CN104577198A - Core/shell structure fiber film-based gel polymer electrolyte and preparation method thereof - Google Patents
Core/shell structure fiber film-based gel polymer electrolyte and preparation method thereof Download PDFInfo
- Publication number
- CN104577198A CN104577198A CN201310472346.7A CN201310472346A CN104577198A CN 104577198 A CN104577198 A CN 104577198A CN 201310472346 A CN201310472346 A CN 201310472346A CN 104577198 A CN104577198 A CN 104577198A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- core
- polymer electrolyte
- preparation
- gel
- 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
Landscapes
- Secondary Cells (AREA)
- Cell Separators (AREA)
Abstract
The invention relates to a polymer electrolyte, especially relates to a micropore polymer electrolyte skeletal material prepared by a coaxial electrospinning technology and a method for preparing a gel polymer electrolyte from the skeletal material, and belongs to the field of polymer lithium ion batteries. The preparation method comprises the following steps of 1, preparing core and shell layer electrostatic spinning solutions, 2, preparing a core/shell structure nanometer fiber film by a coaxial electrospinning technology, 3, drying and cutting the nanometer fiber film, and carrying out lamination to obtain a polymer gel electrolyte skeleton, and 4, putting the skeleton into an electrolyte in a glove box and carrying out activation and gelation. The electrolyte skeleton has ultra-strong electrolyte adsorptivity and retentivity. The prepared gel polymer electrolyte has high ion conductivity, a stable electrochemical window, good charging and discharging performances and good interface compatibility with a lithium electrode, satisfies common button cell assembling requirements and can be used for preparation of a secondary lithium ion battery.
Description
Technical field
The present invention relates generally to a kind of microporous polymer electrolyte framework material utilizing coaxial electrostatic spinning technology to prepare, and utilizes this framework material to prepare the method for gel-type polymer electrolyte, belongs to polymer Li-ion battery field.
Background technology
Polymer Li-ion battery adopt there is ionic conductivity and have concurrently barrier film effect polymer dielectric replace liquid electrolyte, its operation principle and liquid lithium ionic cell basically identical.In the charge and discharge process of battery, lithium ion is by embedding between both positive and negative polarity of the polymer dielectric with ionic conductivity and deintercalation, realizes chemically arriving electric conversion of energy.Compared with liquid lithium ionic cell, polymer Li-ion battery energy density is high, there is not the leakage problem existing for liquid electrolyte battery, improve the capacitance of battery, and can be made into large-area ultrathin film, ensure fully to contact with between electrode, be convenient to the developing direction to miniaturized, lightweight and filming of electronic product.
Microporous network is the key property of framework material in gel-type polymer electrolyte, some typical methods preparing polymer porous film comprise: extraction-activation method (Bellcore method), thermally induced phase separation, control Evaporation Precipitation, the vapor phase precipitation method, immersion precipitation, self-assembly method etc., generally all need a large amount of organic solvents, can cause environmental pollution, the residual solvent in film can affect its chemical property and mechanical property.In addition, these methods are often difficult to the size and the uniformity that control micropore in electrolyte, and the porosity of acquisition is also lower, and process repeatability is poor.Method of electrostatic spinning is that preparation has the effective ways of nanometer to the tunica fibrosa in micron order aperture.By controlling electrostatic spinning process parameter, the thin polymer film that porosity is 30%-90% can be prepared easily.In addition, between mutually through fiber, microcellular structure can provide large specific area and good ion transmission channel, promotes compatibility and the stability of polymeric matrix and electrolyte, improves high-rate battery discharge performance and cycle performance.
In gel polymer electrolyte, gel state is formed after polymer matrices adsorptive liquid electrolyte, polymer mainly plays mechanical support, and lithium ion, mainly through the liquid electrolyte conduction of absorption, makes its conductivity at room temperature can close to liquid electrolyte.Current commercial polymer Li-ion battery mainly adopts gel-type polymer electrolyte, as Sony's portable power source commercialization gel polyelectrolyte realizes large-scale production, its main advantage is that gel structure is stablized, be convenient to cutting and be suitable for extensive manufacture, but its conductivity at room temperature need further raising.The technology of preparing of current gel-type polyelectrolyte mainly contains film/casting method and emerging method of electrostatic spinning.Film/casting method is widely used relatively, and its advantage to ensure higher mechanical property, but electric property is relatively poor, and the product obtained not is " gel " truly.And utilize the development in recent years polymer dielectric that faster prepared by electrostatic spinning technique to have " gel " proterties of real meaning, electric property has very large advantage, but be thisly at present rich in the remarkable decline that the micromolecular structural system of liquid result in mechanical property, therefore hinder commercial applications.Adopt add reinforcing agent, the method such as crosslinked improves its mechanical property, but can lose chemical property, solve this contradiction also needs to develop new technological means.
This patent this application coaxial electrostatic spinning technology, by selecting the sandwich layer that is applicable to and sheath polymers, a kind of polymer dielectric framework material being rich in microcellular structure has been prepared in design, and utilizes this framework material to prepare gel-type polymer electrolyte.The compatibility of sheath polymers and electrolyte and lithium electrode is good, and core layer polymer had both had good mechanical property, also ion transmission channel can be provided, both are collaborative solves polymer dielectric and the problem such as lithium electrode interface passivation and poor mechanical property, also achieve the higher liquid absorption of polymer dielectric and confining force simultaneously, obtained gel polymer electrolyte has higher ionic conductivity, stable electrochemical window and good charge-discharge performance, the assembling needs of conventional button cell can be met, be suitable for the preparation of secondary lithium battery.
Summary of the invention
The object of the present invention is to provide a kind of gel polymer electrolyte based on core/shell structural nano tunica fibrosa and preparation method thereof, concrete technology contents is as follows.
The microporous polymer electrolyte framework material utilizing coaxial electrostatic spinning technology to prepare, and utilize this framework material to prepare the method for gel-type polymer electrolyte, it is characterized in that, comprise following component and step:
Component 1: nanofiber core layer polymer, comprises polyacrylonitrile or polyvinylidene fluoride, and in nanofiber, content is 33% ~ 45wt%.Core layer polymer will meet as mechanics enhancing and the needs providing ion transmission channel, meets spinnability, and immiscible with sheath polymers.
Component 2: nanofiber sheath polymers, comprises polymethyl methacrylate or polyethylene glycol oxide, and in nanofiber, content is 55% ~ 67wt%.Sheath polymers will have good compatibility to lithium electrode and electrolyte, meets spinnability, and immiscible with core layer polymer.
Component 3: preferred electrolyte, comprises LiPF
6/ DEC-EC (mol ratio is l:1) or LiPF
6/ DMC-EC (mol ratio is l:1).
Step I: core, sheath polymers are prepared spinning solution respectively, adopts coaxial electrostatic spinning technology preparation to have the polymer nanofibre film of core/shell structure, at 50 ° of C vacuum oven 8h;
Step II: nano fibrous membrane step I obtained is cut to disk, by stacked for disk compacting, is placed in 60 ° of C vacuum oven 20h, obtains gel-form solid polymer electrolyte framework material;
Step III: the framework material that step II obtains is placed in electrolyte in glove box and carries out activating and gelation, blot remained on surface electrolyte with filter paper, obtain transparent gel-form solid polymer electrolyte, encapsulate for subsequent use under ar gas environment.
The cutting of polymer dielectric framework material and activation, gelation flow process are shown in accompanying drawing 1.
Core/shell structure porous polymer electrolyte the framework material of this patent design, the compatibility of sheath polymers and electrolyte and lithium electrode is good, and core layer polymer had both had good mechanical property, also can provide ion transmission channel, both work in coordination with and solve polymer dielectric and the problem such as lithium electrode interface passivation and poor mechanical property.By the design of core/shell structure, the advantage of different polymeric material can be made full use of, avoid the deficiency of homogenous material, realize nano level structure " compound " and have complementary functions.Compared with common gel-type polymer electrolyte preparation method-film/casting method, preparation technology's flow process of the present invention is simple, to the absorption of liquid electrolyte and hold facility stronger, chemical property has clear superiority.This gel polymer electrolyte has higher ionic conductivity, stable electrochemical window and good charge-discharge performance, can meet the assembling needs of conventional button cell, be suitable for the preparation of secondary lithium battery.
Invention effect by above-mentioned technology contents can obtain below: saturated pick up>=870% of polymer dielectric framework material room temperature, places conservation rate>=86% of Electolyte-absorptive after 15 days; Polymer dielectric room temperature lithium ion conductivity>=4.4 × 10
-3scm
-1, electrochemical window>=4.5V, compared with pure component gel electrolyte, stable charge/discharge and capacitance conservation rate all has obvious advantage.
Accompanying drawing explanation
The cutting of Fig. 1 concentric polymer electrolyte framework material and activation, gelation flow process.
Fig. 2 is front 50 the circulation volume curves of core shell gel electrolyte and pure component electrolytic cell, and charging and discharging currents is 0.1C, and abscissa is Cycle numbers, and ordinate is Q/mAh.
detailed description of the invention:
By following examples, the present invention is described in detail.Pick up and liquid-keeping property are obtained by weight method; The curve that ionic conductivity is recorded by AC impedence method calculates, and testing arrangement is stainless steel/gel electrolyte/stainless steel system; Electrochemical stability window is obtained by linear voltammetric scan method, and testing arrangement is stainless steel/gel electrolyte/lithium metal system; The relation of battery capacity and cycle-index is obtained by constant current charge-discharge curve, charging and discharging currents 0.1C.
Embodiment 1:
Component 1 is polyacrylonitrile, and molecular weight is 10
5g/mol (Mw), manufacturer is UK Courtaulds Co.Component 2 is polymethyl methacrylate, and molecular weight is 1.0 ~ 1.3 × 10
5g/mol(Mw), manufacturer is Aldrich Chemical Co.Component 3 is the LiPF of 1mol/L
6/ DEC-EC (mol ratio is l:1) electrolyte, manufacturer is Beijing Chemical Plant.Sandwich layer and shell layer spinning solution solvent for use are DMF, and its center core layer concentration of dope is 14wt%, and shell layer spinning solution concentration is 20wt%, and coaxial electrostatic spinning process center core layer spinning solution and shell layer spinning solution velocity ratio are 0.5.The polymer fiber film obtained by electrostatic spinning is placed in 50 ° of C vacuum oven 8h, removes remaining moisture and solvent.Then be cut to the disk of diameter 22mm, stacked compacting, gross weight is 78mg, vacuumize 20h under 60 ° of C, obtains electrolyte framework material.Be that 1:15 takes electrolyte according to the weight ratio of framework material and electrolyte, in the glove box being full of argon gas, polymer matrices is soaked 40h in the electrolytic solution under room temperature, taking-up filter paper blots remained on surface electrolyte, complete activation and gelation, obtain transparent gel-form solid polymer electrolyte.
The saturated pick up of room temperature of polymer dielectric framework material is 870%, and placing the conservation rate of Electolyte-absorptive after 15 days is 86.4%; Polymer dielectric room temperature lithium ion conductivity is 4.4 × 10
-3scm
-1, electrochemical window is 4.5V.Take metal lithium sheet as negative pole, cobalt acid lithium is that positive pole is assembled into half-cell, test constant current charge-discharge performance, and charging and discharging currents is 0.1C, tests the capacity of front 50 circulations.Can be seen by accompanying drawing 2, polymer electrolyte prepared by the present embodiment, in stable charge/discharge and capacitance conservation rate, all obviously be better than pure PAN component gel electrolyte (comparative example).
Embodiment 2:
Component 1 is polyvinylidene fluoride, molecular weight 5.3 × 10
5g/mol(Mw), manufacturer is Aldrich Chemical Co.Component 2 is polyethylene glycol oxide, and molecular weight is 10
5g/mol (Mw), manufacturer is Shanghai Lian Sheng chemical company.Component 3 is LIPF6/DMC-EC (mol ratio the is l:1) electrolyte of 1mol/L.Sandwich layer and shell layer spinning solution solvent for use are DMF, and its center core layer concentration of dope is 10wt%, and shell layer spinning solution concentration is 16wt%, and coaxial electrostatic spinning process center core layer spinning solution and shell layer spinning solution velocity ratio are 0.7.The polymer fiber film obtained by electrostatic spinning is placed in 50 ° of C vacuum oven 8h, removes remaining moisture and solvent.Then be cut to the disk of diameter 24mm, stacked compacting, gross weight is 85mg, vacuumize 20h under 60 ° of C, obtains electrolyte framework material.Be that 1:20 takes electrolyte according to the weight ratio of framework material and electrolyte, in the glove box being full of argon gas, polymer matrices is soaked 50h in the electrolytic solution under room temperature, taking-up filter paper blots remained on surface electrolyte, complete activation and gelation, obtain transparent gel-form solid polymer electrolyte.
The saturated pick up of room temperature of polymer dielectric framework material is 1006%, and placing the conservation rate of Electolyte-absorptive after 15 days is 90.6%; Polymer dielectric room temperature lithium ion conductivity is 4.8 × 10
-3scm
-1, electrochemical window is 4.7V.Take metal lithium sheet as negative pole, cobalt acid lithium is that positive pole is assembled into half-cell, test constant current charge-discharge performance, and charging and discharging currents is 0.1C, tests the capacity of front 50 circulations.Can be seen by accompanying drawing 2, polymer electrolyte prepared by the present embodiment, in stable charge/discharge and capacitance conservation rate, all obviously be better than pure PAN component gel electrolyte (comparative example).
Embodiment 3:
Component 1 is polyacrylonitrile, and molecular weight is 10
5g/mol (Mw), manufacturer is UK Courtaulds Co.Component 2 is for being polyethylene glycol oxide, and molecular weight is 10
5g/mol (Mw), manufacturer is Shanghai Lian Sheng chemical company.Component 3 is LIPF6/DEC-EC (mol ratio the is l:1) electrolyte of 1mol/L.Sandwich layer and shell layer spinning solution solvent for use are DMF, and its center core layer concentration of dope is 12wt%, and shell layer spinning solution concentration is 18wt%, and coaxial electrostatic spinning process center core layer spinning solution and shell layer spinning solution velocity ratio are 0.8.The polymer fiber film obtained by electrostatic spinning is placed in 50 ° of C vacuum oven 8h, removes remaining moisture and solvent.Then be cut to the disk of diameter 20mm, stacked compacting, gross weight is 70mg, vacuumize 20h under 60 ° of C, obtains electrolyte framework material.Be that 1:18 takes electrolyte according to the weight ratio of framework material and electrolyte, in the glove box being full of argon gas, polymer matrices is soaked 45h in the electrolytic solution under room temperature, taking-up filter paper blots remained on surface electrolyte, complete activation and gelation, obtain transparent gel-form solid polymer electrolyte.
The saturated pick up of room temperature of polymer dielectric framework material is 1082%, and placing the conservation rate of Electolyte-absorptive after 15 days is 91.6%; Polymer dielectric room temperature lithium ion conductivity is 4.4 × 10
-3scm
-1, electrochemical window is 5.0V.Take metal lithium sheet as negative pole, cobalt acid lithium is that positive pole is assembled into half-cell, test constant current charge-discharge performance, and charging and discharging currents is 0.1C, tests the capacity of front 50 circulations.Can be seen by accompanying drawing 2, polymer electrolyte prepared by the present embodiment, in stable charge/discharge and capacitance conservation rate, all obviously be better than pure PAN component gel electrolyte (comparative example).
Comparative example:
In order to contrast with the embodiment of the gel polymer electrolyte based on core/shell structural nano tunica fibrosa, select virgin pp nitrile to prepare the nano fibrous membrane not having core/shell structure, molecular weight is 10
5g/mol (Mw), manufacturer is UK Courtaulds Co.Concentration of dope is 14wt%, and other electrospinning parameters are all consistent with embodiment 1.The polymer fiber film obtained by electrostatic spinning is placed in 50 ° of C vacuum oven 8h, removes remaining moisture and solvent.Then be cut to the disk of diameter 22mm, stacked compacting, gross weight is 78mg, vacuumize 20h under 60 ° of C, obtains electrolyte framework material.Select the LIPF6/DEC-EC of 1mol/L (mol ratio is l:1) electrolyte, be that 1:15 takes electrolyte according to the weight ratio of framework material and electrolyte, in the glove box being full of argon gas, polymer matrices is soaked 40h in the electrolytic solution under room temperature, taking-up filter paper blots remained on surface electrolyte, complete activation and gelation, obtain transparent gel-form solid polymer electrolyte.
The saturated pick up of room temperature of polyacrylonitrile fibre membrane electrolyte framework material is 675%, and placing the conservation rate of Electolyte-absorptive after 15 days is 84.3%; Polymer dielectric room temperature lithium ion conductivity is 1.7 × 10
-3scm
-1, electrochemical window is 5.2V.Compared with embodiments of the invention, the advantage that the gel polymer electrolyte based on core/shell structural nano tunica fibrosa has can be given prominence to.
Claims (8)
1. gel polymer electrolyte based on core/shell structural nano tunica fibrosa and preparation method thereof, is characterized in that, comprise following component and step:
Component 1: nanofiber core layer polymer;
Component 2: nanofiber sheath polymers;
Component 3: preferred electrolyte;
Step I: core, sheath polymers are prepared spinning solution respectively, adopts coaxial electrostatic spinning technology preparation to have the polymer nanofibre film of core/shell structure, at 50 ° of C vacuum oven 8h;
Step II: nano fibrous membrane step I obtained is cut to disk, by stacked for disk compacting, is placed in 60 ° of C vacuum oven 20h, obtains gel-form solid polymer electrolyte framework material;
Step III: the framework material that step II obtains is placed in electrolyte in glove box and carries out activating and gelation, blot remained on surface electrolyte with filter paper, obtain transparent gel-form solid polymer electrolyte, encapsulate for subsequent use under ar gas environment.
2. a kind of gel polymer electrolyte based on core/shell structural nano tunica fibrosa according to claim 1 and preparation method thereof, wherein, nanofiber core layer polymer described in component 1 is polyacrylonitrile or polyvinylidene fluoride, and in nanofiber, content is 33% ~ 45wt%.
3. a kind of gel polymer electrolyte based on core/shell structural nano tunica fibrosa according to claim 1 and preparation method thereof, wherein, nanofiber sheath polymers described in component 2 is polymethyl methacrylate or polyethylene glycol oxide, and in nanofiber, content is 55% ~ 67wt%.
4. a kind of gel polymer electrolyte based on core/shell structural nano tunica fibrosa according to claim 1 and preparation method thereof, wherein, the preferred electrolyte described in component 3 comprises LiPF
6/ DEC-EC (mol ratio is l:1) or LiPF
6/ DMC-EC (mol ratio is l:1).
5. a kind of gel polymer electrolyte based on core/shell structural nano tunica fibrosa according to claim 1 and preparation method thereof, wherein, step I center core layer polymer dope concentration controls at 10 ~ 14wt%, and sheath polymers concentration of dope controls at 16 ~ 20wt%.
6. a kind of gel polymer electrolyte based on core/shell structural nano tunica fibrosa according to claim 1 and preparation method thereof, wherein, step I center core layer spinning solution and shell layer spinning solution velocity ratio are 0.5 ~ 0.8.
7. a kind of gel polymer electrolyte based on core/shell structural nano tunica fibrosa according to claim 1 and preparation method thereof, wherein, the framework material gross weight of step II middle level poststack controls between 70 ~ 85mg, disk diameter 20 ~ 24mm.
8. a kind of gel polymer electrolyte based on core/shell structural nano tunica fibrosa according to claim 1 and preparation method thereof, wherein, step III polymer dielectric framework material activation and gelation process in, the weight ratio of framework material and electrolyte is 1:15 ~ 1:20, and the overall time of activation and gelation is 40 ~ 50h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310472346.7A CN104577198A (en) | 2013-10-11 | 2013-10-11 | Core/shell structure fiber film-based gel polymer electrolyte and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310472346.7A CN104577198A (en) | 2013-10-11 | 2013-10-11 | Core/shell structure fiber film-based gel polymer electrolyte and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104577198A true CN104577198A (en) | 2015-04-29 |
Family
ID=53092755
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310472346.7A Pending CN104577198A (en) | 2013-10-11 | 2013-10-11 | Core/shell structure fiber film-based gel polymer electrolyte and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104577198A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105734696A (en) * | 2016-04-21 | 2016-07-06 | 北京理工大学 | Preparation method for polystyrene-polyvinylidene fluoride coaxial electrospun fiber |
| CN110512306A (en) * | 2019-08-20 | 2019-11-29 | 成都新柯力化工科技有限公司 | A kind of preparation method for the dielectric film inhibiting solid state lithium battery lithium dendrite growth |
| CN110656442A (en) * | 2019-08-20 | 2020-01-07 | 苏州大学 | Lithium ion battery diaphragm and preparation method thereof |
| CN110707357A (en) * | 2019-10-23 | 2020-01-17 | 北京卫蓝新能源科技有限公司 | Gel polymer electrolyte with core-shell structure and preparation method and application thereof |
| CN113054248A (en) * | 2019-12-27 | 2021-06-29 | 张家港市国泰华荣化工新材料有限公司 | Composite solid electrolyte and preparation method and application thereof |
| CN116864801A (en) * | 2023-09-04 | 2023-10-10 | 浙江久功新能源科技有限公司 | Preparation method of ultrathin continuous network structure composite electrolyte membrane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1727530A (en) * | 2005-07-26 | 2006-02-01 | 天津大学 | Superfine fiber membrane material in core/shell structure, and preparation method |
| CN101409364A (en) * | 2008-11-19 | 2009-04-15 | 华南师范大学 | Self-supporting lithium ion battery gel polymer electrolyte and preparation method thereof |
-
2013
- 2013-10-11 CN CN201310472346.7A patent/CN104577198A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1727530A (en) * | 2005-07-26 | 2006-02-01 | 天津大学 | Superfine fiber membrane material in core/shell structure, and preparation method |
| CN101409364A (en) * | 2008-11-19 | 2009-04-15 | 华南师范大学 | Self-supporting lithium ion battery gel polymer electrolyte and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| XINHONG ZHOU等: "A Core-Shell Structured Polysulfonamide-Based Composite Nonwoven Towards High Power Lithium Ion Battery Separator", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 * |
| 黄再波等: "高压静电纺丝法制备P(VDF-HFP)聚合物电解质", 《化学学报》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105734696A (en) * | 2016-04-21 | 2016-07-06 | 北京理工大学 | Preparation method for polystyrene-polyvinylidene fluoride coaxial electrospun fiber |
| CN105734696B (en) * | 2016-04-21 | 2018-02-02 | 北京理工大学 | A kind of preparation method of polystyrene Kynoar coaxial electrostatic spinning silk fiber |
| CN110512306A (en) * | 2019-08-20 | 2019-11-29 | 成都新柯力化工科技有限公司 | A kind of preparation method for the dielectric film inhibiting solid state lithium battery lithium dendrite growth |
| CN110656442A (en) * | 2019-08-20 | 2020-01-07 | 苏州大学 | Lithium ion battery diaphragm and preparation method thereof |
| CN110707357A (en) * | 2019-10-23 | 2020-01-17 | 北京卫蓝新能源科技有限公司 | Gel polymer electrolyte with core-shell structure and preparation method and application thereof |
| CN110707357B (en) * | 2019-10-23 | 2021-05-07 | 北京卫蓝新能源科技有限公司 | Gel polymer electrolyte with core-shell structure and preparation method and application thereof |
| CN113054248A (en) * | 2019-12-27 | 2021-06-29 | 张家港市国泰华荣化工新材料有限公司 | Composite solid electrolyte and preparation method and application thereof |
| CN113054248B (en) * | 2019-12-27 | 2022-11-29 | 张家港市国泰华荣化工新材料有限公司 | Composite solid electrolyte and preparation method and application thereof |
| CN116864801A (en) * | 2023-09-04 | 2023-10-10 | 浙江久功新能源科技有限公司 | Preparation method of ultrathin continuous network structure composite electrolyte membrane |
| CN116864801B (en) * | 2023-09-04 | 2023-12-26 | 浙江久功新能源科技有限公司 | Preparation method of ultrathin continuous network structure composite electrolyte membrane |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Flexible, mechanically robust, solid-state electrolyte membrane with conducting oxide-enhanced 3D nanofiber networks for lithium batteries | |
| CN107611340B (en) | Flexible all-solid-state battery and preparation method thereof | |
| CN110581314B (en) | Multilayer-structure composite solid electrolyte membrane, preparation method thereof and solid battery | |
| CN110581311B (en) | Composite solid electrolyte membrane, preparation method thereof and solid battery | |
| Zhu et al. | Cheap glass fiber mats as a matrix of gel polymer electrolytes for lithium ion batteries | |
| CN107959049B (en) | Preparation method of gel electrolyte, gel electrolyte and lithium ion battery | |
| CN104124414B (en) | A kind of lithium ion battery compound electric pole piece and preparation method thereof and lithium ion battery | |
| CN111430788A (en) | Composite solid electrolyte membrane, preparation method and solid lithium battery | |
| CN104681864B (en) | A kind of gel-type polymer electrolyte of high-energy-density and ionic conductivity | |
| CN104577198A (en) | Core/shell structure fiber film-based gel polymer electrolyte and preparation method thereof | |
| CN104934579B (en) | A kind of porous graphite doping and the preparation method of carbon coating graphite cathode material | |
| US20130143115A1 (en) | Three-dimensional nanosized porous metal oxide electrode material of lithium ion battery and preparation method thereof | |
| CN102185158A (en) | Lithium sulfur battery provided with adsorption layer | |
| CN102199846A (en) | Porous polymer electrolyte supporting membrane material, preparation method thereof and application thereof | |
| CN103618056B (en) | A kind of preparation method of lithium ion battery separator three-dimensional porous structure nano fibrous membrane | |
| CN103367791B (en) | A kind of new type lithium ion battery | |
| CN104466168A (en) | Preparation method of cobaltosic oxide-carbon porous nanofiber and application of cobaltosic oxide-carbon porous nanofiber to preparation of lithium ion battery | |
| CN114094179B (en) | Nanofiber polyvinylidene fluoride composite solid electrolyte and preparation method and application thereof | |
| CN104638294B (en) | A kind of mixed nanometer lattice method for preparing gel polymer electrolyte | |
| CN105119012B (en) | A kind of lithium ion battery gel polymer electrolyte and preparation method thereof | |
| CN102104171A (en) | Lithium ion battery gel polymer electrolyte, preparation method and application thereof | |
| CN103560243A (en) | Preparation method for synthesizing LiNi1/3Co1/3Mn1/3O2 nanometer fiber by using electro-spinning technique | |
| CN114335701A (en) | Composite solid electrolyte membrane and preparation method thereof | |
| CN1331935C (en) | Composite microporous polymer electrolyte and its preparing method | |
| CN106450441B (en) | A kind of cellulose/polyurethane gle polymer dielectric and its preparation and the application in lithium ion 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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150429 |