CN118054084B - Electrolyte additive, lithium metal battery electrolyte and lithium metal battery - Google Patents
Electrolyte additive, lithium metal battery electrolyte and lithium metal battery Download PDFInfo
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- CN118054084B CN118054084B CN202410447329.6A CN202410447329A CN118054084B CN 118054084 B CN118054084 B CN 118054084B CN 202410447329 A CN202410447329 A CN 202410447329A CN 118054084 B CN118054084 B CN 118054084B
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- vinyl ether
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 133
- 239000003792 electrolyte Substances 0.000 title claims abstract description 122
- 239000002000 Electrolyte additive Substances 0.000 title claims abstract description 64
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims abstract description 93
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 51
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003999 initiator Substances 0.000 claims abstract description 21
- 125000005843 halogen group Chemical group 0.000 claims abstract description 15
- 238000011065 in-situ storage Methods 0.000 claims abstract description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 30
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 27
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 21
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 14
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims description 9
- 159000000002 lithium salts Chemical class 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 6
- 239000012044 organic layer Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910000733 Li alloy Inorganic materials 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- 239000001989 lithium alloy Substances 0.000 claims description 4
- 239000007773 negative electrode material Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims 1
- ZJPPTKRSFKBZMD-UHFFFAOYSA-N [Li].FS(=N)F Chemical compound [Li].FS(=N)F ZJPPTKRSFKBZMD-UHFFFAOYSA-N 0.000 claims 1
- JJYJSKHTGGQVMD-UHFFFAOYSA-N [Li].[SH2]=N.FC(F)F.FC(F)F Chemical compound [Li].[SH2]=N.FC(F)F.FC(F)F JJYJSKHTGGQVMD-UHFFFAOYSA-N 0.000 claims 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 abstract description 41
- 150000002367 halogens Chemical class 0.000 abstract description 39
- 229910052731 fluorine Inorganic materials 0.000 abstract description 38
- 239000011737 fluorine Substances 0.000 abstract description 38
- 239000000460 chlorine Chemical group 0.000 abstract description 35
- 229910052801 chlorine Inorganic materials 0.000 abstract description 35
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract description 23
- 239000000654 additive Substances 0.000 abstract description 18
- 229910052751 metal Inorganic materials 0.000 abstract description 18
- 239000002184 metal Substances 0.000 abstract description 18
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 16
- 230000000996 additive effect Effects 0.000 abstract description 13
- 239000010410 layer Substances 0.000 abstract description 10
- 230000014759 maintenance of location Effects 0.000 abstract description 5
- 239000011241 protective layer Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 2
- 229920002554 vinyl polymer Polymers 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 74
- 238000002156 mixing Methods 0.000 description 27
- 239000000243 solution Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 23
- 239000000376 reactant Substances 0.000 description 20
- 239000003960 organic solvent Substances 0.000 description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 17
- 229910001416 lithium ion Inorganic materials 0.000 description 17
- 239000004743 Polypropylene Substances 0.000 description 16
- 239000010406 cathode material Substances 0.000 description 16
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 16
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 15
- 239000010405 anode material Substances 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 15
- 239000011888 foil Substances 0.000 description 15
- 239000000284 extract Substances 0.000 description 12
- 238000000605 extraction Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 210000001787 dendrite Anatomy 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229940021013 electrolyte solution Drugs 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 238000007614 solvation Methods 0.000 description 2
- TXHFHCPKVSDSIL-UHFFFAOYSA-N 1,3-dioxolan-2-one;4-methyl-1,3-dioxolan-2-one Chemical compound O=C1OCCO1.CC1COC(=O)O1 TXHFHCPKVSDSIL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses an electrolyte additive, lithium metal battery electrolyte and a lithium metal battery. The electrolyte additive comprises an azo initiator and halogen substituted vinyl ether, wherein the halogen substituted vinyl ether comprises one or more than two of fluorine substituted vinyl ether, chlorine substituted vinyl ether, fluorine and chlorine substituted vinyl ether. According to the invention, the functional groups are optimized by adjusting the types and the amounts of halogen on the halogen substituted vinyl ether branched chains, so that the prepared halogen substituted vinyl can be decomposed preferentially to generate an SEI film rich in inorganic components so as to stabilize the metal lithium anode; meanwhile, an azo initiator initiates halogen substituted vinyl ether monomer to polymerize in situ on a negative electrode to form an organic protective layer, and the double-layer SEI structure can effectively relieve reconstruction of an electrode/electrolyte interface. The electrolyte containing the additive is beneficial to improving the cycle performance and capacity retention rate of the high-voltage lithium metal battery and prolonging the cycle life.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to an electrolyte additive for a lithium metal battery, a lithium metal battery electrolyte and a lithium metal battery.
Background
The energy density of commercial lithium ion batteries based on graphite cathodes has approached its upper limit (350 Wh kg -1). In order to replace graphite cathode, lithium metal cathode is a bright cathode material with theoretical capacity as high as 3860 mAh.g -1, ten times as much as graphite capacity. Further, lithium metal has excellent characteristics such as the lowest standard electrode potential (minus 3.04V to the standard hydrogen electrode), and good electrical conductivity.
However, the lithium metal anode still has a plurality of problems, because of the difficulty in controlling the lithium ion deposition process, the high reactivity of the lithium metal can produce a fragile and unstable solid electrolyte membrane (SEI film) with the electrolyte, so that the growth of lithium dendrites can be caused, the loss of battery capacity and the expansion of battery volume can be caused, and the continuous growth of the lithium dendrites in the circulation process can finally pierce through a diaphragm, thereby causing the safety problems of battery short circuit and the like. Thus, the large-scale application of lithium metal batteries still faces serious challenges. The regulation and control of electrolyte components are important to the composition and structure regulation and control of SEI films and the inhibition of dendrite growth. The additive is one of the means for improving the performance of the electrolyte with high efficiency and simplicity, and the traditional electrolyte additive is gradually consumed along with continuous rupture of the SEI film, so that the battery performance is suddenly reduced, and therefore, the development of the electrolyte additive capable of stabilizing the SEI film of the lithium metal battery for a long time is imperative.
Disclosure of Invention
In order to solve all or part of the technical problems, the invention provides the following technical scheme:
One of the objects of the present invention is to provide an electrolyte additive for lithium metal batteries, which comprises an azo initiator and a halogen-substituted vinyl ether, wherein the halogen-substituted vinyl ether comprises one or a combination of more than two of fluorine-substituted vinyl ether, chlorine-substituted vinyl ether, fluorine and chlorine-substituted vinyl ether, and an azo initiator.
In the electrolyte additive, halogen substituted vinyl ether can be decomposed in preference to lithium salt and solvent in the electrolyte so as to form a stable solid electrolyte interface film rich in inorganic components on the surface of a negative electrode, and deposition of lithium ions can be homogenized; meanwhile, the azo initiator in the additive can initiate partial halogen substituted vinyl ether monomer to polymerize on the surface of the negative electrode in situ to form an organic protective layer, so that the reconstruction of an electrode/electrolyte interface can be relieved, and the direct contact area of metal lithium and electrolyte is reduced; the SEI film rich in inorganic components and the organic protective layer formed by in-situ polymerization form a double-layer SEI structure, and the double-layer SEI structure effectively improves uniform deposition of lithium ions at an interface, further inhibits growth of lithium dendrites, and effectively improves long cycle and high rate performance of a lithium metal battery.
In some embodiments, the halogen-substituted vinyl ether has a structure of formula i:
；
Wherein R 1、R2、R3 is independently selected from any one of-H, -F, and-Cl, and at least one of R 1、R2、R3 is selected from any one of-F and-Cl.
In some embodiments, the halogen-substituted vinyl ether comprises a combination of one or more of the following compounds:
。
Compared with a plurality of fluorine substituted vinyl ether compounds, the vinyl ether formed by substituting single fluorine and chlorine has stronger solvation effect due to strong electron-withdrawing effect and asymmetric structure, has stronger binding capacity with lithium ions, is preferentially reduced in the charge and discharge process, forms a more stable electrode/electrolyte interface, and has higher mechanical strength; compared with fluorine substitution, the intermediate phase formed by the vinyl ether substituted by chlorine has higher ionic conductivity; fluorine and chlorine co-substituted vinyl ethers are capable of balancing the difference between ionic conductance and interfacial strength.
In some embodiments, the azo initiator includes at least one of azobisisobutyronitrile, azobisisoheptonitrile, and dimethyl azobisisobutyrate.
In some embodiments, the azo initiator is 1-2wt% of the total electrolyte additive.
In some embodiments, the azo initiator induces at least part of halogen substituted vinyl ether to form an organic layer on the negative electrode of the lithium metal battery in situ, and the material of the organic layer has a structure shown in formula II:
；
Wherein R 1、R2、R3 is independently selected from any one of-H, -F, and-Cl, and at least one of R 1、R2、R3 is selected from any one of-F and-Cl.
In some embodiments, the method of preparing a halogen-substituted vinyl ether comprises: reacting halogen substituted ethanol with acetylene in the presence of a basic catalyst to obtain the halogen substituted vinyl ether, wherein the halogen substituted ethanol has a structure shown in a formula III:
；
Wherein R 1、R2、R3 is independently selected from any one of-H, -F, and-Cl, and at least one of R 1、R2、R3 is selected from any one of-F and-Cl.
In some embodiments, the molar ratio of the halogen substituted ethanol to the acetylene is (1-1.2): 1.
In some embodiments, the amount of the basic catalyst is 2 wt% -5% wt% of acetylene.
In some embodiments, the alkaline catalyst includes at least one of potassium hydroxide and soda lime, but is not limited thereto.
In some embodiments, the temperature of the reaction is 180 ℃ to 200 ℃.
In some embodiments, the reaction time is 8-10 h.
In some embodiments, the reaction is performed under a pressure of 3 MPa to 5 MPa.
In some embodiments, after the reaction is completed, the method further comprises filtering, extracting and distilling the reaction product.
Further, the extraction specifically includes: the extractant is anhydrous diethyl ether, the volume ratio of the extract to the diethyl ether is 1 (1-2), the mixture is vibrated in a separating funnel, and finally the mixture is kept stand for ten minutes for layering, and the upper layer solution is collected.
Further, the distillation specifically includes: and distilling the collected extraction solution at the normal pressure at the temperature of 40-60 ℃ to obtain the required halogen substituted vinyl ether electrolyte additive.
In one exemplary embodiment, the method of preparing includes: mixing halogen substituted ethanol with a structure shown in a formula III and acetylene with a formula IV in a certain proportion, starting to react under the action of an alkaline catalyst, and filtering, extracting and distilling a synthesized reaction product to obtain the halogen substituted vinyl ether for the lithium metal battery, wherein R 1、R2、R3 in the structure shown in the formula III is respectively and independently selected from any one of-H, -F and-Cl, and at least one of R 1、R2、R3 is selected from any one of-F and-Cl.
The second object of the invention is to provide the application of the electrolyte additive in any one of the above technical schemes in preparing lithium metal battery electrolyte or lithium metal battery.
It is a third object of the present invention to provide a lithium metal battery electrolyte comprising the electrolyte additive, lithium salt and solvent as described in any one of the above technical solutions.
The halogen substituted vinyl ether provided by the invention has the advantages that due to the structural asymmetry, the interaction between the halogen substituted vinyl ether and lithium ions can be enhanced by the strong electron-withdrawing-F, -Cl, so that the combination of solvent molecules, anions, additives and lithium ions is tighter, the halogen substituted vinyl ether can be reduced preferentially, and in-situ polymerization can be performed under the action of an initiator to form a stable double-layer SEI structure.
In some embodiments, the content of the electrolyte additive is 2-10wt% of the total mass of the electrolyte, if the content of the additive is too low, the effect is not obvious, a complete double-layer interface cannot be formed, if the content of the electrolyte is too high, the interface becomes thicker, the impedance is increased, and the deposition of lithium is affected.
In some embodiments, the lithium metal battery electrolyte comprises 10 wt% -18% wt% lithium salt, 80 wt% -90 wt% solvent, and the balance of the electrolyte additive.
In some embodiments, the lithium salt includes any one or a combination of two or more of lithium hexafluorophosphate, lithium difluorosulfonimide, lithium bistrifluoromethane sulfonimide, lithium tetrafluoroborate, lithium bisoxalato borate, and lithium difluorooxalato borate, but is not limited thereto.
In some embodiments, the solvent includes any one or a combination of two or more of ethylene carbonate propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, y-butyrolactone, methyl formate, methyl acetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether and diethylene glycol dimethyl ether, but is not limited thereto.
In some embodiments, the solvent for the lithium metal battery electrolyte is preferably an ether, because the electrolyte additive works better in ether electrolytes. Ethylene glycol dimethyl ether is particularly preferred because of its better compatibility with lithium metal.
The fourth object of the present invention is to provide a lithium metal battery, comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and the lithium metal battery electrolyte as defined in any one of the above technical solutions.
In some embodiments, the positive electrode includes a positive electrode active material including a material capable of storing and releasing lithium ions, and a positive electrode current collector.
Further, the positive electrode active material includes any one or a combination of two or more of lithium ion intercalation transition metal oxide having a layered structure, lithiated transition metal mixed oxide having a spinel structure, lithiated transition metal phosphate having an olivine structure, but is not limited thereto.
Further, the positive electrode active material includes any one or a combination of two or more of nickel cobalt lithium manganate, lithium cobaltate, lithium iron phosphate and sulfur carbon composite positive electrode, but is not limited thereto.
In some embodiments, the negative electrode includes a negative electrode active material including a material capable of storing and releasing lithium ions, and a negative electrode current collector.
Further, the negative active material includes any one or a combination of two or more of lithium, a lithium alloy, and a material capable of forming a lithium alloy, but is not limited thereto.
In some embodiments, the separator may include any one or a combination of two or more of polyvinylidene fluoride, polyethylene, polypropylene, and surface-modified composite separator, but is not limited thereto.
Compared with the prior art, the invention has at least the following beneficial effects:
Compared with the traditional electrolyte additive, the halogen substituted vinyl ether provided by the invention can be decomposed in preference to lithium salt and solvent in the electrolyte so as to form a stable electrolyte/electrode contact interface on the surface of the negative electrode, and meanwhile, as the asymmetry of the halogen substituted vinyl ether structure and-F, -Cl have strong electron-withdrawing property, the interaction between electrolyte components can be enhanced, a more compact and stable SEI film with low film-forming impedance is formed, so that lithium ion deposition is homogenized;
In addition, the azo initiator in the electrolyte additive provided by the invention can initiate partial halogen substituted vinyl ether to polymerize on the surface of the negative electrode in situ, and the formed organic layer can further reduce the direct contact area of metallic lithium and electrolyte;
The SEI film which is formed by decomposing halogen substituted vinyl ether and is rich in inorganic components and the organic protective layer which is formed by in-situ polymerization form a double-layer SEI structure, so that uniform deposition of lithium ions at an interface can be effectively improved, growth of lithium dendrites is further inhibited, and problems of serious side reactions of electrolyte and metal lithium and the like are effectively avoided, so that the cycle performance and the rate performance of a lithium metal battery are improved.
Detailed Description
The following detailed description of the present invention is provided in connection with specific embodiments so that those skilled in the art may better understand and practice the present invention. Specific functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed embodiment.
In view of the defects existing in the prior art, the inventor of the present invention has long-term research and a great deal of practice, and has proposed the technical scheme of the present invention, mainly by regulating and controlling the degree of halogen atom substitution and halogen type in the vinyl ether structure, the synthesized halogen substituted vinyl ether can be decomposed before the lithium salt and solvent in the electrolyte system; and is matched with azo initiator to be used as an additive of lithium metal battery electrolyte. The synthetic route and the reaction equation of the halogen substituted vinyl ether provided by the invention are as follows:
。
the technical scheme, the implementation process, the principle and the like are further explained as follows.
Example 1
Mixing halogen substituted ethanol with a structure shown in a formula (a-1) and acetylene according to a molar ratio of 1:1, adding potassium hydroxide as an alkaline catalyst, wherein the content of potassium hydroxide is 2wt% of that of acetylene to obtain a mixed reactant, reacting the mixed reactant with 8. 8 h under the conditions that the temperature is 185 ℃ and the pressure is 3.5 MPa, sequentially filtering, extracting and distilling the obtained product to obtain fluorine substituted vinyl ether, wherein an extracting agent adopted in the extraction is anhydrous diethyl ether, the volume ratio of an extract to diethyl ether is 1:1, oscillating in a separating funnel, mixing, standing for ten minutes for layering, collecting an upper solution, and distilling the collected extracting solution at the normal pressure at 40 ℃ to obtain the fluorine substituted vinyl ether:
。
the structural formula of the fluorine-substituted vinyl ether prepared in the embodiment is as follows:
。
The fluorine substituted vinyl ether and the azodiisobutyronitrile are adopted as electrolyte additives, and the content of the azodiisobutyronitrile is 1 weight percent of the total amount of the fluorine substituted vinyl ether and the azodiisobutyronitrile.
The electrolyte is prepared by adopting the electrolyte additive, and the electrolyte comprises the following components in percentage by weight: 10 wt% of lithium bis (fluorosulfonyl) imide, 85 wt% of ethylene glycol dimethyl ether (solvent) and the balance of the electrolyte additive.
The lithium metal battery is assembled by adopting the electrolyte, the anode material of the lithium metal battery is LiNi 0.8Co0.1Mn0.1O2, the cathode material of the lithium metal battery is metal lithium foil with the thickness of 100 mu m, the diaphragm is a PP diaphragm, the battery core is manufactured, the electrolyte of the embodiment is respectively injected, and the soft package battery of 3.8 Ah is manufactured through the steps of formation, capacity division and the like.
Example 2
Mixing halogen substituted ethanol with a structure shown in a formula (a-2) and acetylene according to a molar ratio of 1:1, adding potassium hydroxide as an alkaline catalyst, wherein the content of potassium hydroxide is 2wt% of that of acetylene to obtain a mixed reactant, reacting the mixed reactant with 8.5 h under the conditions that the temperature is 190 ℃ and the pressure is 3.5 MPa, sequentially filtering, extracting and distilling the obtained product to obtain fluorine substituted vinyl ether, wherein the extractant is anhydrous diethyl ether, the volume ratio of the extract to the diethyl ether is 1:1.2, oscillating in a separating funnel, mixing, standing for ten minutes for layering, collecting an upper solution, and distilling the collected extract solution at normal pressure at 40 ℃ to obtain the fluorine substituted vinyl ether:
。
the structural formula of the fluorine-substituted vinyl ether prepared in the embodiment is as follows:
。
The fluorine substituted vinyl ether and the azodiisobutyronitrile are adopted as electrolyte additives, and the content of the azodiisobutyronitrile is 2 weight percent of the total amount of the fluorine substituted vinyl ether and the azodiisobutyronitrile.
The electrolyte is prepared by adopting the electrolyte additive, and the electrolyte comprises the following components in percentage by weight: 10 wt% of lithium bis (fluorosulfonyl) imide, 85 wt% of ethylene glycol dimethyl ether (solvent) and the balance of the electrolyte additive.
The lithium metal battery is assembled by adopting the electrolyte, the anode material of the lithium metal battery is LiNi 0.8Co0.1Mn0.1O2, the cathode material of the lithium metal battery is metal lithium foil with the thickness of 100 mu m, the diaphragm is a PP diaphragm, the battery core is manufactured, the electrolyte of the embodiment is respectively injected, and the soft package battery of 3.8 Ah is manufactured through the steps of formation, capacity division and the like.
Example 3
Mixing halogen substituted ethanol with a structure shown in a formula (a-3) and acetylene according to a molar ratio of 1.1:1, adding potassium hydroxide as an alkaline catalyst, wherein the content of potassium hydroxide is 2 wt% of that of acetylene to obtain a mixed reactant, reacting the mixed reactant with 8.5 h under the conditions that the temperature is 190 ℃ and the pressure is 4.0 MPa, sequentially filtering, extracting and distilling the obtained product to obtain fluorine substituted vinyl ether, wherein an extracting agent adopted for extraction is anhydrous diethyl ether, the volume ratio of the extract to the diethyl ether is 1:1.5, oscillating in a separating funnel, mixing, finally standing for ten minutes for layering, collecting an upper solution, and distilling the collected extracting solution at 50 ℃ under normal pressure to obtain the fluorine substituted vinyl ether:
。
the structural formula of the fluorine-substituted vinyl ether prepared in the embodiment is as follows:
。
The fluorine substituted vinyl ether and the azodiisobutyronitrile are adopted as electrolyte additives, and the content of the azodiisobutyronitrile is 1.5 weight percent of the total amount of the fluorine substituted vinyl ether and the azodiisobutyronitrile.
The electrolyte is prepared by adopting the electrolyte additive, and the electrolyte comprises the following components in percentage by weight: 10 wt% of lithium bis (fluorosulfonyl) imide, 85 wt% of ethylene glycol dimethyl ether (solvent) and the balance of the electrolyte additive.
The lithium metal battery is assembled by adopting the electrolyte, the anode material of the lithium metal battery is LiNi 0.8Co0.1Mn0.1O2, the cathode material of the lithium metal battery is metal lithium foil with the thickness of 100 mu m, the diaphragm is a PP diaphragm, the battery core is manufactured, the electrolyte of the embodiment is respectively injected, and the soft package battery of 3.8 Ah is manufactured through the steps of formation, capacity division and the like.
Example 4
Mixing halogen substituted ethanol with a structure shown in a formula (a-4) and acetylene according to a molar ratio of 1.1:1, adding potassium hydroxide as an alkaline catalyst, wherein the content of potassium hydroxide is 3 wt% of that of acetylene to obtain a mixed reactant, reacting the mixed reactant with 9. 9 h under the conditions that the temperature is 190 ℃ and the pressure is 4.0 MPa, sequentially filtering, extracting and distilling the obtained product to obtain chlorine substituted vinyl ether, wherein the extracting agent adopted in the extraction is anhydrous diethyl ether, the volume ratio of the extract to the diethyl ether is 1:1.5, oscillating in a separating funnel, mixing, standing for ten minutes and layering, collecting an upper solution, and distilling the collected extracting solution at the normal pressure at 50 ℃ to obtain the required chlorine substituted vinyl ether:
。
The structural formula of the chloro-substituted vinyl ether prepared in the embodiment is as follows:
。
The chlorine substituted vinyl ether and the azodiisoheptonitrile are adopted as electrolyte additives, and the content of the azodiisoheptonitrile is 1.5 weight percent of the total amount of the chlorine substituted vinyl ether and the azodiisoheptonitrile.
The electrolyte is prepared by adopting the electrolyte additive, and the electrolyte comprises the following components in percentage by weight: 12 wt% of lithium bis (fluorosulfonyl) imide, 86 wt% of ethylene glycol dimethyl ether (solvent), and the balance of the electrolyte additive.
The lithium metal battery is assembled by adopting the electrolyte, the anode material of the lithium metal battery is LiNi 0.8Co0.1Mn0.1O2, the cathode material of the lithium metal battery is metal lithium foil with the thickness of 100 mu m, the diaphragm is a PP diaphragm, the battery core is manufactured, the electrolyte of the embodiment is respectively injected, and the soft package battery of 3.8 Ah is manufactured through the steps of formation, capacity division and the like.
Example 5
Mixing halogen substituted ethanol with a structure shown in a formula (a-5) and acetylene according to a molar ratio of 1.1:1, adding potassium hydroxide as an alkaline catalyst, wherein the content of potassium hydroxide is 3wt% of that of acetylene to obtain a mixed reactant, reacting the mixed reactant at a temperature of 190 ℃ and a pressure of 4.0 MPa for 10h, sequentially filtering, extracting and distilling the obtained product to obtain chlorine substituted vinyl ether, wherein the extracting agent adopted in the extraction is anhydrous diethyl ether, the volume ratio of the extract to the diethyl ether is 1:1.5, oscillating in a separating funnel, mixing, standing for ten minutes for layering, collecting an upper solution, and distilling the collected extracting solution at a normal pressure at 50 ℃ to obtain the required chlorine substituted vinyl ether:
。
The structural formula of the chloro-substituted vinyl ether prepared in the embodiment is as follows:
。
The chlorine substituted vinyl ether and the azodiisoheptonitrile are adopted as electrolyte additives, and the content of the azodiisoheptonitrile is 2 weight percent of the total amount of the chlorine substituted vinyl ether and the azodiisoheptonitrile.
The electrolyte is prepared by adopting the electrolyte additive, and the electrolyte comprises the following components in percentage by weight: 13 wt% of lithium bis (fluorosulfonyl) imide, 85 wt% of ethylene glycol dimethyl ether (solvent) and the balance of the electrolyte additive.
The lithium metal battery is assembled by adopting the electrolyte, the anode material of the lithium metal battery is LiNi 0.8Co0.1Mn0.1O2, the cathode material of the lithium metal battery is metal lithium foil with the thickness of 100 mu m, the diaphragm is a PP diaphragm, the battery core is manufactured, the electrolyte of the embodiment is respectively injected, and the soft package battery of 3.8 Ah is manufactured through the steps of formation, capacity division and the like.
Example 6
Mixing halogen substituted ethanol with a structure shown in a formula (a-6) and acetylene according to a molar ratio of 1.1:1, adding potassium hydroxide as an alkaline catalyst, wherein the content of potassium hydroxide is 4 wt% of that of acetylene to obtain a mixed reactant, reacting the mixed reactant at a temperature of 195 ℃ and a pressure of 4.0 MPa for 10 h, sequentially filtering, extracting and distilling the obtained product to obtain chlorine substituted vinyl ether, wherein the extracting agent adopted in the extraction is anhydrous diethyl ether, the volume ratio of the extract to the diethyl ether is 1:2, oscillating in a separating funnel, mixing, standing for ten minutes finally for layering, collecting an upper solution, and distilling the collected extracting solution at a constant pressure at 50 ℃ to obtain the required chlorine substituted vinyl ether:
。
The structural formula of the chloro-substituted vinyl ether prepared in the embodiment is as follows:
。
The chlorine substituted vinyl ether and the dimethyl azodiisobutyrate are adopted as electrolyte additives, and the content of the dimethyl azodiisobutyrate is 1 weight percent of the total amount of the two.
The electrolyte is prepared by adopting the electrolyte additive, and the electrolyte comprises the following components in percentage by weight: 10 wt% of lithium bis (fluorosulfonyl) imide, 80 wt% of ethylene glycol dimethyl ether (solvent) and the balance of the electrolyte additive.
The lithium metal battery is assembled by adopting the electrolyte, the anode material of the lithium metal battery is LiNi 0.8Co0.1Mn0.1O2, the cathode material of the lithium metal battery is metal lithium foil with the thickness of 100 mu m, the diaphragm is a PP diaphragm, the battery core is manufactured, the electrolyte of the embodiment is respectively injected, and the soft package battery of 3.8 Ah is manufactured through the steps of formation, capacity division and the like.
Example 7
Mixing halogen substituted ethanol with a structure shown in a formula (a-7) and acetylene according to a molar ratio of 1.1:1, adding potassium hydroxide as an alkaline catalyst, wherein the content of potassium hydroxide is 3 wt% of that of acetylene to obtain a mixed reactant, reacting the mixed reactant with 10. 10h under the conditions that the temperature is 195 ℃ and the pressure is 4.0 MPa, sequentially filtering, condensing, filtering, extracting and distilling the obtained product to obtain fluorine and chlorine substituted vinyl ether, wherein the extracting agent adopted in the extraction is anhydrous diethyl ether, the volume ratio of the extract to diethyl ether is 1:2, oscillating and mixing in a separating funnel, standing for ten minutes finally for layering, collecting an upper solution, and distilling the collected extracting solution at 50 ℃ under normal pressure to obtain the required fluorine and chlorine substituted vinyl ether:
。
The structural formula of the fluorine and chlorine substituted vinyl ether prepared in the embodiment is as follows:
。
The fluorine and chlorine substituted vinyl ether and the dimethyl azodiisobutyrate are adopted as electrolyte additives, and the content of the dimethyl azodiisobutyrate is 1.5 weight percent of the total amount of the two.
The electrolyte is prepared by adopting the electrolyte additive, and the electrolyte comprises the following components in percentage by weight: 10 wt% of lithium bis (fluorosulfonyl) imide, 80 wt% of ethylene glycol dimethyl ether (solvent) and the balance of the electrolyte additive.
The lithium metal battery is assembled by adopting the electrolyte, the anode material of the lithium metal battery is LiNi 0.8Co0.1Mn0.1O2, the cathode material of the lithium metal battery is metal lithium foil with the thickness of 100 mu m, the diaphragm is a PP diaphragm, the battery core is manufactured, the electrolyte of the embodiment is respectively injected, and the soft package battery of 3.8 Ah is manufactured through the steps of formation, capacity division and the like.
Example 8
Mixing halogen substituted ethanol with a structure shown in a formula (a-8) and acetylene according to a molar ratio of 1.1:1, adding potassium hydroxide as an alkaline catalyst, wherein the content of potassium hydroxide is 5wt% of acetylene to obtain a mixed reactant, reacting the mixed reactant at a temperature of 200 ℃ and a pressure of 4.0 MPa for 10h, sequentially filtering, extracting and distilling the obtained product to obtain fluorine and chlorine substituted vinyl ether, wherein an extracting agent adopted in the extraction is anhydrous diethyl ether, the volume ratio of the extract to the diethyl ether is 1:2, oscillating in a separating funnel, mixing, standing for ten minutes finally for layering, collecting an upper solution, and distilling the collected extracting solution at a normal pressure at 60 ℃ to obtain the required fluorine and chlorine substituted vinyl ether:
。
The structural formula of the fluorine and chlorine substituted vinyl ether prepared in the embodiment is as follows:
。
the fluorine and chlorine substituted vinyl ether and the dimethyl azodiisobutyrate are adopted as electrolyte additives, and the content of the dimethyl azodiisobutyrate is 1 weight percent of the total amount of the two.
The electrolyte is prepared by adopting the electrolyte additive, and the electrolyte comprises the following components in percentage by weight: 12 The electrolyte comprises, by weight, lithium bis (fluorosulfonyl imide), 82 wt% ethylene glycol dimethyl ether (solvent), and the balance of the electrolyte additive.
The lithium metal battery is assembled by adopting the electrolyte, the anode material of the lithium metal battery is LiNi 0.8Co0.1Mn0.1O2, the cathode material of the lithium metal battery is metal lithium foil with the thickness of 100 mu m, the diaphragm is a PP diaphragm, the battery core is manufactured, the electrolyte of the embodiment is respectively injected, and the soft package battery of 3.8 Ah is manufactured through the steps of formation, capacity division and the like.
Example 9
Mixing halogen substituted ethanol with a structure shown in a formula (a-9) and acetylene according to a molar ratio of 1.2:1, adding potassium hydroxide as an alkaline catalyst, wherein the content of potassium hydroxide is 5 wt% of that of acetylene to obtain a mixed reactant, reacting the mixed reactant at a temperature of 200 ℃ and a pressure of 5.0 MPa for 10 h, sequentially filtering, extracting and distilling the obtained product to obtain fluorine and chlorine substituted vinyl ether, wherein an extracting agent adopted in the extraction is anhydrous diethyl ether, the volume ratio of the extract to the diethyl ether is 1:2, oscillating and mixing in a separating funnel, standing for ten minutes finally for layering, collecting an upper solution, and distilling the collected extracting solution at a normal pressure at 60 ℃ to obtain the required fluorine and chlorine substituted vinyl ether:
。
The structural formula of the fluorine and chlorine substituted vinyl ether prepared in the embodiment is as follows:
。
the fluorine and chlorine substituted vinyl ether and the azodiisoheptonitrile are adopted as electrolyte additives, and the content of the azodiisoheptonitrile is 2 weight percent of the total amount of the fluorine and chlorine substituted vinyl ether and the azodiisoheptonitrile.
The electrolyte is prepared by adopting the electrolyte additive, and the electrolyte comprises the following components in percentage by weight: 10 wt% of lithium bis (fluorosulfonyl) imide, 85 wt% of ethylene glycol dimethyl ether (solvent) and the balance of the electrolyte additive.
The lithium metal battery is assembled by adopting the electrolyte, the anode material of the lithium metal battery is LiNi 0.8Co0.1Mn0.1O2, the cathode material of the lithium metal battery is metal lithium foil with the thickness of 100 mu m, the diaphragm is a PP diaphragm, the battery core is manufactured, the electrolyte of the embodiment is respectively injected, and the soft package battery of 3.8 Ah is manufactured through the steps of formation, capacity division and the like.
Example 10
Mixing halogen substituted ethanol with a structure shown in a formula (a-9) with acetylene according to a molar ratio of 1.2:1, adding soda lime serving as an alkaline catalyst, wherein the content of the soda lime is 5wt% of that of the acetylene to obtain a mixed reactant, reacting the mixed reactant at a temperature of 180 ℃ and a pressure of 5.0 MPa for 10h, sequentially filtering, extracting and distilling the obtained product to obtain fluorine and chlorine substituted vinyl ether, wherein an extracting agent adopted in the extraction is anhydrous diethyl ether, the volume ratio of the extract to the diethyl ether is 1:2, oscillating and mixing in a separating funnel, standing for ten minutes finally for layering, collecting an upper solution, and distilling the collected extraction solution at a normal pressure at a temperature of 60 ℃ to obtain the required fluorine and chlorine substituted vinyl ether;
The fluorine and chlorine substituted vinyl ether and the azodiisobutyronitrile are adopted as electrolyte additives, and the content of the azodiisobutyronitrile is 2 weight percent of the total amount of the fluorine and chlorine substituted vinyl ether and the azodiisobutyronitrile.
The electrolyte is prepared by adopting the electrolyte additive, and the electrolyte comprises the following components in percentage by weight: 10 wt% of lithium bis (fluorosulfonyl) imide, 85 wt% of ethylene glycol dimethyl ether (solvent) and the balance of the electrolyte additive.
The lithium metal battery is assembled by adopting the electrolyte, the anode material of the lithium metal battery is LiNi 0.8Co0.1Mn0.1O2, the cathode material of the lithium metal battery is metal lithium foil with the thickness of 100 mu m, the diaphragm is a PP diaphragm, the battery core is manufactured, the electrolyte of the embodiment is respectively injected, and the soft package battery of 3.8 Ah is manufactured through the steps of formation, capacity division and the like.
Example 11
The electrolyte is prepared by adopting the electrolyte additive in the embodiment 9, the weight percentage of lithium bis (fluorosulfonyl) imide is 10 percent based on the total weight of the electrolyte, the weight percentage of the electrolyte additive in the invention is 5 percent, the balance is organic solvent, and the organic solvent comprises ethylene carbonate and methyl ethyl carbonate according to the mass ratio of 3:7, mixing.
The lithium metal battery is assembled by adopting the electrolyte, the anode material of the lithium metal battery is LiNi 0.8Co0.1Mn0.1O2, the cathode material of the lithium metal battery is metal lithium foil with the thickness of 100 mu m, the diaphragm is a PP diaphragm, the battery core is manufactured, the electrolyte of the embodiment is respectively injected, and the soft package battery of 3.8 Ah is manufactured through the steps of formation, capacity division and the like.
Example 12
The electrolyte is prepared by adopting the electrolyte additive in the embodiment 9, the weight percentage of lithium hexafluorophosphate is 10 percent based on the total weight of the electrolyte, the weight percentage of the electrolyte additive in the invention is 5 percent, and the balance is organic solvent, wherein the organic solvent comprises propylene carbonate and dimethyl carbonate according to the mass ratio of 3:7, mixing.
The lithium metal battery is assembled by adopting the electrolyte, the anode material of the lithium metal battery is LiNi 0.8Co0.1Mn0.1O2, the cathode material of the lithium metal battery is metal lithium foil with the thickness of 100 mu m, the diaphragm is a PP diaphragm, the battery core is manufactured, the electrolyte of the embodiment is respectively injected, and the soft package battery of 3.8 Ah is manufactured through the steps of formation, capacity division and the like.
Example 13
The electrolyte is prepared by adopting the electrolyte additive in the embodiment 9, the weight percentage of the lithium bistrifluoromethane sulfonyl imide is 12 percent based on the total weight of the electrolyte, the weight percentage of the electrolyte additive in the invention is 5 percent, and the balance is organic solvent, wherein the organic solvent comprises diethyl carbonate and methyl propyl carbonate according to the mass ratio of 3:7, mixing.
The lithium metal battery is assembled by adopting the electrolyte, the anode material of the lithium metal battery is LiNi 0.8Co0.1Mn0.1O2, the cathode material of the lithium metal battery is metal lithium foil with the thickness of 100 mu m, the diaphragm is a PP diaphragm, the battery core is manufactured, the electrolyte of the embodiment is respectively injected, and the soft package battery of 3.8 Ah is manufactured through the steps of formation, capacity division and the like.
Example 14
The electrolyte is prepared by adopting the electrolyte additive in the embodiment 9, the weight percentage of lithium tetrafluoroborate is 15 percent based on the total weight of the electrolyte, the weight percentage of the electrolyte additive in the invention is 5 percent, and the balance is organic solvent, wherein the organic solvent comprises y-butyrolactone and methyl formate according to the mass ratio of 3:7, mixing.
The lithium metal battery is assembled by adopting the electrolyte, the anode material of the lithium metal battery is LiNi 0.8Co0.1Mn0.1O2, the cathode material of the lithium metal battery is metal lithium foil with the thickness of 100 mu m, the diaphragm is a PP diaphragm, the battery core is manufactured, the electrolyte of the embodiment is respectively injected, and the soft package battery of 3.8 Ah is manufactured through the steps of formation, capacity division and the like.
Example 15
The electrolyte is prepared by adopting the electrolyte additive in the embodiment 9, wherein the weight percentage of lithium bis (oxalato) borate is 5 percent, the weight percentage of lithium difluoro (oxalato) borate is 5 percent, the weight percentage of the electrolyte additive in the invention is 5 percent, and the balance is organic solvent, and the organic solvent is prepared from ethylene glycol diethyl ether and diethylene glycol dimethyl ether according to the mass ratio of 3:7, mixing.
The lithium metal battery is assembled by adopting the electrolyte, the anode material of the lithium metal battery is LiNi 0.8Co0.1Mn0.1O2, the cathode material of the lithium metal battery is metal lithium foil with the thickness of 100 mu m, the diaphragm is a PP diaphragm, the battery core is manufactured, the electrolyte of the embodiment is respectively injected, and the soft package battery of 3.8 Ah is manufactured through the steps of formation, capacity division and the like.
Comparative example 1
The composition of the electrolyte of this comparative example was: based on the total weight of the electrolyte, the weight percentage of lithium bis (fluorosulfonyl) imide is 10%, the weight percentage of lithium nitrate as an additive is 5%, and the balance is an organic solvent, wherein the organic solvent comprises ethylene carbonate and methyl ethyl carbonate according to the mass ratio of 3:7, mixing. The preparation method of the electrolyte comprises the following steps: and in a glove box filled with argon, weighing lithium bis (fluorosulfonyl) imide, dissolving in the organic solvent, adding the additive lithium nitrate, and uniformly stirring to obtain the lithium metal battery electrolyte.
The same positive electrode, negative electrode and separator as in example 1 were used with the electrolyte of this comparative example, and the battery was assembled in the same manner, to obtain a flexible battery of 3.8 Ah.
Comparative example 2
The composition of the electrolyte of this comparative example was: based on the total weight of the electrolyte, the weight percentage of lithium bis (fluorosulfonyl) imide is 10%, the weight percentage of lithium nitrate as an additive is 5%, and the balance is an organic solvent, wherein the organic solvent is ethylene glycol dimethyl ether. The preparation method of the electrolyte comprises the following steps: and in a glove box filled with argon, weighing lithium bis (fluorosulfonyl) imide, dissolving in the organic solvent, adding the additive lithium nitrate, and uniformly stirring to obtain the lithium metal battery electrolyte.
The same positive electrode, negative electrode and separator as in example 1 were used with the electrolyte of this comparative example, and the battery was assembled in the same manner, to obtain a flexible battery of 3.8 Ah.
Comparative example 3
The composition of the electrolyte of this comparative example was: based on the total weight of the electrolyte, the weight percentage of lithium bis (fluorosulfonyl) imide is 10%, the weight percentage of fluoroethylene carbonate as an additive is 5%, and the balance is an organic solvent, wherein the organic solvent is ethylene glycol dimethyl ether. The preparation method of the electrolyte comprises the following steps: and in a glove box filled with argon, weighing lithium bis (fluorosulfonyl) imide, dissolving in the organic solvent, adding an additive fluoroethylene carbonate, and uniformly stirring to obtain the lithium metal battery electrolyte.
The same positive electrode, negative electrode and separator as in example 1 were used with the electrolyte of this comparative example, and the battery was assembled in the same manner, to obtain a flexible battery of 3.8 Ah.
Comparative example 4
The only difference from example 1 is that the additives in example 1 are replaced by the following compounds, the remainder being carried out in the same way as example 1:
。
comparative example 5
The only difference from example 1 is that the additives in example 1 are replaced by the following compounds, the remainder being carried out in the same way as example 1:
。
Comparative example 6
The difference from example 1 is that the additives in example 1 are replaced by the following compounds, the remainder being carried out in the same way as example 1:
。
Comparative example 7
Comparative example 7 was conducted in the same manner as in example 1 except that azobisisobutyronitrile was not contained in the electrolyte additive.
The electrolyte and the battery prepared in examples 1-11 and comparative examples 1-7 were subjected to performance test, and the test method is as follows:
The electrolyte solutions prepared in examples 1 to 11 and comparative examples 1 to 7 were taken, respectively, and the ionic conductivity of each electrolyte solution was measured by a conductivity meter, and the measurement data was recorded, and the results are shown in table 1.
The internal resistance of each battery was measured by an internal resistance meter using the soft pack batteries of 3.8 Ah prepared in examples 1 to 11 and comparative examples 1 to 7, and the measured data were recorded, and the results are shown in table 1.
The soft pack batteries of 3.8 Ah prepared in examples 1 to 11 and comparative examples 1 to 7 were cycled at room temperature according to a charge/discharge current of 0.2/0.5C, a test voltage range of 3 to 4.3V, and a cycle number at a recording capacity retention rate of 80% were recorded, and the results are shown in table 2.
The battery packs of 3.8 Ah prepared in examples 1 to 11 and comparative examples 1 to 7 were cycled for 5 cycles at room temperature according to charge and discharge currents of 0.2/0.2C, 0.2/0.5C, 0.2/1C, 0.2/3C and 0.2/5C, respectively, the test voltage ranges from 3 to 4.3V, and the capacity retention rate at 0.2/5C in charge and discharge was recorded, and the results are shown in table 2.
Table 1 results of ionic conductivity and cell impedance tests of the electrolytes of examples and comparative examples
Table 2 results of lithium metal battery performance test in examples, comparative examples
As can be seen from table 1, the halogen substituted vinyl ether composite additive provided by the invention does not affect the ionic conductivity of the electrolyte itself, has good compatibility with the electrolyte, and is an ester or ether electrolyte in the comparative example due to the strong reducibility of the lithium metal anode, which is continuously generated at the anode/electrolyte interface, and the continuous rupture of the SEI leads to the increase of the battery polarization impedance value by about 61.2mΩ; in the embodiments 1-15, the halogen substituted vinyl ether composite additive of the invention is used, so that the ionic conductivity of the electrolyte itself can be maintained, meanwhile, due to the fact that the halogenated ether is decomposed preferentially to generate SEI with high inorganic components, and the double-layer SEI constructed by the organic layers formed by in-situ polymerization under the action of the initiator can greatly reduce side reaction at the interface, interface impedance is obviously reduced, when the initiator is not present, the ionic conductivity of the electrolyte is not greatly influenced, but due to the fact that the generated single-layer SEI is easy to crack and recombine, impedance is far greater than that of the scheme in which the initiator is present; meanwhile, when different lithium salts and solvents are used, the optimization effect on the interface is obvious. In the structure of the halogen substituted vinyl, the halogen substituted vinyl ether has stronger solvation effect due to the strong electron-withdrawing effect and the asymmetric structure of single fluorine and chlorine, has stronger binding capacity with lithium ions, is preferentially reduced in the charge and discharge process, and forms a more stable electrode/electrolyte interface; in addition, examples 1, 4, and 7 exhibited smaller interfacial resistance and more excellent long cycle and rate performance due to the higher mechanical strength of the polymer protective layer formed by the strong polarity of fluorine and chlorine, whereas the polyfluoro-substituted vinyl ethers of comparative examples 4, 5, and 6 had a large steric hindrance due to the longer molecular structure and affected the transmission of lithium ions in the electrolyte, and the formed polymer had a large impedance and limited optimization effect on the interface.
As can be seen from table 2, by adjusting the types and amounts of halogen atoms, the electrolyte additive formed by the different series of halogen substituted vinyl ethers and azo initiators can be decomposed preferentially to form SEI rich in inorganic components, and can be polymerized in situ to form compact, stable and high mechanical strength double-layer SEI, so that side reactions between the electrolyte and electrode materials are greatly reduced, and the battery cycle is generally over 360 circles, and meanwhile, in a high-rate discharge performance test, the halogen substituted vinyl ether composite electrolyte has higher capacity retention rate (more than 80%) and cycle number, and has more excellent electrochemical performance than those of the esters and ethers without halogen substituted vinyl ether, the commonly used fluoro additives and the multi-fluoro substituted vinyl ether with different branched lengths.
In conclusion, the vinyl ether is substituted by halogen atoms with different degrees and numbers, and meanwhile, the initiator is matched, so that the prepared lithium metal electrolyte has good positive and negative stability, meanwhile, the stability of lithium ions at an electrode/electrolyte interface is improved, the cycle performance and capacity retention rate of the lithium metal battery under the condition of high multiplying power are improved, and the cycle life is prolonged. The action mechanism is as follows: the substitution of halogen element makes ether with stronger compatibility with lithium metal generate more stable electrolyte/electrode contact interface, so as to form a compact stable SEI film with higher inorganic component content and low film forming impedance, and the existence of initiator further optimizes SEI, so that interface with composite double-layer structure is formed, and the problems of serious side reaction of electrolyte and lithium metal and the like are effectively avoided. Meanwhile, the lithium metal electrolyte has good oxidation stability, and the transmission rate of lithium ions at an interface is enhanced.
The various aspects, embodiments, features and examples of the invention are to be considered in all respects as illustrative and not intended to limit the invention, the scope of which is defined solely by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
While the invention has been described with reference to an illustrative embodiment, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (12)
1. A lithium metal battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, the negative electrode comprising a negative electrode active material and a negative electrode current collector, the negative electrode active material comprising any one or a combination of two or more of lithium, a lithium alloy, and a material capable of forming a lithium alloy; the method is characterized in that: the electrolyte comprises lithium salt, a solvent and an electrolyte additive, wherein the content of the electrolyte additive is 2-10wt% of the total mass of the electrolyte;
the electrolyte additive comprises azo initiator and halogen substituted vinyl ether, wherein the content of the azo initiator is 1-2wt% of the total amount of the electrolyte additive;
wherein the halogen substituted vinyl ether has a structure shown in formula I:
；
Wherein R 1、R2、R3 is independently selected from any one of-H, -F, and-Cl, and at least one of R 1、R2、R3 is selected from any one of-F and-Cl.
2. The lithium metal battery of claim 1, wherein: the azo initiator comprises at least one of azodiisobutyronitrile, azodiisoheptonitrile and dimethyl azodiisobutyrate.
3. The lithium metal battery of claim 1, wherein: the halogen-substituted vinyl ethers include one or more of the following compounds:
。
4. The lithium metal battery of claim 1, wherein: the azo initiator induces part of halogen substituted vinyl ether to form an organic layer on a negative electrode of a lithium metal battery in situ, and the material of the organic layer has a structure shown in a formula II:
；
Wherein R 1、R2、R3 is independently selected from any one of-H, -F, and-Cl, and at least one of R 1、R2、R3 is selected from any one of-F and-Cl.
5. The lithium metal battery according to claim 1, wherein the method for preparing the halogen-substituted vinyl ether comprises: reacting halogen substituted ethanol with acetylene in the presence of a basic catalyst to obtain halogen substituted vinyl ether, wherein the halogen substituted ethanol has a structure shown in a formula III:
；
Wherein R 1、R2、R3 is independently selected from any one of-H, -F, and-Cl, and at least one of R 1、R2、R3 is selected from any one of-F and-Cl.
6. The lithium metal battery of claim 5, wherein: in the preparation method, the molar ratio of the halogen substituted ethanol to the acetylene is (1-1.2): 1.
7. The lithium metal battery of claim 5, wherein: the dosage of the alkaline catalyst is 2wt% -5% wt% of that of acetylene.
8. The lithium metal battery of claim 5, wherein: the alkaline catalyst comprises at least one of potassium hydroxide and caustic lime.
9. The lithium metal battery of claim 5, wherein: the temperature of the reaction is 180-200 ℃, the reaction time is 8-10 h, and the reaction is carried out under the pressure condition of 3-5 MPa.
10. The lithium metal battery of claim 5, wherein: after the reaction is finished, the method further comprises the steps of filtering, extracting and distilling the reaction product.
11. The lithium metal battery of claim 1, wherein: the lithium salt comprises one or more of lithium hexafluorophosphate, lithium difluorosulfimide, lithium bistrifluoromethane sulfimide, lithium tetrafluoroborate, lithium bisoxalato borate and lithium difluorooxalato borate.
12. The lithium metal battery of claim 1, wherein: the solvent comprises one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, y-butyrolactone, methyl formate, methyl acetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether and diethylene glycol dimethyl ether.
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