CN114957129A - Method for preparing 4, 5-dicyano-2-trifluoromethyl imidazole lithium - Google Patents
Method for preparing 4, 5-dicyano-2-trifluoromethyl imidazole lithium Download PDFInfo
- Publication number
- CN114957129A CN114957129A CN202210813394.7A CN202210813394A CN114957129A CN 114957129 A CN114957129 A CN 114957129A CN 202210813394 A CN202210813394 A CN 202210813394A CN 114957129 A CN114957129 A CN 114957129A
- Authority
- CN
- China
- Prior art keywords
- dicyano
- lithium
- trifluoromethylimidazole
- solvent
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/90—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing 4, 5-dicyano-2-trifluoromethyl imidazole lithium, which comprises the following steps: (1) preparation of 4, 5-dicyano-2-trifluoromethylimidazole: dissolving diaminomaleonitrile in a solvent, performing cyclization reaction with trifluoroacetic anhydride in a micron-sized tubular reactor, evaporating a by-product and the solvent A from a reaction solution, and decoloring, filtering and crystallizing to obtain a TDI pure product; (2) preparation of lithium 4, 5-dicyano-2-trifluoromethylimidazole: and (2) reacting the TDI pure product prepared in the step (1) with lithium or a lithium-containing compound LiY in a solvent B, and performing solid-liquid separation, crystallization and purification to obtain a LiTDI product. The cyclization reaction is carried out in a microchannel reactor, so that the problems of low boiling point of trifluoroacetic anhydride and extreme volatility at room temperature can be effectively solved, the raw materials are fully contacted, the temperature is accurately controlled, the reaction efficiency is high, and the reaction time is greatly shortened.
Description
Technical Field
The invention relates to a method for preparing 4, 5-dicyano-2-trifluoromethyl imidazole lithium, belonging to the field of lithium ion battery electrolyte additives.
Background
4, 5-dicyano-2-trifluoromethyl imidazole lithium, LiTDI for short, with a molecular weight of 192, is a novel lithium ion battery electrolyte lithium salt or additive. Compared with the mainstream electrolyte lithium hexafluorophosphate at the present stage, the LiTDI has the decomposition temperature of over 250 ℃, has large anion radius, is easy to dissociate into lithium ions in the electrolyte, and can stably exist under the voltage of 4.5V, so the electrolyte added with the LiTDI has better thermal stability and lithium ion migration capability. According to the report, the addition of a small amount of LiTDI can obviously prolong the normal-temperature and high-temperature storage life of the lithium ion battery, and can also improve the cycle performance of the lithium ion battery, and the product is expected to be widely applied to the field of high-energy-density lithium ion batteries. Research results show that the additive prepared from the lithium salt can greatly improve the performance of the electrolyte. In addition to its inherent stability, litid is an important moisture scavenger in the electrolyte. The lithium ion and the carbon nitrile group interact with water molecules and capture the water molecules through hydrogen bonds, so that LiPF is effectively inhibited 5 Hydrolysis of (3). LiPF 5 Is LiPF 6 The decomposition product on the negative electrode, which is a strong lewis acid, is a main cause of degradation of the electrolyte solvent. In addition, since LiPF 6 The degradation of the nitrile group, interaction with the HF molecule, can further mitigate parasitic reactions on the positive side. By reducing the influence of impurities on different electrolyte components, only 1% of LiTDI is added, so that the electrolyte stability can be improved, and the service life of the battery can be prolonged.
In the lithium ion battery, the LiTDI additive and the traditional SEI additive act synergistically, the battery impedance is reduced, and the rapid charge and discharge performance is obviously improved. LiTDI is a good electrolyte additive, and the service life of the battery can be obviously prolonged no matter a graphite cathode or a silicon-based anode is adopted.
