CN109935757A - A kind of preparation method of composite lithium ion cell diaphragm - Google Patents
A kind of preparation method of composite lithium ion cell diaphragm Download PDFInfo
- Publication number
- CN109935757A CN109935757A CN201811434060.9A CN201811434060A CN109935757A CN 109935757 A CN109935757 A CN 109935757A CN 201811434060 A CN201811434060 A CN 201811434060A CN 109935757 A CN109935757 A CN 109935757A
- Authority
- CN
- China
- Prior art keywords
- lithium ion
- cotton fiber
- sodium alginate
- preparation
- ion cell
- 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.)
- Granted
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
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to lithium ion battery fields, more particularly to a kind of preparation method of composite lithium ion cell diaphragm, including following preparation step: 1) cotton fiber and sodium alginate being dissolved in sodium hydroxide/urea mixed solution, glutaraldehyde solution is added, aquagel membrane is prepared in film；2) its gel mould is dried to obtain using supercritical carbon dioxide extracting；3) polyisobornyl methacrylate is coated on silicon dioxide granule；4) by silica emulsion coating in aerogel film surface；The present invention obtains imbibition rate height by the modification of glutaraldehyde using sodium alginate and cotton fiber, lyophily is strong, the big aeroge of intensity, and the silica emulsion coating by carrying out polyisobornyl methacrylate cladding on aeroge surface, so that aeroge surface will form fine and close polyisobornyl methacrylate film layer when battery temperature increases suddenly, the hole on aeroge surface is blocked, so that lithium ion battery is stopped working, increases its safety.
Description
Technical field
The present invention relates to lithium ion battery field more particularly to a kind of preparation methods of composite lithium ion cell diaphragm.
Background technique
Lithium ion battery is the secondary cell of rechargeable electric discharge type, is made of anode, cathode, diaphragm and electrolyte,
In, it is the important component of lithium ion battery that diaphragm, which is otherwise known as " the third pole " of lithium ion battery,.Its main function is
For the positive and negative polarities that insulate physical contact and caused by short circuit, furthermore act also as ion conductor, ion made to pass through diaphragm
The free shuttling between positive and negative polarities realizes insertion and deintercalation process of the lithium ion between positive and negative polarities.Therefore, diaphragm material
Quality can play conclusive effect to the basic electric property of lithium ion battery, and diaphragm not only needs to have good insulating properties,
Because having suitable pore size and porosity, however, the not only polyalkene diaphragm mechanical performance of successful commercialization is not high at present,
And heat resisting temperature is lower, environment temperature is excessively high or when battery current is excessive in battery use process, and polyalkene diaphragm is easy
By thermal softening, it is easy to cause the short circuit of lithium ion battery and explodes.
For example, a kind of one kind invention disclosed patent " improvement polyethylene lithium battery diaphragm surface in Chinese patent literature
Active method ", notification number CN104821382B, a method of improving polyethylene lithium battery diaphragm surface-active, comprising:
Modified polyolefine material is dissolved in white oil, the white oil mixture containing modified polyolefine material is obtained；By polyethylene powders with
White oil mixture containing improved polyalkene feeds double screw extruder together, obtains through metering, filtering, extrusion die and cooling device
To oil-containing slab；Oil-containing slab obtains oil-containing diaphragm through biaxial tension；Oil-containing diaphragm enters in extraction tank, will be contained using extractant
White oil in oily diaphragm extracts；Diaphragm extracted is dried using hot wind or hot-rolling, obtains dry diaphragm；Through
After horizontal drawing expanding and thermal finalization processing, winding obtains finished product diaphragm, using polyethylene as the material for preparing diaphragm in the present invention,
Since polyethylene is lower using temperature, when lithium ion battery heat release is larger, polyethylene diagrams can soften, and lose the work of barrier
With easily leading to the short circuit of battery and explode.
Summary of the invention
The present invention is to propose a kind of compound lithium ion including middle layer and upper and lower surface layer to overcome the above problem
Battery diaphragm, improves the mechanical strength of diaphragm, and assigns its heat blocking performance.
To achieve the goals above, the invention adopts the following technical scheme:
A kind of preparation of composite lithium ion cell diaphragm, including following preparation step；
(1) cotton fiber and sodium alginate are dissolved in the mixed aqueous solution of 5-10wt% sodium hydroxide and 10-15wt% urea,
5-10min is stirred at 20-30 DEG C, obtains mixed solution；
(2) at 20-30 DEG C, the glutaraldehyde water solution of 20-30wt% is added in mixed solution, after film, is placed in 50-70 DEG C
5-8h is reacted under environment, obtains cotton fiber/Sodium Alginate Hydrogel Films film；
(3) cotton fiber/Sodium Alginate Hydrogel Films film is successively submerged in deionized water and acetone and is washed, then, placed it in
In autoclave, being passed through carbon dioxide to pressure is 8.5-10Mpa, extracts 10-15h at 30-50 DEG C, is then slowly reduced
Pressure to atmospheric pressure, subsequent near room temperature obtains cotton fiber/sodium alginate aerogel film in kettle；
(4) dehydrated alcohol is dispersed by silicon dioxide granule, methacryloxy third is then added in ultrasonic disperse 30-50min
Base trimethoxy silane reacts 12-18h, after suction filtration, dries at 100-120 DEG C, obtains silane-modified silicon dioxide granule；
(5) it disperses silane-modified silicon dioxide granule in deionized water, isobornyl methacrylate is added, is then added
Neopelex, sodium bicarbonate and ammonium persulfate, are warming up to 60-80 DEG C, obtain polyisobornyl methacrylate packet
The silica lotion covered；
(6) the silica lotion of polyisobornyl methacrylate cladding carries out cotton fiber/sodium alginate aerogel film
Double spread obtains composite lithium ion cell diaphragm finished product after drying 4-8h at 50-70 DEG C.
The present invention passes through the dissolution of sodium alginate and cotton fiber, collosol and gel, glutaraldehyde cross-linking modification and overcritical two
Carbonoxide, which is dried, is successfully prepared sodium alginate/cotton fiber aeroge.In the dissolution of sodium alginate and cotton fiber, hydroxide
Sodium and urea liquid weaken the hydrogen bond in cotton fiber, destroy cotton fiber crystallization plot structure, open the free chain of cotton fiber
Section, also, carbonyl, amino isopolarity group synergistic effect and cotton fiber molecule formation hydrogen bond in solution, thus be allowed to dissolve,
Subsequently, as sodium alginate and cotton fiber are added after glutaraldehyde solution, sodium alginate and cotton fiber exist rich in hydroxyl and carboxyl
Continuous crosslinking condensation is reunited under the action of glutaraldehyde, forms the cotton fiber with network structure/Sodium Alginate Hydrogel Films film, with
Afterwards, remove gel internal residual molecule using deionized water and acetone soak, displace the decentralized medium in gel, and to its into
Row carbon dioxide abstraction gradually displaces deionized water and acetone in hydrogel, obtains cotton fiber/sodium alginate aeroge
Film, to make carbon dioxide reach postcritical state, makes it have preferable mobility and extraction in carbon dioxide abstraction
Property, the carbon dioxide in autoclave pour pressure and necessarily are greater than 8.5Mpa, and environment temperature necessarily is greater than 30 DEG C, and cotton fiber/
Sodium alginate aerogel film porosity with higher and gas permeability, also, it is modified by glutaraldehyde cross-linking, it is higher to assign it
Intensity.
Then, using the silica lotion of polyisobornyl methacrylate cladding to cotton fiber/sodium alginate airsetting
The upper and lower surface of glue film is coated, and forms polymethylacrylic acid isoborneol on cotton fiber/sodium alginate aerogel film surface
The silicon dioxide granule layer of ester cladding, is prepared composite lithium ion cell diaphragm.Due to polyisobornyl methacrylate
Glass transition temperature is 110 DEG C or so, when battery temperature increases, more than the glass transition of polyisobornyl methacrylate
When temperature, the polyisobornyl methacrylate being coated on silicon dioxide granule can gradually soften, bonding, thus in cotton fibre
Dimension/sodium alginate aerogel film surface forms one layer of fine and close film, has blocked the hole on aerogel film surface so that lithium from
Son can not be transmitted through diaphragm, and lithium ion battery is made to stop working, and prevent the contingencies such as the excessively high generation explosion of battery temperature, and
And the addition of silicon dioxide granule, cotton fiber/sodium alginate aerogel film thermal stability is also increased, effectively prevent cotton fine
Dimension/sodium alginate aerogel film is shunk when heated.
Preferably, the mass ratio of cotton fiber described in step (1) and sodium alginate is 3-5:1.
Preferably, the additional amount of glutaraldehyde described in step (2) be cotton fiber and sodium alginate quality and 0.5%-
1.5%.
Preferably, the partial size of silicon dioxide granule described in step (4) is 50-200nm.
Preferably, the volume ratio of dehydrated alcohol and methacryloxypropyl trimethoxy silane is in step (4)
100:0.5-2。
Preferably, step (5) preparation includes the quality proportioning of following components and each component are as follows: silane-modified dioxy
1-1.5 parts of SiClx particle, 100-150 parts of isobornyl methacrylate, 0.1-0.3 parts of neopelex, bicarbonate
0.05-0.1 parts of sodium, 1-1.5 parts of ammonium persulfate.
Preferably, cotton fiber described in step (3)/sodium alginate aerogel film is with a thickness of 15-25 μm.
Preferably, the cladding of silicon dioxide granule described in step (5) is with a thickness of 50-120nm.
The partial size of silicon dioxide granule and the cladding thickness of silicon dioxide granule are unsuitable too high or too low, if partial size and thickness
It spends low, is not easy to form fine and close film after the softening of polyisobornyl methacrylate on silicon dioxide granule, to can not block up
The firmly hole on aerogel film surface, and partial size and thickness are excessively high, when the silica cream of polyisobornyl methacrylate cladding
When liquid is coated on aerogel film surface, its surface hole defect can be blocked, influences its porosity.
Preferably, the silica emulsion coating thickness of the cladding of polyisobornyl methacrylate described in step (6)
It is 2-5 μm.
Therefore, the invention has the following beneficial effects: the present invention passes through changing for glutaraldehyde using sodium alginate and cotton fiber
Property obtain imbibition rate height, lyophily is strong, the big cotton fiber of intensity/sodium alginate aeroge, and by aeroge surface carry out
The silica emulsion coating of polyisobornyl methacrylate cladding, so that when battery temperature increases suddenly, aeroge table
Face will form fine and close polyisobornyl methacrylate film layer, blocks the hole on aeroge surface, stops lithium ion battery
Work, increases its safety.
Specific embodiment
The present invention program is more clearly and completely described below in conjunction with specific embodiment, it is clear that described implementation
Example is only a part of the embodiment of the present invention, rather than whole embodiments.Based on the embodiments of the present invention, ordinary skill
Personnel's every other embodiment obtained without making creative work, belongs to protection scope of the present invention.
Embodiment 1: a kind of preparation of composite lithium ion cell diaphragm, including following preparation step；
(1) 8g cotton fiber and 1.6g sodium alginate are dissolved in the 10wt% sodium hydroxide of 100ml and the mixing water of 10wt% urea
In solution, 7min is stirred at 25 DEG C, obtains mixed solution；
(2) at 20 DEG C, the glutaraldehyde water solution of the 25wt% of 0.2g is added in mixed solution, after film, is placed in 60 DEG C of rings
7h is reacted under border, obtains cotton fiber/Sodium Alginate Hydrogel Films film；
(3) cotton fiber/Sodium Alginate Hydrogel Films film is successively submerged in deionized water and acetone and is washed, then, placed it in
In autoclave, being passed through carbon dioxide to pressure is 8.5Mpa, extracts 10h at 50 DEG C, then slowly reduces pressure in kettle
To atmospheric pressure, subsequent near room temperature obtains the cotton fiber with a thickness of 15 μm/sodium alginate aerogel film；
(4) silicon dioxide granule that 0.25g partial size is 100nm is dissolved in 100ml dehydrated alcohol, ultrasonic disperse 40min then adds
Enter 1g methacryloxypropyl trimethoxy silane, react 16h, after suction filtration, dries, obtain silane-modified at 110 DEG C
Silicon dioxide granule；
(5) it disperses silane-modified silicon dioxide granule in 100ml deionized water, 25g isobornyl methacrylate is added,
0.025g neopelex, 0.0125g sodium bicarbonate and 0.25g ammonium persulfate is then added, is warming up to 60 DEG C, obtains
The silica lotion of polyisobornyl methacrylate cladding, coats with a thickness of 100nm；
(6) the silica lotion of polyisobornyl methacrylate cladding carries out cotton fiber/sodium alginate aerogel film
Double spread, coating thickness are 2 μm, after drying 6h at 60 DEG C, obtain composite lithium ion cell diaphragm finished product.
Embodiment 2: a kind of preparation of composite lithium ion cell diaphragm, including following preparation step；
(1) 10g cotton fiber and 3.4g sodium alginate are dissolved in the 5wt% sodium hydroxide of 120ml and the mixing water of 15wt% urea
In solution, 5min is stirred at 30 DEG C, obtains mixed solution；
(2) at 30 DEG C, the glutaraldehyde water solution of the 30wt% of 0.67g is added in mixed solution, after film, is placed in 50 DEG C of rings
8h is reacted under border, obtains cotton fiber/Sodium Alginate Hydrogel Films film；
(3) cotton fiber/Sodium Alginate Hydrogel Films film is successively submerged in deionized water and acetone and is washed, then, placed it in
In autoclave, be passed through carbon dioxide to pressure be 10Mpa, extract 15h at 30 DEG C, then slowly reduce kettle in pressure extremely
Atmospheric pressure, subsequent near room temperature, obtains the cotton fiber with a thickness of 25 μm/sodium alginate aerogel film；
(4) silicon dioxide granule that 0.25g partial size is 200nm is dissolved in 100ml dehydrated alcohol, ultrasonic disperse 50min then adds
Enter 2g methacryloxypropyl trimethoxy silane, react 18h, after suction filtration, dries, obtain silane-modified at 100 DEG C
Silicon dioxide granule；
(5) it disperses silane-modified silicon dioxide granule in 100ml deionized water, 37.5g methacrylic acid isoborneol is added
Ester is then added 0.075g neopelex, 0.025g sodium bicarbonate and 0.075g ammonium persulfate, is warming up to 80 DEG C,
The silica lotion of polyisobornyl methacrylate cladding is obtained, is coated with a thickness of 50nm；
(6) the silica lotion of polyisobornyl methacrylate cladding carries out cotton fiber/sodium alginate aerogel film
Double spread, coating thickness are 5 μm, after drying 4h at 70 DEG C, obtain composite lithium ion cell diaphragm finished product.
Embodiment 3: a kind of preparation of composite lithium ion cell diaphragm, including following preparation step；
(1) mixing for the 8wt% sodium hydroxide and 12wt% urea that 10g cotton fiber and 5g sodium alginate are dissolved in 100ml is water-soluble
In liquid, 10min is stirred at 20 DEG C, obtains mixed solution；
(2) at 25 DEG C, the glutaraldehyde water solution of the 20wt% of 0.75g is added in mixed solution, after film, is placed in 70 DEG C of rings
5h is reacted under border, obtains cotton fiber/Sodium Alginate Hydrogel Films film；
(3) cotton fiber/Sodium Alginate Hydrogel Films film is successively submerged in deionized water and acetone and is washed, then, placed it in
In autoclave, be passed through carbon dioxide to pressure be 9Mpa, extract 13h at 40 DEG C, then slowly reduce kettle in pressure extremely
Atmospheric pressure, subsequent near room temperature, obtains the cotton fiber with a thickness of 20 μm/sodium alginate aerogel film；
It (4) is that 50nm silicon dioxide granule is dissolved in 100ml dehydrated alcohol by 0.25g partial size, ultrasonic disperse 30min is then added
0.5g methacryloxypropyl trimethoxy silane reacts 12h, after suction filtration, dries, obtains silane-modified at 120 DEG C
Silicon dioxide granule；
(5) it disperses silane-modified silicon dioxide granule in 100ml deionized water, 30g isobornyl methacrylate is added,
0.05g neopelex, 0.018g sodium bicarbonate and 0.049g ammonium persulfate is then added, is warming up to 70 DEG C, obtains
The silica lotion of polyisobornyl methacrylate cladding, coats with a thickness of 120nm；
(6) the silica lotion of polyisobornyl methacrylate cladding carries out cotton fiber/sodium alginate aerogel film
Double spread, coating thickness are 3 μm, after drying 8h at 50 DEG C, obtain composite lithium ion cell diaphragm finished product.
Comparative example 1: the difference from embodiment 1 is that, it is modified without glutaraldehyde cross-linking.
Embodiment 1 and the compression strength of comparative example 1 are tested, as a result such as following table.
| Compression strength (MPa) | |
| Embodiment 1 | 5.89 |
| Comparative example 1 | 3.57 |
Self-crosslinking reaction can occur between sodium alginate and cotton fiber strand, and the addition of glutaraldehyde can promote strand
Between cross-linking reaction further carry out, form more complicated spacial framework, assign cotton fiber/sodium alginate aeroge
The higher compression strength of film.
Comparative example 2, the difference from embodiment 1 is that, the partial size using silicon dioxide granule is 300nm or so, and dioxy
The cladding of SiClx particle is with a thickness of 200nm or so.
Comparative example 3, the difference from embodiment 1 is that, the partial size using silicon dioxide granule is 30nm or so, and titanium dioxide
The cladding of silicon particle is with a thickness of 20nm or so.
Embodiment 1 and the porosity under the different temperatures of comparative example 2,3 are measured, as a result such as following table.
Porosity is higher at 40 DEG C in embodiment 1, the porosity at 150 DEG C, illustrates to be higher than poly- methyl when temperature
When the softening point of isobornyl acrylate, polyisobornyl methacrylate softens the film to be formed can be preferably to cotton fibre
Dimension/sodium alginate aerogel film hole is covered, compared with Example 1, the partial size of the silicon dioxide granule of comparative example 2 compared with
Small, with silicon dioxide granule cladding thinner thickness, the porosity at 40 DEG C and 150 DEG C is higher and is not much different, explanation
When temperature be higher than polyisobornyl methacrylate softening point when, polyisobornyl methacrylate soften the film to be formed without
Method preferably covers cotton fiber/sodium alginate aerogel film hole, so that barrier action can not be played preferably；It is right
The partial size of the silicon dioxide granule of ratio 3 is larger, thicker with the cladding thickness of silicon dioxide granule, at 40 DEG C porosity compared with
It is small, and porosity also sharply declines at 150 DEG C, illustrates that the cladding of silicon dioxide granule is thick when silicon dioxide granule is larger
When spending thicker, when being less than the softening point of polyisobornyl methacrylate, cotton fiber/sodium alginate aerogel film hole is just
It has been capped.
Claims (9)
1. a kind of preparation method of composite lithium ion cell diaphragm, which is characterized in that including following preparation step；
(1) cotton fiber and sodium alginate are dissolved in the mixed aqueous solution of 5-10wt% sodium hydroxide and 10-15wt% urea,
5-10min is stirred at 20-30 DEG C, obtains mixed solution；
(2) at 20-30 DEG C, the glutaraldehyde water solution of 20-30wt% is added in mixed solution, after film, is placed in 50-70 DEG C
5-8h is reacted under environment, obtains cotton fiber/Sodium Alginate Hydrogel Films film；
(3) cotton fiber/Sodium Alginate Hydrogel Films film is successively submerged in deionized water and acetone and is washed, then, placed it in
In autoclave, being passed through carbon dioxide to pressure is 8.5-10Mpa, extracts 10-15h at 30-50 DEG C, is then slowly reduced
Pressure to atmospheric pressure, subsequent near room temperature obtains cotton fiber/sodium alginate aerogel film in kettle；
(4) dehydrated alcohol is dispersed by silicon dioxide granule, methacryloxy third is then added in ultrasonic disperse 30-50min
Base trimethoxy silane reacts 12-18h, after suction filtration, dries at 100-120 DEG C, obtains silane-modified silicon dioxide granule；
(5) it disperses silane-modified silicon dioxide granule in deionized water, isobornyl methacrylate is added, is then added
Neopelex, sodium bicarbonate and ammonium persulfate, are warming up to 60-80 DEG C, obtain polyisobornyl methacrylate packet
The silica lotion covered；
(6) the silica lotion of polyisobornyl methacrylate cladding carries out cotton fiber/sodium alginate aerogel film
Double spread obtains composite lithium ion cell diaphragm finished product after drying 4-8h at 50-70 DEG C.
2. a kind of preparation method of composite lithium ion cell diaphragm according to claim 1, which is characterized in that step (1)
Described in the mass ratio of cotton fiber and sodium alginate be 3-5:1.
3. a kind of preparation method of composite lithium ion cell diaphragm according to claim 1, which is characterized in that step (2)
Described in glutaraldehyde additional amount be cotton fiber and sodium alginate quality and 0.5%-1.5%.
4. a kind of preparation method of composite lithium ion cell diaphragm according to claim 1, which is characterized in that step (4)
Described in silicon dioxide granule partial size be 50-200nm.
5. a kind of preparation method of composite lithium ion cell diaphragm according to claim 1, which is characterized in that step (4)
The volume ratio of middle dehydrated alcohol and methacryloxypropyl trimethoxy silane is 100:0.5-2.
6. a kind of preparation method of composite lithium ion cell diaphragm according to claim 1, which is characterized in that step (5)
The preparation includes the quality proportioning of following components and each component are as follows: and silane-modified silicon dioxide granule 1-1.5 parts, metering system
Sour isobornyl thiocyanoacetate 100-150 parts, 0.1-0.3 parts of neopelex, 0.05-0.1 parts of sodium bicarbonate, ammonium persulfate 1-
1.5 part.
7. a kind of preparation method of composite lithium ion cell diaphragm according to claim 1, which is characterized in that step (5)
Described in silicon dioxide granule cladding with a thickness of 50-120nm.
8. a kind of preparation method of composite lithium ion cell diaphragm according to claim 1-7, which is characterized in that
Cotton fiber described in step (3)/sodium alginate aerogel film is with a thickness of 15-25 μm.
9. a kind of preparation method of composite lithium ion cell diaphragm according to claim 8, which is characterized in that step (6)
Described in polyisobornyl methacrylate cladding silica emulsion coating with a thickness of 2-5 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811434060.9A CN109935757B (en) | 2018-11-28 | 2018-11-28 | Preparation method of composite lithium ion battery diaphragm |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811434060.9A CN109935757B (en) | 2018-11-28 | 2018-11-28 | Preparation method of composite lithium ion battery diaphragm |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109935757A true CN109935757A (en) | 2019-06-25 |
| CN109935757B CN109935757B (en) | 2021-09-07 |
Family
ID=66984651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811434060.9A Active CN109935757B (en) | 2018-11-28 | 2018-11-28 | Preparation method of composite lithium ion battery diaphragm |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109935757B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003000060A1 (en) * | 2001-06-22 | 2003-01-03 | Kalle Gmbh & Co. Kg | Chewable film containing cellulose |
| AU2006266151A1 (en) * | 2005-06-29 | 2007-01-11 | The University Of Alabama | Ionic liquid reconstituted cellulose composites as solid support matrices |
| US20070270070A1 (en) * | 2006-05-19 | 2007-11-22 | Hamed Othman A | Chemically Stiffened Fibers In Sheet Form |
| WO2010135234A2 (en) * | 2009-05-18 | 2010-11-25 | Cornell University | Bacterial cellulose based 'green' composites |
| CN102030873A (en) * | 2010-10-27 | 2011-04-27 | 华南理工大学 | Method for preparing nano silicon/polyacrylate composite emulsion |
| CN105565774A (en) * | 2015-05-11 | 2016-05-11 | 天津城建大学 | High-strength high-thermal-insulation silica aerogel and preparation method thereof |
| CN105837861A (en) * | 2016-04-03 | 2016-08-10 | 苏鑫 | Composite natural polymer gel material |
| CN106221480A (en) * | 2016-07-26 | 2016-12-14 | 广东工业大学 | A kind of lithium ion battery separator coating and its preparation method and application |
| CN106450108A (en) * | 2016-10-29 | 2017-02-22 | 曲阜师范大学 | Preparation method of modified cellulose lithium battery diaphragm under sodium hydroxide/urea system |
| CN107591512A (en) * | 2016-07-08 | 2018-01-16 | 天津森材料科技有限公司 | A kind of battery diaphragm of high temperature-resistant cellulose fiber base material and preparation method thereof |
| CN108359124A (en) * | 2018-01-29 | 2018-08-03 | 四川大学 | A kind of preparation method of waste textile bismuth tungstate composite aerogel |
-
2018
- 2018-11-28 CN CN201811434060.9A patent/CN109935757B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003000060A1 (en) * | 2001-06-22 | 2003-01-03 | Kalle Gmbh & Co. Kg | Chewable film containing cellulose |
| AU2006266151A1 (en) * | 2005-06-29 | 2007-01-11 | The University Of Alabama | Ionic liquid reconstituted cellulose composites as solid support matrices |
| US20070270070A1 (en) * | 2006-05-19 | 2007-11-22 | Hamed Othman A | Chemically Stiffened Fibers In Sheet Form |
| WO2010135234A2 (en) * | 2009-05-18 | 2010-11-25 | Cornell University | Bacterial cellulose based 'green' composites |
| CN102030873A (en) * | 2010-10-27 | 2011-04-27 | 华南理工大学 | Method for preparing nano silicon/polyacrylate composite emulsion |
| CN105565774A (en) * | 2015-05-11 | 2016-05-11 | 天津城建大学 | High-strength high-thermal-insulation silica aerogel and preparation method thereof |
| CN105837861A (en) * | 2016-04-03 | 2016-08-10 | 苏鑫 | Composite natural polymer gel material |
| CN107591512A (en) * | 2016-07-08 | 2018-01-16 | 天津森材料科技有限公司 | A kind of battery diaphragm of high temperature-resistant cellulose fiber base material and preparation method thereof |
| CN106221480A (en) * | 2016-07-26 | 2016-12-14 | 广东工业大学 | A kind of lithium ion battery separator coating and its preparation method and application |
| CN106450108A (en) * | 2016-10-29 | 2017-02-22 | 曲阜师范大学 | Preparation method of modified cellulose lithium battery diaphragm under sodium hydroxide/urea system |
| CN108359124A (en) * | 2018-01-29 | 2018-08-03 | 四川大学 | A kind of preparation method of waste textile bismuth tungstate composite aerogel |
Non-Patent Citations (1)
| Title |
|---|
| 孟祥军: "纤维素/海藻酸共混材料的制备及应用", 《工程科技Ⅰ辑》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109935757B (en) | 2021-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102122704B (en) | Composite microporous membrane used as lithium ion battery diaphragm as well as preparation method and application thereof | |
| CN104157815B (en) | A kind of Bacterial cellulose porous membrane and preparation method thereof | |
| CN106450115B (en) | Inorganic coating bacteria cellulose porous membrane and preparation method thereof | |
| CN103682218A (en) | Organic-inorganic composite lithium ion battery diaphragm and preparation method thereof | |
| CN108134036B (en) | Organic-inorganic composite electrolyte membrane, preparation method and application thereof | |
| CN105367696A (en) | Elastic raindrop impression resisting styrene-acrylic emulsion and preparation method thereof | |
| CN105585732A (en) | Ultraviolet crosslinking polyaryletherketone porous membrane, preparation method and application of ultraviolet crosslinking polyaryletherketone porous membrane | |
| CN103603178B (en) | Coating for flexible lithium-ion battery membrane, membrane containing same and preparation method thereof | |
| CN104466063A (en) | Polydopamine surface modified polyether sulfone nanofiber composite diaphragm and preparation method and applications | |
| CN108847470A (en) | A kind of lithium electric separator and preparation method thereof of mixed coating coating | |
| CN106265129A (en) | A kind of fibroin albumen alginate composite membrane and its preparation method and application | |
| CN109167007A (en) | Heat-resisting lithium ion battery coated separator and preparation method thereof | |
| CN113745757A (en) | Preparation method of lithium battery safety diaphragm material | |
| CN103113607B (en) | Preparation method of microporous polymer diaphragm with high-temperature self-enhancing mechanism | |
| CN104577011B (en) | A kind of battery diaphragm reinforcing material | |
| CN109935757A (en) | A kind of preparation method of composite lithium ion cell diaphragm | |
| CN106531929A (en) | Drying process of ceramic coated bacterial cellulose porous thin film | |
| CN104201313B (en) | The lithium ion battery method of PP film with the composite diaphragm modification of PTFE film | |
| CN103441228A (en) | Polysulfonamide base lithium ion battery separator prepared through wet papermaking process | |
| CN117175138A (en) | Preparation method of functionalized nano cellulose membrane | |
| CN108807788B (en) | Composite diaphragm for lithium ion power battery and preparation method thereof | |
| CN107417979B (en) | A kind of gelatinous fibre element composite membrane and preparation method thereof | |
| CN109346644A (en) | A method of preparing sheath-core fiber structures composite diaphragm | |
| CN112694635B (en) | Preparation method of cellulose/PAA anion exchange membrane with double-network structure | |
| CN106784522B (en) | A kind of solid lithium ion battery battery diaphragm and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211117 Address after: No.855, Jianshe 2nd Road, Xiaoshan Economic and Technological Development Zone, Hangzhou City, Zhejiang Province Patentee after: Wanxiang A123 Co.,Ltd. Address before: No.855 Jianshe Er Road, Xiaoshan Economic and Technological Development Zone, Xiaoshan District, Hangzhou City, Zhejiang Province Patentee before: Wanxiang A123 Co.,Ltd. Patentee before: Wanxiang Group Co., Ltd |