CN102496464B - Super capacitance battery diaphragm, preparing method thereof and application thereof - Google Patents
Super capacitance battery diaphragm, preparing method thereof and application thereof Download PDFInfo
- Publication number
- CN102496464B CN102496464B CN201110411949.7A CN201110411949A CN102496464B CN 102496464 B CN102496464 B CN 102496464B CN 201110411949 A CN201110411949 A CN 201110411949A CN 102496464 B CN102496464 B CN 102496464B
- Authority
- CN
- China
- Prior art keywords
- barrier film
- sulfonation
- fiber
- super capacitance
- acrylic monomer
- 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.)
- Active
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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to a super capacitance battery diaphragm, wherein permanent hydrophilic group hydrophilic groups and crylic acid series monomers simultaneously exist on the surface of fiber forming the diaphragm, the fiber forming the diaphragm is composed of polyolefin skin core type type fiber or polypropylene fiber or both the polyolefin skin core type core fiber and the polypropylene fiber in matching mode, is formed through a wet papermaking method or a dry carding process, and is manufactured into a laminated diaphragm base body. The super capacitance battery diaphragm has the advantages of excellent water retainability, high strength, strong ion migration ability, high charge retention ratio, low internal resistance and the like, meets large current charge and discharge requirements of super capacitance batteries, and has excellent low temperature performance.
Description
Technical field
The present invention relates to the barrier film that a kind of battery is used; Especially relate to a kind of super capacitance cell barrier film and its preparation method and application.
Background technology
History enters into 21 century; continuous intensification along with global energy crisis; the harm aggravation of the exhaustion increasingly of petroleum resources and air pollution, global warning; national governments and Automobile Enterprises generally recognize that energy-conservation and reduction of discharging is the main direction of future automobile technical development, and Development of EV becomes the optimal path that solves these two technological difficulties.Electric automobile also becomes a focus of selection and the technology competition of countries in the world thereupon.From the angle close examination of the energy, environment, development new-energy automobile is the inevitable choice of China.
Super capacitance cell (being a kind of of ultracapacitor) is to have taked combination property balanced design thinking, dexterously active carbon material is introduced to nickel-hydrogen battery negative pole, an electrode adopts electrode activity carbon electrode, and another electrode adopts capacitance electrode material or battery electrode, realize common ultracapacitor and battery and be combined as a whole, thereby had the excellent properties of general ultracapacitor and storage battery concurrently.Super capacitance cell is a kind of dual-use new type power power supply, have that energy density is large, power density is high, efficiency for charge-discharge is high, high temperature performance is good, have extended cycle life, the various features such as safety and environmental protection, cost performance height, efficiently solve domestic electric car power supply technical bottleneck problem, also can in surface ship, submarine, type aircraft, guided missile and space industry, apply.
The large critical material of super capacitance cell three comprises positive and negative electrode material and diaphragm material.Because super capacitance cell is the combination of common ultracapacitor and storage battery, therefore diaphragm material must meet its corresponding specification requirement, must have that excellent liquid-keeping property, intensity are high, the high and low internal resistance of strong, the charged conservation rate of ion transfer ability, meet the requirement of super capacitance cell high current charge-discharge, and there is the excellent features such as cryogenic property.
The battery diaphragm material circulating in the market, mainly for Ni-MH battery, lithium ion battery, common ultracapacitor etc., the excellent characteristics of super capacitance cell cannot be met or bring into play, therefore the instructions for use that a kind of new diaphragm material meets super capacitance cell must be researched and developed.
Summary of the invention
Technical problem solved by the invention is to provide a kind of super capacitance cell barrier film, there is the characteristics such as excellent liquid-keeping property, intensity are high, the high and low internal resistance of strong, the charged conservation rate of ion transfer ability, meet the requirement of super capacitance cell high current charge-discharge, and there is excellent cryogenic property.
Further aim of the present invention is to provide the preparation method of described super capacitance cell barrier film.
In order to achieve the above object, the technical solution used in the present invention is:
A barrier film, its fiber surface that forms barrier film has sulfonic group and acrylic monomer simultaneously, and the fiber of described composition barrier film is comprised of polyolefin sheath core fiber and/or polypropylene fibre.