At present, the method for preparing LiTDI is mainly divided into two steps: the first step is the synthesis of 4, 5-dicyano-2-Trifluoromethylimidazole (TDI), and the presently disclosed synthesis of 4, 5-dicyano-2-Trifluoromethylimidazole (TDI) has three types: 1. reacting diaminomaleonitrile with trifluoroacetic anhydride in a traditional kettle-type container to synthesize 4, 5-dicyano-2-Trifluoromethylimidazole (TDI), belonging to exothermic reaction, wherein the trifluoroacetic anhydride is required to be dropwise added at low temperature and the reaction time is long; 2. preparing TDI from diaminomaleonitrile and trifluoroacetic acid under the action of phosphorus pentoxide, wherein phosphoric acid byproducts are generated; 3. diaminomaleonitrile reacts with trifluoroacetate to obtain TDI, and the traditional kettle type reactor is used, so that the mass transfer and heat transfer efficiency is low, and the problem of long reaction time is also existed. The second step is to prepare LiTDI, in the existing preparation method, TDI reacts with lithium carbonate, lithium hydroxide, lithium polybasic acid, lithium polybasic carboxylate and the like in a water system or an organic solvent to prepare a 4, 5-dicyano-2-trifluoromethyl imidazole lithium product, and the LiTDI product has high water content and difficult water removal due to the fact that water is used as the solvent or water is generated in the reaction process. In summary, the LiTDI has excellent performance in the lithium ion battery, but the synthesis requirement is high, the reported process method is limited, and a new preparation method is urgently needed to be developed.
Disclosure of Invention
The invention aims to provide a method for preparing 4, 5-dicyano-2-trifluoromethyl imidazole lithium, which has the advantages of high mass transfer and heat transfer efficiency, short reaction time, high product yield, low moisture content and small amount of process wastewater.
In order to achieve the above object, the technical solution of the present invention is a method for preparing 4, 5-dicyano-2-trifluoromethylimidazole lithium, comprising the steps of:
(1) preparation of 4, 5-dicyano-2-trifluoromethylimidazole: dissolving diaminomaleonitrile in a solvent, performing cyclization reaction with trifluoroacetic anhydride in a micron-sized tubular reactor, evaporating a by-product and the solvent A from a reaction solution, and decoloring, filtering and crystallizing to obtain a TDI pure product;
(2) preparation of 4, 5-dicyano-2-trifluoromethylimidazole lithium: and (2) reacting the TDI pure product prepared in the step (1) with lithium or a lithium-containing compound LiY in a solvent B, and performing solid-liquid separation, crystallization and purification to obtain a LiTDI product.
In the step (1), the molar ratio of the diaminomaleonitrile to the trifluoroacetic anhydride is (0.9-1): 1.
in the step (1), the micron-sized tubular reactor is a small-sized high-flux reactor, and preferably, the size of a reaction pipeline is 10-1000 microns.
In the step (1), the solvent A is one or any combination of acetonitrile, 1, 4-dioxane, tetrahydrofuran, methyl tert-butyl ether and anisole;
for better separation of solvent A and the by-product trifluoroacetic acid (boiling point 72.4 ℃), 1, 4-dioxane is preferably selected as the solvent.
In the step (1), the dosage of the solvent A is 2-3 times of the mass of the diaminomaleonitrile.
In the step (1), the cyclization reaction is a gradient heating process, and the first stage is reaction at the temperature of 25-40 ℃ for 5-10 min; the second stage is reaction at 50-60 deg.c for 5-10 min.
In the step (1), the consumption of high-purity water is 2-3 times of the theoretical mass of TDI.
In the step (1), the decoloring condition is 100 ℃ reflux for 1-2 h, and the crystallization mode is cooling crystallization after concentration and water evaporation.
In the step (2), the solvent B is one or any combination of acetonitrile, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate and ethyl acetate.
The dosage of the solvent B is 1-2 times of the mass of TDI.
In the step (2), the lithium-containing compound LiY is LiH or LiNH 2 。
In the step (2), the molar ratio of the 4, 5-dicyano-2-trifluoromethylimidazole to the lithium-containing compound LiY is 1: 1-1.05. In the step (2), the reaction temperature is 25-50 ℃, the crystallization purification mode is gradient cooling crystallization, and the cooling rate is 5-10 ℃/h.
By adopting the method for preparing the 4, 5-dicyano-2-trifluoromethyl imidazole lithium LiTDI, the cyclization reaction is carried out in the microchannel reactor, so that the problems of low boiling point of trifluoroacetic anhydride and extreme volatility at room temperature can be effectively solved, the raw materials are fully contacted, the temperature is accurately controlled, the reaction efficiency is high, the reaction time is greatly shortened, and the TDI yield is high; the salt forming working section of the 4, 5-dicyano-2-trifluoromethyl imidazole lithium is carried out in a high-purity low-water organic solvent, no water is generated, the subsequent water removal step and drying time are reduced, and the product purity is high; the whole process has short reaction time, high product yield, low water content and less waste water.
