CN113903889A - Lithium metal negative electrode and preparation method and application thereof - Google Patents
Lithium metal negative electrode and preparation method and application thereof Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 119
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000011241 protective layer Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims description 11
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 10
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- -1 alkyl lithium Chemical compound 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 239000011669 selenium Substances 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- ARNWQMJQALNBBV-UHFFFAOYSA-N lithium carbide Chemical compound [Li+].[Li+].[C-]#[C-] ARNWQMJQALNBBV-UHFFFAOYSA-N 0.000 claims description 2
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 claims description 2
- PEXNRZDEKZDXPZ-UHFFFAOYSA-N lithium selenidolithium Chemical compound [Li][Se][Li] PEXNRZDEKZDXPZ-UHFFFAOYSA-N 0.000 claims description 2
- CSSYKHYGURSRAZ-UHFFFAOYSA-N methyl 2,2-difluoroacetate Chemical compound COC(=O)C(F)F CSSYKHYGURSRAZ-UHFFFAOYSA-N 0.000 claims description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims 3
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims 1
- 229910052808 lithium carbonate Inorganic materials 0.000 claims 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims 1
- 229910001947 lithium oxide Inorganic materials 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 210000001787 dendrite Anatomy 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 150000002641 lithium Chemical class 0.000 description 15
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 13
- 239000011630 iodine Substances 0.000 description 13
- 229910052740 iodine Inorganic materials 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 239000011888 foil Substances 0.000 description 6
- 238000005498 polishing Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- 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 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of 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
- 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
- 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
- H01M4/13—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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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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Abstract
The invention discloses a lithium metal cathode and a preparation method and application thereof, wherein pretreated lithium metal and a precursor react for 0.5-24 h at a heating temperature of 50-200 ℃, and after the precursor volatilizes at the heating temperature and reacts with the lithium metal, a protective layer with the thickness of 1 nm-100 mu m is generated in situ on the surface of the lithium metal, so that stable and effective protection can be provided for the lithium metal. The invention can be quickly finished only by a thermal driving mode in the preparation process, is easy to implement in industry, greatly reduces the production cost and the preparation time, and promotes the practical process of the lithium metal cathode battery. The prepared lithium metal negative electrode can realize uniform deposition and stripping processes and can effectively inhibit the generation of lithium dendrites, so that the cycle stability and the safety performance of the battery are obviously improved.
Description
Technical Field
The invention belongs to the field of electrochemistry, and particularly relates to a lithium metal negative electrode and a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high specific energy, small self-discharge, no memory effect and the like, so that the lithium ion battery is widely applied to the fields of electric automobiles, smart power grids, portable electronic equipment and the like. However, with the rapid development of energy technology, higher requirements are put on the energy density and power density of lithium ion batteries. The traditional lithium ion battery adopts graphite as a negative electrode material, the theoretical specific capacity of the graphite negative electrode is low (372mAh/g), the energy density of the graphite negative electrode is difficult to break through the limit value of 300 Wh.kg < -1 >, and the further development of the graphite negative electrode is severely limited. Therefore, the development of higher specific capacity negative electrode materials is particularly important for improving the energy density of batteries, such as silicon-based negative electrodes and lithium metal negative electrodes.
Lithium metal is known as "holy cup" in the negative electrode material because of its advantages of extremely high theoretical specific capacity (3860mAh/g), lowest redox potential (-3.04V vs. standard hydrogen electrode), and low density (0.534g/cm 3). Therefore, the energy density of the lithium ion battery can be remarkably improved by using lithium metal as the negative electrode. In addition, lithium metal batteries can employ positive electrode materials (e.g., sulfur, oxygen, etc.) having higher energy densities than lithium ion batteries, and thus can form high specific energy battery systems. However, lithium metal negative electrodes have some problems during use, which severely restrict their further development. The method comprises the following points: firstly, the Solid Electrolyte Interphase (SEI) generated on the surface of lithium metal is not uniform, so that the lithium metal is not uniformly deposited and stripped; secondly, a large amount of volume expansion exists in the deposition and stripping processes of lithium metal, so that the SEI is further unstable; and thirdly, the lithium metal has high reactivity with the electrolyte, so that the lithium metal and the electrolyte are continuously consumed.
In view of the above problems, researchers have proposed various improvements in electrolyte modification and lithium metal surface modification, mainly using strong lewis acid AlI3As an electrolyte additive, the reaction conditions are harsh and the process is complex; or using fluorocarbonic acidThe strategy of constructing artificial SEI on the surface of lithium metal by vinyl ester (FEC), the thickness and the component regulation of the SEI are difficult to realize quickly and conveniently by the traditional solution soaking method, and therefore, the method is greatly limited in the aspect of industrial application.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides a lithium metal negative electrode and a preparation method and application thereof, and solves the problems in the background art.
