CN102544414B - A kind of preparation method of high-temperature-resistant safe diaphragm - Google Patents
A kind of preparation method of high-temperature-resistant safe diaphragm Download PDFInfo
- Publication number
- CN102544414B CN102544414B CN201210034723.4A CN201210034723A CN102544414B CN 102544414 B CN102544414 B CN 102544414B CN 201210034723 A CN201210034723 A CN 201210034723A CN 102544414 B CN102544414 B CN 102544414B
- Authority
- CN
- China
- Prior art keywords
- preparation
- stretch
- aluminium oxide
- temperature
- nano aluminium
- 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.)
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 210000002469 basement membrane Anatomy 0.000 claims abstract description 13
- 239000012982 microporous membrane Substances 0.000 claims abstract description 12
- 238000012805 post-processing Methods 0.000 claims abstract description 6
- 238000004513 sizing Methods 0.000 claims abstract description 6
- -1 polypropylene Polymers 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 208000013201 Stress fracture Diseases 0.000 claims description 5
- 230000007547 defect Effects 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 3
- 230000006641 stabilisation Effects 0.000 abstract 1
- 230000004888 barrier function Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 210000004379 membrane Anatomy 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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
- Y02E60/10—Energy storage using batteries
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a kind of preparation method of high-temperature-resistant safe diaphragm, realized by following step：(1) nano aluminium oxide is carried out into surface preparation in the titanate esters of tetra isopropyl two；(2) pretreated nano aluminium oxide is uniformly blended into polymer, addition is the 0.3%~3.0% of polymer quality, is well mixed post-processing into basement membrane；(3) in 5~155 DEG C, draw speed it is 0.1~30m/min by basement membrane, draw ratio is to carry out cold stretch and hot-stretch successively under conditions of 1~5 times, forms microporous membrane；(4) microporous membrane carries out negative stretch, and 100~165 DEG C of sizings form the uniform micropore high temperature resistant products in space.Product of the present invention can prevent inorganic particulate from coming off, and strengthen diaphragm stabilisation and mechanical property, than using outside coating method reduction production cost.
Description
Technical field
The present invention relates to a kind of preparation method of high-temperature-resistant safe diaphragm, belong to lithium ion battery every
Technical field of membrane.
Background technology
Lithium battery has become the most frequently used a kind of battery in daily life, and blowout disk is lithium electricity
Its seepage is prevented outside pond and ensures the membrane structure of its insulation.
In the preparation, in order to strengthen its performance, meeting is in common barrier film for existing blowout disk
Add inorganic particulate, its preparation method to be typically the coated inorganic particle outside common diaphragm, lack
Point is that inorganic particulate easily comes off, and production technology is loaded down with trivial details.The inorganic particulate of addition have titanium dioxide,
Silica, this inorganic particulate stability is general, easy with polymer and lithium battery electrolytes
React or dissolve.Summarize above-mentioned, it has the disadvantage that inorganic particulate easily comes off, product is stablized
Performance is not high, barrier film poor mechanical property, coating mode production cost it is high.This explanation is existing
Barrier film be required to improve in the addition of inorganic raw material and the aspect of technique productions two.
Also have in the prior art using aluminium as inorganic particulate, the inorganic particulate of selection is fine aluminium,
This preparation method generally needs steam to heat generation aluminum oxide, and relatively costly, membrane structure is unstable
It is fixed；In addition, during selective oxidation aluminium is as the preparation method of inorganic particulate, aluminum oxide does not have in itself
By treatment, however it remains stability problem not high.
The content of the invention
The present invention provides a kind of preparation method of high-temperature-resistant safe diaphragm, from the treatment of inorganic particulate
Improved with process aspect, using surface treated nano aluminium oxide as inorganic grain
Son, and prepared in the form of generation colloid is mixed into, make product resistance to elevated temperatures stronger, surely
Qualitative high, good mechanical properties.
The present invention is realized by following technical scheme：
A kind of preparation method of high-temperature-resistant safe diaphragm, is realized by following step：
(1) nano aluminium oxide is carried out into surface preparation in the titanate esters of tetra isopropyl two, specifically
Be by the 1~4% of the nano aluminium oxide quality titanate esters of tetra isopropyl two and polypropylene with receive
Rice aluminum oxide is mixed, and 20min is vulcanized under the conditions of 120~145 DEG C, then in 150 DEG C of bars
Post-cure 3h under part；
(2) by pretreated nano aluminium oxide, particle diameter is 20nm~50nm, is uniformly blended into
In polymer, addition for polymer quality 0.3%~3.0%, be well mixed post-processing into
Basement membrane；
(3) basement membrane is carried out into cold stretch under 5~100 DEG C and 1~5 times of stretching ratio, is seen
Examine to shish-kebab structure rupture, stop when forming micro-fractures defect；Cold stretch terminate after 90~
155 DEG C, hot-stretch is carried out under 1~4 times of stretching ratio, terminated after forming microporous membrane structure；
(4) microporous membrane carries out negative stretch, 100~165 DEG C of sizings, reach porosity 35~
60%, form the uniform micropore high temperature resistant products in space.
Preprocessing process in the step (1) is in order to nano alumina particles and polymer
Between have good compatibility, good dispersity can be formed.
Polymer in the step (2) is the one kind in polyethylene or polypropylene；By raw material
After mixing, the extruding process thereof that basement membrane is commonly used for those skilled in the art is processed into.
The speed of cold stretch is 0.1~30.0m/min in the step (3).
The time of heat treatment is 5min~10h in the step (4).
Beneficial effects of the present invention are：The inorganic particulate material that the present invention is selected is nano oxidized
Aluminium, belongs to a kind of ceramic material, high temperature resistant, stable chemical performance, not with polymer and lithium electricity
Pond electrolyte reacts or dissolves.Compared with titanium dioxide and silica dioxide granule, with more
The excellent ability for hindering electronics conduction, can reduce inside battery leakage under battery normal condition
Electricity, can prevent both positive and negative polarity short circuit under the emergency that battery runs into high temperature or ambient pressure,
By the way of being mixed into inside barrier film by the inorganic particulate of surface preparation, in combination property
It is substantially higher in the mode of exterior coated inorganic particle, reason has three：One can be prevented from
Inorganic particulate comes off, and strengthens the stability of barrier film, and two is the mechanical property for strengthening barrier film, and three are
Than outside coating method reduction production cost.High temperature safe barrier film high temperature resistant temperature of the invention can
With 170~180 DEG C significantly.
Specific embodiment
With reference to embodiments, the present invention will be further described.
Embodiment 1
Using polyethylene 100kg as raw material.
(1) nano aluminium oxide is carried out into surface preparation in the titanate esters of tetra isopropyl two；
(2) particle diameter that will be screened is for 20nm~50nm, pretreated nano aluminium oxide are uniform
It is mixed into polymer, addition is the 0.3kg of polymer quality, is well mixed co-extrusion post-processing
Into basement membrane；
(3) basement membrane is carried out into cold stretch under 5 DEG C and 5 times of stretching ratio, draw speed is
0.25m/min, observation stops to shish-kebab structure rupture when forming micro-fractures defect；It is cold drawn
Stretch after terminating at 90 DEG C, hot-stretch is carried out under 2 times of stretching ratio, form microporous membrane structure
After terminate；
(4) microporous membrane carries out negative stretch, and 100 DEG C of sizing 10min form space uniform
Micropore high temperature resistant products, it is desirable to which porosity is 35%.
Embodiment 2
Using polyethylene 100kg as raw material.
(1) nano aluminium oxide is carried out into surface preparation in the titanate esters of tetra isopropyl two；
(2) particle diameter that will be screened is for 20nm~50nm, pretreated nano aluminium oxide are uniform
Be mixed into polymer, addition for polymer quality 3kg, be well mixed co-extrusion post-processing into
Basement membrane；
(3) basement membrane is carried out into cold stretch, draw speed under 65 DEG C and 2 times of stretching ratio
It is 10m/min, observation stops to shish-kebab structure rupture when forming micro-fractures defect；It is cold drawn
Stretch after terminating at 120 DEG C, hot-stretch is carried out under 1 times of stretching ratio, form microporous membrane knot
Terminate after structure；
(4) microporous membrane carries out negative stretch, and 165 DEG C of sizing 3h form the uniform micropore in space
High temperature resistant products, it is desirable to which porosity is 45%.
Embodiment 3
Using polyethylene 100kg as raw material.
(1) nano aluminium oxide is carried out into surface preparation in the titanate esters of tetra isopropyl two；
(2) particle diameter that will be screened is for 20nm~50nm, pretreated nano aluminium oxide are uniform
Be mixed into polymer, addition for polymer quality 1kg, be well mixed co-extrusion post-processing into
Basement membrane；
(3) basement membrane is carried out into cold stretch, draw speed under 100 DEG C and 1 times of stretching ratio
It is 30m/min, observation stops to shish-kebab structure rupture when forming micro-fractures defect；It is cold drawn
Stretch after terminating at 155 DEG C, hot-stretch is carried out under 3 times of stretching ratio, form microporous membrane knot
Terminate after structure；
(4) microporous membrane carries out negative stretch, and 125 DEG C of sizing 10h form space uniformly micro-
Hole high temperature resistant products, it is desirable to which porosity is 60%.
The product of above-described embodiment 1-3 carries out high temperature resistant test, its high temperature resistant test result difference
For 170 DEG C, 180 DEG C and 178 DEG C.
Claims (4)
1. a kind of preparation method of high-temperature-resistant safe diaphragm, it is characterised in that realized by following step：
(1) nano aluminium oxide is carried out into surface preparation in tetra isopropyl titanate, specially tetra isopropyl titanate and polypropylene are mixed with nano aluminium oxide, vulcanize 20min under the conditions of 120~145 DEG C, the post-cure 3h under the conditions of 150 DEG C again, the tetra isopropyl titanate of the addition and polyacrylic quality sum are the 1~4% of the nano aluminium oxide quality；
(2) by pretreated nano aluminium oxide, particle diameter is 20nm~50nm, is uniformly blended into polymer, and addition is the 0.3%~3.0% of polymer quality, is well mixed post-processing into basement membrane；
(3) basement membrane is carried out into cold stretch under 5~100 DEG C and 1~5 times of stretching ratio, observation stops to shish-kebab structure rupture when forming micro-fractures defect；Cold stretch terminate after at 90~155 DEG C, carry out hot-stretch under 1~4 times of stretching ratio, terminate after forming microporous membrane structure；
(4) microporous membrane carries out negative stretch, and 100~165 DEG C of sizings reach porosity 35~60%, form the uniform micropore high temperature resistant products in space.
2. a kind of preparation method of high-temperature-resistant safe diaphragm as claimed in claim 1, it is characterised in that the polymer in the step (2) is the one kind in polyethylene or polypropylene.
3. a kind of preparation method of high-temperature-resistant safe diaphragm as claimed in claim 1, it is characterised in that the speed of cold stretch is 0.1~30.0m/min in the step (3).
4. a kind of preparation method of high-temperature-resistant safe diaphragm as claimed in claim 1, it is characterised in that the time of heat treatment is 5min~10h in the step (4).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210034723.4A CN102544414B (en) | 2012-02-16 | 2012-02-16 | A kind of preparation method of high-temperature-resistant safe diaphragm |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210034723.4A CN102544414B (en) | 2012-02-16 | 2012-02-16 | A kind of preparation method of high-temperature-resistant safe diaphragm |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102544414A CN102544414A (en) | 2012-07-04 |
| CN102544414B true CN102544414B (en) | 2017-06-20 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201210034723.4A Expired - Fee Related CN102544414B (en) | 2012-02-16 | 2012-02-16 | A kind of preparation method of high-temperature-resistant safe diaphragm |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110165129A (en) * | 2019-05-28 | 2019-08-23 | 大连中比动力电池有限公司 | Anti-oxidant high puncture strength dry method diaphragm of one kind and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101695869B (en) * | 2009-10-30 | 2012-05-30 | 沧州明珠塑料股份有限公司 | Preparation method of polyolefin microporous film |
| CN102064299A (en) * | 2010-12-25 | 2011-05-18 | 佛山塑料集团股份有限公司 | Polyolefin multi-layer porous diaphragm for lithium ion battery and preparation method thereof |
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| CN102544414A (en) | 2012-07-04 |
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Owner name: FAN JIANGUO Free format text: FORMER OWNER: NANTONG TIANFENG NEW ELECTRONIC MATERIALS CO., LTD. Effective date: 20130827 |
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Effective date of registration: 20130827 Address after: 226000 Rugao City, Jiangsu province Bai Pu Zhen Pu Tang Road No. 54 Applicant after: Fan Jianguo Address before: 226000, No. 14, No. 21 Road, Sutong science and Technology Industrial Park, Jiangsu, Nantong Applicant before: NANTONG TIANFENG NEW ELECTRONIC MATERIALS Co.,Ltd. |
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Effective date of registration: 20181225 Address after: 362000 Shishi Avenue, Xiangzhi Town, Shishi City, Quanzhou City, Fujian Province, near Shixiang Second Road Patentee after: Shishi Shentai New Material Technology Co.,Ltd. Address before: 343000 Annwa Avenue, Anfu county industrial park, Ji'an, Jiangxi Patentee before: Jiangxi Zhongtai new Mstar Technology Ltd. |
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