CN112803012B - Lithium ion battery cathode, preparation method and application thereof, and lithium ion battery - Google Patents
Lithium ion battery cathode, preparation method and application thereof, and lithium ion battery Download PDFInfo
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- CN112803012B CN112803012B CN202110318303.8A CN202110318303A CN112803012B CN 112803012 B CN112803012 B CN 112803012B CN 202110318303 A CN202110318303 A CN 202110318303A CN 112803012 B CN112803012 B CN 112803012B
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- lithium
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- ion battery
- lithium ion
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011241 protective layer Substances 0.000 claims abstract description 164
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 130
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000010410 layer Substances 0.000 claims abstract description 57
- 229910052751 metal Inorganic materials 0.000 claims abstract description 52
- 239000002184 metal Substances 0.000 claims abstract description 52
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 38
- -1 nitrogen-containing compound Chemical class 0.000 claims abstract description 30
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 23
- 239000011574 phosphorus Substances 0.000 claims abstract description 23
- 239000003792 electrolyte Substances 0.000 claims abstract description 21
- 238000011065 in-situ storage Methods 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 22
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 18
- 239000004014 plasticizer Substances 0.000 claims description 13
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 13
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 12
- 239000011245 gel electrolyte Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 8
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 7
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- IDNHOWMYUQKKTI-UHFFFAOYSA-M lithium nitrite Chemical compound [Li+].[O-]N=O IDNHOWMYUQKKTI-UHFFFAOYSA-M 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000007086 side reaction Methods 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000011888 foil Substances 0.000 description 7
- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical compound [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 229910003480 inorganic solid Inorganic materials 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000016507 interphase Effects 0.000 description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 3
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- JKNHZOAONLKYQL-UHFFFAOYSA-K Indium(III) bromide Inorganic materials Br[In](Br)Br JKNHZOAONLKYQL-UHFFFAOYSA-K 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910003405 Li10GeP2S12 Inorganic materials 0.000 description 2
- 229910007562 Li2SiO3 Inorganic materials 0.000 description 2
- 229910007822 Li2ZrO3 Inorganic materials 0.000 description 2
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 2
- 229910010854 Li6PS5Br Inorganic materials 0.000 description 2
- 229910010848 Li6PS5Cl Inorganic materials 0.000 description 2
- 229910011201 Li7P3S11 Inorganic materials 0.000 description 2
- 229910010092 LiAlO2 Inorganic materials 0.000 description 2
- 229910003327 LiNbO3 Inorganic materials 0.000 description 2
- 229910012463 LiTaO3 Inorganic materials 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 229910018057 ScCl3 Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- CEMTZIYRXLSOGI-UHFFFAOYSA-N lithium lanthanum(3+) oxygen(2-) titanium(4+) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Ti+4].[La+3] CEMTZIYRXLSOGI-UHFFFAOYSA-N 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000002203 sulfidic glass Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 2
- 229910009160 xLi2S Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5805—Phosphides
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a lithium ion battery cathode, a preparation method and application thereof and a lithium ion battery, wherein the lithium ion battery cathode comprises metal lithium and at least two protective layers which are sequentially arranged on the surface of the metal lithium; the at least two protective layers comprise a first protective layer attached to the surface of the metallic lithium, the first protective layer comprises an artificial SEI film layer, and the artificial SEI film layer is formed by in-situ growth of a nitrogen-containing compound and a phosphorus-containing compound on the surface of the metallic lithium; the at least two protective layers further comprise a second protective layer which is arranged on the first protective layer and is far away from the surface of the lithium metal, and the second protective layer comprises a solid electrolyte layer; according to the lithium ion battery cathode, the first protective layer containing the artificial SEI film layer and the second protective layer containing the solid electrolyte layer are arranged on the surface of the metal lithium, so that the surface stability of the metal lithium is improved, the metal lithium is prevented from generating side reactions with electrolyte or other components, the protective layers have strong affinity for lithium ions, the influence on the performance of the battery is small, and the cycle life of the battery is prolonged.
Description
Technical Field
The invention relates to the technical field of new energy, and particularly relates to a lithium ion battery cathode, a preparation method and application thereof, and a lithium ion battery.
Background
The high specific energy secondary lithium ion battery has the characteristics of high theoretical energy density, low reduction potential, long cycle life and no memory effect, and has the advantages of safety, reliability, rapid charge and discharge and the like, thereby becoming a hotspot of the research of novel power supply technology in recent years.
The metal lithium negative electrode has the advantages of ultrahigh specific capacity and very low electrochemical potential. However, safety problems and side reactions, etc. caused by the growth of lithium dendrites, greatly limit the application of metallic lithium negative electrodes.
In a liquid battery, metallic lithium readily reacts with an electrolyte; in the solid-state battery, the interfacial reaction between the metallic lithium and the solid-state electrolyte is also one of the important factors that prevent the metallic lithium from being stabilized.
At present, in order to overcome the problems of the lithium metal negative electrode, a method of forming a protective layer on the surface of the lithium metal negative electrode or providing a lithium-philic layer between the lithium metal and the solid electrolyte is generally used. For example, CN105280886B discloses a technique for growing a lithium phosphate protective layer in situ on the surface of lithium metal, however, practice proves that it is still difficult to completely avoid the generation of lithium dendrite in this manner, and improvement on prolonging the battery life is limited; CN111710904B discloses a method for disposing a lithium affinity layer between lithium metal and a solid electrolyte layer to solve the problem of lithium dendrite caused by different roughness, however, the active ingredient of the affinity layer adopted in this scheme is nitrile rubber, which is a synthetic rubber, and is prone to aging and failure during repeated charge and discharge processes, and it is used in a battery negative electrode to affect the battery performance.
However, in all of the above methods, the metallic lithium is treated by a single method, and there is no document that the surface treatment of the metallic lithium negative electrode is carried out by a composite method.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a lithium ion battery cathode, a preparation method and application thereof, and a lithium ion battery, which can effectively improve the stability of the lithium ion battery and prolong the service life of the lithium ion battery.
In order to solve the technical problem, a first aspect of the present invention provides a lithium ion battery negative electrode, including metallic lithium and at least two protective layers sequentially disposed on a surface of the metallic lithium;
the at least two protective layers comprise a first protective layer adhered to the metallic lithium surface, the first protective layer comprising an artificial SEI film layer formed by in-situ growth of a nitrogen-containing compound and a phosphorus-containing compound on the metallic lithium surface;
the at least two protective layers further comprise a second protective layer arranged on the first protective layer and far away from the surface of the lithium metal, and the second protective layer comprises a solid electrolyte layer.
In a preferred embodiment, the at least two protective layers further include a third protective layer disposed between the first protective layer and the second protective layer, and the third protective layer is formed by coating a mixture of a gel electrolyte and a plasticizer on the surface of the first protective layer.
Preferably, the plasticizer comprises at least one of dibutyl phthalate, carbonate, ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, 1, 2-dimethoxyethane;
the gel electrolyte comprises at least one of polymethyl methacrylate, polyvinylidene fluoride and polyacrylonitrile.
Preferably, the plasticizer comprises any one combination of ethylene carbonate and carbonic ester, ethylene carbonate and ethyl methyl carbonate, ethylene carbonate and 1, 2-dimethoxyethane.
In a preferred embodiment, the nitrogen-containing compound comprises at least one of lithium nitrate, lithium nitrite;
the phosphorus-containing compound comprises at least one of polyphosphoric acid, phosphoric acid, phosphorous acid, metaphosphoric acid and polyphosphoric acid.
In a preferred embodiment, the second protective layer includes at least one of a sulfide solid electrolyte, a halide solid electrolyte, an oxide solid electrolyte, an inorganic solid electrolyte, and a polymer solid electrolyte.
Preferably, the sulfide solid state electrolyte comprises Li10GeP2S12、xLi2S·(100-x)P2S5 (60≤x≤80)、Li7P3S11、Li6PS5Cl、Li6PS5Br、Li6PS5ClxBr1-x (x=0~1.0)、Li6+xP1-xGexS5I、Li5PS4X2(X = Cl，Br，I)、Li10MP2S12(M=Si，Ge，Sn)、Li5PS4X2(X = Cl，Br，I)、Li9.54Si1.74P1.44S11.7Cl0.3At least one of (1).
