CN109659468A - A kind of composite diaphragm and its preparation and application with hot off function - Google Patents

A kind of composite diaphragm and its preparation and application with hot off function Download PDF

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Publication number
CN109659468A
CN109659468A CN201710940702.1A CN201710940702A CN109659468A CN 109659468 A CN109659468 A CN 109659468A CN 201710940702 A CN201710940702 A CN 201710940702A CN 109659468 A CN109659468 A CN 109659468A
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China
Prior art keywords
preparation
diaphragm
lithium ion
composite diaphragm
composite
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CN201710940702.1A
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Chinese (zh)
Inventor
李先锋
张华民
李丹
史丁秦
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Priority to CN201710940702.1A priority Critical patent/CN109659468A/en
Publication of CN109659468A publication Critical patent/CN109659468A/en
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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
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M50/411—Organic 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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous 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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Cell Separators (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a kind of preparation method of the lithium ion battery composite separation membrane of high-temperature stability with hot off function and its applications in lithium ion battery.Using polyolefin porous membrane as matrix, on the surface of this matrix, using the method for inversion of phases, at least it is coated with one layer of heat resistant coating and forms composite porous film.Composite diaphragm for lithium ion battery provided by the invention has the advantage that the porosity of composite membrane is high, good with the affinity of electrolyte, is conducive to the raising of battery high rate performance；The temperature classification of composite membrane is high, improves the security performance of battery；Composite membrane also has high temperature fuse function, further enhances the security performance of battery.In addition, this method and process is simple, at low cost, strong operability, is conducive to further genralrlization use, is a kind of lithium ion battery separator of great application prospect.

