CN104577011B - A kind of battery diaphragm reinforcing material - Google Patents
A kind of battery diaphragm reinforcing material Download PDFInfo
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- CN104577011B CN104577011B CN201410826772.0A CN201410826772A CN104577011B CN 104577011 B CN104577011 B CN 104577011B CN 201410826772 A CN201410826772 A CN 201410826772A CN 104577011 B CN104577011 B CN 104577011B
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
Abstract
The present invention provides a kind of battery diaphragm reinforcing material, is made up of following components：Aramid short fiber：30%~95% parts by weight；Aramid fiber fibrid：5%~70% parts by weight；Described aramid short fiber is aramid fiber 1313 or Fanglun l414 fiber, and length is 6 ± 3mm, and fibre number is 1.2~3.2dtex；Described aramid fiber fibrid is aramid fiber 1313 fibrid or Fanglun l414 fibrid, and beating degree is 20~85 ° of SR.The material of the present invention uses between being placed in various battery diaphragms, and compared to the plastic battery barrier film of exclusive use traditional before, the heat resistance and chemical stability that with the addition of the battery diaphragm of the reinforcing material all increase.
Description
Technical field
The present invention relates to ion battery field, and in particular to the barrier film reinforcing material of ion battery.
Background technology
Since in the early 1990s, Sony (SONY) company successfully develops lithium battery, lithium ion battery is with its energy
Density is high, service life cycle is long and voltage height etc. is excellent electrical property and obtain rapid development.Widely at present
Applied to electronics fields such as mobile phone, portable computer, camera, video cameras, and the field applied still constantly is being expanded
Among exhibition.Lithium ion battery is made up of both positive and negative polarity, electrolyte and barrier film.Wherein, battery diaphragm refers in anode and negative pole
Between one layer of diaphragm material, be part very crucial in battery, have a direct impact to battery security and cost, it is mainly made
With being：Isolation positive and negative electrode simultaneously is allowed to directly to contact, and the ion allowed in electrolyte solution passes freely through between both positive and negative polarity.Electricity
The ionic conductivity of pond barrier film is directly connected to the overall performance of battery, and it, which isolates the effect of positive and negative electrode, makes battery excessive
The rise of electric current can be limited in the case of charging or temperature are elevated, prevents battery short circuit from setting off an explosion, there is the self-closing guarantor of micropore
Shield acts on, and plays a part of safeguard protection to battery user and equipment.
At present, barrier film with the preparation method of microporous barrier be divided into dry method (fusion drawn, MSCS) and wet method (Thermal inactive,
TIPS) two kinds of technologies.Above two material of preparing is the polyolefin plastics such as polyethylene, polypropylene, and its heat resistance is poor, serious shadow
Application of the battery diaphragm in wider field is rung, with the development of the high capacity cells such as lithium-ion-power cell, commodity
Change the temperature tolerance of polyalkene diaphragm and the limitation of gas permeability and significant threat is formed to the security performance of battery.Patent
It is a kind of with aramid fiber superbhort fiber (＜ 1.5mm) and heavy to be described in 201010204780.3 " battery diaphragms based on aramid fiber "
The battery diaphragm and its production method of fiber composition are analysed, but because quantitative and thickness is higher, therefore limit its application.Specially
A kind of sharp 201210425855.X " high-temperature resistant aromatic polysulfonamide base lithium ion battery diaphragm " describes one kind with aromatic polysulfonamide
For the battery diaphragm of matrix, but its industrialized production is restricted due to it using the production method of Static Spinning.Patent
201410372541.7 " the heavy-duty battery barrier films that aramid fiber is formed " describe one kind with PPTA
For the battery diaphragm of main material, but which are added materials such as pyridine, esters, potassium bichromates, which has limited its application.
In summary, existing aramid fiber battery diaphragm technology is in actual use, it is clear that there is inconvenience and defect, so having
Necessity is improved.
The content of the invention
For disadvantages described above, it is an object of the present invention to provide a kind of battery being placed between multi-layer cell barrier film every
Film reinforcing material, the battery diaphragm reinforcing material based on aramid short fiber, with addition of aramid fiber fibrid and Fanglun slurry cake
Manufacture paper with pulp and form, the material has more excellent combination property, i.e., excellent heat resistance, high intensity, fatigue durability, low change in itself
The advantages that shape, fire resistant flame retardant performance, resistance to chemical corrosion.
Another object of the present invention is a kind of lithium ion battery using battery diaphragm reinforcing material of the present invention of offer.
The technical scheme is that：
A kind of battery diaphragm reinforcing material being placed between multi-layer cell barrier film, the battery diaphragm reinforcing material is by following
Component is made：
Aramid short fiber：30%~95% parts by weight；
Aramid fiber fibrid：5%~70% parts by weight；
Wherein, the length of the aramid short fiber is 6 ± 3mm.
Further, above-mentioned battery diaphragm reinforcing material is preferably made up of following components：
Aramid short fiber：50%~90% parts by weight；
Aramid fiber fibrid：10%~50% parts by weight；
Further, above-mentioned aramid short fiber is selected from aramid fiber 1313 or Fanglun l414 fiber；Described aramid fiber sinks
Analysis fiber is selected from aramid fiber 1313 fibrid or Fanglun l414 fibrid.
Term " fibrid " specifically described herein is different from " pulp ", refers to that substantially two-dimensional film shape is short grained thin
Divide polymeric articles, it is with 100~1000 μm of length and width and 0.1~1 μm of thickness.Generally by making polymer molten
Liquid is flowed in the coagulating bath of the liquid immiscible with the solvent of the solution to be prepared.Polymer solution flow is coagulated in polymer
Gu when by strenuous shearing forces and turbulent flow influenceed.Its prepare method detailed be：The amide resin solution of certain viscosity is defeated
Deliver in precipitation machine, solidify polymer using controllable solidification composition, 4000~8000rpm of rotor speed of precipitation machine,
The shearing force of the good quality fibrid of suitable papermaking has been produced under high rotating speed, has separated out the fibre of the tiny film strip of two dimension
Dimension, finally by washing, after mashing is refined, obtain aligning fibrid slurry entirely.By mashing, make the fiber being intertwined
Discongest out, and add the specific surface area of fibrid, and then enhance interfibrous bond energy.The fibrid quality of preparation
Quality, the mechanical strength of synthetic paper will be directly influenced.
Term " pulp " refers to the fibrous material for having fine handle and having fine handle and the fibril generally extended from fine handle, wherein fine
Handle is usually cylindricality and a diameter of about 10~50 μm, and fibril is the fine, soft fur hair-like component being generally connected with fine handle, its diameter
One or several μm of only some points, and length is about 10 to 100 μm.
The battery diaphragm reinforcing material of the present invention uses simultaneously with traditional battery diaphragm, can be positioned over powerful lithium electricity
Between the barrier film of pond, the mechanical isolation function of improving battery plus-negative plate can be realized, improves its security performance.
It is main to include system it is a further object to provide a kind of preparation method of above-mentioned battery diaphragm reinforcing material
Starch dispensing, shaping of manufacturing paper with pulp, dry the simultaneously step such as high temperature hot rolling.Wherein, in slurrying blending process, by aramid fiber (aramid fiber
1313 fibers or Fanglun l414 fiber) prescind to 6 ± 3mm or so, in water evacuation come standby；By aramid fiber fibrid
(1313 fibrids or 1414 fibrids) are evacuated and are beaten standby for 20 ° of SR~85 ° SR to the beating degree of slurry.Will system
After the slurry obtained is uniformly mixed according to a ratio, shaped using cylinder mould machine.When preparing battery diaphragm reinforcing material of the present invention, because of aramid fiber
The hydrophobicity of fiber, it is extremely difficult scattered in water, in order to promote aramid fiber scattered in water, quality is added in mixed slurry
Fraction is 0.2%~0.8% deflocculant, increases resistance of the fiber in underwater exercise, alleviates intertexture of the fiber in water and twines
It is poly- around wadding, so as to reach the purpose for the evenness for improving battery diaphragm reinforcing material.
Manufacture paper with pulp shaping stage, using cylinder mould machine.It is impartial then through head box that slurry is equal through slurry-stablizing case regulation slurry pressure
Even is dispersed on former, and unnecessary slurry overflow, which returns to copy in forebay, to be recycled.After slurry shaping, delivered to through woollen blanket
Squeezing, removes unnecessary moisture, then batched after drying cylinder is dried.