Detailed Description
The method for preparing 4, 5-dicyano-2-trifluoromethyl imidazole lithium comprises the following specific steps:
(1) simultaneously pumping diaminomaleonitrile and trifluoroacetic anhydride dissolved in a solvent into a microchannel reactor through peristaltic pumps respectively, maintaining the temperature of the system at 25-40 ℃ for cyclic reaction for 5-10 min, and then heating to 50-60 ℃ for cyclic reaction again for 5-10 min;
the reaction mechanism of 4, 5-dicyano-2-trifluoromethylimidazole is as follows:
C 4 H 4 N 4 +C 4 F 6 O 3 ＝C 6 F 3 HN 4 +C 2 F 3 O 2 H+H 2 O
carrying out negative pressure distillation separation on the TDI reaction liquid to respectively obtain trifluoroacetic acid and a solvent; under the action of phosphorus pentoxide, trifluoroacetic anhydride is obtained by dehydration condensation of trifluoroacetic acid and is used as a TDI reaction raw material;
trifluoroacetic acid post-treatment involves the following reaction mechanism:
2C 2 F 3 O 2 H＝C 4 F 6 O 3 +H 2 O
adding high-purity water and activated carbon into the TDI crude product at the bottom of the distillation kettle, heating to 100 ℃, performing reflux decolorization reaction for 1-2 h, filtering while hot, concentrating the filtrate, cooling for crystallization, and drying crystals in nitrogen at 40-50 ℃ to obtain a pure TDI product.
(2) Dissolving the TDI pure product into a salifying solvent, cooling, adding a lithium-containing compound in batches, maintaining the system temperature at-5-15 ℃ in the charging process, then heating to 25-50 ℃ for reaction for 2-4 h, and removing tail gas from a receiving device.
The reaction mechanism of 4, 5-dicyano-2-trifluoromethylimidazole lithium is as follows:
C 6 F 3 HN 4 +Li＝LiC 6 F 3 N 4 +1/2H 2 ↑
C 6 F 3 HN 4 +LiH＝LiC 6 F 3 N 4 +H 2 ↑
C 6 F 3 HN 4 +LiNH 2 ＝LiC 6 F 3 N 4 +NH 3 ↑
filtering the LiTDI salified solution, carrying out gradient cooling crystallization, carrying out solid-liquid separation, washing the crystal with a fresh solvent, then placing the crystal in drying equipment under the protection of nitrogen gas, drying at 100-150 ℃ to obtain a 4, 5-dicyano-2-trifluoromethyl imidazole lithium product, and mixing the crystallization mother solution and the washing solution for cyclic use.
Example 1
This example illustrates a method for preparing lithium 4, 5-dicyano-2-trifluoromethylimidazole, including the following steps:
cleaning a micron-sized tubular reactor (a small-size high-flux reactor, preferably, the size of a reaction pipeline is 10-1000 microns) by using a solvent 1, 4-dioxane, dissolving 48.6g (0.45mol) of diaminomaleonitrile into 97.2g of 1, 4-dioxane, then respectively introducing 105g (0.5mol) of trifluoroacetic anhydride into a microchannel reactor by using a peristaltic pump, circularly reacting for 10min at the reaction temperature of 25 ℃, and then heating to 50 ℃ for circularly reacting for 10 min. Transferring the generated TDI reaction liquid into a distillation kettle, and respectively evaporating trifluoroacetic acid and 1, 4-dioxane under negative pressure. Adding 167.4g of high-purity water and 4.2 g of activated carbon into the bottom of the kettle, stirring and heating, carrying out reflux decoloration reaction for 1h, cooling to 70 ℃, filtering while the solution is hot, evaporating 83.7g of water from the filtrate, cooling to room temperature, filtering, and drying the crystal for 8h at 40 ℃ in a nitrogen atmosphere to obtain 75.3g of TDI pure product with the yield of 90%. And (5) recycling the crystallization mother liquor.