Description

A kind of composite diaphragm and its preparation and application with hot off function
Technical field
The present invention relates to a kind of lithium ion battery composite separation membranes and its preparation method and application, more specifically a kind of to have heat The composite diaphragm for lithium ion battery of disconnected function and its preparation and application.
Background technique
With the development of society, the progress of science and technology, environmental pollution becomes a urgent problem to be solved.In order to alleviate due to The greenhouse gases and poisonous and harmful substance of the burning and exhausting of fossil fuel, construct more harmonious living environment, electric car by More and more extensive concern is arrived.Power part used in electric car is battery, and lithium ion battery is due to energy density Height, memory-less effect, have extended cycle life, advantages of environment protection has broad application prospects in electric car field.
Lithium ion battery is mainly made of electrode, electrolyte, diaphragm three parts.One of critical component as battery, it Effect be to prevent battery short circuit, keep Electolyte-absorptive, provide lithium ion transmitting channel.Current commercialized lithium-ion electric Pond diaphragm is mainly polyolefins diaphragm, but polyalkene diaphragm fusing point is relatively low, and under extreme case, diaphragm fusing be will lead to just Negative electrode material contact, so as to cause danger such as fire, explosions.
In order to improve the security performance of lithium ion battery, for the angle of diaphragm, prepare a kind of with hot off function High-temperature-resistant membrane is that one kind efficiently solves measure.
Summary of the invention
Present invention aims at for current lithium ion battery commercialization polyolefin micropore barrier diaphragm existing for temperature classification it is low, The problems such as wetability is poor provides a kind of composite diaphragm for lithium ion battery with hot off function and its preparation and application.
To achieve the goals above, it is matrix that the present invention, which selects commercialization polyalkene diaphragm (polyethylene or polypropylene), is used Heat resistance fiber is coating, has composite diaphragm for lithium ion battery and its preparation of hot off function using the method preparation of inversion of phases And application.
The preparation method of the composite diaphragm, which is characterized in that including following preparation step:
(1) polyalkene diaphragm is immersed in 12h or more in aqueous isopropanol, in drying at room temperature；
(2) heat resistance fiber is dissolved in organic solvent, and homogeneous solution formed above for 24 hours is sufficiently stirred at room temperature；
(3) polyalkene diaphragm is impregnated in 8h or more in the homogeneous solution of step (2) preparation under stirring, is taken out, Then by its mass-impregnation, 5-20min, formation perforated membrane impregnate remove remnants in deionized water in the poor solvent of resin Solvent obtains composite diaphragm after taking out drying.
The heat resistance fiber is polyamide, polyimides, polybenzimidazoles, sulfonated polyether-ether-ketone, one in polypyrrole Kind is two or more.
The organic solvent is N-Methyl pyrrolidone, in dimethyl acetamide, dimethylformamide, dimethyl sulfoxide One or more.
The mass concentration of heat resistance fiber in homogeneous solution is formed by between 1-10%.
The poor solvent is one or more of methanol, water, ethyl alcohol, isopropanol.
The coating aperture of prepared composite diaphragm is having a size of 0.01-10um, and coating layer thickness is between 1-10um, composite diaphragm Heat break 130-160 DEG C of temperature, the polyalkene diaphragm melting layer at the disconnected temperature of heat blocks the duct of coating, realizes and block ion The function of transmitting.
Beneficial outcomes:
The present invention is compared in the prior art, the advantage is that:
(1) present invention makes the composite diaphragm for having porous coating using the method preparation of inversion of phases.
(2) composite diaphragm prepared by the present invention has hot off function (130-160 DEG C), improves the security performance of battery.
(3) diaphragm prepared by the present invention has good wetability, thermal stability and mechanical performance, meets power battery pair In the requirement of diaphragm: there is no deformation at 200 DEG C for diaphragm, have good high-temperature stability.
(4) preparation process of the present invention is simple, strong operability, is conducive to further genralrlization use.
(5) present invention has widened the use scope of lithium ion battery separator.
(6) selecting commercialization polyalkene diaphragm (polyethylene or polypropylene) is matrix, is coating with heat resistance fiber, utilizes phase The method of conversion prepares multi-functional composite diaphragm for lithium ion battery.Due in the preparation method and cellulosic backbone of inversion of phases Polar group, the porosity with higher of prepared composite membrane, with the affinity of good electrolyte, be conducive to battery The raising of high rate performance；The high temperature resistance of polyalkene diaphragm can be improved in the introducing of heat resistance fiber coating, improves battery Security performance；The composite membrane of preparation also has high temperature fuse function, further enhances the security performance of battery.In addition, this Method and process is simple, at low cost, strong operability,
Be conducive to further genralrlization use, be a kind of lithium ion battery separator of great application prospect.
Detailed description of the invention
Fig. 1 is SEM figure in composite diaphragm surface prepared by embodiment 2.
Fig. 2 is that composite diaphragm prepared by embodiment 2 is schemed by 140 DEG C of section polyethylene layer SEM before and after the processing.
Fig. 3 is the section coating SEM figure of composite diaphragm prepared by comparative example 1.
Fig. 4 is composite diaphragm and high rate performance comparison diagram of the comparative example 2 in lithium ion battery prepared by embodiment 2.
Specific embodiment:
The present invention is further detailed below in conjunction with case study on implementation, rather than limits the scope of the invention.
Embodiment 1
(1) polyalkene diaphragm is immersed in 12h in aqueous isopropanol, in drying at room temperature；
(2) poly- polybenzimidazoles is dissolved in dimethyl acetamide, is sufficiently stirred forms the uniform of 1wt.% for 24 hours at room temperature Solution；
(3) polyalkene diaphragm is impregnated in 8h in the homogeneous solution of step (2) preparation under stirring, is taken out, then By its mass-impregnation in water 10min, be formed by curing perforated membrane, in deionized water impregnate remove residual solvent, take out drying After obtain composite diaphragm.
The coating aperture of prepared composite diaphragm is having a size of 0.05-1um, coating layer thickness 3um, and diaphragm does not have at 180 DEG C There is generation dimensional contraction, the disconnected temperature of heat is 140 DEG C.It is tested using the composite diaphragm assembling lithium ion battery of preparation. LiFePO4, lithium piece be respectively anode and cathode, 1M LiPF6(EC/DMC/EMC, volume ratio 1:1:1) is electrolyte.Wherein, Anode by 80wt.% LiFePO4, the Super P carbon of 10wt.%, the Kynoar composition of 10wt.%, active material LiFePO4Content is 2.5-3.0mg/cm2.Group installs after battery stands 5h at 25 DEG C, the quality relative to positive active material Charge-discharge test is carried out under different multiplying.As a result, it has been found that it is with good high rate performance, and under the multiplying power of 5C, first circle electric discharge Specific capacity reaches 120mAh/g.
Embodiment 2
(1) polyalkene diaphragm is immersed in 12h in aqueous isopropanol, in drying at room temperature；
(2) polybenzimidazoles is dissolved in dimethyl acetamide, is sufficiently stirred forms the uniform molten of 3wt.% for 24 hours at room temperature Liquid；
(3) polyalkene diaphragm is impregnated in 8h in the homogeneous solution of step (2) preparation under stirring, is taken out, then By its mass-impregnation in water 10min, be formed by curing perforated membrane, in deionized water impregnate remove residual solvent, take out drying After obtain composite diaphragm.
The coating aperture of prepared composite diaphragm is having a size of 50-500nm, coating layer thickness 4um, the disconnected temperature of heat It 140 DEG C, can be seen that from Fig. 1 and Fig. 2, the polyalkene diaphragm layer in the composite membrane at the disconnected temperature of heat melts, and plugs The duct of porous coating realizes the function of blocking ion transport；When temperature is 200 DEG C, there is no size receipts for diaphragm simultaneously Contracting.Then, under the same conditions as example 1, lithium ion battery is assembled using the composite diaphragm of preparation.In the multiplying power of 5C Under, first circle specific discharge capacity is 120mAh/g..
Embodiment 3
(1) polyalkene diaphragm is immersed in 12h in aqueous isopropanol, in drying at room temperature；
(2) polybenzimidazoles is dissolved in dimethyl acetamide, is sufficiently stirred forms the uniform molten of 5wt.% for 24 hours at room temperature Liquid；
(3) polyalkene diaphragm is impregnated in 8h in the homogeneous solution of step (2) preparation under stirring, is taken out, then By its mass-impregnation in isopropanol 10min, be formed by curing perforated membrane, in deionized water impregnate remove residual solvent, take out Composite diaphragm is obtained after drying.
The coating aperture of prepared composite diaphragm is having a size of 50-350nm, coating layer thickness 5um, and diaphragm does not have at 200 DEG C There is generation dimensional contraction, the disconnected temperature of heat is 140 DEG C.Then, under the same conditions as example 1, the compound of preparation is utilized Diaphragm assembles lithium ion battery.Under the multiplying power of 5C, first circle specific discharge capacity is 115mAh/g.
Embodiment 4
(1) polyalkene diaphragm is immersed in 12h in aqueous isopropanol, in drying at room temperature；
(2) polyimides is dissolved in N-Methyl pyrrolidone, is sufficiently stirred forms the uniform molten of 8wt.% for 24 hours at room temperature Liquid；
(3) polyalkene diaphragm is impregnated in 8h in the homogeneous solution of step (2) preparation under stirring, is taken out, then By its mass-impregnation in water 10min, be formed by curing perforated membrane, in deionized water impregnate remove residual solvent, take out drying After obtain composite diaphragm.
The coating aperture of prepared composite diaphragm is having a size of 0.1-1um, coating layer thickness 4um, and diaphragm does not have at 200 DEG C Dimensional contraction occurs, the disconnected temperature of heat is 140 DEG C.Then, under the same conditions as example 1, using preparation it is compound every Film assembles lithium ion battery.Under the multiplying power of 5C, first circle specific discharge capacity is 119mAh/g.
Embodiment 5
(1) polyalkene diaphragm is immersed in 12h in aqueous isopropanol, in drying at room temperature；
(2) polybenzimidazoles and sulfonated polyether-ether-ketone are dissolved in dimethyl acetamide, are sufficiently stirred are formed for 24 hours at room temperature The homogeneous solution of 4wt.%；
(3) polyalkene diaphragm is impregnated in 8h in the homogeneous solution of step (2) preparation under stirring, is taken out, then By its mass-impregnation in ethyl alcohol 10min, be formed by curing perforated membrane, impregnate remove residual solvent in deionized water, take out dry Composite diaphragm is obtained after dry.
The coating aperture of prepared composite diaphragm is having a size of 50-300nm, coating layer thickness 5um, and diaphragm does not have at 200 DEG C There is generation dimensional contraction, the disconnected temperature of heat is 140 DEG C.Then, under the same conditions as example 1, the compound of preparation is utilized Diaphragm assembles lithium ion battery.Under the multiplying power of 5C, first circle specific discharge capacity is 110mAh/g..
Comparative example 1
(1) polyalkene diaphragm is immersed in 12h in aqueous isopropanol, in drying at room temperature；
(2) poly- polybenzimidazoles is dissolved in dimethyl acetamide, is sufficiently stirred forms the uniform of 4wt.% for 24 hours at room temperature Solution；
(3) polyalkene diaphragm is impregnated in 8h in the homogeneous solution of step (2) preparation under stirring, is taken out, it is dry, Obtain composite diaphragm.
The coating of prepared composite diaphragm is relatively compact structure, coating layer thickness 0.5um.With 1 phase of embodiment With under conditions of, lithium ion battery is assembled using the composite diaphragm of preparation, under the multiplying power of 0.5C, battery charging and discharging capacity is 0mAh/g.As can be seen from Figure 3, compared to porous coating prepared by inversion of phases, the directly prepared coating of drying is densification Structure, lithium ion transport resistance greatly increase, and are unfavorable for the conduction of lithium ion, hinder the normal operation of battery.
Comparative example 2
Commercialized polyethylene diagrams aperture is between 50-350nm；With a thickness of 20um；Heat stability testing is carried out, as a result When reaching 120 DEG C for temperature, film form is shunk obviously, and when temperature reaches 200 DEG C or more, film melts completely；When meeting open fire It is inflammable.
Fig. 4 can be seen that the present invention and comparative example 2 utilize commercialized polyethylene diagrams assembling lithium ion battery battery performance It compares, under the multiplying power of 5C, specific discharge capacity 120mAh/g, high rate performance is good.
In conclusion the present invention prepares composite diaphragm using phase inversion, this method and process is simple, strong operability, Be conducive to further genralrlization use.By the control to film forming procedure, the thermal stability and chemical property of film are all obtained very well Unification.From heat stability testing and fusing result it can be found that the present invention increases substantially the thermal stability of diaphragm, mention significantly The high safety of battery, is more suitable for being applied in lithium ion battery.

