CN103545548A - Method for preparing three-dimensional porous polymer electrolyte film - Google Patents
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- CN103545548A CN103545548A CN201310545313.0A CN201310545313A CN103545548A CN 103545548 A CN103545548 A CN 103545548A CN 201310545313 A CN201310545313 A CN 201310545313A CN 103545548 A CN103545548 A CN 103545548A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
The invention provides a method for preparing a three-dimensional porous polymer electrolyte film. The method comprises the following steps of synthesizing sodium carbonate and calcium chloride in water to form nanometer CaCO3 by using an oleic acid and ethanol as dispersing agents; modifying the nanometer CaCO3 by using a titanate coupling agent to synthesize modified nanometer CaCO3; ultrasonically dispersing the modified nanometer CaCO3 into a first organic solvent, adding and dissolving polymer powder to obtain a polymer solution in which the modified nanometer CaCO3 is suspended, casting the polymer solution on the surface of a smooth substrate after room-temperature vacuum defoaming, and drying the substrate at constant temperature to form a polymer film; impregnating the polymer film in an aqueous solution of HCl until no foams are formed, washing the polymer film for many times by using distilled water until the pH is 7, and performing vacuum drying to obtain a three-dimensional porous polymer film; and impregnating the three-dimensional porous polymer film in a liquid electrolyte solution in a water-free and oxygen-free glove box to obtain the three-dimensional porous polymer electrolyte film. The method has the advantages of simplicity, easiness, environmental friendliness and the like, and porosity, aperture distribution and the like in the polymer electrolyte film are easy to control.
Description
Technical field
The preparation method who the present invention relates to a kind of porous polymer electrolyte film, belongs to electrochemical field.
Background technology
Polymer Li-ion battery has been widely used as the chemical power source of the portable electric appts such as mobile phone, notebook computer and digital camera.Owing to having than the better security performance of liquid lithium ionic cell, polymer Li-ion battery can be applicable to the main equipments such as electric automobile future.The ionic conductivity of polymer dielectric is generally lower than liquid electrolyte, and the quality of its chemical property becomes the key factor that affects polymer Li-ion battery charge-discharge performance and cycle performance.
Because containing a large amount of microcellular structures, in porous polymer electrolyte, absorbed a large amount of electrolyte solutions, generally all have 10
-3the conductivity at room temperature of S/cm, approaches the ionic conductivity of liquid electrolyte, in polymer Li-ion battery, is used widely.The preparation method of porous polymer electrolyte film mainly contains solution casting method, phase separation method, method of electrostatic spinning, foaming and template etc., a large amount of micropores of the inner formation of polymer film matrix of preparation, and between micropore, have connection to a certain degree.Wherein, a large amount of micropores can adsorb more electrolyte solution, and more transportable lithium ion number is provided; Higher degree of communication provides lithium ion more passages that can move continuously, thereby improves the ionic conductivity of polymer dielectric.Therefore, porosity and micropore degree of communication become the important technological parameters of porous polymer electrolyte.
The method of template synthesis porous polymer electrolyte film has a lot, as two kinds of incompatible polymers are prepared as to polymer blend film, then with organic solvent, remove wherein a kind of polymer, prepare three-dimensional porous polymer film, adsorbing electrolyte solution forms three-dimensional porous polymer dielectric film.This method needs to use a large amount of organic solvents, contaminated environment and complex process in last handling process.In addition, also can use SiO
2for template, prepare three-dimensional porous polymer film, then use the HF solution removal SiO of severe corrosive
2template, prepares three-dimensional porous polymer dielectric, yet HF solution is very big to harm, and industrial accident easily occurs in generative process.Therefore, how to use environment protection method to prepare simply three-dimensional porous polymer dielectric, become the key technology of preparing the superior polymer Li-ion battery of chemical property.
Summary of the invention
The preparation method who the object of the invention is to a kind of three-dimensional porous polymer dielectric film.Solve operation inconvenience, complex procedures and template in existing template and remove the problems such as condition harshness, environmental pollution.
The technical solution adopted in the present invention is to comprise following steps:
(1) the synthesis of nano CaCO in the water of making dispersant with oleic acid and ethanol with sodium carbonate and calcium chloride
3;
(2) with titanate coupling agent modified, synthesis modification nanometer CaCO
3, there is better compatibility with polymeric matrix;
(3) by modified Nano CaCO
3ultrasonic being dispersed in the first organic solvent, then adds polymer powder to dissolve, and obtains suspension modified nanometer CaCO
3polymer solution, after room temperature vacuum defoamation, by this polymer solution curtain coating, at smooth matrix surface, 70～90 ℃ of freeze-day with constant temperature are removed the first organic solvent, become self-supporting polymer film;
(4) described polymer film is soaked in the HCl aqueous solution of 1.2 mol/L, to without after Bubble formation, more repeatedly washs to pH=7 with distilled water, vacuum 70-90 ℃ obtains three-dimensional porous polymer film after dry;
(5) in the glove box of anhydrous and oxygen-free, the three-dimensional porous polymer film of step (3) gained is soaked 0.5～1.5 hour in liquid electrolyte solution, obtain three-dimensional porous polymer dielectric film;
Described the first organic solvent is one or more in 1-METHYLPYRROLIDONE NMP, dimethyl formamide DMF, acetone, tetrahydrofuran THF;
Described polymer powder is one or more in polyethylene glycol oxide PEO, polyvinylchloride, polyacrylonitrile (PAN), polymetylmethacrylate, Kynoar PVDF, Kynoar-hexafluoropropylene PVDF-HFP;
Described liquid electrolyte solution is ion liquid type electrolyte, and it is comprised of ionic liquid, lithium salts and the second organic solvent.Described ionic liquid is 1-ethyl-3-methylimidazole tetrafluoroborate EMIBF
4, 1-butyl-3-methylimidazole lithium hexafluoro phosphate BMIPF
6, N-methyl-N-propyl pyrrole alkane-bis-fluoroform sulfimide salt PYR
13one or more in TFSI; The second described organic solvent is ethylene carbonate EC, propene carbonate PC, diethyl carbonate DEC, dimethyl carbonate DMC, one or several in methyl ethyl carbonate EMC; Described lithium salts is LiBF4 LiBF
4, lithium hexafluoro phosphate LiPF
6, lithium perchlorate LiClO
4, N, one or more in N '-bis trifluoromethyl sulfimide base lithium LiTFSI, dioxalic acid lithium borate LiBOB, the mass fraction of lithium salts in electrolyte is 5%～10%.
In order to realize better the present invention:
Described polymer powder and described modified Nano CaCO
3mass fraction in described polymer solution is 5%～15%, wherein polymer powder and modified Nano CaCO
3mass ratio be 1:(1～3).
In step (2), the mass fraction of titanate coupling agent is nanometer CaCO
31%-5%.
Described in step (2), polymer powder is PVDF-HFP.
The first organic solvent described in step (3) is 1-METHYLPYRROLIDONE (NMP), polymer powder and modified Nano CaCO
3mass fraction in polymer suspension is 7%～10%.
The micro-pore diameter of three-dimensional porous polymer film described in step (5) is 0.014 μ m～2.125 μ m, has the three-dimensional microcellular structure of intercommunication continuously, and porosity is 57%～88%, and pick up is 140%～230%.
In step (5), liquid electrolyte solution is 1 mol/L LiBF
4/ EMIBF
4-EC-DMC (1:1:1, mass ratio) or 1 mol/L LiTFSI/PYR
13tFSI-EC-DMC (1:1:1, mass ratio).
Titanate coupling agent described in step (2) is pyrophosphoric acid type monoalkoxy class titanate coupling agent TC-114.
The present invention has following advantage and effect with respect to prior art:
The present invention adopts a kind of modified Nano CaCO
3hard template method is prepared three-dimensional porous polymer dielectric film, easy to operate, mild condition, and aperture is controlled and be evenly distributed.This polymer film has higher porosity and pick up than the lithium ion battery separator of common industrialization, and ionic conductivity is greatly improved, and is a kind of simple and feasible method;
The present invention adopts a kind of ion liquid type electrolyte, and this electrolyte is comprised of ionic liquid, organic solvent and lithium salts.Because ionic liquid has advantages of Heat stability is good, steam, force down, not volatile, nonflammable and electrochemical window is wide, is applied in polymer Li-ion battery, can improve the high temperature safe performance of battery.In ionic liquid, add appropriate carbonates organic solvent and be conducive to reduce the viscosity of ionic liquid, thereby improve the ionic conductivity of liquid electrolyte;
The even aperture distribution of three-dimensional porous polymer dielectric film prepared by the present invention, has higher porosity and pick up, has 10
-3the conductivity at room temperature of S/cm.Polymer Li-ion battery with its assembling has superior charge-discharge magnification performance and stable circulation performance.The porous polymer electrolyte film of preparing with other method is compared, and this preparation method is simple, environmental friendliness, easily controls porosity and the pore-size distribution of polymer dielectric film inside.
Accompanying drawing explanation
Fig. 1 is the surperficial SEM photo of the three-dimensional porous polymer dielectric film prepared of the present invention.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
(1) configure 0.2 mol/L CaCl
2solution and 0.2 mol/L Na
2cO
3each 50ml of solution.In being with churned mechanically three mouthfuls of round-bottomed flasks, add 0.8422g oleic acid, 180ml ethanol and Na
2cO
3solution, under rapid stirring, slowly drips CaCl
2solution, drips off rear continuation reaction 2-3 hour, the precipitation (CaCO obtaining
3nano particle) placement, natural drying stand-by after suction filtration, washing, alcohol wash.
(2), in filling the 100ml round-bottomed flask of 50ml ethanol and 10ml distilled water, add the CaCO of 6 grams of steps (1) gained
3nano particle, rapid stirring, is warmed up to 50 ℃, more slowly adds and be equivalent to CaCO
3the titanate coupling agent TC-114 of quality 3%, continue to stir 4 hours, and cooling, centrifugation, distilled water washing, ethanol washing, natural drying, obtain modified Nano CaCO
3.
(3) take 1 gram of modified Nano CaCO
3, ultrasonic being dispersed in 10 milliliters of NMP, then add 0.5 gram of PVDF-HFP powder, stir and make polymer dissolution, obtain polymer mucus.This polymer mucus is cast in clean glass sheet, and 80 ℃ are dried 12 hours.Then, dried polymer film is soaked in 1.2 mol/L HCl solution, without being taken out after Bubble, is washed to pH=7,80 ℃ of vacuumize 24 hours, obtains three-dimensional porous polymer film.As shown in Figure 1, micropore size 1-2 μ m, has the hole of many 100nm to be communicated with to its surface topography between micropore, and porosity is 74%.
(4), in being full of the glove box of argon gas, the three-dimensional porous polymer film obtaining be impregnated in to 1 mol/L LiBF
4/ EMIBF
4in-EC-DMC (1:1:1, mass ratio) electrolyte solution one hour, obtain three-dimensional porous polymer dielectric film.The pick up of three-dimensional porous polymer dielectric film is 169%, and conductivity at room temperature is 1.38 * 10
-3s/cm.
(5) by the three-dimensional porous polymer dielectric film of step (4) gained, be barrier film, with LiMn
2o
4anodal and lithium sheet is assembled 2032 type button cells, carries out charge-discharge test.At 0.1C, 0.2C, under 0.5C and 1C multiplying power, first discharge specific capacity is respectively 119,114, and 104 and 100mAh/g, after 100 circulations, capability retention is respectively 92%, 90%, and 84% and 81%.
Adopt the three-dimensional porous polymer film of gained, impregnated in liquid electrolyte 1 mol/L LiTFSI/PYR
13in TFSI-EC-DMC (1:1:1, mass ratio) one hour, then take it as barrier film and LiFePO
4electrode and lithium sheet are assembled 2032 type button cells, carry out charge-discharge test.At 0.1C, 0.2C, under 0.5C and 1C multiplying power, first discharge specific capacity is respectively 159,148, and 134 and 122mAh/g, after 100 circulations, capability retention is respectively 95%, 92%, and 87% and 85%.
Above-described embodiment is the execution mode of the best of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other are any does not deviate from change, the modification done under principle of the present invention, substitute, combination, simplify; all can think equivalent substitute mode, within being included in protection scope of the present invention.
Claims (6)
1. a preparation method for three-dimensional porous polymer dielectric film, is characterized in that, comprises the steps:
(1) the synthesis of nano CaCO in the water of making dispersant with oleic acid and ethanol with sodium carbonate and calcium chloride
3;
(2) with titanate coupling agent modified, synthesis modification nanometer CaCO
3, there is better compatibility with polymeric matrix;
(3) by modified Nano CaCO
3ultrasonic being dispersed in the first organic solvent, then adds polymer powder to dissolve, and obtains suspension modified nanometer CaCO
3polymer solution, after room temperature vacuum defoamation, by this polymer solution curtain coating, at smooth matrix surface, 70～90 ℃ of freeze-day with constant temperature become polymer film;
(4) described polymer film is soaked in the HCl aqueous solution of 1.2 mol/L, to without after Bubble formation, more repeatedly washs to pH=7 with distilled water, after 70～90 ℃, vacuum is dry, obtain three-dimensional porous polymer film;
(5) in the glove box of anhydrous and oxygen-free, the three-dimensional porous polymer film of step (3) gained is soaked 0.5～1.5 hour in liquid electrolyte solution, obtain three-dimensional porous polymer dielectric film.
Described the first organic solvent is one or more in 1-METHYLPYRROLIDONE NMP, dimethyl formamide DMF, acetone, tetrahydrofuran THF;
Described polymer powder is one or more in polyethylene glycol oxide PEO, polyvinylchloride, polyacrylonitrile (PAN), polymetylmethacrylate, Kynoar PVDF, Kynoar-hexafluoropropylene PVDF-HFP;
Described liquid electrolyte solution is ion liquid type electrolyte, and it is comprised of ionic liquid, lithium salts and the second organic solvent; Described ionic liquid is 1-ethyl-3-methylimidazole tetrafluoroborate EMIBF
4, 1-butyl-3-methylimidazole lithium hexafluoro phosphate BMIPF
6, N-methyl-N-propyl pyrrole alkane-bis-fluoroform sulfimide salt PYR
13one or more in TFSI; The second described organic solvent is ethylene carbonate EC, propene carbonate PC, diethyl carbonate DEC, dimethyl carbonate DMC, one or several in methyl ethyl carbonate EMC; Described lithium salts is LiBF4 LiBF
4, lithium hexafluoro phosphate LiPF
6, lithium perchlorate LiClO
4, N, one or more in N '-bis trifluoromethyl sulfimide base lithium LiTFSI, dioxalic acid lithium borate LiBOB; The mass fraction of described lithium salts in described electrolyte is 5%～10%.
2. the preparation method of a kind of three-dimensional porous polymer dielectric film according to claim 1, is characterized in that: described polymer powder and described modified Nano CaCO
3mass fraction in described polymer solution is 5%～15%, wherein polymer powder and modified Nano CaCO
3mass ratio be 1:(1～3).
3. the preparation method of a kind of three-dimensional porous polymer dielectric film according to claim 1, is characterized in that, the mass fraction of described titanate coupling agent is described nanometer CaCO
31%～5%.
4. the preparation method of a kind of three-dimensional porous polymer dielectric film according to claim 1, is characterized in that, described polymer powder and modified Nano CaCO
3mass fraction in polymerization supernatant liquid is 7%～10%.
5. the preparation method of a kind of three-dimensional porous polymer dielectric film according to claim 1, it is characterized in that, the micro-pore diameter of described three-dimensional porous polymer film is 0.014 μ m～2.125 μ m, there is the three-dimensional microcellular structure of intercommunication continuously, porosity is 57%～88%, and pick up is 140%～230%.
6. the preparation method of a kind of three-dimensional porous polymer dielectric film according to claim 1, is characterized in that, described titanate coupling agent is pyrophosphoric acid type monoalkoxy class titanate coupling agent TC-114.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106220888A (en) * | 2016-08-22 | 2016-12-14 | 王利萍 | A kind of microporous polymer electrolyte preparation method of compound ion liquid |
| CN107556671A (en) * | 2017-09-22 | 2018-01-09 | 北京爱吾尔德技术开发有限公司 | A kind of modified PVDF materials, preparation method and applications |
| CN109585917A (en) * | 2018-12-11 | 2019-04-05 | 广东永邦新能源股份有限公司 | A kind of polymer dielectric and preparation method thereof and the battery including the polymer dielectric |
| CN110212242A (en) * | 2019-06-17 | 2019-09-06 | 凤凰新能源(惠州)有限公司 | A kind of porous gel polymer dielectric and preparation method thereof |
| CN111261932A (en) * | 2018-12-03 | 2020-06-09 | 中国科学院苏州纳米技术与纳米仿生研究所 | Ionic plastic crystal-polymer-inorganic composite electrolyte membrane, and preparation method and application thereof |
| CN111341975A (en) * | 2020-03-16 | 2020-06-26 | 四川优源新能源有限公司 | Diaphragm for high-efficiency lithium ion secondary battery and preparation method thereof |
| CN111394891A (en) * | 2020-03-25 | 2020-07-10 | 武汉理工大学 | Preparation method of chitosan oligosaccharide and polyester composite material |
| CN112742204A (en) * | 2020-12-30 | 2021-05-04 | 铜陵铜冠神虹化工有限责任公司 | Flue gas sulfur-fixing agent used in sodium sulfide synthesis process and preparation process thereof |
| CN117976972A (en) * | 2024-03-28 | 2024-05-03 | 瑞浦兰钧能源股份有限公司 | Gel polymer electrolyte, preparation method thereof and double-ion battery |
| WO2024109000A1 (en) * | 2022-11-24 | 2024-05-30 | 安徽绿沃循环能源科技有限公司 | Lithium battery separator and preparation method therefor |
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Cited By (14)
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| CN106220888A (en) * | 2016-08-22 | 2016-12-14 | 王利萍 | A kind of microporous polymer electrolyte preparation method of compound ion liquid |
| CN107556671A (en) * | 2017-09-22 | 2018-01-09 | 北京爱吾尔德技术开发有限公司 | A kind of modified PVDF materials, preparation method and applications |
| CN111261932A (en) * | 2018-12-03 | 2020-06-09 | 中国科学院苏州纳米技术与纳米仿生研究所 | Ionic plastic crystal-polymer-inorganic composite electrolyte membrane, and preparation method and application thereof |
| CN111261932B (en) * | 2018-12-03 | 2021-08-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | Ionic plastic crystal-polymer-inorganic composite electrolyte membrane, and preparation method and application thereof |
| CN109585917A (en) * | 2018-12-11 | 2019-04-05 | 广东永邦新能源股份有限公司 | A kind of polymer dielectric and preparation method thereof and the battery including the polymer dielectric |
| CN110212242A (en) * | 2019-06-17 | 2019-09-06 | 凤凰新能源(惠州)有限公司 | A kind of porous gel polymer dielectric and preparation method thereof |
| CN110212242B (en) * | 2019-06-17 | 2020-05-08 | 凤凰新能源(惠州)有限公司 | Porous gel polymer electrolyte and preparation method thereof |
| CN111341975A (en) * | 2020-03-16 | 2020-06-26 | 四川优源新能源有限公司 | Diaphragm for high-efficiency lithium ion secondary battery and preparation method thereof |
| CN111341975B (en) * | 2020-03-16 | 2022-11-15 | 四川优源新能源有限公司 | Diaphragm for high-efficiency lithium ion secondary battery and preparation method thereof |
| CN111394891A (en) * | 2020-03-25 | 2020-07-10 | 武汉理工大学 | Preparation method of chitosan oligosaccharide and polyester composite material |
| CN112742204A (en) * | 2020-12-30 | 2021-05-04 | 铜陵铜冠神虹化工有限责任公司 | Flue gas sulfur-fixing agent used in sodium sulfide synthesis process and preparation process thereof |
| CN112742204B (en) * | 2020-12-30 | 2022-07-19 | 铜陵铜冠环保科技有限公司 | Flue gas sulfur-fixing agent used in sodium sulfide synthesis process and preparation process thereof |
| WO2024109000A1 (en) * | 2022-11-24 | 2024-05-30 | 安徽绿沃循环能源科技有限公司 | Lithium battery separator and preparation method therefor |
| CN117976972A (en) * | 2024-03-28 | 2024-05-03 | 瑞浦兰钧能源股份有限公司 | Gel polymer electrolyte, preparation method thereof and double-ion battery |
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