CN104681864A - Gel type polymer electrolyte with high energy density and high ionic conductivity - Google Patents
Gel type polymer electrolyte with high energy density and high ionic conductivity Download PDFInfo
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Abstract
The invention relates to a polymer nano fiber electrolyte framework material prepared by combining micropore foaming with a coaxial electrostatic spinning technique, and a method for preparing the gel type polymer electrolyte by utilizing the framework material, and belongs to the field of polymer lithium ion batteries. The preparation method comprises the following steps: (1) preparing a core/shell polymer nano fiber membrane by utilizing the coaxial electrostatic spinning technique; (2) carrying out micropore foaming on a nano fiber shell; and (3) drying and cutting the foamed nano fiber membrane, and stacking and pressing to prepare the polymer gel electrolyte framework, and activating and gelating in an electrolytic solution under argon shield. The electrolyte framework material has relatively high adsorption and retentivity to the electrolytic solution; the prepared gel polymer electrolyte is high in energy density and ion conductivity, has a stable electrochemical window and good charge and discharge performances, can meet the assembling need of a common button battery, and is applied to the preparation of secondary lithium ion batteries.
Description
Technical field
The present invention relates to the polymer nanofibre film electrolyte framework material that a kind of microporous foam is prepared in conjunction with coaxial electrostatic spinning technology, and utilize this framework material to prepare the method for gel-type polymer electrolyte, belong to polymer Li-ion battery field.
Background technology
Polymer dielectric not only has good conductivity, and have the feature of the distinctive lightweight of macromolecular material, corrosion-resistant, easy-formation concurrently, meet new forms of energy development trend that is safe, efficient, environmental protection, be widely used in recent years in the chemical power sources such as lithium ion battery, fuel cell and ultracapacitor.Because the conductivity at room temperature of pure solid polymer electrolyte is lower, be of limited application, current commercial polymer Li-ion battery mainly adopts gel form polymer dielectric, it forms gel state after adsorbing electrolyte by polymeric matrix, polymer plays mechanical support effect, and lithium ion is mainly through the electrolyte conduction of absorption.At electrolyte structure design aspect, if polymeric matrix has a large amount of microcellular structures, fully can adsorb electrolyte, just can have good ionic conductivity and low interface impedance, coordinate suitable materials and process, the polymer dielectric of function admirable can be obtained.The technology of preparing of gel-type polyelectrolyte skeleton mainly contains film/casting method and method of electrostatic spinning.Film/casting method is widely used relatively, its advantage to ensure higher mechanical property, but chemical property is relatively poor, 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 " character of real meaning, chemical property has very large advantage.
The chemical property of different polymer differs greatly.Such as, polyacrylonitrile is a kind of polymeric material of heat-resisting, chemically stable, good flame resistance, has certain ion transfer, but the poor compatibility of itself and lithium electrode.And in the gel polymer electrolyte prepared at polymethyl methacrylate, lithium ion transference number, conductivity and electrochemical stability window numerical value are higher, but its bad mechanical property is difficult to direct application.In gel-type polymer electrolyte, even if having employed there is ion transfer function polymer as skeleton, because the migration of lithium ion is mainly carried out in the amorphous area of polymer, transport number is less, compared with liquid electrolyte, its conductivity in room temperature is still lower, improve its scope of application, must continue the energy density and the ionic conductivity that improve polymer dielectric in existing research level.The many employings of existing achievement in research are blended, copolymerization, the method such as crosslinked obtain the polymer dielectric framework material that some conductivity are high, degree of crystallinity is low, sub-chain motion ability is strong, but for the improvement limited efficiency of polymer dielectric energy density and ionic conductivity.
This patent is from the structural design of gel-form solid polymer electrolyte framework material, 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, can provide ion transfer passage again.Simultaneously, for realizing the higher liquid absorption of polymer dielectric, improve the energy density of lithium ion battery, pore foaming agent is added in sheath polymers spinning solution, by the distillation of blowing agent under heating condition or decompose and produce microcellular structure at nanofiber shell, can not residual impurity, this both can increase polymer fiber membrane bone frame material further to the absorption of electrolyte, be beneficial to again electrolyte permeability and enter core fiber layer, extend the transmission channel of lithium ion, also achieve the higher liquid absorption of polymer dielectric and confining force simultaneously, obtained gel polymer electrolyte has higher energy density, ionic conductivity, electrochemical window and good electrochemical stability, 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 the polymer nanofibre film electrolyte framework material that a kind of microporous foam is prepared in conjunction with coaxial electrostatic spinning technology, and utilizing this framework material to prepare the method for the gel-type polymer electrolyte of high-energy-density and ionic conductivity, concrete technology contents is as follows.
A preparation method for the gel-type polymer electrolyte of high-energy-density and ionic conductivity, is characterized in that, comprises following component and step:
Component 1: nanofiber core layer polymer, comprises polyethylene glycol oxide or Polyetherimide, and in nanofiber, content is 35% ~ 50wt%.Core layer polymer will provide ion transfer path and mechanics humidification, meets electrostatic spinning process requirement, and immiscible with sheath polymers, and its softening point should higher than the distillation of component 3 or decomposition temperature.
Component 2: nanofiber sheath polymers, comprises polymethyl methacrylate or polyvinylidene fluoride, and in nanofiber, content is 50% ~ 65wt%.Sheath polymers is good with lithium electrode compatibility, meets electrostatic spinning process requirement, and immiscible with core layer polymer, and its softening point should higher than the distillation of component 3 or decomposition temperature.
Component 3: pore foaming agent, comprises salicylic acid or azodiisobutyronitrile, and consumption is 0.5% of component 2.Pore foaming agent, under heating state, produces microcellular structure by distilling or decomposing at nanofiber shell, and its distillation or decomposition temperature lower than the softening point of component 1 and component 2, should guarantee that fabric integer pattern is not destroyed.
Step I: component 1 is mixed with sandwich layer spinning solution, component 2 and component 3 mix and are mixed with shell layer spinning solution, adopt coaxial electrostatic spinning technology preparation to have the polymer nanofibre film of core/shell structure, at 50 ° of C vacuum oven 12h.Core layer polymer concentration of dope controls at 10 ~ 15wt%, and sheath polymers concentration of dope controls at 15 ~ 20wt%, and sandwich layer spinning solution and shell layer spinning solution velocity ratio are 0.4 ~ 0.8.
Step II: nano fibrous membrane step I obtained slowly is heated to 80 DEG C, obtain the polymer nanofibre film that shell has microcellular structure, firing rate is 1 ~ 2 ° of C/min.
Step III: nano fibrous membrane step II obtained is cut to the disk stacked compacting that diameter is 20 ~ 25mm, and total weight controls between 65 ~ 80mg, is placed in 50 ° of C vacuum oven 24h, obtains gel-form solid polymer electrolyte framework material.Under argon shield, electrolyte framework material is placed in electrolyte to carry out activating and gelation; the weight ratio of framework material and electrolyte is 1:10 ~ 1:15; the overall time of activation and gelation is 50h, blots remained on surface electrolyte, obtain transparent gel-form solid polymer electrolyte with filter paper.
This patent devises the electrolyte framework material of porous surface nanofiber composition, the shell of coaxial configuration fiber presents microcellular structure, both the absorption of thin polymer film to liquid electrolyte can be increased further, be beneficial to again electrolyte permeability and enter sandwich layer, extend the transmission channel of lithium ion, the higher adsorbance to electrolyte can be realized, improve energy density and the ionic conductivity of lithium ion battery, obtain the novel polymer electrolyte of excellent electrochemical performance, be applicable to the assembling of button cell, and the preparation of secondary lithium battery.
Invention effect by above-mentioned technology contents can obtain below: saturated pick up>=920% of polymer dielectric framework material room temperature, places conservation rate>=89% of Electolyte-absorptive after 15 days; Polymer dielectric room temperature lithium ion conductivity>=4.5 × 10
-3scm
-1, electrochemical window>=4.6V, the capacity stablizes in 50 circulations, after circulation, capacity is more than 90% of initial capacity.
embodiment:
By following examples and comparative example, 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 apparatus is stainless steel/gel electrolyte/stainless steel system; Electrochemical stability window is obtained by linear voltammetric scan method, and testing apparatus 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 polyethylene glycol oxide, and molecular weight is 10
5g/mol(Mw), Lian Sheng chemical company in Shanghai produces.Component 2 is polymethyl methacrylate, and molecular weight is 1.2 × 10
5g/mol(Mw), U.S. Aldrich chemical company produces.Component 3 is salicylic acid, purity >=99%, and favorable to the people chemical plant, Zibo produces.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 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 12h, removes residual solvent.Dried nano fibrous membrane is slowly heated to 80 DEG C, and obtain the polymer nanofibre film that shell has microcellular structure, firing rate is 1 DEG C/min.Be cut to the disk of diameter 20mm, stacked compacting, total weight is 65mg, vacuumize 24h under 50 ° of C, obtains electrolyte framework material.Be that 1:10 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 this polymer dielectric framework material is 1150%, and placing the conservation rate of Electolyte-absorptive after 15 days is 92%; Polymer dielectric room temperature lithium ion conductivity is 4.9 × 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, the capacity stablizes of front 50 circulations, and after 50 circulations, capacity is 93% of initial capacity.
Embodiment 2:
Component 1 is Polyetherimide, and the trade mark is Ultem 1000, and density is 1.27g/cm3, and AM General chemical company produces.Component 2 is polymethyl methacrylate, and molecular weight is 1.2 × 105 g/mol(Mw), Aldrich chemical company of the U.S. produces.Component 3 is azodiisobutyronitrile, purity >=99%, and Guangzhou produces with Chemical Co., Ltd. of side.Sandwich layer spinning solution solvent for use is N, dinethylformamide, shell layer spinning solution solvent for use is 1-METHYLPYRROLIDONE, and its center core layer concentration of dope is 12wt%, shell layer spinning solution concentration is 15wt%, and coaxial electrostatic spinning process center core layer spinning solution and shell layer spinning solution velocity ratio are 0.6.The polymer fiber film obtained by electrostatic spinning is placed in 50 ° of C vacuum oven 12h, removes residual solvent.Dried nano fibrous membrane is slowly heated to 80 DEG C, and obtain the polymer nanofibre film that shell has microcellular structure, firing rate is 1.5 DEG C/min.Be cut to the disk of diameter 22mm, stacked compacting, total weight is 72mg, vacuumize 24h under 50 ° of C, obtains electrolyte framework material.Be that 1:12 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 this polymer dielectric framework material is 1080%, and placing the conservation rate of Electolyte-absorptive after 15 days is 90%; Polymer dielectric room temperature lithium ion conductivity is 4.8 × 10
-3scm
-1, electrochemical window is 4.8V.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, the capacity stablizes of front 50 circulations, and after 50 circulations, capacity is 91% of initial capacity.
Embodiment 3:
Component 1 is Polyetherimide, and the trade mark is Ultem 1000, and density is 1.27g/cm
3, AM General chemical company produces.Component 2 is polyvinylidene fluoride, molecular weight 5.3 × 10
5g/mol(Mw), Shanghai Sanaifu New Material Co., Ltd produces.Component 3 is azodiisobutyronitrile, purity >=99%, and Guangzhou produces with Chemical Co., Ltd. of side.Sandwich layer spinning solution solvent for use is N, dinethylformamide, shell layer spinning solution solvent for use is 1-METHYLPYRROLIDONE, and its center core layer concentration of dope is 15wt%, 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 0.4.The polymer fiber film obtained by electrostatic spinning is placed in 50 ° of C vacuum oven 12h, removes residual solvent.Dried nano fibrous membrane is slowly heated to 80 DEG C, and obtain the polymer nanofibre film that shell has microcellular structure, firing rate is 2 DEG C/min.Be cut to the disk of diameter 25mm, stacked compacting, total weight is 80mg, 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 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 this polymer dielectric framework material is 1020%, and placing the conservation rate of Electolyte-absorptive after 15 days is 89%; Polymer dielectric room temperature lithium ion conductivity is 4.6 × 10
-3scm
-1, electrochemical window is 4.8V.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, the capacity stablizes of front 50 circulations, and after 50 circulations, capacity is 90% of initial capacity.
Comparative example:
Component 1 is polyethylene glycol oxide, and molecular weight is 10
5g/mol(Mw), Lian Sheng chemical company in Shanghai produces.Component 2 is polymethyl methacrylate, and molecular weight is 1.2 × 10
5g/mol(Mw), U.S. Aldrich chemical company produces.Sandwich layer and shell layer spinning solution solvent for use are N, dinethylformamide, its center core layer concentration of dope is 10wt%, and shell layer spinning solution concentration is 18wt%, coaxial electrostatic spinning process center core layer spinning solution and shell layer spinning solution velocity ratio are 0.8, do not add pore foaming agent in shell layer spinning solution.The polymer fiber film obtained by electrostatic spinning is placed in 50 ° of C vacuum oven 12h, removes residual solvent.Dried nano fibrous membrane is cut to the disk of diameter 20mm, stacked compacting, total weight is 65mg, vacuumize 24h under 50 ° of C, obtains electrolyte framework material.Be that 1:10 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 this polymer dielectric framework material is 890%, and placing the conservation rate of Electolyte-absorptive after 15 days is 86%; Polymer dielectric room temperature lithium ion conductivity is 4.5 × 10
-3scm
-1, electrochemical window is 4.6V.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, the capacity stablizes of front 50 circulations, and after 50 circulations, capacity is 87% of initial capacity.Contrast with embodiments of the invention 1, the film framework material that can demonstrate porous surface nanofiber formation is preparing the advantage had in gel polymer electrolyte.
Claims (7)
1. a preparation method for the gel-type polymer electrolyte of high-energy-density and ionic conductivity, is characterized in that, comprises following component and step:
Component 1: the nanofiber core layer polymer with ionic conductivity, meets electrostatic spinning process requirement, and immiscible with sheath polymers, its softening point should higher than the distillation of component 3 or decomposition temperature;
Component 2: with lithium electrode and the good nanofiber sheath polymers of compatibility of electrolyte, meet electrostatic spinning process requirement, and immiscible with core layer polymer, and its softening point should higher than the distillation of component 3 or decomposition temperature;
Component 3: pore foaming agent, its distillation or decomposition temperature should lower than the softening points of component 1 and component 2;
Step I: component 1 is mixed with sandwich layer spinning solution, component 2 and component 3 mix and are mixed with shell layer spinning solution, adopt coaxial electrostatic spinning technology preparation to have the polymer nanofibre film of core/shell structure, at 50 ° of C vacuum oven 12h;
Step II: nano fibrous membrane step I obtained slowly is heated to 80 ° of C, there is distillation or decompose in component 3, obtains the polymer nanofibre film that shell has microcellular structure;
Step III: nano fibrous membrane step II obtained is cut to the disk of certain size and stacked compacting; be placed in 50 ° of C vacuum oven 24h; obtain gel-form solid polymer electrolyte framework material; under argon shield, electrolyte framework material is placed in electrolyte to carry out activating and gelation; blot remained on surface electrolyte with filter paper, obtain transparent or semitransparent gel-form solid polymer electrolyte.
2. the preparation method of the gel-type polymer electrolyte of a kind of high-energy-density according to claim 1 and ionic conductivity, wherein, nanofiber core layer polymer described in component 1 is polyethylene glycol oxide or Polyetherimide, and in nanofiber, content is 35% ~ 50wt%.
3. the preparation method of the gel-type polymer electrolyte of a kind of high-energy-density according to claim 1 and ionic conductivity, wherein, nanofiber sheath polymers described in component 2 is polymethyl methacrylate or polyvinylidene fluoride, and in nanofiber, content is 50% ~ 65wt%.
4. the preparation method of the gel-type polymer electrolyte of a kind of high-energy-density according to claim 1 and ionic conductivity, wherein, the pore foaming agent described in component 3 comprises salicylic acid or azodiisobutyronitrile, and component 3 consumption is 0.5% of component 2.
5. the preparation method of the gel-type polymer electrolyte of a kind of high-energy-density according to claim 1 and ionic conductivity, wherein, step I center core layer polymer dope concentration controls at 10 ~ 15wt%, sheath polymers concentration of dope controls at 15 ~ 20wt%, and sandwich layer spinning solution and shell layer spinning solution velocity ratio are 0.4 ~ 0.8.
6. the preparation method of the gel-type polymer electrolyte of a kind of high-energy-density according to claim 1 and ionic conductivity, wherein, in step II, nano fibrous membrane is slowly heated to 80 ° of C at ambient pressure, and firing rate is 1 ~ 2 ° of C/min.
7. the preparation method of the gel-type polymer electrolyte of a kind of high-energy-density according to claim 1 and ionic conductivity, wherein, in step III, tunica fibrosa disk diameter is 20 ~ 25mm, and the framework material total weight after stacked controls between 65 ~ 80mg; In the activation of electrolyte framework material and gelation process, the weight ratio of framework material and electrolyte is 1:10 ~ 1:15, and the overall time of activation and gelation is 50h.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105742700A (en) * | 2016-03-17 | 2016-07-06 | 北京化工大学 | Polyetherimide gel polymer electrolyte and preparation method thereof |
| CN106207108A (en) * | 2016-07-09 | 2016-12-07 | 太原理工大学 | Si-C composite material based on macromolecule foaming microsphere and preparation method and application |
| WO2018226162A1 (en) * | 2017-06-07 | 2018-12-13 | Nanyang Technological University | Core-shell nanofibers for capacitive sensing and triboelectric applications |
| CN111628211A (en) * | 2018-02-11 | 2020-09-04 | 中国科学院苏州纳米技术与纳米仿生研究所 | Lithium ion battery and preparation method thereof |
| CN110875493A (en) * | 2018-09-03 | 2020-03-10 | 丰田自动车株式会社 | Composite solid electrolyte layer, method for producing same, and method for producing all-solid-state battery |
| CN110875493B (en) * | 2018-09-03 | 2023-06-20 | 丰田自动车株式会社 | Composite solid electrolyte layer, method for producing same, and method for producing all-solid battery |
| 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 |
| CN111816910A (en) * | 2020-08-31 | 2020-10-23 | 珠海冠宇电池股份有限公司 | Composite solid electrolyte membrane, preparation method thereof and lithium ion battery |
| CN111816910B (en) * | 2020-08-31 | 2022-04-22 | 珠海冠宇电池股份有限公司 | Composite solid electrolyte membrane, preparation method thereof and lithium ion battery |
| CN112652813A (en) * | 2020-12-21 | 2021-04-13 | 中南大学 | Biological gel electrolyte composed of PAN and modified PLLA and preparation method thereof |
| CN112652813B (en) * | 2020-12-21 | 2022-04-08 | 中南大学 | Biological gel electrolyte composed of PAN and modified PLLA and preparation method thereof |
| CN114204217A (en) * | 2021-12-10 | 2022-03-18 | 东华大学 | Gel electrolyte diaphragm and preparation method and application thereof |
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