CN102651466A - High-safety ceramic composite lithium-ion isolating membrane and lithium battery thereof - Google Patents
High-safety ceramic composite lithium-ion isolating membrane and lithium battery thereof Download PDFInfo
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- CN102651466A CN102651466A CN2012101668374A CN201210166837A CN102651466A CN 102651466 A CN102651466 A CN 102651466A CN 2012101668374 A CN2012101668374 A CN 2012101668374A CN 201210166837 A CN201210166837 A CN 201210166837A CN 102651466 A CN102651466 A CN 102651466A
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- ceramic material
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- lithium ion
- material layer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a high-safety ceramic composite lithium-ion isolating membrane and a lithium battery thereof. The high-safety ceramic composite lithium-ion isolating membrane can improve the safety of a lithium-ion power battery and is high in reliability and safety. The isolating membrane comprises a composite porous thin-film material layer, a high-molecule compound copolymer layer and a ceramic material layer, wherein the composite porous thin-film material layer is subjected to surface treatment; the high-molecule compound copolymer layer is arranged on the composite porous thin-film material layer; and the ceramic material layer is arranged on the high-molecule compound copolymer layer and is subjected to surface nanocrystallization. The lithium battery comprises a positive plate, a negative positive plate and a core body formed by the ceramic composite lithium-ion isolating membrane.
Description
Technical field
The present invention relates to a kind of lithium battery; Relate in particular to a kind of high safe ceramics compound lithium ion barrier film and lithium battery thereof.
Background technology
Conventional power lithium battery barrier film is the single or multiple lift porous polyolefin product that dry method or wet processing stretch; Though thickness has been brought up to 40 microns; Thickness is the twice of the used barrier film of conventional digital lithium electricity product; Though can the puncture intensity of barrier film be improved like this, the dendrite that still can not stop Li dendrite or metal impurities to produce fully penetrates barrier film; Simultaneously, barrier film is to understand extensive shrinkage equally about 140 ℃, causes the both positive and negative polarity contact, and the danger that battery is on fire even explode is arranged equally.Therefore, develop a kind of high safety, high strength, high-temperature resistant, the product that does not influence the battery correlated performance simultaneously will become lithium electric separator Development Trend.In conjunction with the characteristics of utilizing organic flexibility and inorganic matter good thermal stability, in the method for porous polyolefin surface recombination inorganic ceramic oxide coating, to realize the preparation of the lithium battery diaphragm that organic counterdie/inorganic coating is compound.This lithium battery diaphragm is in battery charge and discharge process; Even organic counterdie melts; Inorganic coating still can keep the integrality of barrier film; Prevent large tracts of land just/appearance of negative pole short circuit phenomenon, make the security performance that the compound barrier film of this organic/inorganic can improve powerful lithium battery to a greater extent.
Summary of the invention
The objective of the invention is deficiency, a kind of high safe ceramics compound lithium ion barrier film and lithium battery thereof are provided to the prior art existence.This high safe ceramics compound lithium ion barrier film can improve the security performance of lithium-ion-power cell, improves the heat resistance of lithium ion battery etc., and the consistency of battery pack during combination of monomers; This lithium battery stable performance, safety, reliable.
Technical scheme of the present invention comprises diaphragm body; Said diaphragm body comprises barrier film basic unit and is located at the ceramic material layer in this barrier film basic unit; The copolymer layer that said barrier film basic unit comprises surface treated composite porous film material layer and is located at the high score compound on this surface treated composite porous film material layer, said ceramic material layer comprises the ceramic material through the nanometer processing.
Said barrier film basic unit processes for the copolymer with said macromolecule chemical combination is sprayed at surface treated composite porous film material surface; Said diaphragm body for through the ceramic material of nanometer processing and ceramic material adhesive by a solid content than the mode that is coated with shoe after mixing, with extruding be coated with shoe in above-mentioned barrier film basic unit of processing after dried in barrier film substrate surface formation ceramic material layer, again under a temperature to this barrier film basic unit and be formed at its surperficial ceramic material layer and carry out the compound heat stabilisation process of hot pressing and process.
The temperature that said ceramic material layer and barrier film basic unit carry out the compound heat stabilisation process of hot pressing is 40 ℃～60 ℃; Said ceramic material through the nanometer processing is 80%～96%:20%～4% with the solid content ratio of ceramic material adhesive.
Said ceramic material adhesive is a polymer binder.
Said ceramic material polymer binder comprises that molecular weight is 30～1,200,000 polyacrylate dispersion or Kynoar.
Said ceramic material comprises α-Al
2O
3And/or SiO2; The copolymer of said macromolecule chemical combination comprises that molecular weight is 30～1,200,000 polyacrylate dispersion or Kynoar; The porosity of said composite porous film material is 40%～56%.
The weight ratio of said α-Al2O3 and SiO2 is 55%～98%:45%～2%.
The thickness of the copolymer layer of said macromolecular compound is 0.3～0.5 micron, and the thickness of said ceramic material layer is 1～1.5 micron; The surface treatment of said composite porous film material comprises ultraviolet reaming processing.
Said composite porous film material comprises that porosity is the polypropylene and/or the polyethylene composite porous film material of stretching 40%～56%, that handle through ultraviolet reaming.
The copolymer layer of said macromolecule chemical combination comprise be added with macromolecule solvent, molecular weight is 30～1,200,000 polyacrylate dispersion or Kynoar binding agent; Said macromolecule solvent comprises the N-methylpyrrole.
The present invention is with the compound barrier film of organic counterdie/inorganic coating; In battery charge and discharge process; Even organic counterdie melts, inorganic coating still can keep the integrality of barrier film, prevent large tracts of land just/appearance of negative pole short circuit phenomenon; Can not only improve the lithium ion battery heat resistance, reduce the probability that lithium ion battery takes place as the electrokinetic cell potential safety hazard; And can improve the consistency of lithium ion single battery, the combination that is beneficial to battery is used.Battery of the present invention is isolated lithium ion battery plus-negative plate through using Ceramic Composite lithium ion barrier film, guarantees that battery potential safety hazard do not occur in the condition of high temperature.
Description of drawings
Figure is the high safe ceramics compound lithium ion of a present invention barrier film structural representation.
The specific embodiment mode
Existing through embodiment and combine accompanying drawing that the present invention is described further, as shown in the figure, the high safe ceramics compound lithium ion barrier film (diaphragm body) 4 of present embodiment comprises that barrier film basic unit and the ceramic material layer of being located at this barrier film basic unit two sides 3 constitute; Barrier film basic unit is by polypropylene or the polyethylene composite porous film material layer 1 handled through ultraviolet reaming, stretch, and the molecular weight that is sprayed at the relative two sides of that this is handled through ultraviolet reaming, the polypropylene that stretches or polyethylene composite porous film material layer 1 is that 30～1,200,000 the polyacrylate dispersion or the copolymer layer 2 of Kynoar macromolecular compound are processed; Ceramic material layer is by ceramic material α-Al
2O
3With SiO
2Carrying out the nanometer processing after the weight ratio mixing with 65% ~ 96%:35% ~ 4% processes.
It is specifically made through following process:
Earlier respectively with ceramic material α-Al
2O
3With SiO
2Carrying out the nanometer processing after above-mentioned weight ratio is mixed and process the ceramic material compound, is that 30 ~ 1,200,000 polyacrylate dispersion or Kynoar are processed polymer ceramic material adhesive agent emulsion with molecular weight; With above-mentioned molecular weight is that the N-methylpyrrole macromolecule solvent that 30～1,200,000 polyacrylate dispersion or Kynoar add a certain amount of (being as the criterion with convenient spraying) is processed the high polymer binder emulsion, the polypropylene that stretches or polyethylene composite porous film material is carried out ultraviolet reaming handle and process the composite porous film material layer; After relative two surfaces of the composite porous film material layer of processing apply the above-mentioned high polymer binder emulsion of processing with 0.3 ~ 0.5 micron thickness respectively, carry out dried again, form the copolymer layer 2 of macromolecular compound in composite porous film material layer 1 two sides and then process the barrier film matrix; Again the ceramic material compound of processing is carried out after the nanometer processing being mixed and made into ceramic size with the above-mentioned polymer ceramic material adhesive agent emulsion of processing by the solid content ratio of 80% ~ 96%:20% ~ 4%, this ceramic size is carried out dried, forms ceramic material layers 3 in barrier film matrix two table (wall) faces with 1～1.5 micron thickness extrusion coated respectively behind the relative two sides of the above-mentioned barrier film matrix of processing; In 40 ℃ ~ 60 ℃ temperature range, the copolymer layer that is formed at this ceramic material layer and macromolecular compound in the barrier film basic unit is carried out the compound stability of hot pressing and handle, promptly process diaphragm body.
In the another embodiment of the present invention, ceramic material α-Al
2O
3With SiO
2,Weight ratio is that 75% ~ 89%:25% ~ 11% ratio is mixed; The ceramic material adhesive is that molecular weight is 60,80 or 1,000,000 polyacrylate dispersion or Kynoar; Ceramic material after the nanometer processing is 70% ~ 86%:30% ~ 14% with the solid content ratio of polymer ceramic material adhesive agent emulsion, and it is 1.1,1,3 or 1.5 microns every that being coated with of ceramic size carried out thickness; Its high polymer binder of the copolymer layer of macromolecular compound is that molecular weight is 40,80 or 1,200,000 polyacrylate dispersion or Kynoar, and every coating thickness of the emulsion of high polymer binder is 0.35,0.4 or 0.45 micron; The composite porous film material is polyethylene and the compound porous film material of polypropylene that handle through ultraviolet reaming, porosity 40%, 45% or 50% stretching; It is 45,52 or 58 ℃ that the copolymer layer of the ceramic material layer of barrier film basic unit and macromolecular compound is carried out the compound temperature of hot pressing; All the other structures and manufacture craft can with the foregoing description roughly the same.
Lithium battery of the present invention comprises that positive plate, negative plate and barrier film coiling constitute, and said barrier film is an above-mentioned high safe ceramics compound lithium ion barrier film of the present invention.
Other modified products based on the technical scheme of this high safe ceramics compound lithium ion barrier film and lithium battery thereof all belong to protection scope of the present invention; The foregoing description is not the exhaustive of embodiment of the present invention.
Claims (10)
1. one kind high safe ceramics compound lithium ion barrier film; Comprise diaphragm body; It is characterized in that said diaphragm body comprises barrier film basic unit and is located at the ceramic material layer in this barrier film basic unit; The copolymer layer that said barrier film basic unit comprises surface treated composite porous film material layer and is located at the high score compound on this surface treated composite porous film material layer, said ceramic material layer comprises the ceramic material through the nanometer processing.
2. according to the said high safe ceramics compound lithium ion barrier film of claim 1, it is characterized in that said barrier film basic unit processes for the copolymer with said macromolecule chemical combination is sprayed at surface treated composite porous film material surface; Said diaphragm body for through the ceramic material of nanometer processing and ceramic material adhesive by a solid content than the mode that is coated with shoe after mixing, with extruding be coated with shoe in above-mentioned barrier film basic unit of processing after dried in barrier film substrate surface formation ceramic material layer, again under a temperature to this barrier film basic unit and be formed at its surperficial ceramic material layer and carry out the compound heat stabilisation process of hot pressing and process.
3. according to the said high safe ceramics compound lithium ion barrier film of claim 2, it is characterized in that the temperature that said ceramic material layer and barrier film basic unit carry out the compound heat stabilisation process of hot pressing is 40 ℃～60 ℃; Said ceramic material through the nanometer processing is 80%～96%:20%～4% with the solid content ratio of ceramic material adhesive.
4. according to claim 2 or 3 said high safe ceramics compound lithium ion barrier films, it is characterized in that said ceramic material adhesive is a polymer binder.
5. according to the said high safe ceramics compound lithium ion barrier film of claim 4, it is characterized in that said ceramic material polymer binder comprises that molecular weight is 30～1,200,000 polyacrylate dispersion or Kynoar.
6. according to claim 1 or 2 said high safe ceramics compound lithium ion barrier films, it is characterized in that said ceramic material comprises α-Al
2O
3And/or SiO2; The copolymer of said macromolecule chemical combination comprises that molecular weight is 30～1,200,000 polyacrylate dispersion or Kynoar; The porosity of said composite porous film material is 40%～56%.
7. according to the said high safe ceramics compound lithium ion barrier film of claim 6, the weight ratio that it is characterized in that said α-Al2O3 and SiO2 is 55%～98%:45%～2%.
8. according to claim 1 or 2 said high safe ceramics compound lithium ion barrier films, the thickness that it is characterized in that the copolymer layer of said macromolecular compound is 0.3～0.5 micron, and the thickness of said ceramic material layer is 1～1.5 micron; The surface treatment of said composite porous film material comprises ultraviolet reaming processing.
9. according to claim 1 or 2 said high safe ceramics compound lithium ion barrier films, it is characterized in that said composite porous film material comprises that porosity is the polypropylene and/or the polyethylene composite porous film material of stretching 40%～56%, that handle through ultraviolet reaming.
10. according to claim 1 or 2 said high safe ceramics compound lithium ion barrier films, the copolymer layer that it is characterized in that said macromolecule chemical combination comprise be added with macromolecule solvent, molecular weight is 30～1,200,000 polyacrylate dispersion or Kynoar binding agent; Said macromolecule solvent comprises the N-methylpyrrole.
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| CN201210166837.4A CN102651466B (en) | 2012-05-27 | 2012-05-27 | High-safety ceramic composite lithium-ion isolating membrane and lithium battery thereof |
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| CN201210166837.4A CN102651466B (en) | 2012-05-27 | 2012-05-27 | High-safety ceramic composite lithium-ion isolating membrane and lithium battery thereof |
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| CN102651466A true CN102651466A (en) | 2012-08-29 |
| CN102651466B CN102651466B (en) | 2014-12-10 |
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| CN201210166837.4A Expired - Fee Related CN102651466B (en) | 2012-05-27 | 2012-05-27 | High-safety ceramic composite lithium-ion isolating membrane and lithium battery thereof |
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Cited By (11)
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| CN103474602A (en) * | 2013-08-30 | 2013-12-25 | 深圳市泰百科技有限公司 | Pore-forming ceramic isolating membrane of lithium ion battery and preparation method thereof |
| CN104143615A (en) * | 2013-08-26 | 2014-11-12 | 河南师范大学 | A kind of lithium-ion battery composite diaphragm and preparation method thereof |
| CN106463711A (en) * | 2014-03-24 | 2017-02-22 | 康奈尔大学 | Dendrite inhibiting electrolytes for metal-based batteries |
| CN106848160A (en) * | 2016-03-11 | 2017-06-13 | 住友化学株式会社 | Porous layer |
| US10950838B2 (en) | 2017-12-19 | 2021-03-16 | Sumitomo Chemical Company, Limited | Nonaqueous electrolyte secondary battery |
| US10957941B2 (en) | 2017-12-19 | 2021-03-23 | Sumitomo Chemical Company, Limited | Nonaqueous electrolyte secondary battery |
| US11038208B2 (en) | 2017-12-19 | 2021-06-15 | Sumitomo Chemical Company, Limited | Nonaqueous electrolyte secondary battery |
| US11094997B2 (en) | 2017-05-29 | 2021-08-17 | Sumitomo Chemical Company, Limited | Nonaqueous electrolyte secondary battery |
| US11158907B2 (en) | 2017-12-19 | 2021-10-26 | Sumitomo Chemical Company, Limited | Nonaqueous electrolyte secondary battery |
| US11158883B2 (en) | 2017-12-19 | 2021-10-26 | Sumitomo Chemical Company, Limited | Nonaqueous electrolyte secondary battery |
| US11205799B2 (en) | 2017-12-19 | 2021-12-21 | Sumitomo Chemical Company, Limited | Nonaqueous electrolyte secondary battery |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104143615A (en) * | 2013-08-26 | 2014-11-12 | 河南师范大学 | A kind of lithium-ion battery composite diaphragm and preparation method thereof |
| CN104143615B (en) * | 2013-08-26 | 2016-08-03 | 河南师范大学 | A kind of lithium ion battery composite separation membrane and preparation method thereof |
| CN103474602B (en) * | 2013-08-30 | 2018-01-02 | 深圳市泰百科技有限公司 | A kind of lithium ion battery pore-creating ceramics barrier film and preparation method thereof |
| CN103474602A (en) * | 2013-08-30 | 2013-12-25 | 深圳市泰百科技有限公司 | Pore-forming ceramic isolating membrane of lithium ion battery and preparation method thereof |
| CN106463711B (en) * | 2014-03-24 | 2021-05-07 | 康奈尔大学 | Dendrite inhibiting electrolyte for metal-based batteries |
| CN106463711A (en) * | 2014-03-24 | 2017-02-22 | 康奈尔大学 | Dendrite inhibiting electrolytes for metal-based batteries |
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| CN106848160A (en) * | 2016-03-11 | 2017-06-13 | 住友化学株式会社 | Porous layer |
| US9876210B2 (en) | 2016-03-11 | 2018-01-23 | Sumitomo Chemical Company, Limited | Porous layer |
| US11094997B2 (en) | 2017-05-29 | 2021-08-17 | Sumitomo Chemical Company, Limited | Nonaqueous electrolyte secondary battery |
| US10957941B2 (en) | 2017-12-19 | 2021-03-23 | Sumitomo Chemical Company, Limited | Nonaqueous electrolyte secondary battery |
| US11038208B2 (en) | 2017-12-19 | 2021-06-15 | Sumitomo Chemical Company, Limited | Nonaqueous electrolyte secondary battery |
| US10950838B2 (en) | 2017-12-19 | 2021-03-16 | Sumitomo Chemical Company, Limited | Nonaqueous electrolyte secondary battery |
| US11158907B2 (en) | 2017-12-19 | 2021-10-26 | Sumitomo Chemical Company, Limited | Nonaqueous electrolyte secondary battery |
| US11158883B2 (en) | 2017-12-19 | 2021-10-26 | Sumitomo Chemical Company, Limited | Nonaqueous electrolyte secondary battery |
| US11205799B2 (en) | 2017-12-19 | 2021-12-21 | Sumitomo Chemical Company, Limited | Nonaqueous electrolyte secondary battery |
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Effective date of registration: 20221130 Address after: 336100 building 7, high-end manufacturing industrial park, industrial park, Wanzai County, Yichun City, Jiangxi Province Patentee after: Jiangxi Xinhai New Energy Technology Co.,Ltd. Address before: 336000 No. 2, Chunshui Road, Yichun Economic Development Zone, Jiangxi Province Patentee before: JIANGXI JINLU NEW ENERGY CO.,LTD. |
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