CN103545548B - A kind of preparation method of three-dimensional porous polymer dielectric film - Google Patents
A kind of preparation method of three-dimensional porous polymer dielectric film Download PDFInfo
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- CN103545548B CN103545548B CN201310545313.0A CN201310545313A CN103545548B CN 103545548 B CN103545548 B CN 103545548B CN 201310545313 A CN201310545313 A CN 201310545313A CN 103545548 B CN103545548 B CN 103545548B
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- dimensional porous
- polymer
- porous polymer
- dielectric film
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
Abstract
The invention provides a kind of preparation method of three-dimensional porous polymer dielectric film.The synthesis of nano CaCO in the water making dispersant with oleic acid and ethanol with sodium carbonate and calcium chloride
3; With titanate coupling agent modified, synthesis modification Nano-meter CaCO3
3; By modified Nano CaCO
3ultrasonic disperse, in the first organic solvent, then adds polymer powder and dissolves, obtain suspension modified Nano-meter CaCO3
3polymer suspension, after room temperature in vacuo deaeration, by polymer suspension curtain coating smooth substrate surface, freeze-day with constant temperature becomes polymer film; Polymer film is soaked in the HCl aqueous solution, after producing to bubble-free, more repeatedly washs to pH=7 with distilled water, after vacuumize, obtain three-dimensional porous polymer film; In the glove box of anhydrous and oxygen-free, three-dimensional porous polymer film is soaked in liquid electrolyte solution, obtain three-dimensional porous polymer dielectric film.The present invention has simple, advantages of environment protection, and the porosity of easy control polymer dielectric film inside and pore-size distribution etc.
Description
Technical field
The present invention relates to a kind of preparation method of porous polymer electrolyte film, belong 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 security performance more better than 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 affecting polymer Li-ion battery charge-discharge performance and cycle performance.
Because of containing a large amount of microcellular structures, absorb a large amount of electrolyte solutions in porous polymer electrolyte, generally all have 10
-3the conductivity at room temperature of S/cm, close to the ionic conductivity of liquid electrolyte, is used widely in polymer Li-ion battery.The preparation method of porous polymer electrolyte film mainly contains solution casting method, phase separation method, method of electrostatic spinning, foaming and template etc., and the polymer film intrinsic silicon of preparation forms a large amount of micropore, and has connection to a certain degree between micropore.Wherein, a large amount of micropores can adsorb more electrolyte solution, provides more transportable lithium ion number; Higher degree of communication provides lithium ion more passages that can move continuously, thus improves the ionic conductivity of polymer dielectric.Therefore, porosity and microporous connectivity degree 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 polymer blend film, then remove wherein a kind of polymer with organic solvent, 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 solvent in last handling process, contaminated environment and complex process.In addition, also SiO can be used
2for the three-dimensional porous polymer film of Template preparation, then use the HF solution removal SiO of severe corrosive
2template, prepares three-dimensional porous polymer dielectric, but HF solution is very big to harm, easily industrial accident occurs in generative process.Therefore, how to use environment protection method to prepare three-dimensional porous polymer dielectric simply, become the key technology preparing the superior polymer Li-ion battery of chemical property.
Summary of the invention
The object of the invention is to a kind of preparation method 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, comprises following steps:
(1) the synthesis of nano CaCO in the water making dispersant with oleic acid and ethanol with sodium carbonate and calcium chloride
3;
(2) with titanate coupling agent modified, synthesis modification Nano-meter CaCO3
3, with polymeric matrix, there is better compatibility;
(3) by modified Nano CaCO
3ultrasonic disperse, in the first organic solvent, then adds polymer powder and dissolves, obtain suspension modified Nano-meter CaCO3
3polymer suspension, after room temperature in vacuo deaeration, by this polymer solution curtain coating on smooth substrate surface, 70 ~ 90 DEG C of freeze-day with constant temperature remove 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, after producing to bubble-free, more repeatedly washs to pH=7 with distilled water, in vacuum, after 70-90 DEG C of drying, obtain three-dimensional porous polymer film;
(5) in the glove box of anhydrous and oxygen-free, step (4) resulting polymers film is soaked 0.5 ~ 1.5 hour in liquid electrolyte solution, obtains three-dimensional porous polymer dielectric film;
Described 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 made up 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 pyrrolidines-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, one or more in N, N '-bis trifluoromethyl sulfimide base lithium LiTFSI, dioxalic acid lithium borate LiBOB, lithium salts mass fraction is in the electrolytic solution 5% ~ 10%.
In order to realize the present invention better:
Described polymer powder and described modified Nano CaCO
3the mass fraction of summation in described polymer solution be 5% ~ 15%, wherein polymer powder and modified Nano CaCO
3mass ratio be 1: (1 ~ 3).
In step (2), the quality of titanate coupling agent is Nano-meter CaCO3
31%-5%.
Described in step (2), polymer powder is PVDF-HFP.
First organic solvent described in step (3) is 1-METHYLPYRROLIDONE (NMP), polymer powder and modified Nano CaCO
3the mass fraction of summation in polymer suspension be 7% ~ 10%.
Described in step (5), the micro-pore diameter of three-dimensional porous polymer film is 0.014 μm ~ 2.125 μm, and have the microcellular structure of three-dimensional intercommunication continuously, 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 TC-114.
The present invention has following advantage and effect relative to prior art:
The present invention adopts a kind of modified Nano CaCO
3hard template method prepares 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 general industry change, 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 made up of ionic liquid, organic solvent and lithium salts.Due to the advantage that ionic liquid has Heat stability is good, steam forces down, not volatile, nonflammable and electrochemical window is wide, be applied in polymer Li-ion battery, the high temperature safe performance of battery can be improved.In ionic liquid, add the viscosity that appropriate carbonate based organic solvent is conducive to reducing ionic liquid, thus 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.With the polymer Li-ion battery of its assembling, there is superior charge-discharge magnification performance and stable circulation performance.Compared with the porous polymer electrolyte film prepared with other method, 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 three-dimensional porous polymer dielectric film prepared by 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 thereto.
(1) 0.2 mol/L CaCl is configured
2solution and 0.2 mol/L Na
2cO
3the each 50ml of solution.0.8422g oleic acid, 180ml ethanol and Na is added in the churned mechanically three mouthfuls of round-bottomed flasks of band
2cO
3solution, under rapid stirring, slowly drips CaCl
2solution, drips off rear continuation reaction 2-3 hour, the precipitation (CaCO obtained
3nano particle) place after suction filtration, washing, alcohol wash, natural drying is stand-by.
(2) in the 100ml round-bottomed flask filling 50ml ethanol and 10ml distilled water, the CaCO of 6 grams of step (1) gained is added
3nano particle, rapid stirring, is warmed up to 50 DEG C, more slowly adds and be equivalent to CaCO
3the titanate coupling agent TC-114 of quality 3%, continues stirring 4 hours, and cooling, centrifugation, distilled water washing, ethanol washing, natural drying, obtain modified Nano CaCO
3.
(3) 1 gram of modified Nano CaCO is taken
3, ultrasonic disperse in 10 milliliters of NMP, then adds 0.5 gram of PVDF-HFP powder, stirs and makes dissolution of polymer, obtain polymer mucus.This polymer mucus is cast in clean glass sheet, 80 DEG C of dryings 12 hours.Then, be soaked in by dried polymer film in 1.2 mol/L HCl solution, bubble-free is taken out after separating out, and is washed to pH=7, and 80 DEG C of vacuumize 24 hours, obtains three-dimensional porous polymer film.As shown in Figure 1, micropore size 1-2 μm, have the hole of many 100nm to be communicated with between micropore, porosity is 74% to its surface topography.
(4) in the glove box being full of argon gas, the three-dimensional porous polymer film obtained be impregnated in 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) be barrier film by the three-dimensional porous polymer dielectric film of step (4) gained, with LiMn
2o
4positive pole and lithium sheet assemble 2032 type button cells, carry out charge-discharge test.Under 0.1C, 0.2C, 0.5C and 1C multiplying power, first discharge specific capacity is respectively 119, and 114,104 and 100mAh/g, after 100 circulations, capability retention is respectively 92%, 90%, 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 be barrier film and LiFePO with it
4electrode and lithium sheet assemble 2032 type button cells, carry out charge-discharge test.Under 0.1C, 0.2C, 0.5C and 1C multiplying power, first discharge specific capacity is respectively 159, and 148,134 and 122mAh/g, after 100 circulations, capability retention is respectively 95%, 92%, 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 do not deviate from principle of the present invention under do change, modification, substitute, combination, to simplify; all can think the substitute mode of equivalence, be included within 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 making dispersant with oleic acid and ethanol with sodium carbonate and calcium chloride
3;
(2) with titanate coupling agent modified, synthesis modification Nano-meter CaCO3
3, with polymeric matrix, there is better compatibility;
(3) by modified Nano CaCO
3ultrasonic disperse, in the first organic solvent, then adds polymer powder and dissolves, obtain suspension modified Nano-meter CaCO3
3polymer suspension, after room temperature in vacuo deaeration, by this polymer suspension curtain coating smooth substrate surface, 70 ~ 90 DEG C 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, after producing to bubble-free, more repeatedly washs to pH=7 with distilled water, in vacuum, after 70 ~ 90 DEG C of dryings, obtain three-dimensional porous polymer film;
(5) in the glove box of anhydrous and oxygen-free, step (4) resulting polymers film is soaked 0.5 ~ 1.5 hour in liquid electrolyte solution, obtains three-dimensional porous polymer dielectric film;
Described 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 made up 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 pyrrolidines-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, one or more in N, 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
3the mass fraction of summation in described polymer suspension be 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 quality of described titanate coupling agent is described Nano-meter CaCO3
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
3the mass fraction of summation in polymer suspension be 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 μm ~ 2.125 μm, there is the microcellular structure of three-dimensional 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 TC-114.
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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 |
| 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 |
| CN109585917B (en) * | 2018-12-11 | 2022-02-08 | 广东永邦新能源股份有限公司 | Polymer electrolyte, preparation method thereof and battery comprising polymer electrolyte |
| 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 |
| 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 |
| CN111394891B (en) * | 2020-03-25 | 2021-04-16 | 武汉理工大学 | Preparation method of chitosan oligosaccharide and polyester composite material |
| 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 |
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