film in the field of batteries, can effectively inhibit the generation of lithium dendrites, reduce the occurrence of side reactions and improve the performance of lithium cathodes.
Preferably, the solid electrolyte interface material is WS 2 Is a composite material doped with Se in the two-dimensional material.
According to the solid electrolyte interface material with the brand new structure, S, se crystal lattice is co-doped, selenium is doped into the sandwich type layered structure of S-W-S, more lithium ion diffusion channels can be generated, meanwhile, the film is more compact and flat, a metal lithium negative electrode can be better protected, generation of lithium dendrites is suppressed, and side reactions are reduced.
The research of the inventor finds that S, se lattice co-doping is a key for endowing the material with excellent performance, and the research also finds that the effect of the material serving as an artificial SEI film can be further improved by further controlling the range of x.
Preferably, x is 0.3 to 0.9; preferably 0.4 to 0.8; still more preferably 0.5 to 0.7, in which preferable range, a dense pore-free film material can be obtained.
The invention also provides a lithium metal battery anode precursor material: comprising a current collector and the artificial two-dimensional solid electrolyte interface material layer covered on the surface of the current collector.
Preferably, the current collector comprises a planar current collector and a three-dimensional current collector.
Preferably, the planar current collector material is at least one of titanium, chromium, manganese, iron, cobalt, nickel and copper, and most preferably copper foil or nickel foil.
Preferably, the three-dimensional current collector is a carbon-based current collector and/or a metal-based current collector.
The carbon-based current collector is at least one of three-dimensional carbon fiber, carbon paper, carbon cloth, carbon nano tube, hard carbon, soft carbon, graphite, graphene oxide and reduced graphene oxide.
The metal-based current collector is porous metal (also called foam metal); the metal is at least one of titanium, chromium, manganese, iron, cobalt, nickel and copper. For example, the metal-based current collector is at least one of foam titanium, foam chromium, foam manganese, foam iron, foam cobalt, foam nickel and foam copper.
The lithium metal battery cathode precursor material is characterized in that a compact solid electrolyte interface material layer is compounded on the plane of a plane current collector, or a compact solid electrolyte interface material layer is compounded on the surface of a framework of a three-dimensional current collector.
Preferably, the artificial two-dimensional solid electrolyte interface material layer has a thickness of 5 to 500nm; further preferably 100 to 500nm; still more preferably 300 to 400nm.
The invention also provides a preparation method of the lithium metal battery anode precursor material, which comprises the steps of preparing WS on a current collector 2 Preformed layer (WS) 2 Two-dimensional material layer) and then to WS 2 The preformed layer is subjected to selenizing annealing to form W on the surface of the current collector (S x Se 1-x ) 2 A material layer.
The present inventors have unexpectedly found that WS is preformed 2 Prefabrication of the layers followed by selenization is critical to ensure material properties.
The preparation method comprises the following steps: forming WS on current collector by magnetron sputtering 2 Prefabricating a layer.
Preference is given to using either scheme A-1 or scheme A-2:
scheme A-1: preparing a layer of WS on a current collector by magnetron sputtering by taking tungsten sulfide as a target material, taking the current collector as a substrate and taking protective atmosphere as working gas 2 Prefabricating a layer.
Scheme a-2: preparing WS on a current collector by magnetron sputtering by taking metal tungsten as a target material, taking the current collector as a substrate and taking gas containing hydrogen sulfide as working gas 2 Prefabricating a layer; in the gas containing hydrogen sulfide, hydrogen sulfideNot less than 0.01% by volume.
It was found that controlling the gas flow, operating pressure, power, and substrate temperature and time of the magnetron sputtering process helps to further control the WS produced 2 The morphology and crystallization characteristics of the preformed layer help to further enhance the properties of the resulting material.
Preferably, in schemes A-1 and A-2; the flow rate of the working gas is 1-500sccm, the working gas pressure is controlled to be preferably 0.05-7.5Pa, and the sputtering power density is controlled to be preferably 0.05-300W/cm 2 The temperature of the substrate is controlled to be preferably 0-450 ℃, the distance from the target to the substrate is controlled to be preferably 3-40cm, and the sputtering time is controlled to be preferably 0.1-200min.
Further preferably, the flow rate of the working gas is 10-100sccm, the working gas pressure is 0.1Pa-5Pa, and the sputtering power density is 1-100W/cm 2 The temperature of the substrate is 20-420 ℃, the distance from the target material to the substrate is 5-35 cm, and the sputtering time is 2-100min.
Most preferably, the flow rate of the working gas is 10-100sccm, the working gas pressure is 0.4-5Pa, and the sputtering power density is 10-50W/cm 2 The temperature of the substrate is 25-100 ℃, the distance from the target to the substrate is 8-20cm, and the sputtering time is 3-45min.
