CN109860701B - All-solid-state electrolyte for lithium ion battery and preparation method thereof - Google Patents
All-solid-state electrolyte for lithium ion battery and preparation method thereof Download PDFInfo
- Publication number
- CN109860701B CN109860701B CN201910118374.6A CN201910118374A CN109860701B CN 109860701 B CN109860701 B CN 109860701B CN 201910118374 A CN201910118374 A CN 201910118374A CN 109860701 B CN109860701 B CN 109860701B
- Authority
- CN
- China
- Prior art keywords
- solid
- lithium ion
- acid
- parts
- electrolyte
- 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.)
- Active
Links
Classifications
-
- 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
Abstract
The invention discloses an all-solid-state electrolyte for a lithium ion battery and a preparation method thereof, wherein the preparation method comprises the following steps: 1) all-solid-state lithium ion electrolyte matrixPreparing; 2) preparing an all-solid-state lithium ion electrolyte intermediate; 3) and preparing the all-solid-state lithium ion electrolyte. The invention designs and synthesizes a series of all-solid-state lithium ion electrolytes which can conduct electricity by taking dicarboxyl imidazole, boric acid, lithium hydroxide and the like as main raw materials, has low melting point and room-temperature ionic conductivity of 10‑3S cm‑1The synthesis method is simple, the raw materials are easy to obtain, and the method has great application potential in the field of all-solid-state lithium ion secondary batteries.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to an all-solid-state electrolyte for a lithium ion battery and a preparation method thereof.
Background
Nowadays, lithium ion batteries are widely applied to small electronic products such as mobile phones, video cameras, notebook computers and the like, market demand is rapidly increasing, and due to popularization of new energy concepts, electric automobiles and hybrid electric vehicles are widely put into the market, electric vehicles become visible in the future development direction, and lithium ion batteries serving as the preferred power source of electric automobiles are widely applied and researched due to excellent performance.
At present, liquid lithium ion batteries are used more, and the batteries have the defects of poor cycle performance, poor safety performance and the like.
Disclosure of Invention
The invention aims to provide a preparation method of an all-solid-state electrolyte for a lithium ion battery, the all-solid-state electrolyte prepared by the method has good safety and environmental friendliness, and the ionic conductivity at room temperature is as high as 10- 3S cm-1。
In addition, the invention also provides the all-solid-state electrolyte prepared by the preparation method.
The invention is realized by the following technical scheme:
a preparation method of an all-solid-state electrolyte for a lithium ion battery comprises the following steps:
1) and preparing the all-solid-state lithium ion electrolyte matrix:
adding solid strong base and deionized water into a reaction kettle for reaction for a period of time, sequentially adding carboxylic acid imidazole, micromolecule halogenated alkane and strong acid solution at intervals for reaction at room temperature, filtering out precipitates after the reaction, and washing and drying the precipitates to obtain a full-solid lithium ion electrolyte matrix;
2) and preparing an all-solid-state lithium ion electrolyte intermediate:
mixing the all-solid-state lithium ion electrolyte matrix prepared in the step 1), NaOH aqueous solution and borate in proportion, reacting at normal temperature, filtering, washing and drying precipitates to obtain an all-solid-state lithium ion electrolyte intermediate;
3) and preparing the all-solid-state lithium ion electrolyte:
mixing the all-solid-state lithium ion electrolyte intermediate obtained in the step 2), boric acid and DMAc in proportion, stirring and reacting for a period of time, and adding SOCl2Adding LiOH-DMAc solution after reaction for a period of time, heating to 80 ℃ for reaction, then carrying out vacuum filtration on reaction liquid, dissolving obtained solid in a mixed solvent, recrystallizing at-25-40 ℃, drying obtained crystals to obtain the all-solid-state lithium ion electrolyte, wherein the electrolyte has double functions of lithium salt and electrolyte, and the ionic conductivity is as high as 10-3S cm-1And the orders of magnitude are not reported similarly at present.