Dissolving 75.3g of TDI into 75.3g of acetonitrile, stirring, maintaining the temperature of a system at-5 ℃, adding 2.83g of metal lithium in batches, heating to 25 ℃ after the metal lithium is dissolved, reacting for 4 hours, filtering to obtain an acetonitrile solution of the LiTDI, cooling to 10 ℃ in a gradient manner at a speed of 5 ℃/h, crystallizing, separating solid from liquid, washing, drying the crystal at 100 ℃ under a nitrogen atmosphere for 8 hours to obtain 66.1g of the LiTDI product, wherein the purity is 99.9%, the yield is 85%, and the crystallization mother liquor is recycled.
Example 2
This example illustrates a method for preparing lithium 4, 5-dicyano-2-trifluoromethylimidazole, including the following steps:
a micron-sized tubular reactor system is cleaned by acetonitrile serving as a solvent, 54g (0.5mol) of diaminomaleonitrile is dissolved into 108g of acetonitrile, then the dissolved diaminomaleonitrile and 105g (0.5mol) of trifluoroacetic anhydride are respectively introduced into a microchannel reactor simultaneously by using a peristaltic pump, the reaction temperature is 40 ℃, the cyclic reaction is carried out for 5min, and then the temperature is raised to 60 ℃, and the cyclic reaction is carried out for 5 min. Transferring the generated TDI reaction liquid into a distillation kettle, and respectively evaporating trifluoroacetic acid and acetonitrile under negative pressure. 279g of high-purity water and 4.7 g of activated carbon are added to the bottom of the kettle, the mixture is stirred and heated up, the reflux decolorization reaction is carried out for 1h, the temperature is reduced to 70 ℃, the hot mixture is filtered, 186g of water is evaporated from the filtrate, the temperature is reduced to room temperature, the filtration is carried out, and the crystal is dried for 4h under the nitrogen atmosphere at 50 ℃ to obtain 84.6g of TDI pure product with the yield of 91%. And (5) recycling the crystallization mother liquor.
Dissolving 84.6g of TDI into 169.2g of dimethyl carbonate, stirring, maintaining the temperature of a system at 15 ℃, adding 3.64g of lithium hydride in batches, heating to 50 ℃ after the lithium hydride is dissolved, reacting for 2h, filtering to obtain a LiTDI dimethyl carbonate solution, cooling to 15 ℃ at a gradient of 10 ℃/h for crystallization, carrying out solid-liquid separation, washing, drying the crystals at 150 ℃ under nitrogen atmosphere for 4h to obtain 76.0g of LiTDI product, wherein the purity is 99.91%, the yield is 87%, and the crystallization mother liquor is recycled.
Example 3
This example illustrates a method for preparing lithium 4, 5-dicyano-2-trifluoromethylimidazole, including the following steps:
a micron-sized tubular reactor system is cleaned by using a solvent anisole, 54g (0.5mol) of diaminomaleonitrile is dissolved into 162g of anisole, then the dissolved diaminomaleonitrile and 105g (0.5mol) of trifluoroacetic anhydride are respectively introduced into a microchannel reactor simultaneously by using a peristaltic pump, the reaction temperature is 30 ℃ for cyclic reaction for 8min, and then the temperature is raised to 55 ℃ for cyclic reaction for 8 min. Transferring the generated TDI reaction liquid into a distillation kettle, and respectively evaporating trifluoroacetic acid and anisole under negative pressure. Adding 186g of high-purity water and 4.7 g of activated carbon into the bottom of the kettle, stirring and heating, carrying out reflux decolorization reaction for 2h, cooling to 70 ℃, filtering while the solution is hot, evaporating 93g of water from the filtrate, cooling to room temperature, filtering, and drying crystals for 6h at 45 ℃ in a nitrogen atmosphere to obtain 84.6g of a TDI pure product with the yield of 91%. And (5) recycling the crystallization mother liquor.
Dissolving 84.6g of TDI into 84.6g of ethyl acetate, stirring, maintaining the temperature of a system at 0 ℃, adding 10.5g of lithium amide in batches, heating to 30 ℃ after the lithium amide is dissolved, reacting for 3 hours, filtering to obtain an ethyl acetate solution of the LiTDI, cooling to 10 ℃ in a gradient manner at a speed of 5 ℃/h, crystallizing, separating solid from liquid, washing, drying the crystals at 120 ℃ under nitrogen atmosphere for 6 hours to obtain 75.1g of the LiTDI product, wherein the purity is 99.9%, the yield is 86%, and the crystallization mother liquor is recycled.
