CN111599982B - Lithium metal negative electrode, preparation method thereof and metal lithium secondary battery - Google Patents
Lithium metal negative electrode, preparation method thereof and metal lithium secondary battery Download PDFInfo
- Publication number
- CN111599982B CN111599982B CN201910131087.9A CN201910131087A CN111599982B CN 111599982 B CN111599982 B CN 111599982B CN 201910131087 A CN201910131087 A CN 201910131087A CN 111599982 B CN111599982 B CN 111599982B
- Authority
- CN
- China
- Prior art keywords
- lithium
- negative electrode
- lithium metal
- metal
- protective layer
- 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.)
- Active
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 126
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 22
- 239000002184 metal Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000011241 protective layer Substances 0.000 claims abstract description 23
- 150000001923 cyclic compounds Chemical class 0.000 claims abstract description 21
- 230000003287 optical effect Effects 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 239000011230 binding agent Substances 0.000 claims description 16
- 229910003002 lithium salt Inorganic materials 0.000 claims description 15
- 159000000002 lithium salts Chemical class 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910013553 LiNO Inorganic materials 0.000 claims description 3
- 229910012258 LiPO Inorganic materials 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical group [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 210000001787 dendrite Anatomy 0.000 abstract description 26
- 239000003792 electrolyte Substances 0.000 abstract description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 17
- 238000007086 side reaction Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 7
- 238000007600 charging Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 230000035515 penetration Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- 125000000547 substituted alkyl group Chemical group 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 125000005843 halogen group Chemical group 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 230000002401 inhibitory effect Effects 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 125000005415 substituted alkoxy group Chemical group 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 125000004185 ester group Chemical group 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 125000004776 1-fluoroethyl group Chemical group [H]C([H])([H])C([H])(F)* 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000013065 commercial product Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- 125000004790 1-fluoroethoxy group Chemical group FC(C)O* 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- STSCVKRWJPWALQ-UHFFFAOYSA-N TRIFLUOROACETIC ACID ETHYL ESTER Chemical group CCOC(=O)C(F)(F)F STSCVKRWJPWALQ-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- VMVNZNXAVJHNDJ-UHFFFAOYSA-N methyl 2,2,2-trifluoroacetate Chemical group COC(=O)C(F)(F)F VMVNZNXAVJHNDJ-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N methyl acetate Chemical group COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- 206010067484 Adverse reaction Diseases 0.000 description 1
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- VIEVWNYBKMKQIH-UHFFFAOYSA-N [Co]=O.[Mn].[Li] Chemical compound [Co]=O.[Mn].[Li] VIEVWNYBKMKQIH-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000006838 adverse reaction Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 1
- OPHUWKNKFYBPDR-UHFFFAOYSA-N copper lithium Chemical compound [Li].[Cu] OPHUWKNKFYBPDR-UHFFFAOYSA-N 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000004804 winding Methods 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
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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 provides a lithium metal negative electrode, a preparation method thereof and a metal lithium secondary battery. The lithium metal anode provided by the invention comprises: the lithium metal cathode plate and the protective layer compounded on the surface of the lithium metal cathode plate; the protective layer comprises a main material; the main material is selected from one or more of a cyclic compound of formula (I) and optical isomers thereof. The annular structure can effectively promote lithium ion penetration and induce lithium ions to deposit on the surface of metal lithium, so that lithium dendrite is inhibited; the substances are not dissolved in the electrolyte, so that side reactions of the electrolyte and the lithium metal in a battery charging state can be well inhibited; through the above effects, the cycle performance of the battery can be obviously improved.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a lithium metal negative electrode, a preparation method thereof and a metal lithium secondary battery.
Background
Conventional LIBs (lithium ion batteries) include several important parts: positive and negative electrode materials, positive and negative electrode current collectors, electrolyte and a diaphragm. While graphite has proven to be the best and most reliable material for making cathodes to date, it contains a limited number of ions. Researchers have been desiring to replace graphite with lithium metal, which can accommodate more ions, with extremely high theoretical capacity (3860 mAh g -1 ) And the lowest negative potential (-3.04V relative to a standard hydrogen electrode); however, the lithium metal is usually too active and is particularly easy to generate adverse reaction with electrolyte, an SEI film is formed on the surface of Li, and the volume is almost infinitely changed in the process of lithium stripping deposition, so that the fragile SEI film is seriously damaged and causedMechanical instability, cracks are generated, the cracks locally enhance the passing of Li, dendrites are generated at the position where the current density is locally enhanced; in the charge and discharge process, continuous damage and repair of the Li dendrite with high specific surface area and the SEI film bring continuous side reaction, so that electrolyte is continuously consumed and a lithium negative electrode is severely corroded, and the cycle life of the battery is severely shortened. Therefore, solving the dendrite problem during cycling of lithium metal cathodes is a great challenge in the current battery research field. Thus, inhibition of lithium dendrite formation and growth is one of the serious problems that need to be solved urgently in the application and development of lithium metal secondary batteries.
