CN110600677A - Lithium metal negative electrode, preparation method thereof and lithium metal, lithium sulfur and lithium air battery - Google Patents
Lithium metal negative electrode, preparation method thereof and lithium metal, lithium sulfur and lithium air battery Download PDFInfo
- Publication number
- CN110600677A CN110600677A CN201910765069.6A CN201910765069A CN110600677A CN 110600677 A CN110600677 A CN 110600677A CN 201910765069 A CN201910765069 A CN 201910765069A CN 110600677 A CN110600677 A CN 110600677A
- Authority
- CN
- China
- Prior art keywords
- lithium
- lithium metal
- negative electrode
- battery
- liquid metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 247
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title abstract description 30
- 229910001338 liquidmetal Inorganic materials 0.000 claims abstract description 98
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 90
- 239000000956 alloy Substances 0.000 claims abstract description 90
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 44
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 42
- 229910052718 tin Inorganic materials 0.000 claims description 40
- 229910052738 indium Inorganic materials 0.000 claims description 38
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 37
- 229910052733 gallium Inorganic materials 0.000 claims description 37
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 abstract description 27
- 210000001787 dendrite Anatomy 0.000 abstract description 15
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 8
- 239000010410 layer Substances 0.000 description 60
- 239000007774 positive electrode material Substances 0.000 description 18
- 238000005520 cutting process Methods 0.000 description 14
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 12
- 239000002131 composite material Substances 0.000 description 11
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 10
- 229910013872 LiPF Inorganic materials 0.000 description 10
- 101150058243 Lipf gene Proteins 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000002033 PVDF binder Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000011267 electrode slurry Substances 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- -1 polypropylene Polymers 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000002161 passivation Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000006256 anode slurry Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 229910013716 LiNi Inorganic materials 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000002482 conductive additive Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007770 graphite material Substances 0.000 description 3
- 239000003273 ketjen black Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 125000006091 1,3-dioxolane group Chemical group 0.000 description 2
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 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
- 238000011068 loading method Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PYUKXGCMRFTISX-UHFFFAOYSA-N [O].[Ta].[Zr].[La].[Li] Chemical compound [O].[Ta].[Zr].[La].[Li] PYUKXGCMRFTISX-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000007704 transition 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
- 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
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to the technical field of lithium batteries, and particularly provides a lithium metal negative electrode, a preparation method of the lithium metal negative electrode, and a lithium metal, lithium sulfur and lithium air battery. The lithium metal negative electrode comprises a lithium metal sheet and a liquid metal alloy layer attached to the surface of the lithium metal sheet. The surface of the lithium metal cathode is attached with the liquid metal alloy layer, the liquid metal alloy layer can effectively reduce or even stop the possibility of dendrite formation of the lithium metal sheet after the lithium metal cathode is assembled into a lithium metal battery or a lithium sulfur battery or a lithium air battery, and also reduce the possibility of large consumption of electrolyte, and meanwhile, the liquid metal alloy layer has good lithium ion conductivity and electronic conductivity, so that the electrochemical properties of the lithium metal battery, the lithium sulfur battery, the lithium air battery, such as capacity, cycle life and the like, can be effectively improved.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a lithium metal negative electrode, a preparation method of the lithium metal negative electrode, and a lithium metal, lithium sulfur and lithium air battery.
Background
The negative electrode material used by the commercial lithium battery at present mainly comprises graphite, and the theoretical specific capacity of the graphite material is only 372mAh/g, so that the application requirement of a novel high-energy-density lithium battery is difficult to meet. Compared with the graphite material, the specific capacity of lithium metal is 3860mAh/g, the reduction potential is-3.040V, the specific capacity is far higher than that of the graphite material, the reduction potential reaches the lowest value of the current negative electrode material, and the lithium metal has the advantages of lower density, excellent mechanical flexibility and the like, is considered to be a next generation high-energy density secondary battery negative electrode material with high competitiveness, and is considered to be a 'holy cup' of a lithium battery. However, lithium dendrites are easy to grow in the charging process of the lithium metal negative electrode, and the existence of the lithium dendrites can puncture a diaphragm on one hand, so that the negative electrode is in contact with the positive electrode to cause short circuit in the battery, thermal failure is generated, and risks such as spontaneous combustion or explosion are caused; on the other hand, the lithium dendrites are loose and porous structures and are easy to fall off to form dead lithium without electrochemical activity, and the capacity is lost. In addition, the specific surface area of the negative electrode is increased due to the growth of lithium dendrites, and a large amount of electrolyte is consumed to form a new solid electrolyte membrane (SEM membrane), resulting in the degradation of the capacity and the reduction of the cycle life of the battery. Therefore, the use of lithium metal as a negative electrode has seriously hindered the commercial application of lithium metal batteries, lithium sulfur batteries and lithium air batteries.
Disclosure of Invention
The invention provides a lithium metal negative electrode and a preparation method thereof, aiming at the problems that dendritic crystals are easily generated when lithium metal is used as the negative electrode of a lithium metal battery, a lithium sulfur battery or a lithium air battery at present, and the battery capacity and the cycle life are influenced.
Further, the present invention also provides a lithium metal battery, a lithium sulfur battery and a lithium air battery including the lithium metal negative electrode.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a lithium metal negative electrode comprising a lithium metal sheet and a liquid metal alloy layer attached to a surface of the lithium metal sheet.
