CN108063209A - A kind of lithium ion battery ceramic diaphragm and preparation method thereof - Google Patents
A kind of lithium ion battery ceramic diaphragm and preparation method thereof Download PDFInfo
- Publication number
- CN108063209A CN108063209A CN201711197317.9A CN201711197317A CN108063209A CN 108063209 A CN108063209 A CN 108063209A CN 201711197317 A CN201711197317 A CN 201711197317A CN 108063209 A CN108063209 A CN 108063209A
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- Prior art keywords
- ceramic
- lithium ion
- ion battery
- diaphragm
- binding agent
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Classifications
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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
-
- 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 invention discloses a kind of lithium ion battery ceramic diaphragms, and including diaphragm matrix, at least one surface of diaphragm matrix is coated with ceramic slurry, and the ceramic slurry includes binding agent, and the binding agent is epoxy resin.The invention also discloses the preparation methods of above-mentioned lithium ion battery ceramic diaphragm.The present invention applies the ceramic layer that a layer thickness is 1 4um on the surface of lithium ion battery base material membrane, its binding agent is epoxy resin, pass through ultraviolet light, so that epoxy resin of binder crosslinks curing, improve ceramic layer heat resisting temperature and and the adhesion strength of ceramic layer and basement membrane, the thermal contraction of membrane is reduced, the heat resistance of membrane is improved, so as to improve the security performance of lithium ion battery.
Description
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of lithium ion battery ceramic diaphragm and its preparation side
Method.
Background technology
In lithium battery, the major function of membrane is to maintain anode and cathode separates, and to prevent short circuit, while allows ion
Fast transfer, be composition more important in lithium ion battery.The performance of membrane can directly affect the characteristic of battery, such as battery
The performances such as capacity, internal resistance, multiplying power, cycling and self discharge.At present, the material of lithium ion battery separator is usually polyolefins material
Material, heat resistance is poor, and when battery temperature constantly raises, membrane occurs thermal contraction, even fuses, and positive and negative anodes will directly connect
It touches and generates internal short-circuit, battery temperature is caused drastically to raise, reaches positive and negative pole material heat decomposition temperature, battery is in turn resulted in and emits
Cigarette catches fire or even explodes.
In order to improve the thermal stability of membrane, the method used at present is by inorganic ceramic and binding agent in coating on base films
The ceramic layer of composition since inorganic, ceramic layer has preferable thermal stability and mechanical performance, significantly improves the peace of battery
Full performance.Since the thermal contraction of ceramic diaphragm is caused at first by the fusion and decomposition of binding agent in ceramic layer, and go out currently on the market
The binding agent for the ceramic diaphragm sold is mostly relatively polyacrylate binding agent, there are low melting point, the shortcomings that thermal stability is poor.
The content of the invention
Technical problems based on background technology, the present invention propose a kind of lithium ion battery ceramic diaphragm and its preparation
Method the problems such as to solve current ceramic diaphragm thermal contraction and poor stability, improves lithium ion battery safety performance.
A kind of lithium ion battery ceramic diaphragm proposed by the present invention, including diaphragm matrix, the diaphragm matrix is at least one
Surface is coated with ceramic slurry, and the ceramic slurry includes binding agent, and the binding agent is epoxy resin.
Preferably, the diaphragm matrix in PE membranes, PP membranes, PP/PE/PP membranes, nonwoven cloth diaphragm at least
It is a kind of.
Preferably, the thickness of the diaphragm matrix is 1-100um.
Preferably, the thickness of the ceramic slurry coating is 1-4um.
Preferably, the ceramic slurry includes the following raw material formed by weight：20-35 parts of ceramic powder, dispersant
0.1-2 parts, 0.2-2 parts of wetting agent, 0.5-2 parts of antifoaming agent, 60-90 parts of deionized water, 8-20 parts of binding agent.
Preferably, the dispersant is selected from ammonium polyacrylate salt copolymerized solution, polyvinylpyrrolidonesolution solution, polyvinyl alcohol
At least one of solution.
Preferably, the epoxy resin is one-pack type epoxy resin.
Preferably, the preparation method of the ceramic slurry is：By ceramic powder, deionized water, dispersant, wetting agent, defoaming
Agent mixes, and stirs to get pre-dispersed liquid；Binding agent is added in into pre-dispersed liquid, stirs to get ceramic slurry.
Preferably, the ceramic powder in alundum (Al2O3), chromium oxide, magnesia, calcium oxide, zirconium oxide at least one
Kind.
Preferably, the particle size of the ceramic powder is 0.1-5um.
The present invention also provides a kind of preparation methods of the lithium ion battery ceramic diaphragm, comprise the following steps：By described in
Ceramic slurry is coated on diaphragm matrix surface, is dried successively, ultraviolet light.
Preferably, the speed of the coating is 20-100m/min.
Preferably, the one kind of the mode of the coating in micro- intaglio plate coating, dip-coating, extrusion coated, transfer type coating.
Preferably, the temperature of the drying is 60-85 DEG C, time 1-40min.
Preferably, the wavelength of the ultraviolet light is 256-400nm, irradiation time 0.1-2h.
The species of above-mentioned antifoaming agent is not construed as limiting, and is made choice as the case may be.
Above-mentioned ammonium polyacrylate salt copolymerized solution, polyvinylpyrrolidonesolution solution, the solvent of poly-vinyl alcohol solution and concentration
It is not construed as limiting, makes choice as the case may be.
Beneficial effects of the present invention are：The present invention coats a layer thickness on the surface of lithium ion battery base material membrane as 1-
The ceramic slurry coating of 4um, and the binding agent in ceramic slurry is epoxy resin, passes through ultraviolet light so that epoxy resin
Crosslink curing, improve ceramic slurry coating heat resisting temperature and and the bonding of ceramic slurry coating and diaphragm matrix it is strong
Degree, and then the thermal contraction of membrane is reduced, the heat resistance of membrane is improved, improves the security performance of lithium ion battery.
Specific embodiment
In the following, technical scheme is described in detail by specific embodiment.
Embodiment 1
A kind of lithium ion battery ceramic diaphragm, including diaphragm matrix, described one surface of diaphragm matrix is coated with ceramic slurry
Material, the ceramic slurry include binding agent, and the binding agent is epoxy resin.
The preparation method of the lithium ion battery ceramic diaphragm, comprises the following steps：By the ceramic slurry be coated on every
Film matrix surface is dried, ultraviolet light successively.
Embodiment 2
A kind of lithium ion battery ceramic diaphragm, including diaphragm matrix, described one surface of diaphragm matrix is coated with ceramic slurry
Material, the ceramic slurry include binding agent, and the binding agent is epoxy resin；
Wherein, the diaphragm matrix is PE membranes；
The thickness of the diaphragm matrix is 16um；
The thickness of the ceramic slurry coating is 3um；
The ceramic slurry includes the following raw material formed by weight：30 parts of ceramic powder, 1.5 parts of dispersant, wetting agent 1
Part, 1 part of antifoaming agent, 70 parts of deionized water, 10 parts of binding agent；
The dispersant is ammonium polyacrylate salt copolymerized solution；
The epoxy resin is one-pack type epoxy resin；
The preparation method of the ceramic slurry is：Ceramic powder, deionized water, dispersant, wetting agent, antifoaming agent are mixed,
Stir to get pre-dispersed liquid；Binding agent is added in into pre-dispersed liquid, stirs to get ceramic slurry；
The ceramic powder is alundum (Al2O3)；
The particle size of the ceramic powder is 0.5um.
The preparation method of the lithium ion battery ceramic diaphragm, comprises the following steps：The ceramic slurry is used into nick
The mode of plate coating is coated on diaphragm matrix surface, is dried successively, ultraviolet light；
Wherein, the speed of the coating is 50m/min；
The temperature of the drying is 65 DEG C, time 40min；
The wavelength of the ultraviolet light is 365nm, irradiation time 10min.
Embodiment 3
A kind of lithium ion battery ceramic diaphragm, including diaphragm matrix, described one surface of diaphragm matrix is coated with ceramic slurry
Material, the ceramic slurry include binding agent, and the binding agent is epoxy resin；
Wherein, the diaphragm matrix is PP membranes；
The thickness of the diaphragm matrix is 20um；
The thickness of the ceramic slurry coating is 2um；
The ceramic slurry includes the following raw material formed by weight：35 parts of ceramic powder, 2 parts of dispersant, wetting agent 1
Part, 1.5 parts of antifoaming agent, 85 parts of deionized water, 12 parts of binding agent；
The dispersant is polyvinylpyrrolidonesolution solution；
The epoxy resin is one-pack type epoxy resin；
The preparation method of the ceramic slurry is：Ceramic powder, deionized water, dispersant, wetting agent, antifoaming agent are mixed,
Stir to get pre-dispersed liquid；Binding agent is added in into pre-dispersed liquid, stirs to get ceramic slurry；
The ceramic powder is chromium oxide；
The particle size of the ceramic powder is 0.5um.
The preparation method of the lithium ion battery ceramic diaphragm, comprises the following steps：The ceramic slurry is used into nick
The mode of plate coating is coated on diaphragm matrix surface, is dried successively, ultraviolet light；
Wherein, the speed of the coating is 35m/min；
The temperature of the drying is 60 DEG C, time 1min；
The wavelength of the ultraviolet light is 254nm, irradiation time 8min.
Embodiment 4
A kind of lithium ion battery ceramic diaphragm, including diaphragm matrix, described one surface of diaphragm matrix is coated with ceramic slurry
Material, the ceramic slurry include binding agent, and the binding agent is epoxy resin；
Wherein, the diaphragm matrix is PE membranes；
The thickness of the diaphragm matrix is 12um；
The thickness of the ceramic slurry coating is 4um；
The ceramic slurry includes the following raw material formed by weight：25 parts of ceramic powder, 0.8 part of dispersant, wetting agent 1
Part, 1 part of antifoaming agent, 65 parts of deionized water, 12 parts of binding agent；
The dispersant is poly-vinyl alcohol solution；
The epoxy resin is one-pack type epoxy resin；
The preparation method of the ceramic slurry is：Ceramic powder, deionized water, dispersant, wetting agent, antifoaming agent are mixed,
Stir to get pre-dispersed liquid；Binding agent is added in into pre-dispersed liquid, stirs to get ceramic slurry；
The ceramic powder is magnesia；
The particle size of the ceramic powder is 1um.
The preparation method of the lithium ion battery ceramic diaphragm, comprises the following steps：The ceramic slurry is used into nick
The mode of plate coating is coated on diaphragm matrix surface, is dried successively, ultraviolet light；
Wherein, the speed of the coating is 30m/min；
The temperature of the drying is 60 DEG C, time 10min；
The wavelength of the ultraviolet light is 365nm, irradiation time 20min.
Embodiment 5
A kind of lithium ion battery ceramic diaphragm, including diaphragm matrix, described one surface of diaphragm matrix is coated with ceramic slurry
Material, the ceramic slurry include binding agent, and the binding agent is epoxy resin；
Wherein, the diaphragm matrix is PP/PE/PP membranes；
The thickness of the diaphragm matrix is 1um；
The thickness of the ceramic slurry coating is 3um；
The ceramic slurry includes the following raw material formed by weight：20 parts of ceramic powder, 2 parts of dispersant, wetting agent 0.2
Part, 0.5 part of antifoaming agent, 90 parts of deionized water, 8 parts of binding agent；
The dispersant is ammonium polyacrylate salt copolymerized solution；
The epoxy resin is one-pack type epoxy resin；
The preparation method of the ceramic slurry is：Ceramic powder, deionized water, dispersant, wetting agent, antifoaming agent are mixed,
Stir to get pre-dispersed liquid；Binding agent is added in into pre-dispersed liquid, stirs to get ceramic slurry；
The ceramic powder is calcium oxide；
The particle size of the ceramic powder is 5um.
The preparation method of the lithium ion battery ceramic diaphragm, comprises the following steps：The ceramic slurry is used into dip-coating
Mode be coated on diaphragm matrix surface, be dried successively, ultraviolet light；
Wherein, the speed of the coating is 20m/min；
The temperature of the drying is 85 DEG C, time 30min；
The wavelength of the ultraviolet light is 256nm, irradiation time 2h.
Embodiment 6
A kind of lithium ion battery ceramic diaphragm, including diaphragm matrix, described one surface of diaphragm matrix is coated with ceramic slurry
Material, the ceramic slurry include binding agent, and the binding agent is epoxy resin；
Wherein, the diaphragm matrix is nonwoven cloth diaphragm；
The thickness of the diaphragm matrix is 100um；
The thickness of the ceramic slurry coating is 1um；
The ceramic slurry includes the following raw material formed by weight：35 parts of ceramic powder, 0.1 part of dispersant, wetting agent 2
Part, 2 parts of antifoaming agent, 60 parts of deionized water, 20 parts of binding agent；
The dispersant is polyvinylpyrrolidonesolution solution；
The epoxy resin is one-pack type epoxy resin；
The preparation method of the ceramic slurry is：Ceramic powder, deionized water, dispersant, wetting agent, antifoaming agent are mixed,
Stir to get pre-dispersed liquid；Binding agent is added in into pre-dispersed liquid, stirs to get ceramic slurry；
The ceramic powder is zirconium oxide；
The particle size of the ceramic powder is 0.1um.
The preparation method of the lithium ion battery ceramic diaphragm, comprises the following steps：By the ceramic slurry using extruding
The mode of coating is coated on diaphragm matrix surface, is dried successively, ultraviolet light；
Wherein, the speed of the coating is 100m/min；
The temperature of the drying is 75 DEG C, time 35min；
The wavelength of the ultraviolet light is 400nm, irradiation time 0.1h.
Test example 1
Polyacrylics is used to prepare ceramic slurry for binding agent to be coated, wherein, diaphragm matrix is PE membranes,
Membrane thicknesses are 16um, and single side coated ceramic slurry, the thickness of ceramic slurry coating is 4um.
Carry out the test of coating stripping intensity and thermal contraction respectively to the ceramic diaphragm that embodiment 2-4 and test example 1 are obtained,
As a result such as following table：
| Project | Binding agent in ceramic slurry | The peel strength N/m of membrane | The percent thermal shrinkage (%) (130 DEG C/2h) of membrane |
| Embodiment 2 | Epoxy resin | 140 | 2.0 |
| Embodiment 3 | Epoxy resin | 120 | 1 |
| Embodiment 4 | Epoxy resin | 135 | 3.5 |
| Test example 1 | Acrylate | 100 | 7 |
As seen from the above table, using epoxy resin as binding agent ceramic slurry prepare ceramic diaphragm, ceramic slurry coating with
The adhesion strength of diaphragm matrix is high, and the thermal contraction of membrane is small.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
- A kind of 1. lithium ion battery ceramic diaphragm, including diaphragm matrix, which is characterized in that at least one surface of diaphragm matrix Coated with ceramic slurry, the ceramic slurry includes binding agent, and the binding agent is epoxy resin.
- 2. lithium ion battery ceramic diaphragm according to claim 1, which is characterized in that the diaphragm matrix be selected from PE membranes, At least one of PP membranes, PP/PE/PP membranes, nonwoven cloth diaphragm；Preferably, the thickness of the diaphragm matrix is 1- 100um；Preferably, the thickness of the ceramic slurry coating is 1-4um.
- 3. lithium ion battery ceramic diaphragm according to claim 1 or claim 2, which is characterized in that the ceramic slurry includes following The raw material formed by weight：20-35 parts of ceramic powder, 0.1-2 parts of dispersant, 0.5-2 parts of antifoaming agent, are gone 0.2-2 parts of wetting agent 60-90 parts of ionized water, 8-20 parts of binding agent.
- 4. according to any one of the claim 1-3 lithium ion battery ceramic diaphragms, which is characterized in that the dispersant is selected from poly- At least one of acrylic acid ammonium salt copolymerized solution, polyvinylpyrrolidonesolution solution, poly-vinyl alcohol solution.
- 5. according to any one of the claim 1-4 lithium ion battery ceramic diaphragms, which is characterized in that the epoxy resin is single Component-type epoxy resin.
- 6. according to any one of the claim 1-5 lithium ion battery ceramic diaphragms, which is characterized in that the system of the ceramic slurry Preparation Method is：Ceramic powder, deionized water, dispersant, wetting agent, antifoaming agent are mixed, stir to get pre-dispersed liquid；To pre-dispersed Binding agent is added in liquid, stirs to get ceramic slurry.
- 7. lithium ion battery ceramic diaphragm according to claim 6, which is characterized in that the ceramic powder is selected from three oxidations two At least one of aluminium, chromium oxide, magnesia, calcium oxide, zirconium oxide；Preferably, the particle size of the ceramic powder is 0.1- 5um。
- A kind of 8. preparation method based on any one of the claim 1-7 lithium ion battery ceramic diaphragms, which is characterized in that bag Include following step：The ceramic slurry is coated on diaphragm matrix surface, is dried successively, ultraviolet light.
- 9. the preparation method of lithium ion battery ceramic diaphragm according to claim 8, which is characterized in that the speed of the coating For 20-100m/min；Preferably, the mode of the coating is in micro- intaglio plate coating, dip-coating, extrusion coated, transfer type coating One kind；Preferably, the temperature of the drying is 60-85 DEG C, time 1-40min.
- 10. lithium ion battery ceramic diaphragm according to claim 8 or claim 9, which is characterized in that the wavelength of the ultraviolet light is 256-400nm, irradiation time 0.1-2h.
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| CN201711197317.9A CN108063209A (en) | 2017-11-25 | 2017-11-25 | A kind of lithium ion battery ceramic diaphragm and preparation method thereof |
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| CN201711197317.9A CN108063209A (en) | 2017-11-25 | 2017-11-25 | A kind of lithium ion battery ceramic diaphragm and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108933219A (en) * | 2018-09-29 | 2018-12-04 | 杨晓丽 | A kind of preparation method of lithium battery diaphragm |
| CN108963150A (en) * | 2018-06-20 | 2018-12-07 | 上海恩捷新材料科技股份有限公司 | Isolation film coating paste, battery isolating film, lithium ion battery and preparation method |
| CN109360921A (en) * | 2018-09-17 | 2019-02-19 | 湖北江升新材料有限公司 | A kind of lithium ion battery ceramic diaphragm and manufacturing method |
| CN109461872A (en) * | 2018-09-29 | 2019-03-12 | 湖北江升新材料有限公司 | A kind of ceramic slurry and lithium ion battery separator |
| CN109638203A (en) * | 2018-11-26 | 2019-04-16 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of lithium ion battery separator |
| CN112909432A (en) * | 2021-01-26 | 2021-06-04 | 东莞维科电池有限公司 | High-hardness lithium ion battery |
| CN113161684A (en) * | 2021-03-18 | 2021-07-23 | 河北金力新能源科技股份有限公司 | High-temperature-resistant and high-strength diaphragm and preparation method thereof |
| CN116073073A (en) * | 2023-03-09 | 2023-05-05 | 合肥长阳新材料科技有限公司 | High-liquid-absorption lithium battery diaphragm and preparation method thereof |
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| CN113161684A (en) * | 2021-03-18 | 2021-07-23 | 河北金力新能源科技股份有限公司 | High-temperature-resistant and high-strength diaphragm and preparation method thereof |
| CN116073073A (en) * | 2023-03-09 | 2023-05-05 | 合肥长阳新材料科技有限公司 | High-liquid-absorption lithium battery diaphragm and preparation method thereof |
| CN116073073B (en) * | 2023-03-09 | 2023-06-13 | 合肥长阳新材料科技有限公司 | High-liquid-absorption lithium battery diaphragm and preparation method thereof |
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Application publication date: 20180522 |