CN115394958A - Lithium metal negative electrode, preparation method thereof and lithium metal battery - Google Patents
Lithium metal negative electrode, preparation method thereof and lithium metal battery Download PDFInfo
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- CN115394958A CN115394958A CN202110565047.2A CN202110565047A CN115394958A CN 115394958 A CN115394958 A CN 115394958A CN 202110565047 A CN202110565047 A CN 202110565047A CN 115394958 A CN115394958 A CN 115394958A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 158
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 31
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 31
- 239000000956 alloy Substances 0.000 claims abstract description 26
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 24
- -1 lithium halide Chemical class 0.000 claims abstract description 22
- 239000011241 protective layer Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 229910000733 Li alloy Inorganic materials 0.000 claims abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 38
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- 239000003960 organic solvent Substances 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229910001507 metal halide Inorganic materials 0.000 claims description 15
- 150000005309 metal halides Chemical class 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000011065 in-situ storage Methods 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 6
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 5
- LTRVAZKHJRYLRJ-UHFFFAOYSA-N lithium;butan-1-olate Chemical group [Li+].CCCC[O-] LTRVAZKHJRYLRJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005275 alloying Methods 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- KLRHPHDUDFIRKB-UHFFFAOYSA-M indium(i) bromide Chemical compound [Br-].[In+] KLRHPHDUDFIRKB-UHFFFAOYSA-M 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- 229910000807 Ga alloy Inorganic materials 0.000 claims description 2
- 229910000846 In alloy Inorganic materials 0.000 claims description 2
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- LHJOPRPDWDXEIY-UHFFFAOYSA-N indium lithium Chemical compound [Li].[In] LHJOPRPDWDXEIY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000000151 deposition Methods 0.000 description 21
- 230000008021 deposition Effects 0.000 description 21
- 238000012360 testing method Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 16
- 239000003792 electrolyte Substances 0.000 description 15
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 12
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 230000007774 longterm Effects 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 6
- 210000001787 dendrite Anatomy 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 4
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005137 deposition process Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 2
- 229910010199 LiAl Inorganic materials 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical group CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- VVKLZHZYBZPWIN-UHFFFAOYSA-N lithium;pentan-1-olate Chemical compound [Li]OCCCCC VVKLZHZYBZPWIN-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- 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
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to the technical field of lithium metal batteries, and discloses a lithium metal negative electrode, a preparation method thereof and a lithium metal battery. The lithium metal negative electrode at least comprises a composite protective layer, the composite protective layer comprises a composition containing at least two of lithium halide, organic lithium salt and alloy components, and the content of the lithium halide is 25-55 wt%, the content of the organic lithium salt is 5-30 wt% and the content of the alloy components is 30-60 wt% based on the total weight of the composition. The lithium metal battery has higher cycle stability and cycle life.
Description
Technical Field
The invention relates to the technical field of lithium metal batteries, in particular to a lithium metal negative electrode, a preparation method thereof and a lithium metal battery.
Background
With the development of new energy automobiles, the development of power batteries with energy density higher than 300Wh/kg becomes a main way for improving the endurance mileage of automobiles. The lithium metal is used as a negative electrode, which is the key for realizing the breakthrough of the energy density of the battery. When lithium metal is used as a negative electrode of a secondary battery, the lithium metal is repeatedly deposited and dissolved during charge and discharge, but the interface of a solid electrolyte formed by the reaction of lithium with the electrolyte is unstable, so that lithium dendrites are easily formed, and the electrolyte is consumed, thereby limiting the life and safety of a rechargeable lithium battery. Various research organizations propose various solutions to the interface problem in order to inhibit the growth of dendrites and improve the safety, utilization rate and cycle life of lithium metal batteries, such as changing the composition of an electrolyte, thereby changing the composition of a solid electrolyte mesophase; introducing a physical barrier layer with high mechanical strength on the surface of the lithium metal; constructing an artificial solid electrolyte intermediate phase; changing the current collector structure, increasing lithium deposition sites to reduce local current density, etc.