In the prior art, methods for protecting the negative electrode and solving the lithium dendrite can be classified into the following categories:
electrolyte and additive thereof
Patent application CN106252722a proposes an electrolyte additive with dual lithium dendrite inhibition effect, which inhibits the formation of lithium dendrite on the electrode surface from two aspects, firstly, reduces the surface tension of the electrolyte to improve the wettability of the electrolyte and the separator, and increases the transmission channel of lithium ions in the separator, so that the lithium ion flow is uniformly distributed on the electrode surface, and finally, the purpose of inhibiting the formation of lithium dendrite is achieved; secondly, the additive further improves deposition sites of lithium ions on the surface of the electrode by adsorbing the lithium ions on the surface of the electrode, thereby inhibiting the formation of lithium dendrites. In addition, patent application CN105789704a provides a nonaqueous solvent, nonaqueous electrolyte (one or more kinds of carbonates and one or more kinds of specific amines) that can suppress lithium dendrites, which can effectively suppress growth of lithium dendrites due to charging in a lithium ion secondary battery. Besides, patent application CN103531839a discloses a rechargeable lithium metal secondary battery capable of preventing generation of lithium dendrite, the battery system is composed of lithium salt, nonaqueous solvent and/or electrolyte additive, and by selecting a proper system and modulating the salt and solvent ratio in the system, the physical and chemical properties of electrolyte lithium ion solvation degree and viscosity and the physical and chemical properties of solid intermediate phase film generated on the surface of lithium metal in the electrochemical process are changed, thereby effectively inhibiting the growth of dendrite lithium dendrite caused by uneven electrochemical deposition on the surface of lithium metal of the negative electrode, and finally achieving the purpose of improving the safety performance of the rechargeable lithium metal secondary battery.
In summary, most of the above technologies utilize an electrolyte to inhibit the growth of negative electrode SEI, thereby protecting the negative electrode. Currently, most additives improve or inhibit dendrite formation by participating in the formation of a protective film, and such additives generally decrease with increasing cycle times.
(II) Artificial negative electrode protective layer
Patent application CN106299244a provides a metallic lithium anode, the anode surface having a protective film of improved mechanical properties, said protective film comprising at least one first polymer selected from the group consisting of: polyvinyl alcohol graft copolymers, crosslinked polyvinyl alcohol copolymers, and blends thereof. CN106486699a discloses a lithium metal negative electrode protective layer and a lithium metal battery, the protective layer comprising a polymer, and at least one selected from the group consisting of metal salts containing group 1 or group 2 elements and nitrogen-containing additives. CN107068971a adopts an electroplating method to perform electrochemical pretreatment on the metal lithium sheet, so that the surface of the lithium electrode contains a solid electrolyte protective layer. The university of south Beijing, professor Zhu Jia (AdvancedMaterial, 2017,29,1603755,DOI:10.1002/adma. 201603755) proposes a common, inexpensive Polydimethylsiloxane (PDMS) as a metallic lithium negative electrode protective layer. The PDMS separates the metallic lithium and the electrolyte well, stabilizes the interface and inhibits the growth of lithium dendrites.
(III) three-dimensional skeleton
Lu et al used copper nanowires as a current collector for metallic lithium to reduce the current density of the negative electrode, thereby extending the Sand's time and inhibiting lithium dendrite growth (Nano Letters 2016,16,4431). CN 107732204a utilizes porous carbon material to construct a multi-stage pore structure in the pores of macroporous material, thereby constructing a multi-stage contact interface between electrolyte and metal lithium, and simultaneously dividing and binding the metal lithium in a micrometer-scale space, which is beneficial to the full reaction and deposition of the metal lithium; the multi-stage structure provides a three-dimensional passage for electron conduction, inhibits the growth of metal lithium dendrites, and enables the metal lithium composite material to have higher specific capacity, better multiplying power performance and better cycle stability.