Accordingly, a method of making a lithium metal anode, comprising the steps of:
mixing and melting at least one metal of indium and tin and gallium metal to obtain a liquid metal alloy;
and depositing the obtained liquid metal alloy on two surfaces of a lithium metal sheet to form liquid metal alloy layers, thereby obtaining the lithium metal cathode.
Further, a lithium metal battery comprises a negative electrode, wherein the negative electrode is the lithium metal negative electrode;
or the negative electrode is the lithium metal negative electrode prepared by the preparation method of the lithium metal negative electrode.
A lithium-sulfur battery comprising a negative electrode, including a negative electrode, said negative electrode being the lithium metal negative electrode described above;
or the negative electrode is the lithium metal negative electrode prepared by the preparation method of the lithium metal negative electrode.
A lithium-air battery comprising a negative electrode, said negative electrode being the lithium metal negative electrode described above;
or the negative electrode is the lithium metal negative electrode prepared by the preparation method of the lithium metal negative electrode.
The invention has the technical effects that:
compared with the prior art, the lithium metal negative electrode is characterized in that the lithium metal sheet is modified and coated by the liquid metal alloy layer, so that a lithiated liquid metal interface modification layer is formed between the liquid metal alloy layer and the lithium metal sheet, the lithium metal sheet is isolated from air by the liquid metal alloy layer, the liquid metal alloy layer is used as a passivation layer when contacting with the air, the possibility of lithium metal dendrite crystallization after the lithium metal negative electrode is assembled into a lithium metal battery or a lithium sulfur battery or a lithium air battery is effectively reduced or even eliminated, and the possibility of large consumption of electrolyte is also reduced.
According to the preparation method of the lithium metal cathode, the liquid metal alloy is deposited on the surface of the lithium metal sheet in a deposition mode, so that a good modified coating layer is formed on the surface of the lithium metal sheet, the contact between the lithium metal sheet and air is effectively inhibited or even avoided, the oxidation of the lithium metal sheet is inhibited or even avoided, the whole preparation process is simple, and the production efficiency is high.
The lithium metal battery provided by the invention has the advantages that the used negative electrode is the lithium metal negative electrode containing the liquid metal alloy layer, the liquid metal alloy layer and the lithium metal sheet are used as the lithium liquid metal interface modification layer on the mutually contacted interface, the interface resistance can be reduced, meanwhile, the surface of the liquid metal alloy layer is also used as the passivation layer, the possibility that the lithium metal sheet is contacted with the electrolyte and the lithium metal sheet dendrite crystallization is inhibited is effectively avoided, the possibility that the electrolyte is greatly consumed due to dendrite formation is reduced, and the capacity and the cycle life of the lithium metal battery are improved due to the good lithium ion conductivity and electronic conductivity of the liquid metal alloy layer.
The lithium-sulfur battery provided by the invention has the advantages that the used negative electrode is the lithium metal negative electrode containing the liquid metal alloy layer, the liquid metal alloy layer and the lithium metal sheet are used as lithium liquid metal interface modification layers on the mutually contacted interfaces, the interface resistance can be reduced, meanwhile, the surface of the liquid metal alloy layer is also used as a passivation layer, the possibility that the lithium metal sheet is contacted with electrolyte and the lithium metal sheet dendrite crystallization is inhibited is effectively avoided, the possibility that the electrolyte is greatly consumed due to dendrite formation is reduced, and the capacity and the cycle life of the lithium-sulfur battery are improved due to the good lithium ion conductivity and electronic conductivity of the liquid metal alloy layer.
The lithium-air battery provided by the invention has the advantages that the used negative electrode is the lithium metal negative electrode containing the liquid metal alloy layer, the liquid metal alloy layer and the lithium metal sheet are used as the lithium liquid metal interface modification layer on the mutually contacted interface, the interface resistance can be reduced, meanwhile, the surface of the liquid metal alloy layer is also used as the passivation layer, the possibility that the lithium metal sheet is contacted with the electrolyte and the lithium metal sheet dendrite crystallization is inhibited is effectively avoided, the possibility that the electrolyte is greatly consumed due to dendrite formation is reduced, and the capacity and the cycle life of the lithium-air battery are improved due to the good lithium ion conductivity and electronic conductivity of the liquid metal alloy layer.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an SEM image of a liquid metal alloy provided in example 1 of the present invention;
fig. 2 is an SEM image of a lithium metal negative electrode provided in example 1 of the present invention;
fig. 3 is a sectional SEM image of a lithium metal negative electrode provided in example 1 of the present invention, cut out using focused ion beam analysis (FIB), in which a shows a cut portion and b shows an enlarged view of the cut portion;
FIG. 4 shows a lithium metal negative electrode and LiNi according to example 1 of the present invention0.6Co0.2Mn0.2O2A charge-discharge cycle curve and a coulombic efficiency cycle curve chart of the full cell assembled with the positive electrode active material, and comparative example 1 and comparative example 2;
fig. 5 is a charge-discharge cycle curve and a coulombic efficiency cycle curve chart of a lithium-sulfur battery assembled by a lithium metal negative electrode and a sulfur-carbon composite as a positive electrode active material according to example 2 of the present invention;
fig. 6 is a charge-discharge cycle curve and coulombic efficiency cycle curve chart of a full battery assembled by using a lithium metal negative electrode and lithium iron phosphate as positive active materials according to embodiment 3 of the present invention and a comparative example 3;
fig. 7 is a charge-discharge cycle curve and coulombic efficiency chart of a sulfur-carbon battery assembled by using a lithium metal negative electrode and a sulfur-carbon composite as a positive electrode active material according to embodiment 4 of the present invention;
fig. 8 is a charge-discharge cycle curve and coulombic efficiency chart of a lithium metal battery assembled by using a lithium metal negative electrode and lithium iron phosphate as positive electrode active materials according to embodiment 5 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In a first aspect of the present invention, a lithium metal negative electrode is provided, which includes a lithium metal sheet and a liquid metal alloy layer attached to a surface of the lithium metal sheet.
