CN101407625A - Hyperbranched polyether type solid polymer elecrolytes and preparation thereof - Google Patents
Hyperbranched polyether type solid polymer elecrolytes and preparation thereof Download PDFInfo
- Publication number
- CN101407625A CN101407625A CNA2008101824130A CN200810182413A CN101407625A CN 101407625 A CN101407625 A CN 101407625A CN A2008101824130 A CNA2008101824130 A CN A2008101824130A CN 200810182413 A CN200810182413 A CN 200810182413A CN 101407625 A CN101407625 A CN 101407625A
- Authority
- CN
- China
- Prior art keywords
- lithium
- solid polymer
- hyperbranched polyether
- elecrolytes
- type solid
- 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.)
- Granted
Links
Images
Classifications
-
- Y02E60/122—
Landscapes
- Secondary Cells (AREA)
- Conductive Materials (AREA)
Abstract
The invention relates to a hyperbranched polyether type solid polymer electrolyte and a preparation method thereof. The polymer electrolyte material comprises a polymer substrate material (A), a polymer substrate material (B) and lithium salt (C), wherein, the polymer substrate material (A) is hyperbranched polyether which contains ether oxygen group and has completely amorphous structure; and the polymer substrate material (B) is polymer substrate material with excellent and mechanical property. The solid polymer substrate electrolyte membrane is prepared by one step method of volatile solvent, has simple preparation technique, higher ion electrical conductivity and electrical and chemical stability, has good mechanical performance and heat stability, and can be applied to the preparation of second lithium ion cells.
Description
Technical field
The present invention relates to a kind ofly can be applied to solid polymer electrolyte of lithium ion battery and preparation method thereof, especially relate to a kind of hyperbranched polyether type solid polymer elecrolytes material and preparation method thereof.
Background technology
Copolymer solid electrolyte, promptly has the ionic conduction ability, high-molecular complex by superpolymer and inorganic salt generation, have good reliability, do not have characteristics such as leakage, easy-formation, and keeping high molecular essential characteristic, its application aspect lithium ion battery has caused people's extensive concern, and Chinese scholars has been launched in succession to the electrolytical research work of new polymers.The more polymer electrolyte system of research mainly contains several big classes such as PEO, PAN, PMMA, PVDF, PVC at present, and wherein, electrolyte system polyoxyethylene (PEO) receives much concern all the time owing to have the constitutional features of the ionic conduction of being easy to.Yet the polymer dielectric that traditional PEO system and an alkali metal salt form has higher crystallization phases when room temperature, the electrolytical room-temperature conductivity that forms low excessively, thereby limit its practical application.
In the solid polymer electrolyte system, two kinds of effective ways that are commonly used to improve specific conductivity are the second-order transition temperatures that suppress crystallization and reduce polymkeric substance.Thereby the polyethers that research has highly branched structure can effectively prevent the segmental crystallization, reduces second-order transition temperature.But when polyethers system degree of crystallinity reduced, its mechanical property also was damaged, can't the self-supporting film forming, be unfavorable for that the mechanics of dielectric film is stable.Comparing, have the good mechanical performance though PVDF, PAN, PMMA etc. have the polymer electrolyte of better mechanical property, is that the specific conductivity of solid polymer electrolyte of matrix is often too low with it, can't reach application requiring.
As mentioned above, a major issue that develops the solid polymer electrolyte system at present is to solve the contradiction between mechanical property and the ionic conductivity.
Summary of the invention
The objective of the invention is in order to solve the contradictory problems between the mechanical property and ionic conductivity in the solid polymer electrolyte system, and hyperbranched type polyethers solid polymer electrolyte of a kind of ionic conductivity height, good mechanical property, Heat stability is good, stable electrochemical property and preparation method thereof is provided.
Hyperbranched polyether type solid polymer elecrolytes of the present invention comprises a kind of hyperbranched polyether A, conduct with lower glass transition temperatures and high conductivity and supports mutually matrix material B and electric conducting lithium salt C.Wherein, A and B constitute the matrix system of polymer dielectric, and its quality proportioning is 1: 3～3: 1; Lithium salts C accounts for 5%～50% of hyperbranched polyether type solid polymer elecrolytes total mass.
In above-mentioned solid polymer electrolyte, described polymer electrolyte matrices material B is polyvinylidene difluoride (PVDF) (PVDF), polyvinylidene difluoride (PVDF)-R 1216 (brief note is PVDF-HFP), polyethylene terephthalate (PET) and derivative thereof, polyacrylonitrile (brief note is PAN), polymethylmethacrylate (brief note is PMMA), polyvinyl chloride (brief note is PVC), polyvinyl alcohol (PVA), polyvinyl butyral acetal (PVB), polyoxybutylene, polymeric amide, polyacrylamide, polyvinyl acetate, polyvinylpyrrolidone, poly-diacrylate Tetraglycol 99 ester, polysulfones, any or several in the polysiloxane series.Described lithium salts C comprises any or several in two (sulphonyl) imines lithiums of lithium perchlorate, lithium hexafluoro phosphate, LiBF4, trifluoromethyl sulfonic acid lithium, two (trifluoromethyl sulphonyl) imines lithium, two second dioxalic acid lithium tetraborate, fluoro Lithium bis (oxalate) borate, two (polyfluoro alkoxyl group sulphonyl) imines lithium, ring-type perfluoroalkyl, three (trifluoromethyl sulphonyl) lithium methide.
A kind of method for preparing hyperbranched polyether type solid polymer elecrolytes of the present invention, concrete steps are as follows:
(1) with 3-(2-hydroxyl triethoxy)-3 '-methyl trimethylene oxide as repeating unit, with BF
3Ether is as initiator, and polymerization makes the hyperbranched polyether A that a class does not contain phenyl ring;
(2) hyperbranched polyether A, matrix material B and lithium salts are carried out drying;
(3) getting hyperbranched polyether A and matrix material B is 1: 3～3: 1 according to mass ratio, with the tetrahydrofuran (THF) dissolving, is stirred to evenly, makes the polymer electrolyte matrices system;
(4) in the described matrix system of step (3), add the lithium salts C that accounts for hyperbranched polyether type solid polymer elecrolytes total mass 5%～50%, be stirred well to evenly;
(5) above-mentioned solution is watered on the flat board, evaporating solvent, dry under 50～100 ℃ of conditions then, promptly make the solid polymer electrolyte that is used for lithium ion battery.
The present invention also is applied to prepared hyperbranched polyether type solid polymer elecrolytes in the lithium ion battery, the test proof, prepared solid polymer electrolyte has higher ionic conductivity, good mechanical property, Heat stability is good, stable electrochemical property.
Beneficial effect
The present invention is by carrying out blend to hyperbranched type polyethers with complete amorphous structure and the matrix material with good mechanical properties, and carries out compositely with lithium salts, makes solid polymer electrolyte.Because hyperbranched polyether A has complete unbodied structure, and has highly branched structure, can effectively prevent the segmental crystallization; And its molecular conformation almost spherical has effectively increased the free volume of polymkeric substance, helps sub-chain motion, effectively reduces second-order transition temperature, makes prepared solid polymer electrolyte have higher ionic conductivity, and room temperature can reach 1 * 10
-4More than the S/cm.Simultaneously,, make prepared solid polymer electrolyte also have the good mechanical performance, have excellent self-supporting effect because selected matrix material such as PVDF-HFP, PET have excellent mechanical property.Proof after tested, prepared solid polymer electrolyte has higher ionic conductivity, and its good mechanical property, Heat stability is good, stable electrochemical property.
Description of drawings
Fig. 1 prepares the XRD figure of sample for press embodiment 1: (a)-PVDF-HFP wherein; (b)-polyethers A/PVDF-HFP matrix system (mass ratio is 2: 1);
Fig. 2 is for pressing the specific conductivity curve of polyethers A/PVDF-HFP/LiTFSI polymer dielectric under differing temps of embodiment 1 preparation;
Fig. 3 presses the PVDF-HFP of embodiment 1 preparation and the TGA curve of polyethers A/PVDF-HFP/LiTFSI polymer dielectric;
Fig. 4 presses the polyethers A of embodiment 1 preparation and the DSC curve of polyethers A/PVDF-HFP/LiTFSI polymer dielectric;
Fig. 5 is temperature and the conductivity relation figure that presses the polyethers A/PET/LiTFSI polymer dielectric (Different L iTFSI content) of embodiment 2 preparations;
Fig. 6 is the multiplying power discharging curve that adopts the lithium ion battery of solid polymer electrolyte assembling among the embodiment 2;
Wherein, PVDF-HFP is the abbreviation of poly-(biasfluoroethylene-hexafluoropropylene); LiTFSI is the abbreviation of two (trifluoromethyl sulphonyl) imines lithium; PET is the abbreviation of polyethylene terephthalate; σ represents specific conductivity; T
gThe expression second-order transition temperature.
Embodiment
The present invention will be further described below in conjunction with drawings and Examples:
With BF
3Ether is as initiator, and polymerization makes the hyperbranched polyether A that a class does not contain phenyl ring, and its weight-average molecular weight is 10000; Used polymer electrolyte matrices material B is PVDF-HFP for poly-(biasfluoroethylene-hexafluoropropylene) brief note; Lithium salts C selects two (trifluoromethyl sulphonyl) imines lithium, notes by abridging to be LiTFSI.All raw materials are process vacuum-drying before using.With hyperbranched polyether (brief note for polyethers A) with to gather (biasfluoroethylene-hexafluoropropylene) be respectively to get a certain amount of at 2: 1 according to mass ratio (PVDF-HFP), dissolve with tetrahydrofuran (THF), be stirred to evenly, add mass percent then and be 20% LiTFSI (mass percent is calculated according to the total mass of solid polymer electrolyte), continue to be stirred to lithium salts and in solution, be evenly distributed.With this solution casting in polytetrafluoroethyldisk disk, evaporating solvent, 50 ℃ of dry 18h in vacuum drying oven then, prepared electrolytical thickness is about 1.5mm.Prepared sample is carried out: XRD (Fig. 1) test analysis, the XRD test is carried out on Rigaku Dmax-2400 type X-ray diffractometer to obtain the structural information of polymer dielectric film, the research parameter is: the Cu/K alpha-ray, λ=0.15406nm, voltage 40kV, electric current 100mA, 8 °/min of sweep velocity, 10 °-90 ° of sweep limits.Thermal performance test (Fig. 2, Fig. 3), the thermostability of solid polymer electrolyte is by DSC test and TGA test analysis, the NetzschPC-200 differential scanning calorimeter is adopted in the DSC test, use nitrogen protection, sudden colder to eliminate thermal history after heating up earlier, the proper testing temperature rise rate is 10 ℃/min; TGA2000 type thermogravimetric analyzer is adopted in the TGA test, and heat-up rate is 20 ℃/min, nitrogen protection.The test of ionic conductivity σ (Fig. 4) is measured as follows, adopt the obstructive type battery to form stainless steel/solid polymer electrolyte/stainless steel system, by electrochemical workstation (CHI660A, Shanghai occasion China instrument company) finishes, adopt ac impedance technology, in the ionic conductivity of 303～353K temperature range build-in test system, range of frequency 10～10
5Hz.
Embodiment 2
To prepare polymer dielectric as embodiment 1 identical mode, difference is, matrix material B selects the PET material of better mechanical property for use, is respectively to get a certain amount of at 1: 3 with hyperbranched type polyethers (polyethers A) and polyethylene terephthalate (PET) according to mass ratio, dissolve with tetrahydrofuran (THF), be stirred to evenly, add the LiTFSI (mass percent is calculated according to the total mass of polymer dielectric film) of different mass per-cent then respectively, continue to be stirred to lithium salts and in solution, be evenly distributed.With this solution casting in the poly tetrafluoroethylene tool, evaporating solvent, 50 ℃ of dry 18h in vacuum drying oven then.
The solid polymer electrolyte (SPE) of preparation gained is clipped between two stainless steels (SS) electrode, forms the SS/SPE/SS battery, test its ionic conductivity prepared sample is carried out ionic conductivity (Fig. 5).Use prepared solid polymer electrolyte as dielectric film, the lithium sheet metal is as negative pole, iron lithium phosphate (LiFePO
4) as anodal, (as glove box) assembling becomes lithium-ion secondary cell under the exsiccant environment, and it is carried out the charge and discharge cycles test, charging stopping potential 4.5V, discharge cut-off voltage 2.5V is under the room temperature, with 0.3,1 and the 2C current discharge, its multiplying power discharging curve is seen accompanying drawing 6 respectively.
Claims (5)
1. hyperbranched polyether type solid polymer elecrolytes is characterized in that it comprises:
(1) a kind of hyperbranched polyether A with lower glass transition temperatures and high conductivity;
(2) as the matrix material B that supports phase; With
(3) electric conducting lithium salt C;
Wherein, A and B constitute the matrix system of polymer dielectric, and its quality proportioning is 1: 3～3: 1; Lithium salts C accounts for 5%～50% of hyperbranched polyether type solid polymer elecrolytes total mass.
2. a kind of hyperbranched polyether type solid polymer elecrolytes according to claim 1 is characterized in that: solid polymer electrolyte substrate material B is selected from any or several in polyvinylidene difluoride (PVDF), polyvinylidene difluoride (PVDF)-R 1216, polyethylene terephthalate and derivative thereof, polyacrylonitrile, polymethylmethacrylate, polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral acetal, polyoxybutylene, polymeric amide, polyacrylamide, polyvinyl acetate, polyvinylpyrrolidone, poly-diacrylate Tetraglycol 99 ester, polysulfones, the polysiloxane.
3. a kind of hyperbranched polyether type solid polymer elecrolytes according to claim 1 is characterized in that: wherein lithium salts C comprises any or several in two (sulphonyl) imines lithiums of lithium perchlorate, lithium hexafluoro phosphate, LiBF4, trifluoromethyl sulfonic acid lithium, two (trifluoromethyl sulphonyl) imines lithium, two second dioxalic acid lithium tetraborate, fluoro Lithium bis (oxalate) borate, two (polyfluoro alkoxyl group sulphonyl) imines lithium, ring-type perfluoroalkyl, three (trifluoromethyl sulphonyl) lithium methide.
4. the preparation method of a hyperbranched polyether type solid polymer elecrolytes is characterized in that comprising following steps:
(1) with 3-(2-hydroxyl triethoxy)-3 '-methyl trimethylene oxide as repeating unit, with BF
3Ether is as initiator, and polymerization makes the hyperbranched polyether A that a class does not contain phenyl ring;
(2) hyperbranched polyether A, matrix material B and lithium salts are carried out drying;
(3) getting hyperbranched polyether A and matrix material B is 1: 3～3: 1 according to mass ratio, with the tetrahydrofuran (THF) dissolving, is stirred to evenly, makes the polymer electrolyte matrices system;
(4) in the described matrix system of step (3), add the lithium salts C that accounts for hyperbranched polyether type solid polymer elecrolytes total mass 5%～50%, be stirred well to evenly;
(5) above-mentioned solution is watered on the flat board, evaporating solvent, dry under 50～100 ℃ of conditions then, promptly make hyperbranched polyether type solid polymer elecrolytes.
5. the application of a kind of hyperbranched polyether type solid polymer elecrolytes according to claim 1 is characterized in that: be applied in the lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101824130A CN101407625B (en) | 2008-12-05 | 2008-12-05 | Hyperbranched polyether type solid polymer elecrolytes and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101824130A CN101407625B (en) | 2008-12-05 | 2008-12-05 | Hyperbranched polyether type solid polymer elecrolytes and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101407625A true CN101407625A (en) | 2009-04-15 |
| CN101407625B CN101407625B (en) | 2011-04-27 |
Family
ID=40570845
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101824130A Expired - Fee Related CN101407625B (en) | 2008-12-05 | 2008-12-05 | Hyperbranched polyether type solid polymer elecrolytes and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101407625B (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891848A (en) * | 2010-07-06 | 2010-11-24 | 上海纳米技术及应用国家工程研究中心有限公司 | Polyvinyl alcohol base single ionomer electrolyte and preparation method thereof |
| CN102659720A (en) * | 2012-04-18 | 2012-09-12 | 郑州大学 | 3, 3-di[(methyl) methylpropenoateyl ] oxetane compound and preparation method thereof |
| CN103367799A (en) * | 2013-07-18 | 2013-10-23 | 北京科技大学 | All-solid-state polyelectrolyte film, its preparation and application method |
| CN103985900A (en) * | 2014-04-24 | 2014-08-13 | 中山大学 | Modified polymer electrolyte, preparing method of modified polymer electrolyte and application of modified polymer electrolyte to lithium battery |
| CN104466240A (en) * | 2013-09-22 | 2015-03-25 | 中国科学院大学 | Ionic liquid polymer electrolyte and preparation method thereof |
| CN104937748A (en) * | 2013-02-27 | 2015-09-23 | 大曹株式会社 | Positive electrode and nonaqueous electrolyte secondary battery |
| CN105552437A (en) * | 2015-12-16 | 2016-05-04 | 中山大学 | Polyether/polyacrylate polymer electrolyte and preparation method and application thereof |
| CN105762403A (en) * | 2016-04-12 | 2016-07-13 | 中国科学院大学 | All-solid-state lithium-ion battery based on topological-structured polymer electrolyte |
| CN106129470A (en) * | 2016-09-09 | 2016-11-16 | 哈尔滨理工大学 | A kind of lithium ion battery solid polymer electrolyte membrane |
| CN106410269A (en) * | 2016-04-12 | 2017-02-15 | 中国科学院大学 | All-solid-state composite polymer electrolyte and preparation method thereof |
| CN108148156A (en) * | 2017-12-27 | 2018-06-12 | 吉晟光电（深圳）有限公司 | A kind of polymer-modified and its application based on polyvinyl butyral |
| CN108463912A (en) * | 2016-10-11 | 2018-08-28 | 菲尔齐费尔公司 | Polymer dielectric and electrochromic device including polymer dielectric |
| CN109716556A (en) * | 2016-07-13 | 2019-05-03 | 格勒诺布尔理工学院 | Ionic conductivity material and preparation method for electrochemical generator |
| CN110429333A (en) * | 2019-07-29 | 2019-11-08 | 北京理工大学 | All-solid sodium ion battery and its composite polymer electrolyte |
| CN110459823A (en) * | 2019-08-16 | 2019-11-15 | 北京理工大学 | A kind of method that polymer-modified diaphragm is used for the protection of metal battery cathode |
| CN111009684A (en) * | 2019-12-02 | 2020-04-14 | 常州乾艺智能制造科技有限公司 | Preparation method of polyether type lithium sulfone amide for solid lithium battery electrolyte |
| CN111342123A (en) * | 2020-03-09 | 2020-06-26 | 中国科学院青岛生物能源与过程研究所 | Selective wetting polymer electrolyte and preparation and application thereof |
| CN112358624A (en) * | 2020-11-09 | 2021-02-12 | 中国科学院化学研究所 | Polymer electrolyte capable of working in wide temperature range and preparation method thereof |
-
2008
- 2008-12-05 CN CN2008101824130A patent/CN101407625B/en not_active Expired - Fee Related
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891848B (en) * | 2010-07-06 | 2012-10-31 | 上海纳米技术及应用国家工程研究中心有限公司 | Polyvinyl alcohol base single ionomer electrolyte and preparation method thereof |
| CN101891848A (en) * | 2010-07-06 | 2010-11-24 | 上海纳米技术及应用国家工程研究中心有限公司 | Polyvinyl alcohol base single ionomer electrolyte and preparation method thereof |
| CN102659720A (en) * | 2012-04-18 | 2012-09-12 | 郑州大学 | 3, 3-di[(methyl) methylpropenoateyl ] oxetane compound and preparation method thereof |
| CN102659720B (en) * | 2012-04-18 | 2014-04-30 | 郑州大学 | 3, 3-di[(methyl) methylpropenoateyl ] oxetane compound and preparation method thereof |
| CN104937748A (en) * | 2013-02-27 | 2015-09-23 | 大曹株式会社 | Positive electrode and nonaqueous electrolyte secondary battery |
| CN104937748B (en) * | 2013-02-27 | 2019-03-08 | 株式会社大阪曹达 | Anode and non-aqueous electrolyte secondary battery |
| CN103367799A (en) * | 2013-07-18 | 2013-10-23 | 北京科技大学 | All-solid-state polyelectrolyte film, its preparation and application method |
| CN104466240A (en) * | 2013-09-22 | 2015-03-25 | 中国科学院大学 | Ionic liquid polymer electrolyte and preparation method thereof |
| CN103985900A (en) * | 2014-04-24 | 2014-08-13 | 中山大学 | Modified polymer electrolyte, preparing method of modified polymer electrolyte and application of modified polymer electrolyte to lithium battery |
| CN105552437A (en) * | 2015-12-16 | 2016-05-04 | 中山大学 | Polyether/polyacrylate polymer electrolyte and preparation method and application thereof |
| CN105552437B (en) * | 2015-12-16 | 2018-10-02 | 中山大学 | A kind of polyethers/polyacrylate polymers electrolyte and its preparation method and application |
| CN105762403A (en) * | 2016-04-12 | 2016-07-13 | 中国科学院大学 | All-solid-state lithium-ion battery based on topological-structured polymer electrolyte |
| CN106410269A (en) * | 2016-04-12 | 2017-02-15 | 中国科学院大学 | All-solid-state composite polymer electrolyte and preparation method thereof |
| JP2019530128A (en) * | 2016-07-13 | 2019-10-17 | アンスティテュ・ポリテクニック・ドゥ・グルノーブル | Ion conductive material for electrochemical power generation apparatus and manufacturing method |
| CN109716556A (en) * | 2016-07-13 | 2019-05-03 | 格勒诺布尔理工学院 | Ionic conductivity material and preparation method for electrochemical generator |
| JP7189122B2 (en) | 2016-07-13 | 2022-12-13 | アンスティテュ・ポリテクニック・ドゥ・グルノーブル | Ion-conducting material and manufacturing method for electrochemical generator |
| CN106129470B (en) * | 2016-09-09 | 2019-05-24 | 哈尔滨理工大学 | A kind of lithium ion battery solid polymer electrolyte membrane |
| CN106129470A (en) * | 2016-09-09 | 2016-11-16 | 哈尔滨理工大学 | A kind of lithium ion battery solid polymer electrolyte membrane |
| CN108463912A (en) * | 2016-10-11 | 2018-08-28 | 菲尔齐费尔公司 | Polymer dielectric and electrochromic device including polymer dielectric |
| CN108148156A (en) * | 2017-12-27 | 2018-06-12 | 吉晟光电（深圳）有限公司 | A kind of polymer-modified and its application based on polyvinyl butyral |
| CN110429333B (en) * | 2019-07-29 | 2021-02-02 | 北京理工大学 | All-solid-state sodium ion battery and composite polymer electrolyte thereof |
| CN110429333A (en) * | 2019-07-29 | 2019-11-08 | 北京理工大学 | All-solid sodium ion battery and its composite polymer electrolyte |
| CN110459823A (en) * | 2019-08-16 | 2019-11-15 | 北京理工大学 | A kind of method that polymer-modified diaphragm is used for the protection of metal battery cathode |
| CN111009684A (en) * | 2019-12-02 | 2020-04-14 | 常州乾艺智能制造科技有限公司 | Preparation method of polyether type lithium sulfone amide for solid lithium battery electrolyte |
| CN111342123A (en) * | 2020-03-09 | 2020-06-26 | 中国科学院青岛生物能源与过程研究所 | Selective wetting polymer electrolyte and preparation and application thereof |
| CN111342123B (en) * | 2020-03-09 | 2023-06-13 | 中国科学院青岛生物能源与过程研究所 | Selectively-infiltrated polymer electrolyte, and preparation and application thereof |
| CN112358624A (en) * | 2020-11-09 | 2021-02-12 | 中国科学院化学研究所 | Polymer electrolyte capable of working in wide temperature range and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101407625B (en) | 2011-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101407625B (en) | Hyperbranched polyether type solid polymer elecrolytes and preparation thereof | |
| CN108232293B (en) | Preparation method of organic-inorganic composite solid electrolyte | |
| Shi et al. | Co-polymerization and blending based PEO/PMMA/P (VDF-HFP) gel polymer electrolyte for rechargeable lithium metal batteries | |
| Yang et al. | A sodium ion conducting gel polymer electrolyte | |
| CN109608592B (en) | Cross-linking polymerization preparation method of polyion liquid solid electrolyte | |
| Li et al. | A dense cellulose-based membrane as a renewable host for gel polymer electrolyte of lithium ion batteries | |
| CN105591154B (en) | The all solid state serondary lithium battery and its preparation of polycarbonate-based full solid state polymer electrolyte and its composition and application | |
| US6033804A (en) | Highly conductive ion exchange polymer and process | |
| CN107959049B (en) | Preparation method of gel electrolyte, gel electrolyte and lithium ion battery | |
| CN102709597B (en) | Composite all solid-state polymer electrolyte lithium ion battery and preparation method of composite all solid-state polymer electrolyte lithium ion battery | |
| Deng et al. | Gel polymer electrolyte with high performances based on biodegradable polymer polyvinyl alcohol composite lignocellulose | |
| CN100467504C (en) | Preparing method and application of polymer gel electrolyte for lithium ion cell | |
| CN111786018B (en) | High-voltage polymer electrolyte, high-voltage polymer lithium metal battery and preparation method of battery | |
| Zuo et al. | Enhanced performance of a novel gel polymer electrolyte by dual plasticizers | |
| CN101409364B (en) | Self-supporting lithium ion battery gel polymer electrolyte and preparation method thereof | |
| Wen et al. | A new solid-state electrolyte based on polymeric ionic liquid for high-performance supercapacitor | |
| CN101381429B (en) | Self-supporting lithium ionic cell gel polymer electrolyte, special polymer and preparation method and application thereof | |
| CN110994014A (en) | All-solid-state polymer electrolyte, preparation method and lithium ion battery | |
| CN111234240A (en) | Polycaprolactone-based hyperbranched polymer all-solid-state electrolyte and lithium ion battery | |
| CN114335711A (en) | Preparation method and application of PVDF-HFP-PEO double-layer solid polymer electrolyte doped with MOF in situ | |
| Zheng et al. | Cross-linking copolymers of acrylates’ gel electrolytes with high conductivity for lithium-ion batteries | |
| CN112952192B (en) | Preparation method and application of organic polymer electrolyte film doped with polyaminoazulene | |
| CN111342123B (en) | Selectively-infiltrated polymer electrolyte, and preparation and application thereof | |
| Chen et al. | Novel poly (epichlorohydrin)-based matrix for monolithic ionogel electrolyte membrane with high lithium storage performances | |
| CN116544498A (en) | Composite polymer electrolyte based on supermolecule interaction, preparation method and metal lithium secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110427 Termination date: 20111205 |