CN116283601A - 一种双氟磺酰亚胺有机铵盐的制备方法 - Google Patents
一种双氟磺酰亚胺有机铵盐的制备方法 Download PDFInfo
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- 150000003863 ammonium salts Chemical class 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- -1 difluoro sulfonimide Chemical compound 0.000 title claims description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 21
- 239000011230 binding agent Substances 0.000 claims abstract description 21
- 239000005935 Sulfuryl fluoride Substances 0.000 claims abstract description 12
- XPVRBHCXMWRJEY-UHFFFAOYSA-N difluoro(imino)-$l^{4}-sulfane Chemical compound FS(F)=N XPVRBHCXMWRJEY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000002798 polar solvent Substances 0.000 claims abstract description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 4
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 3
- 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 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 8
- 150000003839 salts Chemical class 0.000 abstract description 8
- 239000007789 gas Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 239000007795 chemical reaction product Substances 0.000 abstract description 5
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 4
- 238000003682 fluorination reaction Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 abstract description 3
- 239000011737 fluorine Substances 0.000 abstract description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 3
- 239000002341 toxic gas Substances 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- ZJPPTKRSFKBZMD-UHFFFAOYSA-N [Li].FS(=N)F Chemical compound [Li].FS(=N)F ZJPPTKRSFKBZMD-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 238000006138 lithiation reaction Methods 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 2
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical class FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- AJGPQPPJQDDCDA-UHFFFAOYSA-N azanium;hydron;oxalate Chemical compound N.OC(=O)C(O)=O AJGPQPPJQDDCDA-UHFFFAOYSA-N 0.000 description 1
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- 230000015556 catabolic process Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- WRJWRGBVPUUDLA-UHFFFAOYSA-N chlorosulfonyl isocyanate Chemical compound ClS(=O)(=O)N=C=O WRJWRGBVPUUDLA-UHFFFAOYSA-N 0.000 description 1
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- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/087—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms
- C01B21/093—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms containing also one or more sulfur atoms
- C01B21/096—Amidosulfonic acid; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/086—Compounds containing nitrogen and non-metals and optionally metals containing one or more sulfur atoms
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- 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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- 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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Abstract
本发明公开了一种双氟磺酰亚胺有机铵盐的制备方法,属于化学合成技术领域,其特征在于,包括如下步骤:以硫酰氟和铵盐为反应原料,在非质子极性溶剂和有机碱性缚酸剂作用下,在高压釜中反应获得双氟磺酰亚胺有机铵盐反应液,减压蒸馏回收反应溶剂,所得反应产物水洗纯化;加入溶剂溶解,在氮气气氛下可用于不同的化学反应,如加入金属盐试剂,搅拌反应,经纯化操作后可得到相应的双氟磺酰亚胺金属盐;本发明提供了一种双氟磺酰亚胺有机盐的制备方法,反应步骤少、收率高,且规避了高温高压条件下的氟化反应步骤,不使用氟化氢、氟气等高危险性有毒气体物料,反应安全性高,易操作及设备要求不苛刻,适合工业化生产。
Description
技术领域
本发明涉及一种双氟磺酰亚胺有机铵盐的制备方法,属于化学合成技术领域。
背景技术
近年来,随着国家对新能源汽车产业的支持,促进新能源电动汽车(ElectricVehicle,EV),储能等产业的快速发展,随之对新能源关键核心技术的锂离子电池能量密度、循环寿命、安全性和环保等要求不断提高。为了确保新能源市场健康地发展,迫切地需要开发高性能、高安全性和环保,并又能以较合理成本生产锂离子电池产业技术。考虑到锂离子电池生产成本、电化学、安全和环保等综合性能,六氟磷酸锂(LiPF6)是目前已经产业化的锂离子电池最被广泛采用的电解质,起到输送电荷作用,是决定电池性能优劣的关键要素之一,但LiPF6具有无法克服对热和化学稳定性、安全性和低温循环效率差等天然缺陷,比如60℃左右LiPF6就开始分解,这一过程如再遇微量水将进一步加快电解质的降解。伴随着LiPF6降解过程还会产生高腐蚀性的氟化氢(HF)气体,不仅会破坏电解质的化学结构而降低电解质浓度,同时还可能会引发电解液和电极化学结构的变化,破坏电池可逆循环工作条件,导致电池容量快速衰减,给实际生产和应用带来了巨大挑战和安全隐患。因此开发更安全、更高效、并能适用于低温和高温等苛刻条件下的优质电解质,将是改善各类离子电池的综合性能以及拓展它们应用范围最经济和最有效的途径。双氟磺酰亚胺锂(Lithium bisfluorosulfonylimide,LiFSI)及其它金属双氟磺酰亚胺盐的电导率、耐热稳定性、耐水稳定性、以及低温循环效率等综合电化学性能均比相应的六氟磷酸盐(MPF6)更优异。双氟磺酰亚胺盐已被国内外业内专家公认为是替代六氟磷酸盐电解质的下一代新型离子电池电解质,是当前最具有产业化前景的理想电解质,将成为新能源锂电企业的核心竞争力。
双氟磺酰亚胺锂及其它金属盐的制备首先是通过合成双氟磺酰亚胺;最初在实验室中,双氟磺酰亚胺的制备是通过氨基磺酸和五氯化磷为原料经多步反应合成得到(J.K.Ruff,et.al.,Inorg.Synth.1968,11,138;J.M.Shreeve,et al.,Inorg.Chem.1998,37,6295.),但该反应工艺路线复杂、中间产物种类多、产物提纯困难、致使生产难度大且生产成本高,制约其商业化使用。近年来,随着双氟磺酰亚胺生产技术的突破以及生产成本不断下降,双氟磺酰亚胺已具备产业化生产及大规模商业化应用的条件。目前已经产业化的双氟磺酰亚胺合成路线主要有两条:
(1).基于传统合成反应工艺的优化,通过改变原材料的选择,以氯磺酸和氨基磺酸或者氯磺酰异氰酸酯为原料先通过反应合成双氯磺酰亚胺(HClSI)中间产物,随后通过氟化反应并蒸馏得到双氟磺酰亚胺(HFSI)中间产物,最后通过锂化等三步反应得到LiFSI(例如:CN105731399B和CN106044728B等)。相比传统反应工艺,上述优化后的生产工艺减少了反应步骤和反应中间产物种类,生产难度和生产成本均比传统工艺有显著的降低,目前大多数化工企业如多氟多等公司都采用该反应工艺生产双氟磺酰亚胺锂。但该工艺所采用的氟化过程通常采用氟化氢或氟气等腐蚀性极强的原料在高温高压下反应,反应工艺过程风险大,并且对生产设备要求很高。由于需要经过三步反应合成才能得到双氟磺酰亚胺锂,反应步骤多、反应复杂、提纯困难、收率低、污染大、生产成本较高,导致其综合性价比很难满足锂离子电池市场井喷式发展对高质量和高产能生产双氟磺酰亚胺锂等盐的需求和期待。
(2).以硫酰氟和氨气为原料直接反应合成双氟磺酰亚胺(HFSI)中间产物,随后经过锂化两步反应合成生产双氟磺酰亚胺锂(例如:CN 111620315A)。尽管该合成反应工艺收率高、步骤少、但由于反应涉及到两种有毒气体同时参与反应,反应控制难度大,目前仅少部分企业正在开发采用该生产工艺,如操作不当极易引起安全事故等隐患。
发明内容
本发明目的在于解决当前双氟磺酰亚胺盐生产过程中的部分缺陷,提供一种反应产物纯度好、收率高、安全、环保、及高效的双氟磺酰亚胺有机铵盐的全新制备方法。为实现上述目的,本发明采用的技术方案是:
一种双氟磺酰亚胺有机铵盐的制备方法,其特征在于,包括如下步骤:以硫酰氟和铵盐为反应原料,在非质子极性溶剂和有机碱性缚酸剂作用下反应,获得双氟磺酰亚胺有机铵盐。
本发明的合成路线如下所示:
进一步的设置在于:
步骤(1)中:所述非质子性溶剂为:乙腈、丙酮、酯类如碳酸二甲酯、碳酸二乙酯、乙酸乙酯等、醚类如四氢呋喃、甲基叔丁基醚、乙二醇二甲醚等的任意一种,优选为乙腈。
所述有机碱性缚酸剂为:三甲胺、三乙胺、N,N-二异丙基乙胺、三正丙胺、三正丁胺、吡啶等的任意一种,优选为三乙胺。
所述硫酰氟、有机碱性缚酸剂与铵盐的摩尔比为1:1~10:0.2~1,优选为1:1.5:0.5。
步骤(1)的反应温度为0~60℃,优选为10~30℃。
本发明制备的双氟磺酰亚胺有机铵盐,可用于进一步通过金属交换反应制备双氟磺酰亚胺金属盐,如用于制备双氟磺酰亚胺锂盐。具体方法是:将本发明制备的双氟磺酰亚胺有机铵盐,加入溶剂溶解,在氮气气氛下加入LiOH(氢氧化锂)试剂,搅拌反应,经纯化操作后,得到双氟磺酰亚胺锂盐。所述反应溶剂选自乙腈、丙酮、酯类如碳酸二甲酯、碳酸二乙酯、乙酸乙酯等、醚类如四氢呋喃、甲基叔丁基醚、乙二醇二甲醚等、卤代烷烃如二氯甲烷、二氯乙烷等的任意一种;优选为乙腈。
与现有技术相比,本发明的有益效果主要体现在:
1、本发明提供了一种双氟磺酰亚胺有机盐的制备方法,反应步骤少、安全、环保、易操作、产品纯度好、收率高等优点。
2、本发明规避了高温高压条件下的氟化反应步骤,不使用氟化氢、氟气等高危险性有毒气体物料,反应安全性高,易操作及设备要求不苛刻,适合工业化生产等优点。
3、本发明原料便宜和易得,且主反应原料铵盐可通过简单的粉末固体或配成准确浓度的溶液方式加到反应体系中,避免多种有毒气体原料的同时使用,有效的降低反应控制难度以及反应风险。
下面结合具体实施例对本发明进行进一步描述,但本发明的保护范围并不仅限于此。
附图说明
图1为本发明实施例1制备的产物的1HNMR谱图。
具体实施方式
实施例1
氮气气氛下,250mL高压反应釜中,加入氟化铵9.3g,控温至10℃,依次泵入三乙胺75.5g,乙腈60.0g,搅拌0.5小时,控温10℃缓慢通入硫酰氟气体51.0g,连续保温10℃,4小时,结束反应。反应液减压蒸馏回收反应溶剂,浓缩液水洗得到有机相65.0g,收率95%。
产物确认:
反应产物经LC/MS检测表明,负离子分子量(m/e)为180,与双氟磺酰亚胺负离子的化学结构(IV)一致,
反应产物的1HNMR谱图如图1所示,与双氟磺酰亚胺三乙铵盐(II)(R=CH2CH3)的化学结构一致。
实施例2
制备方法的实验条件同实施例1,区别在于:调整铵盐的选择与用量,并检测其对反应收率的影响,如表1所示。
表1、不同铵盐的选择与用量对反应收率的影响
序号 | 铵盐 | 用量 | 收率 |
实施例2-1 | 氯化铵 | 13.4克(0.25摩尔) | 92% |
实施例2-2 | 溴化铵 | 24.5克(0.25摩尔) | 95% |
实施例2-3 | 硫酸氢铵 | 28.8克(0.25摩尔) | 95% |
实施例2-4 | 碳酸氢铵 | 19.8克(0.25摩尔) | 93% |
实施例2-5 | 草酸氢铵 | 26.8克(0.25摩尔) | 90% |
。
实施例3
制备方法的实验条件同实施例1,区别在于:调整非质子极性溶剂,并检测其对反应收率的影响,如表2所示。
表2、不同非质子极性溶剂对反应收率的影响
序号 | 非质子极性溶剂 | 收率 |
实施例3-1 | 乙腈 | 95% |
实施例3-2 | 丙酮 | 70% |
实施例3-3 | 碳酸二乙酯 | 80% |
实施例3-4 | 乙酸乙酯 | 55% |
。
如表2所示:由于反应物和产物都是强极性离子型化合物,故极性溶剂有利于反应进行完全,并获得相应较高的反应产率,很明显乙腈是优选的反应溶剂。
实施例4
制备方法的实验条件同实施例1,区别在于:调整有机碱性缚酸剂的化学结构,并检测其对反应收率的影响,如表3所示。
表3、不同有机碱性缚酸剂对反应收率的影响
序号 | 有机碱性缚酸剂 | 收率 |
实施例4-1 | 三甲胺 | 90% |
实施例4-2 | 三乙胺 | 95% |
实施例4-3 | N,N-二异丙基乙胺 | 92% |
实施例4-4 | 三丙胺 | 85% |
实施例4-5 | 三正丁胺 | 65% |
。
如表3所示:选择不同化学结构的有机碱性缚酸剂,反应收率随着缚酸剂中烷基变大而逐渐降低,可能与缚酸剂吸附反应所生成的氢氟酸副产物的能力有关。很明显,三乙胺是优选有机碱性缚酸剂。
实施例5
制备方法的实验条件同实施例1,区别在于:调整硫酰氟、有机碱性缚酸剂与铵盐的摩尔比,并检测其对反应纯度的影响,如表4所示。
表4、不同反应物料比对反应收率的影响
序号 | 硫酰氟、有机碱性缚酸剂与铵盐(摩尔比) | 收率 |
实施例5-1 | 1:1:0.5 | 81% |
实施例5-2 | 1:1:1 | 80% |
实施例5-3 | 1:1.5:0.5 | 95% |
实施例5-4 | 1:1.5:0.3 | 60% |
实施例5-5 | 1:1.5:1 | 94% |
实施例5-6 | 1:2:0.5 | 94.5% |
。
如表4所示:有机碱性缚酸剂不仅参与吸附反应所生成的氢氟酸副产物,同时也参与反应产物的成盐过程,因此选择不同的反应物料比,对反应产物的收率有较大影响,一般而言,硫酰氟、有机碱性缚酸剂与铵盐的摩尔比为1:1~10:0.2~1,最佳实施例为硫酰氟、有机碱性缚酸剂与铵盐优选的摩尔比为1:1.5:0.5。
实施例6:
制备方法的实验条件同实施例1,区别在于:调整反应温度,并检测其对反应收率的影响,如表5所示。
表5、不同反应温度对反应收率的影响
序号 | 反应温度 | 保温时间 | 收率 |
实施例6-1 | 0℃ | 4h | 90% |
实施例6-2 | 10℃ | 4h | 95% |
实施例6-3 | 30℃ | 4h | 90% |
实施例6-4 | 60℃ | 4h | 75% |
。
如表5所示:反应温度为0℃时,反应收率为90%。当反应温度升高到10℃时,反应收率达到95%,继续升高反应温度,反应产率不但没有明显地提高,反而逐渐降低,推测在较高反应温度下,生成副产物的速度也许增加得更快。
Claims (10)
1.一种双氟磺酰亚胺有机铵盐的制备方法,其特征在于,包括如下步骤:以硫酰氟和铵盐为反应原料,在非质子极性溶剂和有机碱性缚酸剂作用下反应,获得双氟磺酰亚胺有机铵盐。
2.根据权利要求1所述的一种双氟磺酰亚胺有机铵盐的制备方法,其特征在于:所述非质子极性溶剂选自以下任意一种:乙腈,丙酮,碳酸二甲酯,碳酸二乙酯,乙酸乙酯,四氢呋喃、甲基叔丁基醚或乙二醇二甲醚。
3.根据权利要求2所述的一种双氟磺酰亚胺有机铵盐的制备方法,其特征在于:所述非质子极性溶剂为乙腈。
4.根据权利要求1所述的一种双氟磺酰亚胺有机铵盐的制备方法,其特征在于:所述铵盐选自以下任意一种铵盐:氟化铵,氯化铵,溴化铵,硫酸氢铵,碳酸氢铵,草酸氢铵。
5.根据权利要求1所述的一种双氟磺酰亚胺有机铵盐的制备方法,其特征在于:所述有机碱性缚酸剂为:三甲胺、三乙胺、N,N-二异丙基乙胺、三正丙胺、三正丁胺、吡啶的任意一种。
6.根据权利要求5所述的一种双氟磺酰亚胺有机铵盐的制备方法,其特征在于:所述有机碱性缚酸剂为三乙胺或三正丁胺。
7.根据权利要求1所述的一种双氟磺酰亚胺有机铵盐的制备方法,其特征在于:所述硫酰氟、有机碱性缚酸剂与铵盐的摩尔比为1:1~10:0.2~1。
8.根据权利要求7所述的一种双氟磺酰亚胺有机铵盐的制备方法,其特征在于:所述硫酰氟、有机碱性缚酸剂与铵盐优选的摩尔比为1:1.5:0.5。
9.根据权利要求1所述的一种双氟磺酰亚胺有机铵盐的制备方法,其特征在于:所述反应温度为0~60℃。
10.根据权利要求9所述的一种双氟磺酰亚胺有机铵盐的制备方法,其特征在于:所述反应温度为10~30℃。
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CN114031053B (zh) * | 2021-12-15 | 2023-05-09 | 江苏华盛锂电材料股份有限公司 | 一种双氟磺酰亚胺盐的制备方法 |
CN114506829A (zh) * | 2022-03-01 | 2022-05-17 | 国药集团化学试剂有限公司 | 一种双氟磺酰亚胺锂的制备方法 |
CN116283601A (zh) * | 2023-03-16 | 2023-06-23 | 浙江中欣氟材股份有限公司 | 一种双氟磺酰亚胺有机铵盐的制备方法 |
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CN117049486A (zh) * | 2023-03-16 | 2023-11-14 | 浙江中欣氟材股份有限公司 | 一种双氟磺酰亚胺钠的制备方法 |
CN117069077A (zh) * | 2023-03-16 | 2023-11-17 | 浙江中欣氟材股份有限公司 | 一种双氟磺酰亚胺锂的制备方法 |
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