CN115477297B - 一种二氟磷酸锂的制备方法及其所得产品 - Google Patents
一种二氟磷酸锂的制备方法及其所得产品 Download PDFInfo
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- CN115477297B CN115477297B CN202211272875.8A CN202211272875A CN115477297B CN 115477297 B CN115477297 B CN 115477297B CN 202211272875 A CN202211272875 A CN 202211272875A CN 115477297 B CN115477297 B CN 115477297B
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- reaction
- difluorophosphate
- ammonium
- lithium
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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 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 84
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 69
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 64
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 59
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 58
- SAEOCANGOMBQSP-UHFFFAOYSA-N diazanium;fluoro-dioxido-oxo-$l^{5}-phosphane Chemical compound [NH4+].[NH4+].[O-]P([O-])(F)=O SAEOCANGOMBQSP-UHFFFAOYSA-N 0.000 claims abstract description 47
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical group COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims abstract description 38
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 239000000706 filtrate Substances 0.000 claims description 51
- 238000002390 rotary evaporation Methods 0.000 claims description 47
- 238000000967 suction filtration Methods 0.000 claims description 35
- 239000012065 filter cake Substances 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000007795 chemical reaction product Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000654 additive Substances 0.000 abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 20
- 239000000463 material Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 229910012258 LiPO Inorganic materials 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 8
- 238000010907 mechanical stirring Methods 0.000 description 8
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 7
- 238000010025 steaming Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000013065 commercial product Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000806 fluorine-19 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000013094 purity test Methods 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- UZVUSORDFOESJG-UHFFFAOYSA-N 2-bromo-3-methyl-6-propan-2-ylphenol Chemical compound CC(C)C1=CC=C(C)C(Br)=C1O UZVUSORDFOESJG-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- VUKHDQTWBFTHTO-UHFFFAOYSA-N azanium difluorophosphinate Chemical compound P(=O)([O-])(F)F.[NH4+] VUKHDQTWBFTHTO-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- MRVHOJHOBHYHQL-UHFFFAOYSA-M lithium metaphosphate Chemical compound [Li+].[O-]P(=O)=O MRVHOJHOBHYHQL-UHFFFAOYSA-M 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
Images
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
- H01M10/056—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
-
- 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)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
Abstract
Description
纯度% | 水分PPM | 酸值 | 收率% | |
实施例1 | 99.927 | 132 | 9.1 | 86.769 |
实施例2 | 99.881 | 121 | 9.2 | 74.926 |
实施例3 | 99.601 | 176 | 9.8 | 72.952 |
实施例4 | 99.512 | 199 | 9.9 | 71.693 |
对比例1 | 93.323 | 264 | 10.4 | 51.208 |
对比例2 | 41.231 | 254 | 178.2 | 3.649 |
对比例3 | 72.800 | 221 | 32.1 | 33.962 |
对比例4 | 62.651 | 2243 | 3225 | 20.577 |
对比例5 | 43.323 | 195 | 10.4 | 1.444 |
Claims (6)
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CN202211272875.8A CN115477297B (zh) | 2022-10-18 | 2022-10-18 | 一种二氟磷酸锂的制备方法及其所得产品 |
PCT/CN2023/111383 WO2024002386A1 (zh) | 2022-10-18 | 2023-08-07 | 二氟磷酸锂的制备方法及其所得产品 |
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CN202211272875.8A CN115477297B (zh) | 2022-10-18 | 2022-10-18 | 一种二氟磷酸锂的制备方法及其所得产品 |
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CN115477297B true CN115477297B (zh) | 2023-06-20 |
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WO (1) | WO2024002386A1 (zh) |
Families Citing this family (1)
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CN115477297B (zh) * | 2022-10-18 | 2023-06-20 | 山东海科创新研究院有限公司 | 一种二氟磷酸锂的制备方法及其所得产品 |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1475556A (fr) * | 1966-04-13 | 1967-03-31 | Fr Albert Soc | Procédé pour la préparation de fluorphosphates métalliques |
JP4560132B2 (ja) * | 2008-12-02 | 2010-10-13 | 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 |
FR2952367B1 (fr) * | 2009-11-10 | 2012-09-28 | Commissariat Energie Atomique | Synthese d'un fluorophosphate metallique et utilisation comme materiau actif d'electrode pour accumulateur |
KR20130041183A (ko) * | 2010-07-08 | 2013-04-24 | 솔베이(소시에떼아노님) | LiPO2F2의 제조법 및 결정형 LiPO2F2 |
JP5893522B2 (ja) * | 2012-07-06 | 2016-03-23 | 関東電化工業株式会社 | ジハロゲノリン酸リチウムの製造方法 |
JP5715725B2 (ja) * | 2013-06-07 | 2015-05-13 | ステラケミファ株式会社 | ジフルオロリン酸塩の精製方法 |
JP5666734B2 (ja) * | 2013-06-07 | 2015-02-12 | 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 |
JP6405745B2 (ja) * | 2014-06-27 | 2018-10-17 | ダイキン工業株式会社 | ジフルオロリン酸リチウムの製造方法 |
KR102332334B1 (ko) * | 2015-03-12 | 2021-11-29 | 삼성에스디아이 주식회사 | 유기전해액 및 이를 포함하는 리튬 전지 |
CN106744781A (zh) * | 2016-12-26 | 2017-05-31 | 惠州市宙邦化工有限公司 | 一种二氟磷酸锂的提纯方法 |
CN106882782B (zh) * | 2017-03-25 | 2019-02-12 | 山东永浩新材料科技有限公司 | 一种二氟磷酸锂的合成方法 |
CN107720717B (zh) * | 2017-10-27 | 2020-06-16 | 天津金牛电源材料有限责任公司 | 一种二氟磷酸锂的制备方法 |
JP7028405B2 (ja) * | 2018-02-26 | 2022-03-02 | 三井化学株式会社 | ジフルオロリン酸リチウムの製造方法 |
JP6610701B2 (ja) * | 2018-04-23 | 2019-11-27 | ダイキン工業株式会社 | ジフルオロリン酸リチウムの製造方法 |
KR101925051B1 (ko) * | 2018-08-02 | 2019-02-22 | 주식회사 천보 | 디플루오로인산리튬염 결정체를 고순도로 제조하는 방법 및 이를 이용한 2차 전지용 비수계 전해액 |
US20230065400A1 (en) * | 2020-02-26 | 2023-03-02 | Tesla, Inc. | Difluorophosphate additive compounds and methods thereof for use in energy storage devices |
CN112897494B (zh) * | 2021-02-08 | 2022-07-01 | 湖北迈可凯科技有限公司 | 二氟磷酸锂的合成工艺及合成装置 |
CN113148970A (zh) * | 2021-03-12 | 2021-07-23 | 九江天赐高新材料有限公司 | 一种高纯二氟磷酸锂的制备方法 |
CN113148971B (zh) * | 2021-04-23 | 2022-10-14 | 荣成青木高新材料有限公司 | 一种二氟磷酸锂的制备方法 |
CN114852987B (zh) * | 2022-05-31 | 2023-07-21 | 山东海科创新研究院有限公司 | 一种二氟磷酸锂的制备方法 |
CN115477297B (zh) * | 2022-10-18 | 2023-06-20 | 山东海科创新研究院有限公司 | 一种二氟磷酸锂的制备方法及其所得产品 |
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2022
- 2022-10-18 CN CN202211272875.8A patent/CN115477297B/zh active Active
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- 2023-08-07 WO PCT/CN2023/111383 patent/WO2024002386A1/zh unknown
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