CN114604832A - Preparation method of lithium bis (fluorosulfonyl) imide and application of lithium bis (fluorosulfonyl) imide - Google Patents
Preparation method of lithium bis (fluorosulfonyl) imide and application of lithium bis (fluorosulfonyl) imide Download PDFInfo
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- CN114604832A CN114604832A CN202210275612.6A CN202210275612A CN114604832A CN 114604832 A CN114604832 A CN 114604832A CN 202210275612 A CN202210275612 A CN 202210275612A CN 114604832 A CN114604832 A CN 114604832A
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- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- -1 fluorosulfonic acid isocyanate Chemical class 0.000 claims abstract description 36
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012948 isocyanate Substances 0.000 claims abstract description 19
- 238000006138 lithiation reaction Methods 0.000 claims abstract description 17
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 15
- 150000004673 fluoride salts Chemical class 0.000 claims abstract description 15
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- WRJWRGBVPUUDLA-UHFFFAOYSA-N chlorosulfonyl isocyanate Chemical compound ClS(=O)(=O)N=C=O WRJWRGBVPUUDLA-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 7
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 claims description 7
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000010409 thin film Substances 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- GUNJVIDCYZYFGV-UHFFFAOYSA-K antimony trifluoride Chemical compound F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical group Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 3
- 229940090181 propyl acetate Drugs 0.000 claims description 3
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims 2
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 9
- 150000001768 cations Chemical class 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 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 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 150000002500 ions Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ODNBVEIAQAZNNM-UHFFFAOYSA-N 1-(6-chloroimidazo[1,2-b]pyridazin-3-yl)ethanone Chemical compound C1=CC(Cl)=NN2C(C(=O)C)=CN=C21 ODNBVEIAQAZNNM-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- PPFAPKNCEXDZNN-UHFFFAOYSA-N N=[SH2].F.F Chemical compound N=[SH2].F.F PPFAPKNCEXDZNN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 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 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical group FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 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
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of lithium bis (fluorosulfonyl) imide and application of lithium bis (fluorosulfonyl) imide, wherein the preparation method comprises a fluorination reaction in step (1), a catalytic reaction in step (2) and a lithiation reaction in step (3). The invention adopts fluoride salt as the fluorinating reagent, avoids using HF, has lower requirements on the material of production equipment and mild reaction conditions, and is easy to carry out large-scale industrial production. Firstly, raw materials are fluorinated to obtain fluorosulfonic acid isocyanate and fluorosulfonic acid, and then, the raw materials are subjected to catalytic reaction to obtain bis-fluorosulfonyl imide, compared with bis-chlorosulfonyl imide which is difficult to purify after being fluorinated, the fluorosulfonic acid obtained by fluorination in the first step is easier to purify, so that fewer cations are left in a system in fluoride salts, and the purity of the lithium bis-fluorosulfonyl imide obtained after purification in each step is higher. The reactions of the three steps in the preparation method of the lithium bis (fluorosulfonyl) imide are easy to carry out, so that the yield of the obtained lithium bis (fluorosulfonyl) imide is high.
Description
Technical Field
The invention relates to the technical field of compound synthesis, in particular to a preparation method of lithium bis (fluorosulfonyl) imide and application of the lithium bis (fluorosulfonyl) imide.
Background
With the improvement of the requirements of people on the performance of the battery, the development of the battery with high energy density, strong environmental adaptability, high safety and quick charging capability has important demand theory and practical application prospect, and the development of the matched electrolyte and electrolyte material is a key technology for restricting the improvement of the performance of the battery. Compared with lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide (LiFSI) has higher electrochemical stability and thermal stability, better adaptability with anode and cathode materials, excellent low-temperature performance and higher safety. The lithium salt is a key high-performance electrolyte material in new energy devices such as primary lithium batteries, secondary lithium ion batteries, super capacitors and the like, has high industrial application value, and is a novel lithium salt with the most industrial prospect at present.
Most of the current methods for preparing LiFSI are: firstly, chlorosulfonic acid, thionyl chloride and sulfamic acid or chlorosulfonic acid and chlorosulfonyl isocyanate react to obtain dichlorosulfonimide (HClSI), dichlorosulfonimide (HClSI) reacts with a fluorinating reagent to obtain difluorosulfonimide (HFSI) or a difluorosulfonimide metal salt, and the HFSI or the difluorosulfonimide metal salt is ion-exchanged with a lithiation reagent to obtain LiFSI.
For example, patents CN106044728, CN107055493 and CN108002355 report the fluorination of HClSI with HF to produce HFSI, followed by reaction with HFSI and lithiating reagents to produce LiFSI. The method needs to use HF as a reaction raw material, and the HF is a chemical substance with high toxicity, high corrosivity and high volatility, has high requirements on production equipment materials and has great pollution to the environment. The fluorination reaction process needs to be carried out in a high-pressure reaction kettle, the requirement on the tightness of equipment is high, and the large-scale industrial production is difficult.
Patent CN101747242 reports the use of SbF3And K2CO3Fluorination of HClSI to KFSI followed by KFSI and LiClO4And performing ion exchange to obtain LiFSI. The LiFSI prepared by the method contains high metal ion impurities, the content of potassium ions is difficult to meet the requirements, and LiClO4Is an explosive substance and has high price.
Patent CN108275666 reports that HClSI and LiF react directly in one step to produce LiFSI. The method can generate HF byproducts, and HF as a chemical substance with high toxicity, high corrosivity and high volatility has high requirements on production equipment materials and great environmental pollution, and crown ether used in the reaction has extremely high price and is difficult to realize industrialized production. The product of the reaction, namely chloride ions, is difficult to control and qualify, and LiFSI with the quality meeting the requirements is difficult to obtain.
Patent CN102917979 reports HClSI and ZnF2Reacting to obtain the zinc bis (fluorosulfonyl) imide salt, reacting the zinc bis (fluorosulfonyl) imide salt with ammonia water to obtain ammonium bis (fluorosulfonyl) imide salt, and exchanging the ammonium bis (fluorosulfonyl) imide salt with lithium hydroxide ions to obtain LiFSI. The method has more steps, needs multiple times of extraction, generates a large amount of waste water and has lower yield; it is difficult to remove clean residual metal cations and to obtain high quality acceptable LiFSI.
Patent CN107814364 reports the reaction of halogenated sulfonic acids, halogenated sulfonic acid isocyanates and halogenated salts to obtain LiFSI. LiFSI synthesized by the method is difficult to remove chloride ions, and qualified LiFSI cannot be obtained.
The above patents have the following defects that hydrofluoric acid is used as a fluorinating agent, the hydrofluoric acid has strong corrosivity, high requirement on equipment, high equipment investment, dangerous reaction and difficult guarantee of safety; secondly, fluorinating HClSI by using fluoride salt as a fluorinating reagent to generate HFSI, wherein HClSI is difficult to purify, so that a large amount of metal cations are left, and qualified LiFSI products are difficult to obtain; ③ CN102917979 the raw material is fluorinated, but LiFSI prepared by the one-pot reaction has a large amount of chloride ion residue.
Therefore, it is necessary to develop a process route for the synthetic preparation of LiFSI that can circumvent the above-mentioned drawbacks.
Disclosure of Invention
Based on the above problems, the present invention aims to provide a method for preparing lithium bis (fluorosulfonyl) imide and applications thereof, wherein the method can avoid using hydrofluoric acid as a fluorination reagent, thereby avoiding ion residues, and the obtained lithium bis (fluorosulfonyl) imide has high purity and yield, is suitable for large-scale industrial production, and is beneficial to popularization and application in lithium ion batteries.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing lithium bis (fluorosulfonyl) imide, comprising the steps of:
(1) fluorination reaction
Reacting chlorosulfonic acid isocyanate with fluoride salt and purifying to obtain fluorosulfonic acid isocyanate, reacting potassium bifluoride with fuming sulfuric acid and purifying to obtain fluorosulfonic acid;
(2) catalytic reaction
Reacting fluorosulfonic acid isocyanate and fluorosulfonic acid under the action of a catalyst and purifying to obtain bis-fluorosulfonyl imide;
(3) lithiation reaction
Reacting the bis-fluorosulfonyl imide and the lithiation reagent in an organic solvent system, and drying.
The invention adopts fluoride salt as the fluorinating reagent, avoids using HF, has lower requirements on the material of production equipment and mild reaction conditions, and is easy to carry out large-scale industrial production. Firstly, raw materials are fluorinated to obtain fluorosulfonic acid isocyanate and fluorosulfonic acid, and then, the raw materials are subjected to catalytic reaction to obtain bis-fluorosulfonyl imide, compared with bis-chlorosulfonyl imide which is difficult to purify after being fluorinated, the fluorosulfonic acid isocyanate and fluorosulfonic acid obtained by fluorination are easier to purify by rectification, so that fewer cations in fluoride salt are left in a system, and the purity of bis-fluorosulfonyl imide lithium obtained after purification in each step is higher. The reactions of the three steps in the preparation method of the lithium bis (fluorosulfonyl) imide are easy to carry out, so that the yield of the obtained lithium bis (fluorosulfonyl) imide is high.
Preferably, the fluoride salt is NaF, KF or SbF3、SbF5、SnF4Or ZnF2The raw materials are easy to obtain and react.
Preferably, SO in the oleum3The mass fraction of the sulfur trioxide is 60%, and the molar ratio of the sulfur trioxide in the oleum to the potassium bifluoride is 1: 1-4.
Preferably, in the step (2), the molar ratio of the fluorosulfonic acid isocyanate to the fluorosulfonic acid is 1: 0.5-1.5.
Preferably, the catalyst is FeCl2、FeCl3、ZnCl2Or SnCl2。
Preferably, the lithiation reagent is LiOH or Li2CO3Or CH3COOLi。
Preferably, the organic solvent is at least one of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethyl acetate, propyl acetate, butyl acetate, ethylene glycol dimethyl ether and acetonitrile.
Preferably, in the step (1), the reaction temperature of the chlorosulfonic acid isocyanate and the fluoride salt is 50-90 ℃, the reaction temperature of the potassium bifluoride and the fuming sulfuric acid is-30 ℃, the catalytic reaction temperature in the step (2) is 80-150 ℃, and the lithiation reaction temperature in the step (3) is 10-80 ℃.
Preferably, in the step (1), the chlorosulfonic acid isocyanate is purified by atmospheric distillation after reacting with the fluoride salt, the potassium bifluoride is purified by reduced pressure distillation after reacting with the oleum, the step (2) is purified by reduced pressure distillation, and the step (3) is dried by thin film evaporation.
The invention provides an application of the lithium bis (fluorosulfonyl) imide, and the lithium bis (fluorosulfonyl) imide prepared by the preparation method is used as a lithium salt or an additive of a lithium ion battery. The purity and the yield of the lithium bis (fluorosulfonyl) imide are high, and the lithium bis (fluorosulfonyl) imide is favorable for popularization and application in lithium ion batteries.
Detailed Description
The preparation method of the lithium bis (fluorosulfonyl) imide comprises the steps of (1) fluorination reaction, (2) catalytic reaction and (3) lithiation reaction, and the reaction route is shown as follows.
Preparation of fluorosulfonic acid isocyanate:
wherein: m is cation such as Na, K, Sb and Zn.
Preparation of fluorosulfonic acid:
preparation of HFSI:
preparation of LiFSI:
wherein X is OH-、CO3 2-Plasma anion
Wherein, the fluorination reaction in the step (1) comprises the following steps: a. reacting chlorosulfonic acid isocyanate with fluoride salt and purifying to obtain fluorosulfonic acid isocyanate; b. reacting potassium bifluoride with oleum and purifying to obtain fluorosulfonic acid.
Step a, adding a fluorination reagent and chlorosulfonic acid isocyanate into a reaction kettle, controlling the reaction temperature to be 50-90 ℃, preferably 60-70 ℃, stirring and reacting for 24-48 hours, after the reaction is completed, carrying out atmospheric distillation at 100 ℃, collecting 80 ℃ fractions, and removing unreacted chlorosulfonic acid isocyanate and fluorination reagent to obtain fluorosulfonic acid isocyanate. And the fluoride salt is NaF, KF, SbF3、SbF5、SnF4Or ZnF2The raw materials are available and the reaction is easy to proceed.
And b, adding potassium bifluoride into fuming sulfuric acid, controlling the reaction temperature to be-30 ℃, preferably-10-0 ℃, stirring and reacting for 12-24 hours, after the reaction is completed, carrying out reduced pressure distillation at 125 ℃, and collecting a fraction with the vacuum degree of 25mmHg at 95 ℃ to remove unreacted potassium bifluoride and fuming sulfuric acid to obtain the fluorosulfonic acid. Wherein SO is contained in oleum3The mass fraction of (b) is 60%, and the molar ratio of sulfur trioxide to potassium bifluoride in the oleum is 1: 1-4, preferably 1: 1.5-2.
The catalytic reaction in the step (2) can be that fluorosulfonic acid isocyanate and fluorosulfonic acid (the molar ratio is 1: 0.5-1.5, preferably 1: 0.95-1.05) are added into a reaction bottle, the reaction temperature is controlled to be 80-150 ℃ under the action of a catalyst, and preferably the reaction temperature is controlled to be 80-150 DEG CStirring and reacting for 24-36 h at 110-130 ℃, after the reaction is completed, carrying out reduced pressure distillation at 135 ℃, and collecting 110 ℃ and 25mmHg of vacuum degree fraction to remove unreacted fluorosulfonic acid isocyanate and fluorosulfonic acid to obtain the bis-fluorosulfonyl imide. Wherein the catalyst is FeCl2、FeCl3、ZnCl2Or SnCl2。
The lithiation reaction in the step (3) can be implemented by putting the bis-fluorosulfonyl imide and a lithiation reagent in an organic solvent system, adjusting the pH value to 5-7, controlling the reaction temperature to 10-80 ℃, preferably 25-35 ℃, stirring for reacting for 2-4 h, and after the reaction is completed, evaporating and drying the thin film at 35-50 ℃. The organic solvent can be at least one of dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, ethyl acetate, propyl acetate, butyl acetate, ethylene glycol dimethyl ether and acetonitrile, and the organic solvent commonly used by lithium ion batteries is used as a reaction medium, so that the influence of excessive other substances introduced in the reaction on the subsequent use can be avoided. The lithiation reagent is LiOH or Li2CO3Or CH3COOLi。
To better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples. It should be noted that the following implementation of the method is a further explanation of the present invention, and should not be taken as a limitation of the present invention.
Example 1
The preparation method of the lithium bis (fluorosulfonyl) imide comprises the following steps:
(1) fluorination reaction
Adding 142.8g (0.81mol) of antimony trifluoride into a dry 1000ml three-neck flask, placing the three-neck flask in an oil bath pot, heating and stirring, setting the temperature of the water bath pot to be constant at 70 ℃, slowly dropwise adding 339.6g (2.4mol) of chlorosulfonic acid isocyanate, stirring, refluxing and reacting for 48 hours, gradually heating to 100 ℃ after the reaction is completed, carrying out normal pressure distillation, collecting 240g of colorless transparent liquid fluorosulfonic acid isocyanate fraction at 80 ℃, wherein the purity is 99.9%, and the yield is 80%;
333.3g (wherein 2.5mol of sulfur trioxide) (containing 60% of sulfur trioxide) fuming sulfuric acid is added into a dry 1000ml three-neck flask, the three-neck flask is placed in an ice water bath at 0 ℃ for stirring, 351g (4.5mol) of potassium bifluoride is slowly and dropwise added, stirring and refluxing reaction are carried out for 12 hours, after the reaction is completed, nitrogen is blown, the temperature is increased to 125 ℃ for reduced pressure distillation, 187.5g of fraction fluorosulfonic acid with the vacuum degree of 25mmHg at 95 ℃ is collected, the purity is 99.9%, and the yield is 75%.
(2) Catalytic reaction
100g (1mol) of fluorosulfonic acid, 125g (1mol) of fluorosulfonic acid isocyanate and 2g of ferric chloride are added into a dry 500ml three-neck flask, the mixture is placed in an oil bath at 125 ℃ and stirred for reflux reaction for 24 hours, after the reaction is finished, the temperature is raised to 135 ℃ for reduced pressure distillation, 110 ℃ and 25mmHg fractions of difluoride sulfimide HFSI are collected, the yield is 76%, and the purity is 99.9%.
(3) Lithiation reaction
Adding 90g (0.5mol) of HFSI and 400g of dimethyl carbonate into a dry 1000ml three-neck flask, placing the flask in a water bath at 25 ℃, uniformly stirring, adding 21g (0.5mol) of lithium hydroxide monohydrate to reach the pH value of 6-7, stirring for reaction for 2 hours, and after the reaction is completed, carrying out thin film evaporation drying at 40 ℃ to obtain 91.6g of dry LiFSI, wherein the purity of the dry LiFSI is 99.9%, and the yield of the dry LiFSI is 98%.
Example 2
The preparation method of the lithium bis (fluorosulfonyl) imide comprises the following steps:
(1) fluorination reaction
Adding 125.6g (1.215mol) of zinc fluoride into a dry 1000ml three-neck flask, placing the three-neck flask in an oil bath pot, heating and stirring, setting the temperature of the water bath pot to be 70 ℃, slowly dropwise adding 339.6g (2.4mol) of chlorosulfonic acid isocyanate, stirring, refluxing and reacting for 48 hours, gradually heating to 100 ℃ after the reaction is completed, carrying out normal pressure distillation, collecting 234g of 80 ℃ colorless transparent liquid fluorosulfonic acid isocyanate fraction, wherein the purity is 99.9%, and the yield is 78%;
333.3g (2.5mol of sulfur trioxide) (containing 60 percent of sulfur trioxide) fuming sulfuric acid is added into a dry 1000ml three-neck flask, the three-neck flask is placed in an ice water bath at 0 ℃ to be stirred, 351g (4.5mol) of potassium bifluoride is slowly and dropwise added, the stirring reflux reaction is carried out for 14h, after the reaction is finished, nitrogen is swept, the temperature is increased to 125 ℃ to carry out reduced pressure distillation, 190.0g of fraction fluorosulfonic acid with the vacuum degree of 25mmHg at 95 ℃ is collected, the purity is 99.9 percent, and the yield is 76 percent.
(2) Catalytic reaction
100g (1mol) of fluorosulfonic acid, 125g (1mol) of fluorosulfonic acid isocyanate and 2g of zinc dichloride are added into a dry 500ml three-neck flask, the mixture is placed in an oil bath at 125 ℃ and stirred for reflux reaction for 24 hours, after the reaction is finished, the temperature is raised to 135 ℃ for reduced pressure distillation, and then 132.2g of the distillate HFSI with the temperature of 110 ℃ and the vacuum degree of 25mmHg is collected, the yield is 73 percent, and the purity is 99.9 percent.
(3) Lithiation reaction
Adding 90g (0.5mol) of HFSI and 400g of ethyl acetate into a dry 1000ml three-neck flask, placing the flask in a water bath at 25 ℃, uniformly stirring, adding 18.5g (0.25mol) of lithium carbonate to the pH value of 6-7, stirring for reaction for 2 hours, and after the reaction is completed, carrying out thin film evaporation drying at 40 ℃ to obtain 92.6g (0.495mol) of dry LiFSI with the purity of 99.9% and the yield of 99%.
The content of impurity ions in the lithium bis (fluorosulfonyl) imide obtained in example 1 and example 2 was measured, wherein the metal ions were the sum of Na, K, Ca, Fe, Cu, Zn, Al, Mg, As, Pb, Cd, Ni, Cr, and Hg, and the results are shown in table 1.
TABLE 1 parameters of the materials obtained in each of the steps of example 1 and example 2
The results in table 1 show that the lithium bis (fluorosulfonyl) imide obtained by the preparation method of the present invention has high purity and yield, especially the purity is higher than 99.9%, and the contents of metal ions, chloride ions and sulfate ions are less than 5ppm, which indicates that the present invention can effectively improve the purity by fluorinating the raw material and then performing the catalysis and lithiation reactions, thereby avoiding the introduction of various ionic impurities due to the fluorination of HClSI.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it is not limited to the embodiments, and those skilled in the art should understand that the technical solutions of the present invention can be modified or substituted with equivalents without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The preparation method of the lithium bis (fluorosulfonyl) imide is characterized by comprising the following steps:
(1) fluorination reaction
Reacting chlorosulfonic acid isocyanate with fluoride salt and purifying to obtain fluorosulfonic acid isocyanate, reacting potassium bifluoride with fuming sulfuric acid and purifying to obtain fluorosulfonic acid;
(2) catalytic reaction
Reacting the fluorosulfonic acid isocyanate and the fluorosulfonic acid under the action of a catalyst and purifying to obtain bis (fluorosulfonyl) imide;
(3) lithiation reaction
And reacting the bis-fluorosulfonyl imide and a lithiation reagent in an organic solvent system, and drying.
2. The method for preparing lithium bis (fluorosulfonyl) imide according to claim 1, wherein said fluoride salt is NaF, KF, SbF3、SbF5、SnF4Or ZnF2。
3. The method for producing lithium bis (fluorosulfonyl) imide according to claim 1, wherein SO in oleum is used as a source of SO3The mass fraction of the sulfur trioxide is 60%, and the molar ratio of the sulfur trioxide in the oleum to the potassium bifluoride is 1: 1-4.
4. The method for preparing lithium bis (fluorosulfonyl) imide according to claim 1, wherein in step (2), the molar ratio of fluorosulfonic acid isocyanate to fluorosulfonic acid is 1:0.5 to 1.5.
5. The bis-fluorosulfonylidene of claim 1The preparation method of the lithium amine is characterized in that the catalyst is FeCl2、FeCl3、ZnCl2Or SnCl2。
6. The method for preparing lithium bis (fluorosulfonyl) imide according to claim 1, wherein said lithiation reagent is LiOH or Li2CO3Or CH3COOLi。
7. The method for preparing lithium bis (fluorosulfonyl) imide according to claim 1, wherein said organic solvent is at least one of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethyl acetate, propyl acetate, butyl acetate, ethylene glycol dimethyl ether, and acetonitrile.
8. The preparation method of lithium bis (fluorosulfonyl) imide according to claim 1, wherein in step (1), the reaction temperature of chlorosulfonic acid isocyanate and the fluoride salt is 50 to 90 ℃, the reaction temperature of potassium bifluoride and the oleum is-30 to 30 ℃, the catalytic reaction temperature in step (2) is 80 to 150 ℃, and the lithiation reaction temperature in step (3) is 10 to 80 ℃.
9. The method for preparing lithium bis (fluorosulfonyl) imide according to claim 1, wherein in step (1), the chlorosulfonic acid isocyanate and the fluoride salt are purified by atmospheric distillation after reaction, the potassium bifluoride and the oleum are purified by vacuum distillation after reaction, the step (2) is purified by vacuum distillation, and the step (3) is dried by thin film evaporation.
10. The application of the lithium bis (fluorosulfonyl) imide is characterized in that the lithium bis (fluorosulfonyl) imide prepared by the preparation method of the lithium bis (fluorosulfonyl) imide disclosed by any one of claims 1-9 is used as a lithium salt or an additive of a lithium ion battery.
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