In summary, these methods provide many new ideas for inhibiting lithium dendrites, but are limited by many conditions in the application process, such as that a certain additive can only be applied in a certain specific solvent, and the effect of inhibiting lithium dendrites is weakened with the increase of the cycle number, and the circularity is poor; the artificial protective layer and the three-dimensional nano-skeleton bring more side reactions to consume electrolyte and the like. Therefore, how to directionally modify the metal lithium interface, inhibit the growth of lithium dendrite, reduce side reaction and electrolyte consumption, thereby improving the utilization rate and cycle life of the battery has been widely paid attention in the industry.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a lithium metal negative electrode, a method for producing the same, and a lithium metal secondary battery. The lithium metal negative electrode provided by the invention can effectively inhibit the growth of lithium dendrite and reduce the side reaction of electrolyte and metal lithium, thereby improving the utilization rate and the cycle life of the battery.
The invention provides a lithium metal anode, comprising: the lithium metal cathode plate and a cathode protective layer compounded on the surface of the lithium metal cathode plate;
the negative electrode protective layer comprises a main material;
the main material is selected from one or more of a cyclic compound of the formula (I) and optical isomers thereof:
wherein R is 1 And R is 2 Each independently selected from unsubstituted or substituted alkyl, hydroxy, unsubstituted or substituted alkoxy, unsubstituted or substituted ester; n is an integer of 3 to 6.
Preferably, in the unsubstituted or substituted alkyl group, the number of carbon atoms is 1 to 10, and the substituent is selected from a halogen atom, an alkyl group or an aryl group;
in the substituted alkoxy group, the substituent is selected from halogen atoms;
in the substituted ester group, the substituent is selected from halogen atoms.
Preferably, the unsubstituted or substituted alkyl is selected from methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, fluoromethyl, difluoromethyl, trifluoromethyl or 1-fluoroethyl;
the unsubstituted or substituted alkoxy is selected from methoxy, trifluoromethoxy, ethoxy or 1-fluoroethoxy;
the unsubstituted or substituted ester group is selected from methyl acetate group, methyl trifluoroacetate group, ethyl acetate group or ethyl trifluoroacetate group.
Preferably, the cyclic compound shown in the formula (I) is selected from one or more of the following compounds:
wherein n is an integer of 3 to 6.
Preferably, the negative electrode protection layer comprises the following components in proportion:
the mass ratio of the main material to the lithium salt to the binder is 55-100:0-15:0-30.
Preferably, the lithium salt is selected from LiTFSI, liFSI, liODFB, liPO 2 F 2 、LiPO 3 、LiNO 3 And Li (lithium) 2 SO 4 One or more of them.
Preferably, the binder is selected from one or more of vinylidene fluoride-hexafluoropropylene copolymer, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate and polytetrafluoroethylene.
The invention also provides a preparation method of the lithium metal anode in the technical scheme, which comprises the following steps:
a) Dispersing the main material, lithium salt and binder in a solvent to obtain a mixed solution;
b) And coating the mixed solution on the surface of the lithium metal negative electrode plate and drying to obtain the lithium metal negative electrode.
Preferably, the solvent comprises one or more of acetone, tetrahydrofuran and N-methylpyrrolidone.
The invention also provides a metal lithium secondary battery, which comprises a positive electrode, a negative electrode and a diaphragm; the negative electrode is the lithium metal negative electrode in the technical scheme or the lithium metal negative electrode prepared by the preparation method in the technical scheme.
The invention provides a lithium metal anode, comprising: the lithium metal cathode plate and the protective layer compounded on the surface of the lithium metal cathode plate; the protective layer comprises a main material; the main material is selected from one or more of the cyclic compounds of the formula (I) and optical isomers thereof. The annular structure can effectively promote lithium ion penetration and induce lithium ions to deposit on the surface of metal lithium, so that lithium dendrite is inhibited; the substances are not dissolved in the electrolyte, so that side reactions of the electrolyte and the lithium metal in a battery charging state can be well inhibited; through the above effects, the cycle performance of the battery can be obviously improved.
The test result shows that the lithium metal anode provided by the invention has excellent cycle performance after being cycled for 100 times at 2-4.6V and 1C, and the cycle retention rate is more than 85%.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic view of a negative electrode obtained in example 1 of the present invention.
Detailed Description
The invention provides a lithium metal anode, comprising: the lithium metal cathode plate and a cathode protective layer compounded on the surface of the lithium metal cathode plate;
the negative electrode protective layer comprises a main material;
the main material is selected from one or more of a cyclic compound of the formula (I) and optical isomers thereof:
wherein R is 1 And R is 2 Each independently selected from unsubstituted or substituted alkyl, hydroxy, unsubstituted or substituted alkoxy, unsubstituted or substituted ester; n is an integer of 3 to 6.
In the present invention, R 1 And R is 2 In the case of an unsubstituted or substituted alkyl group, the structure of the alkyl group is not particularly limited, and may be a chain structure, a cyclic structure, a cage structure, a combination thereof, or the like. The chain structure may be a straight chain structure or a branched structure. In the ring structure or the cage structure, the number of rings and the number of elements of each ring are not particularly limited, and when a plurality of rings are provided, each ring may be condensed.
In the present invention, R 1 And R is 2 In the case of an unsubstituted or substituted alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5. If the number of carbon atoms of each substituent group in the cyclic structure of the formula (I) is too large, the migration steric hindrance of lithium ions can be increased, and the cycle performance of the battery can be influenced.
In the present invention, R 1 And R is 2 In the case of unsubstituted or substituted alkyl groups, the substituent is preferably a halogen atom, alkyl group or aryl group.
Among them, alkyl groups of chain structure which are unsubstituted or substituted with alkyl groups are more preferable: methyl, ethyl, n-propyl, 1-methylethyl or n-butyl.
Among them, the alkyl group of a chain structure substituted with a halogen atom is more preferably: fluoromethyl, difluoromethyl, trifluoromethyl or 1-fluoroethyl.
In summary, the unsubstituted or substituted alkyl groups are more preferably: methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, fluoromethyl, difluoromethyl, trifluoromethyl or 1-fluoroethyl.
In the present invention, R 1 And R is 2 In the case of unsubstituted or substituted alkoxy, the substituent is preferably a halogen atom. More preferably, the unsubstituted or substituted alkoxy group is: methoxy (methoxy)A radical, trifluoromethoxy, ethoxy or 1-fluoroethoxy.
In the present invention, R 1 And R is 2 In the case of an unsubstituted or substituted ester group, the substituent is preferably a halogen atom. More preferably, the unsubstituted or substituted ester group is: methyl acetate, methyl trifluoroacetate, ethyl acetate or ethyl trifluoroacetate.
In the present invention, n is an integer of 3 to 6. In some embodiments of the invention, n is 3, 4, 5 or 6.
In the present invention, it is further preferable that the cyclic compound represented by the formula (i) is selected from one or more of the following compounds:
wherein n is an integer of 3 to 6.
In a preferred embodiment of the present invention, the cyclic compound represented by formula (i) is selected from one or more of the following compounds:
the source of the cyclic compound of formula (I) is not particularly limited, and the cyclic compound can be a general commercial product or can be prepared according to a preparation method well known to a person skilled in the art, such as a substitution reaction with a cyclotriveratrole as a base material to form a compound with various substituents. In an embodiment of the invention, the cyclic compound of formula (I) is prepared by:
reacting a benzene-containing compound of formula (II) with formaldehyde in a solvent under acidic conditions to produce a cyclic compound of formula (I);
wherein R is 1 And R is 2 The kind of (C) is the same as that described in the above technical scheme, inThis will not be described in detail. The reaction route of the above reaction is as follows:
in the present invention, the acidic substance providing the acidic condition is preferably a strong acid solution. The kind of the strong acid solution is not particularly limited, and is a conventional strong acid solution known to those skilled in the art, such as sulfuric acid, perchloric acid or hydrochloric acid. In the invention, the strong acid solution is preferably high-concentration strong acid solution, and the mass concentration of the strong acid solution is preferably more than or equal to 20%; specifically, the mass concentration of the sulfuric acid is preferably 60% -80%; the mass concentration of the perchloric acid is preferably 50% -70%; the concentration of the hydrochloric acid is preferably 20% -30%.
