WO2018066896A2 - Procédé de préparation de difluorophosphate de lithium - Google Patents
Procédé de préparation de difluorophosphate de lithium Download PDFInfo
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- WO2018066896A2 WO2018066896A2 PCT/KR2017/010853 KR2017010853W WO2018066896A2 WO 2018066896 A2 WO2018066896 A2 WO 2018066896A2 KR 2017010853 W KR2017010853 W KR 2017010853W WO 2018066896 A2 WO2018066896 A2 WO 2018066896A2
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- WIPO (PCT)
- Prior art keywords
- lithium
- lithium difluorophosphate
- formula
- mixture
- difluorophosphate
- Prior art date
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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 80
- 238000000034 method Methods 0.000 title claims abstract description 35
- -1 silyl halide Chemical class 0.000 claims abstract description 106
- 239000000203 mixture Substances 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000000460 chlorine Substances 0.000 claims description 26
- 229910052801 chlorine Inorganic materials 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 4
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 claims description 4
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 150000001298 alcohols Chemical class 0.000 claims description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- QTZBTBLHYPSFMG-UHFFFAOYSA-N 5-chloro-3-methylpyridin-2-amine Chemical compound CC1=CC(Cl)=CN=C1N QTZBTBLHYPSFMG-UHFFFAOYSA-N 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 150000002170 ethers Chemical class 0.000 claims 1
- 239000000047 product Substances 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 13
- 238000002360 preparation method Methods 0.000 abstract description 10
- 239000007858 starting material Substances 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 4
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 4
- 159000000002 lithium salts Chemical class 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 3
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 34
- 150000003839 salts Chemical class 0.000 description 15
- 239000000843 powder Substances 0.000 description 14
- 239000005051 trimethylchlorosilane Substances 0.000 description 12
- 229910013870 LiPF 6 Inorganic materials 0.000 description 9
- 150000004820 halides Chemical class 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910012258 LiPO Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- CTIKAHQFRQTTAY-UHFFFAOYSA-N fluoro(trimethyl)silane Chemical compound C[Si](C)(C)F CTIKAHQFRQTTAY-UHFFFAOYSA-N 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- DGTVXEHQMSJRPE-UHFFFAOYSA-M difluorophosphinate Chemical compound [O-]P(F)(F)=O DGTVXEHQMSJRPE-UHFFFAOYSA-M 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 2
- 229910008284 Si—F Inorganic materials 0.000 description 2
- FXXACINHVKSMDR-UHFFFAOYSA-N acetyl bromide Chemical compound CC(Br)=O FXXACINHVKSMDR-UHFFFAOYSA-N 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- SXWUDUINABFBMK-UHFFFAOYSA-L dilithium;fluoro-dioxido-oxo-$l^{5}-phosphane Chemical compound [Li+].[Li+].[O-]P([O-])(F)=O SXWUDUINABFBMK-UHFFFAOYSA-L 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- XRRDNAZMVAXXQP-UHFFFAOYSA-N difluoro(dimethyl)silane Chemical compound C[Si](C)(F)F XRRDNAZMVAXXQP-UHFFFAOYSA-N 0.000 description 1
- RKLWISLCSWAWJI-UHFFFAOYSA-L dilithium;difluoride Chemical compound [Li+].[Li+].[F-].[F-] RKLWISLCSWAWJI-UHFFFAOYSA-L 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- 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
- C01B25/30—Alkali metal phosphates
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
Definitions
- the present invention relates to a method for producing lithium difluorophosphate, and more particularly, to produce lithium difluorophosphate, a lithium salt used in an electrolyte for a lithium secondary battery, in a high purity and high yield without a simple and economically dangerous process. And a method for producing lithium difluorophosphate.
- Table 1 shows a specification for sufficiently exhibiting the performance required in the battery as a material used as an electrolyte additive of a lithium secondary battery.
- MnXm in the scheme 1 is lithium chloride, lithium bromide, silicon tetrachloride, phosphorus trichloride, acetyl chloride, acetyl bromide, propionyl chloride, oxalyl chloride and the like.
- lithium difluorophosphate (LiPO 2 F 2 ) is prepared by reacting lithium hexafluorophosphate (LiPF 6 ) with water and a halogen compound as a starting material.
- lithium difluorophosphate should be free of impurities such as inorganic salts because lithium difluoride is used in the electrolyte.
- the method according to Scheme 2 is a method for producing lithium difluorophosphate by heating a variety of siloxane and lithium hexafluorophosphate in the absence of water.
- Lithium difluorophosphate manufacturing method has the advantage that does not generate acid gas and inorganic salts, but the price of siloxane is expensive and the reactivity is low, the reaction does not proceed at room temperature, and also to about 60 °C In the case of the heating reaction, insoluble impurities are generated in a large amount, which is not suitable for use as an electrolyte of a lithium secondary battery.
- An object of the present invention is to solve the problems of the prior art as described above, and to produce lithium difluorophosphate, which is a lithium salt used in an electrolyte for a lithium secondary battery, in a high purity and high yield without a simple and economically dangerous process, It is to provide a method for producing lithium difluorophosphate.
- the present invention comprises the steps of preparing a first mixture by mixing a lithium hexafluorophosphate and a solvent; Preparing a second mixture by adding water to the first mixture; Adding an organic silyl halide mixture to the second mixture, followed by stirring to react; It provides a method for producing lithium difluorophosphate comprising the step of heating the reaction product, depressurizing and then filtration to prepare a lithium difluorophosphate (lithium difluorophosphate) represented by the following formula (1).
- the present invention comprises the steps of reacting by adding water (H 2 O) and the organosylsilyl halide at the same time to the lithium hexafluorophosphate solution; Or it provides a method for producing lithium difluorophosphate represented by the following formula (1) comprising the step of adding water to the lithium hexafluoro phosphate solution and then organosyl halide to react sequentially.
- the method for producing lithium difluorophosphate according to the present invention is economical by using a mixture of organosilyl halides in place of the expensive siloxanes used in the conventional production of lithium difluorophosphate, and is a high-purity difluoro having a low content of various impurities. Lithium phosphate can be obtained, and there is an advantage of ensuring safety due to less corrosiveness during the process.
- the conventional manufacturing method has to remove impurities by an additional process due to the occurrence of unavoidable by-products, such as chloride or insoluble content, the present invention can produce a high yield and high purity lithium difluorophosphate without a special purification by a simple process There is an advantage.
- the inventors of the present invention can reduce the content of chloride impurities generated as a reaction by-product by sequentially adding water and organosilyl halide to the lithium hexafluorophosphate solution, thereby producing high yield and high purity lithium difluorophosphate. Revealed to complete the present invention.
- the present invention comprises the steps of preparing a first mixture by mixing a lithium hexafluorophosphate and a solvent; Preparing a second mixture by adding water to the first mixture; Adding an organic silyl halide mixture to the second mixture, followed by stirring to react; It provides a method for producing lithium difluorophosphate comprising the step of heating the reaction product, depressurizing and then filtration to prepare a lithium difluorophosphate (lithium difluorophosphate) represented by the following formula (1).
- lithium difluorophosphate of the present invention may be prepared as in Scheme 3 below.
- the method for preparing lithium difluorophosphate according to the present invention is made by using lithium hexafluorophosphate (LiPF 6 ) as a starting material and reacting with water and organosilyl halides in an appropriate ratio and order. Lithium phosphate can be prepared.
- LiPF 6 lithium hexafluorophosphate
- the organosilyl halide mixture may be a mixture of organosilyl halides represented by Formulas 2 and 3 below, but is not limited thereto.
- R 1 to R 5 are the same as or different from each other, C 1 to C 10 straight or branched alkyl, C 2 to C 10 straight or branched alkenyl or aryl,
- X 1 to X 3 are the same as or different from each other, and are chlorine (Cl), bromine (Br), or iodine (I).
- R 1 to R 5 may be any one selected from the group consisting of methyl, ethyl, propyl, and vinyl, but is not limited thereto.
- the organosilyl halide represented by Formula 2 is preferably trimethylsilyl chloride
- the organosilyl halide represented by Formula 3 is preferably dimethylsilyl dichloride.
- Dimethylsilyl dichloride is cheaper than trimethylsilyl chloride and can use only 1/2 equivalent of trimethylsilyl chloride equivalent, which is economical when used in combination with trimethylsilyl chloride and dimethylsilyl dichloride. Excellent in terms of corrosiveness and degradability.
- the organosilyl halide mixture is an organic silyl halide represented by Formula 2 relative to lithium hexafluorophosphate in a ratio of 0.02 to 2.0 equivalents, and an organosilyl halide represented by Formula 3 relative to lithium hexafluorophosphate is 0.99 to 2.08. It may be an equivalent ratio, but is not limited thereto.
- the organosilyl halide is preferably added in an amount of 3.98 to 4.20 equivalents in a halide equivalent ratio of total organosilyl halide to lithium hexafluorophosphate.
- the organosilyl halide represented by Formula 2 is 1 mol per mol of lithium hexafluorophosphate
- the organosilyl halide represented by Formula 3 reacts with 2 mol per mol of lithium hexafluorophosphate.
- Low Phosphate It is desirable to adjust between 3.98 and 4.20 equivalent ratios in total.
- the organosilyl halide represented by lithium hexafluoro phosphate reacts directly and there is a problem that impurities contaminated with lithium monofluoromonophosphate are generated.
- the amount of Cl impurity including the same should be 100 ppm or less, preferably 20 ppm or less, but depending on the conditions, there are problems ranging from several thousand ppm to several hundred ppm in lithium difluorophosphate.
- organosilyl halide represented by Formula 3 can be suppressed to some extent by using the organosilyl halide represented by Formula 3 to solve the above problem.
- organosilyl halide represented by Formula 3 since C 1 to C 10 linear or branched alkyl, C 2 to C 10 linear or branched alkenyl or aryl groups in the intramolecular silicon, This is because the number of the organosilyl halides represented by the general formula (3) is smaller than that of the organosilyl halide.
- there are two halogen atoms it is more difficult for the halogen elements to be released as anions in the molecule.
- halogen anions may be released and react with lithium hexafluorophosphate to significantly reduce the probability of producing halogen-bound impurities.
- organosilyl halide represented by the formula (3) when using the organosilyl halide represented by the formula (3) alone, in the presence of a small amount of water to form a siloxane oligomer to a lower polymer may also be a factor of lowering the purity because insoluble impurities are generated.
- dimethylsilyldichloride is used alone in the organosilyl halide represented by Formula 3, the yield of lithium difluorophosphate drops to 85.0% or less, and the purity falls to 99.0% or less, requiring an additional purification process. have.
- Such a phenomenon is because two halogens are attached to the organosilyl halide molecule represented by Chemical Formula 3 so that the oligomer or the polymer can be formed.
- the organosilyl halide represented by the formula (2) has only one halogen in the molecule, so that the reaction can proceed to the oligomer or the polymer, thus preventing the generation of impurities that lower the purity.
- the use of the organosilyl halide represented by the formula (2) and the organosilyl halide represented by the formula (3) is higher than that of using each alone, and the purity, Cl content, HF content, yield, and economic efficiency of lithium difluorophosphate are high. You can see the excellent.
- the equivalent ratio of the organosyl silyl halide represented by the formula (3) and the organosyl silyl halide represented by the formula (2) is 1: 2 to 1: 0.01, and considering the economic efficiency and purity, the optimum equivalent ratio is 1: It is preferable that it is 0.5-1: 0.02.
- the reacting may be performed by adding an organic silyl halide mixture to the second mixture, followed by stirring at 40 to 80 rpm and reaction at ⁇ 10 to 60 ° C., but is not limited thereto.
- reaction conditions such as said reaction temperature
- the upper limit of reaction temperature becomes like this.
- it is 60 degreeC, More preferably, it is 40 degrees C or less, and a minimum is preferable.
- it is -10 degreeC, More preferably, it is 0 degreeC or more. If it exceeds 60 ° C, decomposition of LiPF 6 occurs and PF 5 is generated to decompose the solvent, which is not preferable, and at a temperature lower than -10 ° C, the progress of the reaction is not economical.
- the present invention comprises the steps of reacting by adding water (H 2 O) and the organosylsilyl halide at the same time to the lithium hexafluorophosphate solution; Or it provides a method for producing lithium difluorophosphate represented by the following formula (1) comprising the step of adding water to the lithium hexafluoro phosphate solution and then organosyl halide to react sequentially.
- lithium difluorophosphate of the present invention may be prepared as in Scheme 4 below.
- the lithium difluorophosphate represented by Chemical Formula 1 may be prepared by reacting water with an organosilyl halide using lithium hexafluorophosphate (LiPF 6 ) as a starting material. .
- the organosilyl halide may be an organosilyl halide represented by Formula 4 below, but is not limited thereto.
- n is an integer of 1 to 3
- m is an integer of 1 to 3
- R is C 1 ⁇ C 10 linear or branched alkyl, C 2 to C 10 linear or branched alkenyl or Aryl
- X may be chlorine (Cl), bromine (Br), or iodine (I), and in particular, the use of trimethylsilyl chloride as the organosilylide halide is preferred in terms of stability, corrosiveness and degradability.
- the organosilyl halide may be added in an amount of 1.33 to 4.0 equivalents to lithium hexafluorophosphate, in particular, R 1 SiX 3 is preferably 1.33 equivalents, R 2 SiX 2 is 2.0 equivalents, and R 1 SiX 3 is preferably 4.0 equivalents. Do.
- the order of addition of water (H 2 O) and organosilyl halides is particularly important in the reaction. It is preferable to add (i) water (H 2 O) to the lithium hexafluorophosphate solution, and then add organosilyl halide or (ii) simultaneously add water (H 2 O) and organosilyl halide. .
- reaction conditions such as said reaction temperature
- the upper limit of reaction temperature becomes like this.
- it is 80 degreeC, More preferably, it is 60 degrees C or less, and a minimum is preferable.
- it is -10 degreeC, More preferably, it is 0 degreeC or more. It is not preferable to decompose LiPF 6 when it exceeds 80 deg. C to generate PF 5 to decompose the solvent, and it is not economical because the progress of the reaction is slow at a temperature lower than -10 deg.
- the temperature of the reactant was raised to 25 ° C., and the generated acid gas was removed under reduced pressure, and then, the produced lithium difluorophosphate was filtered and dried to obtain the lithium difluorophosphate of the present invention (Formula 1). It can manufacture.
- the solvent may be in an amount of 0.5 to 100 equivalents based on lithium hexafluorophosphate, but is not limited thereto.
- the solvent may be any one selected from the group consisting of diethyl ether, diisopropyl ether, and methyl t-butyl ether; Dimethoxyethane and alkoxyethanes of diethoxyethane; Ester, which is any one selected from the group consisting of methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; Nitriles which are any one selected from the group consisting of acetonitrile, propionitrile, and butyronitrile; Hydrocarbons which are any one selected from the group consisting of pentane, hexane, and heptane; Alcohols which are any one selected from the group consisting of methanol, ethanol, propanol, and butanol; Ketones which are any one selected from the group consisting of acetone, methyl ethyl ketone, and methyl isopropyl ketone; And carbonates which are any one selected from
- the water may be in a ratio of 1.00 to 2.05 equivalents relative to lithium hexafluorophosphate, but is not limited thereto.
- the water may be added in reverse amount from the required amount of lithium difluorophosphate to determine the amount of water, but from 1.90 to Lithium fluorophosphate. It is preferable to use water in a 2.05 equivalent ratio, or to use it in 1.0 to 3.0 equivalent ratio, especially 2.0 equivalent ratio.
- the first mixture was cooled to 5 ° C. using an ice bath, and 21.3 g of water (H 2 O) was added to prepare a second mixture.
- reaction mixture was gradually heated up to 20 ° C, and the generated hydrochloric acid gas, dimethylsilyldifluoride, and trimethylsilylfluoride were removed under reduced pressure to 30 mmHg.
- the prepared salt was filtered off with a filter paper and then washed with 21 g of dimethylcarbonate.
- the washed salt was recovered and dried to 50 ° C. or less to obtain a lithium powder, difluorophosphate compound (yield: 91.0%, purity: 99.7%, Cl content: 8 ppm).
- a lithium powder of difluorophosphate a white powder, was obtained under the same conditions as in Example 1 except that 159.81 g of dimethylsilyldichloride and 0.64 g of trimethylsilyl chloride were added to the second mixture (yield: 83.0%, purity). : 98.3%, Cl content: 8 ppm).
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Abstract
La présente invention concerne un procédé de préparation de difluorophosphate de lithium, et concerne plus particulièrement un procédé de préparation de difluorophosphate de lithium, qui permet une préparation simple et économique de difluorophosphate de lithium, qui est un sel de lithium utilisé dans un électrolyte d'une batterie secondaire au lithium, présentant un haut niveau de pureté et à haut rendement sans traitement dangereux. En utilisant un mélange d'halogénure de silyle organique plutôt que du siloxane coûteux utilisé dans la préparation du difluorophosphate de lithium, le procédé de préparation de difluorophosphate de lithium selon la présente invention est économique, permet d'obtenir du difluorophosphate de lithium de haute pureté présentant de faibles quantités d'impuretés diverses, et assure la sécurité du fait d'une faible corrosivité lors du traitement. De plus, la présente invention permet la préparation de difluorophosphate de lithium à haut rendement et de haute pureté au moyen d'un traitement simple sans raffinage particulier, tandis que, dans des procédés de préparation existants, des sous-produits inévitables sont générés, tels que du chlorure ou des matières insolubles, des impuretés devant ainsi être éliminées par le biais d'un traitement supplémentaire. En outre, en faisant réagir un composé bis(chlorosulfonyl)amine, qui est un matériau de départ, avec de l'eau (H2O) et un halogénure de silyle organique, la présente invention permet de résoudre les problèmes de l'état de la technique et de rendre possible une préparation simple et économique de difluorophosphate de lithium de haute pureté et à haut rendement sans traitement dangereux.
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JP4650627B2 (ja) * | 2005-09-14 | 2011-03-16 | 信越化学工業株式会社 | 環状カーボネート変性シロキサン及びその製造方法並びに非水電解液、二次電池及びキャパシタ |
CN102134065B (zh) * | 2006-08-22 | 2013-06-12 | 三菱化学株式会社 | 二氟磷酸锂的制备方法、非水电解液以及使用该非水电解液的非水电解质二次电池 |
JP5277550B2 (ja) * | 2007-03-12 | 2013-08-28 | セントラル硝子株式会社 | ジフルオロリン酸リチウムの製造方法及びこれを用いた非水電解液電池 |
EP2611731A1 (fr) * | 2010-08-04 | 2013-07-10 | Solvay Sa | Fabrication de lipo2f2 à partir de pof3 ou de pf5 |
JP5687792B2 (ja) * | 2013-06-07 | 2015-03-18 | ステラケミファ株式会社 | ジフルオロリン酸塩の製造方法 |
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