CN109004276A discloses a lithium cathode protective film, a preparation method and a lithium metal secondary battery, wherein the protective film consists of lithium salt, ionic liquid, inorganic nanoparticles and a lithiated Nafion polymer; however, the solution preparation process involves the procedures of ball milling and the like, the procedures of Nafion lithiation and the like, and the process is complicated; and completely through physical coating, no chemical bond effect and weak interface combination.
CN106935800A discloses a protective layer for the negative electrode of a secondary lithium battery, which is limited to a few inorganic salts, and has no data of inhibiting dendrites to support its claimed effect, and the inorganic salt layer has no chemical effect on the lithium metal interface, and has the same weak binding property with lithium by physical adsorption.
Therefore, it is of great importance to research and develop a lithium metal negative electrode having a stable surface protective layer.
Disclosure of Invention
The invention aims to overcome the problem of dendritic growth in a lithium metal negative electrode in the prior art, and provides a lithium metal negative electrode, a preparation method thereof and a lithium metal battery.
In order to achieve the above object, a first aspect of the present invention provides a lithium metal negative electrode, wherein the lithium metal negative electrode includes at least one composite protective layer, the composite protective layer includes a composition including at least two of a lithium halide, an organic lithium salt, and an alloy component, and the content of the lithium halide is 25 to 55 wt%, the content of the organic lithium salt is 5 to 30 wt%, and the content of the alloy component is 30 to 60 wt%, based on the total weight of the composition.
The second aspect of the present invention provides a preparation method of the foregoing lithium metal negative electrode, wherein the preparation method includes:
(1) Contacting and mixing metal halide and an organic solvent to obtain a mixed solution;
(2) And contacting the mixed solution with lithium metal to perform in-situ reaction to obtain the lithium metal cathode.
The third aspect of the invention provides a lithium metal battery, wherein the lithium metal battery comprises the lithium metal negative electrode.
Through the technical scheme, the technical scheme of the invention has the following advantages:
(1) According to the invention, the lithium metal cathode with a composite structure is obtained in an in-situ reaction mode, can simultaneously conduct lithium ions and has certain electronic conductivity, and the distribution uniformity of the lithium ions in the deposition process is effectively improved, so that the formation of lithium dendrites is delayed.
(2) The metal halide and the organic solvent are matched for use in the invention, a protective layer with specific components can be formed on the surface of the lithium metal, and the protective layer has organic, inorganic and alloyed composite structure distribution.
(3) The lithium metal battery of the invention has higher cycle stability and cycle life.
Detailed Description
The following describes the embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a lithium metal negative electrode, wherein the lithium metal negative electrode at least comprises a composite protective layer, the composite protective layer comprises a composition containing at least two of lithium halide, organic lithium salt and alloy components, and the content of the lithium halide is 25-55 wt%, the content of the organic lithium salt is 5-30 wt% and the content of the alloy components is 30-60 wt% based on the total weight of the composition.
The inventors of the present invention have surprisingly found that: on one hand, the metal halide and the organic solvent are matched for use, a protective layer with specific components can be formed on the surface of the lithium metal, and the protective layer has organic, inorganic and alloyed composite structure distribution; on the other hand, a lithium metal negative electrode with a composite structure is obtained by means of in-situ reaction, and the negative electrode has higher cycle stability and service life.
According to the present invention, it is preferable that the content of the lithium halide is 30 to 50% by weight, the content of the organic lithium salt is 5 to 25% by weight, and the content of the alloy component is 35 to 55% by weight, based on the total weight of the composition; more preferably, the content of the lithium halide is 35 to 45 wt%, the content of the organic lithium salt is 10 to 20 wt%, and the content of the alloy component is 40 to 50 wt%, based on the total weight of the composition. In the invention, the content of the lithium halide, the organic lithium salt and the alloy component is limited to be within the range, so that the structure of the composite protective layer has the optimal ion conduction function and certain electronic conductivity, the overpotential of lithium in the deposition process can be reduced, the deposition process is easier to carry out, the formation and growth process of dendrite is hindered, and the service life of the lithium cathode is prolonged.