Specifically, liquid metal alloy layers are attached to two surfaces of the lithium metal sheet, the lithium metal sheet is isolated from the outside through the liquid metal alloy layers, the lithium metal sheet is prevented from being oxidized by air, meanwhile, an interface where the liquid metal alloy layers are in contact with the lithium metal sheet is used as a lithium liquid metal interface modification layer, so that the interface resistance between the lithium metal sheet and the liquid metal alloy layers is reduced, good lithium ion conductivity and electronic conductivity are provided, and the surface of the liquid metal alloy layer, which is opposite to the surface of the lithium metal sheet, is also used as a passivation layer when encountering air, so that the contact between the lithium metal sheet and the air is avoided, and the lithium metal cathode stably existing in the air is obtained.
In addition, the liquid metal alloy layer has good electronic conductivity, so that the lithium metal negative electrode can omit a negative electrode current collector.
The liquid metal alloy layer is obtained by melting and depositing at least one metal of indium and tin and gallium metal on the surface of the lithium metal sheet. The purity of these metals is not less than 98%, and if the purity is too low, impurities can affect the performance of the lithium metal negative electrode and further affect the performance of the assembled battery.
Preferably, in the liquid metal alloy layer, the ratio of gallium, indium and tin is, gallium: indium (b): tin (5-10): (0-5): (0-2), wherein the indium and the tin do not simultaneously take 0 value, for example, the indium and the tin can be gallium: indium (b): tin is 5:1:1 or 5:1:2 or 5:5:2 or 5:4:2 or 8:3:2 or 9:4:2 or 10:5:2 or 7:2:1, etc. For example, when only gallium and indium are contained in the liquid metal alloy layer, the mass ratio of the metals in the liquid metal alloy layer is gallium: indium (5-10): (0-5), indium does not take 0 value, and for example, gallium: 1:1 or 2:1 or 6:1 or 3:1 or 9:5 or 8:3, etc.; when only gallium and tin exist in the liquid metal alloy layer, the mass ratio of the metal in the liquid metal layer is gallium: tin (5-10): (0-2), wherein tin does not take a value of 0, and for example, may be gallium: tin is 5:1 or 5:2 or 6:1 or 3:1 or 7:2 or 8:1 or 4:1 or 9:2 or 10:1, etc.
In the lithium metal negative electrode, the thickness of the liquid metal alloy layer is (1-10) μm, the thickness of the liquid metal alloy layer is not too thick, if the thickness exceeds 10 μm, the total thickness of the liquid metal alloy layers on two sides of the lithium metal sheet reaches more than 20 μm, the liquid metal alloy layer occupies the internal space of the battery, so that the content of the negative electrode active material and the positive electrode active material is reduced, the liquid metal alloy layer is not too thin, and if the thickness is less than 1 μm, the possibility that the lithium metal sheet cannot be completely coated is easy to occur.
The lithium metal negative electrode provided by the invention has the advantages that the liquid metal alloy layers are deposited on the two surfaces of the lithium metal sheet, the liquid metal alloy layers and the surfaces of the lithium metal sheet are used as lithium liquid metal interface modification layers with transition states, the possibility of contact between the lithium metal sheet and air is reduced and even eliminated, the interface resistance can be reduced, lithium ions and electrons have bidirectional conduction characteristics in the liquid metal alloy layers, the deintercalation of the lithium ions and the conduction of the electrons are not hindered, the liquid metal alloy layers are used as passivation layers, the stable structure of the lithium metal negative electrode and the shuttle of the lithium ions can be effectively ensured, the lithium metal negative electrode can be effectively inhibited and even eliminated, the probability of large consumption of electrolyte due to the dendrite is reduced, and the lithium metal battery, the lithium sulfur battery and the lithium metal battery assembled by adopting the lithium metal negative electrode are improved, Cycling stability and capacity of lithium air batteries.
As a second aspect of the present invention, there is also provided a method for producing the above lithium metal negative electrode.
In one embodiment, the method of making the lithium metal anode includes the steps of:
s01, mixing and melting at least one metal of indium and tin and gallium metal to obtain a liquid metal alloy;
and S02, depositing the obtained liquid metal alloy on two surfaces of a lithium metal sheet to form liquid metal alloy layers to obtain the lithium metal cathode.
In step S01, when the formed liquid metal alloy contains three elements, i.e., indium, tin, and gallium, the mass ratio of the components in the liquid metal alloy is gallium: indium (b): tin (5-10): (0-5): (0-2), wherein the indium and the tin do not take 0 value; when the liquid metal alloy contains only indium and gallium, the ratio of gallium: indium (5-10): (0-5), the value of indium is not 0; when the liquid metal alloy contains only tin and gallium, the ratio of gallium: tin (5-10): (0-2), wherein tin does not take a value of 0. In the liquid metal alloy, the purity of each element is not less than 98%, and if the purity is too low, impurities may affect the battery performance.
In the step S02, the deposition method may be to directly dip the lithium metal sheet with clean surface and no oxide layer into the liquid metal alloy formed in the step S01; the liquid metal alloy obtained in step S01 above may be deposited on both surfaces of the lithium metal sheet by an electrochemical deposition method.
No matter what method is adopted to make the liquid metal alloy adhere to the surface of the lithium metal sheet to form the liquid metal alloy layer, the thickness of the formed liquid metal alloy layer is between (1-10) mu m, the liquid metal alloy layer is not too thin, if the thickness is less than 1 mu m, the possibility that the lithium metal sheet cannot be completely covered is easy to occur, and if the thickness is more than 10 mu m, the liquid metal alloy layer occupies too much space of the battery, so that the content of the positive electrode active material and the negative electrode active material in the battery is reduced, and the capacity of the battery is reduced.
Since the lithium metal negative electrode of the present invention has an effect of inhibiting the dendrite crystallization of the lithium metal sheet and also can omit the current collector of the negative electrode, the lithium metal negative electrode of the present invention can be used as a negative electrode of a lithium metal battery or a negative electrode of a lithium sulfur battery or a negative electrode of a lithium air battery.
Thus, the invention further provides a lithium metal battery, a lithium sulfur battery and a lithium air battery.
In the lithium metal battery, the negative electrode is the lithium metal negative electrode provided in the first and second aspects, and the positive electrode active material may be any one of lithium iron phosphate, lithium cobaltate, a ternary material, and the like. The diaphragm and the electrolyte related to the lithium metal battery are conventional materials in the technical field of lithium metal batteries, and are not described herein again.
In the lithium-sulfur battery, the related negative electrode is the lithium metal negative electrode provided in the first aspect and the second aspect, the positive active material is a sulfur-carbon composite material, and the electrolyte and the diaphragm are respectively conventional electrolyte and diaphragm of the lithium-sulfur battery, which are not described herein again.
The sulfur-carbon composite is prepared by mixing sublimed sulfur and a conductive additive, wherein the mass ratio of the sublimed sulfur to the conductive additive can be 3:1, and the sublimed sulfur and the conductive additive are mixed and then heated at the constant temperature of 155 ℃ for 9-12 hours to obtain the sulfur-carbon composite. The conductive additive can be carbon black materials such as acetylene black, Super P, Super S, 350G, carbon fiber (VGCF), Carbon Nano Tube (CNTs), Ketjen black and the like.
In the lithium-air battery, the related negative electrode is the lithium metal negative electrode provided in the first aspect and the second aspect, the positive active material is oxygen, and the related electrolyte and the related separator are common electrolyte and separator of the lithium-air battery, and details are not repeated here.
In order to more effectively explain the technical solution of the present invention, the technical solution of the present invention is explained below by a plurality of specific examples.
Example 1
A lithium metal negative electrode, a preparation method thereof and a lithium metal battery are provided.
The preparation method of the lithium metal negative electrode comprises the following steps:
s11, selecting gallium with the purity of more than 99.9%, indium with the purity of more than 99.9% and tin with the purity of more than 99.9%, weighing 2g of indium, 1g of tin and 7g of gallium, placing the weighed indium and tin in a platinum crucible, heating to 400 ℃, after the indium and the tin are completely melted, uniformly stirring, then adding the weighed gallium, continuously stirring to be uniform, and cooling to obtain the liquid metal alloy.
S12, using an electrochemical deposition method (current density is 1 mA/cm)2Discharging for 10 hours and electrodepositing for 10mA/cm2) And (4) depositing the liquid metal alloy obtained in the step (S11) on two surfaces of a pure lithium metal sheet with the thickness of 0.6mm, wherein the thickness of each surface deposit is 8 mu m, and cutting the pure lithium metal sheet into a lithium metal negative plate with the diameter of 12 mm.
SEM scanning was performed on the liquid metal alloy obtained in step S11 and the lithium metal negative electrode sheet obtained in step S12, and the specific results are shown in fig. 1, 2, and 3.
As can be seen from fig. 1, the lithiated liquid metal alloy is uniformly deposited on the separator; from fig. 2, it can be seen that the lithium metal negative electrode under the protection of lithiated liquid metal has a flat surface and no lithium dendrites; fig. 3 is a cross-sectional SEM image obtained by FIB cutting the lithium metal negative electrode obtained in example 1, and it can be seen from fig. 3 that there is a clear two-layer structure, and the lithium metal negative electrode is protected by the lithiated liquid metal alloy coating.
The lithium metal negative electrode sheet prepared in example 1 and LiNi0.6Co0.2Mn0.2O2(NCM622) positive electrode assembly of positive electrode active material lithium metal battery:
(1) mixing LiNi with a solvent0.6Co0.2Mn0.2O2Mixing the anode slurry with conductive carbon black and polyvinylidene fluoride (PVDF) binder according to the mass ratio of 9.6:0.15:0.25, adding N-methylpyrrolidone (NMP) to prepare anode slurry, coating the anode slurry on the surface of an aluminum foil, drying, tabletting and cutting into a 16mm pole piece to obtain the anode piece.
(2) Assembling the positive plate, the lithium metal negative plate and the polypropylene diaphragm into a 2025 type lithium metal battery, wherein LiPF is used6As electrolyte, dimethyl carbonate (DMC) is used in volume ratio: formation of 1M LiPF with Ethylene Carbonate (EC) ═ 1:1 as the electrolyte6After standing for 24 hours, the electrolyte solution was placed in a novyi cell tester and subjected to charge-discharge cycle test at a charge-discharge current of 0.5C/0.5C, and the specific results are shown in fig. 4.
Example 2
A lithium metal negative electrode, a preparation method thereof and a lithium-sulfur battery are provided.
The preparation method of the lithium metal negative electrode comprises the following steps:
s21, selecting gallium with the purity of more than 99.9%, indium with the purity of more than 99.9% and tin with the purity of more than 99.9%, weighing 1g of indium, 0.5g of tin and 5g of gallium, placing the weighed indium and tin in a platinum crucible, heating to 400 ℃, after the indium and the tin are completely melted, uniformly stirring, then adding the weighed gallium, continuously stirring to be uniform, and cooling to obtain the liquid metal alloy.
S22, coating the liquid metal alloy obtained in the step S21 on two surfaces of a pure lithium metal sheet with the thickness of 0.1mm by using a dipping method, wherein the thickness of each surface deposit is 5 micrometers, and cutting the pure lithium metal sheet into a lithium metal negative plate with the diameter of 12 mm.
The lithium metal negative electrode sheet prepared in example 2 and a positive electrode using a sulfur-carbon composite as a positive electrode active material were assembled into a lithium-sulfur battery:
(1) mixing sublimed sulfur and Ketjen black according to the mass ratio of 3:1 at 155 ℃ and heating for 11 hours to obtain a sulfur-carbon composite, preparing slurry from the obtained sulfur-carbon composite and polyvinylidene fluoride (PVDF) according to the mass ratio of 9:1, coating the slurry on carbon fiber cloth, drying to obtain a lithium-sulfur battery positive electrode, cutting the positive electrode into positive plates with the diameter of 12mm, wherein the sulfur negative loading capacity is 2mg/cm2。
(2) Assembling the positive plate, the lithium metal negative plate and the polypropylene diaphragm into the 2025 type lithium-sulfur battery, wherein the electrolyte is 1, 3-Dioxolane (DOL): ethylene glycol dimethyl ether (DME) ═ 1:1 vol%, LiTFSI 1M, 1 wt% LiNO3After standing for 24 hours, the cells were placed in a neowei cell tester and subjected to a charge-discharge cycle test (charge-discharge voltage 1.7 to 3.0V) at a charge-discharge current of 0.5C/0.5C, and the results are shown in FIG. 5.
Example 3
A lithium metal negative electrode, a preparation method thereof and a lithium metal battery are provided.
The preparation method of the lithium metal negative electrode comprises the following steps:
s31, selecting gallium with the purity of more than 99.9%, indium with the purity of more than 99.9% and tin with the purity of more than 99.9%, weighing 5g of indium, 2g of tin and 10g of gallium, placing the weighed indium and tin in a platinum crucible, heating to 400 ℃, after the indium and the tin are completely melted, uniformly stirring, then adding the weighed gallium, continuously stirring to be uniform, and cooling to obtain the liquid metal alloy.
S32, soaking a pure lithium metal sheet with the thickness of 0.6mm in the liquid metal alloy obtained in the step S31 by using a soaking method, taking out and leveling the pure lithium metal sheet so that the thickness of the liquid metal alloy on each surface of the lithium metal sheet is 6 microns, and cutting the pure lithium metal sheet into a lithium metal negative electrode sheet with the diameter of 12 mm.
The lithium metal negative electrode sheet prepared in example 3 and a positive electrode using lithium iron phosphate as a positive electrode active material were assembled into a lithium metal battery:
(1) adding NMP into the lithium iron phosphate, the conductive carbon black and the PVDF binder according to the mass ratio of 9.6:0.15:0.25 to prepare positive electrode slurry, then coating the positive electrode slurry on the surface of an aluminum foil, drying, tabletting and cutting into 12mm pole pieces to obtain positive pole pieces, wherein the surface density of the positive pole pieces is 10mg/cm2。
(2) Assembling the positive plate, the lithium metal negative plate and the polypropylene diaphragm into a 2025 type lithium metal battery, wherein LiPF is used6As electrolyte, dimethyl carbonate (DMC) is used in volume ratio: formation of 1M LiPF with Ethylene Carbonate (EC) ═ 1:1 as the electrolyte6After standing for 24 hours, the electrolyte solution was placed in a novyi cell tester and subjected to charge-discharge cycle test at a charge-discharge current of 0.5C/0.5C, and the specific results are shown in fig. 6.
Example 4
A lithium metal negative electrode, a preparation method thereof and a lithium-sulfur battery are provided.
The preparation method of the lithium metal negative electrode comprises the following steps:
s41, selecting gallium with the purity of 99.9% and indium with the purity of 99.9%, weighing 5g of indium and 5g of gallium, placing the weighed indium in a platinum crucible, heating to 300 ℃, completely melting, uniformly stirring, then adding the weighed gallium, continuously stirring to be uniform, and cooling to obtain the liquid metal alloy.
S42, rolling the lithium metal sheet to a thickness of 100 microns, then soaking the lithium metal sheet in the liquid metal alloy obtained in the step S41 to enable the liquid metal alloy to be deposited on two surfaces of the lithium metal sheet, wherein the thickness of the liquid metal alloy layer on each surface is 5 microns, and cutting the lithium metal sheet into a lithium metal negative plate with the diameter of 16 mm.
The lithium metal negative electrode sheet prepared in example 4 and a positive electrode using a sulfur-carbon composite as a positive electrode active material were assembled into a lithium-sulfur battery:
(1) mixing sublimed sulfur and Ketjen black at 155 ℃ for 11h according to the mass ratio of 3:1 to obtain a sulfur-carbon composite, and preparing slurry from the obtained sulfur-carbon composite and polyvinylidene fluoride according to the mass ratio of 9:1Coating the carbon fiber cloth on a lithium sulfur battery anode, drying to obtain a lithium sulfur battery anode, and cutting the lithium sulfur battery anode into an anode plate with the diameter of 12mm, wherein the sulfur loading capacity is 2.9mg/cm2。
(2) Assembling the positive plate, the lithium metal negative plate and the polypropylene diaphragm into the 2025 type lithium-sulfur battery, wherein the electrolyte is 1, 3-Dioxolane (DOL): ethylene glycol dimethyl ether (DME) ═ 1:1 vol%, LiTFSI 1M, 1 wt% LiNO3After standing for 24 hours, the cells were placed in a neowei cell tester and subjected to a charge-discharge cycle test (charge-discharge voltage 1.7-3.0V) at a charge-discharge current of 0.5C/0.5C, and the results are shown in FIG. 7.
Example 5
A lithium metal negative electrode, a preparation method thereof and a lithium metal battery are provided.
The preparation method of the lithium metal negative electrode comprises the following steps:
s51, selecting gallium with the purity of more than 99.9 percent and tin with the purity of more than 99.9 percent, weighing 1g of tin and 9g of gallium, placing the weighed tin in a platinum crucible, heating to 400 ℃, stirring uniformly after the tin is completely melted, then adding the weighed gallium, continuously stirring uniformly, and cooling to obtain the liquid metal alloy.
S52, soaking a pure lithium metal sheet with the thickness of 0.6mm in the liquid metal alloy obtained in the step S51 by using a soaking method, taking out and leveling the pure lithium metal sheet so that the thickness of the liquid metal alloy on each surface of the lithium metal sheet is 6 microns, and cutting the pure lithium metal sheet into a lithium metal negative plate with the diameter of 16 mm.
A lithium metal battery was assembled using the lithium metal negative electrode sheet prepared in example 5 and lithium iron phosphate as a positive active material:
(1) adding NMP into the lithium iron phosphate, the conductive carbon black and the binder according to the mass ratio of 9.6:0.15:0.25 to prepare positive electrode slurry, then coating the positive electrode slurry on the surface of an aluminum foil, drying, tabletting and cutting into 12mm pole pieces to obtain positive pole pieces, wherein the surface density of the positive pole pieces is 10mg/cm2。
(2) The positive plate, the lithium metal negative plate and the lithium lanthanum zirconium tantalum oxygen solid electrolyte ceramic plate are assembled into a 2025 type lithium metal battery, the battery is placed in a Xinwei battery tester, and a charge-discharge cycle test (charge-discharge voltage is 2.5-4.0V) is carried out according to the charge-discharge current of 0.5C/0.5C, and the specific result is shown in figure 8.
Comparative example 1
A lithium metal battery, a lithium metal negative plate has the same size as that of the battery in example 1, the surface of the lithium metal negative plate is not modified by a liquid metal alloy, and a positive active material is LiNi0.6Co0.2Mn0.2O2(LiNi)0.6Co0.2Mn0.2O2Adding NMP into the conductive carbon and PVDF binder according to the mass ratio of 9.6:0.15:0.25 to prepare positive electrode slurry, then coating the positive electrode slurry on the surface of an aluminum foil, drying, tabletting and cutting into a 16mm pole piece to obtain a positive electrode piece), wherein the diaphragm is a polypropylene diaphragm, the model of the lithium metal battery is 2025, and LiPF is used6As electrolyte, dimethyl carbonate (DMC) is used in volume ratio: formation of 1M LiPF with Ethylene Carbonate (EC) ═ 1:1 as the electrolyte6The electrolyte solution of (1) was assembled and left to stand for 24 hours, and then placed in a novice battery tester to perform a charge-discharge cycle test at a charge-discharge current of 0.5C/0.5C, and the specific results are shown in fig. 4.
Comparative example 2
A lithium metal battery, a lithium metal negative plate has the same size as that of the lithium metal negative plate in example 1, the surface of the lithium metal negative plate is not modified by liquid metal alloy, copper foil is used as a current collector of the negative plate, and a positive active material is LiNi0.6Co0.2Mn0.2O2(LiNi)0.6Co0.2Mn0.2O2Adding deionized water into the conductive carbon and PVDF binder according to the mass ratio of 9:1:1 to prepare anode slurry, coating the anode slurry on the surface of an aluminum foil, drying, tabletting and cutting into a pole piece with the thickness of 16mm to obtain an anode piece), wherein the diaphragm is a polypropylene diaphragm, the type of the lithium metal battery is 2025, and LiPF is used6As electrolyte, dimethyl carbonate (DMC) is used in volume ratio: formation of 1M LiPF with Ethylene Carbonate (EC) ═ 1:1 as the electrolyte6The electrolyte solution of (1) was assembled and left to stand for 24 hours, and then placed in a novice battery tester to perform a charge-discharge cycle test at a charge-discharge current of 0.5C/0.5C, and the specific results are shown in fig. 4.
Comparative example 3
A lithium metal battery having a negative electrode similar to the negative electrode sheet of example 3, but assembled with copper foil as a current collector and lithium iron phosphate as a positive electrode active material:
(1) adding deionized water into the lithium iron phosphate, the conductive carbon black and the PVDF binder according to the mass ratio of 9.6:0.15:0.25 to prepare positive electrode slurry, then coating the positive electrode slurry on the surface of an aluminum foil, drying, tabletting and cutting into a 12mm pole piece to obtain a positive plate, wherein the surface density of the positive plate is 10mg/cm2。
(2) Assembling the positive plate, the lithium metal negative plate and the polypropylene diaphragm into a 2025 type lithium metal battery, wherein LiPF is used6As electrolyte, dimethyl carbonate (DMC) is used in volume ratio: formation of 1M LiPF with Ethylene Carbonate (EC) ═ 1:1 as the electrolyte6After standing for 24 hours, the electrolyte solution was placed in a novyi cell tester and subjected to charge-discharge cycle test at a charge-discharge current of 0.5C/0.5C, and the specific results are shown in fig. 6.
As can be seen from fig. 4, the NCM622 battery assembled with the lithium metal negative electrode of example 1 has better cycle stability
As can be seen from fig. 5, the lithium sulfur battery assembled by the lithium metal negative electrode in example 2 has better cycle stability, and the capacity retention rate is higher than 70% under 200 cycles;
as can be seen from fig. 6, the lithium metal battery assembled with the lithium metal negative electrode of example 3 has better cycle stability;
as can be seen from fig. 7, the lithium sulfur battery assembled by the lithium metal negative electrode in example 4 has better cycle stability, and the capacity retention rate is higher than 80% under 300 cycles;
as can be seen from fig. 8, the lithium metal battery assembled by the lithium metal negative electrode of example 5 has better cycle stability, and the capacity retention rate is higher than 90% at 700 cycles.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A lithium metal negative electrode comprising a lithium metal sheet and a liquid metal alloy layer attached to a surface of the lithium metal sheet.
2. The lithium metal anode of claim 1, wherein the liquid metal alloy layer is a liquid metal alloy layer formed of at least one of indium and tin and gallium metal.
3. The lithium metal negative electrode of claim 1 or 2, wherein the liquid metal alloy layer comprises, in mass ratio, gallium: indium (b): tin (5-10): (0-5): (0-2), wherein the indium and the tin do not simultaneously take a value of 0.
4. The lithium metal negative electrode according to claim 1 or 2, wherein the liquid metal alloy layer has a thickness of (1 to 10) μm.
5. A method for preparing a lithium metal negative electrode, comprising the steps of:
mixing and melting at least one metal of indium and tin and gallium metal to obtain a liquid metal alloy;
and depositing the obtained liquid metal alloy on two surfaces of a lithium metal sheet to form liquid metal alloy layers, thereby obtaining the lithium metal cathode.
6. The method of manufacturing a lithium metal negative electrode according to claim 5, wherein the ratio by mass of gallium: indium (b): tin (5-10): (0-5): (0-2), wherein the indium and the tin do not simultaneously take a value of 0.
7. The method of manufacturing a lithium metal negative electrode according to claim 5 or 6, wherein the thickness of the liquid metal alloy layer is (1 to 10) μm.
8. A lithium metal battery comprising a negative electrode, wherein the negative electrode is the lithium metal negative electrode according to any one of claims 1 to 4;
or the negative electrode is the lithium metal negative electrode prepared by the preparation method of the lithium metal negative electrode as claimed in any one of claims 5 to 7.
9. A lithium-sulfur battery comprising a negative electrode, wherein the negative electrode is the lithium metal negative electrode according to any one of claims 1 to 4;
or the negative electrode is the lithium metal negative electrode prepared by the preparation method of the lithium metal negative electrode as claimed in any one of claims 5 to 7.
10. A lithium-air battery comprising a negative electrode, wherein the negative electrode is the lithium metal negative electrode according to any one of claims 1 to 4;
or the negative electrode is the lithium metal negative electrode prepared by the preparation method of the lithium metal negative electrode as claimed in any one of claims 5 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910765069.6A CN110600677A (en) | 2019-08-19 | 2019-08-19 | Lithium metal negative electrode, preparation method thereof and lithium metal, lithium sulfur and lithium air battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910765069.6A CN110600677A (en) | 2019-08-19 | 2019-08-19 | Lithium metal negative electrode, preparation method thereof and lithium metal, lithium sulfur and lithium air battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110600677A true CN110600677A (en) | 2019-12-20 |
Family
ID=68854924
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910765069.6A Pending CN110600677A (en) | 2019-08-19 | 2019-08-19 | Lithium metal negative electrode, preparation method thereof and lithium metal, lithium sulfur and lithium air battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110600677A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111129573A (en) * | 2019-12-28 | 2020-05-08 | 横店集团东磁股份有限公司 | Heat treatment method of all-solid-state lithium metal battery |
| CN111509211A (en) * | 2020-04-29 | 2020-08-07 | 广西师范大学 | Preparation method of L M/L i composite material |
| CN111668450A (en) * | 2020-06-22 | 2020-09-15 | 吉林大学 | Paper-based aluminum air battery with liquid alloy modified anode and preparation method |
| CN111682182A (en) * | 2020-06-22 | 2020-09-18 | 吉林大学 | Printable's novel flexible paper base aluminium air battery |
| CN111755699A (en) * | 2020-07-08 | 2020-10-09 | 山东大学 | High-stability long-life metal lithium negative electrode material and preparation method and application thereof |
| CN111916744A (en) * | 2020-07-31 | 2020-11-10 | 中南大学 | Liquid metal composite cathode of zinc ion battery and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008098075A (en) * | 2006-10-16 | 2008-04-24 | Toyota Central R&D Labs Inc | Air battery |
| CN108713267A (en) * | 2016-08-19 | 2018-10-26 | 株式会社Lg化学 | Including the cathode of multiple protective layer and the lithium secondary battery including the cathode |
| CN109390585A (en) * | 2018-09-27 | 2019-02-26 | 武汉大学 | A kind of protective film and preparation method thereof for being used to inhibit Li dendrite based on liquid metal |
| CN109888182A (en) * | 2019-01-25 | 2019-06-14 | 天津理工大学 | A kind of alkali metal electrode of in-situ conservation, preparation method and application |
-
2019
- 2019-08-19 CN CN201910765069.6A patent/CN110600677A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008098075A (en) * | 2006-10-16 | 2008-04-24 | Toyota Central R&D Labs Inc | Air battery |
| CN108713267A (en) * | 2016-08-19 | 2018-10-26 | 株式会社Lg化学 | Including the cathode of multiple protective layer and the lithium secondary battery including the cathode |
| CN109390585A (en) * | 2018-09-27 | 2019-02-26 | 武汉大学 | A kind of protective film and preparation method thereof for being used to inhibit Li dendrite based on liquid metal |
| CN109888182A (en) * | 2019-01-25 | 2019-06-14 | 天津理工大学 | A kind of alkali metal electrode of in-situ conservation, preparation method and application |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111129573A (en) * | 2019-12-28 | 2020-05-08 | 横店集团东磁股份有限公司 | Heat treatment method of all-solid-state lithium metal battery |
| CN111509211A (en) * | 2020-04-29 | 2020-08-07 | 广西师范大学 | Preparation method of L M/L i composite material |
| CN111668450A (en) * | 2020-06-22 | 2020-09-15 | 吉林大学 | Paper-based aluminum air battery with liquid alloy modified anode and preparation method |
| CN111682182A (en) * | 2020-06-22 | 2020-09-18 | 吉林大学 | Printable's novel flexible paper base aluminium air battery |
| CN111682182B (en) * | 2020-06-22 | 2021-09-21 | 吉林大学 | Printable's novel flexible paper base aluminium air battery |
| CN111755699A (en) * | 2020-07-08 | 2020-10-09 | 山东大学 | High-stability long-life metal lithium negative electrode material and preparation method and application thereof |
| CN111916744A (en) * | 2020-07-31 | 2020-11-10 | 中南大学 | Liquid metal composite cathode of zinc ion battery and preparation method and application thereof |
| CN111916744B (en) * | 2020-07-31 | 2022-03-08 | 中南大学 | Liquid metal composite cathode of zinc ion battery and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110635113B (en) | Lithium cathode or sodium cathode, and preparation method and application of lithium cathode or sodium cathode | |
| CN110600677A (en) | Lithium metal negative electrode, preparation method thereof and lithium metal, lithium sulfur and lithium air battery | |
| US11211635B2 (en) | Battery, battery pack, and uninterruptible power supply | |
| JP7551169B2 (en) | Lithium secondary battery | |
| CN113488637B (en) | Composite negative electrode material, negative plate and lithium ion battery | |
| CN110911689A (en) | Current collector and preparation method thereof, electrode plate and secondary battery | |
| JP2008059765A (en) | Nonaqueous secondary battery | |
| JP5151329B2 (en) | Positive electrode body and lithium secondary battery using the same | |
| CN113594468B (en) | Current collector and preparation method and application thereof | |
| JP6509363B2 (en) | ELECTRODE FOR ELECTROCHEMICAL DEVICE, METHOD FOR MANUFACTURING THE SAME, AND ELECTROCHEMICAL DEVICE INCLUDING THE SAME | |
| CN111009650A (en) | Metallic lithium surface protection method, negative electrode and metallic lithium secondary battery | |
| KR20140058928A (en) | The non-aqueous and high-capacity lithium secondary battery | |
| CN112216876B (en) | Lithium ion battery repeating unit, lithium ion battery, using method of lithium ion battery, battery module and automobile | |
| CN112216875B (en) | Lithium ion battery repeating unit, lithium ion battery, using method of lithium ion battery, battery module and automobile | |
| US9281526B1 (en) | Batteries with replenishable storage capacities | |
| CN112216878B (en) | Lithium ion battery repeating unit, lithium ion battery, using method of lithium ion battery, battery module and automobile | |
| CN108987673B (en) | Lithium negative electrode containing conductive protection film and preparation method and application thereof | |
| CN116470003A (en) | Pre-lithiated negative electrode piece and lithium ion battery | |
| KR20210021777A (en) | Lithium Anode-free All Solid State Battery Using Sacrificial Cathode Materials | |
| CN116190652A (en) | Positive electrode lithium supplementing material, preparation method thereof, positive electrode material, positive electrode plate and secondary battery | |
| KR20160053708A (en) | Electrode for rechargeable lithium battery and rechargeable lithium battery including the same | |
| CN213150817U (en) | Copper current collector | |
| CN112216812B (en) | Lithium ion battery repeating unit, lithium ion battery, using method of lithium ion battery, battery module and automobile | |
| CN112216809B (en) | Metal cathode, preparation method thereof and lithium ion battery | |
| CN114649502A (en) | Liquid metal coating, preparation method thereof and application thereof in lithium-free metal lithium battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191220 |
|
| RJ01 | Rejection of invention patent application after publication |