CN104022247A - Multi-element composite lithium ion battery diaphragm and preparation method thereof - Google Patents
Multi-element composite lithium ion battery diaphragm and preparation method thereof Download PDFInfo
- Publication number
- CN104022247A CN104022247A CN201410284850.9A CN201410284850A CN104022247A CN 104022247 A CN104022247 A CN 104022247A CN 201410284850 A CN201410284850 A CN 201410284850A CN 104022247 A CN104022247 A CN 104022247A
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- Prior art keywords
- lithium ion
- barrier film
- ion battery
- pvdf
- composite lithium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
Abstract
The invention relates to a multi-element composite lithium ion battery diaphragm. The multi-element composite lithium ion battery diaphragm comprises one or more multi-element coatings and a digraph basal body, and is characterized in that one side or two sides of the diaphragm basal body are respectively coated with the multi-element coating, the thickness of the coating is 0.5 to 5 micrometers, and the thickness of the diaphragm basal body is 20 to 150 micrometers. The multi-element composite lithium ion battery diaphragm is high in mechanical strength and safety and large in ion conductivity. A lithium ion battery produced with the composite diaphragm is excellent in power characteristic and high in safety performance.
Description
Technical field
The present invention relates to a kind of polynary compound lithium ion battery separator and preparation thereof, particularly relate to barrier film of polynary compound high-liquid absorbing rate, high conductance for a kind of lithium ion battery and preparation method thereof, belong to lithium ion battery material technical field.
Background technology
Lithium ion battery is a kind of very effectively very safe stored energy and conversion equipment, along with the development in scientific and technological progress and epoch is more and more accepted by people, application is also more and more extensive, comprises the fields such as portable type electronic product, mobile phone, electric automobile.Diaphragm material is the very important part of lithium ion battery, and it can realize the function of electronic isolation, prevents the direct contact between both positive and negative polarity, avoids short circuit.In addition, diaphragm material or well ion conductor, can realize lithium ion repeatedly moving between positive and negative electrode, completes the charge and discharge function of lithium battery.
Traditional barrier film mostly is polyolefin porous membrane, mainly by dry method or wet method preparation, obtains.The common thermal stability of this polyalkene diaphragm is lower, 135
oduring C left and right, closed pore can occur, the passage of the lithium ion migration of blocking-up battery, stops electrochemical reaction.In addition, due to polyalkene diaphragm self character, when it directly contacts with electrolyte, effect of impregnation is unsatisfactory, causes battery high rate performance to decrease.The measure of taking for the numerous researchers of this problem is, membrane surface is coated with and is covered with inorganic nano-particle, by nano particle, compared with bigger serface, improves the pick up of barrier film.But, once inorganic particulate is coated to the Micro porosity of barrier film, form " steric hindrance " of lithium ion transmission, cannot meet lithium ion battery multiplying power discharging characteristic.
For this reason, this patent will apply a small amount of very Li of macroion conductivity that has on the polyalcohol stephanoporate membrane surface traditional
10geP
2s
12, part substitutes inorganic nano-particle, at the ionic conductance that guarantees can also improve when barrier film has compared with high-liquid absorbing rate and mechanical strength barrier film, even if also can guarantee that when inorganic particulate content is higher barrier film has certain ionicconductive function.In addition,, in order further to improve the ion transmission efficiency of barrier film, this patent has also added a small amount of graphene oxide in inorganic nano-particle.
Summary of the invention
The object of the present invention is to provide a kind of polynary compound lithium ion battery separator, have higher mechanical strength, fail safe and larger ionic conductance, the lithium ion battery power characteristic of making of this composite diaphragm is outstanding, and security performance is higher.
Technical scheme of the present invention is achieved in that a kind of polynary compound lithium ion battery separator, comprise multi-element coating and barrier film matrix, it is characterized in that: multi-element coating is coated in a side or the both sides of barrier film matrix, coating layer thickness is 0.5 ~ 5 μ m, and barrier film matrix thickness is 20 ~ 150 μ m.
Described multi-element coating comprises 15 ~ 26% binding agent, 40 ~ 60% inorganic nano-particle, 1 ~ 8% graphene oxide, 15 ~ 35% Li
10geP
2s
12; Described barrier film matrix comprises polyethylene (PE) perforated membrane, polypropylene (PP) perforated membrane and polyethylene terephthalate (PET) based nonwoven, Kynoar (PVDF) and copolymer thereof, polyimides (PI), cellulose.
Described binding agent can adopt a kind of in PVDF, PVDF-HFP copolymer or PAN, and described inorganic nano-particle comprises Al
2o
3, SiO
2, ZrO
2, ZnO and TiO
2in one or more mixture.
A preparation method for multi-component composite lithium ion cell barrier film, is characterized in that concrete preparation process is as follows:
A) by business-like 40 ~ 60% inorganic nano-particle powder, 1 ~ 8% graphene oxide, 15 ~ 35% Li
10geP
2s
12after mixing with 15 ~ 26% binding agent, be dissolved in NMP or acetone soln the suspension-turbid liquid that to form solid content be 60 ~ 93%;
B) adopt the tape casting step a) gained solution to be coated in equably to a side or the both sides of polyolefin (PP, PE) barrier film or polyethylene terephthalate (PET) based nonwoven;
C) apply metacneme and be placed in 50 ~ 80
oat C temperature, dry 10 ~ 60 minutes, get final product to obtain polynary compound lithium ion battery separator.
Inorganic particulate in described step a) comprises Al
2o
3, SiO
2, ZrO
2, ZnO and TiO
2in one or more mixture, particle size is 30 ~ 200nm; Described binding agent comprises PVDF, PVDF-HFP copolymer, PAN.
Good effect of the present invention is that it has higher mechanical strength, fail safe and larger ionic conductance, and the lithium ion battery power characteristic of making of this composite diaphragm is outstanding, and security performance is higher.
Accompanying drawing explanation
Fig. 1 is the structural representation of multi-component composite lithium ion cell barrier film of the present invention, and wherein " 1 " is barrier film matrix, and " 2 " are multi-element coating.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the invention will be further described:
embodiment 1
As shown in Figure 1, by 60% commercialization Al
2o
3powder (particle size is 30nm), 8% graphene oxide, 15% Li
10geP
2s
12after mixing with 17% PVDF-HFP copolymer, be dissolved in nmp solution the suspension-turbid liquid that to form solid content be 93%; Adopt the tape casting that above-mentioned solution is coated in to the polyethylene PP barrier film both sides that 20 μ m are thick equably, the coating thickness on two sides is 1 μ m; Apply metacneme and be placed in 50
oat C temperature, dry 60 minutes, get final product to obtain polynary compound lithium ion battery separator.
embodiment 2
By 40% commercialization ZrO
2powder (particle size is 200nm), 1% graphene oxide, 33% Li
10geP
2s
12after mixing with 26% PVDF-HFP copolymer, be dissolved in acetone soln the suspension-turbid liquid that to form solid content be 60%; Adopt the tape casting that above-mentioned solution is coated in to the polypropylene PP barrier film both sides that 30 μ m are thick equably, the coating thickness on two sides is 5 μ m; Apply metacneme and be placed in 80
oat C temperature, dry 10 minutes, get final product to obtain polynary compound lithium ion battery separator.
embodiment 3
By 45% commercialization SiO
2and TiO
2mixture (SiO
2and TiO
2mass ratio be 1:1, particle size is 50nm), 5% graphene oxide, 35% Li
10geP
2s
12after mixing with 15% PVDF, be dissolved in acetone soln the suspension-turbid liquid that to form solid content be 75%; Adopt the tape casting that above-mentioned solution is coated in to PET based nonwoven one side that 150 μ m are thick equably, coating thickness is 2 μ m; Apply metacneme and be placed in 80
oat C temperature, dry 30 minutes, get final product to obtain polynary compound lithium ion battery separator.
embodiment 4
By 38% commercialization ZnO
2powder (particle size is 45nm), 6% graphene oxide, 31% Li
10geP
2s
12after mixing with 25% PAN, be dissolved in acetone soln the suspension-turbid liquid that to form solid content be 73%; Adopt the tape casting that above-mentioned solution is coated in to the polythene PE barrier film both sides that 30 μ m are thick equably, the coating thickness on two sides is 2 μ m; Apply metacneme and be placed in 50
oat C temperature, dry 50 minutes, get final product to obtain polynary compound lithium ion battery separator.
Claims (5)
1. a polynary compound lithium ion battery separator, comprises multi-element coating and barrier film matrix, it is characterized in that: multi-element coating is coated in a side or the both sides of barrier film matrix, and coating layer thickness is 0.5 ~ 5 μ m, and barrier film matrix thickness is 20 ~ 150 μ m.
2. multi-component composite lithium ion cell barrier film according to claim 1, is characterized in that described multi-element coating comprises 15 ~ 26% binding agent, 40 ~ 60% inorganic nano-particle, 1 ~ 8% graphene oxide, 15 ~ 35% Li
10geP
2s
12; Described barrier film matrix comprises polyethylene (PE) perforated membrane, polypropylene (PP) perforated membrane and polyethylene terephthalate (PET) based nonwoven, Kynoar (PVDF) and copolymer thereof, polyimides (PI), cellulose.
3. multi-component composite lithium ion cell barrier film according to claim 2, is characterized in that described binding agent can adopt a kind of in PVDF, PVDF-HFP copolymer or PAN, and described inorganic nano-particle comprises Al
2o
3, SiO
2, ZrO
2, ZnO and TiO
2in one or more mixture.
4. a preparation method for multi-component composite lithium ion cell barrier film, is characterized in that concrete preparation process is as follows:
A) by business-like 40 ~ 60% inorganic nano-particle powder, 1 ~ 8% graphene oxide, 15 ~ 35% Li
10geP
2s
12after mixing with 15 ~ 26% binding agent, be dissolved in NMP or acetone soln the suspension-turbid liquid that to form solid content be 60 ~ 93%;
B) adopt the tape casting step a) gained solution to be coated in equably to a side or the both sides of polyolefin (PP, PE) barrier film or polyethylene terephthalate (PET) based nonwoven;
C) apply metacneme and be placed in 50 ~ 80
oat C temperature, dry 10 ~ 60 minutes, get final product to obtain polynary compound lithium ion battery separator.
5. a kind of preparation method of multi-component composite lithium ion cell barrier film according to claim 4, is characterized in that the inorganic particulate in described step a) comprises Al
2o
3, SiO
2, ZrO
2, ZnO and TiO
2in one or more mixture, particle size is 30 ~ 200nm; Described binding agent comprises PVDF, PVDF-HFP copolymer, PAN.
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|---|---|---|---|
| CN201410284850.9A CN104022247A (en) | 2014-06-24 | 2014-06-24 | Multi-element composite lithium ion battery diaphragm and preparation method thereof |
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|---|---|---|---|
| CN201410284850.9A CN104022247A (en) | 2014-06-24 | 2014-06-24 | Multi-element composite lithium ion battery diaphragm and preparation method thereof |
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ID=51438896
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104538573A (en) * | 2014-12-30 | 2015-04-22 | 刘剑洪 | Diaphragm for lithium ion battery and preparation method of diaphragm |
| CN105680119A (en) * | 2015-07-13 | 2016-06-15 | 中国第一汽车股份有限公司 | Hybrid energy-storing device and manufacturing method thereof |
| CN105970605A (en) * | 2016-05-26 | 2016-09-28 | 厦门大学 | Graphene oxide composite non-woven fabric and preparation method and application thereof |
| CN106299208A (en) * | 2016-10-12 | 2017-01-04 | 河北金力新能源科技股份有限公司 | A kind of preparation method of high temperature resistant low-resistivity lithium ion battery separator |
| CN106848384A (en) * | 2017-03-10 | 2017-06-13 | 合肥中航新能源技术研究院有限责任公司 | A kind of long-life lithium sulphur electrokinetic cell of high-energy-density |
| CN106876636A (en) * | 2017-04-08 | 2017-06-20 | 深圳市佩成科技有限责任公司 | A kind of preparation method of Fluorinated graphene oxide/Celgard composite diaphragms |
| WO2018050067A1 (en) * | 2016-09-13 | 2018-03-22 | 河北金力新能源科技股份有限公司 | Heat-resistant multi-layer composite lithium-ion battery separator, and coating device and manufacturing method for same |
| CN109860487A (en) * | 2019-01-18 | 2019-06-07 | 合肥国轩高科动力能源有限公司 | A kind of lithium ion battery composite separation membrane and preparation method thereof |
| WO2024011404A1 (en) * | 2022-07-12 | 2024-01-18 | 宁德时代新能源科技股份有限公司 | Separator, secondary battery using same, battery module, battery pack, and electric apparatus |
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| CN103137929A (en) * | 2011-11-24 | 2013-06-05 | 比亚迪股份有限公司 | Lithium ion battery diaphragm, preparation method of the lithium ion battery diaphragm, and lithium ion battery containing the lithium ion battery diaphragm |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104538573B (en) * | 2014-12-30 | 2017-07-04 | 深圳市本征方程石墨烯技术股份有限公司 | A kind of diaphragm for lithium ion battery and preparation method thereof |
| CN104538573A (en) * | 2014-12-30 | 2015-04-22 | 刘剑洪 | Diaphragm for lithium ion battery and preparation method of diaphragm |
| CN105680119A (en) * | 2015-07-13 | 2016-06-15 | 中国第一汽车股份有限公司 | Hybrid energy-storing device and manufacturing method thereof |
| CN105970605A (en) * | 2016-05-26 | 2016-09-28 | 厦门大学 | Graphene oxide composite non-woven fabric and preparation method and application thereof |
| JP2019522344A (en) * | 2016-09-13 | 2019-08-08 | フーベイ ジェレック ニュー エナジー マテリアル サイエンスアンドテクノロジー カンパニー リミテッドＨｅｂｅｉ Ｇｅｌｌｅｃ Ｎｅｗ Ｅｎｅｒｇｙ Ｍａｔｅｒｉａｌ Ｓｃｉｅｎｃｅ＆Ｔｅｃｈｎｏｌｏｇｙ Ｃｏ．，Ｌｔｄ． | High temperature resistant multi-layer composite lithium ion battery separator, coating apparatus and manufacturing method thereof |
| US11223089B2 (en) * | 2016-09-13 | 2022-01-11 | Hebei Gellec New Energy Material Science & Technology Co., Ltd. | Heat-resistant multi-layer composite lithium-ion battery separator, and coating device and manufacturing method for same |
| KR102205116B1 (en) * | 2016-09-13 | 2021-01-20 | 허베이 겔렉 뉴 에너지 머티리얼 사이언스앤테크놀러지 컴퍼니 리미티드 | Heat-resistant multi-layer composite lithium-ion battery separator, and coating device and manufacturing method for same |
| EP3514855A4 (en) * | 2016-09-13 | 2020-04-01 | Hebei Gellec New Energy Material Science&Technology Co., Ltd. | Heat-resistant multi-layer composite lithium-ion battery separator, and coating device and manufacturing method for same |
| WO2018050067A1 (en) * | 2016-09-13 | 2018-03-22 | 河北金力新能源科技股份有限公司 | Heat-resistant multi-layer composite lithium-ion battery separator, and coating device and manufacturing method for same |
| KR20190023097A (en) | 2016-09-13 | 2019-03-07 | 허베이 겔렉 뉴 에너지 머티리얼 사이언스앤테크놀러지 컴퍼니 리미티드 | Heat-resistant multi-layer composite lithium-ion battery separator, and coating device and manufacturing method for same |
| CN106299208B (en) * | 2016-10-12 | 2018-12-25 | 河北金力新能源科技股份有限公司 | A kind of preparation method of high temperature resistant low-resistivity lithium ion battery separator |
| CN106299208A (en) * | 2016-10-12 | 2017-01-04 | 河北金力新能源科技股份有限公司 | A kind of preparation method of high temperature resistant low-resistivity lithium ion battery separator |
| CN106848384A (en) * | 2017-03-10 | 2017-06-13 | 合肥中航新能源技术研究院有限责任公司 | A kind of long-life lithium sulphur electrokinetic cell of high-energy-density |
| CN106876636A (en) * | 2017-04-08 | 2017-06-20 | 深圳市佩成科技有限责任公司 | A kind of preparation method of Fluorinated graphene oxide/Celgard composite diaphragms |
| CN109860487A (en) * | 2019-01-18 | 2019-06-07 | 合肥国轩高科动力能源有限公司 | A kind of lithium ion battery composite separation membrane and preparation method thereof |
| WO2024011404A1 (en) * | 2022-07-12 | 2024-01-18 | 宁德时代新能源科技股份有限公司 | Separator, secondary battery using same, battery module, battery pack, and electric apparatus |
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