CN201689929U - Sulfonated battery diaphragm - Google Patents
Sulfonated battery diaphragm Download PDFInfo
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- CN201689929U CN201689929U CN2009203524605U CN200920352460U CN201689929U CN 201689929 U CN201689929 U CN 201689929U CN 2009203524605 U CN2009203524605 U CN 2009203524605U CN 200920352460 U CN200920352460 U CN 200920352460U CN 201689929 U CN201689929 U CN 201689929U
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- Prior art keywords
- fiber
- battery diaphragm
- base cloth
- barrier film
- sulfonated
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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 utility model discloses a sulfonated battery diaphragm which belongs to a new structure of a nickel-hydride power battery diaphragm. The sulfonated battery diaphragm is formed by uniformly grafting a diaphragm base fabric and a sulfo group 5 the outer surface of which is sulfonated on the surface. The sulfonated battery diaphragm is characterized in that the diaphragm base fabric is randomly arranged by an organic fiber 1 and an organic fiber 2; a metallic oxide 3 and an organic adhesive 4 are fully filled between the fibers to form a single-layer diaphragm base fabric; and the diaphragm base fabric is formed by more than two layers of the single-layer diaphragm base fabric. The sulfonated battery diaphragm has the advantages of low thermal shrinkage rate, good antioxidant performance, and large tensile strength, which reduces thermal shrinkage rate, improves high temperature resistance, improves liquid absorption volume, quickens ion transferring speed, reduces internal resistances, and improves charge retention rate.
Description
(1) technical field
The utility model relates to a kind of new construction of Ni-MH power cell barrier film, is a kind of sulfonated battery diaphragm specifically.
(2) background technology
Along with socioeconomic fast development, world fuel is exhausted day by day, and people are more and more higher to environmental protection requirement simultaneously, and Ni-MH battery has become one of " green energy resource " battery of at present tool development prospect.Along with Ni-MH battery in the electric automobile successful Application on the motor vehicle driven by mixed power particularly, demands for higher performance to battery, not only will have powerful input and output ability, and battery to have good normal temperature and the retention of charge under the high temperature.Battery diaphragm is as the indispensable important component part of Ni-MH battery, and the quality of its performance is to the capacity of battery, charge-discharge performance, self discharge and recycle aspects such as life-span and all produce bigger influence.Therefore the various aspects of performance development of the excellent sulfonated battery diaphragm ever more important that seems more.
The collocation of the various materials of battery diaphragm, the aftertreatment technology of barrier film is very big to the performance index influence of battery diaphragm.
The main material of current battery barrier film is formed, and Fypro, vinylon fibre, polyolefine fiber and part inorfil are arranged.From combination property analysis, polyolefine fiber and part inorfil have than high temperature tolerance because of it, good alkali resistance, non-oxidizability and insulating properties, and also material price is cheap, so the most suitable manufacturing battery diaphragm.But the polyolefine fiber barrier film that surperficial non-modified is handled is because its hydrocarbon bond lacks polar group, and hydrophily is poor, causes the internal resistance of cell big, and ion transport between unfavorable electrode influences battery capacity and cycle life.For the advantage of performance polyolefine fiber barrier film, must carry out hydrophilic treated to the polyolefine fiber barrier film, to increase barrier film Electolyte-absorptive ability.The employed method of hydrophilic treated mainly contains sulfonation processing and plasma grafting processing method at present.The barrier film that method of plasma processing is handled, exist the big and higher defective of internal resistance of self discharge, and, show charged conservation rate height through barrier film function admirable in battery uses that sulfonation is handled, internal resistance is little, is particularly suitable for the battery of Ni-MH battery and other heavy-current discharge.In detail comprehensively contrast in " barrier film is to the influence and the feature of Ni-MH battery heavy-current discharge performance " literary composition in 2006 the 1st phases " process engineering journal ", it is good to draw sulfonated membrane heavy-current discharge performance in Ni-MH battery; Draw with regard to the contrast test that influences of several barrier films in " barrier film is to the influence of MH/Ni battery capacity, internal resistance and self discharge " literary composition in 2009 the 2nd phases " non-ferrous metal ", adopt sulfonated battery diaphragm can improve the performance of MH/Ni battery battery performance.Therefore the battery diaphragm of handling through sulfonation is the first-selected diaphragm material of present Ni-MH power cell.The technology that sulfonation is now handled mainly contains processing modes such as oleum, the concentrated sulfuric acid, chlorosulfonic acid, sulfur trioxide.Application number is 200610015843.4, publication number is the Chinese invention patent application " a kind of preparation method of nickel-hydrogen battery separator and goods thereof " of CN1747199A, a kind of polyolefine fiber barrier film that contains low density polyethylene (LDPE) is disclosed, shortcoming is to select for use the concentrated sulfuric acid to carry out the sulfonation treatment process, this technology requires very strict to the control of temperature, time, select for use the concentrated sulfuric acid to make reagent and can produce a large amount of spent acid, disposal cost is big and cost is high.Application number is 00108570.0, publication number is the Chinese patent application " battery diaphragm is battery extremely " of CN1294416A, the barrier film that the Splittable superfine fibre that used methylpentene and polyolefin two class materials and formation thereof is made is disclosed, shortcoming is to use sulfonating agents such as oleum to carry out the sulfonation processing, the easy carbonization of superfine fibre, barrier film intensity reduces, the production cost height, and do not provide concrete process for sulfonation and condition.
The sulfonation of battery diaphragm is handled, and uses different materials and different fiber collocation modes in the barrier film base cloth, uses different sulfonation treatment process and condition, and the various aspects of performance index of battery diaphragm is had bigger influence.
(3) summary of the invention
The purpose of this utility model is to have the easy carbonization of battery diaphragm fine fibre in order to overcome, and the big shortcoming that influences the battery performance index that waits of high-temperature shrinkage rate proposes low, the high sulfonated battery diaphragm of protecting fluidity, highly-breathable, highly charged conservation rate of a kind of high-temperature shrinkage rate.
The utility model purpose is realized by following technical scheme: this kind sulfonated battery diaphragm, the sulfonic group of being handled by barrier film base cloth and outer surface sulfonation thereof 5 is grafted on surface composition equably, it is characterized in that the barrier film base cloth is by organic fiber 1 and inorfil 2 random alignment, be full of metal oxide 3 and organic bond 4 composition single-layer septum base cloths between the fiber, by the bonding one-tenth barrier film of two-layer above single-layer septum base cloth base cloth.
Inorfil 2 is Zirconium oxide fibre, titanium dioxide fiber, magnesia fibers, and fibre diameter is nano level or micron-sized, fibre length in 2mm～51mm scope, Zirconium oxide fibre preferably.
Inorganic, metal oxide 3 is nano level or micron-sized Zirconium oxide powder, titanium dioxide powder, magnesium oxide powder, lanthanide oxide powder, preferably titanium dioxide powder.
The barrier film base cloth is by two kinds in the organic fiber 1, press the certain weight ratio collocation: polyolefin sheath core fiber 50%～90%, collocation polypropylene superfine fiber 10%～50% is preferably polyolefin sheath core fiber 70%, the surface density 40g/m that polypropylene superfine fiber 30%, random alignment are made
2～70g/m
2The barrier film base cloth, be preferably 55g/m
2The barrier film base cloth.
The surface density 40g/m that the barrier film base cloth is made by the polyolefin sheath core fiber random alignment in the organic fiber 1
2～70g/m
2Base cloth, be preferably 60g/m
2, be coated with organic bond 4 again, coating weight 0～40g/m
2, be preferably 20g/m
2, form the barrier film base cloth.
The barrier film base cloth can be mixed into by weight by organic fiber 1 and inorfil 2: organic fiber 70%～99.9%, inorfil 0.1%～30% is preferably polyolefine fiber 80%, zirconia 20%, the barrier film base cloth 40g/m that random alignment is formed
2～70g/m
2, be preferably 60g/m
2
With above-mentioned by organic fiber and inorfil by weight the barrier film base cloth that random alignment mixes into, be coated with organic bond or standard binders 0～40g/m again
2, be another surface density 45g/m
2～75g/m
2The barrier film base cloth.
The battery diaphragm that any barrier film base cloth in aforementioned the is formed battery of packing into can improve the self-discharge performance, is specially adapted to hybrid vehicle (HEV).
Aforesaid any one battery diaphragm base cloth, can become independently battery diaphragm base cloth, use the gaseous sulfur trioxide of 95% above concentration that the barrier film base cloth is carried out the sulfonation processing, subtract again after sulfonation finishes and wash, wash, add surfactant, and pressure rolling promptly obtains sulfonated battery diaphragm to nominal thickness.
The utility model has the advantages that the different organic fibers collocation of employing or organic fiber and inorfil collocation, fill inorganic, metal oxide and also be coated with organic bond, re-use sulfur trioxide and carry out the sulfonation processing, is a kind of technological means that does not have in the past.Since adopted organic fiber and inorfil arrange in pairs or groups mode, so dimensional stability to heating in house is low, antioxygenic property is good; Because of having adopted liquid random polypropylene organic bond and rational sulfonation mode, most of sulfonic group is grafted on random polypropylene organic bond and organic fiber surface equably during sulfonation, fiber is not subject to destruction, and sulfonation is even, so tensile strength is big; Because of having adopted inorganic, metal oxide powder and inorfil, improved resistance to elevated temperatures, improved liquid absorption, reduce the fiber high temperature rate of closed hole, accelerated ion transport speed, reduced internal resistance, sulfonic acid group has stopped that polygamy ions such as ammonia pass through, and have improved charged conservation rate.
(4) description of drawings
Fig. 1 is a kind of sulfonated battery diaphragm structure enlarged drawing,
Fig. 2 also is a kind of sulfonated battery diaphragm structure enlarged drawing, different among the fiber of its organic fiber 1 and inorfil 2 and Fig. 1.
(5) embodiment
Below in conjunction with embodiment the utility model is further specified.
Barrier film base cloth preparation: polyolefin core-skin fibre 1, polypropylene superfine fiber 1 or inorfil 2 are cut into the short fiber of 15mm～51mm, use carding equipment, the combing moulding is carried out the water thorn again and is dried into the barrier film base cloth.Or various fibers are cut into superbhort fiber into 5mm～15mm, use wet papermaking process, through making beating, moulding, dehydration, water thorn, be dried into the barrier film base cloth.Require to be coated with an amount of organic bond 4 according to product design technology then, carry out two-layer or three layers be combined into and satisfy the barrier film base cloth that surface density requires.Barrier film base cloth through sulfonation evenly is grafted on the surface by sulfonic group 5, makes the sulfonated battery diaphragm of Ni-MH power cell.
Embodiment 1:
Above-mentioned composition material by weight, promptly the polyolefin sheath core fiber 1, promptly skin is that polyethylene, core are polypropylene, fibre diameter 8 μ m～10 μ m, length 38mm, content 80%; Zirconium oxide fibre 2, diameter 3 μ m～6 μ m, length 30mm～50mm, content 20% adopts carding machine combing moulding with above-mentioned fiber, and above-mentioned fiber alignment presents stochastic regime.Reinforce through the water thorn, 120 ℃ of hot air dries are made the single-layer septum base cloth, use aerosol mode coating adhesive 4 again, coating weight 20g/m
2Two layers compound, make the barrier film base cloth, be heated to 130 ℃ for when vacuum tank is bled the barrier film base cloth, be pressed onto desired thickness, be transported to that the sulfur trioxide with 95% carries out sulfonation in the sulphonator, surface after the sulfonation evenly is grafted with sulfonic barrier film base cloth and is transported to alkaline bath, its naoh concentration 1%, and the alkali cleaning speed control is at 10 meters/minute, again through pure water rinsing, pressure rolling oven dry, bake out temperature is controlled at 100 ℃, and 5 ‰ concentration surfactants are added in the oven dry back, and its temperature is controlled at 50 ℃, oven dry back rolling press is handled, and obtains surface density to being 70g/m
2, thickness is the sulfonated battery diaphragm of 0.18mm.
Embodiment 2:
The first above-mentioned composition material is made the barrier film base cloth by weight collocation, it is polyolefin sheath core fiber 70%, length 5mm～15mm, fibre diameter 8 μ m～10 μ m, polypropylene superfine fiber 30%, length 5mm～15mm, fibre diameter 3 μ m～4 μ m, adopt the i.e. making beating of wet papermaking moulding process, starching, moulding, oven dry, compound, make the barrier film base cloth.And then through the oversulfonate processing, (pressing the post processing mode of embodiment 1) obtains surface density to being 55g/m
2, thickness is the sulfonated battery diaphragm of 0.12mm.
Embodiment 3:
The first above-mentioned composition polyolefine fiber, its fibre length 38mm, fibre diameter 8 μ m～10 μ m adopt carding machine combing moulding, and the water thorn is reinforced, and 120 ℃ of hot air dries are made the single-layer septum base cloth, use aerosol mode coating adhesive again, coating weight 40g/m
2, two layers compound, makes the barrier film base cloth, presses the post processing mode of embodiment 1 then, obtains surface density to being 65g/m
2, thickness is the sulfonated battery diaphragm of 0.18mm.
Embodiment 4:
In above-mentioned organic fiber 1 material in polyolefin sheath core fiber and inorfil 2 materials Zirconium oxide fibre by weight the collocation make base cloth, promptly the polyolefin sheath core fiber 80%, its length 5mm～15mm, fibre diameter 8 μ m～10 μ m; Zirconium oxide fibre 20%, length 5mm～15mm, fibre diameter 3 μ m～6 μ m.Adopt the i.e. making beating of wet papermaking moulding process, starching, moulding, oven dry, compound, make the barrier film base cloth, press the post processing mode of embodiment 1 then, obtain surface density to being 6g/m
2, thickness is the sulfonated battery diaphragm of 0.18mm.
Adopt above-mentioned batching mode, battery diaphragm performance index such as the following table made:
Claims (3)
1. sulfonated battery diaphragm, the sulfonic group of being handled by barrier film base cloth and outer surface sulfonation thereof (5) is grafted on surface composition equably, it is characterized in that the barrier film base cloth is by organic fiber (1) and inorfil (2) random alignment, be full of metal oxide (3) and organic bond (4) between the fiber and form the single-layer septum base cloth, by the bonding one-tenth barrier film of two-layer above single-layer septum base cloth base cloth.
2. according to the described sulfonated battery diaphragm of claim 1, it is characterized in that organic fiber (1) is a polyolefine fiber, the polyolefin sheath core fiber, be that skin is a polyethylene, core is a polypropylene, and polypropylene superfine fiber, and fibre diameter is that 3 μ m～15 its length of μ m are in 5mm～51mm scope.
3. according to the described sulfonated battery diaphragm of claim 1, it is characterized in that inorfil (2) is Zirconium oxide fibre, titanium dioxide fiber, magnesia fibers, fibre diameter is nano level or micron-sized, fibre length in 2mm～51mm scope, Zirconium oxide fibre preferably.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009203524605U CN201689929U (en) | 2009-12-30 | 2009-12-30 | Sulfonated battery diaphragm |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009203524605U CN201689929U (en) | 2009-12-30 | 2009-12-30 | Sulfonated battery diaphragm |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN201689929U true CN201689929U (en) | 2010-12-29 |
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ID=43378207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009203524605U Expired - Fee Related CN201689929U (en) | 2009-12-30 | 2009-12-30 | Sulfonated battery diaphragm |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102496464A (en) * | 2011-12-09 | 2012-06-13 | 莱州联友金浩新型材料有限公司 | Super capacitance battery diaphragm, preparing method thereof and application thereof |
| US10141558B2 (en) | 2013-08-28 | 2018-11-27 | Byd Company Limited | Separator for lithium-ion battery and method for preparing the same |
-
2009
- 2009-12-30 CN CN2009203524605U patent/CN201689929U/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102496464A (en) * | 2011-12-09 | 2012-06-13 | 莱州联友金浩新型材料有限公司 | Super capacitance battery diaphragm, preparing method thereof and application thereof |
| US10141558B2 (en) | 2013-08-28 | 2018-11-27 | Byd Company Limited | Separator for lithium-ion battery and method for preparing the same |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20101229 Termination date: 20131230 |