The fiber surface that super capacitance cell barrier film provided by the invention forms barrier film has permanent hydrophilic group sulfonic group and acrylic monomer simultaneously, the fiber that forms barrier film is comprised of polyolefin sheath core fiber or is formed or be comprised of polyolefin sheath core fiber and polypropylene fibre collocation by polypropylene fibre, through wet papermaking or dry carding technological forming, make lamination type barrier film matrix.Such super capacitance cell barrier film has that excellent liquid-keeping property, intensity are high, the high and low internal resistance of strong, the charged conservation rate of ion transfer ability, meets the requirement of super capacitance cell high current charge-discharge, and has excellent cryogenic property.
Super capacitance cell barrier film of the present invention, wherein said sulfonic group can be processed and is grafted on equably the fiber surface that forms barrier film by sulfonation, and sulfonation degree is preferably 0.7%～1.0%; Also can adopt other known sulfonic group grafting means.
Super capacitance cell barrier film of the present invention, wherein said acrylic monomer can be grafted on the fiber surface of the composition barrier film that sulfonation processed equably by physical chemistry emulsification diffusion technique, and monomer-grafted rate is preferably 0.1%～2.0%; Also can adopt other known acrylic monomer grafting means.Described acrylic monomer is the mixture of one or more compositions in acrylic monomers, methacrylic acid, methyl acrylate, ethyl acrylate, itaconic acid, unsaturated Sheep's-parsley ketone acid, sulfamic acid, olefin sulfonic acid.
Super capacitance cell barrier film of the present invention, the fiber that wherein forms barrier film preferably consists of: polyolefin sheath core fiber part by weight is 80%～100%, and polypropylene fibre part by weight is 20%～100%.The fiber number of described polyolefin sheath core fiber is 0.6D～1.0D, and fibre length is 3mm～38mm; The fiber number of polypropylene fibre is 0.6D～0.8D, and fibre length is 5mm～38mm.
Further, the invention provides the preparation method of described super capacitance cell barrier film, first polyolefin sheath core fiber and/or polypropylene fibre are made to lamination type barrier film matrix, again barrier film matrix is carried out to sulfonation processing, sulfonation metacneme carries out emulsification diffusion grafting again to be processed, and makes acrylic monomer be grafted on equably the fiber surface after sulfonation.
Above-mentioned preparation method, wherein polyolefin sheath core fiber and/or polypropylene fibre can pass through wet papermaking or dry carding technological forming, make lamination type barrier film matrix.
Above-mentioned preparation method, wherein said sulfonation is processed can adopt known technological means, a kind of preferred implementation process is: the gaseous sulfur trioxide that uses 90% above concentration, in sulfonation reactor, barrier film matrix is carried out to sulfonation processing, temperature in sulfonation reactor is 60 ℃～100 ℃, sulfur trioxide concentration 90%, 20 ms/min of sulfonation speed, through oversulfonate, process, sulfonic group is grafted on the fiber surface that forms barrier film uniformly, through alkali, carry out neutralisation treatment, wherein the concentration of alkali lye potassium hydroxide or NaOH is 1%, and then be washed till neutrality with deionized water, dry.
Above-mentioned preparation method, wherein said emulsification diffusion grafting is processed and can be adopted known technological means, implementation process is: acrylic monomer, emulsification diffusant and deionized water are made into a graft modification liquid, and wherein the weight concentration of acrylic monomer is 10%～30%; The weight concentration of emulsification diffusant is 0.1%～0.6%; The sulfonation metacneme of operation is continuously etched after processing under normal temperature and pressure conditions, enters in graft modification liquid, and keep successively passing into inert gas in modification liquid, under 75 ℃ of conditions, carry out abundant graft polymerization reaction.Described emulsification diffusant is preferably alkyl ether sulfate and alkyl phenol ether disulfonate.
According to the preferred embodiment of the present invention, the preparation method of super capacitance cell barrier film provided by the invention specifically comprises the following steps:
(1) barrier film matrix preparation: polyolefin sheath core fiber or polypropylene fibre or polyolefin sheath core fiber and polypropylene fibre collocation are cut into the short fiber of 25mm～38mm, use dry carding technological forming, makes low grammes per square metre single-layer septum matrix; Or polyolefin sheath core fiber or polyolefin sheath core fiber and the polypropylene fibre various fibers of arranging in pairs or groups are cut into the superbhort fiber of 3mm～10mm, and use wet papermaking technology, through making beating, moulding, dehydration, oven dry, make low grammes per square metre single-layer septum matrix; Use laminating machine compound the low grammes per square metre single-layer septum of multilayer matrix, the above control that requires to carry out surface density according to product design technology, adjusts to the barrier film matrix of desired thickness by rolling press.
(2) sulfonation is processed: the gaseous sulfur trioxide that uses 90% above concentration, in sulfonation reactor, barrier film matrix is carried out to sulfonation processing, the temperature in sulfonation reactor is 60 ℃～100 ℃, preferably 70 ℃, sulfur trioxide concentration 90%, 20 ms/min of sulfonation speed, process through oversulfonate, and sulfonic group is grafted on the fiber surface that forms barrier film uniformly, through alkali, carry out neutralisation treatment, wherein the concentration of alkali lye potassium hydroxide or NaOH is 1%, and then is washed till neutrality with deionized water, dries.Control sulfonation degree in 0.7%～1.0% scope, O/C is between 0.01～0.05.
(3) grafting of physical chemistry emulsification diffusion technique is processed: acrylic monomer, emulsification diffusant and deionized water are made into graft modification liquid, and acrylic monomer (weight) concentration is 10%～30%; Emulsification diffusant (weight) concentration is 0.1%～0.6%; The sulfonation metacneme of operation is continuously etched after processing under normal temperature and pressure conditions, enter in the acrylic monomer solution that contains emulsification diffusant, and keep successively passing in modification liquid inert gas, under 75 ℃ of conditions, carry out abundant graft polymerization reaction, control monomer-grafted rate in 0.1%～2.0% scope.
(4) by the barrier film matrix of processing through oversulfonate and the grafting of physical chemistry emulsification diffusion technique, carry out product standard thickness compacting, batch, pack, make super capacitance cell barrier film.
The beneficial effect of super capacitance cell barrier film of the present invention is:
(1) fiber surface of composition barrier film has permanent hydrophilic group sulfonic group and acrylic monomer simultaneously, the fiber that forms barrier film is comprised of polyolefin sheath core fiber or is formed or be comprised of polyolefin sheath core fiber and polypropylene fibre collocation by polypropylene fibre, through wet papermaking or dry carding technological forming, make lamination type barrier film matrix.Super capacitance cell barrier film has that excellent liquid-keeping property, intensity are high, the high and low internal resistance of strong, the charged conservation rate of ion transfer ability like this, meets the requirement of super capacitance cell high current charge-discharge, and has excellent cryogenic property.
(2) the present invention preferably adopts sulfonation processing and two kinds of hydrophilic treated modes of physical chemistry emulsification diffusion technique grafting to process forming the fiber of barrier film simultaneously, and sulfonic acid group and acrylic monomer are all effectively grafted on the carbon atom of fiber surface, can guarantee that like this barrier film has permanent hydrophilic ability and liquid-keeping property, ion transfer ability and exchange capacity have been improved, effectively reduce internal resistance, improve large current density power, and there is excellent retention of charge.The grafting of simultaneously physical chemistry emulsification diffusion technique is processed and has effectively been made up sulfonation and process the destruction to barrier film intensity, homogenizing pore size, reduced short circuit ratio, make super capacitance cell barrier film meet better the use of super capacitance cell.Adopt described physical chemistry emulsification diffusion technique, described hydrophilic radical sulfonic group and acrylic monomer are all to combine with carbon (C) atom of fiber surface, have permanent.
Embodiment
For further illustrating the present invention, illustrate with the following Examples:
Sulfonation degree and the sulfonic acid group (SO that is processed at fiber surface
3h) sulphur atom (S) number, oxygen atom (O) number with and fiber surface carbon atom (C) number between ratio correlate, wherein with O/C ratio, carry out nominal O/C than in 0.005～0.05, O wherein, C do not wrap O in acrylic monomer, C; The molar ratio range of element sulphur and carbon is 0.2～1.5mass%; The ion-exchange capacity of barrier film meets 0.001～0.15 (equivalent/m
2).
Embodiment 1
Fiber material is prepared burden by weight, i.e. polyolefin sheath core fiber, fibre number 0.8D, length 38mm, content 80%; Polypropylene fibre, fiber number 0.8D, length 38mm, content 20%, adopts dry carding technological forming by above-mentioned fiber, in 120 ℃ of hot-airs, dries, and making density of single layer is 18g/m
2barrier film matrix, by 3 layers of density, be 18g/m
2single-layer septum matrix use laminating machine compound, with adjustment of rolling mill, to certain thickness, make barrier film matrix, the surface density of barrier film matrix is 54g/m
2.
Barrier film matrix is transported in sulfonation reactor, with the gaseous sulfur trioxide of 90% concentration, carry out sulfonation processing, matrix after sulfonation is transported to alkaline bath and carries out neutralization reaction, concentration of potassium hydroxide is 1%, alkali cleaning speed is controlled at 20 ms/min, through rinsed with deionized water and pressure rolling, oven dry bake out temperature, be controlled at 100 ℃ again, the sulfonation degree that obtains barrier film base cloth is 0.8%, O/C is 0.04.
Then the sulfonation metacneme of operation is continuously etched after processing under normal temperature and pressure conditions, enters in the acrylic monomer solution that contains emulsification diffusant, carry out emulsification diffusion grafting and process, make acrylic monomer be grafted on equably the fiber surface after sulfonation.
Acrylic monomers, alkyl ether sulfate and deionized water are made into graft modification liquid, and acrylic monomers (weight) concentration is 10%; Alkyl ether sulfate (weight) concentration is 0.2%; The sulfonation metacneme of operation is continuously etched after processing under normal temperature and pressure conditions, enters in graft modification liquid, and keep successively passing into inert gas in modification liquid, under 75 ℃ of conditions, carry out abundant graft polymerization reaction, control monomer-grafted rate 0.2%.
By the barrier film matrix of processing through oversulfonate and the grafting of physical chemistry emulsification diffusion technique, carry out product standard thickness compacting, batch, pack, making surface density is 55g/m
2, the super capacitance cell barrier film that thickness is 0.12mm.
Embodiment 2
Adopt polyolefin sheath core fiber 100%, make barrier film matrix, fibre number is 0.8D, and fibre length is 3mm～10mm, uses wet papermaking technology, and through making beating, moulding, dehydration, oven dry, making density of single layer is 18g/m
2barrier film matrix, by 3 layers of density, be 18g/m
2single-layer septum matrix use laminating machine compound, with adjustment of rolling mill, to certain thickness, make barrier film matrix, the surface density of barrier film matrix is 54g/m
2.
Then by the sulfonation processing of embodiment 1 and physical chemistry emulsification diffusion technique grafting processing mode, process with order, making surface density is 55g/m
2, the super capacitance cell barrier film that thickness is 0.12mm, sulfonation degree is that 0.8%, O/C is 0.041, monomer-grafted rate is 0.2%.
Embodiment 3
First adopt polypropylene fibre 100%, its medium titre is 0.8D, and length is that 38mm adopts dry carding technological forming, in 130 ℃ of hot-airs, dries, and making density of single layer is 24g/m
2barrier film matrix.
Adopt polyolefin sheath core fiber 100%, fibre number is 0.8D again, and fibre length is 3mm～10mm, uses wet papermaking technology, and through making beating, moulding, dehydration, oven dry, making density of single layer is 23g/m
2barrier film matrix.
Use laminating machine compound 3 layers of single-layer septum matrix, wherein, intermediate layer is the single-layer septum matrix of 100% polypropylene fibre, other two individual layers are the single-layer septum matrix of 100% polyolefin sheath core fiber, with adjustment of rolling mill, arrive certain thickness, make barrier film matrix, the surface density of barrier film matrix is 70g/m
2.
Barrier film matrix is transported in sulfonation reactor, with the gaseous sulfur trioxide of 90% concentration, carry out sulfonation processing, matrix after sulfonation is transported to alkaline bath and carries out neutralization reaction, concentration of potassium hydroxide is 1%, alkali cleaning speed is controlled at 20 ms/min, through rinsed with deionized water and pressure rolling, oven dry bake out temperature, be controlled at 105 ℃ again, the sulfonation degree that obtains barrier film base cloth is 0.9%, O/C is 0.043.
Then the sulfonation metacneme of operation is continuously etched after processing under normal temperature and pressure conditions, enters in the acrylic monomer solution that contains emulsification diffusant, carry out emulsification diffusion grafting and process, make acrylic monomer be grafted on equably the fiber surface after sulfonation.
Methyl acrylate, alkyl phenol ether disulfonate and deionized water are made into graft modification liquid, and methyl acrylate (weight) concentration is 20%; Alkyl phenol ether disulfonate (weight) concentration is 0.4%; The sulfonation metacneme of operation is continuously etched after processing under normal temperature and pressure conditions, enters in graft modification liquid, and keep successively passing into inert gas in modification liquid, under 75 ℃ of conditions, carry out abundant graft polymerization reaction, control monomer-grafted rate 0.5%.
By the barrier film matrix of processing through oversulfonate and the grafting of physical chemistry emulsification diffusion technique, carry out product standard thickness compacting, batch, pack, making surface density is 72g/m
2, the super capacitance cell barrier film that thickness is 0.22mm.
Embodiment 4
Adopt polyolefin sheath core fiber 100%, make barrier film matrix, fibre number is 0.8D, fibre length is 3mm～10mm, uses wet papermaking technology, through making beating, moulding, dehydration, oven dry, making density of single layer is the barrier film matrix of 20g/m2, by 3 layers of density, is 20g/m
2single-layer septum matrix use laminating machine compound, with adjustment of rolling mill, to certain thickness, make barrier film matrix, the surface density of barrier film matrix is 60g/m
2.
Then by the sulfonation processing of embodiment 3 and physical chemistry emulsification diffusion technique grafting processing mode, process with order, making surface density is 62g/m
2, the super capacitance cell barrier film that thickness is 0.18mm, sulfonation degree is that 0.85%, O/C is 0.042, monomer-grafted rate is 0.4%.
Adopt above-mentioned batching condition and processing mode, the super capacitance cell membrane properties index of making is as table 1.
Table 1
Super capacitance cell barrier film of the present invention has permanent hydrophilic group sulfonic group and acrylic monomer owing to forming the fiber surface of barrier film simultaneously, sulfonic group is processed and is grafted on equably the fiber surface that forms barrier film by sulfonation, acrylic monomer is grafted on the fiber surface of the composition barrier film that sulfonation processed equably by physical chemistry emulsification diffusion technique, the fiber that forms barrier film is comprised of polyolefin sheath core fiber or is formed or be comprised of polyolefin sheath core fiber and polypropylene fibre collocation by polypropylene fibre, through wet papermaking or dry carding technological forming, make lamination type barrier film matrix.Super capacitance cell barrier film has that excellent liquid-keeping property, intensity are high, the high and low internal resistance of strong, the charged conservation rate of ion transfer ability like this, meets the requirement of super capacitance cell high current charge-discharge, and has excellent cryogenic property.Owing to adopting sulfonation processing and two kinds of hydrophilic treated modes of physical chemistry emulsification diffusion technique grafting simultaneously, to forming the fiber of barrier film, process, and sulfonic acid group and acrylic monomer are all effectively grafted on the carbon atom of fiber surface, guaranteed that like this barrier film has permanent hydrophilic ability and liquid-keeping property, ion transfer ability and exchange capacity have been improved, effectively reduce internal resistance, improved large current density power, and there is excellent retention of charge, physical chemistry emulsification diffusion technique grafting is simultaneously processed and has effectively been made up the destruction of sulfonation processing to barrier film intensity, homogenizing pore size, reduced short circuit ratio, make super capacitance cell barrier film meet better the use of super capacitance cell.
Comparative example:
The battery diaphragm material of circulation, is mainly for Ni-MH battery, lithium ion battery, common ultracapacitor etc. in the market, cannot meet or bring into play the excellent characteristics of super capacitance cell.
For further illustrating product excellent properties of the present invention and wider range of application, by this product and other barrier films contrast test on Ni-MH battery.By the embodiment of the present invention 2 gained super capacitance cell barrier films, carry out conventional index test with 700/71 these two kinds battery diaphragms that use for nickel-hydrogen battery of Japanese FV4365 and Britain (Sigma is special) abroad and for the part battery performance test of model AAA700 battery, as table 2.
Table 2
From the data of table 2, relatively can learn, the barrier film each side combination property of embodiments of the invention 2 gained is best, especially aspect internal resistance.
700/71 these the two kinds battery diaphragms that abroad use for nickel-hydrogen battery of the prepared super capacitance cell barrier film of the embodiment of the present invention 2 and Japanese FV4365 and Britain (Sigma is special) are used on automotive nickel-metal hydride battery and carry out electric performance test, as table 3.
Table 3
From the data of upper table, can relatively learn, the barrier film of the embodiment of the present invention 2 gained is very excellent in aspect performances such as heavy-current discharge, internal resistances.
Above-described embodiment is described the preferred embodiment of the present invention; not scope of the present invention is limited; design under the prerequisite of spirit not departing from the present invention; various distortion and improvement that the common engineers and technicians in this area make technical scheme of the present invention, all should fall in the definite protection range of claims of the present invention.
Claims (3)
1. a super capacitance cell barrier film, is characterized in that: the fiber surface that forms barrier film has sulfonic group and acrylic monomer simultaneously, and the fiber of described composition barrier film is comprised of polyolefin sheath core fiber and/or polypropylene fibre; Described sulfonic group is processed and is grafted on equably the fiber surface that forms barrier film by sulfonation, and sulfonation degree is 0.7%～1.0%; Described acrylic monomer is grafted on the fiber surface of the composition barrier film that sulfonation processed equably by physical chemistry emulsification diffusion technique, monomer-grafted rate is 0.1%～2.0%; Described acrylic monomer is the mixture of one or more compositions in acrylic monomers, methacrylic acid, methyl acrylate, ethyl acrylate, itaconic acid, unsaturated Sheep's-parsley ketone acid, sulfamic acid, olefin sulfonic acid; Described polyolefin sheath core fiber part by weight is 80%～100%, and polypropylene fibre part by weight is 20%～100%; The fiber number of described polyolefin sheath core fiber is 0.6D～1.0D, and fibre length is 3mm～38mm; The fiber number of polypropylene fibre is 0.6D～0.8D, and fibre length is 5mm～38mm.
2. the preparation method of super capacitance cell barrier film claimed in claim 1, it is characterized in that: first polyolefin sheath core fiber and/or polypropylene fibre are made to lamination type barrier film matrix, again barrier film matrix is carried out to sulfonation processing, sulfonation metacneme carries out emulsification diffusion grafting again to be processed, and makes acrylic monomer be grafted on equably the fiber surface after sulfonation;
Described sulfonation processing procedure is: the gaseous sulfur trioxide that uses 90% above concentration, in sulfonation reactor, barrier film matrix is carried out to sulfonation processing, temperature in sulfonation reactor is 60 ℃～100 ℃, sulfur trioxide concentration 90%, 20 ms/min of sulfonation speed, through oversulfonate, process, sulfonic group is grafted on the fiber surface that forms barrier film uniformly, through alkali, carries out neutralisation treatment, and wherein the concentration of alkali lye potassium hydroxide or NaOH is 1%, and then be washed till neutrality with deionized water, dry;
Described emulsification diffusion grafting processing procedure is: acrylic monomer, emulsification diffusant and deionized water are made into graft modification liquid, and wherein the weight concentration of acrylic monomer is 10%～30%; The weight concentration of emulsification diffusant is 0.1%～0.6%; The sulfonation metacneme of operation is continuously etched after processing under normal temperature and pressure conditions, enters in graft modification liquid, and keep successively passing into inert gas in modification liquid, under 75 ℃ of conditions, carry out abundant graft polymerization reaction.
3. the super capacitance cell that contains super capacitance cell barrier film claimed in claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110411949.7A CN102496464B (en) | 2011-12-09 | 2011-12-09 | Super capacitance battery diaphragm, preparing method thereof and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110411949.7A CN102496464B (en) | 2011-12-09 | 2011-12-09 | Super capacitance battery diaphragm, preparing method thereof and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102496464A CN102496464A (en) | 2012-06-13 |
| CN102496464B true CN102496464B (en) | 2014-01-15 |
Family
ID=46188276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110411949.7A Active CN102496464B (en) | 2011-12-09 | 2011-12-09 | Super capacitance battery diaphragm, preparing method thereof and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102496464B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105280862A (en) * | 2015-09-16 | 2016-01-27 | 浙江理工大学 | Preparation method of cooled lithium battery diaphragm |
| CN106229450B (en) * | 2016-09-29 | 2020-04-10 | 河南科高辐射化工科技有限公司 | Diaphragm suitable for sealed high-power nickel-metal hydride battery |
| CN112133870A (en) * | 2020-09-24 | 2020-12-25 | 湖南省凯纳方科技有限公司 | Preparation process of battery diaphragm for increasing ion exchange capacity |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3221337B2 (en) * | 1996-12-13 | 2001-10-22 | 松下電器産業株式会社 | Alkaline storage battery separator |
| US8822082B2 (en) * | 2007-03-15 | 2014-09-02 | Hitachi Maxwell, Ltd. | Separator for electrochemical device, electrode for electrochemical device, and electrochemical device |
| CN101267028B (en) * | 2008-04-10 | 2011-02-16 | 深圳市星源材质科技股份有限公司 | A sulphur-modified polyolefin battery separation film and its making method |
| CN101442112B (en) * | 2008-12-30 | 2010-10-13 | 莱州联友金浩新型材料有限公司 | Battery diaphragm sulphonation equipment and sulphonation treatment technique |
| CN201689929U (en) * | 2009-12-30 | 2010-12-29 | 莱州联友金浩新型材料有限公司 | Sulfonated battery diaphragm |
| CN102569696B (en) * | 2010-12-15 | 2014-05-21 | 莱州联友金浩新型材料有限公司 | Novel nickel-hydrogen battery diaphragm |
-
2011
- 2011-12-09 CN CN201110411949.7A patent/CN102496464B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN102496464A (en) | 2012-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102569696B (en) | Novel nickel-hydrogen battery diaphragm | |
| US20210371565A1 (en) | Cross-linked sbr microsphere binder and preparation method thereof and lithium-ion battery containing the binder | |
| CN105428575B (en) | A kind of preparation of the acrylic acid modified nickel-hydrogen battery separator paper of plasma Inducing Graft | |
| CN109638205B (en) | Fiber-mesh-shaped modified diaphragm of lithium-sulfur battery and preparation method and application thereof | |
| CN110808360A (en) | Silicon-carbon negative electrode material, preparation method thereof, battery negative electrode plate and lithium ion battery | |
| CN102496464B (en) | Super capacitance battery diaphragm, preparing method thereof and application thereof | |
| CN101267028A (en) | A sulphur-modified polyolefin battery separation film and its making method | |
| CN107293681B (en) | A kind of preparation method of novel lithium sulphur battery functi on diaphragm | |
| CN114695968B (en) | Lithium ion battery with NP ratio less than 1 and preparation method thereof | |
| CN102108635B (en) | Method for preparing battery diaphragm material by irradiation grafting of acrylic acid | |
| CN109616657B (en) | High-nickel composite positive electrode material and preparation method and application thereof | |
| CN113328207A (en) | Lithium ion battery composite diaphragm and preparation method thereof | |
| CN111584844B (en) | Titanium dioxide nano composite electrode material and preparation method thereof | |
| CN1967906A (en) | Method for preparing gelatin membrane by radiation grafting method | |
| CN111403661A (en) | Composite diaphragm for power lithium ion battery and preparation method thereof | |
| CN113991244A (en) | Preparation method of polyvinylidene fluoride membrane material with uniform pore diameter | |
| CN100362676C (en) | Production of nickel-hydrogen diaphragm and products thereof | |
| CN117175138A (en) | Preparation method of functionalized nano cellulose membrane | |
| CN110911619A (en) | Lithium battery diaphragm, preparation method thereof and lithium battery | |
| CN114361708B (en) | Environment-friendly water-based battery and preparation method thereof | |
| CN101777635B (en) | Sulfonated battery diaphragm | |
| CN107170944B (en) | Self-supporting polymer film material for lithium ion secondary battery and preparation method thereof | |
| CN101740745B (en) | Novel electron beam radiation grafting preparation process of polyolefin non-woven fabric alkaline battery diaphragm | |
| CN110867593B (en) | Composite diaphragm for flow battery and preparation method | |
| CN201689929U (en) | Sulfonated battery diaphragm |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |