CN111137870B - Lithium difluorophosphate, preparation method thereof and lithium ion battery electrolyte - Google Patents
Lithium difluorophosphate, preparation method thereof and lithium ion battery electrolyte Download PDFInfo
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- CN111137870B CN111137870B CN201811313073.0A CN201811313073A CN111137870B CN 111137870 B CN111137870 B CN 111137870B CN 201811313073 A CN201811313073 A CN 201811313073A CN 111137870 B CN111137870 B CN 111137870B
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- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 title claims abstract description 69
- 239000003792 electrolyte Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 17
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 239000000376 reactant Substances 0.000 claims abstract description 21
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 16
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 150000002367 halogens Chemical class 0.000 claims abstract description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 7
- 125000003172 aldehyde group Chemical group 0.000 claims abstract description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- 125000001424 substituent group Chemical group 0.000 claims abstract description 6
- 125000000547 substituted alkyl group Chemical group 0.000 claims abstract description 6
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims abstract description 5
- 238000009835 boiling Methods 0.000 claims description 14
- 229910003002 lithium salt Inorganic materials 0.000 claims description 13
- 159000000002 lithium salts Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 9
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 8
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 claims description 8
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 8
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- 230000003287 optical effect Effects 0.000 claims description 6
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 4
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 4
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 4
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 4
- 229940090181 propyl acetate Drugs 0.000 claims description 4
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 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 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 23
- 239000000047 product Substances 0.000 description 34
- 238000012360 testing method Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002000 Electrolyte additive Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- HTWIZMNMTWYQRN-UHFFFAOYSA-N 2-methyl-1,3-dioxolane Chemical compound CC1OCCO1 HTWIZMNMTWYQRN-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910012258 LiPO Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- UZZWBUYVTBPQIV-UHFFFAOYSA-N dme dimethoxyethane Chemical compound COCCOC.COCCOC UZZWBUYVTBPQIV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000004334 fluoridation Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/455—Phosphates containing halogen
-
- 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
- H01M10/05—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
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/86—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- 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
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Abstract
The invention provides lithium difluorophosphate, a preparation method thereof and a lithium ion battery electrolyte. The preparation method of the lithium difluorophosphate provided by the invention comprises the following steps: a) reacting lithium hexafluorophosphate with a compound of formula (1) in a non-aqueous solvent to obtain a reactant; b) removing low-boiling-point components in the reactant to obtain lithium difluorophosphate; wherein R is1～R8Each independently selected from hydrogen, substituted or unsubstituted hydrocarbyl, halogen, nitro, amino or cyano; the alkyl is selected from C1-C10 alkyl; in the substituted alkyl, the substituent is selected from hydroxyl, amino, nitro, cyano, carboxyl, ether or aldehyde group. The lithium difluorophosphate prepared by the preparation method disclosed by the invention is high in purity and low in water content, is a high-quality lithium difluorophosphate product, is simple and feasible, is low in cost and high in yield, and can be used for conveniently and effectively obtaining the high-quality lithium difluorophosphate product.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to lithium difluorophosphate, a preparation method thereof and a lithium ion battery electrolyte.
Background
In recent years, the technology of lithium ion batteries has been greatly developed, and the proportion of lithium ion batteries in various small mobile electronic products, electric vehicles (hybrid vehicles), and energy storage devices has been increasing. Nevertheless, there is still a great potential to be exploited in lithium ion battery technology, especially in the field of electrolytes. At present, commercial electrolyte is difficult to match with the development of positive and negative electrode materials, and the development of high-performance electrolyte has important significance. The electrolyte additive is one of the key components of the electrolyte, is used as the core secret of electrolyte manufacturers, and has extremely high economic value and social effect.
Lithium difluorophosphate (LiPO)2F2) As an excellent electrolyte additive, the lithium ion battery electrolyte additive has the function of improving the cycle performance and the rate capability of the battery, and becomes an important additive of the lithium ion battery electrolyte. The lithium difluorophosphate has a large influence on the electrolyte, and if the impurity type is large and the impurity content is high, the performance of the electrolyte is influenced, and if the water content is high, the water content in the electrolyte is too high, side reactions occur, and the performance of the battery is influenced. Therefore, the preparation of high-quality lithium difluorophosphate is of great significance。
Currently, lithium difluorophosphate is mainly prepared by two ways: one is obtained by fluoridation of phosphoric acid or phosphoric acid derivatives, and the other is obtained by decomposition of hexafluorophosphate; the former is the addition of fluorine atoms to the starting materials and the latter is the removal of fluorine atoms from the starting materials. However, the two methods have the disadvantages of complex preparation process, severe conditions, high production cost, low efficiency, poor purity of the obtained product and incapability of large-scale production and application; moreover, the obtained product has high water content, and is easy to cause side reaction of the electrolyte, thereby seriously affecting the performance of the battery. If high-purity lithium difluorophosphate is to be obtained, the amounts of fluorine, oxygen, phosphorus and lithium and the like are strictly controlled, so that an effective controllable method is difficult to provide at present, and even if various materials and conditions in the preparation process are strictly controlled, a high-purity product is difficult to obtain; and the control of the water content of the product is also difficult. Therefore, how to simply and effectively prepare high-quality lithium difluorophosphate becomes an urgent problem to be solved.
Disclosure of Invention
In view of the above, the invention provides lithium difluorophosphate, a preparation method thereof and a lithium ion battery electrolyte. The preparation method provided by the invention is simple and feasible, has high yield, and the obtained lithium difluorophosphate has high purity, low water content, higher comprehensive quality and is convenient for large-scale production and application.
The invention provides a preparation method of lithium difluorophosphate, which comprises the following steps:
a) reacting lithium hexafluorophosphate with a compound of formula (1) in a non-aqueous solvent to obtain a reactant;
b) removing low-boiling-point components in the reactant to obtain lithium difluorophosphate;
wherein R is1～R8Each independently selected from hydrogen, substituted or unsubstituted hydrocarbyl, halogen, nitro, amino or cyano;
the alkyl is selected from C1-C10 alkyl;
in the substituted alkyl, the substituent is selected from hydroxyl, amino, nitro, cyano, carboxyl, ether or aldehyde group.
Preferably, in the formula (1), the hydrocarbon group is selected from the group consisting of-CH3、-CH2CH3、-CH＝CH2-C.ident.CH or-C6H5。
Preferably, the compound of formula (1) is selected from one or more of the following compounds and optical isomers thereof:
wherein, each X is independently selected from F, Cl, Br, I and NO3、NH2Or CN.
Preferably, the non-aqueous solvent is selected from one or more of ethylene carbonate, propylene carbonate, butylene carbonate, fluoroethylene carbonate, vinylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate, ethyl butyrate and propyl butyrate.
Preferably, the molar ratio of the lithium hexafluorophosphate to the compound of the formula (1) is 1 to (2-4);
the concentration of the lithium hexafluorophosphate in the non-aqueous solvent is 0.5-3 mol/L.
Preferably, the reaction temperature is 50-70 ℃ and the reaction time is 12-15 hours.
Preferably, the step b) further comprises crystallization after removing low boiling point components in the reactants.
The invention also provides lithium difluorophosphate prepared by the preparation method in the technical scheme.
The invention also provides a lithium ion battery electrolyte, which comprises: lithium salt, organic solvent and lithium difluorophosphate described in the above technical scheme.
Preferably, the lithium salt is selected from one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium bis (trifluoromethylsulfonyl) imide and lithium bis (fluorosulfonato) imide;
the concentration of the lithium salt in the organic solvent is 0.5-2M;
the concentration of the lithium difluorophosphate in the electrolyte is 0.1 to 1.5 weight percent
The invention provides a preparation method of lithium difluorophosphate, which comprises the following steps: a) reacting lithium hexafluorophosphate with a compound of formula (1) in a non-aqueous solvent to obtain a reactant; b) removing low-boiling-point components in the reactant to obtain lithium difluorophosphate; wherein R is1～R8Each independently selected from hydrogen, substituted or unsubstituted hydrocarbyl, halogen, nitro, amino or cyano; the alkyl is selected from C1-C10 alkyl; in the substituted alkyl, the substituent is selected from hydroxyl, amino, nitro, cyano, carboxyl, ether or aldehyde group. Lithium hexafluorophosphate and a compound of a formula (1) with a specific structure react in a non-aqueous solvent to generate a lithium difluorophosphate reactant, and low boiling point components are removed to obtain the lithium difluorophosphate. The lithium difluorophosphate prepared by the preparation method disclosed by the invention is high in purity and low in water content, is a high-quality lithium difluorophosphate product, is simple and feasible, is low in cost and high in yield, and can be used for conveniently and effectively obtaining the high-quality lithium difluorophosphate product.
The test result shows that the yield of the lithium difluorophosphate prepared by the preparation method is over 86 percent, the purity is over 96 percent, and the water content is below 138 ppm.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 shows the product obtained in example 131F-NMR spectrum.
Detailed Description
The invention provides a preparation method of lithium difluorophosphate, which comprises the following steps:
a) reacting lithium hexafluorophosphate with a compound of formula (1) in a non-aqueous solvent to obtain a reactant;
b) removing low-boiling-point components in the reactant to obtain lithium difluorophosphate;
wherein R is1～R8Each independently selected from hydrogen, substituted or unsubstituted hydrocarbyl, halogen, nitro, amino or cyano;
the alkyl is selected from C1-C10 alkyl;
in the substituted alkyl, the substituent is selected from hydroxyl, amino, nitro, cyano, carboxyl, ether or aldehyde group.
Lithium hexafluorophosphate and a compound of a formula (1) with a specific structure react in a non-aqueous solvent to generate a lithium difluorophosphate reactant, and low boiling point components are removed to obtain the lithium difluorophosphate. The lithium difluorophosphate prepared by the preparation method disclosed by the invention is high in purity and low in water content, is a high-quality lithium difluorophosphate product, is simple and feasible, is low in cost and high in yield, and can be used for conveniently and effectively obtaining the high-quality lithium difluorophosphate product.
According to the invention, lithium hexafluorophosphate and the compound of formula (1) are firstly reacted in a non-aqueous solvent to obtain a reactant.
In the present invention, the lithium hexafluorophosphate (i.e., LiPF)6) The source of (b) is not particularly limited, and may be a commercially available product. The concentration of the lithium hexafluorophosphate in the nonaqueous solvent is preferably 0.5 to 3mol/L, and more preferably 1 to 3 mol/L.
In the present invention, the compound of formula (1) is:
wherein R is1～R8Each independently selected from hydrogen, substituted or unsubstituted hydrocarbyl, halogen, nitro (i.e., NO)3) Amino (i.e. NH)2) Or cyano (i.e., CN).
In the present invention, the hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. When the alkyl group is a saturated alkyl group, the structure of the alkyl group is not particularly limited, and may be a chain structure, a ring structure, a cage structure, or a structure in which these structures are combined with each other. The chain structure may be a straight chain structure or a branched chain structure. In the cyclic structure or cage structure, the number of rings is not particularly limited, and when there are plural rings, these rings may be condensed. In the present invention, the hydrocarbon group is selected from the group consisting of C1-C10 hydrocarbon groups, preferably C1-C6 hydrocarbon groups, and more preferably-CH3、-CH2CH3、-CH＝CH2-C.ident.CH or-C6H5。
In the substituted alkyl, the substituent is selected from hydroxyl, amino, nitro, cyano, carboxyl, ether or aldehyde group. When R1 to R8 are each a hydrocarbon group or a substituted hydrocarbon group, these may be the same or different, as compared with any two or more of them.
The halogen is preferably F, Cl, Br or I.
In the present invention, preferably, the compound of formula (1) is selected from one or more of the following compounds and optical isomers thereof:
wherein, each X is independently selected from F, Cl, Br, I and NO3、NH2Or CN.
In each of the above formulae, the group not shown at the terminal is a methyl group (CH)3) Methylene (CH)2) Or methine (CH). In the present invention, the compound of formula (1) is selected from one or more of the compounds of the above formulae and their optical isomers, which means that when some of the compounds have asymmetric centers, the compound of formula (1) can be selected from its optical isomers. The invention is rightThe source of the compound of formula (1) is not particularly limited, and may be a general commercial product or obtained according to a preparation method well known to those skilled in the art.
More preferably, the compound of formula (1) is selected from one or more of the following compounds and optical isomers thereof:
in each of the above formulae, the group not shown at the terminal is a methyl group (CH)3) Or methylene (CH)2)。
According to the invention, the compound with a specific structure shown in the formula (1) reacts with lithium hexafluorophosphate, so that lithium difluorophosphate can be successfully generated, the yield of the method is high, and the obtained lithium difluorophosphate has high purity, low water content and higher comprehensive quality. In the prior art, a compound containing Si-O-Si with a specific structure is reacted with lithium hexafluorophosphate to prepare lithium difluorophosphate, and although lithium difluorophosphate with certain purity can be prepared by the scheme, the lithium difluorophosphate has high water content and is easy to generate side reaction, so that the performance of electrolyte is influenced, and further the performance of a battery is influenced. The method of the invention has the advantages of high yield, high purity, low water content of the obtained product and capability of obtaining lithium difluorophosphate with higher comprehensive performance.
In the present invention, the molar ratio of the lithium hexafluorophosphate to the compound of formula (1) is preferably 1: (2-4).
In the invention, the non-aqueous solvent is preferably one or more of ethylene carbonate, propylene carbonate, butylene carbonate, fluoroethylene carbonate, vinylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate, ethyl butyrate and propyl butyrate; more preferably one or more of dimethyl carbonate and ethyl methyl carbonate; most preferred is dimethyl carbonate. In the present invention, the source of the nonaqueous solvent is not particularly limited, and may be any commercially available product.
In the invention, the reaction temperature is preferably 50-70 ℃, and more preferably 60 ℃. The reaction time is preferably 12 to 15 hours, and more preferably 12 hours.
In the present invention, the reaction is preferably carried out in an inert gas atmosphere. The inert gas used in the present invention is not particularly limited, and may be any inert gas known to those skilled in the art.
The reaction pressure in the present invention is not particularly limited, and the reaction may be carried out under normal pressure.
Reacting lithium hexafluorophosphate with a compound of formula (1) in a non-aqueous solvent to obtain a reactant; most of the obtained reactants are lithium difluorophosphate, and the rest are impurities such as by-products with a boiling point lower than that of the compound of the formula (1), residual lithium hexafluorophosphate, solvents and the like. Specifically, the concentration of lithium difluorophosphate in the obtained reactant reaches 5X 10-3mol/L～1mol/L。
According to the present invention, after obtaining the reactant, low boiling point components in the reactant are removed to obtain lithium difluorophosphate.
In the present invention, the low boiling point component is mainly a by-product having a boiling point lower than that of the compound of formula (1), and may be removed by a method well known to those skilled in the art for removing low boiling point material. In some embodiments of the invention, the low boiling components are removed by distillation under reduced pressure; specifically, after the reaction, N can be introduced into the reaction kettle2Controlling the air pressure between-0.1 MPa and-0.2 MPa, evaporating low boiling point components, and absorbing by an absorption tower. After the treatment, the by-product is basically removed, and a high-purity lithium difluorophosphate product is obtained.
In the present invention, it is preferable to further perform crystallization after removing low boiling point components in the reaction product. Specifically, the product from which the low-boiling point components are removed is filtered, the filtered solid is dissolved in a solvent, and then cooled to room temperature for crystallization. In some embodiments of the invention, the solvent is diethyl ether.
In the present invention, after the crystallization, filtration is preferably further performed to obtain a solid product. In the present invention, it is preferable to further perform drying after obtaining the solid product. The drying conditions are not particularly limited, and the product can be dried. In some embodiments, the drying is performed under reduced pressure, specifically at a temperature of 80 ℃ and a pressure of-0.1 MPa for 6 hours, to obtain a white powder, i.e., a high-purity lithium difluorophosphate product.
The preparation method is simple and easy to implement, the yield is high, and the purity of the obtained product is high; in addition, the raw materials usually contain trace water, and moisture is easily introduced in the production operation, so that the water content of the product is higher, while the compound of the formula (1) is adopted for reaction, so that the water content is extremely low, and the low-water-content product is favorably obtained. Experimental results show that the lithium difluorophosphate prepared by the preparation method has the yield of over 86 percent, the purity of over 96 percent and the water content of below 138 ppm.
The invention also provides lithium difluorophosphate prepared by the preparation method in the technical scheme. The obtained lithium difluorophosphate has high purity and low water content, and can enable the electrolyte to show excellent electrochemical performance.
The invention also provides a lithium ion battery electrolyte, which comprises: lithium salt, organic solvent and lithium difluorophosphate described in the above technical scheme. The electrolyte provided by the invention takes the high-quality lithium difluorophosphate as an additive, and is matched with lithium salt and an organic solvent, so that the lithium ion battery shows excellent cycle performance.
In the invention, the lithium salt is preferably one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium bis (trifluoromethylsulfonyl) imide and lithium bis (fluorosulfonato) imide. In the present invention, the source of the lithium salt is not particularly limited, and may be any commercially available product.
In the invention, the organic solvent is preferably one or more of ethylene carbonate, propylene carbonate, butylene carbonate, fluoroethylene carbonate, vinylene carbonate, dimethyl carbonate, methylethyl carbonate, diethyl carbonate, methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate, ethyl butyrate, propyl butyrate, gamma-butyrolactone, delta-valerolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, 4-methyl-1, 3-dioxolane, 2-methyl-1, 3-dioxolane, dimethoxymethane, ethylene glycol dimethyl ether dimethoxyethane, diethylene glycol dimethyl ether, sulfolane and dimethyl sulfoxide. In the present invention, the source of the organic solvent is not particularly limited, and may be any commercially available product.
In the present invention, the concentration of the lithium salt in the organic solvent is preferably 0.5 to 2M.
In the invention, the lithium difluorophosphate is the lithium difluorophosphate in the technical scheme. The concentration of the lithium difluorophosphate in the electrolyte is preferably 0.1 wt% to 1.5 wt%. Compared with other low-purity and/or high-water-content lithium difluorophosphates, the lithium difluorophosphate provided by the invention is matched with the lithium salt and the organic solvent in a certain proportion, so that the cycle performance of the lithium ion battery can be obviously improved.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Examples 1 to 12
Dissolving lithium hexafluorophosphate in non-aqueous solvent dimethyl carbonate to prepare a solution with a certain molar concentration (1mol/L), putting the solution and the compound shown in the formula (1) into a reaction kettle in a certain proportion, and reacting for 12 hours at 60 ℃ in inert gas (helium gas) to obtain a reactant. Then, N is introduced into the reaction kettle2Treating at 80 deg.C and-0.1 MPa for 12 hr, evaporating low boiling point component, crystallizing, filtering, and drying at 80 deg.C under reduced pressure for 6 hr to obtain white powder, i.e. lithium difluorophosphate.
Specific substances and test conditions used in examples 1 to 12 are shown in table 1.
By using19F-NMR analyses were performed on the products obtained in examples 1 to 12, wherein NMR was performed using deuterated DMSO as a solvent and TMS as a standard. The results show that the product obtained is lithium difluorophosphate. Wherein, example 1 givesOf products19The F-NMR spectra are shown in FIG. 1, and FIG. 1 shows the product obtained in example 131F-NMR spectrum; it can be seen that the resulting product was lithium difluorophosphate with a purity of 99.5%.
The product yield was calculated from the products obtained in examples 1 to 12 and the input amount of raw materials, the purity of the product was measured by nuclear magnetic F spectroscopy, and the water content of the product was measured by a KLS701 trace moisture meter, and the results are shown in table 1.
TABLE 1 test conditions and test results for examples 1-12
According to the test results, the lithium difluorophosphate prepared by the preparation method disclosed by the invention is high in yield, high in purity, low in water content and high in quality.
Examples 13 to 14
The procedure is as in example 1 except that the non-aqueous solvent dimethyl carbonate is replaced by diethyl carbonate as in example 13.
The procedure is as in example 1 except that the nonaqueous solvent dimethyl carbonate is replaced by vinylene carbonate and is described as example 14.
The products obtained in examples 13 to 14 were tested for yield, purity and water content according to the test methods of example 1 and compared with example 1, with the results shown in Table 2.
Table 2 test conditions and test results of examples 13 to 14
In addition, the solvents in example 1 were each replaced with ethyl methyl carbonate. As a result, the yield, purity and water content of the product were comparable to those of example 1.
From the above test results, although examples 13 to 14 also showed good yield, purity and water content, the yield was significantly increased, the purity was also increased and the water content was significantly decreased in example 1, in comparison. Therefore, the quality of the lithium difluorophosphate product can be further improved by adopting the preferable solvent in the foregoing.
Examples 15 to 26, comparative example 1
Lithium salt, organic solvent and lithium difluorophosphate are prepared into electrolyte according to a certain proportion, and ternary high nickel material NCM622 (LiNi)0.6Co0.2Mn0.2O2) And Li is used as a positive electrode, Celgard PE is used as a counter electrode, and the button type half cell is assembled. And (3) carrying out cycle performance test on the obtained button half cell by adopting a LAND test system under the following test conditions: the charge and discharge test was carried out at a rate of 0.5C under a voltage of 3 to 4.4V.
The specific kinds, amounts, test effects, and the like of the substances used in examples 15 to 26 and comparative example 1 are shown in Table 3.
TABLE 3 test conditions and test results for examples 15 to 26 and comparative example 1
From the test results, the electrolyte provided by the invention can obviously improve the cycle performance of the lithium ion battery.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of lithium difluorophosphate is characterized by comprising the following steps:
a) reacting lithium hexafluorophosphate with a compound of formula (1) in a non-aqueous solvent to obtain a reactant;
b) removing low-boiling-point components in the reactant to obtain lithium difluorophosphate;
wherein R is1～R8Each independently selected from hydrogen, substituted or unsubstituted hydrocarbyl, halogen, nitro, amino or cyano;
the alkyl is selected from C1-C10 alkyl;
in the substituted alkyl, the substituent is selected from hydroxyl, amino, nitro, cyano, carboxyl, ether or aldehyde group.
2. The process according to claim 1, wherein the hydrocarbon group in the formula (1) is selected from the group consisting of-CH3、-CH2CH3、-CH＝CH2-C.ident.CH or-C6H5。
3. The process according to claim 1, wherein the compound of formula (1) is selected from one or more of the following compounds and optical isomers thereof:
wherein, each X is independently selected from F, Cl, Br, I and NO3、NH2Or CN.
4. The method according to claim 1, wherein the non-aqueous solvent is one or more selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, fluoroethylene carbonate, vinylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate, ethyl butyrate, and propyl butyrate.
5. The preparation method according to claim 1, wherein the molar ratio of the lithium hexafluorophosphate to the compound of formula (1) is 1: 2 to 4;
the concentration of the lithium hexafluorophosphate in the non-aqueous solvent is 0.5-3 mol/L.
6. The method according to claim 1, wherein the reaction is carried out at a temperature of 50 to 70 ℃ for 12 to 15 hours.
7. The method according to claim 1, wherein the step b) further comprises crystallization after removing low boiling components from the reactants.
8. Lithium difluorophosphate prepared by the preparation method of any one of claims 1 to 7.
9. A lithium ion battery electrolyte comprising: a lithium salt, an organic solvent and the lithium difluorophosphate of claim 8.
10. The electrolyte of claim 9, wherein the lithium salt is selected from one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium bis (trifluoromethylsulfonyl) imide, and lithium bis (fluorosulfonato) imide;
the concentration of the lithium salt in the organic solvent is 0.5-2M;
the concentration of the lithium difluorophosphate in the electrolyte is 0.1-1.5 wt%.
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