The method takes carboxylic acid imidazole, solid strong base, borate and the like as main raw materials to synthesize a series of all-solid-state lithium ion electrolytes which can be conductive, and has great application potential in the field of all-solid-state lithium ion secondary batteries; in the preparation method, no volatile micromolecular plasticizer is added, and the room-temperature ionic conductivity of the prepared all-solid-state lithium ion electrolyte exceeds 10-3S cm-1。
In addition, by changing reaction raw materials, a series of all-solid-state lithium ion electrolytes with lower dissociation energy (namely, the electrolytes can be dissociated into ionic states with high movement capability at normal temperature or lower temperature) are developed, and the selection range of lithium salts in the field of lithium batteries is effectively widened.
Further, the solid strong base, the deionized water, the carboxylic acid imidazole, the small molecule halogenated alkane and the strong acid solution in the step 1) are added in the following amounts:
1-2 parts, 15-20 parts, 2-4 parts, 3-5 parts and 4-8 parts by weight, wherein the concentration of the strong acid solution is 30 wt.%.
The feeding is carried out according to the chemical equivalent, and the operation can obtain the target product as much as possible.
Further, the adding amounts of the all-solid-state lithium ion electrolyte matrix, the NaOH aqueous solution and the borate in the step 2) are respectively as follows:
3-5 parts, 10-15 parts and 7-10 parts by weight, wherein the concentration of the NaOH aqueous solution is 10%.
The feeding is carried out according to the chemical equivalent, and the operation can obtain the target product as much as possible.
Further, the all-solid-state lithium ion electrolyte intermediate in the step 2), boric acid, DMAc and SOCl2And the addition amount of the LiOH-DMAc solution is respectively as follows:
4 to 6 parts by weight, 1 to 3 parts by weight, 60 to 80 parts by weight, 3 to 5 parts by weight, 1 to 2 parts by weight.
The feeding is carried out according to the chemical equivalent, and the operation can obtain the target product as much as possible.
Further, the carboxylic acid imidazole comprises at least one of 4-thiodicarboxylic acid imidazole, imidazole-4, 5-di-n-propionic acid, imidazole-4, 5-di-n-butyric acid, imidazole-4, 5-di-isobutyric acid, imidazole-4, 5-di-neobutyric acid, imidazole-4, 5-diisopropyl acid and benzimidazole-4, 5-dicarboxylic acid.
Further, the small molecule halogenated alkane at least comprises one of 2-bromobutane, 2-methyl-2-bromopropane, 2-methyl-1-bromopropane, bromoethane, 1-bromopropane, 2-bromopropane, 1-chloropropane and 1-chlorobutane.
Further, the solid strong base at least comprises one of sodium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, solid sodium propoxide, solid sodium pentoxide, solid sodium octanol and sodium isomer thereof; the strong acid solution at least comprises one of hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, permanganic acid, hydrobromic acid, hydroiodic acid, trifluoroacetic acid and methanesulfonic acid; the borate at least comprises one of lithium fluoroborate, indium fluoroborate, gallium fluoroborate, tin fluoroborate, potassium fluoroborate and sodium fluoroborate.
Further, the LiOH-DMAc solution is prepared from LiOH and DMAc according to the mass ratio of 2-6: 15 to 30 parts by weight.
The feeding is carried out according to the chemical equivalent, and the operation can obtain the target product as much as possible.
Further, the mixed solvent is acetonitrile, trichloromethane and chloropropane according to a mass ratio of 20-30: 10-15: 6-8 by mixing.
The feeding is carried out according to the chemical equivalent, and the operation can obtain the target product as much as possible.
An all-solid electrolyte prepared by the preparation method.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the lithium salt prepared by the invention has the properties of ionic liquid and traditional solid lithium salt, and has great application potential in the field of all-solid-state lithium ion secondary batteries.
2. The preparation method does not add volatile micromolecular plasticizer, and the room-temperature ionic conductivity of the all-solid-state lithium ion electrolyte prepared by the method exceeds 10-3S cm-1。
3. According to the preparation method, a series of all-solid-state lithium ion electrolytes with lower dissociation energy are developed by changing reaction raw materials, so that the selection range of lithium salts in the field of lithium batteries is effectively widened.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not used as limitations of the present invention.
Example 1:
a preparation method of an all-solid-state electrolyte for a lithium ion battery comprises the following steps:
1) and preparing the all-solid-state lithium ion electrolyte matrix:
adding 2 parts of solid sodium propoxide and 18 parts of deionized water into a reaction kettle, and stirring and reacting at 70 ℃ for 30 min; then adding 3 parts of benzimidazole-4, 5-dicarboxylic acid into the system, and reacting for 60 min; then adding 3 parts of 1-chlorobutane, and reacting for 12 hours; 7 parts of a 30 wt.% trifluoroacetic acid solution were added thereto, and the reaction was carried out at room temperature for 2 hours. The reaction solution was filtered and the resulting precipitate was washed repeatedly with deionized water until the filtrate had a pH of approximately 7. Drying the precipitate at 80 ℃ for 50 hours to obtain a full-solid lithium ion electrolyte matrix;
2) and preparing an all-solid-state lithium ion electrolyte intermediate:
weighing 5 parts of the all-solid-state lithium ion electrolyte matrix, 12 parts of 10% NaOH aqueous solution and 9 parts of potassium fluoborate, reacting at normal temperature for 24 hours, filtering, washing the obtained precipitate with deionized water for 3 times, and then drying in vacuum for 48 hours to obtain an all-solid-state lithium ion electrolyte intermediate;
3) and preparing the all-solid-state lithium ion electrolyte:
weighing 4 parts of all-solid-state lithium ion electrolyte intermediate, 3 parts of boric acid and 70 parts of DMAc, stirring and reacting for 2 hours, and then adding 3 parts of SOCl2Adding the mixture into a reaction kettle, reacting at room temperature for 2 hours, and then quickly adding 1 part of LiOH and DMAc according to a mass ratio of 6: 20 to obtain LiOH-DMAc solution, and heating to 80 ℃ to react for 6 hours. And (3) carrying out vacuum filtration on the reaction solution under reduced pressure, carrying out rotary evaporation on the filtrate to remove DMAc, dissolving the obtained solid in a mixed solvent, recrystallizing at-30 ℃, and carrying out vacuum drying on the obtained crystal at 125 ℃ for 24 hours to obtain the all-solid-state lithium ion electrolyte.
Example 2:
a preparation method of an all-solid-state electrolyte for a lithium ion battery comprises the following steps:
1) and preparing the all-solid-state lithium ion electrolyte matrix:
adding 2 parts of solid sodium pentol and 15 parts of deionized water into a reaction kettle, and stirring and reacting at 70 ℃ for 30 min; then adding 3 parts of imidazole-4, 5-dineobutyric acid into the system, and reacting for 60 min; then adding 4 parts of 1-chloropropane, and reacting for 12 hours; 7 parts of a 30 wt.% solution of methanesulfonic acid were added and reacted at room temperature for 2 hours. The reaction solution was filtered and the resulting precipitate was washed repeatedly with deionized water until the filtrate had a pH of approximately 7. Drying the precipitate at 80 ℃ for 60 hours to obtain a full-solid lithium ion electrolyte matrix;
2) and preparing an all-solid-state lithium ion electrolyte intermediate:
weighing 3 parts of the all-solid-state lithium ion electrolyte matrix, 15 parts of 10% NaOH aqueous solution and 7 parts of tin fluoborate, reacting at normal temperature for 24 hours, filtering, washing the obtained precipitate with deionized water for 3 times, and then drying in vacuum for 60 hours to obtain an all-solid-state lithium ion electrolyte intermediate;
3) and preparing the all-solid-state lithium ion electrolyte:
weighing 5 parts of all-solid-state lithium ion electrolyte intermediate, 2 parts of boric acid and 80 parts of DMAc, stirring for reacting for 2 hours, and adding 4 parts of SOCl2Adding the mixture into a reaction kettle, reacting at room temperature for 2 hours, and then quickly adding 1 part of LiOH and DMAc according to a mass ratio of 2: 15 to obtain LiOH-DMAc solution, and heating to 80 ℃ to react for 6 hours. And (3) carrying out vacuum filtration on the reaction solution under reduced pressure, carrying out rotary evaporation on the filtrate to remove DMAc, dissolving the obtained solid in a mixed solvent, recrystallizing at the temperature of minus 40 ℃, and carrying out vacuum drying on the obtained crystal at the temperature of 125 ℃ for 24 hours to obtain the all-solid-state lithium ion electrolyte.
Example 3:
a preparation method of an all-solid-state electrolyte for a lithium ion battery comprises the following steps:
1) and preparing the all-solid-state lithium ion electrolyte matrix:
adding 1 part of cesium hydroxide and 15 parts of deionized water into a reaction kettle, and stirring and reacting at 65 ℃ for 30 min; then adding 2 parts of imidazole-4, 5-di-n-butyric acid into the system, and reacting for 60 min; then adding 3 parts of 2-methyl-1-bromopropane, and reacting for 12 hours; 4 parts of a 30 wt.% perchloric acid solution were added and the reaction was carried out at room temperature for 2 hours. The reaction solution was filtered and the resulting precipitate was washed repeatedly with deionized water until the filtrate had a pH of approximately 7. Drying the precipitate at 80 ℃ for 40 hours to obtain a full-solid lithium ion electrolyte matrix;
2) and preparing an all-solid-state lithium ion electrolyte intermediate:
weighing 3 parts of the all-solid-state lithium ion electrolyte matrix, 10 parts of 10% NaOH aqueous solution and 7 parts of indium fluoborate, reacting at normal temperature for 24 hours, filtering, washing the obtained precipitate with deionized water for 3 times, and then drying in vacuum for 48 hours to obtain an all-solid-state lithium ion electrolyte intermediate;
3) and preparing the all-solid-state lithium ion electrolyte:
weighing 4 parts of all-solid-state lithium ion electrolyte intermediate, 1 part of boric acid and 60 parts of DMAc, stirring and reacting for 2 hours, and then adding 3 parts of SOCl2Adding the mixture into a reaction kettle, reacting at room temperature for 2 hours, and then quickly adding 1 part of LiOH and DMAc according to a mass ratio of 2: 15 to obtain LiOH-DMAc solution, and heating to 80 ℃ to react for 6 hours. And (3) carrying out vacuum filtration on the reaction solution under reduced pressure, carrying out rotary evaporation on the filtrate to remove DMAc, dissolving the obtained solid in a mixed solvent, recrystallizing at the temperature of minus 25 ℃, and carrying out vacuum drying on the obtained crystal at the temperature of 125 ℃ for 24 hours to obtain the all-solid-state lithium ion electrolyte.
Example 4:
a preparation method of an all-solid-state electrolyte for a lithium ion battery comprises the following steps:
1) and preparing the all-solid-state lithium ion electrolyte matrix:
adding 2 parts of sodium hydroxide and 20 parts of deionized water into a reaction kettle, and stirring and reacting at 70 ℃ for 30 min; then adding 2 parts of 4-thiodicarboxylic acid imidazole into the system, and reacting for 60 min; then adding 5 parts of 2-bromobutane, and reacting for 12 hours; 8 parts of a 30 wt.% perchloric acid solution were added and the reaction was carried out at room temperature for 2 hours. The reaction solution was filtered and the resulting precipitate was washed repeatedly with deionized water until the filtrate had a pH of approximately 7. Drying the precipitate at 80 ℃ for 50 hours to obtain a full-solid lithium ion electrolyte matrix;
2) and preparing an all-solid-state lithium ion electrolyte intermediate:
weighing 4 parts of the all-solid-state lithium ion electrolyte matrix, 10 parts of 10% NaOH aqueous solution and 10 parts of lithium fluoroborate, reacting at normal temperature for 24 hours, filtering, washing the obtained precipitate with deionized water for 3 times, and then drying in vacuum for 60 hours to obtain an all-solid-state lithium ion electrolyte intermediate;
3) and preparing the all-solid-state lithium ion electrolyte:
weighing 6 parts of all-solid-state lithium ion electrolyte intermediate, 3 parts of boric acid and 80 parts of DMAc, stirring for reacting for 2 hours, and adding 5 parts of SOCl2Adding the mixture into a reaction kettle, reacting at room temperature for 2 hours, and then quickly adding 2 parts of LiOH and DMAc according to a mass ratio of 6: 30 to obtain LiOH-DMAc solution, and heating to 80 ℃ to react for 8 hours. And (3) carrying out vacuum filtration on the reaction solution under reduced pressure, carrying out rotary evaporation on the filtrate to remove DMAc, dissolving the obtained solid in a mixed solvent, recrystallizing at the temperature of minus 40 ℃, and carrying out vacuum drying on the obtained crystal at the temperature of 125 ℃ for 24 hours to obtain the all-solid-state lithium ion electrolyte.
An all-solid lithium ion electrolyte prepared according to the preparation method described in examples 1 to 4.
The all-solid lithium ion electrolytes prepared in examples 1 to 4 were subjected to a room temperature conductivity test, and the test results are shown in table 1:
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Melting Point (. degree.C.) | 36.5 | 36.2 | 36.4 | 36.6 |
| Conductivity at room temperature (S cm)-1) | 3.85×10-3.5 | 3.82×10-3.5 | 2.68×10-3.5 | 3.01×10-3.5 |
As can be seen from the data in Table 1, the melting point of the all-solid electrolyte of the formulation of the example was around 36.5 ℃ and the room temperature conductivity was 10-3.5Scm-1In the vicinity, it is shown that the all-solid electrolytes of the present invention exhibit good conductivity approaching the conductivity requirements of commercial batteries (10. about.-3S cm-1)。
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of an all-solid-state electrolyte for a lithium ion battery is characterized by comprising the following steps of:
1) and preparing the all-solid-state lithium ion electrolyte matrix:
adding solid strong base and deionized water into a reaction kettle for reaction for a period of time, sequentially adding carboxylic acid imidazole, micromolecule halogenated alkane and strong acid solution at intervals for reaction at room temperature, filtering out precipitates after the reaction, and washing and drying the precipitates to obtain a full-solid lithium ion electrolyte matrix;
2) and preparing an all-solid-state lithium ion electrolyte intermediate:
mixing the all-solid-state lithium ion electrolyte matrix prepared in the step 1), NaOH aqueous solution and borate in proportion, reacting at normal temperature, filtering, washing and drying precipitates to obtain an all-solid-state lithium ion electrolyte intermediate;
3) and preparing the all-solid-state lithium ion electrolyte:
mixing the all-solid-state lithium ion electrolyte intermediate obtained in the step 2), boric acid and DMAc in proportion, stirring and reacting for a period of time, and adding SOCl2And after reacting for a period of time, quickly adding a LiOH-DMAc solution, heating to 80 ℃ for reaction, then carrying out vacuum filtration on the reaction solution, dissolving the obtained solid in a mixed solvent, recrystallizing at-25-40 ℃, and drying the obtained crystal to obtain the all-solid-state lithium ion electrolyte.
2. The method for preparing all-solid-state electrolyte of lithium ion battery according to claim 1, wherein the solid strong base, deionized water, carboxylic imidazole, small molecule halogenated alkane and strong acid solution are added in step 1) in the following amounts:
1-2 parts, 15-20 parts, 2-4 parts, 3-5 parts and 4-8 parts by weight, wherein the concentration of the strong acid solution is 30 wt.%.
3. The method for preparing the all-solid-state electrolyte of the lithium ion battery according to claim 1, wherein the all-solid-state lithium ion electrolyte matrix, the aqueous NaOH solution and the borate in the step 2) are added in the following amounts:
3-5 parts, 10-15 parts and 7-10 parts by weight, wherein the concentration of the NaOH aqueous solution is 10%.
4. The method for preparing all-solid-state electrolyte of lithium ion battery according to claim 1, wherein the all-solid-state lithium ion electrolyte intermediate in step 2), boric acid, DMAc, SOCl2And the addition amount of the LiOH-DMAc solution is respectively as follows:
4 to 6 parts by weight, 1 to 3 parts by weight, 60 to 80 parts by weight, 3 to 5 parts by weight, 1 to 2 parts by weight.
5. The method of claim 1, wherein the carboxylic imidazole comprises at least one of imidazole 4-thiodicarboxylate, imidazole-4, 5-di-n-propionic acid, imidazole-4, 5-di-n-butyric acid, imidazole-4, 5-di-isobutyric acid, imidazole-4, 5-di-neobutyric acid, imidazole-4, 5-diisopropyl acid, and benzimidazole-4, 5-dicarboxylic acid.
6. The method according to claim 1, wherein the small molecule halogenated alkane comprises at least one of 2-bromobutane, 2-methyl-2-bromopropane, 2-methyl-1-bromopropane, bromoethane, 1-bromopropane, 2-bromopropane, 1-chloropropane and 1-chlorobutane.
7. The method of claim 1, wherein the solid strong base comprises at least one of sodium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, solid sodium propoxide, solid sodium pentoxide, solid sodium octanol, and isomeric sodium salts thereof; the strong acid solution at least comprises one of hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, permanganic acid, hydrobromic acid, hydroiodic acid, trifluoroacetic acid and methanesulfonic acid; the borate at least comprises one of lithium fluoroborate, indium fluoroborate, gallium fluoroborate, tin fluoroborate, potassium fluoroborate and sodium fluoroborate.
8. The preparation method of the all-solid-state electrolyte for the lithium ion battery according to claim 1, wherein the LiOH-DMAc solution is prepared by mixing LiOH and DMAc according to a mass ratio of (2-6): 15 to 30 parts by weight.
9. The preparation method of the all-solid-state electrolyte for the lithium ion battery according to claim 1, wherein the mixed solvent is acetonitrile, chloroform and chloropropane in a mass ratio of 20-30: 10-15: 6-8 by mixing.
10. An all-solid electrolyte prepared by the preparation method according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910118374.6A CN109860701B (en) | 2019-02-15 | 2019-02-15 | All-solid-state electrolyte for lithium ion battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910118374.6A CN109860701B (en) | 2019-02-15 | 2019-02-15 | All-solid-state electrolyte for lithium ion battery and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109860701A CN109860701A (en) | 2019-06-07 |
| CN109860701B true CN109860701B (en) | 2020-09-08 |
Family
ID=66898046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910118374.6A Active CN109860701B (en) | 2019-02-15 | 2019-02-15 | All-solid-state electrolyte for lithium ion battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109860701B (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19836514A1 (en) * | 1998-08-12 | 2000-02-17 | Univ Stuttgart | Modification of engineering polymers with N-basic groups and ion exchange groups in the side chain gives membranes of good thermal and mechanical stability useful for fuel cells, diffusion dialysis, electrodialysis, and reverse osmosis |
| JP2000323278A (en) * | 1999-05-14 | 2000-11-24 | Toray Ind Inc | Light emitter |
| CN101022162B (en) * | 2006-02-15 | 2011-12-07 | 三星Sdi株式会社 | Electrode of fuel cell, fuel cell and method for producing electrode of fuel cell |
| KR102324310B1 (en) * | 2013-12-18 | 2021-11-09 | 미쯔비시 케미컬 주식회사 | Non-aqueous electrolyte solution and non-aqueous electrolyte rechargeable battery using same |
| KR102263059B1 (en) * | 2014-08-26 | 2021-06-09 | 삼성전자주식회사 | Electrolyte Membrane for energy storage device, energy storage device including the same, and method for preparing the lectrolyte membrane for energy storage device |
| US10290898B2 (en) * | 2014-08-29 | 2019-05-14 | Samsung Electronics Co., Ltd. | Composite, method of preparing the composite, electrolyte comprising the composite, and lithium secondary battery comprising the electrolyte |
| CN108218785A (en) * | 2016-12-13 | 2018-06-29 | 中国科学院大连化学物理研究所 | A kind of secondary cell ionic liquid and synthetic method and application |
-
2019
- 2019-02-15 CN CN201910118374.6A patent/CN109860701B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109860701A (en) | 2019-06-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104538670A (en) | All-solid polymer electrolyte, and preparation method and application of all-solid polymer electrolyte | |
| CN109411788B (en) | Aza spiro cation loaded polybiphenyl basic film and preparation method thereof | |
| US10826125B2 (en) | Mono-nuclei cationized magnesium salt, preparation method and applications thereof | |
| CN104671224A (en) | Synthesis method for bis(fluorosulfonyl)imide salt | |
| CN109071570B (en) | Silicon-containing sulfuric acid ester salts | |
| CN111900469A (en) | Flexible solid film based on chemical crosslinking metal-organic framework material, flexible solid electrolyte film and preparation method of flexible solid electrolyte film | |
| CN109860701B (en) | All-solid-state electrolyte for lithium ion battery and preparation method thereof | |
| CN102583301A (en) | Preparation method of lithium hexafluorophosphate | |
| CN112736244B (en) | Preparation method of zinc ion battery positive electrode material and electrode material prepared by preparation method | |
| CN112309724B (en) | Method for constructing zinc ion hybrid supercapacitor based on eutectic solvent electrolyte | |
| CN104829813B (en) | A kind of ionomeric polymer containing phosphine, preparation method and anion-exchange membrane | |
| CN109301317A (en) | A kind of preparation method of high pressure resistant solid polymer electrolyte | |
| CN111755735B (en) | Porous organic compound electrolyte and preparation method and application thereof | |
| CN111180790B (en) | Polymer electrolyte, preparation method thereof and solid-state lithium-air battery | |
| CN102321108A (en) | Purification method of lithium bis(oxalato) borate | |
| CN101704759A (en) | Method for preparing tetrafluoro boric acid organic quaternary ammonium salt | |
| CN102952099A (en) | Pyrrole ionic liquid, and preparation method and application thereof | |
| CN115676855B (en) | Preparation method of sodium ion battery electrolyte sodium salt | |
| CN115477308B (en) | Method for preparing sodium tetrafluoroborate at normal temperature by one-step method | |
| CN114188542B (en) | Zinc-based MOF-loaded vanadium dioxide nano material and preparation and application thereof | |
| CN112289594B (en) | Preparation method of eutectic solvent electrolyte for zinc ion mixed super capacitor | |
| CN112133964A (en) | Magnesium ion electrolyte solution and preparation method thereof | |
| CN107522613B (en) | Anthraquinone-2-cobalt carboxylate salt and preparation method and application thereof | |
| CN111525187A (en) | Sulfonated polyvinyl alcohol solid polymer electrolyte membrane for lithium battery and preparation method thereof | |
| CN103113268A (en) | Iron sulfonate and preparation method of alcoholic solution thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220712 Address after: No. 576, floor 5, building 1, No. 1388, middle section of Tianfu Avenue, high tech Zone, Chengdu, Sichuan 610000 Patentee after: SICHUAN METHYRR TECHNOLOGY CO.,LTD. Address before: 650000 No. 2 Cuihu Road, Wuhua District, Kunming City, Yunnan Province Patentee before: YUNNAN University |