As preferable: the selenizing annealing step is as follows: WS on current collector 2 The prefabricated layer is placed in a reaction furnace, working gas with a selenium source is introduced into the furnace, and selenizing annealing treatment is carried out for 5-600min at 200-500 ℃ (preferably 300-450 ℃, more preferably 350-400 ℃) for more preferably 30-120min.
Preferably, the working gas with the selenium source is a mixed gas of the selenium source gas and the shielding gas; wherein the volume percentage of the selenium source gas is 0.1-99%.
The selenium source gas is gasified gas at 200-500 ℃. Preferably, the selenium source gas is at least one of hydrogen selenide gas, diethyl selenium or selenium vapor. The temperature of the selenium source gas is 200-500 ℃; heating the selenium source to generate selenium source gas at a heating rate of 0.1-30deg.C/s.
The pressure of the working gas with the selenium source gas in the reaction furnace is 0.01-100000Pa.
The invention can also adopt a sputtering method to lead WS on the surface of the current collector 2 Selenizing the prefabricated layer to W (S) x Se 1-x ) 2 . The method comprises the following steps: the selenizing annealing step is as follows: in WS 2 And preparing a layer of elemental selenium on the surface of the prefabricated layer through evaporation or sputtering, and then carrying out heat treatment in an inert atmosphere. Preferably, the heat treatment temperature is 200-500 ℃; the heat treatment time is 5-600min. The temperature rising rate is 0.1-30 ℃/s; the inert gas is at least one of argon, helium and nitrogen, and the air pressure generated by the inert atmosphere is 0.01-100000Pa.
The invention also provides a lithium metal battery cathode which comprises a cathode current collector, a lithium metal layer compounded on the surface of the current collector and the artificial two-dimensional solid electrolyte interface material layer covering the lithium metal layer.
The lithium metal battery cathode comprises a current collector substrate, a metal lithium intermediate layer and a solid electrolyte interface material outer layer. The research shows that the outer layer of the solid electrolyte interface material has good protection and electrolyte wettability to the material, thereby effectively improving the first capacity and the cycling stability of the battery.
Preferably, the lithium loading is in the range of 5 to 100mAh/g.
The invention also provides a preparation method of the lithium metal battery cathode, and the lithium metal is filled between the current collector of the lithium metal battery cathode precursor material and the solid electrolyte interface material layer by an electrodeposition method, so that the lithium metal battery cathode is obtained.
According to the preparation method, a lithium metal battery anode precursor material is used as a working electrode, lithium metal is used as a counter electrode, the electrolyte is electrified for electrolysis, and metal lithium is filled in the precursor material to prepare the lithium metal battery anode.
The invention also provides a lithium metal battery, which is loaded with the lithium metal battery anode.
The lithium metal battery is a lithium ternary battery, a lithium sulfur battery, a lithium oxygen battery, a lithium air battery, a lithium selenium battery, a lithium iodine battery, a lithium tellurium battery or a lithium carbon dioxide battery.
Advantageous effects
1. The invention provides an artificial two-dimensional solid electrolyte interface material with a brand-new structure, and finds that the artificial two-dimensional solid electrolyte interface material is used as an artificial SEI film material in the field of batteries, can effectively inhibit lithium dendrites,
2. the invention also provides a brand new anode precursor and anode of the lithium metal battery.
3. The invention also provides a pre-magnetron sputtering WS 2 And (3) a process for preparing the solid electrolyte interface material by post selenizing and annealing. The research shows that the preparation process sequence can effectively improve the performance of the prepared material.
Drawings
[ FIG. 1 ] is WS 2 Is a lattice structure diagram of (a);
Detailed Description
The following examples are intended to illustrate the present invention in further detail; the scope of the claims is not limited by the examples.
Example 1
Preparing a prefabricated layer: on a copper foil current collector, metal tungsten is used as a target material, direct current sputtering is adopted, the sputtering power is 80W, the sputtering air pressure is 1.2Pa, the substrate temperature is 50 ℃, the distance from the target material to the substrate is 12cm, the flow rate of argon is 60sccm, the flow rate of hydrogen sulfide gas is 10cssm, the sputtering time is 10min, and WS is obtained 2 Prefabricated layers (two-dimensional materials).
The selenizing treatment process comprises the following steps: using solid selenium powder as selenium source, controlling selenium source temperature to be 350 ℃, prefabricating layer temperature to be 350 ℃, preserving heat for 30min, heating up to 3 ℃/min, naturally cooling to obtain artificial SEI film W (S) 0.82 Se 0.18 ) 2 . (film thickness 180 nm).
The battery assembling process comprises the following steps: the current collector is taken as a negative electrode, a lithium sheet is taken as a positive electrode, a glass fiber diaphragm is adopted, and the ratio of DME to DOL (volume ratio) =1: 1 and LiTFSI (1M), 2wt.% of anhydrous lithium nitrate as electrolyte, assembling a CR2032 button cell, placing the prepared cell in a constant temperature chamber at 25 ℃ for standing for 12 hours, and performing cyclic test on a blue charge and discharge tester under the test condition of 2mA/cm 2 The deposition time was 60min. The test results are shown in Table 1.
Comparative example 1
The difference compared to example 1 is that the SEI film is not compounded on the current collector;
copper foil is used as a negative electrode, a lithium sheet is used as a positive electrode, a glass fiber diaphragm is used, and DME is used for: DOL (volume ratio) =1: 1 and LiTFSI (1.0M), 2wt.% anhydrous lithium nitrate are used as electrolyte, a CR2032 button cell is assembled, the prepared cell is placed in a thermostatic chamber at 25 ℃ for standing for 12 hours, and then discharge test is carried out on a blue electric test charge-discharge tester under the test condition of 2mA/cm 2 The deposition was carried out for 60min and the test results are shown in Table 1.
Comparative example 2
In comparison with example 1, the difference is that Se is not atomically doped in the SEI film on the current collector;
on a copper foil current collector, metal tungsten is used as a target material, direct current sputtering is adopted, the sputtering power is 80W, the sputtering air pressure is 1.2Pa, the substrate temperature is 50 ℃, the distance from the target material to the substrate is 12cm, the flow rate of argon is 60sccm, the flow rate of hydrogen sulfide gas is 10cssm, the sputtering time is 10min, and WS is obtained 2 Prefabricating a layer.
The battery assembling process comprises the following steps: the current collector is used as a negative electrode, a lithium sheet is used as a positive electrode, a glass fiber diaphragm is used, and DME is used for: DOL (volume ratio) =1: 1 and LiTFSI (1.0M), 2wt.% anhydrous lithium nitrate are used as electrolyte, a CR2032 button cell is assembled, the prepared cell is placed in a thermostatic chamber at 25 ℃ for standing for 12 hours, and then discharge test is carried out on a blue electric test charge-discharge tester under the test condition of 2mA/cm 2 Depositing for 60min. The test results are shown in Table 1.
Comparative example 3
In comparison with example 1, the difference is that in WSe 2 Sulfur (preparation sequence is different), specifically;
preparing a prefabricated layer: on a copper foil current collector, metal tungsten is used as a target material, direct current sputtering is adopted, the sputtering power is 80W, the sputtering air pressure is 1.2Pa, the substrate temperature is 50 ℃, the distance from the target material to the substrate is 12cm, the flow rate of argon is 60sccm, the flow rate of hydrogen selenide gas is 10cssm, and the sputtering time isFor 10min to obtain WSe 2 Prefabricating a layer.
And (3) vulcanization heat treatment process: solid sulfur powder is used as a sulfur source, the temperature of the sulfur source is 200 ℃, the temperature of the prefabricated layer is 200 ℃, the heat preservation time is 30min, the heating rate is 3 ℃/min, and the artificial SEI film W (S) is obtained by naturally cooling 0.34 Se 0.66 ) 2 The prepared film has more holes and uneven surface.
The battery assembling process comprises the following steps: the current collector is used as a negative electrode, a lithium sheet is used as a positive electrode, a glass fiber diaphragm is used, and DME is used for: DOL (volume ratio) =1: 1 and LiTFSI (1.0M), 2wt.% anhydrous lithium nitrate are used as electrolyte, a CR2032 button cell is assembled, the prepared cell is placed in a thermostatic chamber at 25 ℃ for standing for 12 hours, and then discharge test is carried out on a blue electric test charge-discharge tester under the test condition of 2mA/cm 2 Depositing for 60min. The test results are shown in Table 1.
TABLE 1
From example 1 and comparative examples 1, 2, 3, it can be seen that WS is oriented 2 Atomic doping of Se in two-dimensional materials, compared to blank, undoped Se, and WSe 2 According to the technical scheme of doping S in the two-dimensional material, the coulomb efficiency can be effectively improved, and the cycle performance of the battery can be improved.
Example 2
Preparing a prefabricated layer: on a carbon cloth current collector, metal tungsten is used as a target material, radio frequency sputtering is adopted, the power is 100W, the working air pressure is 1.2Pa, the substrate temperature is 120 ℃, the distance from the target material to the substrate is 15cm, the flow rate of argon is 120sccm, the flow rate of hydrogen sulfide gas is 30sccm, and the sputtering time is 60min, so that WS is obtained 2 Prefabricating a layer.
Selenizing heat treatment process: using diethyl selenium as selenium source, wherein the selenium source temperature is 400 ℃, the prefabricated layer temperature is 300 ℃, the heat preservation time is 60min, and the heating rate and the cooling rate are 5 ℃/min, so as to obtain the artificial SEI film W (S) 0.78 Se 0.22 ) 2 (thickness 400 nm)
Battery packThe process of loading: by electrodeposition of 20mAh/cm in the current collector 2 The metal lithium of (2) is used as the negative electrode of the button cell, the sulfur-carbon composite material (sulfur carrying amount is 60%) is used as the positive electrode, and a polypropylene diaphragm is adopted to make DME: DOL (volume ratio) =1: 1 with LiTFSI (1.0M), 2wt.% of anhydrous lithium nitrate as electrolyte, a CR2016 button cell was assembled, the prepared cell was left to stand in a thermostatic chamber at 25 ℃ for 12 hours, and then a discharge test was performed on a blue electric test charge-discharge tester under a test condition of 0.5C, and the test results are shown in table 2.
Comparative example 3
The difference compared to example 2 is that the interface material is not compounded;
by electrodeposition of 20mAh/cm in a carbon cloth current collector 2 The metal lithium of (a) is used as a negative electrode, a sulfur-carbon composite material (sulfur carrying amount is 60%) is used as a positive electrode, a polypropylene diaphragm is adopted, and DME is used for: DOL (volume ratio) =1: 1 with LiTFSI (1.0M), 2wt.% of anhydrous lithium nitrate as electrolyte, a CR2016 button cell was assembled, the prepared cell was left to stand in a thermostatic chamber at 25 ℃ for 12 hours, and then a discharge test was performed on a blue electric test charge-discharge tester under a test condition of 0.5C, and the test results are shown in table 2.
Comparative example 4
The difference compared to example 2 is that the interface material is not compounded;
preparing a prefabricated layer: on a carbon cloth current collector, metal tungsten is used as a target material, radio frequency sputtering is adopted, the power is 100W, the working air pressure is 1.2Pa, the substrate temperature is 120 ℃, the distance from the target material to the substrate is 15cm, the flow rate of argon is 120sccm, the flow rate of hydrogen sulfide gas is 30sccm, and the sputtering time is 60min, so that WS is obtained 2 Preformed layer (thickness 350 nm);
the battery assembling process comprises the following steps: by electrodeposition of 20mAh/cm in the current collector 2 The metal lithium of (a) is used as a negative electrode, a sulfur-carbon composite material (sulfur carrying amount is 60%) is used as a positive electrode, a polypropylene diaphragm is adopted, and DME is used for: DOL (volume ratio) =1: 1 and LiTFSI (1.0M), 2wt.% of anhydrous lithium nitrate as electrolyte, assembling a CR2016 button cell, placing the prepared cell in a constant temperature chamber at 25 ℃ for standing for 12h, performing discharge test on a blue charge-discharge tester under the test condition of 0.5 ℃,the deposition was carried out for 120min and the test results are shown in Table 2.
TABLE 2
Example 3
Preparing a prefabricated layer: on foam nickel, tungsten is used as a target material, radio frequency sputtering is adopted, the power is 150W, the air pressure is 2Pa, the substrate temperature is 250 ℃, the distance from the target material to the substrate is 18cm, the flow rate of argon is 200sccm, the flow rate of hydrogen sulfide is 40sccm, and the sputtering time is 100min, so that WS is obtained 2 Prefabricating a layer;
selenizing heat treatment process: using solid selenium powder as selenium source, wherein the selenium source temperature is 400 ℃, the preformed layer temperature is 450 ℃, the heat preservation time is 200min, the heating rate is 8 ℃/min, the cooling rate is 10 ℃/min, and the artificial SEI film W (S) is obtained 0.64 Se 0.36 ) 2 . (thickness 500 nm)
The battery assembling process comprises the following steps: by electrodeposition of 30mAh/cm in nickel foam 2 The metal lithium of (2) is used as a negative electrode, air is used as a positive electrode, a glass fiber diaphragm is adopted, and DME is used for: DOL (volume ratio) =1: 1 and LiTFSI (1.0M) are used as electrolyte, a CR2025 button cell is assembled, the prepared cell is placed in a thermostatic chamber at 25 ℃ for standing for 12 hours, and then discharge test is carried out on a blue charge-discharge tester under the test condition of 0.5mA/cm 2 Depositing for 60min. The test results are shown in Table 3.
Comparative example 5
The difference compared to example 3 is that the interface material is not compounded;
by electrodeposition of 30mAh/cm in nickel foam 2 The metal lithium of (2) is used as a negative electrode, air is used as a positive electrode, a glass fiber diaphragm is adopted, and DME is used for: DOL (volume ratio) =1: 1 and LiTFSI (1.0M) as electrolyte, assembling CR2025 button cell, standing in a constant temperature chamber at 25deg.C for 12 hr, and standing in blueDischarge test is carried out on the electric charge-discharge tester, and the test condition is 0.5mA/cm 2 Depositing for 60min.
Comparative example 6
The difference compared to example 3 is that the interface material is not compounded;
preparing a prefabricated layer: on foam nickel, tungsten is used as a target material, radio frequency sputtering is adopted, the power is 150W, the air pressure is 2Pa, the substrate temperature is 250 ℃, the distance from the target material to the substrate is 18cm, the flow rate of argon is 200sccm, the flow rate of hydrogen sulfide is 40sccm, and the sputtering time is 100min, so that WS is obtained 2 (thickness 440 nm);
the battery assembling process comprises the following steps: by electrodeposition of 30mAh/cm in nickel foam 2 The metal lithium of (2) is used as a negative electrode, air is used as a positive electrode, a glass fiber diaphragm is adopted, and DME is used for: DOL (volume ratio) =1: 1 and LiTFSI (1.0M) are used as electrolyte, a CR2025 button cell is assembled, the prepared cell is placed in a thermostatic chamber at 25 ℃ for standing for 12 hours, and then discharge test is carried out on a blue electric test charge-discharge tester under the test condition of 0.5mA/cm 2 Depositing for 60min. The test results are shown in Table 3.
TABLE 3 Table 3
Example 4
Preparing a prefabricated layer: on a carbon fiber current collector, metal tungsten is used as a target material, intermediate frequency sputtering is adopted, the power is 220W, the air pressure is 3Pa, the substrate temperature is 150 ℃, the distance from the target material to the substrate is 22cm, the flow rate of argon is 240sccm, the flow rate of hydrogen sulfide is 60sccm, and the sputtering time is 75min, so that WS is obtained 2 Prefabricating a layer;
selenizing heat treatment process: using diethyl selenium as selenium source, wherein the selenium source temperature is 450 ℃, the prefabricated layer temperature is 360 ℃, the heat preservation time is 20min, the heating rate is 1 ℃/min, the cooling rate is 1 ℃/min, and the artificial SEI film W (S) is obtained 0.41 Se 0.59 ) 2 。
The battery assembling process comprises the following steps: 40mAh/cm by electrodeposition in carbon fiber current collectors 2 As metallic lithium of (2)Negative electrode, air as positive electrode, polypropylene diaphragm with DMSO and LiClO 4 (1.0M) as electrolyte, assembling CR2025 button cell, standing the prepared cell in a constant temperature chamber at 25deg.C for 12 hr, and performing discharge test on a blue electric test charge-discharge tester under test conditions of 1mA/cm 2 Depositing for 120min. The first-turn discharge capacity is 6047mAh/g, the overpotential is 0.87V, and the number of turns for reducing the specific capacity to 1000mAh/g is 124.
Example 5
Preparing a prefabricated layer: on the iron foil, tungsten sulfide is used as a target material, radio frequency sputtering is adopted, the power is 300W, the air pressure is 7.2Pa, the substrate temperature is 180 ℃, the distance from the target material to the substrate is 32cm, the flow rate of argon is 220sccm, and the sputtering time is 32min, so that WS is obtained 2 Prefabricating a layer;
selenizing heat treatment process: using solid selenium powder as a selenium source, wherein the selenium source temperature is 360 ℃, the temperature of the prefabricated layer is 320 ℃, the heat preservation time is 56min, the heating rate is 12 ℃/min, the cooling rate is 8 ℃/min, and the artificial SEI film W (S) is obtained 0.55 Se 0.45 ) 2 . (thickness: 360 nm)
The battery assembling process comprises the following steps: by electrodeposition of 30mAh/cm in the pole piece 2 The metal lithium of (a) is used as a negative electrode, a sulfur-carbon composite material (sulfur carrying amount 70%) is used as a positive electrode, a polypropylene diaphragm is adopted, and DME is used for: DOL (volume ratio) =1: 1 with LiTFSI (1.0M), 1wt.% of anhydrous lithium nitrate as electrolyte, assembling a CR2025 button cell, placing the prepared cell in a constant temperature chamber at 25 ℃ for 12 hours, and then performing discharge test on a blue electric test charge-discharge tester under the test condition of 1C. The test results are shown in Table 4.
Example 6
Preparing a prefabricated layer: on graphene paper, tungsten is used as a target material, direct current sputtering is adopted, the power is 164W, the air pressure is 1.2Pa, the substrate temperature is 320 ℃, the distance from the target material to the substrate is 21cm, the flow rate of argon is 72sccm, and the sputtering time is 48min, so that WS is obtained 2 Prefabricating a layer;
selenizing heat treatment process: solid selenium powder is used as a selenium source, the temperature of the selenium source is 420 ℃, the temperature of the prefabricated layer is 350 ℃, the heat preservation time is 280min, the heating rate is 0.5 ℃/min, and the cooling rate is 15 DEG CAnd/min to obtain artificial SEI film W (S) 0.39 Se 0.61 ) 2 。
The battery assembling process comprises the following steps: by electrodeposition of 30mAh/cm in the pole piece 2 The metal lithium of (a) is used as a negative electrode, a sulfur-carbon composite material (sulfur carrying amount is 64%) is used as a positive electrode, a polypropylene diaphragm is adopted, and DME is used for: DOL (volume ratio) =1: 1 with LiTFSI (1.0M), 2wt.% of anhydrous lithium nitrate as electrolyte, assembling a CR2025 button cell, placing the prepared cell in a constant temperature chamber at 25 ℃ for standing for 12 hours, and performing discharge test on a blue electric test charge-discharge tester under the test condition of 0.5 ℃. The test results are shown in Table 4.
Example 7
Preparing a prefabricated layer: on foam titanium, tungsten sulfide is used as a target material, radio frequency sputtering is adopted, the power is 132W, the air pressure is 1.4Pa, the substrate temperature is 420 ℃, the distance from the target material to the substrate is 18cm, the flow rate of argon is 84sccm, and the sputtering time is 28min, so that WS is obtained 2 Prefabricating a layer;
selenizing heat treatment process: in WS 2 Magnetron sputtering a layer of simple substance selenium on the prefabricated layer, wherein the thickness is 8nm, and heat treatment is performed on WS 2 The temperature of the prefabricated layer is 320 ℃, the heat preservation time is 450min, the heating rate is 4 ℃/min, the cooling rate is 4 ℃/min, and the artificial SEI film W (S) is obtained 0.54 Se 0.46 ) 2 。
The battery assembling process comprises the following steps: by electrodeposition of 30mAh/cm in the pole piece 2 The metal lithium of (a) is used as a negative electrode, a sulfur-carbon composite material (sulfur carrying amount is 52%) is used as a positive electrode, a polypropylene diaphragm is adopted, and DME is used for: DOL (volume ratio) =1: 1 and LiTFSI (1.0M), 2wt.% of anhydrous lithium nitrate are used as electrolyte, a CR2025 button cell is assembled, the prepared cell is placed in a constant temperature chamber at 25 ℃ for standing for 12 hours, then discharge test is carried out on a blue electric test charge-discharge tester under the test condition of 1C, and deposition is carried out for 120 minutes. The test results are shown in Table 4.
TABLE 4 Table 4
Example 8
Preparation of prefabricated layer: on carbon nanotube paper, tungsten is used as a target material, direct current sputtering is adopted, the power is 240W, the air pressure is 3Pa, the substrate temperature is 360 ℃, the distance from the target material to the substrate is 21cm, the flow rate of argon is 180sccm, the flow rate of hydrogen sulfide is 90sccm, and the sputtering time is 5min, so that WS is obtained 2 Prefabricating a layer;
selenizing heat treatment process: in WS 2 Thermally evaporating a layer of elemental selenium on the prefabricated layer with thickness of 24nm, and thermally treating WS 2 The temperature of the prefabricated layer is 360 ℃, the heat preservation time is 400min, the heating rate is 5 ℃/min, the cooling rate is 10 ℃/min, and the artificial SEI film W is obtained (S) 0.39 Se 0.61 ) 2 。
The battery assembling process comprises the following steps: the pole piece is taken as a positive electrode, a lithium piece is taken as a negative electrode, a polypropylene diaphragm is adopted, and DME is adopted: DOL (volume ratio) =1: 1 and LiTFSI (1.0M), 2wt.% anhydrous lithium nitrate are used as electrolyte, CR2025 button cell is assembled, the prepared cell is placed in a thermostatic chamber at 25 ℃ for standing for 12 hours, then discharge test is carried out on a blue electric test charge-discharge tester under the test condition of 0.5mA/cm 2 Depositing for 120min. The test results are shown in Table 5.
Example 9
Preparing a prefabricated layer: on titanium foil, tungsten sulfide is used as a target material, radio frequency sputtering is adopted, the power is 300W, the air pressure is 2.4Pa, the substrate temperature is 100 ℃, the distance from the target material to the substrate is 24cm, the flow rate of argon is 450sccm, and the sputtering time is 30min, so that WS is obtained 2 Prefabricating a layer;
selenizing heat treatment process: using diethyl selenium as a selenium source, wherein the selenium source temperature is 400 ℃, the prefabricated layer temperature is 400 ℃, the heat preservation time is 300min, the heating rate is 15 ℃/min, the cooling rate is 15 ℃/min, and the artificial SEI film W (S) is obtained 0.22 Se 0.78 ) 2 。
The battery assembling process comprises the following steps: the pole piece is used as a negative electrode, iodine is used as a positive electrode, a polypropylene diaphragm is used, and DME is used for: DOL (volume ratio) =1: 1 and LiTFSI (1.0M), 1wt.% anhydrous lithium nitrate as electrolyte, assembling CR2025 button cell, standing the prepared cell in a constant temperature chamber at 25deg.C for 12 hr, and performing discharge test on a blue electric test charge-discharge tester under test conditions of 2mA/cm 2 Depositing for 30min. Test knotThe results are shown in Table 4.
Example 10
Preparing a prefabricated layer: on the nickel foil, tungsten sulfide is used as a target material, radio frequency sputtering is adopted, the power is 100W, the air pressure is 1.6Pa, the substrate temperature is 200 ℃, the distance from the target material to the substrate is 18cm, the flow rate of argon is 80sccm, and the sputtering time is 45min, so that WS is obtained 2 Prefabricating a layer;
selenizing heat treatment process: in WS 2 Sputtering a layer of selenium simple substance on the prefabricated layer, performing heat treatment, wherein the heat treatment temperature is 450 ℃, the heat preservation time is 360min, the heating rate is 10 ℃/min, the cooling rate is 10 ℃/min, and the artificial SEI film W (S) is obtained 0.25 Se 0.75 ) 2 。
The battery assembling process comprises the following steps: the electrode is a negative electrode, the selenium is a positive electrode, a polypropylene diaphragm is adopted, and DME is adopted: DOL (volume ratio) =1: 1 and LiTFSI (1.0M), 2wt.% anhydrous lithium nitrate are used as electrolyte, CR2025 button cell is assembled, the prepared cell is placed in a thermostatic chamber at 25 ℃ for standing for 12 hours, then discharge test is carried out on a blue electric test charge-discharge tester, and the test condition is 3mA/cm 2 Depositing for 60min. The test results are shown in Table 5.
TABLE 5
In conclusion, the artificial SEI material provided by the invention can effectively improve the electrical property of a lithium metal anode.
Claims (24)
1. A lithium metal battery negative electrode precursor material, characterized in that: the artificial two-dimensional solid electrolyte comprises a negative electrode current collector and an artificial two-dimensional solid electrolyte interface material layer which is covered on the surface of the current collector;
the chemical formula of the artificial two-dimensional solid electrolyte interface material is W (S x Se 1-x ) 2 Wherein x is more than 0 and less than 1;
the preparation method of the lithium metal battery anode precursor material comprises the following steps: preparation of WS on Current collector 2 Prefabricating layers and then for WS 2 Prefabricated layeringPerforming selenization annealing to form W on the surface of the current collector (S x Se 1-x ) 2 A material layer.
2. The lithium metal battery anode precursor material according to claim 1, wherein: x is 0.3 to 0.9.
3. The lithium metal battery anode precursor material according to claim 2, wherein: x is 0.4 to 0.8.
4. The lithium metal battery anode precursor material according to claim 1, wherein: the artificial two-dimensional solid electrolyte interface material is a two-dimensional material WS 2 An intermediate Se-doped composite material.
5. The lithium metal battery anode precursor material according to claim 1, wherein: the current collector comprises a planar current collector or a three-dimensional current collector.
6. The lithium metal battery anode precursor material according to claim 5, wherein: the planar current collector material is at least one of titanium, chromium, manganese, iron, cobalt, nickel and copper.
7. The lithium metal battery anode precursor material according to claim 6, wherein: the plane current collector material is copper foil or nickel foil.
8. The lithium metal battery anode precursor material according to claim 6, wherein: the three-dimensional current collector is a carbon-based current collector and/or a metal-based current collector.
9. The lithium metal battery anode precursor material according to claim 8, wherein: the carbon-based current collector is at least one of three-dimensional carbon fiber, carbon paper, carbon cloth, carbon nano tube, hard carbon, soft carbon, graphite, graphene oxide and reduced graphene oxide.
10. The lithium metal battery anode precursor material according to claim 8, wherein: the metal-based current collector is porous metal; the metal is at least one of titanium, chromium, manganese, iron, cobalt, nickel and copper.
11. The lithium metal battery anode precursor material according to claim 1, wherein: the solid electrolyte interface material layer is a compact material layer coated on the surface of the current collector.
12. A method for preparing the lithium metal battery anode precursor material according to any one of claims 1 to 11, which is characterized in that: preparation of WS on Current collector 2 Prefabricating layers and then for WS 2 The preformed layer is subjected to selenizing annealing to form W on the surface of the current collector (S x Se 1-x ) 2 A material layer.
13. The method for preparing a lithium metal battery anode precursor material according to claim 12, wherein: forming WS on current collector by magnetron sputtering 2 Prefabricating a layer.
14. The method for preparing a lithium metal battery anode precursor material according to claim 13, wherein: either scheme A-1 or scheme A-2 was used:
scheme A-1: preparing a layer of WS on a current collector by magnetron sputtering by taking tungsten sulfide as a target material, taking the current collector as a substrate and taking protective atmosphere as working gas 2 Prefabricating a layer;
scheme a-2: preparing WS on a current collector by magnetron sputtering by taking metal tungsten as a target material, taking the current collector as a substrate and taking gas containing hydrogen sulfide as working gas 2 Prefabricating a layer; in the gas containing hydrogen sulfide, the volume percentage of the hydrogen sulfide is not less than 0.01 percent.
15. The lithium metal battery negative electrode precursor material of claim 14The preparation method of (2) is characterized in that: scheme A-1, scheme A-2; the flow rate of the working gas is 1-500sccm, the working air pressure is controlled to be 0.05-7.5Pa, and the sputtering power density is controlled to be 0.05-300W/cm 2 Controlling the temperature of the substrate to be 0-450 ℃, controlling the distance from the target to the substrate to be 3-40cm, and controlling the sputtering time to be 0.1-200min.
16. The method for preparing the lithium metal battery anode precursor material according to any one of claims 12 to 15, wherein the method is characterized by comprising the following steps: the selenizing annealing step is as follows: WS on current collector 2 The prefabricated layer is placed in a reaction furnace, working gas with a selenium source is introduced into the furnace, and selenizing treatment is carried out for 5-600min at 200-500 ℃.
17. The method for preparing a lithium metal battery anode precursor material according to claim 16, wherein: the working gas with the selenium source is the mixed gas of the selenium source gas and the shielding gas; wherein the volume percentage of the selenium source gas is 0.1-99%;
the selenium source gas is gasified gas at 200-500 ℃.
18. The method for preparing a lithium metal battery anode precursor material according to claim 17, wherein: the selenium source gas is at least one of hydrogen selenide gas, diethyl selenium or selenium steam;
the pressure of the working gas with the selenium source gas in the reaction furnace is 0.01-100000Pa.
19. The method for preparing the lithium metal battery anode precursor material according to any one of claims 12 to 15, wherein the method is characterized by comprising the following steps: the selenizing annealing step is as follows: in WS 2 And preparing a layer of elemental selenium on the surface of the prefabricated layer through evaporation or sputtering, and then carrying out heat treatment in an inert atmosphere.
20. The method for preparing a lithium metal battery anode precursor material according to claim 19, wherein: the heat treatment temperature is 200-500 ℃; the heat treatment time is 5-600min.
21. A lithium metal battery negative electrode, characterized in that: the lithium metal composite anode comprises a negative electrode current collector, a lithium metal layer compounded on the surface of the current collector and an artificial two-dimensional solid electrolyte interface material layer covering the lithium metal layer;
the chemical formula of the artificial two-dimensional solid electrolyte interface material is W (S x Se 1-x ) 2 Wherein x is more than 0 and less than 1;
the preparation steps of the lithium metal battery cathode are as follows: filling lithium metal between a current collector and a solid electrolyte interface material layer in the lithium metal battery anode precursor material according to any one of claims 1-11 or the lithium metal battery anode precursor material prepared by the preparation method according to any one of claims 12-20;
the loading of lithium is 5-100mAh/g.
22. A method for preparing a negative electrode of a lithium metal battery as claimed in claim 21, characterized by: filling lithium metal between a current collector and a solid electrolyte interface material layer in the lithium metal battery anode precursor material according to any one of claims 1-11 or the lithium metal battery anode precursor material prepared by any one of claims 12-20 by an electrodeposition method.
23. The method for preparing a negative electrode for a lithium metal battery according to claim 22, wherein: and (3) taking the cathode precursor material as a working electrode, taking lithium metal as a counter electrode, and electrifying and electrolyzing in electrolyte to obtain the cathode.
24. A lithium metal battery characterized in that: a lithium metal battery anode loaded with the lithium metal battery anode of claim 21 or the lithium metal battery anode produced by the production method of any one of claims 22 to 23;
the lithium metal battery is a lithium ternary battery, a lithium sulfur battery, a lithium oxygen battery, a lithium air battery, a lithium selenium battery, a lithium iodine battery, a lithium tellurium battery or a lithium carbon dioxide battery.
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