CN102629519B

CN102629519B - Method for producing diaphragm of super capacitor

Info

Publication number: CN102629519B
Application number: CN201210122263.0A
Authority: CN
Inventors: 王丽华; 刘帅; 刘艳花; 吴杰; 刘必前
Original assignee: Institute of Chemistry CAS
Current assignee: Institute of Chemistry CAS
Priority date: 2012-04-25
Filing date: 2012-04-25
Publication date: 2014-08-27
Anticipated expiration: 2032-04-25
Also published as: CN102629519A

Abstract

A method for producing a diaphragm of a super capacitor belongs to the technical field of ion channel membranes. The method is characterized in that dimethylacetamide is used for dissolving soluble polyimide and hybrid materials having ion channels; the tape casting method is used for forming a film on a smooth solid surface; and the film is heated, so that the hybrid materials are subjected to a sol-gel reaction to form iron transmission channels, and the hybrid materials and the polyimide form the diaphragm of the super capacitor. The novel diaphragm, which has good ion transmission performance and small resistance, of the supper capacitor can be obtained through the method, and the defect of high porosity of present diaphragms is eliminated. The method has the advantages of being simple in producing process and easy to magnify.

Description

A kind of preparation method of diaphragm of supercapacitor

Invention field

The present invention relates to ion channel membrane preparation technology field, particularly manufacture the ion channel membrane preparation method for ultracapacitor.

Background technology

Along with rapid economic development, the mankind increase day by day to the demand of the energy and ambient pressure that a large amount of consumption of fossil energy cause becomes increasingly conspicuous.Save fossil energy, research and development and utilize on a large scale regenerative resource to become the grand strategy of countries in the world energy security and sustainable development.Ultracapacitor, as an emerging energy storage device of current alternative energy source, is being brought into play huge effect at new energy field.

Ultracapacitor (Supercapacitor) city the seventies in last century six takes the lead in occurring in the U.S., and moves towards gradually a kind of emerging energy storage device in market the eighties.Large one more than the order of magnitude of the traditional physical capacitor of energy Ratios that this novel energy device can store, feature simultaneously that kept again the traditional capacitor speed of releasing energy to be exceedingly fast, thereby be with a wide range of applications.Its septation is as one of important component part of ultracapacitor, and the quality of its performance determines the quality of capacitor performance to a certain extent.General Requirements to diaphragm material is: 1) resistance is as far as possible little, makes ion pass through the ability of barrier film strong, and barrier film is little to the resistance of electrolyte ion motion; 2) diaphragm material is the insulator of electronic conductor; 3) stable chemical performance in electrolyte; 4) have certain mechanical strength, isolation performance is good; 5) structural constituent homogeneous, consistency of thickness; 6) rich material resources, cheap.

The materials such as polypropylene (PP) nonwoven fabrics barrier film, cellulose barrier film, diaphragm paper that have that mainly adopt for the commercialization barrier film of ultracapacitor both at home and abroad are now made, require it to there is the gas that stores electrolyte and the anodal generation of conducting to the function of negative pole, thereby thicker, porosity is higher.Make barrier film resistance large compared with thick barrier film, higher porosity can cause electric pole short circuit.Ultracapacitor does not produce gas in charge and discharge process, and also undesirable gas is compound, thereby does not also need to possess more porosity, only need meet the passage of electrolyte ion.Patent (200310112700.1) utilizes asbestos fibre interpolation reinforcing material to prepare a kind of diaphragm of supercapacitor, but utilization is not electrolytical ion channel.The present invention is directed to the feature of diaphragm of supercapacitor, propose a kind of brand-new thinking: taking polymer as matrix material, a kind of hybrid material that can transmit ion that then adulterates dissolves in intensive polar solvent, makes uniform solution after mixing, passes through tape-casting.Basis material wherein possesses good chemical resistance, temperature tolerance and good conductivity, and hybrid material provides the transmission channel of transmission ion.This diaphragm of supercapacitor preparation method is simple, be easy to amplify, both can be for the barrier film of ultracapacitor, also can be used as the separation process occasion of cation selective film for electric field driven.

Summary of the invention:

The object of the invention is to provide a kind of preparation method of ion transport membranes, and especially preparation can be for the barrier film of ultracapacitor.

The invention is characterized in: contain successively following steps;

Step (1), taking dimethylacetylamide as solvent, soluble polyimide and the hybrid material that contains ion channel are dissolved, the concentration of described polyimides in solution is expressed as 10%～25% by percetage by weight, the described hybrid material that contains ion channel refers to a class silicon-containing compound that contains urea groups, and its concentration in solution is expressed as 5%～20% by percetage by weight;

Step (2), the solution that uses the tape casting that step (1) is obtained becomes film in level and smooth glass surface curtain coating, and thickness, between 10～200 microns, forms film after described solvent evaporates, and can peel off from glass surface;

Step (3), film heating to the 60～200 DEG C scope that step (2) is obtained, makes hybrid material form described ion channel.

Described soluble polyimide is synthetic by following dianhydride and diamines:

In described hybrid material, at least contain a urea groups and a silane.

Described solvent is except described dimethylacetylamide, the mixture of one or more in following solvents; Dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE.

By add the concentrated hydrochloric acid as catalyst in described step (1), can make hybrid material that sol gel reaction occurs in described step (3), the concentration of described concentrated hydrochloric acid in solution is expressed as 0.01%～3% by percetage by weight.

Method of the present invention avoids using in existing method the technical process of the complexity such as perforated film, multistep reprocessing.Utilize the ion channel in hybrid material with ion transfer function, use solution casting method to prepare homogeneous phase ion transport membranes.Bring into play polyimides electrochemical corrosion resistant strong, the speciality that temperature tolerance is good, the essential part of composition diaphragm material simultaneously.Described film-forming method is simple, easily realizes amplifying and produces.This barrier film is applicable to ultracapacitor, also can be used as flow battery barrier film for energy storage device.Utilize ion channel barrier film of the present invention can play the advantage that ion passes through fast, provide new approaches to Development of Novel diaphragm of supercapacitor.

Embodiment:

Implementation step of the present invention is as follows:

1) use chemical solvent that soluble polyimide and the hybrid material that contains ion channel are dissolved, add catalyst to make hybrid material generation sol gel reaction, use the tape casting to be applied to thin layer at the level and smooth surface of solids, make solvent evaporates form diaphragm of supercapacitor.

2) step 1) described chemical solvent is dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, and two or more mixture of described solvent;

3) step 1) described in the concentration of soluble polyimide in solution be 10%～25%.(percetage by weight)

4) step 1) described in ion channel hybrid material refer to the compound that contains urea groups and silane, preferentially select 3-(Ureidophenyl) propyl-triethoxysilicane, its concentration in solution is 5-20%.

5) step 1) described the tape casting refers to Polymer Solution is laid in to the level and smooth surface of solids, preferentially selects glass surface.

6) step 1) the curtain coating THICKNESS CONTROL that forms when described tape-casting is at 10～200 micrometer ranges, will after solvent evaporates, form film.

7) step 1) when described hybrid material generation sol gel reaction, add catalyst, can be acid, alkali, chlorine-containing silane, preferentially select concentrated hydrochloric acid, its concentration range is 0.01%～3% (percetage by weight).

8) step 1) described diaphragm of supercapacitor thickness is at 5～150 micrometer ranges.

Embodiment

Embodiment 1

20g soluble polyimide (FBDA-FAPB) and 120g solvent dimethylacetylamide are placed in to there-necked flask, under normal temperature, stir 2 hours, then add 8g hybrid material and 0.1ml concentrated hydrochloric acid, be warming up at 100 DEG C and continue to stir 48 hours, after solution mixes completely, cooling standing 2 hours, on clean glass plate, curtain coating becomes the film of 100 microns, after solvent evaporates, film is taken off from glass plate, at 100 DEG C, be dried 4 hours, obtain the diaphragm of supercapacitor of 60 microns.

Embodiment 2

By 20g soluble polyimide (6FBPDA-3,3 '-TFDB) and 180g solvent dimethyl formamide be placed in there-necked flask, under normal temperature, stir 2 hours, then add 15g hybrid material and 0.3ml concentrated hydrochloric acid, be warming up at 100 DEG C and continue to stir 48 hours, after solution mixes completely, cooling standing 2 hours, on clean glass plate, curtain coating becomes the film of 120 microns, after solvent evaporates, film is taken off from glass plate, at 150 DEG C, be dried 4 hours, obtain the diaphragm of supercapacitor of 85 microns.

Embodiment 3

By 30g soluble polyimide (6FDA-2,2 '-DTFODA) and 250g solvent N methyl pyrrolidone be placed in there-necked flask, at 50 DEG C, add thermal agitation 2 hours, then add 20g hybrid material and 0.5ml concentrated hydrochloric acid, be warming up at 120 DEG C and continue to stir 72 hours, after solution mixes completely, cooling standing 2 hours, on clean glass plate, curtain coating becomes the film of 200 microns, after solvent evaporates, film is taken off from glass plate, at 180 DEG C, be dried 12 hours, obtain the diaphragm of supercapacitor of 150 microns.

Embodiment 4

10g soluble polyimide (6FCDA-4FBDAF) and 100g solvent dimethylacetylamide are placed in to there-necked flask, under normal temperature, stir 2 hours, then add 5g hybrid material and 0.02ml concentrated hydrochloric acid, be warming up at 100 DEG C and continue to stir 48 hours, after solution mixes completely, cooling standing 2 hours, on clean glass plate, curtain coating becomes the film of 10 microns, after solvent evaporates, film is taken off from glass plate, at 120 DEG C, be dried 4 hours, obtain the diaphragm of supercapacitor of 5 microns.

Claims

1. a preparation method for diaphragm of supercapacitor, is characterized in that, contains successively following steps:

Step (1), use dimethylacetylamide as solvent, soluble polyimide and the hybrid material that contains ion channel are dissolved, add a small amount of catalyst, the concentration of described polyimides in solution is expressed as 10%～25% by percetage by weight, the described hybrid material that contains ion channel refers to a class silicon-containing compound that contains urea groups, and its concentration in solution is expressed as 5%～20% by percetage by weight;

Described soluble polyimide is synthetic by dianhydride and diamines,

Described diamines is

In one or more mixture;

Described dianhydride is

In one or more mixture;

Step (3), the film heating to 60 that step (2) is obtained DEG C～200 DEG C of scopes, make silicon-containing compound in hybrid material form silica silicon network and form described ion channel, and film thickness is between 5～150 microns.

2. according to the preparation method of a kind of diaphragm of supercapacitor described in claims 1, it is characterized in that, described in contain ion channel hybrid material at least contain a urea groups and a silane.

3. according to the preparation method of a kind of diaphragm of supercapacitor described in claims 1, it is characterized in that, described solvent is except described dimethylacetylamide, the mixture of one or more in following solvents; Dimethyl formamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE.

4. according to the preparation method of a kind of diaphragm of supercapacitor described in claims 1, it is characterized in that, by add catalyst in described step (1), make hybrid material that sol gel reaction occur in described step (3), the concentration of described catalyst in solution is expressed as by percetage by weight: 0.01%～3%.

5. according to the preparation method of a kind of diaphragm of supercapacitor described in claims 1, it is characterized in that, in described step (2), the solution that use the tape casting obtains step (1) is at level and smooth glass surface casting film-forming, and thickness is between 10～200 microns; After dry, can peel off from described glass pane surface.