In the present invention, the molar ratio of the benzene-containing compound of formula (II) to formaldehyde is preferably 1:1 to 1.5. In the present invention, the solvent is preferably an anhydrous organic solvent; the present invention is not particularly limited in the kind of the organic solvent, and may be an organic solvent well known to those skilled in the art, including, but not limited to, one or more of anhydrous methanol, dichloromethane and N, N-dimethylformamide (i.e., DMF). The temperature of the reaction is not particularly limited, and the reaction is carried out at room temperature; the reaction time is preferably 2 to 3 days.
In the present invention, it is preferable to further include purifying the resultant reactant after the reaction. In the present invention, the purification is preferably recrystallization purification, and the cyclic compound of formula (I) is obtained after purification.
According to the invention, the cyclic compound shown in the formula (I) and/or the optical isomer thereof is used as a negative electrode material of a lithium metal negative electrode, so that lithium ion penetration can be effectively promoted, lithium ions are induced to deposit on the surface of metal lithium, and lithium dendrites are inhibited; the substances are not dissolved in the electrolyte, so that side reactions of the electrolyte and the lithium metal in a battery charging state can be well inhibited; through the above effects, the cycle performance of the battery can be obviously improved.
In the invention, the negative electrode protective layer of the lithium metal negative electrode preferably comprises the following components in proportion: the mass ratio of the main material to the lithium salt to the binder is 55-100:0-15:0-30. The mass ratio of the main material to the lithium salt to the binder is more preferably 70-80:8-10:5-15.
Wherein the lithium salt is preferably LiTFSI (i.e. lithium bis (trifluoromethanesulfonyl imide)), liFSI (i.e. lithium bis (fluorosulfonyl imide)), liODFB (i.e. lithium difluoro (oxalato) borate), liPO 2 F 2 、LiPO 3 、LiNO 3 And Li (lithium) 2 SO 4 One or more of them. The source of the lithium salt is not particularly limited, and the lithium salt is a general commercial product.
Wherein, the binder is preferably one or more of vinylidene fluoride-hexafluoropropylene copolymer, polyvinylidene fluoride (namely PVDF), polyacrylonitrile, polymethyl methacrylate and polytetrafluoroethylene. The source of the binder is not particularly limited, and the binder is a general commercial product.
In the invention, the coverage area of the negative electrode protective layer on the lithium metal negative electrode sheet is not particularly limited, and the negative electrode protective layer can be partially covered or fully covered. In the present invention, the thickness of the negative electrode protective layer is preferably 1 to 2um.
In the invention, the lithium metal negative electrode sheet is preferably a lithium foil sheet, a copper-lithium composite foil sheet or an aluminum-lithium alloy foil sheet.
The invention also provides a preparation method of the lithium metal anode in the technical scheme, which comprises the following steps:
a) Dispersing the main material, lithium salt and binder in a solvent to obtain a mixed solution;
b) And coating the mixed solution on the surface of the lithium metal negative electrode plate and drying to obtain the lithium metal negative electrode.
The types, raw materials, sources and the like of the main materials, the lithium salt and the binder are the same as those in the technical scheme, and are not repeated here.
In the step a), the solvent is preferably one or more of acetone, tetrahydrofuran and N-methylpyrrolidone (i.e. NMP). The invention has no special limit to the dosage of the solvent, and can uniformly disperse the raw materials; preferably, the ratio of the total amount of the main material, the lithium salt and the binder to the solvent is (0.5-2) g to (5-10) mL. The manner of dispersing the above-mentioned raw materials in the solvent is not particularly limited, and the components may be uniformly mixed and dispersed, and may be treated by stirring or the like.
In the step b), the coating method is not particularly limited, and may be performed in a manner of coating an electrode slurry well known to those skilled in the art. The drying conditions are not particularly limited, and the mixed solution can be dried to form a coating; preferably, the drying temperature is preferably 60-100 ℃; the drying time is preferably 8 to 12 hours. In the invention, after the drying, the post-treatment such as rolling and cutting is preferably carried out; the manner of rolling and cutting is not particularly limited, and may be performed according to a conventional electrode preparation operation well known to those skilled in the art. After the above post-treatment, a lithium metal anode was obtained.
In the lithium metal negative electrode provided by the invention, the negative electrode protective layer is arranged on the lithium metal negative electrode plate, and comprises the annular compound shown in the formula (I) and/or an optical isomer thereof, and the annular structure can effectively promote lithium ion penetration and induce lithium ions to deposit on the surface of metal lithium so as to inhibit lithium dendrites; the substances are not dissolved in the electrolyte, so that side reactions of the electrolyte and the lithium metal in a battery charging state can be well inhibited; through the above effects, the cycle performance of the battery can be obviously improved.
The test result shows that the lithium metal anode provided by the invention has excellent cycle performance after being cycled for 100 times at 2-4.6V and 1C, and the cycle retention rate is more than 85%.
The invention also provides a metal lithium secondary battery, which comprises a positive electrode, a negative electrode and a diaphragm; the negative electrode is the lithium metal negative electrode in the technical scheme or the lithium metal negative electrode prepared by the preparation method in the technical scheme.
The active material of the positive electrode is preferably one or more of lithium iron phosphate, lithium cobalt oxide, ternary material, lithium manganate, lithium nickelate and lithium-rich manganese-based material.
The metal lithium secondary battery provided by the invention has excellent cycle performance, and test results show that the cycle retention rate is above 85% after 100 times of cycle under 2-4.6V and 1C.
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
Example 1
S1: mixing and dispersing the following cyclic compound, liTFSI and a binder in a mass ratio of 8:1:1 in NMP to form slurry; wherein the ratio of the total amount of the raw materials to the NMP solvent is 1g to 10mL.
S2: coating the slurry on the surface of a metal lithium foil (with the thickness of 10 um), and drying;
s3: cutting the pole piece into a negative electrode with a coating area with the width of 47mm multiplied by the length of 57mm and an uncoated area with the width of 10mm, wherein the coating thickness of the coating area is 1-2 um; referring to fig. 1, fig. 1 is a schematic view of a negative electrode obtained in example 1 of the present invention, wherein 1 is a coated region and 2 is an uncoated region. The resulting negative electrode was designated as C1.
Example 2
A negative electrode was prepared according to the preparation procedure of example 1, except that the cyclic compound was replaced with the following compound:
the resulting negative electrode was designated as C2.
Example 3
A negative electrode was prepared according to the preparation procedure of example 1, except that the cyclic compound was replaced with the following compound:
the resulting negative electrode was designated as C3.
Example 4
A negative electrode was prepared according to the preparation procedure of example 1, except that the cyclic compound was replaced with the following compound:
the resulting negative electrode was designated as C4.
Example 5
A negative electrode was prepared according to the preparation procedure of example 1, except that the cyclic compound was replaced with the following compound:
the resulting negative electrode was designated as C5.
Example 6
A negative electrode was prepared according to the preparation procedure of example 1, except that the cyclic compound was replaced with the following compound:
the resulting negative electrode was designated as C6.
Example 7
1.1 preparation of positive electrode A:
85 parts by weight of a positive electrode active material nickel-rich manganese lithium cobalt oxide (Li 1.2 Ni 1/6 Mn 1/6 Co 4/6 O 2 ) 8 parts by weight of an acetylene black conductive material and 7 parts by weight of a polyvinylidene fluoride (PVDF) binder are mixed and dispersed in an N-methyl pyrrolidone solvent, wherein the dosage ratio of the positive electrode active material to the solvent is 85 g/120 mL, and electrode slurry is obtained.
The obtained electrode slurry was coated on both sides of an aluminum foil having a thickness of 8 μm and dried, rolled to a thickness of 195 μm by a press, and cut into an active material layer region having a width of 43mm×a length of 53mm and an uncoated region having a width of 10mm, as a positive electrode.
1.2 assembly of lithium ion secondary batteries:
sequentially laminating and winding a positive electrode, a polyethylene diaphragm and a negative electrode so that the positive electrode and the negative electrode are not in direct contact, and manufacturing a battery cell; welding terminals of the positive electrode and the negative electrode with lugs, and packaging the battery cell by using an aluminum plastic film; then, 5mL of an electrolyte (1M LiPF was injected thereinto 6 A solution; solvent EC: EMC: DMC (volume ratio 1:1:1); and after the additive VC (namely vinylene carbonate) accounts for 3 percent of the mass ratio of the electrolyte, carrying out vacuum heat sealing molding to prepare the soft package battery, and taking the soft package battery as a lithium metal battery.
Examples 8 to 15, comparative example 1
Comparative example 1: the negative electrode was a metallic lithium foil without a protective layer, denoted as C0.
The negative electrodes of examples 1 to 6 and comparative example 1 and the positive electrode of example 7 were assembled into lithium metal batteries according to the battery assembly method of example 7, and the electrochemical properties of the batteries were tested as follows:
cycle retention rate:
initial charge and discharge: the charge-discharge cut-off voltage of the assembled lithium metal battery is 2-4.6V. After charging to the upper voltage limit by a constant current constant voltage charging method of 0.2C at 25 ℃, discharging to the lower voltage limit by a constant current of 0.2C. This was subjected to 5 cycles to stabilize the battery, and the discharge capacity at the 5 th cycle was taken as the initial capacity. The current value of the 1-hour discharge rated capacity was set to 1C.
Cycle test: for the battery subjected to initial charge and discharge, 100 cycles were performed at 25 ℃ as follows: after being charged to the upper voltage limit by the constant current and the constant voltage of 1C, the battery is discharged to the lower voltage limit by the constant current and the constant voltage of 1C. The ratio of the 100 th cycle discharge capacity to the 1 st cycle discharge capacity was set as the cycle retention rate.
The test results are shown in Table 1:
table 1 electrochemical properties of examples and comparative examples
As is clear from examples 8 to 15, the use of the negative electrode sheet of the present invention can significantly improve the cycle retention rate of the lithium metal battery as compared with comparative example 1.
The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to aid in understanding the method of the invention and its core concept, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims. The scope of the patent protection is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims (7)
1. A lithium metal anode, comprising: the lithium metal cathode plate and a cathode protective layer compounded on the surface of the lithium metal cathode plate;
the negative electrode protective layer comprises a main material;
the main material is selected from one or more of a cyclic compound of the formula (I) and optical isomers thereof:
the cyclic compound shown in the formula (I) is selected from one or more of the following compounds:
wherein n is an integer of 3 to 6.
2. The lithium metal negative electrode according to claim 1, wherein the negative electrode protective layer comprises the following components in the following proportions:
the mass ratio of the main material to the lithium salt to the binder is 55-100:0-15:0-30.
3. The lithium metal negative electrode according to claim 2, wherein the lithium salt is selected from LiTFSI, liFSI, liODFB, liPO 2 F 2 、LiPO 3 、LiNO 3 And Li (lithium) 2 SO 4 One or more of them.
4. A lithium metal negative electrode according to claim 2 or 3, wherein the binder is selected from one or more of vinylidene fluoride-hexafluoropropylene copolymer, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate and polytetrafluoroethylene.
5. A method for producing a lithium metal anode according to any one of claims 1 to 4, comprising the steps of:
a) Dispersing the main material, lithium salt and binder in a solvent to obtain a mixed solution;
b) And coating the mixed solution on the surface of the lithium metal negative electrode plate and drying to obtain the lithium metal negative electrode.
6. The method according to claim 5, wherein the solvent comprises one or more of acetone, tetrahydrofuran and N-methylpyrrolidone.
7. A metal lithium secondary battery includes a positive electrode, a negative electrode, and a separator; the lithium metal negative electrode according to any one of claims 1 to 4 or the lithium metal negative electrode produced by the production method according to any one of claims 5 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910131087.9A CN111599982B (en) | 2019-02-21 | 2019-02-21 | Lithium metal negative electrode, preparation method thereof and metal lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910131087.9A CN111599982B (en) | 2019-02-21 | 2019-02-21 | Lithium metal negative electrode, preparation method thereof and metal lithium secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111599982A CN111599982A (en) | 2020-08-28 |
| CN111599982B true CN111599982B (en) | 2024-01-30 |
Family
ID=72188815
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910131087.9A Active CN111599982B (en) | 2019-02-21 | 2019-02-21 | Lithium metal negative electrode, preparation method thereof and metal lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111599982B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06168739A (en) * | 1992-11-30 | 1994-06-14 | Canon Inc | Secondary battery |
| JPH06283157A (en) * | 1992-09-14 | 1994-10-07 | Canon Inc | Secondary battery |
| CN1577919A (en) * | 2003-07-08 | 2005-02-09 | 三星Sdi株式会社 | Negative electrode for rechargeable lithium battery, method of producing same and rechargeable lithium battery comprising same |
| CN102498104A (en) * | 2009-08-31 | 2012-06-13 | 三菱瓦斯化学株式会社 | Cyclic compound, process for production of the cyclic compound, radiation-sensitive composition, and method for formation of resist pattern |
| CN107431183A (en) * | 2015-03-24 | 2017-12-01 | 三洋电机株式会社 | Rechargeable nonaqueous electrolytic battery |
| WO2018233413A1 (en) * | 2017-06-20 | 2018-12-27 | 中国科学院化学研究所 | Method for protecting negative electrode of metal secondary battery by using polymer and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102010043111A1 (en) * | 2010-10-29 | 2012-05-03 | Robert Bosch Gmbh | Ex situ production of a lithium anode protective layer |
-
2019
- 2019-02-21 CN CN201910131087.9A patent/CN111599982B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06283157A (en) * | 1992-09-14 | 1994-10-07 | Canon Inc | Secondary battery |
| JPH06168739A (en) * | 1992-11-30 | 1994-06-14 | Canon Inc | Secondary battery |
| CN1577919A (en) * | 2003-07-08 | 2005-02-09 | 三星Sdi株式会社 | Negative electrode for rechargeable lithium battery, method of producing same and rechargeable lithium battery comprising same |
| CN102498104A (en) * | 2009-08-31 | 2012-06-13 | 三菱瓦斯化学株式会社 | Cyclic compound, process for production of the cyclic compound, radiation-sensitive composition, and method for formation of resist pattern |
| CN107431183A (en) * | 2015-03-24 | 2017-12-01 | 三洋电机株式会社 | Rechargeable nonaqueous electrolytic battery |
| WO2018233413A1 (en) * | 2017-06-20 | 2018-12-27 | 中国科学院化学研究所 | Method for protecting negative electrode of metal secondary battery by using polymer and application thereof |
| CN109103517A (en) * | 2017-06-20 | 2018-12-28 | 中国科学院化学研究所 | A kind of method and its application of polymer protection metal secondary batteries cathode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111599982A (en) | 2020-08-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109786708B (en) | Lithium metal negative electrode, preparation method thereof and lithium metal secondary battery | |
| CN102339980B (en) | Positive pole and the lithium battery comprising this positive pole | |
| EP2390944B1 (en) | Rechargeable Lithium Battery | |
| KR101268501B1 (en) | Cathode active material for lithium secondary battery, method for manufacturing the same and lithium secondary battery using the same | |
| KR20140024587A (en) | Rechargeable lithium battery | |
| KR20150057730A (en) | Negative electrode active material layer composition for rechargeable lithium battery, manufacturing method of the same, and negative electrode and rechargeable lithium battery including the same | |
| JP2006252917A (en) | Lithium-ion secondary battery | |
| EP3163654B1 (en) | Rechargeable lithium battery | |
| CN112635766B (en) | Metal lithium battery cathode, preparation method thereof and lithium secondary battery | |
| CN111048749A (en) | Negative pole piece, lithium ion battery and manufacturing method thereof | |
| CN111048755A (en) | High-rate lithium ion battery cathode material and preparation method thereof | |
| CN114552007A (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery | |
| CN114203976A (en) | Mixed solution capable of improving stability of metal lithium cathode, preparation method and application | |
| CN114613963B (en) | Negative electrode material, preparation method thereof, negative electrode sheet and secondary battery | |
| CN111599982B (en) | Lithium metal negative electrode, preparation method thereof and metal lithium secondary battery | |
| KR101736359B1 (en) | Binder for rechargable lithium battery, electrode for rechargable lithium battery, manufacturing method of electrode for rechargable lithium battery and recharable lithium battery including the electrode | |
| CN112310478B (en) | Electrolyte and electrochemical device thereof | |
| CN112635765B (en) | Metal lithium battery cathode, preparation method thereof and lithium secondary battery | |
| CN112768768B (en) | Battery electrolyte containing ammonium iodide additive and preparation method thereof | |
| CN110556579B (en) | Electrolyte and lithium ion battery containing same | |
| CN114497746A (en) | Battery with a battery cell | |
| KR101730958B1 (en) | Electrolyte for lithium secondary battery and lithium secondary battery employing the same | |
| CN108987803B (en) | Lithium metal negative electrode film-forming electrolyte for lithium-sulfur battery and additive thereof | |
| CN112038699A (en) | Method for improving stability of electrolyte of lithium iron phosphate battery and manufacturing method of battery | |
| CN114391194A (en) | Lithium metal battery and method for manufacturing same |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |