CN117175035A - Lithium metal negative electrode bipolar artificial SEI film and preparation method and application thereof - Google Patents
Lithium metal negative electrode bipolar artificial SEI film and preparation method and application thereof Download PDFInfo
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- CN117175035A CN117175035A CN202311366444.2A CN202311366444A CN117175035A CN 117175035 A CN117175035 A CN 117175035A CN 202311366444 A CN202311366444 A CN 202311366444A CN 117175035 A CN117175035 A CN 117175035A
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- sei film
- artificial sei
- lithium metal
- carbonate
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 120
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 229920006112 polar polymer Polymers 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 8
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 8
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 18
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 14
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 125000004386 diacrylate group Chemical group 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 3
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 3
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 3
- WFNRWYYJEFEINI-UHFFFAOYSA-N n-cyano-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NC#N WFNRWYYJEFEINI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 2
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 claims description 2
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 claims description 2
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 claims description 2
- VZFMQGNSZMDJOH-UHFFFAOYSA-N [C].C(OC1=CC=CC=C1)(OC1=CC=CC=C1)=O Chemical compound [C].C(OC1=CC=CC=C1)(OC1=CC=CC=C1)=O VZFMQGNSZMDJOH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 claims description 2
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 claims description 2
- PBWZKZYHONABLN-UHFFFAOYSA-M difluoroacetate Chemical compound [O-]C(=O)C(F)F PBWZKZYHONABLN-UHFFFAOYSA-M 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- ZBUXMZFLCYRTOB-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C.CNC(=O)C=C ZBUXMZFLCYRTOB-UHFFFAOYSA-N 0.000 claims description 2
- 238000000016 photochemical curing Methods 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- JFMGYULNQJPJCY-UHFFFAOYSA-N 4-(hydroxymethyl)-1,3-dioxolan-2-one Chemical compound OCC1COC(=O)O1 JFMGYULNQJPJCY-UHFFFAOYSA-N 0.000 claims 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 3
- DEAZEWBZYSWFCA-UHFFFAOYSA-N C(O)(=O)F.C(O)(=O)F.C(O)(=O)F.C=CC Chemical compound C(O)(=O)F.C(O)(=O)F.C(O)(=O)F.C=CC DEAZEWBZYSWFCA-UHFFFAOYSA-N 0.000 claims 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 claims 1
- 150000003385 sodium Chemical class 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 22
- 230000005012 migration Effects 0.000 abstract description 19
- 238000013508 migration Methods 0.000 abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 210000001787 dendrite Anatomy 0.000 abstract description 6
- 238000000151 deposition Methods 0.000 abstract description 6
- 230000008021 deposition Effects 0.000 abstract description 5
- 238000010923 batch production Methods 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 4
- 230000010287 polarization Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 150000001450 anions Chemical class 0.000 abstract description 2
- 238000004807 desolvation Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 239000007774 positive electrode material Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 8
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000001723 curing Methods 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000011245 gel electrolyte Substances 0.000 description 6
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000009791 electrochemical migration reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CRJXZTRTJWAKMU-UHFFFAOYSA-N 4,4,5-trifluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1(F)F CRJXZTRTJWAKMU-UHFFFAOYSA-N 0.000 description 1
- VIKNRUUWUXUZPY-UHFFFAOYSA-N 4,5-dihydroxypentane-1-sulfonic acid Chemical compound OCC(O)CCCS(O)(=O)=O VIKNRUUWUXUZPY-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000012353 t test Methods 0.000 description 1
- RBYFNZOIUUXJQD-UHFFFAOYSA-J tetralithium oxalate Chemical compound [Li+].[Li+].[Li+].[Li+].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O RBYFNZOIUUXJQD-UHFFFAOYSA-J 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
Classifications
-
- 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
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The artificial SEI film has high ion conductivity and high ion migration number, and contains bipolar functional groups, so that desolvation of lithium ions is promoted, and solvent-induced lithium negative electrode corrosion is reduced; but also can adsorb anions to improve the migration efficiency of lithium ions. The artificial SEI film can reduce concentration polarization of lithium ions, realize uniform deposition of lithium metal ions and inhibit generation of lithium metal dendrites. The artificial SEI film is a self-supporting film formed by mixing a polar polymer, a carbonic ester solvent, lithium salt, a polymer prepolymer and a photoinitiator and then in-situ curing. The artificial SEI film prepared by the method can effectively protect a lithium metal anode; the method has the advantages of simple preparation process, easy obtainment of raw materials by using conventional equipment, safety and no pollution, and is suitable for large-scale batch production. When the artificial SEI film is used for a lithium metal battery, the artificial SEI film can be matched with a high-voltage positive electrode material, and has good cycle performance.
Description
Technical Field
The invention relates to a bipolar artificial SEI film for a lithium metal negative electrode, a preparation method and application thereof, wherein the artificial SEI film is used for protecting a lithium metal negative electrode material in a lithium metal battery, and belongs to the technical field of metal lithium batteries.
Background
The metallic lithium has an ultra-high theoretical specific capacity (3860 mAhg -1 ) And extremely low oxidation-reduction potential (-3.040V vs. standard hydrogen electrode), is a high energy density metal lithium battery>500Wh Kg -1 ) The optimal material for the negative electrode. However, due to the high reactivity of metallic lithium with commercial carbonate-based electrolytes, a heterogeneous organic/inorganic solid electrolyte interface layer (SEI film) is formed. Regulating and controlling the interface of the metal lithium anode is an effective strategy for inhibiting the failure of the metal lithium anode, and comprises electrolyte modification and artificial SEI film construction. Among these, electrolyte modifications are mainly three modes: the high-concentration electrolyte regulates and controls components of the SEI film on the surface of lithium, and utilizes the additive to regulate and control uniform deposition of lithium ions and promote formation of stable SEI film on the surface of metal lithium. However, electrolyte additives, lithium salts, etc. are gradually consumed during the battery cycle, resulting in uneven surface structure and subsequent generation of SEI film components, which in turn causes uneven deposition of lithium and generation of lithium dendrites. Therefore, the exploration of the high-efficiency artificial SEI film which has uniform structure, good strength and toughness, high ion conduction and electronic insulation on the surface has important significance.
At present, an artificial SEI film method can effectively avoid uncontrollable lithium dendrite growth and regulate and control uniform diffusion of lithium ions. The task group Huang Yunhui of the university of Huazhong science and technology reports that the cationic polymer artificial SEI film has high ion migration number and can effectively improve the stable circulation (1 mA cm -2 700 h), the low ionic conductivity and unavoidable solvent corrosion of the artificial SEI film limit its further applications. The Li Hong subject group of the Proc of the academy of sciences in Adv. Mater.2021,33,2007428 reports that a photo-cured polymer artificial SEI film isolates the electrolyte from direct contact with metallic lithium, avoids the corrosion of the lithium negative electrode by solvents, does not effectively protect the metallic lithium negative electrode, and the stable circulation of a lithium-lithium symmetric battery in a carbonate electrolyte system for 700 hours (0.5 mA cm -2 ,1mA h cm -2 ). (Nano Energy 95 (2022) 106983) but the low ionic conductivity and ionic migration number of the artificial SEI film make the battery poor in cycling stability at high multiplying power, and still limit further application. The university of Qinghua Zhang Jiang and the university of Beijing university Huang Jiaqi report an organic-inorganic substanceThe composite artificial SEI film is a high ion migration number artificial SEI film (t) prepared from LLZTO inorganic particles and lithiated perfluorinated sulfonic acid resin Li+ =0.82). The composite protective layer is directly coated on the surface of a metal lithium electrode, can effectively inhibit the formation of lithium dendrites, but has low room-temperature ionic conductivity (3.0X10) -5 S cm -1 ) The application of the lithium metal battery in the lithium metal battery at room temperature is obviously reduced. (adv. Mater.2019, 1808392) therefore, it is desirable to provide a lithium metal negative electrode artificial SEI film material which can be widely applied to lithium secondary batteries, has both high ion conductivity and high ion migration number, can isolate solvents and stabilize the stripping/deposition process of lithium ions, and can inhibit the growth of lithium metal dendrites, thereby improving the safety performance and cycle performance of lithium metal batteries.
Disclosure of Invention
In view of the above, the present invention provides a lithium metal negative electrode bipolar artificial SEI film having both high ion conductivity and high ion migration number, a method of preparing the artificial SEI film, and a lithium metal battery preparation method thereof. The method has the advantages of simple process, easily available raw materials, safety and no pollution, and is suitable for large-scale batch production.
The second purpose of the invention is to provide a preparation method of the bipolar artificial SEI film of the lithium metal cathode; the method has the advantages of simple preparation process, easily available raw materials, safety and no pollution, and is suitable for large-scale batch production.
The invention further aims to provide a metal lithium battery, wherein the artificial SEI film of the metal lithium battery is the bipolar artificial SEI film of the lithium metal negative electrode.
In order to achieve the purpose of the invention, the following technical scheme is provided.
The bipolar artificial SEI film for the lithium metal negative electrode is prepared by uniformly mixing carbonate, a polar polymer, a polymer prepolymer, a photoinitiator and salt in a dark place, directly smearing the mixture on the surface of the lithium metal, and directly curing by ultraviolet light under a protective atmosphere; the shielding gas is inert gas or nitrogen.
The carbonate is at least one of ethylene carbonate, fluoroethylene carbonate, trifluoro ethylene carbonate, difluoro ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate, diphenyl carbonate carbon, butylene carbonate, dibutyl carbonate, tetra-butanol dicarbonate, glycerylenol difluoroacetate, glycerylenol trifluoroacetate and glycerylethyl sulfonate.
The polar polymer is more than one of polyacrylonitrile, polyvinyl alcohol, poly-N-cyano-methacrylamide and polyvinyl alcohol-beta-cyanoethyl ether.
The lithium salt is one or more of lithium perchlorate, lithium bis (fluorosulfonyl) amide, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium bisoxalato borate, lithium dioxaoxalato borate, lithium tetrafluoroborate, lithium phosphate and lithium difluorophosphate.
The polymer prepolymer is more than one of polyethylene glycol diacrylate, butyl acrylate, polyethylene glycol methyl ether methacrylate, ethoxylated trimethylolpropane triacrylate, trimethylolpropane triglycidyl ether, N, N-dimethyl bisacrylamide and N-cyano methacrylamide. Preferably, the number average molecular weight of the polymer prepolymer is 100 to 1000.
The photoinitiator is more than one of 2-hydroxy-2-methyl propiophenone, 2-dimethoxy-2-phenyl acetophenone, benzophenone peroxide, 2-hydroxy-2-methyl-1- [4- (2-hydroxy ethoxy) phenyl ] -1-acetone and bis (2, 4, 6-trimethyl benzoyl) -phenyl phosphine oxide. Among them, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone is commercially available, for example Irgacure 2529 manufactured by Ciba specialty Chemicals; bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide is commercially available, for example Irgacure 819 from Ciba specialty Chemicals.
Preferably, the mass ratio of the polar polymer, the carbonate solvent, the lithium salt, the polymer prepolymer and the photoinitiator is 1-10: 20-75: 1 to 15: 5-25: 0.01 to 0.5.
The invention discloses a preparation method of a bipolar artificial SEI film for a lithium metal negative electrode, which comprises the following steps:
(1) Uniformly mixing 1-10wt% of an artificial SEI film prepolymerization solvent, 20-75wt% of a carbonate solvent, 1-15wt% of lithium salt, 5-25wt% of a polymer prepolymer and 0.01-0.5wt% of a photoinitiator in a temperature range of 20-55 ℃ and in a dry inert atmosphere according to mass percent; (2) Under the protection of protective gas, in a nearly anhydrous and anaerobic environment, directly coating the mixture prepared in the step (1) on the surface of a lithium metal negative electrode by using a scraper; the thickness of the mixture coating is 0.1-10 mu m; and (3) irradiating and curing by an ultraviolet lamp to obtain the bipolar artificial SEI film for the lithium metal negative electrode.
Wherein the protective gas is inert gas or nitrogen, and the purity is more than or equal to 99%.
The mixture is preferably applied to a thickness of 0.1 μm to 10. Mu.m.
Preferably, the wavelength of the ultraviolet lamp is 365nm to 400nm.
Preferably, the ultraviolet lamp irradiates for 1 to 5 minutes for curing.
Advantageous effects
1. The invention provides a bipolar artificial SEI film of a lithium metal negative electrode, wherein a polar polymer is adopted as a component in electrolyte, and ionic conductivity is enhanced through a carbonate solvent and lithium salt; through the ion-dipole interaction between polar cyano (-C.ident.N) functional groups and anions and through the hydrogen bond interaction between alcoholic hydroxyl functional groups and carbonate solvent molecules, the desolvation of lithium ions is promoted, the migration capacity of lithium ions is improved, and the contact between free carbonate molecules and lithium negative electrodes is isolated. The introduction of the polymer prepolymer and the photoinitiator participates in and promotes the formation of a polymer derived SEI film organic layer on the surface of lithium metal through the interaction between the functional group and the lithium metal, so that the artificial SEI film is tightly attached to the surface of the lithium metal negative electrode, and a stable lithium metal negative electrode-artificial SEI film interface can be formed.
2. The bipolar artificial SEI film has high ionic conductivity and high ionic migration number, effectively prevents corrosion of free carbonate solvents, can stabilize the stripping/depositing process of metal lithium, inhibits lithium dendrite growth caused by lithium ion concentration polarization, and shows lower overpotential and long-term cycling stability in the constant current polarization process, thus obviously improving electrochemical performance and safety of a metal lithium battery.
3. The invention provides a preparation method of a bipolar artificial SEI film for a lithium metal negative electrode, which has the advantages of simple preparation process, easy obtainment of raw materials by using conventional equipment, safety and no pollution, no need of using organic solvents such as N, N-Dimethylformamide (DMF), acetonitrile and the like, and suitability for large-scale batch production.
Drawings
Fig. 1 is a scanning electron microscope image of a bipolar artificial SEI film of a lithium metal negative electrode prepared in example 1.
Fig. 2 is an ion migration number chart of a bipolar artificial SEI film for a lithium metal negative electrode prepared in example 1.
FIG. 3 shows a lithium-lithium symmetric battery using a bipolar artificial SEI film of a lithium metal anode prepared in example 1
5mA/cm 2 Constant current plating/stripping plot of current density.
Detailed Description
The present invention will be described in detail with reference to specific embodiments, and it should be noted that the following embodiments are for convenience of understanding the present invention, and are not intended to limit the scope of the present invention, and modifications made by those skilled in the art should fall within the scope of the present invention without departing from the basic concept of the present invention.
In the following examples:
the argon is argon with purity more than or equal to 99%.
A polar polymer network gel electrolyte prepared in the following examples was tested as follows:
(1) And observing the appearance of the bipolar artificial SEI film by adopting a scanning electron microscope.
Test instrument: hitachi S4800
(2) The test system is assembled by adopting the ion migration number of the bipolar artificial SEI film for testing the electrolyte by adopting the combination of alternating current impedance and steady-state currentBipolar artificial SEI film @ lithium metal @ electrolyte @ bipolar artificial SEI film @ lithium metal symmetric battery tested by linear voltammetry on CHI660E electrochemical workstation with impedance test frequency in the range of 0.1 Hz-10 5 Hz; the i-t test polarization voltage was 10mV.
Test instrument: CHI660E electrochemical workstation and Shanghai Chen Hua
(3) Electrochemical performance test
Assembling a lithium symmetrical battery: sequentially placing bipolar artificial SEI film@lithium metal, a diaphragm, electrolyte and bipolar artificial SEI film@lithium metal into a button battery shell with the model of 2025 in a glove box filled with argon with the purity of more than or equal to 99%, and compacting and fastening the two battery shells by using a tablet press to obtain a lithium-lithium symmetrical battery; and standing the assembled lithium battery at 30 ℃ for 48 hours, and then performing electrochemical performance test.
And carrying out deposition/stripping test of metallic lithium and sodium by adopting a LAND battery test system, wherein the constant current density is 5mA/cm < 2 >, and the deposition surface capacity is 1mAh/cm < 2 >.
Test instrument: land battery test System, model CT2001A, available from Wuhan Jinno electronics Inc.
Example 1:
the lithium anode bipolar artificial SEI film provided by the embodiment comprises 5wt% of polyvinyl alcohol-beta-cyanoethyl ether, 55wt% of ethylene carbonate, 15wt% of lithium bistrifluorosulfonimide, 25wt% of polyethylene glycol diacrylate (Mn=400) and 0.02wt% of 2-hydroxy-2-methyl propiophenone.
The preparation method comprises the following steps: in a glove box filled with argon, wherein H 2 O is less than 0.1ppm; o (O) 2 Less than 0.1ppm, adding 15wt% of lithium bistrifluorosulfonimide, 5wt% of polyvinyl alcohol-beta-cyanoethyl ether, 25wt% of polyethylene glycol diacrylate (Mn=400) and 0.02wt% of 2-hydroxy-2-methyl propiophenone into 55wt% of ethylene carbonate in sequence at the temperature of 55 ℃, fully stirring in the adding process to uniformly mix, and directly coating the mixture on the surface of a lithium metal negative electrode by using a scraper; the coating thickness is 5.0 mu m, the wavelength of an ultraviolet lamp is 365 nm-400 nm, and the bipolar artificial SEI film is obtained after irradiation for 5min for photo-curing.
A polar polymer network gel electrolyte prepared in this example was tested as follows:
(1) Observing the morphology of the lithium cathode bipolar artificial SEI film by adopting a scanning electron microscope
The thickness of the bipolar artificial SEI film of the lithium cathode is 3.7 mu m
(2) And testing the ion migration number measurement result of the lithium negative electrode bipolar artificial SEI film by adopting alternating current impedance-steady state current combination: the ion migration number of the lithium negative electrode bipolar artificial SEI film is 0.86, as shown in FIG. 2.
(3) Electrochemical performance test
Test results: lithium-lithium symmetrical battery at 10mA/cm 2 Current density and 2mAh/cm 2 At the surface capacity, the cycle was stabilized for 300h and no short circuit occurred, as shown in fig. 3.
Example 2:
the lithium anode bipolar artificial SEI film provided by the embodiment comprises 7wt% of a polyvinyl alcohol-beta-cyanoethyl ether and polyvinyl alcohol compound, 60wt% of fluoroethylene carbonate, 10wt% of lithium dioxalate borate, 23wt% of polyethylene glycol diacrylate (Mn=400) and 0.02wt% of a photoinitiator.
The preparation method comprises the following steps: in a glove box filled with argon, wherein H 2 O is less than 0.1ppm; o (O) 2 Less than 0.1ppm, sequentially adding 10wt% of lithium dioxalate, 7wt% of polyvinyl alcohol-beta-cyanoethyl ether and polyvinyl alcohol compound, 23wt% of polyethylene glycol diacrylate (Mn=500) and 0.02wt% of photoinitiator into 60wt% of fluoroethylene carbonate at the temperature of 55 ℃, fully stirring in the adding process to uniformly mix, and directly coating the mixture on the surface of a lithium metal negative electrode by using a scraper; the coating thickness of the mixture is 3.0 mu m, the wavelength of an ultraviolet lamp is 365 nm-400 nm, and the artificial SEI film of the lithium metal battery is obtained after light curing by irradiation for 5-15 min.
A polar polymer network gel electrolyte prepared in this example was tested as follows:
(1) Observing the morphology of the lithium cathode bipolar artificial SEI film by adopting a scanning electron microscope
The thickness of the bipolar artificial SEI film of the lithium cathode is 1.8 mu m
(2) And testing the ion migration number measurement result of the lithium negative electrode bipolar artificial SEI film by adopting alternating current impedance-steady state current combination: the ion migration number of the lithium anode bipolar artificial SEI film is 0.89.
(3) Electrochemical performance test
Test results: lithium-lithium symmetrical battery at 10mA/cm 2 Current density and 2mAh/cm 2 At the surface capacity, the cycle was stable for 500h and no short circuit occurred.
Example 3:
the lithium anode bipolar artificial SEI film provided by the embodiment comprises 1wt% of polyacrylonitrile and polyvinyl alcohol compound, 75wt% of methyl ethyl carbonate, 5wt% of lithium hexafluorophosphate, 19wt% of polyethylene glycol diacrylate and 0.02wt% of 2, 2-dimethoxy-2-phenylacetophenone.
The preparation method comprises the following steps of in a glove box filled with argon, wherein H 2 O is less than 0.1ppm; o (O) 2 Less than 0.1ppm, adding 5wt% of lithium hexafluorophosphate, 1wt% of polyacrylonitrile and polyvinyl alcohol compound, 19wt% of polyethylene glycol diacrylate and 0.02wt% of 2, 2-dimethoxy-2-phenylacetophenone into 75wt% of carbonate solvent at the temperature of 55 ℃, fully stirring in the adding process to uniformly mix, and directly coating the mixture on the surface of a lithium metal negative electrode by using a scraper; the mixture is coated with the thickness of 7.0 mu m, the wavelength of an ultraviolet lamp is 365 nm-400 nm, and the artificial SEI film of the lithium metal battery is obtained after light curing by irradiation for 5-15 min.
A polar polymer network gel electrolyte prepared in this example was tested as follows:
(1) Observing the morphology of the lithium cathode bipolar artificial SEI film by adopting a scanning electron microscope
The thickness of the bipolar artificial SEI film of the lithium cathode is 5.1 mu m
(2) And testing the ion migration number measurement result of the lithium negative electrode bipolar artificial SEI film by adopting alternating current impedance-steady state current combination: the ion migration number of the lithium anode bipolar artificial SEI film is 0.66.
(3) Electrochemical performance test
Test results: lithium-lithium symmetrical battery at 10mA/cm 2 Current density and 2mAh/cm 2 At the surface capacity, the cycle was stable for 300h and no short circuit occurred.
Example 4:
the bipolar artificial SEI film for the lithium cathode provided by the embodiment comprises 5wt% of polyvinyl alcohol-beta-cyanoethyl ether, 70wt% of fluoroethylene carbonate, 15wt% of lithium bistrifluorosulfonimide, 10wt% of polymer prepolymer and 0.02wt% of photoinitiator.
The preparation method comprises the following steps: in a glove box filled with argon, wherein H 2 O is less than 0.1ppm; o (O) 2 15wt% of lithium difluorophosphate, 5wt% of polar polymer, 10wt% of polymer prepolymer and 0.02% of photoinitiator are sequentially added into 70wt% of fluoroethylene carbonate at the temperature of 50 ℃, and fully stirred in the adding process to be uniformly mixed, and then the mixture is directly coated on the surface of a lithium metal negative electrode by a scraper; the mixture is coated with the thickness of 10 mu m, the wavelength of an ultraviolet lamp is 365 nm-400 nm, and the artificial SEI film of the lithium metal battery is obtained after light curing by irradiation for 5-15 min.
A polar polymer network gel electrolyte prepared in this example was tested as follows:
(1) Observing the morphology of the lithium cathode bipolar artificial SEI film by adopting a scanning electron microscope
The thickness of the bipolar artificial SEI film of the lithium cathode is 8.3 mu m
(2) And testing the ion migration number measurement result of the lithium negative electrode bipolar artificial SEI film by adopting alternating current impedance-steady state current combination: the ion migration number of the lithium anode bipolar artificial SEI film is 0.78.
(3) Electrochemical performance test
Test results: lithium-lithium symmetrical battery at 10mA/cm 2 Current density and 2mAh/cm 2 At the area capacity, the cycle was stable for 360h and no short circuit occurred.
Example 5:
the lithium anode bipolar artificial SEI film provided by the embodiment comprises 10wt% of poly N-cyano methacrylamide and polyvinyl alcohol compound, 55wt% of ethylene carbonate, 10wt% of lithium bis (fluorosulfonyl) amine, 25wt% of polymer prepolymer and 0.02wt% of photoinitiator (2-hydroxy-2-methyl propiophenone).
The preparation method comprises the following steps: in a glove box filled with argon, wherein H 2 O is less than 0.1ppm; o (O) 2 Less than 0.1ppm, adding 10wt% of lithium bis (fluorosulfonyl) amide, 10wt% of poly-N-cyanomethacrylamide and polyvinyl alcohol compound, 25wt% of polymer prepolymer and 0.05wt% of 2-hydroxy-2-methyl propiophenone into 55wt% of ethylene carbonate in sequence at the temperature of 50 ℃, fully stirring in the adding process to uniformly mix, and directly coating the mixture on the surface of a lithium metal negative electrode by using a scraper; the mixture is coated with the thickness of 1 mu m, the wavelength of an ultraviolet lamp is 365 nm-400 nm, and the artificial SEI film of the lithium metal battery is obtained after light curing by irradiation for 5-15 min.
A polar polymer network gel electrolyte prepared in this example was tested as follows:
(1) Observing the morphology of the lithium cathode bipolar artificial SEI film by adopting a scanning electron microscope
The thickness of the bipolar artificial SEI film of the lithium cathode is 0.3 mu m
(2) And testing the ion migration number measurement result of the lithium negative electrode bipolar artificial SEI film by adopting alternating current impedance-steady state current combination: the ion migration number of the lithium anode bipolar artificial SEI film is 0.83.
(3) Electrochemical performance test
Test results: lithium-lithium symmetrical battery at 10mA/cm 2 Current density and 2mAh/cm 2 At the surface capacity, the cycle was stable for 300h and no short circuit occurred.
Claims (9)
1. A lithium metal negative electrode bipolar artificial SEI film and a preparation method and application thereof are characterized in that the artificial SEI film comprises the following components: 1 to 10 weight percent of polar polymer, 20 to 75 weight percent of carbonate solvent, 1 to 15 weight percent of lithium (sodium/potassium) salt, 5 to 25 weight percent of polymer prepolymer and 0.01 to 0.5 weight percent of photoinitiator.
2. The lithium metal anode bipolar artificial SEI film according to claim 1, wherein at least one of the polar polymers: polyacrylonitrile, polyvinyl alcohol, poly-N-cyanomethacrylamide and polyvinyl alcohol- β -cyanoethyl ether.
3. The lithium metal anode bipolar artificial SEI film according to claim 1, wherein the carbonate solvent comprises at least one of: ethylene carbonate, fluoroethylene carbonate, propylene trifluorocarbonate, difluoroethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, dipropyl carbonate, diphenyl carbonate carbon, butylene carbonate, dibutyl carbonate, tetrabutol dicarbonate, glycerol carbonate alcohol difluoroacetate, glycerol carbonate alcohol trifluoroacetate, glycerol carbonate alcohol ethanesulfonate.
4. The lithium metal negative electrode bipolar artificial SEI film according to claim 1, wherein the lithium salt comprises at least one of: lithium perchlorate, lithium bis (fluorosulfonyl) amide, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium bis (oxalato) borate, lithium dioxaoxalato borate, lithium tetrafluoroborate, lithium phosphate, and lithium difluorophosphate.
5. The lithium metal anode bipolar artificial SEI film according to claim 1, wherein the polymer pre-polymer comprises at least one of: polyethylene glycol diacrylate, butyl acrylate, polyethylene glycol methyl ether methacrylate, ethoxylated trimethylolpropane triacrylate, trimethylolpropane triglycidyl ether, N, N-dimethyl bisacrylamide, N-cyanomethacrylamide.
6. The lithium metal negative electrode bipolar artificial SEI film according to claim 1, wherein the photoinitiator comprises at least one of: 2-hydroxy-2-methylpropionyl ketone, 2-dimethoxy-2-phenylacetophenone, benzophenone peroxide, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone and bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide.
7. A preparation method of a bipolar artificial SEI film for a lithium metal negative electrode is characterized by comprising the steps of uniformly mixing 1-10wt% of polar polymer, 20-75wt% of carbonate solvent, 1-15wt% of lithium salt, 5-25wt% of polymer prepolymer and 0.01-0.5wt% of photoinitiator in a dry inert atmosphere (or nitrogen) at a temperature range of 20-50 ℃.
8. The method for preparing the bipolar artificial SEI film for the lithium metal negative electrode, according to claim 7, is characterized in that: directly coating the surface of the lithium metal negative electrode by using a scraper; the thickness of the mixture coating is 0.1-10 mu m; the wavelength of the ultraviolet lamp is 365 nm-400 nm, and the artificial SEI film of the lithium metal battery is obtained after irradiation for 1 min-5 min for photo-curing.
9. A lithium metal battery, characterized in that the lithium metal battery comprises a lithium metal negative electrode, an artificial SEI bipolar artificial SEI film, an electrolyte, a separator and a positive electrode, wherein the artificial SEI film is the lithium metal negative electrode bipolar artificial SEI film according to any one of claims 1 to 6.
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