Claims (10)
1. A method for preparing 4, 5-dicyano-2-trifluoromethylimidazole lithium, characterized in that: the method comprises the following steps:
(1) preparation of 4, 5-dicyano-2-trifluoromethylimidazole: dissolving diaminomaleonitrile in a solvent, performing cyclization reaction with trifluoroacetic anhydride in a micron-sized tubular reactor, evaporating a by-product and the solvent A from a reaction solution, and decoloring, filtering and crystallizing to obtain a TDI pure product;
(2) preparation of 4, 5-dicyano-2-trifluoromethylimidazole lithium: and (2) reacting the TDI pure product prepared in the step (1) with lithium or a lithium-containing compound LiY in a solvent B, and performing solid-liquid separation, crystallization and purification to obtain a LiTDI product.
2. The process for preparing lithium 4, 5-dicyano-2-trifluoromethylimidazole according to claim 1, characterized in that: in step (1), the molar ratio of diaminomaleonitrile to trifluoroacetic anhydride is (0.9-1): 1.
3. the process for preparing lithium 4, 5-dicyano-2-trifluoromethylimidazole according to claim 1, characterized in that: in the step (1), the solvent A is one or any combination of acetonitrile, 1, 4-dioxane, tetrahydrofuran, methyl tert-butyl ether and anisole.
4. The process for preparing lithium 4, 5-dicyano-2-trifluoromethylimidazole according to claim 1, characterized in that: in the step (1), the dosage of the solvent A is 2-3 times of the mass of the diaminomaleonitrile.
5. The process for preparing lithium 4, 5-dicyano-2-trifluoromethylimidazole according to claim 1, characterized in that: in the step (1), the cyclization reaction is a gradient heating process, and the first stage is reaction at the temperature of 25-40 ℃ for 5-10 min; the second stage is reaction at 50-60 deg.c for 5-10 min.
6. The process for preparing lithium 4, 5-dicyano-2-trifluoromethylimidazole according to claim 1, characterized in that: in the step (1), the decoloring condition is 100 ℃ reflux for 1-2 h, and the crystallization mode is cooling crystallization after concentration and water evaporation.
7. The process for preparing lithium 4, 5-dicyano-2-trifluoromethylimidazole according to claim 1, characterized in that: in the step (2), the solvent B is one or any combination of acetonitrile, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate and ethyl acetate.
8. The process for preparing lithium 4, 5-dicyano-2-trifluoromethylimidazole according to claim 1, characterized in that: in the step (2), the using amount of the solvent B is 1-2 times of the mass of TDI.
9. The process for preparing lithium 4, 5-dicyano-2-trifluoromethylimidazole according to claim 1, characterized in that: in the step (2), the lithium-containing compound LiY is LiH or LiNH 2 。
10. The process for preparing lithium 4, 5-dicyano-2-trifluoromethylimidazole according to claim 1, characterized in that: in the step (2), the molar ratio of the 4, 5-dicyano-2-trifluoromethylimidazole to the lithium-containing compound LiY is 1: 1-1.05; in the step (2), the reaction temperature is 25-50 ℃, the crystallization purification mode is gradient cooling crystallization, and the cooling rate is 5-10 ℃/h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210813394.7A CN114957129A (en) | 2022-07-11 | 2022-07-11 | Method for preparing 4, 5-dicyano-2-trifluoromethyl imidazole lithium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210813394.7A CN114957129A (en) | 2022-07-11 | 2022-07-11 | Method for preparing 4, 5-dicyano-2-trifluoromethyl imidazole lithium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114957129A true CN114957129A (en) | 2022-08-30 |
Family
ID=82970346
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210813394.7A Pending CN114957129A (en) | 2022-07-11 | 2022-07-11 | Method for preparing 4, 5-dicyano-2-trifluoromethyl imidazole lithium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114957129A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103930405A (en) * | 2011-11-14 | 2014-07-16 | 阿克马法国公司 | Method for preparing pentacyclic anion salt |
| CN104447564A (en) * | 2014-11-24 | 2015-03-25 | 广州天赐高新材料股份有限公司 | Preparation method of high-purity 4,5-dicyano-2-trifluoromethylimidazole and salts thereof |
| CN105793244A (en) * | 2013-10-03 | 2016-07-20 | 阿科玛法国公司 | Composition including a pentacyclic anion salt and use thereof as a battery electrolyte |
| CN113277982A (en) * | 2021-05-19 | 2021-08-20 | 江苏理文化工有限公司 | Method and reaction device for continuously preparing 2-trifluoromethyl-4, 5-dicyanoimidazole lithium salt |
| CN113354587A (en) * | 2021-05-19 | 2021-09-07 | 江苏理文化工有限公司 | Drying method of imidazolyl fluorine-containing lithium salt |
-
2022
- 2022-07-11 CN CN202210813394.7A patent/CN114957129A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103930405A (en) * | 2011-11-14 | 2014-07-16 | 阿克马法国公司 | Method for preparing pentacyclic anion salt |
| CN105793244A (en) * | 2013-10-03 | 2016-07-20 | 阿科玛法国公司 | Composition including a pentacyclic anion salt and use thereof as a battery electrolyte |
| CN104447564A (en) * | 2014-11-24 | 2015-03-25 | 广州天赐高新材料股份有限公司 | Preparation method of high-purity 4,5-dicyano-2-trifluoromethylimidazole and salts thereof |
| CN113277982A (en) * | 2021-05-19 | 2021-08-20 | 江苏理文化工有限公司 | Method and reaction device for continuously preparing 2-trifluoromethyl-4, 5-dicyanoimidazole lithium salt |
| CN113354587A (en) * | 2021-05-19 | 2021-09-07 | 江苏理文化工有限公司 | Drying method of imidazolyl fluorine-containing lithium salt |
Non-Patent Citations (1)
| Title |
|---|
| L. NIEDZICKI 等: "New type of imidazole based salts designed specifically for lithium ion batteries", 《ELECTROCHIMICA ACTA》, vol. 55, pages 1452 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108373142B (en) | Preparation method of high-purity lithium bis (fluorosulfonyl) imide | |
| CN108910919B (en) | Preparation method of electronic-grade lithium difluorobis (oxalate) phosphate | |
| CN113800485B (en) | Preparation method of lithium bis (fluorosulfonyl) imide | |
| CN111153918A (en) | Preparation method of lithium bis (oxalato) borate | |
| CN111057079A (en) | Purification method of lithium bis (oxalato) borate and lithium bis (oxalato) borate | |
| CN103483368B (en) | A kind of preparation method of difluorine oxalic acid boracic acid lithium | |
| CN104447828B (en) | A kind of synthesizing progress method of di-oxalate lithium borate | |
| CN115028146A (en) | Preparation method of sodium bis (fluorosulfonyl) imide | |
| CN111138464A (en) | Preparation method of lithium oxalato borate | |
| CN113651306B (en) | Preparation method of lithium difluorophosphate | |
| CN113929711A (en) | Preparation method of lithium difluoroborate | |
| CN113277982B (en) | Method and reaction device for continuously preparing 2-trifluoromethyl-4, 5-dicyanoimidazole lithium salt | |
| CN103342372A (en) | Method for preparing lithium tetrafluoroborate | |
| CN113512052A (en) | Preparation process of lithium difluoroborate | |
| CN114957129A (en) | Method for preparing 4, 5-dicyano-2-trifluoromethyl imidazole lithium | |
| CN113044825B (en) | Production process and production system of lithium difluorophosphate | |
| CN115557980B (en) | Synthesis and purification process of sodium bisoxalato | |
| CN115353087B (en) | Production method of lithium difluorophosphate (LiDFP) | |
| CN114790219A (en) | Preparation method of lithium bis (oxalato) borate | |
| CN115285964A (en) | Preparation method of lithium difluorophosphate | |
| CN104230970B (en) | Preparation method of lithium difluorooxalatoborate electrolyte | |
| CN113045594B (en) | Co-production preparation method of lithium fluorooxalate borate and lithium fluorooxalate phosphate | |
| CN115818592A (en) | Preparation method of sodium bis (fluorosulfonyl) imide | |
| CN112811407B (en) | Preparation method of lithium difluorophosphate | |
| CN111454172A (en) | Production method for preparing glutaronitrile by aminolysis of ester substance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |