CN102130364A - Gel-type polymer electrolyte used for lithium-sulfur secondary battery system and preparation method - Google Patents
Gel-type polymer electrolyte used for lithium-sulfur secondary battery system and preparation method Download PDFInfo
- Publication number
- CN102130364A CN102130364A CN2011100368611A CN201110036861A CN102130364A CN 102130364 A CN102130364 A CN 102130364A CN 2011100368611 A CN2011100368611 A CN 2011100368611A CN 201110036861 A CN201110036861 A CN 201110036861A CN 102130364 A CN102130364 A CN 102130364A
- Authority
- CN
- China
- Prior art keywords
- lithium
- polymer electrolyte
- gel
- type polymer
- battery system
- 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
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a gel-type polymer electrolyte used for a lithium-sulfur secondary battery system, consisting of a polymer support body, an ionic liquid, an organic solvent, a mixed lithium salt and dioxide silicon particles. A preparation method comprises the following steps of: preparing an imidazolium-based ionic liquid, dioxide silicon and composite lithium salt into a gel liquid in a carbonic ester solution dissolved with macromolecular polymers, then coating, drying and obtaining the gel-type polymer electrolyte film. In the gel-type polymer electrolyte prepared by the invention, sulfides in the lithium-sulfur battery system can be effectively prevented from dissolving in a liquid electrolyte solution, the ionic conductivity is high, and noninflammability and no leakage are achieved; and for the polymer electrolyte, the preparation process is simple, and the raw material source is wide, so that the gel-type polymer electrolyte is suitable for industrial production.
Description
Technical field:
The present invention relates to a kind of lithium-sulfur rechargeable battery system with gel-type polymer electrolyte and preparation method, belong to lithium secondary battery material technology field.
Background technology:
Compare present commercial lithium ion battery, the lithium-sulfur cell system has higher energy density, its theoretical specific energy reaches 1200Wh/kg, be considered to the most attractive battery system, have vast potential for future development in fields such as the electric automobile that the high-energy-density demand is arranged, communication equipment, defence and militaries.But the elemental sulfur poorly conductive, electro-chemical activity is low; Discharging product lithium sulphur compound is dissolved by electrolyte solution easily, and with lithium metal negative reaction, thereby produce the problem of a series of life-span and safety, be the main restricting factor of restriction lithium-sulfur cell system practicability.
Study on the modification for sulfur electrode mainly contains compound [CN 1803631A] and coats [Choi Y.J., et al., J Power Sources, 2008,184,548] two kinds of methods, its main way is in the manufacturing process of positive electrode, adds electronic conductor and lithium ion conductor in a large number, high-strength and long time ball milling, solve the nonconducting shortcoming of sulphur, can improve the performance of sulfur electrode to a certain extent.Yet, these researchs all can not thoroughly solve the lithium sulphur compound in organic solvent dissolving and the bad problem of cycle performance that causes.Present discovers that electrolytical composition is very big to the influence of battery.
People such as Joon [Joon Ho Shin, et al., J.power sources, 2008,177,537] adopt solid electrolyte to replace traditional organic electrolyte to prevent the dissolving of sulfide as the electrolyte of lithium-sulfur rechargeable battery.Yet the solid electrolyte ion poorly conductive, its ionic conductivity generally is lower than 10
-3S/cm is difficult to reach the requirement that lithium-sulfur rechargeable battery uses.In order to improve the conductivity at room temperature performance of solid polymer electrolyte, [CN 01108824] adds the carbonates organic compound and makees solvent in system, make polymer gel, to improve the degree of dissociation of lithium salts in gel rubber system, improves the migration rate of lithium ion.Yet the solvent osmotic phenomena can take place in this gellike polymer dielectric film in recycling process, causes shorten the useful life of battery.[CN101635380A] adopts ionic liquid-polymer electrolyte system to solve the problem of solvent dialysis, improved the security performance of battery, and still, most of viscosity of il are bigger under the room temperature, and wetability is bad between electrode; Simultaneously, ionic liquid can't form solid-electrolyte interface film (SEI) in electrode material surface under the room temperature, makes it about 1V reduction reaction will take place, and causes the compatibility between electrolyte system and electrode material bad.
Summary of the invention
The objective of the invention is to solve the problem of electrolyte and positive and negative pole material compatibility difference in the lithium-sulfur cell system, provide a kind of ionic conductivity height, with the lithium-sulfur rechargeable battery system of the elasticity self-supporting gel state electrolyte film that the both positive and negative polarity compatibility is good, pliability is good with gel-type polymer electrolyte and preparation method.
A kind of lithium-sulfur rechargeable battery system of the present invention gel-type polymer electrolyte is counted by weight, is made up of following component:
1 part of high molecular polymer,
1～2 part of ionic liquid,
1～10 part of organic solvent,
0.1～20 part of compound lithium salts,
0.1～0.5 part on pretreated silicon dioxide particle.
A kind of lithium-sulfur rechargeable battery system of the present invention is with in the gel-type polymer electrolyte, and described high molecular polymer is selected from a kind of in polyacrylonitrile, Kynoar, poly(ethylene oxide), poly-(biasfluoroethylene-hexafluoropropylene), poly-(oxirane-epoxychloropropane), the polypyrrole.
A kind of lithium-sulfur rechargeable battery system of the present invention is with in the gel-type polymer electrolyte, and described organic solvent is the carbonates organic solvent; Described organic solvent is selected from the compounded organic solvent of at least two kinds of formations in ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, the Methylethyl carbonic ester, the mass percent of each component is all more than or equal to 10% in the compounded organic solvent, and the percentage by weight sum of each component is 100%.
A kind of lithium-sulfur rechargeable battery system of the present invention is with in the gel-type polymer electrolyte, described ionic liquid is a glyoxaline ion liquid, described ionic liquid is selected from tetrafluoro boric acid 1-methyl-3-butyl imidazole, hexafluorophosphoric acid 1-methyl-3-ethyl imidazol(e), chloro-1-ethyl-3-methyl-imidazoles, trifluoromethane sulfonic acid imines 1-ethyl-3-methylimidazole, difluoromethyl sulfimide 1-methyl-3-ethyl imidazol(e), trifluoromethanesulp-onyl-onyl imide 1-methyl-3-ethyl imidazol(e), difluoromethyl sulfimide 1-methyl-3-butyl imidazole, at least a in trifluoromethanesulp-onyl-onyl imide 1-methyl-3-butyl imidazole, each weight percentages of components is all more than or equal to 10% in the described ionic liquid, each composition weight percent and be 100%.
A kind of lithium-sulfur rechargeable battery system of the present invention is with in the gel-type polymer electrolyte, described compound lithium salts is selected from least two kinds in lithium hexafluoro phosphate, LiBF4, di-oxalate lithium borate, lithium perchlorate, difluoromethyl sulfimide lithium, the trifluoromethane sulfonic acid imines lithium, each weight percentages of components is all more than or equal to 10% in the described compound lithium salts, each composition weight percent and be 100%.
A kind of lithium-sulfur rechargeable battery system of the present invention is with in the gel-type polymer electrolyte, the particle diameter of described pretreated silicon dioxide particle is 10nm-10 μ m, its preprocess method is: adopting silane coupling agent or titanium is that coupling agent is as dispersant, join in the acetone suspension of silicon dioxide granule, obtain after sonic oscillation 2-3 hour through pretreated silicon dioxide granule dispersion liquid, described silane coupling agent or titanium are that the volume ratio of the acetone soln of coupling agent and suspended silica particle is 1: (25-100), and the solid content 5～10% of silicon dioxide granule in acetone soln.
A kind of lithium-sulfur rechargeable battery system of the present invention comprises the steps: with the preparation method of gel-type polymer electrolyte
The first step: the set of dispense by design is got high molecular polymer, ionic liquid than respectively, organic solvent, compound lithium salts, pretreated silicon dioxide dispersion liquid; At first, high molecular polymer is dissolved in the carbonates organic solvent, at room temperature be stirred to solution clarification after; In solution, add ionic liquid, be stirred to evenly; Then, in solution, add pretreated silicon dioxide dispersion liquid and compound lithium salts, be stirred to the coagulant liquid that obtains transparent homogeneous; The addition of described pretreated silicon dioxide dispersion liquid is pressed the conversion of pretreated silicon dioxide particle weight;
Second goes on foot: after first step gained coagulant liquid is left standstill 3-10 minute at normal temperatures, be uniformly coated into the coating that thickness is 20-80 μ m, then, 60 ℃ of-80 ℃ of following vacuumizes 24～48 hours, promptly obtain lithium-sulfur rechargeable battery system gel-type polymer electrolyte film.
The inventor finds that through many tests the composite electrolyte that contains ionic liquid and organic solvent has the high conductivity of ion liquid system, nonflammable and liquid organic electrolyte and the good advantage of electrode material compatibility concurrently.Particularly, in the glyoxaline ion liquid electrolyte of some good stabilities, add carbonates organic solvents such as ethylene carbonate, propene carbonate, can reduce ion liquid viscosity, improve its conductivity, and pass through to add the organic solvent of carbonate-containing component, can guarantee electrolyte stablizing in the lithium-sulfur cell system by forming stable SEI film.
The inventor finds that also in the lithium-sulfur cell system, using the mixing lithium salts is to improve the electrolytical composition of gel-type, thereby realizes the another effective ways of polymer dielectric and electrode material compatibility.Mix lithium salts not only for electrolyte provides the lithium source, and the surface passivation of electrode is played crucial effect, such as LiPF
6With mixing or LiBF of LiBOB
4With LiPF
6Mixing, all can improve stability, high-temperature behavior or even the rate charge-discharge performance of electrode material, show than not adding lithium salts or only adding the compatibility of the electrolyte and the positive and negative electrode material of single lithium salts.
Based on this, the present invention adopts said components proportioning and preparation technology, the lithium-sulfur rechargeable battery system that obtains is made up of polymer support body, ionic liquid, organic solvent, mixing lithium salts and silicon dioxide granule with the gel-type polymer electrolyte film, wherein polymer is as prop carrier, ionic liquid can effectively improve ionic conductivity, organic solvent can reduce viscosity, improve wetability, mix lithium salts can effectively improve passivating film and with the compatibility of negative pole, the silicon dioxide ion can improve conductance and improve interfacial property.
In addition, in this gel-type polymer electrolyte, disperse equably to have passed through pretreated silicon dioxide granule, can improve the mechanical strength and the conductivity of polymer film.Compare and do not mix silicon dioxide or mix electrolyte without pretreated silicon dioxide, the electrolyte of the present invention's preparation shows better interface stability in the lithium-sulfur cell system, the lithium-sulfur cell of forming with this polymer dielectric has good cycle performance.
The present invention prepares the composite electrolyte membrane of polymer and ionic liquid at room temperature by simple coating and film-forming process, two kinds of electrolytical advantages of conjugated polymer and ionic liquid, obtain the electrolyte non-volatile, that room-temperature conductivity is high, fail safe is good, satisfy the needs of high power capacity lithium-sulfur rechargeable battery.Advantage of the present invention and expected effect are as follows:
1. gel state electrolyte has prevented the dissolving of sulfide in liquid electrolyte in the lithium-sulfur cell system, has improved the cycle performance of battery system.
2. introduce high conduction glyoxaline ion liquid, the ionic conductivity height reaches 10
-3More than the S/cm, nonflammable, do not reveal, fail safe is good.
3. adopt each additive component (carbonates organic solvent, compound lithium salts and silicon dioxide granule) can greatly improve the compatibility between electrolyte and the electrode.
4. the present invention is simple to operate, on the basis that does not change original technology, avoids complicated extraction step, does not also have the residual polymer monomer of in-situ polymerization thing method.The raw materials used raw material of industry that all comes from of this method, cost is low, and wide material sources have good cost advantage, are suitable for suitability for industrialized production; Be expected to solve the problem that positive electrode in the present lithium sulfur system is dissolved in electrolyte, make lithium-sulfur cell realize commercial application.
Embodiment:
The present invention will be further described below in conjunction with embodiment, provides concrete execution mode and operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1:
One, the preparation of gel-type polymer electrolyte.1g poly-(biasfluoroethylene-hexafluoropropylene) is dissolved in the compounded organic solvent of 5g by ethylene carbonate and diethyl carbonate (mass ratio 1: 3) formation, is stirred to the solution clarification.Add 1g tetrafluoro boric acid 1-methyl-3-butyl imidazole then, stirring obtains mixed solution.The 0.25g silicon dioxide granule is scattered in the 5ml acetone soln, adding 0.1ml tetraethoxysilane sonic oscillation obtains after 2 hours through pretreated silica dispersions, the salt-mixture of this dispersion liquid and 0.5g lithium hexafluoro phosphate-di-oxalate lithium borate (mass ratio 1: 1) is joined in the mixed solution simultaneously, be stirred to the coagulant liquid that obtains transparent homogeneous.Allow this coagulant liquid leave standstill under 30 ℃ 3 minutes, then apply with coating machine, 80 ℃ of following vacuumizes 30 hours, obtain the polymer dielectric film of homogeneous, thickness is 50 μ m.Measuring its conductivity under the room temperature is 1.2 * 10
-3S/cm.It is stand-by that this dielectric film is washed into diameter 15mm thin rounded flakes.
Two, the assembling of lithium-sulfur cell and test.The performance in the lithium-sulfur cell system for gel-type dielectric film in the check present embodiment is assembled into lithium-sulfur cell with it and tests.The preparation method of sulphur-carbon composite anode material is with reference to patent of invention openly (Li Yong etc., be used for lithium ion cell positive because nanostructure sulphur-mesoporous carbon composite material, application number 200910199577, publication number CN 101728538).Sulphur-carbon composite anode material, Kynoar (binding agent) and acetylene black are mixed by 8: 1: 1 (weight ratio), be modulated into slurry, evenly be coated on the aluminum foil current collector, being washed into diameter after the oven dry is the circular positive plate of 10mm.Gel-type dielectric film in the step 1 is placed between sulphur-carbon positive pole and the lithium anode, in glove box, be assembled into lithium-sulfur cell.Utilize the Land battery test system that above-mentioned half-cell is at room temperature carried out the constant current charge-discharge performance test, charging and discharging currents is 50mA/g, and the charging/discharging voltage scope is 1.5-3V.The discharge capacity of first charge-discharge can reach 492mAh/g, and after through 20 circulations, discharge capacity is stabilized in 415mAh/g, good cycling stability.
Embodiment 2:
One, the preparation of gel-type polymer electrolyte.What the preparation of gel-type polymer electrolyte and embodiment 1 were different in the present embodiment is: adopt the 1g Kynoar, compounded organic solvent is made of 5g ethylene carbonate, diethyl carbonate and dimethyl carbonate (three's mass ratio 1: 3: 1), and the ionic liquid that is adopted is made of 0.5g hexafluorophosphoric acid 1-methyl-3-ethyl imidazol(e) and 0.5g chloro-1-ethyl-3-methyl-imidazoles; The compound lithium salts of the 10g that is adopted is made of LiBF4, di-oxalate lithium borate and lithium perchlorate (three's mass ratio 4: 3: 3); Other is identical with embodiment 1.Measuring its conductivity under the room temperature is 0.9 * 10
-3S/cm.
Two, the assembling of lithium-sulfur cell and test.The performance in the lithium-sulfur cell system for gel-type dielectric film in the check present embodiment is assembled into lithium-sulfur cell with it and tests.The preparation of electrode, the assembling of battery, test condition are with embodiment 1, and the discharge capacity of its first charge-discharge reaches 511mAh/g, and repeatedly the stable circulation capacity remains on 454mAh/g.
Embodiment 3:
One, the preparation of gel-type polymer electrolyte.The 1g polyacrylonitrile is dissolved in the compounded organic solvent of 5g propene carbonate, diethyl carbonate and Methylethyl carbonic ester (three's mass ratio 3: 1: 1) composition, is stirred to the solution clarification.Add the ionic liquid that 1.5g is made of trifluoromethanesulp-onyl-onyl imide 1-methyl-3-ethyl imidazol(e), difluoromethyl sulfimide 1-methyl-3-butyl imidazole, trifluoromethanesulp-onyl-onyl imide 1-methyl-3-butyl imidazole (three's mass ratio 1: 1: 1) then, stirring obtains mixed solution.The 0.2g silicon dioxide granule is scattered in the 4ml acetone soln, adding 0.1ml tetraethoxysilane sonic oscillation obtains after 2 hours through pretreated silica dispersions, this dispersion liquid and 3g are joined in the mixed solution simultaneously by the compound lithium salts that lithium perchlorate, difluoromethyl sulfimide lithium and trifluoromethane sulfonic acid imines lithium (three's mass ratio 1: 1: 1) constitute, be stirred to the coagulant liquid that obtains transparent homogeneous.Allow this coagulant liquid leave standstill under 30 ℃ 10 minutes, then apply with coating machine, 80 ℃ of following vacuumizes 24 hours, obtain the polymer dielectric film of homogeneous, thickness is 70 μ m.Measuring its conductivity under the room temperature is 0.8 * 10
-3S/cm.It is stand-by that this dielectric film is washed into diameter 15mm thin rounded flakes.
Two, the assembling of lithium-sulfur cell and test.The performance in the lithium-sulfur cell system for gel-type dielectric film in the check present embodiment is assembled into lithium-sulfur cell with it and tests.The preparation of electrode, the assembling of battery, test condition are with embodiment 1, and the discharge capacity of its first charge-discharge reaches 475mAh/g, and repeatedly the stable circulation capacity remains on 390mAh/g.
Embodiment 4:
One, the preparation of gel-type polymer electrolyte.What the preparation of gel-type polymer electrolyte and embodiment 3 were different in the present embodiment is: the high molecular polymer polyacrylonitrile is 1 with the mass ratio that mixes lithium salts: 5. other is identical with embodiment 3.Measuring its conductivity under the room temperature is 1.1 * 10
-3S/cm.
Two, the assembling of lithium-sulfur cell and test.The performance in the lithium-sulfur cell system for gel-type dielectric film in the check present embodiment is assembled into lithium-sulfur cell with it and tests.The preparation of electrode, the assembling of battery, test condition are with embodiment 1, and the discharge capacity of its first charge-discharge reaches 488mAh/g, and repeatedly the stable circulation capacity remains on 426mAh/g.
Comparative example 1:(does not add the carbonates organic solvent)
1g poly-(biasfluoroethylene-hexafluoropropylene) is dissolved in the 5g N-methyl pyrrolidone, is stirred to the solution clarification.Add 1g tetrafluoro boric acid 1-methyl-3-butyl imidazole then, stirring obtains mixed solution.The 0.25g silicon dioxide granule is scattered in the 5ml acetone soln, adding 0.1ml tetraethoxysilane sonic oscillation obtains after 2 hours through pretreated silica dispersions, the salt-mixture of this dispersion liquid and 0.5g lithium hexafluoro phosphate-di-oxalate lithium borate (mass ratio 1: 1) is joined in the mixed solution simultaneously, be stirred to the coagulant liquid that obtains transparent homogeneous.Allow this coagulant liquid leave standstill under 30 ℃ 10 minutes, then apply with coating machine, 80 ℃ of following vacuumizes 24 hours, obtain the polymer dielectric film of homogeneous, thickness is 40 μ m.Measuring its conductivity under the room temperature is 0.78 * 10
-3S/cm.
Comparative example 2:(does not add and mixes lithium salts)
1g poly-(biasfluoroethylene-hexafluoropropylene) is dissolved in 5g ethylene carbonate and the diethyl carbonate (mass ratio 1: 3), is stirred to the solution clarification.Add 1g tetrafluoro boric acid 1-methyl-3-butyl imidazole then, stirring obtains mixed solution.The 0.25g silicon dioxide granule is scattered in the 5ml acetone soln, adding 0.1ml tetraethoxysilane sonic oscillation obtains after 2 hours through pretreated silica dispersions, this dispersion liquid is joined in the mixed solution, be stirred to the coagulant liquid that obtains transparent homogeneous.Allow this coagulant liquid leave standstill under 30 ℃ 10 minutes, then apply with coating machine, 80 ℃ of following vacuumizes 24 hours, obtain the polymer dielectric film of homogeneous, thickness is 50 μ m.Measuring its conductivity under the room temperature is 0.56 * 10
-3S/cm.
Comparative example 3:(does not add through pretreated silicon dioxide granule)
1g poly-(biasfluoroethylene-hexafluoropropylene) is dissolved in 5g ethylene carbonate and the diethyl carbonate (mass ratio 1: 3), is stirred to the solution clarification.Add 1g tetrafluoro boric acid 1-methyl-3-butyl imidazole then, stirring obtains mixed solution.The salt-mixture of 0.5g lithium hexafluoro phosphate-di-oxalate lithium borate (mass ratio 1: 1) is joined in the mixed solution, be stirred to the coagulant liquid that obtains transparent homogeneous.Allow this coagulant liquid leave standstill under 30 ℃ 10 minutes, then apply with coating machine, 80 ℃ of following vacuumizes 24 hours, obtain the polymer dielectric film of homogeneous, thickness is 40 μ m.Measuring its conductivity under the room temperature is 0.62 * 10
-3S/cm.
Claims (7)
1. a lithium-sulfur rechargeable battery system gel-type polymer electrolyte is counted by weight, is made up of following component:
1 part of high molecular polymer,
1～2 part of ionic liquid,
1～10 part of organic solvent,
0.1～20 part of compound lithium salts,
0.1～0.5 part on pretreated silicon dioxide particle.
2. a kind of lithium-sulfur rechargeable battery system gel-type polymer electrolyte according to claim 1 is characterized in that: described high molecular polymer is selected from a kind of in polyacrylonitrile, Kynoar, poly(ethylene oxide), poly-(biasfluoroethylene-hexafluoropropylene), poly-(oxirane-epoxychloropropane), the polypyrrole.
3. a kind of lithium-sulfur rechargeable battery system gel-type polymer electrolyte according to claim 2, it is characterized in that: described organic solvent is the carbonates organic solvent; Described organic solvent is selected from the compounded organic solvent of at least two kinds of formations in ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, the Methylethyl carbonic ester, the mass percent of each component is all more than or equal to 10% in the compounded organic solvent, and the percentage by weight sum of each component is 100%.
4. a kind of lithium-sulfur rechargeable battery system gel-type polymer electrolyte according to claim 3, it is characterized in that: described ionic liquid is a glyoxaline ion liquid, described ionic liquid is selected from tetrafluoro boric acid 1-methyl-3-butyl imidazole, hexafluorophosphoric acid 1-methyl-3-ethyl imidazol(e), chloro-1-ethyl-3-methyl-imidazoles, trifluoromethane sulfonic acid imines 1-ethyl-3-methylimidazole, difluoromethyl sulfimide 1-methyl-3-ethyl imidazol(e), trifluoromethanesulp-onyl-onyl imide 1-methyl-3-ethyl imidazol(e), difluoromethyl sulfimide 1-methyl-3-butyl imidazole, at least a in trifluoromethanesulp-onyl-onyl imide 1-methyl-3-butyl imidazole, each weight percentages of components is all more than or equal to 10% in the described ionic liquid, each composition weight percent and be 100%.
5. a kind of lithium-sulfur rechargeable battery system gel-type polymer electrolyte according to claim 4, it is characterized in that: described compound lithium salts is selected from least two kinds in lithium hexafluoro phosphate, LiBF4, di-oxalate lithium borate, lithium perchlorate, difluoromethyl sulfimide lithium, the trifluoromethane sulfonic acid imines lithium, each weight percentages of components is all more than or equal to 10% in the described compound lithium salts, each composition weight percent and be 100%.
6. a kind of lithium-sulfur rechargeable battery system gel-type polymer electrolyte according to claim 1, it is characterized in that: the particle diameter of described pretreated silicon dioxide particle is 10nm-10 μ m, its preprocess method is: adopting silane coupling agent or titanium is that coupling agent is as dispersant, join in the acetone suspension of silicon dioxide granule, obtain after sonic oscillation 2-3 hour through pretreated silicon dioxide granule dispersion liquid, described silane coupling agent or titanium are that the volume ratio of the acetone soln of coupling agent and suspended silica particle is 1: (25-100), and the solid content 5～10% of silicon dioxide granule in acetone soln.
7. a kind of according to claim 1 lithium-sulfur rechargeable battery system of preparation comprises the steps: with the method for gel-type polymer electrolyte
The first step: the set of dispense by design is got high molecular polymer, ionic liquid than respectively, organic solvent, compound lithium salts, pretreated silicon dioxide dispersion liquid; At first, high molecular polymer is dissolved in the carbonates organic solvent, at room temperature be stirred to solution clarification after; In solution, add ionic liquid, be stirred to evenly; Then, in solution, add pretreated silicon dioxide dispersion liquid and compound lithium salts, be stirred to the coagulant liquid that obtains transparent homogeneous; The addition of described pretreated silicon dioxide dispersion liquid is pressed the conversion of pretreated silicon dioxide particle weight;
Second goes on foot: after first step gained coagulant liquid is left standstill 3-10 minute at normal temperatures, be uniformly coated into the coating that thickness is 20-80 μ m, then, 60 ℃ of-80 ℃ of following vacuumizes 24～48 hours, promptly obtain lithium-sulfur rechargeable battery system gel-type polymer electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100368611A CN102130364A (en) | 2011-02-12 | 2011-02-12 | Gel-type polymer electrolyte used for lithium-sulfur secondary battery system and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100368611A CN102130364A (en) | 2011-02-12 | 2011-02-12 | Gel-type polymer electrolyte used for lithium-sulfur secondary battery system and preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102130364A true CN102130364A (en) | 2011-07-20 |
Family
ID=44268314
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100368611A Pending CN102130364A (en) | 2011-02-12 | 2011-02-12 | Gel-type polymer electrolyte used for lithium-sulfur secondary battery system and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102130364A (en) |
Cited By (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324566A (en) * | 2011-09-20 | 2012-01-18 | 南京林业大学 | Preparation method for ionic liquid electrolyte |
| CN102407707A (en) * | 2011-07-27 | 2012-04-11 | 哈尔滨工业大学 | Method for removing bubbles of ink absorption layer |
| CN102509618A (en) * | 2011-10-13 | 2012-06-20 | 北京交通大学 | Preparation method of gel electrolyte of dye-sensitized nanocrystalline solar cell |
| CN103094611A (en) * | 2011-11-07 | 2013-05-08 | 中国科学院上海硅酸盐研究所 | Preparation method for ionic liquid gel electrolyte |
| CN103545548A (en) * | 2013-11-07 | 2014-01-29 | 湘潭大学 | Method for preparing three-dimensional porous polymer electrolyte film |
| CN103545550A (en) * | 2013-11-07 | 2014-01-29 | 湘潭大学 | Preparation method of high-temperature safe nanocomposite conductive ionic glue |
| CN104362003A (en) * | 2014-09-18 | 2015-02-18 | 电子科技大学 | Gel polymer electrolyte preparing method |
| CN105070946A (en) * | 2015-09-15 | 2015-11-18 | 中南大学 | Nanostructured quasi-solid electrolyte applied to lithium ion batteries or lithium sulfur batteries and preparation method and application thereof |
| CN106654364A (en) * | 2016-10-20 | 2017-05-10 | 中国科学院大学 | Ion liquid composite full-solid polymer electrolyte and preparation method and application thereof |
| CN104321922B (en) * | 2012-04-23 | 2017-07-21 | 索尔维公司 | Fluoro-containing copolymer film |
| CN107195963A (en) * | 2017-04-17 | 2017-09-22 | 哈尔滨工业大学无锡新材料研究院 | A kind of polymer dielectric of high conductivity and preparation method thereof |
| CN107732294A (en) * | 2017-10-11 | 2018-02-23 | 中国科学院宁波材料技术与工程研究所 | A kind of electrolyte and lithium metal battery |
| CN108409964A (en) * | 2018-05-18 | 2018-08-17 | 东华大学 | Using ionic liquid as poly ion liquid of skeleton and preparation method thereof |
| CN108461815A (en) * | 2018-04-28 | 2018-08-28 | 清陶（昆山）新能源材料研究院有限公司 | A kind of ECO bases solid polyelectrolyte and preparation method thereof |
| CN108682863A (en) * | 2018-06-11 | 2018-10-19 | 佛山腾鲤新能源科技有限公司 | A kind of lithium battery gel-form solid polymer electrolyte |
| CN108933287A (en) * | 2017-05-26 | 2018-12-04 | 北京师范大学 | It is a kind of for lithium ion battery can gelling system and its preparation method and application |
| CN108933275A (en) * | 2017-05-26 | 2018-12-04 | 北京师范大学 | It is a kind of for lithium-sulfur cell can gelling system and its preparation method and application |
| CN108933285A (en) * | 2017-05-26 | 2018-12-04 | 北京师范大学 | It is a kind of containing straight chain ether compound can gelling system and its preparation method and application |
| CN108933286A (en) * | 2017-05-26 | 2018-12-04 | 北京师范大学 | It is a kind of containing ring-type ethers compound can gelling system and its preparation method and application |
| CN108933284A (en) * | 2017-05-26 | 2018-12-04 | 北京师范大学 | A kind of flexibility all solid state lithium ion secondary cell and preparation method thereof |
| CN108963330A (en) * | 2017-05-26 | 2018-12-07 | 北京师范大学 | It is a kind of containing inorganic nanoparticles can gelling system and its preparation method and application |
| CN108963333A (en) * | 2017-05-26 | 2018-12-07 | 北京师范大学 | A kind of gel and its preparation method and application with adjustable intensity and/or transition temperature |
| CN109449483A (en) * | 2018-11-05 | 2019-03-08 | 浙江众泰汽车制造有限公司 | A kind of compound for lithium-sulfur cell electrolyte, lithium-sulfur cell electrolyte and preparation method thereof, solid-state lithium-sulfur cell |
| CN110858650A (en) * | 2018-08-22 | 2020-03-03 | 哈尔滨工业大学 | Metal lithium cathode with preset stable protective film and preparation method thereof |
| CN111196888A (en) * | 2020-01-06 | 2020-05-26 | 浙江大学 | Gel polymer electrolyte doped with modified particles and preparation method and application thereof |
| CN111224154A (en) * | 2020-02-17 | 2020-06-02 | 中国科学院化学研究所 | Mesoporous nanoparticle gel composite electrolyte with lithium ion conduction and preparation method and application thereof |
| EP3605556A4 (en) * | 2017-03-29 | 2021-01-13 | Hitachi, Ltd. | Semisolid electrolyte layer, battery cell sheet and secondary battery |
| CN112259789A (en) * | 2020-10-13 | 2021-01-22 | 北京卫国创芯科技有限公司 | Polyether solid polymer electrolyte, preparation method thereof and solid battery comprising polyether solid polymer electrolyte |
| CN112467194A (en) * | 2020-12-09 | 2021-03-09 | 中国科学院上海硅酸盐研究所 | Organic-inorganic composite quasi-solid electrolyte and quasi-solid lithium battery |
| CN112510250A (en) * | 2020-12-01 | 2021-03-16 | 北京理工大学 | Gel containing ester compound and sulfide, preparation and application thereof |
| CN114597347A (en) * | 2022-03-15 | 2022-06-07 | 清华大学深圳国际研究生院 | Solid-state lithium-sulfur battery positive electrode and preparation method thereof, and solid-state lithium-sulfur battery and preparation method thereof |
| US11557793B2 (en) | 2017-05-26 | 2023-01-17 | Beijing Normal University | Flexible all-solid-state lithium-ion secondary battery having gelable system containing lithium salt and ether compound, and preparation method thereof |
| US11777142B2 (en) | 2017-05-26 | 2023-10-03 | Beijing Normal University | Gelable system containing ether compounds, preparation method therefor and use thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1310483A (en) * | 2001-01-09 | 2001-08-29 | 长春吉大超越科技开发股份有限公司 | Making process of gel polymer electrolyte diaphragm and stacked-up lithium ion battery |
| CN1838469A (en) * | 2006-04-20 | 2006-09-27 | 武汉大学 | Lithium-sulphur battery electrolyte and chargeable lithium-sulphur battery thereof |
| CN101740813A (en) * | 2009-12-16 | 2010-06-16 | 北京理工大学 | Ionic liquid compound electrolyte material |
| CN101789519A (en) * | 2010-01-25 | 2010-07-28 | 北京理工大学 | Ionic liquid-based composite electrolyte |
-
2011
- 2011-02-12 CN CN2011100368611A patent/CN102130364A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1310483A (en) * | 2001-01-09 | 2001-08-29 | 长春吉大超越科技开发股份有限公司 | Making process of gel polymer electrolyte diaphragm and stacked-up lithium ion battery |
| CN1838469A (en) * | 2006-04-20 | 2006-09-27 | 武汉大学 | Lithium-sulphur battery electrolyte and chargeable lithium-sulphur battery thereof |
| CN101740813A (en) * | 2009-12-16 | 2010-06-16 | 北京理工大学 | Ionic liquid compound electrolyte material |
| CN101789519A (en) * | 2010-01-25 | 2010-07-28 | 北京理工大学 | Ionic liquid-based composite electrolyte |
Cited By (43)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102407707A (en) * | 2011-07-27 | 2012-04-11 | 哈尔滨工业大学 | Method for removing bubbles of ink absorption layer |
| CN102324566B (en) * | 2011-09-20 | 2013-12-18 | 南京林业大学 | Preparation method for ionic liquid electrolyte |
| CN102324566A (en) * | 2011-09-20 | 2012-01-18 | 南京林业大学 | Preparation method for ionic liquid electrolyte |
| CN102509618A (en) * | 2011-10-13 | 2012-06-20 | 北京交通大学 | Preparation method of gel electrolyte of dye-sensitized nanocrystalline solar cell |
| CN103094611B (en) * | 2011-11-07 | 2015-03-25 | 中国科学院上海硅酸盐研究所 | Preparation method for ionic liquid gel electrolyte |
| CN103094611A (en) * | 2011-11-07 | 2013-05-08 | 中国科学院上海硅酸盐研究所 | Preparation method for ionic liquid gel electrolyte |
| CN104321922B (en) * | 2012-04-23 | 2017-07-21 | 索尔维公司 | Fluoro-containing copolymer film |
| US10227462B2 (en) | 2012-04-23 | 2019-03-12 | Solvay Sa | Fluoropolymer film |
| CN103545548A (en) * | 2013-11-07 | 2014-01-29 | 湘潭大学 | Method for preparing three-dimensional porous polymer electrolyte film |
| CN103545550A (en) * | 2013-11-07 | 2014-01-29 | 湘潭大学 | Preparation method of high-temperature safe nanocomposite conductive ionic glue |
| CN103545548B (en) * | 2013-11-07 | 2015-11-25 | 湘潭大学 | A kind of preparation method of three-dimensional porous polymer dielectric film |
| CN104362003A (en) * | 2014-09-18 | 2015-02-18 | 电子科技大学 | Gel polymer electrolyte preparing method |
| CN105070946A (en) * | 2015-09-15 | 2015-11-18 | 中南大学 | Nanostructured quasi-solid electrolyte applied to lithium ion batteries or lithium sulfur batteries and preparation method and application thereof |
| CN105070946B (en) * | 2015-09-15 | 2018-01-09 | 中南大学 | A kind of quasi- solid electrolyte of nanostructured for lithium ion battery or lithium-sulfur cell and its preparation method and application |
| CN106654364A (en) * | 2016-10-20 | 2017-05-10 | 中国科学院大学 | Ion liquid composite full-solid polymer electrolyte and preparation method and application thereof |
| EP3605556A4 (en) * | 2017-03-29 | 2021-01-13 | Hitachi, Ltd. | Semisolid electrolyte layer, battery cell sheet and secondary battery |
| CN107195963A (en) * | 2017-04-17 | 2017-09-22 | 哈尔滨工业大学无锡新材料研究院 | A kind of polymer dielectric of high conductivity and preparation method thereof |
| CN108933275A (en) * | 2017-05-26 | 2018-12-04 | 北京师范大学 | It is a kind of for lithium-sulfur cell can gelling system and its preparation method and application |
| CN108963330A (en) * | 2017-05-26 | 2018-12-07 | 北京师范大学 | It is a kind of containing inorganic nanoparticles can gelling system and its preparation method and application |
| CN108933287A (en) * | 2017-05-26 | 2018-12-04 | 北京师范大学 | It is a kind of for lithium ion battery can gelling system and its preparation method and application |
| US11557793B2 (en) | 2017-05-26 | 2023-01-17 | Beijing Normal University | Flexible all-solid-state lithium-ion secondary battery having gelable system containing lithium salt and ether compound, and preparation method thereof |
| CN108933285A (en) * | 2017-05-26 | 2018-12-04 | 北京师范大学 | It is a kind of containing straight chain ether compound can gelling system and its preparation method and application |
| CN108933286A (en) * | 2017-05-26 | 2018-12-04 | 北京师范大学 | It is a kind of containing ring-type ethers compound can gelling system and its preparation method and application |
| CN108933284A (en) * | 2017-05-26 | 2018-12-04 | 北京师范大学 | A kind of flexibility all solid state lithium ion secondary cell and preparation method thereof |
| US11777142B2 (en) | 2017-05-26 | 2023-10-03 | Beijing Normal University | Gelable system containing ether compounds, preparation method therefor and use thereof |
| CN108963333A (en) * | 2017-05-26 | 2018-12-07 | 北京师范大学 | A kind of gel and its preparation method and application with adjustable intensity and/or transition temperature |
| CN107732294A (en) * | 2017-10-11 | 2018-02-23 | 中国科学院宁波材料技术与工程研究所 | A kind of electrolyte and lithium metal battery |
| CN107732294B (en) * | 2017-10-11 | 2020-05-22 | 中国科学院宁波材料技术与工程研究所 | Electrolyte and lithium metal battery |
| CN108461815A (en) * | 2018-04-28 | 2018-08-28 | 清陶（昆山）新能源材料研究院有限公司 | A kind of ECO bases solid polyelectrolyte and preparation method thereof |
| CN108461815B (en) * | 2018-04-28 | 2021-04-30 | 苏州清陶新能源科技有限公司 | ECO-based solid polyelectrolyte and preparation method thereof |
| CN108409964A (en) * | 2018-05-18 | 2018-08-17 | 东华大学 | Using ionic liquid as poly ion liquid of skeleton and preparation method thereof |
| CN108682863A (en) * | 2018-06-11 | 2018-10-19 | 佛山腾鲤新能源科技有限公司 | A kind of lithium battery gel-form solid polymer electrolyte |
| CN108682863B (en) * | 2018-06-11 | 2020-12-18 | 珠海辰玉新材料科技有限公司 | Lithium battery polymer gel electrolyte |
| CN110858650A (en) * | 2018-08-22 | 2020-03-03 | 哈尔滨工业大学 | Metal lithium cathode with preset stable protective film and preparation method thereof |
| CN109449483A (en) * | 2018-11-05 | 2019-03-08 | 浙江众泰汽车制造有限公司 | A kind of compound for lithium-sulfur cell electrolyte, lithium-sulfur cell electrolyte and preparation method thereof, solid-state lithium-sulfur cell |
| CN111196888A (en) * | 2020-01-06 | 2020-05-26 | 浙江大学 | Gel polymer electrolyte doped with modified particles and preparation method and application thereof |
| CN111224154B (en) * | 2020-02-17 | 2021-09-10 | 中国科学院化学研究所 | Mesoporous nanoparticle gel composite electrolyte with lithium ion conduction and preparation method and application thereof |
| CN111224154A (en) * | 2020-02-17 | 2020-06-02 | 中国科学院化学研究所 | Mesoporous nanoparticle gel composite electrolyte with lithium ion conduction and preparation method and application thereof |
| CN112259789A (en) * | 2020-10-13 | 2021-01-22 | 北京卫国创芯科技有限公司 | Polyether solid polymer electrolyte, preparation method thereof and solid battery comprising polyether solid polymer electrolyte |
| CN112510250A (en) * | 2020-12-01 | 2021-03-16 | 北京理工大学 | Gel containing ester compound and sulfide, preparation and application thereof |
| CN112510250B (en) * | 2020-12-01 | 2021-10-19 | 北京理工大学 | Gel containing ester compound and sulfide, preparation and application thereof |
| CN112467194A (en) * | 2020-12-09 | 2021-03-09 | 中国科学院上海硅酸盐研究所 | Organic-inorganic composite quasi-solid electrolyte and quasi-solid lithium battery |
| CN114597347A (en) * | 2022-03-15 | 2022-06-07 | 清华大学深圳国际研究生院 | Solid-state lithium-sulfur battery positive electrode and preparation method thereof, and solid-state lithium-sulfur battery and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102130364A (en) | Gel-type polymer electrolyte used for lithium-sulfur secondary battery system and preparation method | |
| CN105958011B (en) | Nonaqueous electrolyte secondary battery and positive electrode sheet for same | |
| KR20110136210A (en) | Electrolyte for electrochemical device, the preparation method thereof and electrochemical device comprising the same | |
| CN101747642B (en) | Gel polymer electrolyte, polymer battery and preparing method | |
| CN107706406B (en) | Organic cathode material and preparation method and application thereof | |
| CN107732169B (en) | Silicon-based negative electrode material of lithium battery, preparation method of silicon-based negative electrode material, battery negative electrode and lithium battery | |
| Zhang et al. | Aqueous sodium alginate as binder: dramatically improving the performance of dilithium terephthalate-based organic lithium ion batteries | |
| Chu et al. | A robust polymeric binder based on complementary multiple hydrogen bonds in lithium-sulfur batteries | |
| Gou et al. | To improve the interfacial compatibility of cellulose-based gel polymer electrolytes: A cellulose/PEGDA double network-based gel membrane designed for lithium ion batteries | |
| He et al. | Enabling interfacial stability via 3D networking single ion conducting nano fiber electrolyte for high performance lithium metal batteries | |
| Ye et al. | A blended gel polymer electrolyte for dendrite-free lithium metal batteries | |
| Wu et al. | Dendrite-free solid-state Li metal batteries enabled by bifunctional polymer gel electrolytes | |
| Zhai et al. | Biomimetic plant-cell composite gel polymer electrolyte for boosting rate performance of lithium metal batteries | |
| Vauthier et al. | High-performance pyrrolidinium-based poly (ionic liquid) binders for Li-ion and Li-air batteries | |
| Zhou et al. | Mixed-linker MOFs-derived cross-linked copolymer electrolyte enables high lithium mobility for dendrite-free all-solid-state batteries | |
| CN102237524B (en) | The acid of Surface coating cobalt lithium, preparation method and lithium ion battery | |
| CN106784614A (en) | A kind of high security lithium ion battery and preparation method thereof | |
| Wang et al. | Ionic liquid modified carbon nanotubes doped gel polymer electrolyte for fast charging lithium metal batteries | |
| CN111786017B (en) | High-cohesiveness solid electrolyte prepared by in-situ curing, preparation method and application | |
| Lee et al. | Selective and uniform Li-ion boosting polymer electrolytes for dendrite-less quasi-solid-state batteries | |
| Zhang et al. | Ion-compensation regime between electrolyte and cathode to prepare advanced lithium metal batteries | |
| Xie et al. | Novel quasi solid-state succinonitrile-based electrolyte with low-flammability for lithium-ion battery | |
| CN115832412A (en) | Composite solid electrolyte and preparation method and application thereof | |
| CN104022259A (en) | Multi-hole loose polyaniline-nanometer silicon composite material and preparation method and application thereof | |
| CN109494373A (en) | Adhesive and preparation method thereof, anode and lithium-sulfur cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110720 |