CN113224313A - Metal organic phosphine frame glass modified metal negative current collector and preparation method thereof - Google Patents
Metal organic phosphine frame glass modified metal negative current collector and preparation method thereof Download PDFInfo
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- CN113224313A CN113224313A CN202110480259.0A CN202110480259A CN113224313A CN 113224313 A CN113224313 A CN 113224313A CN 202110480259 A CN202110480259 A CN 202110480259A CN 113224313 A CN113224313 A CN 113224313A
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- metal
- current collector
- organic phosphine
- phosphine
- frame glass
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 61
- 239000002184 metal Substances 0.000 title claims abstract description 61
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 46
- 239000011521 glass Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 31
- 239000011248 coating agent Substances 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 27
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 23
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims abstract description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010949 copper Substances 0.000 claims description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 26
- 229910052802 copper Inorganic materials 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- FXXRPTKTLVHPAR-UHFFFAOYSA-N 1,3,5-triaza-7-phosphaadamantane Chemical compound C1N(C2)CN3CN1CP2C3 FXXRPTKTLVHPAR-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- SVABQOITNJTVNJ-UHFFFAOYSA-N diphenyl-2-pyridylphosphine Chemical compound C1=CC=CC=C1P(C=1N=CC=CC=1)C1=CC=CC=C1 SVABQOITNJTVNJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- BCJVBDBJSMFBRW-UHFFFAOYSA-N 4-diphenylphosphanylbutyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 BCJVBDBJSMFBRW-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims description 2
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical group C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001621 bismuth Chemical class 0.000 claims description 2
- 150000001661 cadmium Chemical class 0.000 claims description 2
- 150000001844 chromium Chemical class 0.000 claims description 2
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 claims description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 150000002751 molybdenum Chemical class 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 150000002940 palladium Chemical class 0.000 claims description 2
- 150000003057 platinum Chemical class 0.000 claims description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 2
- DMEUUKUNSVFYAA-UHFFFAOYSA-N trinaphthalen-1-ylphosphane Chemical compound C1=CC=C2C(P(C=3C4=CC=CC=C4C=CC=3)C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 DMEUUKUNSVFYAA-UHFFFAOYSA-N 0.000 claims description 2
- FQLSDFNKTNBQLC-UHFFFAOYSA-N tris(2,3,4,5,6-pentafluorophenyl)phosphane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1P(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F FQLSDFNKTNBQLC-UHFFFAOYSA-N 0.000 claims description 2
- LFNXCUNDYSYVJY-UHFFFAOYSA-N tris(3-methylphenyl)phosphane Chemical compound CC1=CC=CC(P(C=2C=C(C)C=CC=2)C=2C=C(C)C=CC=2)=C1 LFNXCUNDYSYVJY-UHFFFAOYSA-N 0.000 claims description 2
- UYUUAUOYLFIRJG-UHFFFAOYSA-N tris(4-methoxyphenyl)phosphane Chemical compound C1=CC(OC)=CC=C1P(C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 UYUUAUOYLFIRJG-UHFFFAOYSA-N 0.000 claims description 2
- DLQYXUGCCKQSRJ-UHFFFAOYSA-N tris(furan-2-yl)phosphane Chemical compound C1=COC(P(C=2OC=CC=2)C=2OC=CC=2)=C1 DLQYXUGCCKQSRJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003681 vanadium Chemical class 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 2
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 claims 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims 1
- 239000007983 Tris buffer Substances 0.000 claims 1
- 235000010290 biphenyl Nutrition 0.000 claims 1
- 239000004305 biphenyl Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- HDULBKVLSJEMGN-UHFFFAOYSA-N dicyclohexylphosphane Chemical compound C1CCCCC1PC1CCCCC1 HDULBKVLSJEMGN-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000001294 propane Substances 0.000 claims 1
- 150000003378 silver Chemical class 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 19
- 210000001787 dendrite Anatomy 0.000 abstract description 11
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 238000009713 electroplating Methods 0.000 abstract description 6
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 abstract description 3
- 150000001340 alkali metals Chemical class 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 239000011241 protective layer Substances 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 description 7
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 6
- 239000012266 salt solution Substances 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 239000010410 layer Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- YWNSEABNSURBNE-UHFFFAOYSA-N dicyclohexylphosphane;propane Chemical compound CCC.C1CCCCC1PC1CCCCC1 YWNSEABNSURBNE-UHFFFAOYSA-N 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- WSSMOXHYUFMBLS-UHFFFAOYSA-L iron dichloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Fe+2] WSSMOXHYUFMBLS-UHFFFAOYSA-L 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- -1 sodium metals Chemical class 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
本发明公布了一种金属有机膦框架玻璃涂层修饰的碱金属负极集流体及其制备方法，属于锂和钠金属二次电池技术领域，通过对集流体进行修饰来抑制锂金属和钠金属电池负极的枝晶生长，提高金属负极的库伦效率以及循环寿命。本发明将金属有机膦框架材料涂覆在集流体表面，通过简单的加热处理，框架材料在集流体表面发生熔融，在集流体表面形成均匀、连续、致密的金属有机膦框架玻璃涂层。金属有机膦框架玻璃涂层继承了前驱体的多孔结构，并且具有各向同性的特征，能够诱导碱金属离子均匀电镀，从而抑制了枝晶的生长。此外，金属有机膦框架玻璃涂层作为保护层，能够阻挡电极与电解液直接接触，避免电解液的过度消耗。
The invention discloses an alkali metal negative electrode current collector modified by a metal organic phosphine frame glass coating and a preparation method thereof, belonging to the technical field of lithium and sodium metal secondary batteries, and suppressing the lithium metal and sodium metal batteries by modifying the current collector The dendrite growth of the negative electrode improves the Coulombic efficiency and cycle life of the metal negative electrode. In the present invention, the metal organic phosphine frame material is coated on the surface of the current collector, and through simple heating treatment, the frame material is melted on the surface of the current collector, and a uniform, continuous and dense metal organic phosphine frame glass coating is formed on the surface of the current collector. The metal-organic phosphine framed glass coating inherits the porous structure of the precursor and possesses isotropic characteristics, which can induce uniform electroplating of alkali metal ions, thereby suppressing the growth of dendrites. In addition, the metal organic phosphine frame glass coating acts as a protective layer, which can block the direct contact between the electrode and the electrolyte and avoid excessive consumption of the electrolyte.
Description
Technical Field
The invention relates to the technical field of lithium and sodium metal secondary batteries, in particular to a metal negative current collector modified by a metal organic phosphine frame glass material coating and a preparation method thereof.
Background
With the development of portable electronic devices and electric vehicles, rechargeable batteries with high energy density are urgently required, and alkali metal batteries have received wide attention. Lithium metal cathodes and sodium metal cathodes have higher theoretical capacities, low redox potentials, making them the most ideal cathode materials for next generation energy storage systems. However, both lithium and sodium metal negative electrodes have very high reactivity and are easily reacted with an electrolyte to generate an unstable Solid Electrolyte (SEI) layer. The fragile SEI layer can cause uneven electroplating/stripping of lithium and sodium metals to form metal dendrites, the generation of the dendrites can cause the problems of low coulombic efficiency, dead lithium, dead sodium, capacity attenuation and the like, and the fragile SEI layer can also puncture a diaphragm to cause short circuit of a battery, thereby generating potential safety hazards. Dendrite growth has been the biggest challenge facing lithium and sodium metal negative electrodes, greatly impeding the commercial development of metal secondary batteries.
The current method for solving dendritic crystal growth mainly comprises the following steps: electrolyte optimization, solid electrolyte, artificial SEI layer, current collector and interface engineering and the like. The current collector and interface engineering is a method for directly modifying or modifying the surface of the existing commercial copper or aluminum current collector by using coatings of lithium and sodium-philic organic molecules, metal particles, inorganic ceramics and the like, so as to improve the surface affinity of the current collector. The method has the advantages of simplicity, effectiveness and easy commercial application. The modified current collector is suitable for uniform electroplating/stripping of lithium and sodium, realizes a stable alkali metal cathode structure, can control the electroplating amount of the lithium and sodium metal, and plays a role in saving lithium and sodium metal resources to a certain extent. However, it is a technical difficulty how to design a continuous modified coating on the surface of the current collector, which is easy to induce uniform electroplating of alkali metal ions.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a current collector modified by a metal organic phosphine frame glass coating and a preparation method thereof. The metal organic phosphine frame glass coating enhances the affinity of the current collector to lithium and sodium, inhibits the growth of lithium and sodium metal dendrites, and improves the coulombic efficiency and the cycle life. The preparation method specifically comprises the following steps:
the method comprises the following steps: weighing the organic phosphine ligand and the metal salt according to the molar ratio of 1: 0.1-1: 5, dissolving the organic phosphine ligand and the metal salt in a solvent, mixing the two solutions at room temperature for coordination reaction, filtering or centrifuging after reacting for 0-48 hours, washing unreacted raw materials by using the solvent, and drying to obtain the metal organic phosphine framework material.
Step two: and (3) uniformly coating the metal organic phosphine frame material obtained in the step one on the surface of a current collector, then heating the coated current collector to 100-600 ℃ in an inert atmosphere, preserving heat for 0-5 hours, and naturally cooling to room temperature to obtain the metal organic phosphine frame glass modified current collector.
The further preferable scheme of the invention is as follows:
in the first step, the selected metal salt is one of cobalt salt, copper salt, iron salt, nickel salt, cadmium salt, tin salt, vanadium salt, molybdenum salt, bismuth salt, zinc salt, silver salt, chromium salt, manganese salt, palladium salt and platinum salt.
In the first step, the organic phosphine ligand is selected from 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1, 4-bis (diphenylphosphino) butane, 1,3, 5-triaza-7-phosphaadamantane, tri (p-tolyl) phosphine, tri (o-tolyl) phosphine, tri (m-tolyl) phosphine, diphenyl-2-pyridylphosphine, tricyclohexylphosphine, tris (pentafluorophenyl) phosphine, diphenylphosphine, (S) - (-) -2,2' -bis (diphenylphosphino) -1,1' -binaphthyl, 2-di-t-butylphosphine-2 ' - (N, N-dimethylamino) biphenyl, 2' -bis (diphenylphosphino) -1,1' -binaphthyl, 2-diphenylphosphine-6-methylpyridine, One of tris (4-methoxyphenyl) phosphine, phenyldichlorophosphine, 1, 3-bis (dicyclohexylphosphine) propane, tris (2-furyl) phosphine, and tris (1-naphthyl) phosphine.
In the first step, the selected solvent is one of acetone, ethanol, deionized water, methanol, ethylene glycol, dichloromethane, carbon tetrachloride and ammonia water.
In the second step, the selected current collector is a copper current collector or an aluminum current collector.
In the second step, the selected inert atmosphere is nitrogen or argon.
The method for modifying the current collector is applied to a battery system taking lithium metal or sodium metal as a negative electrode, and comprises the following steps: lithium metal batteries, sodium metal batteries, lithium sulfur batteries, sodium sulfur batteries, lithium air batteries, sodium air battery systems.
The invention has the advantages that (1) the metal organic phosphine frame material is used as a precursor, and is melted on the surface of the current collector through simple heating treatment and is changed into a glass state from a crystalline state, so that a uniform, continuous and compact metal organic phosphine frame glass coating is formed on the surface of the current collector. (2) The metal organic phosphine frame glass coating inherits the porous structure of the precursor, has isotropic glass state, can enhance the strength of an SEI film and induce alkali metal ions to be uniformly electroplated, so that the metal organic phosphine frame glass material is used as a protective layer to modify a copper current collector for a lithium metal cathode and a sodium metal cathode, can effectively improve the problems of dendrites and the like, can prevent the direct contact of an electrode and electrolyte to avoid the excessive consumption of the electrolyte, thereby improving the coulombic efficiency, and is easy to realize commercial application. (3) The metal organic phosphine frame glass material has the advantages of multiple used raw materials, low price, simple preparation process, direct coating on the surface of a current collector, and easy realization of large-scale production, and can form a uniform coating by melting.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of the melting change of a 1, 2-bis (diphenylphosphino) ethane/cobalt chloride framework material.
FIG. 2 is an X-ray diffraction pattern of 1, 2-bis (diphenylphosphino) ethane/cobalt chloride framework material and the resultant glass coating after melting.
FIG. 3 is SEM photographs of a copper current collector before and after melting of a 1, 2-bis (diphenylphosphino) ethane/cobalt chloride framework material to form a glass-modified copper current collector.
Fig. 4 is an SEM photograph of sodium metal plating on the surface of the copper current collector before and after modification.
FIG. 5 is a diagram showing the cycle efficiency of a battery assembled from a copper current collector modified with a metal organic phosphine frame glass coating and an unmodified copper current collector, wherein (a) is a current density of 1.0mA cm-2The surface current capacity is 1.0mA h cm-2Coulombic efficiency of the cell in (b) is a current density of 1.0mA cm-2The surface current capacity is 2.0mA h cm-2Coulombic efficiency of the cell in (c) is a current density of 2.0mA cm-2The surface current capacity is 2.0mA h cm-2Time symmetric battery charge and discharge curves.
Detailed Description
The invention is described in detail below with reference to the following figures and examples:
example 1
1) 5.0g of 1, 2-bis (diphenylphosphino) ethane was dissolved in 500mL of acetone, and 3.0g of cobalt chloride hexahydrate (CoCl)2·6H2O) is dissolved in 150mL of acetone, then a metal salt solution is added into an organic phosphine solution for coordination reaction, after 24 hours of reaction, the obtained coordination framework material is subjected to suction filtration and separation, and is washed three times by using acetone. And (3) placing the obtained product in a vacuum drying oven, and heating and drying at the temperature of 80 ℃ to obtain the metal organic phosphine framework material.
2) And (3) uniformly coating the sample obtained in the step on the surface of a copper current collector, heating to 300 ℃ at a heating rate of 1.0 ℃/min under the protection of nitrogen, and preserving heat for 2 h. And finally, naturally cooling to room temperature to obtain the copper current collector modified by the metal organic phosphine frame glass coating.
As shown in the figure 1 of a scanning electron microscope, the 1, 2-bis (diphenylphosphino) ethane/cobalt chloride framework material is melted through heat treatment and gradually melted from a micron-sized cuboid structure to form a glass coating. The transition of the sample from the crystalline state to the glassy material of amorphous structure can be seen as shown in the X-ray diffraction diagram of figure 2. As shown in the scanning electron micrograph of figure 3, the metal organic phosphine frame glass coating is uniformly coated on the surface of the copper current collector.
The copper current collector modified with the metal organic phosphine frame glass coating prepared in example 1 and the copper current collector without modification were used as sodium metal negative current collectors respectively for sodium electroplating behavior test. As shown in fig. 4, SEM images show that sodium metal is uniformly, smoothly and densely plated on the surface of the copper current collector modified by the metal organic phosphine frame glass coating, and no dendrite growth occurs, while sodium metal is not uniformly plated on the copper current collector without modification, and a large number of dendrites are formed. And assembling the copper current collector modified by the metal organic phosphine frame glass coating and the unmodified copper current collector into a battery for electrochemical test.As shown in FIG. 5, at a current density of 1.0mA cm-2The surface current capacity is 1.0mA h cm-2And a current density of 1.0mA cm-2The surface current capacity is 2.0mA h cm-2Under the condition, the modified copper current collector half-cell can stably circulate for more than 700 times, and the coulomb efficiency is kept at 99.8%. The modified electrode is assembled into a symmetrical battery with the current density of 2.0mA cm-2The surface current capacity is 2.0mA h cm-2Can be stably circulated for 3000 hours under the condition.
Example 2
The operation method is the same as that of the embodiment 1, except that the obtained copper current collector modified by the metal organic phosphorus frame glass coating is used for a lithium metal negative electrode current collector, so that the growth of lithium dendrite can be effectively inhibited.
Example 3
The operation method is the same as that of the embodiment 1, except that the sample is uniformly coated on the surface of the aluminum current collector, and the obtained aluminum current collector modified by the metal organic phosphine framework glass coating can effectively inhibit the growth of dendrites when used for lithium and sodium metal negative current collectors.
Example 4
1) 10.0g of 1,3, 5-triaza-7-phosphaadamantane was dissolved in 500ml of absolute ethanol, and 5.00g of copper nitrate trihydrate (Cu (NO)3)2·3H2O) is dissolved in 300ml of absolute ethyl alcohol, then a metal salt solution is added into an organic phosphine solution for coordination reaction, and after the reaction is carried out for 0.5 hour, the obtained coordination framework material is subjected to suction filtration and separation and is washed by the absolute ethyl alcohol. And heating and drying the obtained product in a vacuum drying oven at the temperature of 80 ℃ to prepare the 1,3, 5-triaza-7-phospha adamantane/copper nitrate framework material.
2) And then placing the sample on the surface of a copper current collector, heating to 150 ℃ at the heating rate of 2.0 ℃/min under the protection of nitrogen, and naturally cooling to room temperature to obtain the copper current collector modified by the 1,3, 5-triaza-7-phospha adamantane/copper nitrate frame glass coating.
Example 5
1) 10.0g of 1,3, 5-triaza-7-phosphaadamantane was dissolved in 500ml of absolute ethanol, and 3.4g of cobalt chloride hexahydrate (CoCl)2·6H2O) is dissolved in 250ml of absolute ethyl alcohol, then the metal salt solution is dripped into the organic phosphine solution for coordination reaction, after the reaction is carried out for 1 hour, the obtained coordination framework material is filtered and separated, and is washed by the absolute ethyl alcohol. And heating and drying the obtained product in a vacuum drying oven at the temperature of 80 ℃ to prepare the 1,3, 5-triaza-7-phospha adamantane/cobalt chloride framework material.
2) And then placing the sample on the surface of a copper current collector, heating to 200 ℃ at the heating rate of 1.0 ℃/min under the protection of nitrogen, and naturally cooling to room temperature to obtain the copper current collector modified by the 1,3, 5-triaza-7-phospha adamantane/cobalt chloride frame glass coating.
Example 6
1) 10.0g of 1, 3-bis (diphenylphosphino) propane was dissolved in 500mL of methanol, and 3.0g of iron chloride tetrahydrate (FeCl)2·4H2O) is dissolved in 200mL of methanol, then the metal salt solution is dripped into the organic phosphine solution for coordination reaction, and after the reaction is carried out for 0.5 hour, the obtained coordination framework material is filtered and separated, and is washed by methanol. And (3) drying the obtained product in an oven at the temperature of 80 ℃. Preparing the 1, 3-bis (diphenylphosphino) propane/ferrous chloride framework material.
2) And then placing the sample on the surface of a copper current collector, heating to 500 ℃ at the heating rate of 2.0 ℃/min in the nitrogen atmosphere, and naturally cooling to room temperature to obtain the copper current collector modified by the 1, 3-bis (diphenylphosphine) propane/ferrous chloride frame glass coating.
Example 7
1) 10.0g of 1, 3-bis (diphenylphosphino) propane was dissolved in 500mL of methanol, and 3.2g of nickel chloride hexahydrate (NiCl)2·6H2O) is dissolved in 200mL of methanol and is completely dissolved under the stirring speed of 400r/min, then the metal salt solution is dripped into the organic phosphine solution for coordination reaction, the obtained coordination framework material is filtered and separated after 24 hours of reaction, and the methanol is used for washing. And (3) drying the obtained product in an oven at the temperature of 60 ℃. Preparing the 1, 3-bis (diphenylphosphino) propane/nickel chloride framework material.
2) And then placing the sample on the surface of a copper current collector, heating to 450 ℃ at the heating rate of 0.5 ℃/min in the nitrogen atmosphere, and naturally cooling to room temperature to obtain the copper current collector modified by the 1, 3-bis (diphenylphosphine) propane/nickel chloride frame glass coating.
Example 8
1) 10.0g of diphenyl-2-pyridylphosphine were dissolved in 300mL of deionized water, and 3.5g of zinc chloride (ZnCl)2) Dissolving in 150mL deionized water, completely dissolving at the stirring speed of 300r/min, then slowly dropwise adding a metal salt solution into an organic phosphine solution for coordination reaction, carrying out suction filtration and separation on the obtained coordination framework material after reacting for 36 hours, and washing with deionized water. And (3) drying the obtained product in an oven at the temperature of 60 ℃ to prepare the diphenyl-2-pyridylphosphine/zinc chloride framework material.
2) And then placing the sample on the surface of a copper current collector, heating to 350 ℃ at the heating rate of 0.5 ℃/min in the nitrogen atmosphere, and naturally cooling to room temperature to obtain the copper current collector modified by the diphenyl-2-pyridylphosphine/zinc chloride frame glass coating.
While the preferred embodiments of the present invention have been illustrated and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
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