One of the technical schemes adopted by the invention for solving the technical problems is as follows: provided is a method for preparing a lithium metal negative electrode, including the steps of:
1) pretreatment: removing the original interface layer on the surface of the lithium metal to obtain a fresh lithium metal surface;
2) thermal driving: placing the lithium metal pretreated in the step 1) and a precursor at a heating temperature of 50-200 ℃ for reacting for 0.5-24 h, wherein the precursor comprises iodine, phosphorus and selenium simple substances or a dispersion liquid formed by iodine, phosphorus, selenium and a solvent, and the dispersion liquid is capable of volatilizing at the heating temperature and reacting with the lithium metal; after the reaction, a protective layer with the thickness of 1 nm-100 mu m is generated on the surface of the lithium metal in situ.
In a preferred embodiment of the present invention, the protective layer includes lithium iodide, lithium phosphide, and lithium selenide.
In a preferred embodiment of the present invention, the protective layer further comprises at least one of lithium nitride, lithium chloride, lithium bromide, lithium carbide, lithium acetate, lithium alkyl, and lithium alkyl.
In a preferred embodiment of the present invention, the solvent includes vinylene carbonate, ethylene carbonate, and methyl difluoroacetate.
In a preferred embodiment of the present invention, the heating temperature is 60 ℃ to 150 ℃, and the reaction pressure is at least one atmosphere.
In a preferred embodiment of the present invention, the thickness of the passivation layer is 100nm to 5 μm.
In a preferred embodiment of the present invention, the pretreatment is a melt recasting method, comprising the steps of: heating the lithium metal to a liquid state, removing all the interface layers native to the surface of the lithium metal, and recasting the interface layers into a fresh lithium metal surface.
The second technical scheme adopted by the invention for solving the technical problems is as follows: the lithium metal negative electrode consists of lithium metal and a protective layer generated in situ on the surface of the lithium metal, and is prepared by adopting the method.
The third technical scheme adopted by the invention for solving the technical problems is as follows: the anode material of the lithium ion battery comprises lithium iron phosphate, lithium cobaltate, a ternary anode or elemental sulfur, oxygen and air.
Compared with the background technology, the technical scheme has the following advantages:
1. according to the scheme, the precursor is heated into steam and reacts with the lithium sheet in a thermal driving mode, a protective layer is generated on the surface of the lithium sheet in situ, the protective layer has high lithium ion conductivity, can provide stable and effective protection for lithium metal, effectively reduces direct contact between electrolyte and the lithium metal, greatly reduces parasitic reaction, effectively reduces loss of active substances of the lithium metal, and finally improves the electrochemical performance of the lithium cathode;
2. the protective layer prepared by the scheme is uniform, flat and compact, so that lithium ions can form uniform ion flux when penetrating through the protective layer, and can be uniformly deposited on the surface of lithium, the generation of lithium dendrites is effectively reduced, the generation of dead lithium is also reduced, and the long-cycle stability of a lithium cathode is promoted finally;
3. the scheme directly drives the precursor to react with the lithium sheet to generate the protective layer, and compared with the traditional solution soaking lithium sheet to construct the protective layer: on the one hand, the thickness of the protective layer and the components are more conveniently regulated, and the uniformity of the components can ensure the functional stability of the protective layer: on the other hand, the thermal driving mode is simpler in industrial operation, the production time can be greatly reduced under the thermal driving, the production cost is greatly reduced, and the industrial production is facilitated.
Drawings
FIG. 1 is a schematic diagram of the preparation principle of example 1.
Fig. 2 is a scanning electron micrograph of the lithium metal negative electrode prepared in example 1.
Fig. 3 is an elemental distribution diagram of iodine in the lithium metal negative electrode prepared in example 1.
Fig. 4 is a scanning electron microscope picture of a cross section of the lithium metal negative electrode prepared in example 1.
Fig. 5 is a scanning electron micrograph of the lithium metal negative electrode prepared in example 1 after cycling 100 cycles.
Fig. 6 is a cycle performance curve of the lithium metal symmetric battery prepared in example 1.
Fig. 7 is a scanning electron micrograph of the lithium metal negative electrode of comparative example 1 before cycling.
Fig. 8 is a scanning electron micrograph of the lithium metal negative electrode of comparative example 1 after cycling for 100 cycles.
Fig. 9 is a cycle performance curve of the lithium metal symmetric battery prepared in comparative example 1.
Fig. 10 is a scanning electron micrograph of a lithium metal negative electrode prepared in example 2.
Fig. 11 is a cycle performance curve of the lithium metal-sulfur full cell prepared in example 7.
Fig. 12 is a cycle performance curve of a lithium metal-NCM 523 full cell prepared in example 8.
Fig. 13 is a cycle performance curve of the lithium metal-lithium iron phosphate full cell prepared in example 9.
Detailed Description
Example 1
The preparation method of the lithium metal negative electrode of the embodiment comprises the following steps:
selecting simple substance iodine as a reaction substance, and adopting a fresh lithium sheet after melting and recasting as the lithium sheet. Referring to FIG. 1, 1g of iodine and 4 lithium sheets are placed in a reaction vessel, heated to 150 ℃, kept at 150 ℃ for reaction for 0.5h, and then naturally cooled. And taking out the lithium sheet, repeatedly washing with a DME solvent and drying in vacuum for 24 hours to obtain the modified lithium metal negative electrode.
As shown in fig. 2, the lithium metal negative electrode prepared in this example has a lithium iodide layer formed by the reaction of lithium metal and iodine uniformly spread on the surface of the lithium sheet, and the thickness is 520nm as shown in fig. 4; the presence of lithium iodide was first confirmed from the electron micrograph of fig. 3 and the corresponding distribution of iodine element, and the uniform distribution of iodine element also confirmed the uniform distribution of lithium iodide produced by the reaction.
The modified lithium metal cathode is used for assembling a Li/Li symmetrical battery under the test condition that the current density is 1mA/cm2And a deposition/dissolution capacity of 1mAh/cm2As shown in fig. 4, it can be seen that the symmetrical battery assembled using the modified lithium metal negative electrode has a very low overpotential and stable cycle performance. The scanning electron micrograph of the electrode surface after 100 cycles is shown in fig. 5, and the result shows that the lithium metal negative electrode surface has a flat and dense morphology and no evidence of lithium dendrites.
Comparative example 1
The lithium foil was subjected to melt polishing to remove the surface oxide layer, thereby obtaining a lithium metal negative electrode of comparative example 1, the surface morphology of which is shown in fig. 6. The Li/Li symmetrical battery is assembled by the lithium metal cathode under the test condition that the current density is 1mA/cm2And a deposition/dissolution capacity of 1mAh/cm2As shown in fig. 7, it can be seen that the unmodified lithium metal negative electrode has increased deposition difficulty after long cycling and shows unstable cycling tendency. The scanning electron micrograph of the electrode surface after 100 cycles is shown in fig. 8, and the result shows that the surface of the lithium metal negative electrode is rough and porous and has serious pulverization, which indicates that a large amount of dead lithium is generated in the cycle process.
Example 2
Selecting simple substance iodine as a reaction substance, removing a surface oxide layer from a lithium sheet by means of melt polishing, weighing 0.5g of iodine to react with the lithium sheet, heating to 150 ℃, maintaining the temperature at 150 ℃ for reaction for 0.5h, and naturally cooling. And then taking out the lithium sheet, repeatedly washing with DME solvent and vacuum drying for 24h to obtain the modified lithium metal negative electrode, wherein the surface appearance of the modified lithium metal negative electrode is shown in figure 8.
Example 3
Selecting phosphorus as a reaction substance, removing a surface oxide layer from a lithium sheet by means of melt polishing, weighing 2g of phosphorus to react with the lithium sheet, heating to 60 ℃, maintaining the temperature at 60 ℃, taking out after reacting for 0.5h, cleaning with CS2 solvent, and drying in vacuum for 24h to obtain the modified lithium metal cathode.
Example 4
Selecting an iodine simple substance and a vinyl ethylene carbonate solvent as reaction substances, preparing 1mol/L iodine vinyl ethylene carbonate solution, removing a surface oxide layer from a lithium sheet by means of melt polishing, measuring 0.5mL solution to react with the lithium sheet, heating to 120 ℃, maintaining the temperature at 120 ℃ for 24 hours, taking out, cleaning with the vinyl carbonate solvent, and drying in vacuum for 24 hours to obtain the modified lithium metal cathode.
Example 5
Iodine simple substance and a difluoroethylene methyl ester solvent are selected as reaction substances, and a difluoroethylene methyl ester solution of iodine with the concentration of 1mol/L is prepared. Removing a surface oxide layer of a lithium sheet by means of melt polishing, measuring 0.5mL of solution to react with the lithium sheet, heating to 100 ℃, maintaining the temperature at 100 ℃ for 24h, taking out, washing with a vinyl carbonate solvent, and drying in vacuum for 24h to obtain the modified lithium metal cathode.
Example 6
Selecting an iodine simple substance and a vinylene carbonate solvent as reaction substances, and preparing a 1mol/L vinylene carbonate solution of iodine. Removing a surface oxide layer of a lithium sheet by means of melt polishing, measuring 0.5mL of solution to react with the lithium sheet, heating to 100 ℃, maintaining the temperature at 100 ℃ for 24h, taking out, washing with a tetrahydrofuran solvent, and drying in vacuum for 24h to obtain the modified lithium metal cathode.
Example 7
The battery was assembled with a sulfur positive electrode material as the positive electrode, the modified lithium foil prepared in example 3 as the negative electrode, 1mol/L LiTFSI (DOL: DME, v/v ═ 1:1) as the electrolyte, and Celgard2400 as the separator, and subjected to electrochemical performance testing.
Example 8
The lithium iron phosphate cathode material is used as a cathode, the modified lithium foil prepared in example 4 is used as a cathode, 1mol/L LiPF6(EC: DMC, v/v ═ 1:1) is used as an electrolyte, and Celgard2400 is used as a diaphragm, and the lithium iron phosphate cathode material, the modified lithium foil and the electrolyte are assembled into a battery to perform electrochemical performance test.
Example 9
The electrochemical performance test was performed on a battery assembled with NCM523 positive electrode material as the positive electrode, the modified lithium foil prepared in example 5 as the negative electrode, 1mol/L LiPF6(EC: DMC, v/v ═ 1:1) as the electrolyte, and Celgard2400 as the separator.
Example 10
The electrochemical performance test was performed on a battery assembled with oxygen as the positive electrode, the modified lithium foil prepared in example 6 as the negative electrode, 1mol/L LiTFSI (DOL: DME, v/v ═ 1:1) as the electrolyte, and Celgard2400 as the separator.
It will be appreciated by those skilled in the art that the same or similar technical effects as those of the above embodiments can be expected when the technical parameters of the present invention are changed within the following ranges:
during the thermal driving, the pressure range can be selected from normal pressure and pressurization, and the pressurized state is preferred.
The negative electrode can also adopt a current collector as a conductive substrate, and the material is at least one of copper, nickel, titanium, iron, silver, platinum, gold, carbon and stainless steel, and preferably copper; if the current collector is adopted, a layer of molten lithium metal is adhered to the surface of the current collector in advance to form a fresh lithium metal surface for subsequent reaction with a precursor.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
Claims (9)
1. A method for preparing a lithium metal negative electrode, comprising: the method comprises the following steps:
1) pretreatment: removing the original interface layer on the surface of the lithium metal to obtain a fresh lithium metal surface;
2) thermal driving: placing the lithium metal pretreated in the step 1) and a precursor at a heating temperature of 50-200 ℃ for reacting for 0.5-24 h, wherein the precursor comprises iodine, phosphorus and selenium simple substances or a dispersion liquid formed by iodine, phosphorus, selenium and a solvent, and the dispersion liquid is capable of volatilizing at the heating temperature and reacting with the lithium metal; after the reaction, a protective layer with the thickness of 1 nm-100 mu m is generated on the surface of the lithium metal in situ.
2. The method of claim 1, wherein the method comprises: the protective layer comprises lithium iodide, lithium phosphide and lithium selenide.
3. The method of claim 2, wherein the method comprises: the protective layer further comprises lithium fluoride, lithium nitride, lithium oxide, lithium chloride, lithium bromide, lithium carbide, lithium carbonate, lithium hydroxide, lithium acetate, alkyl lithium, lithium alkyl, ROCO2Li、ROLi、(ROCO2Li)2At least one of (1).
4. The method of claim 1, wherein the method comprises: the solvent comprises vinylene carbonate, ethylene carbonate and methyl difluoroacetate.
5. The method of claim 1, wherein the method comprises: the heating temperature is 60-150 ℃, and the reaction pressure is at least one atmosphere.
6. The method of claim 1, wherein the method comprises: the thickness of the protective layer is 100 nm-5 μm.
7. The method of claim 1, wherein the method comprises: the pretreatment comprises the following steps: heating the lithium metal to a liquid state, removing all the interface layers native to the surface of the lithium metal, and recasting the interface layers into a fresh lithium metal surface.
8. A lithium metal anode characterized by: the protective layer is composed of lithium metal and a protective layer generated in situ on the surface of the lithium metal, and is prepared by the method as claimed in any one of claims 1 to 7.
9. Use of a lithium metal negative electrode according to claim 8 for the preparation of a lithium ion battery, wherein: the anode material of the lithium ion battery comprises lithium iron phosphate, lithium cobaltate, a ternary anode or elemental sulfur, oxygen and air.
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