CN104045851A - Preparation method of microporous polymer diaphragm with high mechanical strength and heat resistance - Google Patents
Preparation method of microporous polymer diaphragm with high mechanical strength and heat resistance Download PDFInfo
- Publication number
- CN104045851A CN104045851A CN201410252165.8A CN201410252165A CN104045851A CN 104045851 A CN104045851 A CN 104045851A CN 201410252165 A CN201410252165 A CN 201410252165A CN 104045851 A CN104045851 A CN 104045851A
- Authority
- CN
- China
- Prior art keywords
- hfp
- mixed solution
- polymer
- preparation
- mechanical strength
- 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.)
- Pending
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
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Cell Separators (AREA)
Abstract
The invention relates to a preparation method of a microporous polymer diaphragm with high mechanical strength and heat resistance. The preparation method is characterized by comprising the following specific steps: (1) dissolving a polymer PVDF-HFP (Polyvinylidene Fluoride-Hexafluoropropylene) into an organic solvent, heating, intensely stirring, adding high-temperature-resistant resin particles after sufficiently dissolving the polymer PVDF-HFP, continuing to heat and stir for a period of time to obtain a colloid mixed solution with relatively good dispersibility, wherein the mass ratio of the high-temperature-resistant resin particles to the polymer PVDF-HFP is (0.01-0.15):1; (2) dropwise adding a nonsolvent into the colloid mixed solution, and continuing to stir; (3) pouring the colloid mixed solution obtained in the step (2) on a glass plate, and carrying out blade coating to form a film; (4) taking down the film, and carrying out vacuum drying. The prepared microporous polymer diaphragm is favorable in thermal stability, mechanical strength and liquid absorption/retention capacity, and the ionic conductivity, cycle performance and safety performance of a lithium ion battery assembled by using the diaphragm are all greatly improved.
Description
Technical field
The present invention relates to a kind of preparation method with high mechanical strength and thermotolerance micropore polymer diaphragm, belong to battery, electric capacity field.
Background technology
Barrier film, as the key part of battery, will directly affect capacity, cycle performance and the safety performance of battery.In recent years, porous polymeric objects system has caused people's extensive concern, U.S. Bellcore in 1994 for company polyvinylidene difluoride (PVDF)-R 1216 (PVDF-HFP) make the polymeric film of microvoid structure by plasticising/extraction process, increase the pick up of polymer dielectric, but the shortcoming such as PVDF-HFP based polyalcohol barrier film exists that transference number of ions is low, thermostability is bad and interface compatibility is bad.Research shows, adds electrodeless nano material in polymer dielectric, can improve the performance of polymer dielectric.
Patent CN 101260216A discloses PVDF-HFP base composition polymer barrier film and preparation method thereof, be dissolved in organic solvent by PVDF-HFP, after Sodium hexametaphosphate 99, inorganic superfine powder end and distilled water blending and stirring are even, add in PVDF-HFP glue, more obtain PVDF-HFP base composite porous polymer membrane in casting mold.Although this method has improved transference number of ions after adding Sodium hexametaphosphate 99 greatly, the interface compatibility that do not have clear improvement, and also high rate performance and cycle performance after assembled battery is poor.
Patent CN102731944A discloses the preparation of a kind of sylvite/polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer composite membrane.By after raw material silicon-dioxide and polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer blended, casting film-forming on smooth sheet glass, put it into oven drying 10～20h, finally in retort furnace through thermal treatment 0.5～8h, obtain polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer, sylvite composite membrane.Although the standby barrier film of this legal system can improve electroconductibility and thermotolerance,, this preparation technology is loaded down with trivial details, time-consuming.The mentality of designing of this patent is in polymer dielectric, to add the fire resistant resin particle of certain particle diameter.Resin particle, by absorption, cure polymer, is deposited in polymer dielectric in the interface of electrode, thereby strengthens mechanical property and resistance toheat, then by the pore effect of non-solvent, forms abundant hole, thereby improves the imbibition/liquid holdup of barrier film.Resin particle has excellent mechanical property and thermal characteristics, is a kind of fabulous interpolation material.
Summary of the invention
This object is to provide a kind of preparation method with high mechanical strength and thermotolerance micropore polymer diaphragm, its micropore polymer diaphragm making has good thermostability, good mechanical strength and good imbibition/liquid-keeping property, ionic conductivity, cycle performance and the safety performance of the lithium ion battery of assembling with this barrier film have had raising by a relatively large margin.
Technical scheme of the present invention is achieved in that a kind of preparation method with high mechanical strength and thermotolerance micropore polymer diaphragm, it is characterized in that it prepares concrete steps as follows: (1) is dissolved in polymer P VDF-HFP in organic solvent, polymer P VDF-HFP weight-average molecular weight is 400,000～500,000, the mass ratio of organic solvent and polymer P VDF-HFP is 5.2～9.6:1, through heating, strong stirring, after fully dissolving, it adds fire resistant resin particle, the mass ratio of fire resistant resin particle and polymer P VDF-HFP is 0.01～0.15:1, continue heating, stir after for some time, obtain dispersed colloid mixed solution preferably, (2) in the colloid mixed solution in step 1, dropwise add non-solvent, the mass ratio of non-solvent and organic solvent is 0.08～0.21:1, continues to stir, (3) the colloid mixed solution in step (2) is cast on sheet glass, blade coating film forming, film thickness is 18～45 μ m, (4) take off film, at the temperature of 50 DEG C～70 DEG C, film is carried out to 2～10h vacuum drying.
Described organic solvent is acetone, DMF, and one or more in N-Methyl pyrrolidone, particularly, its ratio is acetone/DMF/N-Methyl pyrrolidone=0 ~ 1/0 ~ 1/0 ~ 1.
Described fire resistant resin particle is polyetherketone, polyether-ether-ketone, polyether ether ketone ketone, one or more in polyetherketoneetherketoneketone, polybenzothiozole, polybenzimidazole, polyphenylene sulfide, particularly, its ratio is polyetherketone/polyether-ether-ketone/polyether ether ketone ketone/polyetherketoneetherketoneketone/polybenzothiozole/polybenzimidazole/polyphenylene sulfide=0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1.
Described non-solvent is the one or more combination in propyl carbinol, water, dehydrated alcohol, and particularly, its ratio is n-butanol/water/dehydrated alcohol=0 ~ 1/0 ~ 1/0 ~ 1.
Positively effect of the present invention is that it is by PVDF-HFP glue and the blend of fire resistant resin particle and in conjunction with boring technique, prepared barrier film has higher mechanical strength, thermotolerance and imbibition/liquid holdup, high rate performance, cycle performance and the safety performance of the lithium ion battery entirety being assembled into this barrier film improve greatly, and preparation method of the present invention is simple and easy to do, environmental protection.
Brief description of the drawings
Fig. 1 is the TG graphic representation of the present invention and certain commercialization barrier film.
Fig. 2 is the design sketch that the embodiment of the present invention 2, PVDF-HFP barrier film and certain commercialization barrier film respectively add 1h under 90 DEG C, 135 DEG C, 165 DEG C environment.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the invention will be further described: as shown in Figure 1, a kind of preparation method with high mechanical strength and thermotolerance micropore polymer diaphragm, it is characterized in that its preparation method, concrete steps are as follows: (1) is dissolved in polymer P VDF-HFP in organic solvent, polymer P VDF-HFP weight-average molecular weight is 400,000～500,000, the mass ratio of organic solvent and polymer P VDF-HFP is 5.2～9.6:1, through heating, strong stirring, after fully dissolving, it adds fire resistant resin particle, the mass ratio of fire resistant resin particle and polymer P VDF-HFP is 0.01～0.15:1, continue heating, stir after for some time, obtain dispersed colloid mixed solution preferably, (2) in the colloid mixed solution in step 1, dropwise add non-solvent, the mass ratio of non-solvent and organic solvent is 0.08～0.21:1, continues to stir, (3) the colloid mixed solution in step (2) is cast on sheet glass, blade coating film forming, film thickness is 18～45 μ m, (4) take off film, at the temperature of 50 DEG C～70 DEG C, film is carried out to 2～10h vacuum drying.
Described organic solvent is acetone, DMF, and one or more in N-Methyl pyrrolidone, particularly, its ratio is acetone/DMF/N-Methyl pyrrolidone=0 ~ 1/0 ~ 1/0 ~ 1.
Described fire resistant resin particle is polyetherketone, polyether-ether-ketone, polyether ether ketone ketone, one or more in polyetherketoneetherketoneketone, polybenzothiozole, polybenzimidazole, polyphenylene sulfide, particularly, its ratio is polyetherketone/polyether-ether-ketone/polyether ether ketone ketone/polyetherketoneetherketoneketone/polybenzothiozole/polybenzimidazole/polyphenylene sulfide=0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1.
Described non-solvent is the one or more combination in propyl carbinol, water, dehydrated alcohol, and particularly, its ratio is n-butanol/water/dehydrated alcohol=0 ~ 1/0 ~ 1/0 ~ 1.
embodiment 1
(1) be that 400,000 PVDF-HFP are dissolved in 48g acetone by 5.0g molecular weight, through heating, strong stirring, after it fully dissolves, add ultrafine powder polyether ether ketone ketone 0.05g, continue heating, stir after for some time, obtain dispersed colloid mixed solution preferably; (2) in the colloid mixed solution in step 1, dropwise add 3.84 g propyl carbinols, continue to stir; (3) the colloid mixed solution in step 2 is cast on sheet glass to blade coating film forming; (4) take off film, at the temperature of 70 DEG C, film is carried out to 2h vacuum drying.The membrane thicknesses of preparing taking this embodiment is 18 μ m, as shown in Figure 1.
embodiment 2
(1) be that 500,000 PVDF-HFP are dissolved in 13g N by 5.0g molecular weight, in dinethylformamide, through heating, strong stirring, after fully dissolving, it adds ultrafine powder polyether-ether-ketone 0.25g, continue heating, stir after for some time, obtain dispersed colloid mixed solution preferably; (2) in the colloid mixed solution in step 1, dropwise add 2.73g ethanol, continue to stir; (3) the colloid mixed solution in step 2 is cast on sheet glass to blade coating film forming; (4) take off film, at the temperature of 70 DEG C, film is carried out to 5h vacuum drying.The membrane thicknesses that this embodiment prepares is 45 μ m, the good heat resistance of the barrier film of preparing with this embodiment, and at 165 DEG C, under 1h condition, thermal contraction is only 0.5%, shows excellent resistance toheat.Fig. 2 is the photo that barrier film, PVDF-HFP barrier film and certain commercialization barrier film prepared by embodiment 2 respectively add 1h under 90 DEG C, 135 DEG C, 165 DEG C environment.
embodiment 3
(1) be that 450,000 PVDF-HFP are dissolved in 18g acetone and 14gN-methyl-2-pyrrolidone mixed solvent by 5.0g molecular weight, through heating, strong stirring, after fully dissolving, it adds ultrafine powder polyphenylene sulfide 0.75g, continue heating, stir after for some time, obtain dispersed colloid mixed solution preferably; (2) in the colloid mixed solution in step 1, dropwise add 2.56g water, continue to stir; (3) the colloid mixed solution in step 2 is cast on sheet glass to blade coating film forming; (4) take off film, at the temperature of 60 DEG C, film is carried out to 5h vacuum drying.The membrane thicknesses that this embodiment prepares is 28 μ m, and tensile strength is 12.76MPa, shows excellent mechanical property.
The barrier film that table 1 is prepared for embodiment 3 and the tensile strength experimental data of certain commercialization barrier film.
embodiment 4
(1) be that 450,000 PVDF-HFP are dissolved in 32g acetone by 5.0g molecular weight, through heating, strong stirring, after fully dissolving, it adds the mixture of ultrafine powder 0.3g polyetherketone and 0.3g polyetherketoneetherketoneketone, continue heating, stir after for some time, obtain dispersed colloid mixed solution preferably; (2) in the colloid mixed solution in step 1, dropwise add 1.5g propyl carbinol and 1.5g water, continue to stir; (3) the colloid mixed solution in step 2 is cast on sheet glass to blade coating film forming; (4) take off film, at the temperature of 50 DEG C, film is carried out to 5h vacuum drying.
embodiment 5
(1) be that 400,000 PVDF-HFP are dissolved in 12g N by 5.0g molecular weight, in dinethylformamide and 10gN-crassitude mixed solvent, through heating, strong stirring, after fully dissolving, it adds ultrafine powder polyetherketone 0.05g, continue heating, stir after for some time, obtain dispersed colloid mixed solution preferably; (2) in the colloid mixed solution in step 1, dropwise add 2.0 g propyl carbinols and 2.0g dehydrated alcohol, continue to stir; (3) the colloid mixed solution in step 2 is cast on sheet glass to blade coating film forming; (4) take off film, at the temperature of 70 DEG C, film is carried out to 10h vacuum drying.
embodiment 6
(1) be that 500,000 PVDF-HFP are dissolved in 13g acetone and 12g N by 5.0g molecular weight, in dinethylformamide, through heating, strong stirring, after fully dissolving, it adds ultrafine powder polyether-ether-ketone 0.25g, continue heating, stir after for some time, obtain dispersed colloid mixed solution preferably; (2) in the colloid mixed solution in step 1, dropwise add 2.0g ethanol and 1.5g water, continue to stir; (3) the colloid mixed solution in step 2 is cast on sheet glass to blade coating film forming; (4) take off film, at the temperature of 70 DEG C, film is carried out to 10h vacuum drying.
embodiment 7
(1) be that 450,000 PVDF-HFP are dissolved in 20g acetone and 12gN-methyl-2-pyrrolidone mixed solvent by 5.0g molecular weight, through heating, strong stirring, after fully dissolving, it adds ultrafine powder polybenzimidazole 0.80g, continue heating, stir after for some time, obtain dispersed colloid mixed solution preferably; (2) in the colloid mixed solution in step 1, dropwise add 3.0g water, continue to stir; (3) the colloid mixed solution in step 2 is cast on sheet glass to blade coating film forming; (4) take off film, at the temperature of 60 DEG C, film is carried out to 8h vacuum drying.
embodiment 8
(1) be that 450,000 PVDF-HFP are dissolved in 10g acetone, 10g N by 5.0g molecular weight, in dinethylformamide and 10gN-methyl-2-pyrrolidone mixed solvent, through heating, strong stirring, after fully dissolving, it adds 0.6g polyetherketoneetherketoneketone, continue heating, stir after for some time, obtain dispersed colloid mixed solution preferably; (2) in the colloid mixed solution in step 1, dropwise add 3.0g propyl carbinol, continue to stir; (3) the colloid mixed solution in step 2 is cast on sheet glass to blade coating film forming; (4) take off film, at the temperature of 50 DEG C, film is carried out to 10h vacuum drying.
embodiment 9
(1) be that 450,000 PVDF-HFP are dissolved in 32g N by 5.0g molecular weight, in dinethylformamide, through heating, strong stirring, after fully dissolving, it adds the mixture of ultrafine powder 0.1g polyetherketone, 0.1g polyethers ether copper, 0.1g polyether ether ketone ketone, 0.1g polyetherketoneetherketoneketone, 0.1g polybenzimidazole, 0.1g polybenzothiozole and 0.1g polyphenylene sulfide, continue heating, stir after for some time, obtain dispersed colloid mixed solution preferably; (2) in the colloid mixed solution in step 1, dropwise add 3.0g propyl carbinol, continue to stir; (3) the colloid mixed solution in step 2 is cast on sheet glass to blade coating film forming; (4) take off film, at the temperature of 50 DEG C, film is carried out to 6h vacuum drying.
embodiment 10
(1) be that 450,000 PVDF-HFP are dissolved in 28g N-Methyl pyrrolidone by 5.0g molecular weight, through heating, strong stirring, after fully dissolving, it adds the mixture of ultrafine powder 0.15g polyethers ether copper, 0.15g polyether ether ketone ketone, 0.15g polyetherketoneetherketoneketone and 0.15g polyphenylene sulfide, continue heating, stir after for some time, obtain dispersed colloid mixed solution preferably; (2) in the colloid mixed solution in step 1, dropwise add 1.5g propyl carbinol and 1.5g water, continue to stir; (3) the colloid mixed solution in step 2 is cast on sheet glass to blade coating film forming; (4) take off film, at the temperature of 50 DEG C, film is carried out to 6h vacuum drying.
Claims (4)
1. one kind has the preparation method of high mechanical strength and thermotolerance micropore polymer diaphragm, it is characterized in that it prepares concrete steps as follows: (1) is dissolved in polymer P VDF-HFP in organic solvent, polymer P VDF-HFP weight-average molecular weight is 400,000～500,000, the mass ratio of organic solvent and polymer P VDF-HFP is 5.2～9.6:1, through heating, strong stirring, after fully dissolving, it adds fire resistant resin particle, the mass ratio of fire resistant resin particle and polymer P VDF-HFP is 0.01～0.15:1, continue heating, stir after for some time, obtain dispersed colloid mixed solution preferably, (2) in the colloid mixed solution in step 1, dropwise add non-solvent, the mass ratio of non-solvent and organic solvent is 0.08～0.21:1, continues to stir, (3) the colloid mixed solution in step (2) is cast on sheet glass, blade coating film forming, film thickness is 18～45 μ m, (4) take off film, at the temperature of 50 DEG C～70 DEG C, film is carried out to 2～10h vacuum drying.
2. according to a kind of preparation method with high mechanical strength and thermotolerance micropore polymer diaphragm described in claim 1, it is characterized in that described organic solvent is acetone, N, dinethylformamide, one or more in N-Methyl pyrrolidone, particularly, its ratio is acetone/DMF/N-Methyl pyrrolidone=0 ~ 1/0 ~ 1/0 ~ 1.
3. according to a kind of preparation method with high mechanical strength and thermotolerance micropore polymer diaphragm described in claim 1, it is characterized in that described fire resistant resin particle is polyetherketone, polyether-ether-ketone, polyether ether ketone ketone, one or more in polyetherketoneetherketoneketone, polybenzothiozole, polybenzimidazole, polyphenylene sulfide, particularly, its ratio is polyetherketone/polyether-ether-ketone/polyether ether ketone ketone/polyetherketoneetherketoneketone/polybenzothiozole/polybenzimidazole/polyphenylene sulfide=0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1.
4. according to a kind of preparation method with high mechanical strength and thermotolerance micropore polymer diaphragm described in claim 1, it is characterized in that described non-solvent is the one or more combination in propyl carbinol, water, dehydrated alcohol, particularly, its ratio is n-butanol/water/dehydrated alcohol=0 ~ 1/0 ~ 1/0 ~ 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410252165.8A CN104045851A (en) | 2014-06-10 | 2014-06-10 | Preparation method of microporous polymer diaphragm with high mechanical strength and heat resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410252165.8A CN104045851A (en) | 2014-06-10 | 2014-06-10 | Preparation method of microporous polymer diaphragm with high mechanical strength and heat resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104045851A true CN104045851A (en) | 2014-09-17 |
Family
ID=51499271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410252165.8A Pending CN104045851A (en) | 2014-06-10 | 2014-06-10 | Preparation method of microporous polymer diaphragm with high mechanical strength and heat resistance |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104045851A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111987275A (en) * | 2020-09-01 | 2020-11-24 | 厦门大学 | Preparation method and preparation device of lithium ion battery diaphragm |
| CN112490023A (en) * | 2019-09-12 | 2021-03-12 | 广州汽车集团股份有限公司 | Preparation method of gel electrolyte and preparation method of super capacitor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103545476A (en) * | 2013-10-30 | 2014-01-29 | 中国第一汽车股份有限公司 | PVDF-HFP (Polyvinylidene Fluoride-Hexafluoropropylene) microporous polymer membrane with anchoring and enhancing effects and preparation method thereof |
| CN103618058A (en) * | 2013-12-16 | 2014-03-05 | 中国科学院宁波材料技术与工程研究所 | Membrane and preparation method thereof |
-
2014
- 2014-06-10 CN CN201410252165.8A patent/CN104045851A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103545476A (en) * | 2013-10-30 | 2014-01-29 | 中国第一汽车股份有限公司 | PVDF-HFP (Polyvinylidene Fluoride-Hexafluoropropylene) microporous polymer membrane with anchoring and enhancing effects and preparation method thereof |
| CN103618058A (en) * | 2013-12-16 | 2014-03-05 | 中国科学院宁波材料技术与工程研究所 | Membrane and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112490023A (en) * | 2019-09-12 | 2021-03-12 | 广州汽车集团股份有限公司 | Preparation method of gel electrolyte and preparation method of super capacitor |
| CN112490023B (en) * | 2019-09-12 | 2022-06-21 | 广州汽车集团股份有限公司 | Preparation method of gel electrolyte and preparation method of super capacitor |
| CN111987275A (en) * | 2020-09-01 | 2020-11-24 | 厦门大学 | Preparation method and preparation device of lithium ion battery diaphragm |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Recent progress on biomass‐derived ecomaterials toward advanced rechargeable lithium batteries | |
| CN104362289B (en) | Lithium ion battery pole piece provided with inorganic isolating layers, battery comprising the pole piece and preparation method for pole piece | |
| TWI537996B (en) | Supercapacitor and method of manufacture thereof | |
| CN101447571B (en) | Preparation method of flexible graphite composite bipolar plate of proton exchange membrane fuel cell | |
| CN109786816A (en) | A kind of composite solid electrolyte and preparation method thereof | |
| CN105428571B (en) | Poly-dopamine modified lithium ceramic particle prepares PVDF HFP based polyalcohols membranes and preparation method | |
| CN104157815A (en) | Bacterial cellulose porous thin film and preparation method thereof | |
| CN104681864B (en) | A kind of gel-type polymer electrolyte of high-energy-density and ionic conductivity | |
| CN107706338B (en) | A kind of lithium ion battery separator and preparation method thereof containing positive electrode | |
| CN103545476B (en) | There is PVDF-HFP micropore polymer diaphragm and the preparation method of grappling humidification | |
| CN104022248B (en) | A kind of preparation method of high-performance lithium ion conductive membranes | |
| CN109560235A (en) | A kind of new type lithium ion battery aramid fiber diaphragm preparation method | |
| CN108232089B (en) | A kind of lithium ion battery diatomite diaphragm and preparation method thereof | |
| WO2021248508A1 (en) | Fuel cell bipolar plate and preparation method therefor | |
| WO2016124052A1 (en) | Proton exchange membrane for fuel cells and preparation method therefor | |
| CN108832063A (en) | A kind of lithium electric separator and preparation method thereof of PVDF coating | |
| Maia et al. | Designing versatile polymers for lithium-ion battery applications: a review | |
| CN107799813A (en) | A kind of high-energy-density ternary battery and preparation method thereof | |
| CN104045851A (en) | Preparation method of microporous polymer diaphragm with high mechanical strength and heat resistance | |
| CN110828781B (en) | Positive plate and preparation method and application thereof | |
| CN108630899A (en) | The manufacturing method of sodium-ion battery | |
| CN110323491B (en) | Polymer electrolyte, polymer electrolyte membrane, and lithium ion battery | |
| CN110556558B (en) | Multilayer composite proton exchange membrane and preparation method thereof | |
| CN108807788B (en) | Composite diaphragm for lithium ion power battery and preparation method thereof | |
| CN106784949A (en) | A kind of preparation method of the full interpenetrating type anion-exchange membranes of crosslinking QCS CM Guanidine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140917 |
|
| RJ01 | Rejection of invention patent application after publication |