In high temperature hot rolling stage, using close to the point hot rolling of fibrid condensation temperature, hot rolled machine single hot-roll forming, temperature
Degree between 230 DEG C~320 DEG C, pressure between 2~7Mpa, ensure the density of battery diaphragm reinforcing material 0.30~
Between 0.67g/ ㎡, thickness is between 0.02mm~0.05mm.
The battery diaphragm reinforcing material of the present invention combines the various advantages of aramid fiber, fibrid raw material, is prepared for
A kind of battery diaphragm reinforcing material being prepared by the aramid fiber and aramid fiber fibrid of different ratio, can be placed in various
Used between battery diaphragm, compared to the plastic battery barrier film of exclusive use traditional before, with the addition of the battery of the reinforcing material
The heat resistance and chemical stability of barrier film all increase.
Embodiment
In order that the purpose of the present invention, technical scheme and advantage are more clear, with reference to following embodiment,
The present invention is described in more detail.It should be appreciated that specific embodiment described herein is only explaining this hair
It is bright, it is not intended to limit the present invention.
Material source：It is commercially available
Fanglun l414 fiber：Japanese Di Ren companies production；
Fanglun l414 fibrid：Japanese Di Ren companies production；
Aramid fiber 1313：The color gorgeous production in Xinhui of Guangdong Province；
Aramid fiber 1313 fibrid：The logical Chemical Manufacture of Guanghan fortune.
【Embodiment 1】The preparation of battery diaphragm reinforcing material
The component proportion of the battery diaphragm reinforcing material of the present embodiment is as follows：
Fanglun l414 fiber (4mm)：55% mass parts；
Fanglun l414 fibrid：45% mass parts；
Specifically preparation method is：
Fanglun l414 fiber is evacuated by 0.25% mass fraction concentration with water conservancy pulper it is standby, then by Fanglun l414
Fibrid is evacuated by the concentration of 2% mass fraction with water conservancy pulper, and passes through the further mill of disc mill to beating degree
For 70 ° of SR slurry.Obtained slurry is mixed with water by proportioning described above in slurry commanding tank again, in the process of manufacturing paper with pulp
In, the polyethylene glycol oxide that mass fraction is 0.6%, then Cylinder mould formation are added, by wet pressing, cylinder dried, batches and deposits in rolls
Put, then hot rolled machine high temperature hot-roll forming, temperature is 290 DEG C, pressure 4Mpa, can carry out follow-up trimming processing, obtain
As a result it is as shown in table 1：
The testing result of the battery diaphragm reinforcing material of table 1
【Embodiment 2】It is prepared by battery diaphragm reinforcing material
The component proportion of the battery diaphragm reinforcing material of the present embodiment is as follows：
Aramid fiber 1313 (8mm):65% mass parts；
Fanglun l414 fibrid：35% mass parts；
Specifically preparation method is：
Aramid fiber 1313 is evacuated by 0.4% mass fraction concentration with water conservancy pulper it is standby, then by Fanglun l414
Fibrid is evacuated by the concentration of 2% mass fraction with water conservancy pulper, and passes through the further mill of disc mill to beating
Spend for 75 ° of SR slurry.Obtained slurry is mixed with water in slurry commanding tank by said ratio again, in the process of manufacturing paper with pulp
In, the polyethylene glycol oxide that mass fraction is 0.6%, then Cylinder mould formation are added, by wet pressing, cylinder dried, batches and deposits in rolls
Put, then hot rolled machine high temperature hot-roll forming, temperature is 260 DEG C, pressure 3Mpa, can carry out follow-up trimming processing, obtain
As a result it is as shown in table 2：
The testing result of the present embodiment battery diaphragm reinforcing material of table 2
【Embodiment 3】
The component proportion of the battery diaphragm reinforcing material of the present embodiment is as follows：
Aramid fiber 1313 (6mm):75% mass parts；
Aramid fiber 1313 fibrid：25% mass parts；
Specifically preparation method is：
Aramid fiber 1313 is evacuated by 0.4% mass fraction concentration with water conservancy pulper it is standby, then by aramid fiber 1313
Fibrid is evacuated by 1.3% mass fraction concentration with water conservancy pulper, and passes through the further mill of disc mill to beating
Spend for 55 ° of SR slurry.Obtained slurry is mixed with water in slurry commanding tank by said ratio again, in the process of manufacturing paper with pulp
In, the polyethylene glycol oxide that mass fraction is 0.6%, then Cylinder mould formation are added, by wet pressing, cylinder dried, batches and deposits in rolls
Put, then hot rolled machine high temperature hot-roll forming, temperature are 250 DEG C, pressure 5Mpa, can carry out follow-up trimming processing, obtain
As a result it is as shown in table 3：
The testing result of the present embodiment battery diaphragm reinforcing material of table 3
【Embodiment 4】
The component proportion of the battery diaphragm reinforcing material of the present embodiment is as follows：
Fanglun l414 fiber (6mm):85% mass fraction；
Aramid fiber 1313 fibrid：15% mass fraction；
Specifically preparation method is：
Above-mentioned Fanglun l414 fiber is evacuated by 0.3% mass fraction concentration with water conservancy pulper it is standby, then by virtue
The concentration of the mass fraction of the fibrid 2% of synthetic fibre 1313 is evacuated with water conservancy pulper, and by the further mill of disc mill extremely
Beating degree is 70 ° of SR slurry.Obtained slurry is mixed with water in slurry commanding tank by said ratio again, manufactured paper with pulp
Cheng Zhong, the polyethylene glycol oxide that mass fraction is 0.8%, then Cylinder mould formation are added, by wet pressing, cylinder dried, batched coiled
Storage, then hot rolled machine high temperature hot-roll forming, temperature are 300 DEG C, pressure 5Mpa, can carry out follow-up trimming processing, obtain
Result it is as shown in table 4：
The testing result of the present embodiment battery diaphragm reinforcing material of table 4
【Embodiment 5】
Use the battery and the battery of tradition exclusive use lithium ion battery separator of battery diaphragm reinforcing material of the present invention
Compare.
The battery diaphragm reinforcing material prepared by above example 1-4 is used cooperatively with common battery diaphragm respectively,
Use lamination order that embodiment battery is made for the mode of " positive pole-barrier film-battery diaphragm reinforcing material-negative pole ", then use
Reference examples battery is made for the mode of " positive pole-barrier film-negative pole " in traditional lamination order, carries out contrast test.
Capacity and cycle performance test：According to QC/T 743-2006《Lithium-ions battery used for electric vehicle》Tested.
As a result show, add made of the battery of battery diaphragm reinforcing material of the present invention and traditional exclusive use common batteries barrier film just
Often production battery is compared, and the two battery capacity and cycle performance test are all normal, as shown in table 5 respectively.
Table 5a battery capacities, cycle performance test data (1)
Table 5b battery capacities, cycle performance test data (2)
Security test-pin prick test：According to QC/T 743-2006《Lithium-ions battery used for electric vehicle》Tried
Test.Two Battery pack is subjected to security performance detection, nail thorn experiment is carried out first, nail thorn negative lug position, measures temperature rise；Such as
Without significantly temperature rise or generation of smoldering, change nail thorn positive pole ear position, as a result show：Traditional exclusive use plastic battery barrier film is made
Normal production battery nail thorn experiment when there is Ignition Phenomena；And add the battery nail thorn of battery diaphragm reinforcing material of the present invention
Do not occur Ignition Phenomena during experiment.
6 security tests of table-pin prick test
Security test-elevated temperature impact test：According to QC/T 743-2006《Lithium-ions battery used for electric vehicle》Carry out
Experiment.Two Battery pack is subjected to high temperature impact test, after standard charging, battery is put into baking box, baking box is per minute
5 ± 2 DEG C of heating is until 140 DEG C, and constant temperature 30min, as a result as follows at such a temperature：
7 security tests of table-elevated temperature impact test
As can be seen here, modeling is used alone higher than tradition in the security performance for adding the battery of battery diaphragm reinforcing material of the present invention
Expect the battery of battery diaphragm.
The more existing battery diaphragm material of the present invention, it is long fibre to change chopped fiber, and change pulp is fibrid, together
When without using the third raw material, product only use two kinds of raw material, greatly reduce product and production technology complexity and
Unstability., using after the compatibility of long fibre and fibrid, the quantitative of pattern, thickness decline for it, gas permeability lifting, security
Decline is had no, this is more beneficial for actual application.
Claims (4)
1. a kind of battery diaphragm reinforcing material, it is characterised in that by the aramid fiber 1313 and 35% mass parts of 65% mass parts
Fanglun l414 fibrid manufacture paper with pulp and be made, wherein the length of the aramid fiber 1313 is 8mm；
The pulping method is：
Aramid fiber 1313 is evacuated by 0.4% mass fraction concentration with water conservancy pulper it is standby, then by Fanglun l414 precipitating
Fiber is evacuated by the concentration of 2% mass fraction with water conservancy pulper, and is by the further mill of disc mill to beating degree
75 ° of SR slurry；Again by obtained slurry by the aramid fiber 1313 of 65% mass parts and the Fanglun l414 of 35% mass parts
Fibrid is mixed with water in slurry commanding tank, during manufacturing paper with pulp, adds the polyethylene glycol oxide that mass fraction is 0.6%,
Cylinder mould formation again, by wet pressing, cylinder dried, crimp coiled storage, then hot rolled machine high temperature hot-roll forming, temperature 260
DEG C, pressure 3Mpa, carry out follow-up trimming processing.
2. battery diaphragm reinforcing material as claimed in claim 1, it is characterised in that the thickness of the battery diaphragm reinforcing material
For 0.02mm~0.05mm, quantification of 10~30g/m2。
3. battery diaphragm reinforcing material as claimed in claim 1, it is characterised in that the density of the battery diaphragm reinforcing material
For 0.30~0.67g/m2, porosity is 30~80%, 1~3s of air permeability Gurley values.
4. a kind of lithium ion battery, it is characterised in that claim 1 institute is further included between the battery diaphragm of the battery
The battery diaphragm reinforcing material stated.
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| CN109004149B (en) * | 2017-06-07 | 2021-08-10 | 银隆新能源股份有限公司 | Method for manufacturing lithium ion battery diaphragm |
| CN107663807A (en) * | 2017-11-22 | 2018-02-06 | 西南大学 | A kind of method for lifting aramid insulating paper mechanical performance and hydrophobic oleophobic performance |
| CN110828755B (en) * | 2018-08-10 | 2022-09-16 | 微宏动力系统（湖州）有限公司 | Composite diaphragm, preparation method thereof and secondary battery |
| CN110176569A (en) * | 2019-05-17 | 2019-08-27 | 天津工业大学 | A kind of inorganic micro-nano alumina fibre battery diaphragm |
| CN115207559B (en) * | 2022-06-28 | 2024-03-22 | 陈克复 | High-performance aramid fiber diaphragm and preparation method and application thereof |
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|---|---|---|---|---|
| JP3142692B2 (en) * | 1992-09-11 | 2001-03-07 | 帝人株式会社 | Battery separator and method for producing the same |
| CN101872852A (en) * | 2010-06-21 | 2010-10-27 | 深圳市龙邦新材料有限公司 | Preparation method of cell diaphragm based on aramid fiber |
| CN103298998A (en) * | 2011-01-04 | 2013-09-11 | 帝人芳纶有限公司 | Paper comprising microfilaments |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101867030A (en) * | 2010-06-21 | 2010-10-20 | 深圳市龙邦新材料有限公司 | Battery diaphragm based on aramid fibre |
| CN103943806B (en) * | 2014-05-06 | 2016-02-24 | 烟台民士达特种纸业股份有限公司 | A kind of battery diaphragm be made up of aramid fiber and preparation method thereof |
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- 2014-12-25 CN CN201410826772.0A patent/CN104577011B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3142692B2 (en) * | 1992-09-11 | 2001-03-07 | 帝人株式会社 | Battery separator and method for producing the same |
| CN101872852A (en) * | 2010-06-21 | 2010-10-27 | 深圳市龙邦新材料有限公司 | Preparation method of cell diaphragm based on aramid fiber |
| CN103298998A (en) * | 2011-01-04 | 2013-09-11 | 帝人芳纶有限公司 | Paper comprising microfilaments |
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Effective date of registration: 20211013 Address after: 341900 Futian industrial district, Dingnan Industrial Park, Ganzhou City, Jiangxi Province Patentee after: Ganzhou Longbang Material Technology Co.,Ltd. Address before: 518000 Shenzhen Nanshan High-tech Zone, Shenzhen City, Guangdong Province, 11 902 Rooms A105, Shenzhen Software Park, No. 1 Science and Technology Secondary Road (Phase 2) Patentee before: LONGPONT Co.,Ltd. |
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