CN115304038B - Preparation method of lithium bis (fluorosulfonyl) imide - Google Patents
Preparation method of lithium bis (fluorosulfonyl) imide Download PDFInfo
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- CN115304038B CN115304038B CN202210878085.8A CN202210878085A CN115304038B CN 115304038 B CN115304038 B CN 115304038B CN 202210878085 A CN202210878085 A CN 202210878085A CN 115304038 B CN115304038 B CN 115304038B
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- imide
- lithium salt
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- fluorosulfonyl
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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 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 76
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 73
- 239000007788 liquid Substances 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 difluoro sulfonimide Chemical compound 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical group FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- ZJPPTKRSFKBZMD-UHFFFAOYSA-N [Li].FS(=N)F Chemical compound [Li].FS(=N)F ZJPPTKRSFKBZMD-UHFFFAOYSA-N 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- XPVRBHCXMWRJEY-UHFFFAOYSA-N difluoro(imino)-$l^{4}-sulfane Chemical compound FS(F)=N XPVRBHCXMWRJEY-UHFFFAOYSA-N 0.000 claims description 5
- 150000003949 imides Chemical class 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 238000007872 degassing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 8
- 239000002904 solvent Substances 0.000 abstract description 9
- 230000007547 defect Effects 0.000 abstract description 4
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 abstract description 2
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 238000004255 ion exchange chromatography Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000004811 liquid chromatography Methods 0.000 description 5
- 229910001414 potassium ion Inorganic materials 0.000 description 5
- 229910001415 sodium ion Inorganic materials 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- FRPHFZCDPYBUAU-UHFFFAOYSA-N Bromocresolgreen Chemical compound CC1=C(Br)C(O)=C(Br)C=C1C1(C=2C(=C(Br)C(O)=C(Br)C=2)C)C2=CC=CC=C2S(=O)(=O)O1 FRPHFZCDPYBUAU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000005571 anion exchange chromatography Methods 0.000 description 1
- WVQUCYVTZWVNLV-UHFFFAOYSA-N boric acid;oxalic acid Chemical compound OB(O)O.OC(=O)C(O)=O WVQUCYVTZWVNLV-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
-
- 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)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A preparation method of lithium bis (fluorosulfonyl) imide belongs to the technical field of lithium bis (fluorosulfonyl) imide preparation and overcomes the defect that in the prior art, extra solvent is needed in the process of preparing lithium bis (fluorosulfonyl) imide. The preparation method of the invention comprises the following steps: step 1, preparing liquid lithium salt by adopting a polyhydroxy substrate, alkaline lithium salt and glycidol under the condition of protecting gas; and step 2, mixing the difluoro-sulfonyl imide with the liquid lithium salt, reacting, and carrying out solid-liquid separation to obtain solid difluoro-sulfonyl imide lithium. According to the invention, under the condition that no solvent is additionally added, liquid-liquid reaction is carried out by utilizing the liquid lithium salt and the difluoro sulfonimide, the reaction process is green and environment-friendly, the defect of the traditional solid-liquid reaction is eliminated, and the high-quality difluoro sulfonimide lithium can be obtained through filtration.
Description
Technical Field
The invention belongs to the technical field of preparation of lithium bis (fluorosulfonyl) imide, and particularly relates to a preparation method of lithium bis (fluorosulfonyl) imide.
Background
Most lithium ion batteries currently use lithium hexafluorophosphate (LiPF 6) as an electrolyte, however, the electrolyte of LiPF6 inevitably generates toxic byproduct hydrogen fluoride after hydrolysis, thereby causing dissolution of electrode material metal and bringing the safety risk of the battery. Recently, lithium bis (fluorosulfonyl) imide (LiFSI) is considered as one of the most promising alternatives to LiPF6, applied to new generation lithium salt electrolyte materials for electric vehicles and energy storage lithium ion power batteries. The physicochemical properties of LiFeSI are obviously better than those of LiPF6:1. higher thermal stability, namely the LiFSI melting point is 145 ℃, and the decomposition temperature is higher than 200 ℃;2. better conductivity—lithium ions of LiFSI are more easily dissociated; 3. improve the performances of high-temperature storage, low-temperature discharge and the like, and has excellent characteristics of good compatibility with electrodes and the like. Thus, liFSI is an electrolyte with good prospects in lithium ion batteries.
The prior art discloses the following preparation methods: dissolving difluoro sulfimide acid in a protective solvent, adding the double oxalic acid borate dissolved in a benign solvent into the difluoro sulfimide acid protective solvent solution in a dropwise manner for reaction, and filtering after the reaction is finished to obtain the difluoro sulfimide salt. The method uses solvent, and has low environmental protection.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect that extra solvent is needed in the process of preparing the lithium difluorosulfimide salt in the prior art, thereby providing a preparation method of the lithium difluorosulfimide.
The invention provides a LiFSI product with high purity and stable quality prepared from liquid lithium salt, which provides a basis for realizing industrial application.
For this purpose, the invention provides the following technical scheme.
The preparation method of the lithium bis (fluorosulfonyl) imide comprises the following steps:
step 1, preparing liquid lithium salt by adopting a polyhydroxy substrate, alkaline lithium salt and glycidol under the condition of protecting gas;
and step 2, mixing the difluoro-sulfonyl imide with the liquid lithium salt, reacting, and carrying out solid-liquid separation to obtain solid difluoro-sulfonyl imide lithium.
Further, the method also comprises a step 3 of adding alkaline lithium salt into the liquid obtained after solid-liquid separation to prepare liquid lithium salt again.
Further, step 1 includes:
step 101, mixing a polyhydroxy substrate and alkaline lithium salt under the protection of protective gas, reacting, and decompressing and dehydrating;
step 102, dropwise adding glycidol into the product of the step 101, and reacting to obtain hyperbranched glycidol ether lithium salt, namely liquid lithium salt.
Further, in the step 1,
a polyhydroxy substrate: molar ratio of alkaline lithium salt = 1: (0.1 to 25);
a polyhydroxy substrate: glycidol molar ratio = 1: (1-25).
Further, the step 1 satisfies at least one of the conditions (1) to (3):
(1) The protective gas is nitrogen or argon, preferably nitrogen;
(2) The polyhydric substrate comprises at least one of glycerol or trimethylolpropane;
(3) The alkaline lithium salt includes at least one of lithium hydroxide or lithium carbonate.
Further, the step 1 satisfies at least one of the conditions (1) to (4):
(1) In the step 101, the reaction temperature is 20-120 ℃ and the reaction time is 10 min-3 h;
(2) In the step 101, the pressure of the reduced pressure dehydration is 0.001mbar-950mbar of vacuum negative pressure;
(3) In the step 102, the rate of adding glycidol dropwise: 10. Mu.L/min-500. Mu.L/min, preferably 20. Mu.L/min-200. Mu.L/min;
(4) In the step 102, the reaction is: after the glycidol is added dropwise, stirring is continuously maintained for 2-5 hours, and the reaction temperature is 20-120 ℃.
Further, in the step 2, the liquid lithium salt: molar ratio of bis-fluorosulfonyl imide = 1: (0.1-25).
Further, in the step 2, mixing the bis-fluorosulfonyl imide with the liquid lithium salt includes: controlling the temperature of the liquid lithium salt at-10-40 ℃ and keeping stirring, and dropwise adding the difluoro sulfimide;
the reaction comprises: after the end of the dropwise addition of the bisfluorosulfonyl imide, the temperature is restored to room temperature, and stirring is continued for 2-5 hours.
Further, the step 3 includes: under the condition of protective gas, adding alkaline lithium salt into the liquid obtained after solid-liquid separation, reacting, decompressing and degassing, and filtering to remove unreacted alkaline lithium salt to obtain liquid lithium salt;
and step 4, preparing lithium bis (fluorosulfonyl) imide by utilizing the liquid lithium salt obtained in the step 3.
Further, the step 3 satisfies at least one of the following conditions (1) to (5):
(1) The shielding gas is nitrogen or argon, preferably nitrogen;
(2) The alkaline lithium salt comprises at least one of lithium hydroxide or lithium carbonate;
(3) The reaction temperature is 20-120 ℃;
(4) Vacuum dehydration is carried out to vacuum negative pressure of 0.001mbar-950mbar;
(5) The pore diameter of the filtering membrane is 0.01 mu m-0.45mm; preferably 0.1 μm to 0.8. Mu.m.
The molecular weight of the liquid lithium salt was measured by gel liquid chromatography, and then molar calculation was performed using the number average molecular weight as the calculated molecular weight.
In the step 3, the filtrate is recovered, and when the liquid lithium salt is prepared again, the amount of Li reacted can be calculated according to the amount of HFSI added in the step 2, so that the amount of the alkaline lithium salt added in the step 3 is controlled. Or the hydroxyl value of the filtrate is detected to reversely calculate the hydroxyl amount in the filtrate, so as to judge the maximum amount of the alkaline lithium salt to be added.
The technical scheme of the invention has the following advantages:
1. the preparation method of the lithium bis (fluorosulfonyl) imide provided by the invention comprises the following steps: step 1, preparing liquid lithium salt by adopting a polyhydroxy substrate, alkaline lithium salt and glycidol under the condition of protecting gas; and step 2, mixing the difluoro-sulfonyl imide with the liquid lithium salt, reacting, and carrying out solid-liquid separation to obtain solid difluoro-sulfonyl imide lithium. According to the invention, under the condition that no solvent is additionally added, liquid-liquid reaction is carried out by utilizing the liquid lithium salt and the difluoro sulfonimide, the reaction process is green and environment-friendly, the defect of the traditional solid-liquid reaction is eliminated, and the high-quality difluoro sulfonimide lithium can be obtained through filtration.
2. The preparation method of the lithium bis (fluorosulfonyl) imide provided by the invention further comprises a step 3 of adding alkaline lithium salt into the liquid obtained after solid-liquid separation to prepare liquid lithium salt again. The filtrate can be recycled to prepare liquid lithium salt again and is reused for preparing lithium bis (fluorosulfonyl) imide, so that the cost is well controlled.
3. The invention provides a preparation method of lithium bis (fluorosulfonyl) imide, wherein the step 1 comprises the following steps: step 101, mixing a polyhydroxy substrate and alkaline lithium salt under the protection of protective gas, reacting, and decompressing and dehydrating; step 102, dropwise adding glycidol into the product of the step 101, and reacting to obtain hyperbranched glycidol ether lithium salt, namely liquid lithium salt. Lithium bis (fluorosulfonyl) imide (LiSSI) has relatively high solubility in small molecule alcohol solutions, but after synthesizing alcohol ether structures with hyperbranched structures, the solubility of LiSSI is greatly reduced, so that the product can be obtained by filtration.
4. The invention provides a preparation method of lithium bis (fluorosulfonyl) imide, which comprises the following steps: molar ratio of bis-fluorosulfonyl imide = 1: (0.1-25), the number of moles of lithium ions needs to be greater than the number of moles of bis (fluorosulfonyl) imide (HFSI), ensuring complete conversion of HFSI.
5. According to the preparation method of the lithium bis (fluorosulfonyl) imide, the reaction temperature of the steps 101 and 102 is 20-120 ℃, the temperature of the synthesized liquid lithium salt is controlled, the viscosity of the system can be controlled within a reasonable range, incomplete reaction is avoided, and meanwhile, the synthesized liquid lithium salt is transparent and not turbid; in step 2, mixing the bis-fluorosulfonyl imide with the liquid lithium salt comprises: the temperature of the liquid lithium salt is controlled between-10 ℃ and 40 ℃ and stirring is kept, so that HFSI hydrolysis is avoided.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The embodiment provides a preparation method of lithium bis (fluorosulfonyl) imide, which comprises the following steps:
step 1, preparing liquid lithium salt:
step 101, under the protection of nitrogen, 46 g of glycerin (0.5 mol) and 36 g of lithium hydroxide (1.5 mol) are added into a reactor, the temperature is raised to 70 ℃ for reaction for 1 hour, and then vacuum negative pressure is opened for 10mbar water removal until no bubbles are generated in the reactor.
Step 102, heating to 90 ℃, 110 g of glycidol (1.5 mol) was added dropwise to the reactor at a rate of 100 μl/min. And after the dripping is finished, stirring for 2 hours to obtain the liquid lithium salt. The number average molecular weight of the gel liquid chromatography detection is 330g/mol, and the molecular weight distribution is 1.03.
Step 2, preparing lithium bis (fluorosulfonyl) imide:
in a reactor containing a liquid lithium salt, the reactor temperature was controlled to 10℃and 235 g of bis-fluorosulfonyl imide (1.3 mol) was added dropwise, during which the temperature was controlled to 10.+ -. 5 ℃. After the dripping is finished, the mixture is restored to room temperature and stirred for 2 hours, and then the mixture is filtered by a filter membrane with the diameter of 0.45 micrometers, thus obtaining the lithium bis (fluorosulfonyl) imide solid. 240 g of lithium bis (fluorosulfonyl) imide are obtained, with a conversion of 98.7%.
Example 2
The embodiment provides a preparation method of lithium bis (fluorosulfonyl) imide, wherein steps 1 and 2 are the same as those in embodiment 1, and further include:
step 3, regenerating liquid lithium salt:
the filtrate from the preparation of lithium difluorosulfimide salt was recovered (150 g of recovered filtrate), charged into the reactor under nitrogen protection, and 36 g of lithium hydroxide (1.5 mol) was added into the reactor, heated to 60 ℃ and reacted for 1 hour, followed by opening vacuum negative pressure of 2mbar to remove water until no bubbles were generated in the reactor. And filtering out unreacted lithium hydroxide in the reaction system by using a 0.1-micrometer filter membrane, wherein the remaining filtrate is regenerated liquid lithium salt. The number average molecular weight of the gel liquid chromatography detection is 338g/mol, and the molecular weight distribution is 1.06.
Step 4, preparing lithium difluorosulfimide by using regenerated liquid lithium salt:
the regenerated liquid lithium salt is added into a reactor, the temperature of the reactor is controlled to be 20 ℃, 181 g of bisfluorosulfonyl imide (1 mol) is added dropwise, the dripping process cannot be too fast, and the temperature is controlled to be 20+/-5 ℃ as much as possible. After the completion of the dropwise addition, the reaction was kept under stirring at 25℃for 3 hours, followed by filtration through a 0.1 μm filter membrane to obtain a solid as lithium difluorosulfonimide. 182 g of lithium bis (fluorosulfonyl) imide are obtained with a conversion of 97.3%.
Example 3
The embodiment provides a preparation method of lithium bis (fluorosulfonyl) imide, which comprises the following steps:
step 1, preparing liquid lithium salt:
step 101, 23 g of glycerin (0.25 mol) and 443 g of lithium carbonate (6 mol) are added into a reactor under the protection of nitrogen, the temperature is raised to 110 ℃, the reaction is carried out for 10 minutes, and then vacuum negative pressure 950mbar is opened for water removal until no bubbles are generated in the reactor.
Step 102, heating to 110 ℃, 370 g of glycidol (5 moles) was added dropwise to the reactor at a rate of 200 μl/min. And after the dripping is finished, stirring for 3 hours to obtain the liquid lithium salt. The number average molecular weight was 1680g/mol as measured by gel liquid chromatography, and the molecular weight distribution was 1.03.
Step 2, preparing lithium bis (fluorosulfonyl) imide:
in a reactor containing liquid lithium salt, the reactor temperature was controlled to 20℃and 452 g of bis-fluorosulfonyl imide (2.5 moles) was added dropwise, the addition being not too rapid and the temperature was controlled to 20.+ -. 5℃as much as possible. After the completion of the dropwise addition, the mixture was returned to room temperature and stirred for 3 hours, followed by filtration through a 0.8 μm filter membrane to obtain a lithium difluorosulfimide solid. 458 g of lithium bis (fluorosulfonyl) imide are obtained with a conversion of 98%.
Example 4
The embodiment provides a preparation method of lithium bis (fluorosulfonyl) imide, which comprises the following steps:
step 1, preparing liquid lithium salt:
step 101, 92 g of glycerol (1 mol) and 2.4 g of lithium hydroxide (0.1 mol) are put into a reactor under the protection of nitrogen, reacted for 3 hours at 20 ℃, and then vacuum negative pressure is turned on for 0.001mbar water removal until no bubbles are generated in the reactor.
Step 102, heating to 60 ℃, 74 g of glycidol (1 mole) was added dropwise to the reactor at a rate of 20 μl/min. And after the dripping is finished, stirring for 5 hours to obtain the liquid lithium salt. The number average molecular weight of the gel is 184g/mol and the molecular weight distribution is 1.01.
Step 2, preparing lithium bis (fluorosulfonyl) imide:
in a reactor containing a liquid lithium salt, the reactor temperature was controlled to-10℃and 18.1 g of bis-fluorosulfonyl imide (0.1 mol) was added dropwise, the addition being not too rapid and the temperature was controlled to-10.+ -. 5℃as much as possible. After the completion of the dropwise addition, the mixture was returned to room temperature and stirred for 5 hours, followed by filtration through a 0.1 μm filter membrane to obtain a lithium difluorosulfimide solid. 18.4 g of lithium difluorosulfimide are obtained, with a conversion of 98.2%.
Example 5
The embodiment provides a preparation method of lithium bis (fluorosulfonyl) imide, which comprises the following steps:
step 1, preparing liquid lithium salt:
step 101, under the protection of nitrogen, 40 g of trimethylolpropane (0.3 mol) and 36 g of lithium hydroxide (1.5 mol) are put into a reactor, the temperature is raised to 120 ℃, the reaction is carried out for 10 minutes, and then the vacuum negative pressure is opened for 450mbar for water removal until no bubbles are generated in the reactor.
Step 102, heating to 120 ℃, 220 g of glycidol (3 moles) was added dropwise to the reactor at a rate of 150 μl/min. And after the dripping is finished, stirring for 2 hours to obtain the liquid lithium salt. The number average molecular weight of the gel liquid chromatography detection is 900g/mol, and the molecular weight distribution is 1.04.
Step 2, preparing lithium bis (fluorosulfonyl) imide:
in a reactor containing a liquid lithium salt, the reactor temperature was controlled to 30℃and 181 g of bisfluorosulfonyl imide (1 mole) was added dropwise, the addition being not too rapid and the temperature was controlled to 30.+ -. 5℃as much as possible. After the dripping is finished, the mixture is restored to room temperature and stirred for 2 hours, and then the mixture is filtered by a filter membrane with the size of 0.2 microns, thus obtaining the lithium bis (fluorosulfonyl) imide solid. 184g of lithium bis (fluorosulfonyl) imide are obtained with a conversion of 98.4%.
Test examples
1) The ion chromatography content is detected by conventional anion chromatography, and the proportion of the FSI-anion peak is judged by a peak area method, so that the content of the finished product of the lithium difluorosulfimide salt is obtained.
2) The "acid value" (or referred to as acidic type impurity) is measured by: preparing sodium hydroxide solution, taking bromocresol green as an indicator, titrating until the bluish green color is developed as an end point, and calculating the proportion of the acidic substance in the finished product according to the concentration and the sample weighing according to the HF (hydrogen fluoride) of the acidic substance.
3) "10% dimethyl carbonate solution turbidity" is measured by: electronic grade dimethyl carbonate is used as a solvent, difluoro sulfonimide salt is used as a solute, and after being dissolved according to the proportion of 10% of the solute, the solution is compared with a standard turbidity solution to judge the degree of turbidity.
4) "chromaticity" is measured by: the 50 ml solution of lithium bis (fluorosulfonyl) imide is prepared by using the solution of electronic grade ethylene carbonate, electronic grade dimethyl carbonate and electronic grade methyl ethyl carbonate with the concentration of 1 mol/L to 1:1:1, and the corresponding chromaticity index is confirmed after the comparison is carried out between the 50 ml solution and a standard chromaticity sample.
5) The measurement of metal ions, e.g., sodium, potassium, iron ions, can be detected by inductively coupled plasma spectroscopy (ICP).
6) The chlorine content can be measured by a potentiometric titrator.
7) The measurement of moisture was detected by karl fischer reagent.
In example 1, the purity of the obtained lithium difluorosulfimide was 99.92% in terms of the area ratio of the ion chromatography peak, the sodium ion was 1.5ppm, the potassium ion was 1.2ppm, the chlorine content was 0.3ppm, the acid value was 10ppm, the water content was 40ppm, the turbidity of the 10% dimethyl carbonate solution was 5mg/L, and the color was 8Hazen.
The lithium difluorosulfimide obtained in the step 4 of example 2 had a purity of 99.86% in terms of ion chromatography peak area ratio, a sodium ion of 1.1ppm, a potassium ion of 2.4ppm, a chlorine content of 0.5ppm, an acid value of 15ppm, a moisture of 30ppm, a turbidity of a 10% dimethyl carbonate solution of 3mg/L and a color of 10Hazen.
In example 3, the purity of the obtained lithium difluorosulfimide was 99.90% in terms of the area ratio of the ion chromatography peak, the sodium ion was 3.5ppm, the potassium ion was 0.3ppm, the chlorine content was 0.5ppm, the acid value was 5ppm, the water content was 50ppm, the turbidity of a 10% dimethyl carbonate solution was 3mg/L, and the color was 10Hazen.
In example 4, the purity of the obtained lithium difluorosulfimide was 99.95% in terms of the area ratio of the ion chromatography peak, the sodium ion was 0.4ppm, the potassium ion was 0.8ppm, the chlorine content was 0.9ppm, the acid value was 7ppm, the water content was 27ppm, the turbidity of the 10% dimethyl carbonate solution was 5mg/L, and the color was 7Hazen.
In example 5, the purity of the obtained lithium difluorosulfimide was 99.87% in terms of the area ratio of the ion chromatography peak, 3.7ppm of sodium ion, 2.6ppm of potassium ion, 1.3ppm of chlorine content, 8ppm of acid value, 43ppm of water, and 7mg/L of turbidity of a 10% dimethyl carbonate solution, and 9Hazen in color.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. The preparation method of the lithium bis (fluorosulfonyl) imide is characterized by comprising the following steps:
step 1, preparing liquid lithium salt by adopting a polyhydroxy substrate, alkaline lithium salt and glycidol under the condition of protecting gas;
step 2, mixing the difluoro-sulfonyl imide with the liquid lithium salt, reacting, and carrying out solid-liquid separation to obtain solid difluoro-sulfonyl imide lithium;
the step 1 comprises the following steps:
step 101, mixing a polyhydroxy substrate and alkaline lithium salt under the protection of protective gas, reacting, and decompressing and dehydrating;
step 102, dropwise adding glycidol into the product of the step 101, and reacting to obtain hyperbranched glycidol ether lithium salt, namely liquid lithium salt;
the reaction temperature of the steps 101 and 102 is 20-120 ℃;
the polyhydric substrate comprises at least one of glycerol or trimethylolpropane;
in the step 2, the liquid lithium salt: molar ratio of bis-fluorosulfonyl imide = 1: (0.1-25) the mole number of lithium ions is greater than that of bisfluorosulfonyl imide;
in step 2, mixing the bis-fluorosulfonyl imide with the liquid lithium salt comprises: the temperature of the liquid lithium salt is controlled to be between-10 and 40 ℃ and stirring is kept, and the difluoro sulfimide is added dropwise.
2. The method for producing lithium bis (fluorosulfonyl) imide according to claim 1, further comprising step 3 of adding an alkaline lithium salt to the liquid obtained after the solid-liquid separation to prepare a liquid lithium salt again.
3. The method for producing lithium difluorosulfimide according to claim 1 or 2, wherein in the step 1,
a polyhydroxy substrate: molar ratio of alkaline lithium salt = 1: (0.1 to 25);
a polyhydroxy substrate: glycidol molar ratio = 1: (1-25).
4. The method for producing lithium bis (fluorosulfonyl) imide according to claim 1 or 2, wherein in step 1, the shielding gas is nitrogen or argon;
the alkaline lithium salt includes at least one of lithium hydroxide or lithium carbonate.
5. The method for producing lithium bis (fluorosulfonyl) imide according to claim 1, wherein in step 1,
in the step 101, the reaction time is 10 min-3 h;
in the step 101, the pressure of the reduced pressure dehydration is 0.001mbar-950mbar of vacuum negative pressure;
in the step 102, the rate of adding glycidol dropwise: 10 mu L/min-500 mu L/min;
in the step 102, the reaction is: and after the glycidol is added dropwise, stirring is continuously maintained for 2-5 hours.
6. The method for producing lithium bis (fluorosulfonyl) imide according to claim 1, wherein in the step 102, the rate of dropping glycidol is 20 μl/min to 200 μl/min.
7. The method for producing lithium bis (fluorosulfonyl) imide according to any one of claims 1, 2, and 5, wherein in step 2, the reaction comprises: after the end of the dropwise addition of the bisfluorosulfonyl imide, the temperature is restored to room temperature, and stirring is continued for 2-5 hours.
8. The method for preparing lithium bis (fluorosulfonyl) imide according to claim 2, wherein the step 3 comprises: under the condition of protective gas, adding alkaline lithium salt into the liquid obtained after solid-liquid separation, reacting, decompressing and degassing, and filtering to remove unreacted alkaline lithium salt to obtain liquid lithium salt;
and step 4, preparing lithium bis (fluorosulfonyl) imide by utilizing the liquid lithium salt obtained in the step 3.
9. The method for producing lithium bis (fluorosulfonyl) imide according to claim 8, wherein the step 3 satisfies at least one of the following conditions (1) to (5):
(1) The protective gas is nitrogen or argon;
(2) The alkaline lithium salt comprises at least one of lithium hydroxide or lithium carbonate;
(3) The reaction temperature is 20-120 ℃;
(4) Vacuum dehydration is carried out to vacuum negative pressure of 0.001mbar-950mbar;
(5) The pore size of the filtering membrane is 0.01 μm-0.45mm.
10. The method for producing lithium difluorosulfimide according to claim 8, wherein the pore size of the filtered filter membrane is 0.1 μm to 0.8 μm.
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