According to the invention, the lithium halide is selected from one or more of the group consisting of chloride, bromide, fluoride and iodide of metallic lithium; preferably, the lithium halide is selected from one or more of lithium chloride, lithium bromide and lithium iodide.
According to the invention, the organic lithium salt is a lithium salt formed by an organic solvent and lithium; preferably, the organic solvent is selected from one or more of tetrahydrofuran, polymethylpyrrolidone, dimethylformamide, polycarbonate, alcohol, ether and carboxylic acid; preferably, the organic solvent is selected from one or more of tetrahydrofuran, an alcohol and a carboxylic acid; more preferably, the organic solvent is selected from one or more of tetrahydrofuran, ethanol and n-pentanol; in the present invention, it is still further preferred that the organic lithium salt is selected from lithium butoxide, CH 3 CH 2 One or more of OLi and lithium n-amylate.
According to the invention, the alloy component is an alloy of lithium and a metallic element; preferably, the metal is selected from one or more of aluminium, zinc, gallium, germanium, cadmium, indium and tin; preferably, the alloy component is selected from one or more of a lithium aluminum alloy, a lithium gallium alloy, and a lithium indium alloy.
In a second aspect, the present invention provides a method for preparing a lithium metal negative electrode as claimed in the preceding claim, wherein the method comprises:
(1) Contacting and mixing metal halide and an organic solvent to obtain a mixed solution;
(2) And contacting the mixed solution with lithium metal to perform in-situ reaction to obtain the lithium metal cathode.
According to the invention, the metal halide is selected from the group consisting of chlorides, bromides of transition metalsOne or more of onium, fluoride, and iodide; preferably, the metal halide is selected from one or more of fluoride, chloride, bromide and iodide of transition metal; preferably, the transition metal is selected from one or more of aluminum, zinc, gallium, germanium, cadmium, indium and tin; more preferably, the metal halide is selected from AlCl 3 、InBr 3 And GaI 3 One or more of (a).
The inventors of the present invention found that: the lithium metal battery containing the lithium metal negative electrode has higher cycle stability and cycle life by adopting the metal halide specially limited in the foregoing. And if copper metal is selected, it causes a problem that alloying with lithium cannot be performed; and if sodium metal is selected, it causes a problem of low controllability of the reaction product.
According to the present invention, the organic solvent is selected from one or more of tetrahydrofuran, polymethylpyrrolidone, dimethylformamide, polycarbonate, alcohol, ether and carboxylic acid; preferably, the organic solvent is selected from one or more of tetrahydrofuran, an alcohol and a carboxylic acid; more preferably, the organic solvent is selected from one or more of tetrahydrofuran, ethanol and n-pentanol.
The inventors of the present invention found that: by adopting the organic solvent specifically defined in the foregoing, the lithium metal battery containing the lithium metal negative electrode can be enabled to have higher cycle stability and cycle life. Whereas if water is chosen as the solvent, this leads to the formation of an excess of Li 2 O, leading to a weakening of the alloying reaction and failure to form an effective composite structure; whereas if acetone is chosen as the organic solvent, the effect of the organic components in the composite structure is reduced.
According to the invention, the concentration of the mixed solution is 0.01-5mol/L, preferably 0.02-0.6mol/L. In the present invention, if the concentration of the mixed solution is too high, the resistance of the resulting composite structure is high, and the polarization of the lithium negative electrode becomes large. If the concentration of the mixed solution is too low, the problem that an effective composite structure cannot be formed is caused; in the present invention, the concentration of the mixed solution is limited to the foregoing range, and an excessive interface resistance can be not introduced by the protective layer under the condition that an effective composite structure is formed.
According to the invention, in step (1), the mixing is carried out under conditions in a glove box filled with Ar. In the present invention, the mixing temperature is not particularly limited, and may be performed at room temperature.
According to the present invention, in the step (2), the temperature of the in-situ reaction is not particularly limited, and may be performed at room temperature.
According to the present invention, in the step (2), the manner of contacting the mixed solution with lithium metal may be one or more of spray coating, spin coating, curtain coating, and dipping.
According to the invention, the preparation method further comprises: and (2) contacting the solution with lithium metal to perform in-situ reaction, and then performing drying treatment, wherein the drying condition comprises the following steps: the temperature is 30-100 deg.C, preferably 40-100 deg.C, and the drying time is not limited in particular, and the drying time is preferably 60-720min.
A third aspect of the invention provides a lithium metal battery comprising the lithium metal negative electrode described above.
According to the present invention, the lithium metal battery further includes a positive electrode and an electrolyte.
According to the invention, the positive electrode is prepared from a positive electrode material, wherein the positive electrode material is selected from LiFePO 4 、LiMn 2 O 4 One or more of NCM, NCA and sulphur; preferably, the positive electrode material is selected from NCM and/or sulfur.
According to the present invention, the electrolyte includes a solvent and a lithium salt.
According to the invention, the solvent is an ester solvent and/or an ether solvent; preferably, the ester-based solvent is selected from one or more of Propylene Carbonate (PC), ethylene Carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC) and fluoroethylene carbonate (FEC); more preferably, the ester solvent is selected from one or more of Ethylene Carbonate (EC), dimethyl carbonate (DMC) and fluoroethylene carbonate (FEC).
According to the present invention, the ether solvent is selected from one or more of 1, 2-Dimethoxyethane (DME), dioxolane (DOL) and diethyl ether (DEE), and preferably, the ether solvent is selected from 1, 2-Dimethoxyethane (DME) and/or Dioxolane (DOL).
According to the invention, the lithium salt is selected from lithium hexafluorophosphate (LiPF) 6 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium perchlorate (LiClO) 4 ) Lithium bis (trifluoromethanesulfonylimide) (LiTFSI) and lithium bis (fluorosulfonylimide) (LiFSI).
According to the present invention, the concentration of the lithium salt in the electrolyte is 0.1 to 7mol/L, preferably 0.5 to 4mol/L in terms of Li. In the invention, the concentration of the lithium salt is controlled within the range, so that the viscosity of the electrolyte is not too high, the sufficient quantity distribution of lithium ions at the interface deposition part is ensured, and the deposition of lithium metal is facilitated.
According to the present invention, the lithium metal battery was prepared for testing.
According to the present invention, an assembled battery includes: and spreading, unfolding and punching the lithium metal foil into a circular sheet with the diameter of 12mm, and assembling the circular sheet into the symmetrical button cell.
In addition, the symmetrical button cell assembled by the battery is subjected to alternating current impedance test and charge-discharge cycle test, wherein the frequency range of the alternating current impedance test is 0.1Hz-1MHz, and the bias voltage is 5mV. The current density of the constant current charge and discharge test is 0.1-5mA/cm 2 。
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
(1) First week lithium deposition overpotential test:
the symmetrical battery is tested by a blue electric charge and discharge tester (Land CT2001 in Wuhan blue) at a current density of 1mA/cm 2 And testing to obtain the overpotential value of lithium deposition.
(2) Life test of lithium negative electrode
Testing the symmetrical battery with blue electricity charge and discharge tester (Land CT 2001) at current density of 0.1-5mA/cm 2 And the lithium deposition capacity is 1mAh/cm 2 The battery was tested for cycle stability under the conditions of (1).
(3) Interface impedance testing
The Auto-Lab electrochemical workstation (Switzerland PGSTAT 302N) tests symmetric batteries under conditions including a test frequency of 0.1Hz-1MHz and a bias of 5mV.
Example 1
This example is to illustrate a lithium metal battery prepared using the lithium metal negative electrode of the present invention.
(1) In a glove box filled with Ar, alCl was added 3 Dissolving in THF to obtain 0.02mol/L mixed solution;
(2) 50 mu L of the mixed solution is sprayed on the surface of a 16mm lithium metal wafer for in-situ reaction, and after the reaction is finished, drying treatment is carried out in a glove box at 40 ℃.
As a result, a lithium metal negative electrode having a composite protective layer structure in which a lithium halide (specifically, liCl): organic lithium salt (specifically, lithium butoxide): the ratio of the alloy components (particularly, liAl alloy) was 40:10:50.
in addition, a lithium metal battery was prepared using the lithium metal negative electrode:
wherein the electrolyte is 1mol/LLIPF 6 The EC/DEC solution is assembled into a symmetrical battery to carry out charge-discharge cycle test at 1mA/cm 2 The overpotential for the first cycle of lithium deposition is 0.15V, the average overpotential for deposition during long-term cycling is 0.1V, and no short-circuit signal appears after 100 cycles.
Example 2
This example is intended to illustrate a lithium metal battery prepared using a lithium metal negative electrode of the present invention.
(1) In a glove box filled with Ar, inBr 3 Dissolving in ethanol to prepare a mixed solution of 0.6 mol/L;
(2) Spraying 50 mu L of the mixed solution on the surface of a 16mm lithium metal wafer for in-situ reaction, and drying the wafer in a glove box at the temperature of 80 ℃ after the reaction is finished.
The result is a lithium metal negative electrode having a composite protective layer structure, whereinLithium halide (specifically LiBr): organic lithium salt (specifically CH) 3 CH 2 OLi): the ratio of alloy components (specifically, liIn alloy) was 35:20:45.
in addition, a lithium metal battery was prepared using the lithium metal negative electrode:
wherein the electrolyte is 1mol/LLIPF6 EC/DEC solution, and is assembled into a symmetrical battery for charge-discharge cycle test at 1mA/cm 2 The overpotential for the first cycle of lithium deposition is 0.12V, the average overpotential for deposition in the long-term circulation process is 0.08V, and no short-circuit signal appears after 180 cycles.
Example 3
This example is to illustrate a lithium metal battery prepared using the lithium metal negative electrode of the present invention.
(1) In a glove box filled with Ar, gaI 3 Dissolving in n-amyl alcohol to prepare a mixed solution of 0.2 mol/L;
(2) 50 mu L of the mixed solution is sprayed on the surface of a 16mm lithium metal wafer for in-situ reaction, and after the reaction is finished, the mixed solution is dried in a glove box at the temperature of 80 ℃.
As a result, a lithium metal anode having a composite protective layer structure in which a metal halide (specifically LiI): organic lithium salt (specifically, lithium n-pentanolate): the ratio of the alloy components (specifically, the LiGa alloy) was 45:15:40.
in addition, a lithium metal battery was prepared using the lithium metal negative electrode:
wherein the electrolyte is 1mol/LLIPF6 EC/DEC solution, and is assembled into a symmetrical battery for charge-discharge cycle test at 1mA/cm 2 The first cycle of lithium deposition overpotential is 0.09V, the average deposition overpotential in the long-term cycle process is 0.06V, and no short-circuit signal appears after 200 cycles.
Comparative example 1
Taking a 16mm lithium metal wafer and an EC/DEC solution with electrolyte of 1mol/LLIPF6, assembling the wafer into a symmetrical battery for charge-discharge cycle test at 1mA/cm 2 The overpotential for the first cycle of lithium deposition was 0.20V, the overpotential for the long-term cycle was 0.16V, and short-circuiting occurred in 70 cycles.
Comparative example 2
Lithium was soaked in THF and dried after the reaction was complete, containing only the organic lithium salt. The electrolyte is EC/DEC solution of 1mol/LLIPF6, and is assembled into a symmetrical battery for charge-discharge cycle test at 1mA/cm 2 The overpotential for the first cycle of lithium deposition is 0.19V, the average overpotential for deposition during long-term cycling is 0.15V, and a short-circuit signal appears after 100 cycles.
Comparative example 3
NaCl was dissolved in NMP to prepare a 0.1mol/L solution. Spray 50 μ L of this solution onto the surface of a 16mm lithium metal wafer and dry to give the product halide: the ratio of organic lithium salt is 85. The electrolyte is 1mol/LLiPF6 EC/DEC solution, and a symmetrical battery is assembled to carry out charge-discharge cycle test at 1mA/cm 2 The overpotential for the first cycle of lithium deposition is 0.22V, the average overpotential for deposition during long-term cycling is 0.14V, and a short-circuit signal appears after 120 cycles.
Comparative example 4
A lithium metal negative electrode was prepared according to the same preparation method as example 1, except that: in step (2), by changing the conditions, the lithium halide (specifically LiCl): organic lithium salt (specifically, lithium butoxide): the proportion of alloy components (particularly LiAl alloy) is 10:15:75.
in addition, a lithium metal battery was prepared using the lithium metal negative electrode:
wherein the electrolyte is 1mol/LLIPF 6 The EC/DEC solution is assembled into a symmetrical battery to carry out charge-discharge cycle test at 1mA/cm 2 The overpotential for lithium deposition in the first week is 0.1V, the average overpotential for deposition in the long-term circulation process is 0.08V, and a short-circuit signal appears after 50 weeks of circulation.
Comparative example 5
A lithium metal negative electrode was prepared according to the same preparation method as example 1, except that: in step (1), "will AlCl 3 Dissolved in THF to prepare a 0.02mol/L solution "substituted with" CuCl 2 Dissolved in acetone to prepare a 0.05mol/L solution ".
In addition, a lithium metal battery was prepared using the lithium metal negative electrode:
wherein the electrolyte is 1mol/LLIPF 6 The EC/DEC solution is assembled into a symmetrical battery to carry out charge-discharge cycle test at 1mA/cm 2 The first week of lithium deposition overpotential is 0.2V, the average deposition overpotential in the long-term cycle process is 0.16V, and a short-circuit signal appears after 20 cycles.
In conclusion, the lithium metal batteries fabricated using the lithium metal negative electrodes fabricated in examples 1 to 3 had higher cycle stability and cycle life. The invention can show that the metal halide and the organic solvent are matched for use, a protective layer with a composite structure of specific components can be formed on the surface of the lithium metal, the lithium metal cathode with the composite structure can simultaneously conduct lithium ions and has certain electronic conductivity, the distribution uniformity of the lithium ions in the deposition process is effectively improved, and the formation of lithium dendrites is delayed. Further, it is possible to make a lithium metal battery having the lithium metal negative electrode have higher cycle stability and cycle life.
In contrast, comparative examples 1 and 2, the lithium metal negative electrode having a composite structure according to the present invention was not used, resulting in poor performance of the resulting lithium metal battery.
In contrast, in comparative example 3, naCl, instead of the metal halide specifically defined in the present invention, was used, and the problem of alloying with lithium could not be solved, resulting in poor performance of the resulting lithium metal battery.
In comparative example 4, however, since the lithium halide (particularly LiCl): organic lithium salt (specifically, lithium butoxide): the proportion of alloy components (particularly LiAl alloy) is 10:15:75, which are not within the range specifically defined in the present invention, resulting in poor performance of the resulting lithium metal battery.
In contrast, in comparative example 5, cuCl was added 2 On one hand, the copper element is selected as the metal, so that the problem that the copper element cannot be alloyed with lithium is caused; on the other hand, the organic solvent is acetone, which is not specifically limited in the present invention, resulting in the characteristics of the resulting lithium metal batteryThe performance is not good.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, numerous simple modifications can be made to the technical solution of the invention, including combinations of the specific features in any suitable way, and the invention will not be further described in relation to the various possible combinations in order to avoid unnecessary repetition. Such simple modifications and combinations should be considered within the scope of the present disclosure as well.
Claims (10)
1. A lithium metal anode comprising at least one composite protective layer, wherein the composite protective layer comprises a composition comprising at least two of a lithium halide, an organic lithium salt, and an alloy component, and wherein the lithium halide is present in an amount of 25 to 55 wt%, the organic lithium salt is present in an amount of 5 to 30 wt%, and the alloy component is present in an amount of 30 to 60 wt%, based on the total weight of the composition.
2. The lithium metal anode of claim 1, wherein the lithium halide is present in an amount of 30 to 50 wt.%, the organic lithium salt is present in an amount of 5 to 25 wt.%, and the alloying component is present in an amount of 35 to 55 wt.%, based on the total weight of the composition;
more preferably, the content of the lithium halide is 35 to 45 wt%, the content of the organic lithium salt is 10 to 20 wt%, and the content of the alloy component is 40 to 50 wt%, based on the total weight of the composition.
3. The lithium metal anode of claim 1 or 2, wherein the lithium halide is selected from one or more of the group consisting of chloride, bromide, fluoride, and iodide of metallic lithium;
preferably, the lithium halide is selected from one or more of lithium chloride, lithium bromide and lithium iodide.
4. The lithium metal anode of claim 1 or 2, wherein the organic lithium salt is a lithium salt of an organic solvent with lithium;
preferably, the organic solvent is selected from one or more of tetrahydrofuran, polymethylpyrrolidone, dimethylformamide, polycarbonate, alcohol, ether and carboxylic acid;
preferably, the organic solvent is selected from one or more of tetrahydrofuran, an alcohol and a carboxylic acid;
more preferably, the organic lithium salt is selected from lithium butoxide, CH 3 CH 2 One or more of OLi and lithium n-amylate.
5. The lithium metal anode of claim 1 or 2, wherein the alloy component is an alloy of lithium and a metal element;
preferably, the metal is selected from one or more of aluminium, zinc, gallium, germanium, cadmium, indium and tin;
preferably, the alloy component is selected from one or more of a lithium aluminum alloy, a lithium gallium alloy, and a lithium indium alloy.
6. A method of manufacturing a lithium metal anode according to any one of claims 1 to 5, characterized in that the method comprises:
(1) Contacting and mixing metal halide and an organic solvent to obtain a mixed solution;
(2) And contacting the mixed solution with lithium metal to perform in-situ reaction to obtain the lithium metal cathode.
7. The production method according to claim 6, wherein the metal halide is selected from one or more of a chloride, a bromide, a fluoride and an iodide of a transition metal;
preferably, the metal halide is selected from one or more of fluoride, chloride, bromide and iodide of transition metal;
preferably, the transition metal is selected from one or more of aluminum, zinc, gallium, germanium, cadmium, indium and tin;
more preferably, the metal halide is selected from AlCl 3 、InBr 3 And GaI 3 One or more of (a).
8. The production method according to claim 6, wherein the organic solvent is selected from one or more of tetrahydrofuran, polymethylpyrrolidone, dimethylformamide, polycarbonate, alcohol, ether and carboxylic acid;
preferably, the organic solvent is selected from one or more of tetrahydrofuran, an alcohol and a carboxylic acid.
9. The production method according to claim 6, wherein the concentration of the mixed solution is 0.01 to 5mol/L, preferably 0.02 to 0.6mol/L.
10. A lithium metal battery comprising the lithium metal negative electrode of any one of claims 1 to 5.
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