CN104681764A - Composite lithium ion battery ceramic diaphragm and preparation method thereof - Google Patents
Composite lithium ion battery ceramic diaphragm and preparation method thereof Download PDFInfo
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- CN104681764A CN104681764A CN201510068558.8A CN201510068558A CN104681764A CN 104681764 A CN104681764 A CN 104681764A CN 201510068558 A CN201510068558 A CN 201510068558A CN 104681764 A CN104681764 A CN 104681764A
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- electrostatic spinning
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- ion battery
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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
-
- 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 Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a composite lithium ion battery ceramic diaphragm, wherein single-face or double-face electrostatic spinning is carried out on a ceramic coating diaphragm. The preparation method comprises the following steps: step 1, preparing an electrostatic spinning solution; step 2, carrying out electrostatic spinning; and step 3, treating the composite diaphragm obtained by spinning. The electrostatic spinning is carried out on the surfaces of the existing polyolefin ceramic coating diaphragm and non-woven fabric ceramic coating diaphragm, the electrostatic spinning can be used for fastening and constraining ceramic granules to prevent the ceramic granules from dropping, and moreover, the electrostatic spinning is used as a soft buffering layer to perfect the contact of the diaphragm with the surface of an electrode, so as to reduce the interface impedance of the diaphragm and a battery pole piece and help to improve such properties of the battery as rate discharge and cycle life, etc.
Description
Technical field
The present invention relates to battery diaphragm technical field, be specifically related to a kind of compound lithium ion battery ceramic diaphragm and preparation method thereof.
Background technology
Lithium ion battery separator is for intercepting lithium ion battery plus-negative plate, avoids short circuit.Along with the development in the fields such as new-energy automobile, conventional lithium ion battery barrier film is as PE(polyethylene), PP(polypropylene) disadvantages affect of barrier film fusing point low (lower than 150 DEG C) arrived the fail safe of high-power lithium ion battery, for this reason on the basis of conventional polyolefins barrier film, ceramic coated polyalkene diaphragm and ceramic coated nonwoven fabrics barrier film are developed.Disclosed in patent CN104064713, on polyalkene diaphragm and nonwoven fabrics basis, carry out ceramic coated, while improving barrier film safety in utilization, improve the ability that barrier film keeps electrolyte.But in making cell process, we find that dry linting (ceramic particle comes off) phenomenon easily occurs ceramic coating membrane, ceramic particle moisture absorption is strong, and the contact of ceramic coated face and battery pole piece belongs to firmly-firmly contacts, the interface impedance of barrier film and battery pole piece is comparatively large, affects the combination property of battery.
Electrostatic spinning is that one efficiently prepares high polymer nanometer fiber membrane technique, this technology utilizes polymeric solution under the high voltage electrostatic field of several thousand to several ten thousand volts, the surface tension overcoming Polymer Solution forms electrified jet, and constantly there will be acceleration, stretching phenomenon, with solvent evaporates, finally obtain nano-scale fiber film on the reception device.
Summary of the invention
The object of the present invention is to provide a kind of compound lithium ion battery ceramic diaphragm and preparation method thereof, to improve the performance such as multiplying power discharging and cycle life of battery.
To achieve these goals, the technical solution adopted in the present invention is as follows:
A kind of compound lithium ion battery ceramic diaphragm, ceramic coating membrane carries out single or double electrostatic spinning.
Described ceramic coating membrane is the one in polyethylene ceramic-coated separator, polypropylene ceramic-coated separator, PP/PE/PP ceramic-coated separator (upper and lower two-layer PP, middle PE) and nonwoven fabrics ceramic-coated separator.
Pottery used in described ceramic coating membrane is nano inorganic particle, is specially one or more in alundum (Al2O3), silicon dioxide, titanium dioxide, barium titanate, magnesium oxide, zirconia, zinc oxide, boron nitride, carborundum and silicon nitride.
Described electrostatic spinning adopts one or more polymer in polyvinyl alcohol (PVA), polyoxyethylene (PEO), cellulose, CMC, carboxymethyl cellulose, polyimides (PI), aramid fiber, polyacrylonitrile (PAN), Kynoar (PVDF), Kynoar-hexafluoropropylene (PVDF-HFP), polymethyl methacrylate (PMMA) and PSA fiber.
The one side thickness range of described electrostatic spinning is 1-15 μm, and the fiber diameter range of electrostatic spinning is 10-1500nm.
A kind of compound lithium ion battery ceramic diaphragm, its preparation method comprises the following steps:
1st step, prepared by electrostatic spinning solution: by dissolution of polymer used for electrostatic spinning in a solvent, wherein polymer mass percent concentration is in the solution 5-30wt%, measures the viscosity of described solution between 100-3000mPa.S;
2nd step, electrostatic spinning: the electrostatic spinning solution prepared is carried out single or double continuous electrostatic spinning by nanofiber spinning-drawing machine on ceramic diaphragm, obtain nonwoven fabrics/nano-fiber composite film, the condition of described electrostatic spinning is: temperature 10-40 DEG C, voltage 20-50kV, spinning speed is every meter of wide cut 1-10g per minute, and the one side thickness of nano fibrous membrane is: 1-10 μm;
3rd step, the composite membrane obtained after spinning being completed processes: dry 1-5 minute in 120 DEG C of baking ovens, obtains a kind of compound lithium ion battery ceramic diaphragm.
After adopting such scheme, the present invention carries out electrostatic spinning at existing polyolefin ceramic coating membrane and nonwoven fabrics ceramic coating membrane surface, electrostatic spinning not only can reinforce constraint ceramic particle, prevent from coming off, and, the contact of barrier film and electrode surface can be improved as soft resilient coating, reduce the interface impedance of barrier film and battery pole piece, be conducive to the performances such as the multiplying power discharging of raising battery and cycle life.
Accompanying drawing explanation
Fig. 1 is a kind of electromicroscopic photograph of compound lithium ion battery ceramic diaphragm surface.
Embodiment
Embodiment 1
1) electrostatic spinning solution preparation: be dissolved in by PMMA in NMP (1-METHYLPYRROLIDONE), polyimides mass volume ratio concentration is 5wt %, and the viscosity measuring described polyimide solution is 100mPa.S.
2) electrostatic spinning: the PMMA solution electrostatic spinning solution prepared is carried out one side continuous electrostatic spinning by nanofiber spinning-drawing machine on PET nonwoven fabrics ceramic diaphragm, the condition of described electrostatic spinning is: temperature 10 DEG C, voltage 20kV, spinning speed are every meter of wide cut 1g per minute, and the one side thickness of nano fibrous membrane is 1 μm.
3) composite membrane obtained after spinning being completed processes: drying 1 minute in 120 DEG C of baking ovens, to a kind of compound lithium ion battery ceramic diaphragm, as shown in Figure 1.
Embodiment 2
1) electrostatic spinning solution preparation: be dissolved in by PVA in deionized water, PVA mass volume ratio concentration is 5wt %, and the viscosity measuring described PVA solution is 1500mPa.S.
2) electrostatic spinning: the PVA solution electrostatic spinning solution prepared is carried out two-sided continuous electrostatic spinning by nanofiber spinning-drawing machine on polyethylene ceramic diaphragm, the condition of described electrostatic spinning is: temperature 40 DEG C, voltage 50kV, spinning speed are every meter of wide cut 10g per minute, and the one side thickness of nano fibrous membrane is 10 μm.
3) composite membrane obtained after spinning being completed processes: drying 5 minutes in 120 DEG C of baking ovens, to a kind of compound lithium ion battery ceramic diaphragm.
Embodiment 3
1) electrostatic spinning solution preparation: prepared by electrostatic spinning solution: polyimides is dissolved in DMAc (N, N-dimethylacetylamide) in, polyimides mass volume ratio concentration is 30wt %, and the viscosity measuring described polyimide solution is 3000mPa.S.
2) electrostatic spinning: the polyimide solution electrostatic spinning solution prepared is carried out two-sided continuous electrostatic spinning by nanofiber spinning-drawing machine on PP/PE/PP ceramic-coated separator, the condition of described electrostatic spinning is: temperature 30 DEG C, voltage 40kV, spinning speed are every meter of wide cut 5g per minute, and the one side thickness of nano fibrous membrane is 5 μm.
3) composite membrane obtained after spinning being completed processes: drying 5 minutes in 120 DEG C of baking ovens, obtains a kind of compound lithium ion battery ceramic diaphragm.
Embodiment 4
1) electrostatic spinning solution preparation: prepared by electrostatic spinning solution: be dissolved in by PVDF-HFP in acetone, PVDF-HFP mass volume ratio concentration is 15wt %, and the viscosity measuring described poly-PVDF-HFP solution is 1500mPa.S.
2) electrostatic spinning: the polyacrylonitrile solution electrostatic spinning solution prepared is carried out one side continuous electrostatic spinning by nanofiber spinning-drawing machine on PP non-woven fabrics base material, the condition of described electrostatic spinning is: temperature 25 DEG C, voltage 35kV, spinning speed are every meter of wide cut 6g per minute, and the one side thickness of nano fibrous membrane is 7 μm.
3) composite membrane obtained after spinning being completed processes: drying 3 minutes in 120 DEG C of baking ovens, obtains a kind of compound lithium ion battery ceramic diaphragm.
Claims (6)
1. a compound lithium ion battery ceramic diaphragm, is characterized in that: on ceramic coating membrane, carry out single or double electrostatic spinning.
2. a kind of compound lithium ion battery ceramic diaphragm as claimed in claim 1, is characterized in that: described ceramic coating membrane is the one in polyethylene ceramic-coated separator, polypropylene ceramic-coated separator, PP/PE/PP ceramic-coated separator and nonwoven fabrics ceramic-coated separator.
3. a kind of compound lithium ion battery ceramic diaphragm as claimed in claim 1, it is characterized in that: pottery used in described ceramic coating membrane is nano inorganic particle, be specially one or more in alundum (Al2O3), silicon dioxide, titanium dioxide, barium titanate, magnesium oxide, zirconia, zinc oxide, boron nitride, carborundum and silicon nitride.
4. a kind of compound lithium ion battery ceramic diaphragm as claimed in claim 1, is characterized in that: described electrostatic spinning adopts one or more polymer in PVAC polyvinylalcohol, polyoxyethylene PEO, cellulose, CMC, carboxymethyl cellulose, polyimides PI, aramid fiber, polyacrylonitrile (PAN), Kynoar PVDF, Kynoar-hexafluoropropylene PVDF-HFP, polymetylmethacrylate and PSA fiber.
5. a kind of compound lithium ion battery ceramic diaphragm as claimed in claim 1, it is characterized in that: the one side thickness range of described electrostatic spinning is 1-15 μm, the fiber diameter range of electrostatic spinning is 10-1500nm.
6. a kind of compound lithium ion battery ceramic diaphragm as claimed in claim 1, is characterized in that preparation method comprises the following steps:
1st step, prepared by electrostatic spinning solution: by dissolution of polymer used for electrostatic spinning in a solvent, wherein polymer mass percent concentration is in the solution 5-30wt%, measures the viscosity of described solution between 100-3000mPa.S;
2nd step, electrostatic spinning: the electrostatic spinning solution prepared is carried out single or double continuous electrostatic spinning by nanofiber spinning-drawing machine on ceramic diaphragm, obtain nonwoven fabrics/nano-fiber composite film, the condition of described electrostatic spinning is: temperature 10-40 DEG C, voltage 20-50kV, spinning speed is every meter of wide cut 1-10g per minute, and the one side thickness of nano fibrous membrane is: 1-10 μm;
3rd step, the composite membrane obtained after spinning being completed processes: dry 1-5 minute in 120 DEG C of baking ovens, obtains a kind of compound lithium ion battery ceramic diaphragm.
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| CN201510068558.8A CN104681764A (en) | 2015-02-10 | 2015-02-10 | Composite lithium ion battery ceramic diaphragm and preparation method thereof |
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Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105990037A (en) * | 2016-01-27 | 2016-10-05 | 安徽旭峰电容器有限公司 | Enhanced nonwoven electrostatic spinning fiber membrane composite separator material |
| CN105990035A (en) * | 2016-01-27 | 2016-10-05 | 安徽旭峰电容器有限公司 | Ultrathin low-impedance supercapacitor-used separator material |
| CN105990036A (en) * | 2016-01-27 | 2016-10-05 | 安徽旭峰电容器有限公司 | Supercapacitor composite separator material of high mechanical strength |
| CN106120156A (en) * | 2016-06-24 | 2016-11-16 | 安徽江威精密制造有限公司 | Composite diaphragm material is worn in a kind of ultracapacitor resistance |
| CN106328935A (en) * | 2016-08-30 | 2017-01-11 | 合肥国轩高科动力能源有限公司 | Composite system power battery with high safety and long service life and preparation method of composite system power battery |
| CN106601964A (en) * | 2016-11-25 | 2017-04-26 | 深圳拓邦新能源技术有限公司 | Nanofiber composite membrane and preparation method thereof and lithium-ion battery |
| CN106784539A (en) * | 2017-01-24 | 2017-05-31 | 厦门大学 | A kind of non-woven fabrics ceramic diaphragm and its preparation method and application |
| CN106898814A (en) * | 2015-12-18 | 2017-06-27 | 比亚迪股份有限公司 | A kind of composite membrane of polymer and preparation method thereof, lithium ion battery |
| CN106935772A (en) * | 2017-04-25 | 2017-07-07 | 湖南中智优库科技有限公司 | A kind of electrokinetic cell lithium battery diaphragm and preparation method thereof |
| CN107134555A (en) * | 2017-03-27 | 2017-09-05 | 湖北猛狮新能源科技有限公司 | A kind of complex fire resistant barrier film |
| WO2018040903A1 (en) * | 2016-08-29 | 2018-03-08 | 比亚迪股份有限公司 | Lithium ion battery separator and preparation method therefor, and lithium ion battery |
| CN107785522A (en) * | 2016-08-29 | 2018-03-09 | 比亚迪股份有限公司 | A kind of lithium ion battery separator and lithium ion battery and preparation method thereof |
| CN107910476A (en) * | 2017-11-06 | 2018-04-13 | 上海恩捷新材料科技股份有限公司 | A kind of Ceramic Composite lithium ion battery separator and preparation method thereof |
| CN108242522A (en) * | 2016-12-23 | 2018-07-03 | 比亚迪股份有限公司 | A kind of composite membrane of polymer and preparation method thereof and the lithium ion battery for including it |
| CN108550763A (en) * | 2018-03-16 | 2018-09-18 | 深圳市前海星火同为科技有限公司 | A kind of high capacity lithium ion battery diaphragm protection mechanism and operating system |
| CN109346654A (en) * | 2018-09-10 | 2019-02-15 | 中原工学院 | It is a kind of based on zirconium oxide/aramid fiber composite nano fiber high temperature closed pore function battery diaphragm material and preparation method thereof |
| CN109818054A (en) * | 2018-12-11 | 2019-05-28 | 天津工业大学 | A kind of lithium ion battery electrolyte and preparation method thereof having multilevel structure |
| CN110453372A (en) * | 2019-08-01 | 2019-11-15 | 合肥国轩高科动力能源有限公司 | A kind of composite diaphragm and its preparation method and application |
| CN111916622A (en) * | 2020-08-19 | 2020-11-10 | 北京宇程科技有限公司 | Multifunctional double-sided heterogeneous Janus diaphragm for lithium ion battery and preparation method thereof |
| CN112072054A (en) * | 2020-09-18 | 2020-12-11 | 昆山宝创新能源科技有限公司 | Battery diaphragm and preparation method and application thereof |
| CN112510320A (en) * | 2020-11-18 | 2021-03-16 | 东莞市魔方新能源科技有限公司 | Preparation method of diaphragm for lithium ion battery, diaphragm and lithium ion battery |
| CN112701420A (en) * | 2021-01-23 | 2021-04-23 | 山东天瀚新能源科技有限公司 | Multifunctional diaphragm for lithium battery, preparation method and application |
| CN113140868A (en) * | 2021-04-22 | 2021-07-20 | 中南大学 | In-situ inorganic-organic composite spinning diaphragm and preparation method and application thereof |
| CN113224458A (en) * | 2020-01-17 | 2021-08-06 | 厦门大学 | Preparation method of high-safety long-service-life ceramic diaphragm |
| US11223090B2 (en) | 2016-08-29 | 2022-01-11 | Byd Company Limited | Polymer composite membrane, preparation method thereof, and lithium-ion battery including the same |
| CN113969006A (en) * | 2021-10-21 | 2022-01-25 | 北京宇程科技有限公司 | Polyimide coating modified polyolefin composite diaphragm and preparation method thereof |
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Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106898814A (en) * | 2015-12-18 | 2017-06-27 | 比亚迪股份有限公司 | A kind of composite membrane of polymer and preparation method thereof, lithium ion battery |
| CN105990035A (en) * | 2016-01-27 | 2016-10-05 | 安徽旭峰电容器有限公司 | Ultrathin low-impedance supercapacitor-used separator material |
| CN105990036A (en) * | 2016-01-27 | 2016-10-05 | 安徽旭峰电容器有限公司 | Supercapacitor composite separator material of high mechanical strength |
| CN105990037A (en) * | 2016-01-27 | 2016-10-05 | 安徽旭峰电容器有限公司 | Enhanced nonwoven electrostatic spinning fiber membrane composite separator material |
| CN106120156A (en) * | 2016-06-24 | 2016-11-16 | 安徽江威精密制造有限公司 | Composite diaphragm material is worn in a kind of ultracapacitor resistance |
| CN107799696A (en) * | 2016-08-29 | 2018-03-13 | 比亚迪股份有限公司 | A kind of lithium ion battery separator and preparation method thereof and lithium ion battery |
| US11223090B2 (en) | 2016-08-29 | 2022-01-11 | Byd Company Limited | Polymer composite membrane, preparation method thereof, and lithium-ion battery including the same |
| CN107785522B (en) * | 2016-08-29 | 2021-05-14 | 比亚迪股份有限公司 | Lithium ion battery diaphragm, lithium ion battery and preparation method thereof |
| WO2018040903A1 (en) * | 2016-08-29 | 2018-03-08 | 比亚迪股份有限公司 | Lithium ion battery separator and preparation method therefor, and lithium ion battery |
| CN107785522A (en) * | 2016-08-29 | 2018-03-09 | 比亚迪股份有限公司 | A kind of lithium ion battery separator and lithium ion battery and preparation method thereof |
| CN106328935A (en) * | 2016-08-30 | 2017-01-11 | 合肥国轩高科动力能源有限公司 | Composite system power battery with high safety and long service life and preparation method of composite system power battery |
| CN106601964A (en) * | 2016-11-25 | 2017-04-26 | 深圳拓邦新能源技术有限公司 | Nanofiber composite membrane and preparation method thereof and lithium-ion battery |
| CN108242522A (en) * | 2016-12-23 | 2018-07-03 | 比亚迪股份有限公司 | A kind of composite membrane of polymer and preparation method thereof and the lithium ion battery for including it |
| CN106784539A (en) * | 2017-01-24 | 2017-05-31 | 厦门大学 | A kind of non-woven fabrics ceramic diaphragm and its preparation method and application |
| CN107134555A (en) * | 2017-03-27 | 2017-09-05 | 湖北猛狮新能源科技有限公司 | A kind of complex fire resistant barrier film |
| CN106935772A (en) * | 2017-04-25 | 2017-07-07 | 湖南中智优库科技有限公司 | A kind of electrokinetic cell lithium battery diaphragm and preparation method thereof |
| CN107910476A (en) * | 2017-11-06 | 2018-04-13 | 上海恩捷新材料科技股份有限公司 | A kind of Ceramic Composite lithium ion battery separator and preparation method thereof |
| CN108550763A (en) * | 2018-03-16 | 2018-09-18 | 深圳市前海星火同为科技有限公司 | A kind of high capacity lithium ion battery diaphragm protection mechanism and operating system |
| CN109346654A (en) * | 2018-09-10 | 2019-02-15 | 中原工学院 | It is a kind of based on zirconium oxide/aramid fiber composite nano fiber high temperature closed pore function battery diaphragm material and preparation method thereof |
| CN109818054A (en) * | 2018-12-11 | 2019-05-28 | 天津工业大学 | A kind of lithium ion battery electrolyte and preparation method thereof having multilevel structure |
| CN110453372A (en) * | 2019-08-01 | 2019-11-15 | 合肥国轩高科动力能源有限公司 | A kind of composite diaphragm and its preparation method and application |
| CN113224458A (en) * | 2020-01-17 | 2021-08-06 | 厦门大学 | Preparation method of high-safety long-service-life ceramic diaphragm |
| CN111916622A (en) * | 2020-08-19 | 2020-11-10 | 北京宇程科技有限公司 | Multifunctional double-sided heterogeneous Janus diaphragm for lithium ion battery and preparation method thereof |
| CN112072054A (en) * | 2020-09-18 | 2020-12-11 | 昆山宝创新能源科技有限公司 | Battery diaphragm and preparation method and application thereof |
| CN112510320A (en) * | 2020-11-18 | 2021-03-16 | 东莞市魔方新能源科技有限公司 | Preparation method of diaphragm for lithium ion battery, diaphragm and lithium ion battery |
| CN112701420A (en) * | 2021-01-23 | 2021-04-23 | 山东天瀚新能源科技有限公司 | Multifunctional diaphragm for lithium battery, preparation method and application |
| CN113140868A (en) * | 2021-04-22 | 2021-07-20 | 中南大学 | In-situ inorganic-organic composite spinning diaphragm and preparation method and application thereof |
| CN113969006A (en) * | 2021-10-21 | 2022-01-25 | 北京宇程科技有限公司 | Polyimide coating modified polyolefin composite diaphragm and preparation method thereof |
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Application publication date: 20150603 |