CN113912037B - Lithium difluorophosphate and preparation method and application thereof - Google Patents
Lithium difluorophosphate and preparation method and application thereof Download PDFInfo
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- CN113912037B CN113912037B CN202111487325.3A CN202111487325A CN113912037B CN 113912037 B CN113912037 B CN 113912037B CN 202111487325 A CN202111487325 A CN 202111487325A CN 113912037 B CN113912037 B CN 113912037B
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- lithium difluorophosphate
- lithium
- hexafluorophosphate
- difluorophosphate
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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 115
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- -1 hexafluorophosphate Chemical compound 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 19
- 239000000706 filtrate Substances 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 16
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001947 lithium oxide Inorganic materials 0.000 claims abstract description 12
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- 239000012043 crude product Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000012535 impurity Substances 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 150000002500 ions Chemical class 0.000 claims description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-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
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-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
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 15
- 239000000047 product Substances 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 3
- 125000001309 chloro group Chemical group Cl* 0.000 abstract description 2
- 231100000086 high toxicity Toxicity 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 25
- 239000007787 solid Substances 0.000 description 16
- 229910021645 metal ion Inorganic materials 0.000 description 9
- 239000010453 quartz Substances 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004448 titration Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 231100000171 higher toxicity Toxicity 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- FFUQCRZBKUBHQT-UHFFFAOYSA-N phosphoryl fluoride Chemical compound FP(F)(F)=O FFUQCRZBKUBHQT-UHFFFAOYSA-N 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 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
- C01B25/455—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
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C01P2006/82—Compositional purity water content
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides lithium difluorophosphate and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) mixing hexafluorophosphate, lithium oxide and silicon dioxide, and sintering to obtain a lithium difluorophosphate crude product; (2) mixing the lithium difluorophosphate crude product obtained in the step (1) with an organic solvent, filtering to obtain filtrate, and performing post-treatment on the filtrate to obtain the lithium difluorophosphate. The method disclosed by the invention is green and efficient, the raw materials are cheap, byproducts are easy to separate and convenient to recycle, raw materials containing chlorine atoms are not used, the content of chloride ions in the obtained lithium difluorophosphate product is low, and in addition, phosphorus pentafluoride with high toxicity, flammable siloxane and easily-decomposed lithium hexafluorophosphate are not used, so that the requirements of the technological process on equipment are low, and the reaction is more controllable.
Description
Technical Field
The invention belongs to the technical field of electrolyte additives for lithium ion batteries, and relates to lithium difluorophosphate and a preparation method and application thereof.
Background
As a novel portable power supply, the lithium ion battery has higher specific capacity and discharge voltage than the traditional lead-acid battery and alkaline battery, and has little pollution to the environment. At present, lithium ion batteries are widely used as portable mobile power sources and mobile phone batteries, and are widely used as power batteries of electric vehicles, automobiles and the like. Due to the strong support of national policy, the lithium ion battery industry has been greatly developed along with the accumulation of lithium ion battery technology in recent years, and the lithium ion battery industry has been inevitably continuously developed due to policy encouragement and technological progress. However, the lithium ion battery has many defects, for example, in the development of lithium salt, the traditional lithium hexafluorophosphate can not meet the use requirement of the lithium ion battery under extreme conditions.
The lithium difluorophosphate can improve the high-low temperature performance of the lithium ion battery, obviously improve the cycling stability of the lithium ion battery at minus 20 ℃, form a more stable SEI film under the high-temperature condition, and effectively prevent the electrolyte from corroding electrodes and collectors, thereby improving the high-low temperature performance of the lithium ion battery. In addition, lithium difluorophosphate has better stability than lithium hexafluorophosphate and is significantly more resistant to water and oxygen than lithium hexafluorophosphate. Therefore, the lithium difluorophosphate has great industrial value as a novel lithium salt additive.
The production methods of lithium difluorophosphate are numerous, but the existing preparation method of lithium difluorophosphate has complex process, higher requirements on production equipment, numerous byproducts, difficulty in generating solid and the like, and is very unfavorable for industrialization and popularization of lithium difluorophosphate. In most of the patent documents, lithium hexafluorophosphate is used as a raw material in the synthesis of lithium difluorophosphate, the cost ratio of lithium hexafluorophosphate in the synthesis process of lithium difluorophosphate is high, and the price fluctuation of lithium hexafluorophosphate is large, so that the application of lithium difluorophosphate is restricted.
CN103052592A discloses that phosphorus pentafluoride, phosphorus oxyfluoride and lithium phosphate are reacted to prepare lithium difluorophosphate, wherein the technical route uses expensive, virulent and high-risk phosphorus pentafluoride gas, the process is complex, the requirements on production equipment are strict, and the product cost is high.
CN108147385A discloses that lithium hexafluorophosphate is prepared by reacting lithium hexafluorophosphate with water and a hydrocarbyl silicon halide, and although the hydrocarbyl silicon halide can be decomposed, the lithium hexafluorophosphate is easily decomposed by this method, and the reaction process is not easy to control, and the number of byproducts is large, which is very disadvantageous for the production.
CN101847753A discloses a method for preparing lithium difluorophosphate in an aprotic solvent by using lithium hexafluorophosphate and lithium carbonate, but the method has long reaction time and low conversion rate, and only can obtain a non-aqueous solution of lithium difluorophosphate, and high-purity lithium difluorophosphate can not be obtained, which is very unfavorable for popularization of lithium difluorophosphate, and the salt solution contains more or less organic impurities and lithium fluoride, and the impurities may have adverse effects on the performance of the battery.
The scheme has the problems of high preparation cost and no environmental protection or impure prepared lithium difluorophosphate, so that the development of the lithium difluorophosphate preparation method with low cost, environmental protection and high product purity is necessary.
Disclosure of Invention
The invention aims to provide lithium difluorophosphate and a preparation method and application thereof, the method is green and efficient, the raw materials are cheap, byproducts are easy to separate and convenient to recycle, chlorine atom-containing raw materials are not used, the content of chloride ions in the obtained lithium difluorophosphate product is low, and phosphorus pentafluoride with high toxicity, flammable siloxane and easily-decomposed lithium hexafluorophosphate are not used, so that the requirements of the process on equipment are low, and the reaction is more controllable.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a preparation method of lithium difluorophosphate, comprising the following steps:
(1) mixing hexafluorophosphate, lithium oxide and silicon dioxide, and sintering to obtain a lithium difluorophosphate crude product;
(2) mixing the lithium difluorophosphate crude product obtained in the step (1) with an organic solvent, filtering to obtain filtrate, and performing post-treatment on the filtrate to obtain the lithium difluorophosphate.
The invention adopts a solid phase method to synthesize the lithium difluorophosphate, adopts commonly used hexafluorophosphate, lithium oxide and silicon dioxide as raw materials, is common and cheap chemical medicine, has low preparation cost, avoids the use of raw materials containing chlorine elements, and reduces the content of chloride ions in the lithium difluorophosphate product.
The method does not use phosphorus pentafluoride with higher toxicity, flammable siloxane and easily-decomposed lithium hexafluorophosphate, so the method has low requirement on equipment in the preparation process and has more controllable reaction.
Preferably, the mole ratio of the hexafluorophosphate to the lithium oxide to the silicon dioxide in the hexafluorophosphate in the step (1) is 1 (0.50-0.65) to (0.75-1.00), for example: 1:0.5:0.75, 1:0.55:0.8, 1:0.58:0.18, 1:0.6:0.8 or 1:0.65 or 1, etc.
Preferably, the hexafluorophosphate in step (1) comprises any one or a combination of at least two of potassium hexafluorophosphate, sodium hexafluorophosphate, magnesium hexafluorophosphate, calcium hexafluorophosphate, cesium hexafluorophosphate or ammonium hexafluorophosphate. The hexafluorophosphate salt may be a monovalent salt or a divalent salt containing hexafluorophosphate.
Preferably, the temperature of the sintering treatment in the step (1) is 180-250 ℃, for example: 180 deg.C, 190 deg.C, 200 deg.C, 220 deg.C or 250 deg.C, etc.
Preferably, the time of the sintering treatment is 8-24 h, for example: 8 h, 12 h, 16 h, 20 h or 24h and the like.
Preferably, the organic solvent in step (2) is a polar solvent capable of dissolving lithium difluorophosphate.
Preferably, the polar solvent includes any one of a carboxylic ester solvent, a nitrile solvent, or an ether solvent or a combination of at least two thereof.
Preferably, the polar solvent comprises any one of ethyl acetate, acetonitrile, propionitrile, polyethylene glycol dimethyl ether, tetrahydrofuran or 2-methyl tetrahydrofuran or a combination of at least two thereof.
Preferably, the post-treatment of step (2) comprises concentrating, crystallizing and drying the filtrate.
Preferably, the post-treatment comprises concentrating the filtrate, adding a poor solvent for lithium difluorophosphate to crystallize, and drying the obtained crystals.
Preferably, the poor solvent is a non-polar solvent.
Preferably, the poor solvent includes any one of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, methylene chloride, 1, 2-dichloroethane, 1-dichloroethane, n-hexane, cyclohexane, n-pentane or heptane or a combination of at least two thereof.
Preferably, the temperature of the crystallization is 0 to 10 ℃, for example: 0 ℃,1 ℃,2 ℃, 3 ℃, 4 ℃, 5 ℃, 6 ℃, 7 ℃, 8 ℃ or 10 ℃ and the like.
Preferably, the drying temperature is 80-120 ℃, for example: 80 deg.C, 85 deg.C, 90 deg.C, 100 deg.C, 110 deg.C or 120 deg.C.
In a second aspect, the present invention provides a lithium difluorophosphate, prepared by a process as described in the first aspect; the purity of the lithium difluorophosphate is more than or equal to 99.8 percent; the content of free acid in the lithium difluorophosphate is less than or equal to 50 ppm; the content of water in the lithium difluorophosphate is less than or equal to 10 ppm; the content of chloride ions in the lithium difluorophosphate is less than or equal to 1 ppm; the total content of impurity ions in the lithium difluorophosphate is less than or equal to 2 ppm.
In a third aspect, an electrolyte is characterized in that the electrolyte contains the lithium difluorophosphate as described in the second aspect.
In a fourth aspect, a lithium ion battery is characterized in that the lithium ion battery contains the electrolyte solution of the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method has the advantages of novel preparation process, easily obtained raw materials, low cost, high conversion rate, fewer steps, easy control of the whole process and no byproduct impurities after purification.
(2) The purity of the lithium difluorophosphate prepared by the method can reach more than 99.8 percent, the content of free acid in the lithium difluorophosphate can reach less than 50ppm, the content of water in the lithium difluorophosphate can reach less than 10ppm, the content of chloride ions in the lithium difluorophosphate can reach less than 1ppm, and the total content of impurity ions in the lithium difluorophosphate can reach less than 2 ppm.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The raw materials and instruments used in the invention are as follows:
glove box was purchased from michira mi, model Siemens S7;
the vacuum drying oven is purchased from Shanghai Yiheng, model DZF-6050;
muffle furnace available from YAMATO, Japan, model FO 811C;
ion chromatography is tested by adopting a Switzerland 833 type ion chromatograph;
the Karl Fischer method test adopts a Jingtai SF-3 Karl Fischer moisture tester to carry out moisture test;
an inductively coupled plasma emission spectrometer (ICP-OES) adopts a giga-day instrument ICP-5000 inductively coupled plasma emission spectrometer;
dimethyl carbonate, ethyl acetate, dichloromethane, 1, 2-dichloroethane, acetonitrile, dimethyl ether of polyethylene glycol, n-hexane, etc. were purchased from an avadin reagent net;
potassium hexafluorophosphate, sodium hexafluorophosphate, ammonium hexafluorophosphate, calcium hexafluorophosphate, lithium oxide, silica are available from Shanghai Mecline;
all percentages, parts and ratios used in the present invention are based on mass unless otherwise specified.
Example 1
The embodiment provides lithium difluorophosphate, and the preparation method of the lithium difluorophosphate comprises the following steps:
(1) in a glove box with the water content of less than 10ppm, adding 20.0g (108.66 mmol) of potassium hexafluorophosphate, 1.6234g (54.33 mmol) of lithium oxide and 4.8968g (81.50 mmol) of silicon dioxide into a mortar for grinding and mixing, then transferring the mixture into a quartz sagger, putting the quartz sagger into a muffle furnace, calcining at 200.0 ℃ for 18.0h to obtain a lithium difluorophosphate crude product, and absorbing the generated silicon tetrafluoride gas with sodium hydroxide lye;
(2) the muffle furnace temperature is reduced to room temperature, the calcined product is added into 100ml ethyl acetate to be stirred and dissolved for 2h, the filtration is carried out, the obtained filtrate is concentrated, then 100ml dimethyl carbonate is added to fully crystallize at 0 ℃, the filtration is carried out, the filter cake is put into a vacuum drying oven to be dried for 10h at 80 ℃, and 10.80g (100.08 mmol) of pure white powdery lithium difluorophosphate solid is obtained, and the yield is 92.1%.
The lithium difluorophosphate is a high-purity white powdery solid, the purity of the lithium difluorophosphate is more than or equal to 99.9 percent as detected by a Switzerland 833 ion chromatograph, the free acid content is 25ppm as detected by a Switzerland 916 potentiometric titrator, the moisture content is less than or equal to 10ppm as detected by a Karl Fischer method, and Cl is detected by a titration method-The content was 0.4ppm, and the sum of the contents of impurity metal ions was 0.6ppm as measured by inductively coupled plasma emission spectroscopy (ICP-OES).
Example 2
The embodiment provides lithium difluorophosphate, and the preparation method of the lithium difluorophosphate comprises the following steps:
(1) in a glove box with the water content of less than 10ppm, adding 20.0g (108.66 mmol) of potassium hexafluorophosphate, 2.1105g (70.63 mmol) of lithium oxide and 6.5287g (108.66 mmol) of silicon dioxide into a mortar for grinding and mixing, then transferring the mixture into a quartz sagger, putting the sagger into a muffle furnace, calcining for 24.0 hours at 250.0 ℃ to obtain a lithium difluorophosphate crude product, and absorbing the generated silicon tetrafluoride gas with sodium hydroxide lye;
(2) the muffle furnace temperature is reduced to room temperature, the calcined product is added into 100ml acetonitrile to be stirred and dissolved for 2h, the filtration is carried out, the obtained filtrate is concentrated, then 100ml dichloromethane is added to fully crystallize at the temperature of 5 ℃, the filtration is carried out, the filter cake is placed into a vacuum drying oven to be dried for 10h at the temperature of 100 ℃, and 10.93g (101.29 mmol) of pure white powdery lithium difluorophosphate solid is obtained, wherein the yield is 93.2%.
The lithium difluorophosphate is a high-purity white powdery solid, the purity of the lithium difluorophosphate is more than or equal to 99.9 percent as detected by a Switzerland 930 ion chromatograph, the free acid is 22ppm as detected by a Switzerland 916 potentiometric titrator, the moisture of the lithium difluorophosphate is less than or equal to 10ppm as detected by a Switzerland 917 moisture tester by a Karl Fischer method, and the Cl is detected by a titration method-The content was 0.3ppm, and the sum of the contents of impurity metal ions measured by the ICP-OES method was 0.7 ppm.
Example 3
The embodiment provides lithium difluorophosphate, and the preparation method of the lithium difluorophosphate comprises the following steps:
(1) in a glove box with the water content of less than 10ppm, adding 20.0g (119.08 mmol) of sodium hexafluorophosphate, 2.1350g (71.45 mmol) of lithium oxide and 5.9027g (98.24 mmol) of silicon dioxide into a mortar for grinding and mixing, then transferring the mixture into a quartz sagger, putting the quartz sagger into a muffle furnace, calcining at 180.0 ℃ for 20.0h to obtain a lithium difluorophosphate crude product, and absorbing the generated silicon tetrafluoride gas with sodium hydroxide lye;
(2) and (2) cooling the temperature of the muffle furnace to room temperature, adding the calcined product into 100ml of polyethylene glycol dimethyl ether, stirring and dissolving for 2 hours, filtering, concentrating the obtained filtrate, adding 100ml of n-hexane, fully crystallizing at 0 ℃, filtering, and drying the filter cake in a vacuum drying oven at 90 ℃ for 12 hours to obtain 11.95g (110.74 mmol) of pure white powdery lithium difluorophosphate solid with the yield of 93.0%.
The lithium difluorophosphate is a high-purity white powdery solid, the purity of the lithium difluorophosphate is more than or equal to 99.9 percent as detected by a Switzerland 930 ion chromatograph, the free acid is 30ppm as detected by a Switzerland 916 potentiometric titrator, the moisture of the lithium difluorophosphate is less than or equal to 10ppm as detected by a Switzerland 917 moisture tester by a Karl Fischer method, and the Cl is detected by a titration method-The content was 0.7ppm, and the sum of the contents of impurity metal ions measured by the ICP-OES method was 0.9 ppm.
Example 4
The embodiment provides lithium difluorophosphate, and the preparation method of the lithium difluorophosphate comprises the following steps:
(1) in a glove box with the water content of less than 10ppm, adding 20.0g (108.08 mmol) of calcium hexafluorophosphate, 1.8108g (60.60 mmol) of lithium oxide and 5.4622g (90.91 mmol) of silicon dioxide into a mortar for grinding and mixing, then transferring the mixture into a quartz sagger, putting the quartz sagger into a muffle furnace, calcining for 24.0 hours at 220.0 ℃ to obtain a lithium difluorophosphate crude product, and absorbing the generated silicon tetrafluoride gas with sodium hydroxide lye;
(2) and (2) cooling the temperature of the muffle furnace to room temperature, adding the calcined product into 100ml of ethyl acetate, stirring and dissolving for 2 hours, filtering, concentrating the obtained filtrate, adding 100ml of 1, 2-dichloroethane, fully crystallizing at 0 ℃, filtering, and drying the filter cake in a vacuum drying oven at 80 ℃ for 14 hours to obtain 10.55g (97.77 mmol) of pure white powdery lithium difluorophosphate solid with the yield of 90.5%.
The lithium difluorophosphate is a high-purity white powdery solid, the purity of the lithium difluorophosphate is more than or equal to 99.9 percent as detected by a Switzerland 930 ion chromatograph, the free acid is 35ppm as detected by a Switzerland 916 potentiometric titrator, the moisture of the lithium difluorophosphate is less than or equal to 10ppm as detected by a Switzerland 917 moisture tester by a Karl Fischer method, and the lithium difluorophosphate is a lithium difluorophosphateTitration method for Cl-The content was 0.3ppm, and the sum of the contents of impurity metal ions measured by the ICP-OES method was 0.5 ppm.
Example 5
This example differs from example 1 only in that the temperature of the reaction described in step (1) is 150 ℃ and the other conditions and parameters are exactly the same as in example 1.
The prepared lithium difluorophosphate is high-purity white powdery solid, the purity of the lithium difluorophosphate is more than or equal to 99.0 percent as detected by a Switzerland 930 ion chromatograph, the free acid is 75ppm as detected by a Switzerland 916 potentiometric titrator, the moisture of the lithium difluorophosphate is less than or equal to 10ppm as detected by a Switzerland 917 moisture tester by a Karl Fischer method, and the Cl is detected by a titration method-The content was 1.9ppm, and the sum of the contents of impurity metal ions measured by the ICP-OES method was 3.0 ppm.
Example 6
This example differs from example 1 only in that the temperature of the reaction described in step (1) is 280 ℃ and the other conditions and parameters are exactly the same as in example 1.
The prepared lithium difluorophosphate is high-purity white powdery solid, the purity of the lithium difluorophosphate is more than or equal to 98.0 percent as detected by a Switzerland 930 ion chromatograph, the free acid is 113ppm as detected by a Switzerland 916 potentiometric titrator, the moisture of the lithium difluorophosphate is less than or equal to 10ppm as detected by a Switzerland 917 moisture tester by a Karl Fischer method, and the Cl is detected by a titration method-The content was 0.9ppm, and the sum of the contents of impurity metal ions measured by the ICP-OES method was 1.8 ppm.
Comparative example 1
The comparative example provides a preparation method of lithium difluorophosphate conventionally, which specifically comprises the following steps:
adding 600ml of DEC into a 1L container, adding 73.89g (1.0 mol) of lithium carbonate, heating to 62 ℃, slowly adding 92.03g (0.5 mol) of lithium hexafluorophosphate, controlling the temperature to be 68 ℃, heating to 73 ℃ after the addition, stirring for 2h, filtering the obtained reaction solution, filtering to obtain 102g of wet solid filter cake, adding 153g of ethyl acetate, pulping for 5h, filtering out insoluble filter residue, distilling the obtained filtrate at 60 ℃ under reduced pressure until the filtrate is just saturated, placing the filtrate into a 0 ℃ ice bath, adding a poor solvent dichloromethane, stirring and crystallizing for 4h, placing the obtained lithium difluorophosphate product into a vacuum drying oven, drying at 120 ℃ for 10h to obtain 39.39g (0.365 mol) of lithium difluorophosphate solid, wherein the yield is 73.0%,
the lithium difluorophosphate is a high-purity white powdery solid, the purity of the lithium difluorophosphate is more than or equal to 99.7 percent as detected by a Switzerland 930 ion chromatograph, the free acid is 75ppm as detected by a Switzerland 916 potentiometric titrator, the moisture of the lithium difluorophosphate is less than or equal to 10ppm as detected by a Switzerland 917 moisture tester by a Karl Fischer method, and the Cl is detected by a titration method-The content was 1.0ppm, and the sum of the contents of impurity metal ions measured by the ICP-OES method was 2.3 ppm.
Comparative example 2
(1) In a glove box with the water content of less than 10ppm, adding 20.0g (108.66 mmol) of potassium hexafluorophosphate, 1.6234g (54.33 mmol) of lithium oxide and 9.1405g (163.00 mmol) of calcium oxide into a mortar for grinding and mixing, then transferring the mixture into a quartz sagger, putting the quartz sagger into a muffle furnace, calcining at 200.0 ℃ for 18.0h to obtain a lithium difluorophosphate crude product, and absorbing the generated silicon tetrafluoride gas with sodium hydroxide lye;
(2) the muffle furnace temperature is reduced to room temperature, the calcined product is added into 100ml ethyl acetate to be stirred and dissolved for 2h, the filtration is carried out, the obtained filtrate is concentrated, then 100ml dimethyl carbonate is added to fully crystallize at 0 ℃, the filtration is carried out, the filter cake is put into a vacuum drying oven to be dried for 10h at 80 ℃, and 9.99g (92.58 mmol) of pure white powdery lithium difluorophosphate solid is obtained, and the yield is 85.2%.
The prepared lithium difluorophosphate is high-purity white powdery solid, the purity of the lithium difluorophosphate is more than or equal to 92.0 percent as detected by a Switzerland 930 ion chromatograph, the free acid is 48ppm as detected by a Switzerland 916 potentiometric titrator, the moisture of the lithium difluorophosphate is less than or equal to 10ppm as detected by a Switzerland 917 moisture tester by a Karl Fischer method, and the Cl is detected by a titration method-The content was 3.7ppm, and the sum of the contents of impurity metal ions measured by the ICP-OES method was 9.8 ppm.
By adopting the novel preparation method, the invention avoids using expensive and easily decomposed lithium hexafluorophosphate as a raw material and does not use phosphorus pentafluoride with higher toxicity as a raw material. The lithium difluorophosphate with high purity and yield is successfully prepared by using the raw materials with relatively low price, and the lithium difluorophosphate has low acid value, moisture content and impurity ion content and has great industrial application value. As can be seen from examples 1 to 4, the purity of the lithium difluorophosphate prepared by the method reaches more than 99.8%, the yield reaches more than 90.5%, wherein the content of free acid in the lithium difluorophosphate is less than or equal to 50ppm, the content of water in the lithium difluorophosphate is less than or equal to 10ppm, the content of chloride ions in the lithium difluorophosphate is less than or equal to 1ppm, and the total content of impurity ions in the lithium difluorophosphate is less than or equal to 2 ppm.
As can be seen from comparison between example 1 and examples 5-6, the sintering temperature in step (1) affects the yield and purity of lithium difluorophosphate, and when the sintering temperature is too low, the reactivity of the raw material is insufficient, resulting in insufficient reaction, increased unreacted impurities and increased acid value; when the sintering temperature is too high, partial decomposition of lithium difluorophosphate may occur, resulting in a decrease in purity and an increase in acid value. Therefore, the sintering temperature is controlled to be 180-250 ℃, so that the yield and the purity of lithium difluorophosphate are improved.
As can be seen from comparison of example 1 with comparative example 1, in the conventional production method of comparative example 1, the yield and purity are significantly reduced, the acid value and impurity metal ions become high, and there is a possibility that the reason why lithium hexafluorophosphate is easily decomposed, and in addition, the cost of raw materials used is relatively high. In comparison, the yield and the purity of the lithium difluorophosphate prepared by the method are greatly improved, the content of impurity ions in the product is obviously reduced, the raw materials are cheap and easy to obtain, and the method is favorable for large-scale industrial mass production.
As can be seen from comparison between example 1 and comparative example 2, in comparative example 2, the yield and purity of lithium difluorophosphate obtained after replacing silica with a transition metal oxide such as calcium oxide are significantly reduced, probably because the bonding force of the transition metal element to fluorine atoms is weaker than that of silicon element to fluorine atoms, and it is relatively difficult to promote the reaction, and the transition metal element is introduced, resulting in a significant increase in metal impurities.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (9)
1. A preparation method of lithium difluorophosphate is characterized by comprising the following steps:
(1) mixing hexafluorophosphate, lithium oxide and silicon dioxide, and sintering to obtain a lithium difluorophosphate crude product;
(2) mixing the lithium difluorophosphate crude product obtained in the step (1) with an organic solvent, filtering to obtain filtrate, and performing post-treatment on the filtrate to obtain lithium difluorophosphate;
the hexafluorophosphate in the step (1) comprises any one or the combination of at least two of potassium hexafluorophosphate, sodium hexafluorophosphate, magnesium hexafluorophosphate, calcium hexafluorophosphate, cesium hexafluorophosphate and ammonium hexafluorophosphate.
2. The method according to claim 1, wherein the hexafluorophosphate in the step (1) is a hexafluorophosphate in which the molar ratio of hexafluorophosphate, lithium oxide and silicon dioxide is 1 (0.50 to 0.65) to (0.75 to 1.00).
3. The preparation method according to claim 1, wherein the temperature of the sintering treatment in the step (1) is 180 to 250 ℃, and the time of the sintering treatment is 8 to 24 hours.
4. The method according to claim 1, wherein the organic solvent in step (2) comprises any one or a combination of at least two of ethyl acetate, acetonitrile, propionitrile, dimethyl ether of polyethylene glycol, tetrahydrofuran, or 2-methyltetrahydrofuran.
5. The method according to claim 1, wherein the post-treatment in the step (2) comprises concentrating the filtrate, adding a poor solvent for lithium difluorophosphate to the filtrate to crystallize, and drying the obtained crystals.
6. The method according to claim 5, wherein the poor solvent comprises one or a combination of at least two of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, methylene chloride, 1, 2-dichloroethane, 1-dichloroethane, n-hexane, cyclohexane, n-pentane, and heptane, the crystallization temperature is 0 to 10 ℃, and the drying temperature is 80 to 120 ℃.
7. Lithium difluorophosphate, characterized in that it is obtained by a process according to any one of claims 1 to 6; the purity of the lithium difluorophosphate is more than or equal to 99.8 percent; the content of free acid in the lithium difluorophosphate is less than or equal to 50 ppm; the content of water in the lithium difluorophosphate is less than or equal to 10 ppm; the content of chloride ions in the lithium difluorophosphate is less than or equal to 1 ppm; the total content of impurity ions in the lithium difluorophosphate is less than or equal to 2 ppm.
8. An electrolyte comprising the lithium difluorophosphate of claim 7.
9. A lithium ion battery comprising the electrolyte of claim 8.
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