Preferably, the halide solid state electrolyte comprises Li3InBr6-xClx(x≤4)、Li3InBr3Cl3、LiInBr4、Li3InBr6、Li3InCl6、Li3YX6 (X=Cl，Br，I)、Li3ErX6 (X=Cl，Br，I)、Li3ScX6 (X=Cl，Br，I)、Li3LaI6、Li3LuCl6、Li3-xEr1-xZrxCl6(x≤0.6)、Li3-xY1-xZrxCl6(x≤0.6)、Li3Y1-xInxCl6 (0<x<1)、CsSnCl3、LixScCl3+xOne or a mixture of more of (a);
preferably, the oxide solid state electrolyte comprises at least one of doped or undoped lithium lanthanum zirconium oxide, doped or undoped lithium lanthanum titanium oxide, tantalum doped lithium lanthanum zirconium oxide, doped or undoped lithium titanium aluminum phosphate, doped or undoped lithium lanthanum zirconium oxide.
Preferably, the inorganic solid electrolyte comprises Li3PO4、LiAlO2、Al2O3、LiTaO3、LiNbO3、Li4Ti5O12、Li2SiO3、Li3BO3、Li2ZrO3At least one of (1).
Preferably, the polymer solid electrolyte comprises at least one of polytetrafluoroethylene, polyvinylidene fluoride doped with lithium salt; the lithium salt comprises at least one of lithium perchlorate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium trifluoromethanesulfonate, lithium diimidate, lithium trimethyl and lithium bis (oxalato) borate.
In order to solve the above technical problems, a second aspect of the present invention further provides a method for preparing a negative electrode of a lithium ion battery, where the method includes:
dissolving a nitrogen-containing compound and a phosphorus-containing compound in an organic solvent to form a first mixed solution;
dipping lithium metal in the first mixed solution to enable the nitrogen-containing compound and the phosphorus-containing compound to grow in situ on the surface of the lithium metal to form an artificial SEI film layer so as to form a first protective layer on the surface of the lithium metal;
and a second protective layer is pasted on the surface of the first protective layer to form the lithium ion battery cathode, and the second protective layer comprises a solid electrolyte layer.
In a preferred embodiment, after forming the first protection layer and before attaching the second protection layer, the method further comprises:
and coating a mixture of gel electrolyte and a plasticizer on the surface of the first protective layer to form a third protective layer.
In a preferred embodiment, the total concentration of the phosphorus-containing compounds in the first mixed solution is 1 × 10-4-0.2M; preferably 1X 10-3M-0.1M。
The step of immersing the lithium metal in the first mixed solution to enable the nitrogen-containing compound and the phosphorus-containing compound to grow in situ on the surface of the lithium metal to form an artificial SEI film layer so as to form the first protective layer specifically comprises the following steps:
dipping the metallic lithium in the first mixed solution for 1s-3h at the temperature of the first mixed solution being 20-60 ℃, so that the nitrogen-containing compound and the phosphorus-containing compound grow in situ on the surface of the metallic lithium to form an artificial SEI film layer, thereby forming the first protection layer;
taking out the metal lithium from the first mixed solution, wherein the thickness of the first protective layer formed on the surface of the metal lithium is 1-600 nm;
and removing the solution on the surface of the first protective layer.
In order to solve the above technical problems, a third aspect of the present invention further provides an application of the lithium ion battery negative electrode according to the first aspect or the lithium ion battery negative electrode prepared by the preparation method according to the second aspect in preparing a lithium ion battery.
In order to solve the above technical problem, a fourth aspect of the present invention further provides a lithium ion battery, including an electrolyte, a positive electrode, and the lithium ion battery negative electrode according to the first aspect.
The technical scheme provided by the embodiment of the invention has the following beneficial effects:
the invention provides a lithium ion battery cathode, a preparation method and application thereof and a lithium ion battery, wherein the lithium ion battery cathode comprises metal lithium and at least two protective layers which are sequentially arranged on the surface of the metal lithium; the at least two protective layers comprise a first protective layer attached to the surface of the metallic lithium, the first protective layer comprises an artificial SEI film layer, and the artificial SEI film layer is formed by in-situ growth of a nitrogen-containing compound and a phosphorus-containing compound on the surface of the metallic lithium; the at least two protective layers further comprise a second protective layer which is arranged on the first protective layer and is far away from the surface of the metal lithium, and the second protective layer comprises a solid electrolyte layer; this lithium ion battery negative pole has improved the stability on metal lithium surface through set up the first protective layer that contains artificial SEI rete and the second protective layer that contains solid electrolyte layer on metal lithium surface, avoids metal lithium and electrolyte or other components to take place the side reaction, and each protective layer is strong to lithium ion affinity, and is less to the influence of battery performance, has prolonged battery cycle life, has overcome the problem that single protective layer can not satisfy the protection of metal lithium.
Further, at least two-layer protective layer still including locate the third protective layer between first protective layer and the second protective layer, the third protective layer is formed through the mixture that gel electrolyte and plasticizer constitute at first protective layer surface coating, through set up the third protective layer between first protective layer and second protective layer, can further improve battery stability, improves bonding ability and compatibility between the two-layer protective layer.
It should be noted that the present invention only needs to achieve at least one of the above technical effects.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, features defined as "first", "second", "third" may explicitly or implicitly include one or more of the features. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
Although the SEI film is formed in the first charge and discharge process of the existing secondary battery, the metal lithium has active chemical properties, and is easy to break and fall under the deformation effect caused by repeated charge and discharge processes, so that the service life of the battery is influenced. Therefore, the present embodiment provides a lithium ion battery cathode, a preparation method, an application and a lithium ion battery thereof, which can effectively overcome the above problems.
In a first aspect, the present embodiment provides a lithium ion battery negative electrode, including metallic lithium and at least two protective layers sequentially disposed on a surface of the metallic lithium;
the at least two protective layers comprise a first protective layer adhered to the metallic lithium surface, the first protective layer comprising an artificial SEI film layer formed by in-situ growth of a nitrogen-containing compound and a phosphorus-containing compound on the metallic lithium surface;
the at least two protective layers further comprise a second protective layer arranged on the first protective layer and far away from the surface of the lithium metal, and the second protective layer comprises a solid electrolyte layer.
The metal lithium can be lithium foil or a metal lithium layer which is formed by pasting the metal lithium layer on a foil, and the thickness of the lithium foil, the metal lithium layer and the foil is not particularly limited in the application; when a structure in which a metallic lithium layer is attached to a foil is used, there is no particular requirement on the kind of foil, and any known kind of foil can be used in the present application, such as a copper foil.
The artificial SEI film layer serving as the first protective layer is arranged on the surface of the metal lithium, so that the metal lithium can be passivated, active metal lithium is prevented from contacting the outside, and the stability of the negative electrode of the lithium ion battery is improved. The solid electrolyte layer serving as the second protective layer is arranged on the surface of the metal lithium, so that the problems of dendritic crystal growth and continuous increase of interface impedance of a lithium negative electrode in the circulation process of the lithium ion battery can be solved.
In a preferred embodiment, the at least two protective layers further include a third protective layer disposed between the first protective layer and the second protective layer, and the third protective layer is formed by coating a mixture of a gel electrolyte and a plasticizer on the surface of the first protective layer.
The third protective layer is arranged between the first protective layer and the second protective layer, the third protective layer can effectively improve the elasticity of the first protective layer, further prevent the artificial SEI film layer from being cracked due to deformation in the repeated charge and discharge process, improve the compatibility between the first protective layer and the second protective layer, and simultaneously avoid the increase of the internal resistance of the protective layer due to the adoption of gel electrolyte.
The plasticizer is a low molecular solvent with high boiling point and low viscosity or an oligomer which can be mixed with a high polymer.
Preferably, the plasticizer includes at least one of dibutyl phthalate (DBP), carbonate (PC), Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC), 1, 2-Dimethoxyethane (DME);
the gel electrolyte includes at least one of Polymethylmethacrylate (PMMA), polyvinylidene fluoride (PVDF), Polyacrylonitrile (PAN).
Preferably, the plasticizer comprises any one combination of EC and PC, EC and EMC, EC and DME.
The nitrogen-containing compound comprises at least one of lithium nitrate and lithium nitrite;
the phosphorus-containing compound comprises at least one of polyphosphoric acid, phosphoric acid, phosphorous acid, metaphosphoric acid and polyphosphoric acid.
The second protective layer includes at least one of a sulfide solid electrolyte, a halide solid electrolyte, an oxide solid electrolyte, an inorganic solid electrolyte, and a polymer solid electrolyte.
Preferably, the sulfide solid state electrolyte comprises Li10GeP2S12、xLi2S·(100-x)P2S5 (60≤x≤80)、Li7P3S11、Li6PS5Cl、Li6PS5Br、Li6PS5ClxBr1-x (x=0~1.0)、Li6+xP1-xGexS5I、Li5PS4X2(X = Cl，Br，I)、Li10MP2S12(M=Si，Ge，Sn)、Li5PS4X2(X = Cl，Br，I)、Li9.54Si1.74P1.44S11.7Cl0.3At least one of (1).
Preferably, the halide solid state electrolyte comprises Li3InBr6-xClx(x≤4)、Li3InBr3Cl3、LiInBr4、Li3InBr6、Li3InCl6、Li3YX6 (X=Cl，Br，I)、Li3ErX6 (X=Cl，Br，I)、Li3ScX6 (X=Cl，Br，I)、Li3LaI6、Li3LuCl6、Li3-xEr1-xZrxCl6(x≤0.6)、Li3-xY1-xZrxCl6(x≤0.6)、Li3Y1-xInxCl6 (0≤x<1)、CsSnCl3、LixScCl3+xOne or a mixture of more of (a);
preferably, the oxide solid state electrolyte comprises at least one of doped or undoped Lithium Lanthanum Zirconium Oxide (LLZO), doped or undoped Lithium Lanthanum Titanium Oxide (LLTO), tantalum doped lithium lanthanum zirconium oxide (LLZTO), doped or undoped titanium aluminum lithium phosphate (LATP), doped or undoped lithium lanthanum zirconium oxide (LAO).
Preferably, the inorganic solid electrolyte comprises Li3PO4、LiAlO2、Al2O3、LiTaO3、LiNbO3、Li4Ti5O12、Li2SiO3、Li3BO3、Li2ZrO3At least one of (1).
Preferably, the polymer solid electrolyte comprises at least one of polytetrafluoroethylene, polyvinylidene fluoride doped with lithium salt; the lithium salt comprises at least one of lithium perchlorate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium trifluoromethanesulfonate, lithium diimidate, lithium trimethyl and lithium bis (oxalato) borate.
In a second aspect, this embodiment further provides a method for preparing a negative electrode of a lithium ion battery, where the method includes:
dissolving a nitrogen-containing compound and a phosphorus-containing compound in an organic solvent to form a first mixed solution;
dipping the metallic lithium in the first mixed solution to enable the nitrogen-containing compound and the phosphorus-containing compound to grow in situ on the surface of the metallic lithium to form an artificial SEI film layer so as to form a first protective layer on the surface of the metallic lithium;
and attaching a second protective layer to the surface of the metal lithium after the first protective layer is formed to form a lithium ion battery cathode, wherein the second protective layer comprises a solid electrolyte layer.
After forming the first protective layer and before attaching the second protective layer, the method further comprises:
and coating a mixture of the gel electrolyte and the plasticizer on the surface of the first protective layer to form a third protective layer.
The total concentration of the phosphorus-containing compounds in the first mixed solution is 1 x 10-4-0.2M; preferably 1X 10-3M-0.1M。
The solvent of the first mixed solution is an organic solvent and comprises at least one of tetrahydrofuran, propylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, ethyl acetate, acetonitrile, isopropyl ether, acetone, butanone, isopropanol, butanol, hexane, cyclohexane, N-N dimethylacetamide, N-methyl-2-pyrrolidone, benzene, tetraethylene glycol dimethyl ether, toluene, dimethyl sulfoxide, carbon tetrachloride, trichloroethylene and pyrrole;
the method comprises the following steps of immersing the lithium metal in a first mixed solution to enable a nitrogen-containing compound and a phosphorus-containing compound to grow in situ on the surface of the lithium metal to form an artificial SEI film layer so as to form a first protective layer on the surface of the lithium metal, and specifically comprises the following steps:
dipping the metallic lithium in the first mixed solution for 1s-3h at the temperature of the first mixed solution being 20-60 ℃, so that the nitrogen-containing compound and the phosphorus-containing compound grow in situ on the surface of the metallic lithium to form an artificial SEI film layer, thereby forming the first protection layer;
taking out the metal lithium from the first mixed solution, wherein the thickness of the first protective layer formed on the surface of the metal lithium is 1-600 nm;
and removing the solution on the surface of the first protective layer.
In a third aspect, this embodiment further provides an application of the lithium ion battery negative electrode according to the first aspect or the lithium ion battery negative electrode prepared by the preparation method according to the second aspect in preparing a lithium ion battery.
In a fourth aspect, the present embodiment further provides a lithium ion battery, including an electrolyte, a positive electrode, and the lithium ion battery negative electrode according to the first aspect.
The electrolyte refers to an electrolyte between a positive electrode and a negative electrode, and can be a solid electrolyte or an electrolyte. The kind of the electrolyte is not particularly limited, and any known kind of material that does not violate the inventive concept of the present application can be used in the present application.
The following further describes the lithium ion battery negative electrode, its preparation method and application with reference to specific embodiments.
Example 1
The embodiment provides a preparation method of a lithium ion battery, which comprises the following steps:
s1, dissolving lithium nitrate and polyphosphoric acid in propylene carbonate to form a first mixed solution, wherein the concentration of polyphosphoric acid in the first mixed solution is 0.02M.
And S2, soaking the lithium metal in the first mixed solution for 1S at 60 ℃, so that lithium nitrate and polyphosphoric acid are polymerized on the surface of the lithium metal in situ to form an artificial SEI film layer, and a first protective layer is formed.
And taking the metal lithium out of the first mixed solution, wherein the thickness of the first protective layer formed on the surface of the metal lithium is 1nm, and removing the solution on the surface of the first protective layer by means of drying and the like.
And S3, coating the surface of the metal lithium attached with the first protective layer with a mixture of PAN, lithium perchlorate, EC and PC to form a third protective layer.
And S4, attaching a second protective layer of the LGPS solid electrolyte to the surface of the metal lithium after the third protective layer is formed, and forming the negative electrode of the lithium ion battery.
The lithium ion battery cathode prepared by the preparation method comprises metal lithium, and a first protective layer, a third protective layer and a second protective layer which are sequentially arranged on the surface of the metal lithium, wherein the first protective layer is an artificial SEI (solid electrolyte interphase) film layer formed by in-situ polymerization of lithium nitrate and polyphosphoric acid on the surface of the metal lithium, the second protective layer is a solid electrolyte layer attached to the surface of the third protective layer, and the specific material of the solid electrolyte layer is LGPS.
Example 2
The embodiment provides a preparation method of a lithium ion battery, which comprises the following steps:
s1, dissolving lithium nitrite and metaphosphoric acid in lithium hexafluoroarsenate to form a first mixed solution, wherein the concentration of metaphosphoric acid in the first mixed solution is 0.02M.
And S2, soaking the lithium metal in the first mixed solution for 2 hours at the temperature of 40 ℃ so that the lithium nitrite and the metaphosphoric acid are polymerized in situ on the surface of the lithium metal to form an artificial SEI film layer, thereby forming a first protective layer.
And taking the metal lithium out of the first mixed solution, wherein the thickness of the first protective layer formed on the surface of the metal lithium is 600nm, and removing the solution on the surface of the first protective layer by means of drying and the like.
And S3, coating the surface of the metal lithium attached with the first protective layer with a mixture of PMMA, EC and PC to form a third protective layer.
And S4, attaching a second protective layer of the LLZO solid electrolyte on the surface of the metal lithium after the third protective layer is formed, and forming the lithium ion battery cathode.
The lithium ion battery cathode prepared by the preparation method comprises metal lithium, and a first protective layer, a third protective layer and a second protective layer which are sequentially arranged on the surface of the metal lithium, wherein the first protective layer is an artificial SEI (solid electrolyte interphase) film layer formed by in-situ polymerization of lithium nitrite and metaphosphoric acid on the surface of the metal lithium, the second protective layer is a solid electrolyte layer attached to the surface of the third protective layer, and the specific material of the solid electrolyte layer is LLZO.
Example 3
The embodiment provides a preparation method of a lithium ion battery, which comprises the following steps:
s1, dissolving lithium nitrate and polyphosphoric acid in lithium hexafluoroarsenate to form a first mixed solution, wherein the concentration of lithium polyphosphate in the first mixed solution is 0.02M.
And S2, soaking the lithium metal in the first mixed solution for 2 hours at the temperature of 40 ℃, so that the lithium nitrate and the polyphosphoric acid are polymerized on the surface of the lithium metal in situ to form an artificial SEI film layer, and the first protective layer is formed.
And taking the metal lithium out of the first mixed solution, wherein the thickness of the first protective layer formed on the surface of the metal lithium is 600nm, and removing the solution on the surface of the first protective layer by means of drying and the like.
And S3, attaching a second protective layer made of LGPS to the surface of the metal lithium after the first protective layer is formed, and forming the lithium ion battery cathode.
The lithium ion battery cathode prepared by the preparation method comprises metal lithium, and a first protective layer and a second protective layer which are sequentially arranged on the surface of the metal lithium, wherein the first protective layer is an artificial SEI (solid electrolyte interphase) film layer formed by in-situ polymerization of lithium nitrate and polyphosphoric acid on the surface of the metal lithium, the second protective layer is a solid electrolyte layer directly attached to the surface of the first protective layer, and the specific material of the solid electrolyte layer is LGPS.
Comparative example 1:
the comparative example is otherwise identical to example 1, except that: after the steps S1 and S2 are completed, the preparation of the negative electrode of the lithium ion battery is completed, and the obtained negative electrode of the lithium ion battery only comprises the metallic lithium and the first protective layer formed on the surface of the metallic lithium.
Comparative example 2:
the comparative example is otherwise identical to example 2, except that: after the steps S1 and S2 are completed, the preparation of the negative electrode of the lithium ion battery is completed, and the obtained negative electrode of the lithium ion battery only comprises the metallic lithium and the first protective layer formed on the surface of the metallic lithium.
Comparative example 3:
the comparative example provides a method of making a lithium ion battery, comprising the steps of:
s1', sticking a protective layer made of LGPS on the surface of the metal lithium to form the lithium ion battery cathode.
The negative electrode for a lithium ion battery obtained in this comparative example includes only metallic lithium and a second protective layer formed on the surface thereof.
After the lithium ion battery cathodes prepared in examples 1 to 3 and comparative examples 1 to 3 were stacked and assembled with the positive electrode, the solid electrolyte, and the additive, the following performance tests were performed and the corresponding test results shown in table 1 were obtained.
The performance test method comprises the following steps:
charging to a final voltage at room temperature by 1C or specified current, stopping the current by 0.05C, and standing for 30 min; discharging at 1C to the final discharge voltage (2.75V), recording the discharge capacity, and standing for 30 min;
and (6) circulating the first step and the second step, ending the experiment until the discharge capacity is lower than the initial capacity, and recording the circulation times.
TABLE 1
Based on table 1 above, it can be seen that the cycle life of the lithium ion batteries prepared in examples 1-3 is significantly longer than that of comparative examples 1-3; further, in example 3, compared with example 1, the cycle life of the lithium ion battery can be further improved by providing the third protective layer between the first protective layer and the second protective layer. All the above optional technical solutions may be combined arbitrarily to form optional embodiments of the present invention, that is, any multiple embodiments may be combined to meet the requirements of different application scenarios, which are within the protection scope of the present application and are not described herein again.
It should be understood that the above-mentioned embodiments are merely preferred embodiments of the present invention, and not intended to limit the present invention, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A lithium ion battery cathode is characterized by comprising metal lithium and at least two protective layers which are sequentially arranged on the surface of the metal lithium;
the at least two protective layers comprise a first protective layer adhered to the metallic lithium surface, the first protective layer comprising an artificial SEI film layer formed by in-situ growth of a nitrogen-containing compound and a phosphorus-containing compound on the metallic lithium surface;
the at least two protective layers further comprise a second protective layer which is arranged on the first protective layer and is far away from the surface of the lithium metal, and the second protective layer comprises a solid electrolyte layer;
the at least two protective layers further comprise a third protective layer arranged between the first protective layer and the second protective layer, and the third protective layer is formed by coating a mixture consisting of gel electrolyte and plasticizer on the surface of the first protective layer;
the plasticizer comprises at least one of dibutyl phthalate, carbonic ester, ethylene carbonate, ethyl methyl carbonate, diethyl carbonate and 1, 2-dimethoxyethane;
the gel electrolyte comprises at least one of polymethyl methacrylate, polyvinylidene fluoride and polyacrylonitrile.
2. The lithium ion battery negative electrode of claim 1, wherein the nitrogen-containing compound comprises at least one of lithium nitrate, lithium nitrite;
the phosphorus-containing compound comprises at least one of polyphosphoric acid, phosphoric acid, phosphorous acid, metaphosphoric acid and polyphosphoric acid.
3. The lithium ion battery negative electrode of claim 1, wherein the second protective layer comprises at least one of a sulfide solid state electrolyte, a halide solid state electrolyte, an oxide solid state electrolyte, and a polymer solid state electrolyte.
4. A method for preparing the negative electrode for a lithium ion battery according to any one of claims 1 to 3, comprising:
dissolving a nitrogen-containing compound and a phosphorus-containing compound in an organic solvent to form a first mixed solution;
dipping lithium metal in the first mixed solution to enable the nitrogen-containing compound and the phosphorus-containing compound to grow in situ on the surface of the lithium metal to form an artificial SEI film layer so as to form a first protective layer on the surface of the lithium metal;
a second protective layer is pasted on the surface of the first protective layer to form the lithium ion battery cathode, and the second protective layer comprises a solid electrolyte layer;
after forming the first protective layer and before attaching the second protective layer, the method further comprises:
and coating a mixture of gel electrolyte and a plasticizer on the surface of the first protective layer to form a third protective layer.
5. The method for producing a negative electrode for a lithium ion battery according to claim 4,
the total concentration of the phosphorus-containing compounds in the first mixed solution was 1X 10-4-0.2M；
The method for preparing the protective layer comprises the following steps of immersing lithium metal in the first mixed solution to enable the nitrogen-containing compound and the phosphorus-containing compound to grow in situ on the surface of the lithium metal to form an artificial SEI film layer, and forming a first protective layer on the surface of the lithium metal, and specifically comprises the following steps:
dipping the metallic lithium in the first mixed solution for 1s-3h at the temperature of the first mixed solution being 20-60 ℃, so that the nitrogen-containing compound and the phosphorus-containing compound grow in situ on the surface of the metallic lithium to form an artificial SEI film layer, thereby forming the first protection layer;
and taking the metal lithium out of the first mixed solution, wherein the thickness of the first protective layer formed on the surface of the metal lithium is 1-600 nm.
6. Use of the lithium ion battery negative electrode according to any one of claims 1 to 3 or the lithium ion battery negative electrode prepared by the preparation method according to any one of claims 4 to 5 in the preparation of a lithium ion battery.
7. A lithium ion battery comprising an electrolyte, a positive electrode, and a negative electrode according to any one of claims 1 to 3.
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