Claims (8)

1. a kind of preparation method of the composite diaphragm for lithium ion battery with hot off function, which is characterized in that including following system Standby step:
(1) polyalkene diaphragm is immersed in 12h or more in aqueous isopropanol, in drying at room temperature；
(2) heat resistance fiber is dissolved in organic solvent, and homogeneous solution formed above for 24 hours is sufficiently stirred at room temperature；
(3) 8h or more will be stirred in the homogeneous solution of step (1) treated polyalkene diaphragm is impregnated in step (2) preparation, taken Out, then by its mass-impregnation, 5-20min, formation perforated membrane impregnate in deionized water in the poor solvent of heat resistance fiber Residual solvent is removed, obtains composite diaphragm after taking out drying.
2. preparation method according to claim 1, it is characterised in that: heat resistance fiber be polyamide, polyimides, polyphenyl simultaneously One or more of imidazoles, sulfonated polyether-ether-ketone, polypyrrole.
3. preparation method according to claim 1, it is characterised in that: organic solvent is N-Methyl pyrrolidone, dimethyl One or more of acetamide, dimethylformamide, dimethyl sulfoxide.
4. preparation method according to claim 1, it is characterised in that: the quality of heat resistance fiber is dense in the homogeneous solution of formation Degree is between 1-10%.
5. preparation method according to claim 1, it is characterised in that: the poor solvent is methanol, water, ethyl alcohol, isopropyl One or more of alcohol.
6. preparation method according to claim 1, it is characterised in that: the coating aperture of prepared composite diaphragm having a size of 0.01-10um, for coating layer thickness between 1-10um, the disconnected temperature of the heat of composite diaphragm is 130-160 DEG C.
7. a kind of composite diaphragm obtained by the described in any item preparation methods of such as right 1-6.
8. a kind of application of composite diaphragm as claimed in claim 7 in lithium ion battery.
CN201710940702.1A 2017-10-11 2017-10-11 A kind of composite diaphragm and its preparation and application with hot off function Pending CN109659468A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110828757A (en) * 2019-11-20 2020-02-21 江苏塔菲尔新能源科技股份有限公司 Lithium ion battery diaphragm and preparation method and application thereof
CN113131089A (en) * 2019-12-30 2021-07-16 深圳市研一新材料有限责任公司 Spider-web structure lithium ion battery diaphragm and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103531736A (en) * 2013-10-27 2014-01-22 中国乐凯集团有限公司 High-heat-resistance lithium-ion battery diaphragm 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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103531736A (en) * 2013-10-27 2014-01-22 中国乐凯集团有限公司 High-heat-resistance lithium-ion battery diaphragm 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 (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110828757A (en) * 2019-11-20 2020-02-21 江苏塔菲尔新能源科技股份有限公司 Lithium ion battery diaphragm and preparation method and application thereof
CN113131089A (en) * 2019-12-30 2021-07-16 深圳市研一新材料有限责任公司 Spider-web structure lithium ion battery diaphragm and preparation method thereof

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