CN106816568A - A kind of preparation method of voltage sensitivity barrier film - Google Patents
A kind of preparation method of voltage sensitivity barrier film Download PDFInfo
- Publication number
- CN106816568A CN106816568A CN201710099502.8A CN201710099502A CN106816568A CN 106816568 A CN106816568 A CN 106816568A CN 201710099502 A CN201710099502 A CN 201710099502A CN 106816568 A CN106816568 A CN 106816568A
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- China
- Prior art keywords
- barrier film
- triphenylamine
- bonding agent
- preparation
- voltage sensitivity
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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
- 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
- H01M2200/00—Safety devices for primary or secondary batteries
- H01M2200/20—Pressure-sensitive devices
-
- 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)
- Secondary Cells (AREA)
Abstract
The present invention relates to technical field of chemical power, and in particular to a kind of preparation method of voltage sensitivity barrier film, comprise the following steps that：S1. weigh：Parts by weights another name takes bonding agent, triphenylamine, organic solvent；S2. first the bonding agent that S1 is weighed is dissolved in organic solvent, is subsequently adding triphenylamine, the mixed solution of bonding agent and triphenylamine is obtained after dissolving；S3. commercialization barrier film is invaded in the mixed solution of the bonding agent and triphenylamine obtained by S2, impregnates barrier film；S4. dry：Barrier film after being impregnated to S3 is dried treatment, you can obtain voltage sensitivity barrier film.The present invention is using infusion process by triphenylamine monomer coats in the both sides of barrier film; it is applied in ferric phosphate lithium cell; initial charge is that electroxidation aggregates into poly-triphenylamine; then using the reversible doping/removing impurities of this electroactive polymer of poly-triphenylamine; and its electric conductivity carries out overcharging protection with the feature of the carrying out of doping/removing impurities reversible change between conductive state and insulation state to battery.
Description
Technical field
The present invention relates to technical field of chemical power, and in particular to a kind of preparation method of voltage sensitivity barrier film.
Background technology
Lithium ion battery has been widely used in various portable electric appts, and is considered as electric automobile and preferably matches somebody with somebody
Set battery.At present, the security that to hinder Large Copacity, one of major obstacle of high power lithium ion cell development be battery wait into
One step is improved.Research shows that overcharge is the most hazards for causing lithium ion battery that unsafe acts occur, when battery is in
During overcharging state, the de- lithium potential of negative electrode increases with the degree that overcharges and rises rapidly, more than certain limit after, cause inside battery to have
The irreversible oxidation of organic electrolytic solution is decomposed, and produces imflammable gas simultaneously to release substantial amounts of heat, cause internal temperature of battery and
Pressure rises, and triggers a series of exothermic reactions, so as to cause inside battery thermal runaway.
The potential safety hazard that battery brings is supplied electricity to solve to overcharge, people start to be devoted to developing inside battery self-excitation in recent years
Hair protection mechanism, such as by adding oxidation-reduction pair in the electrolytic solution, or can electropolymerization monomeric additive preventing battery
Overcharge.But because the solubility of the oxidation-reduction pair additive that has now found that in organic electrolyte is smaller, it is only capable of providing non-
Normal limited clamp current, does not have to the practical application of battery and significantly overcharges protective effect；And can electropolymerization additive only
Irreversible protective effect can be provided, battery is lost electrical property in itself while having an effect.
Recent research indicate that, charging electricity can effectively be clamped down on using the conducting polymer barrier film with voltage-sensitive property
Press and prevent voltage out of control, its operation principle is：Using the polymer with electro-chemical activity as battery diaphragm framework material,
In the range of the normal charge and discharge voltage of battery, the electroactive polymer in barrier film is in the eigenstate of undoped p, and barrier film is electronics
Insulator, only provides ion transmission；When battery is in overcharging state, positive electrode potential rises, and electroactive polymer is because being oxidized
And adulterate, become electronic conductor, so as to cause internal short-circuit of battery, external charge current is consumed, prevent cell voltage
It is further up；And work as after stopping overcharges, the internal short-circuit that anodic potentials are formed due to barrier film and reduce, when less than electroactive
During the electroxidation doping potential of polymeric material, conducting polymer reverts to insulation state because of reversible removing impurities, and now barrier film recovers
Its normal function.
Based on this, how to prepare a kind of voltage sensitivity barrier film turns into the problem of present invention research.
The content of the invention
To reach above-mentioned purpose, the technical solution adopted in the present invention is：
A kind of preparation method of voltage sensitivity barrier film, step is as follows：
S1. weigh：Parts by weights another name takes bonding agent, triphenylamine, organic solvent；
S2. first the bonding agent that S1 is weighed is dissolved in organic solvent, is subsequently adding triphenylamine, bonding agent and three are obtained after dissolving
The mixed solution of aniline；
S3. in the bonding agent and the mixed solution of triphenylamine that commercialization barrier film are immersed in obtained by S2, barrier film is impregnated；
S4. dry：Barrier film after being impregnated to S3 is dried treatment, you can obtain voltage sensitivity barrier film.
Further, the bonding agent is the one kind in Kynoar (PVDF), polymethyl methacrylate (PMMA)
Or it is several.
Further, the organic solvent is acetone, chloroform, dimethylformamide (DMF), 1-METHYLPYRROLIDONE
(NMP) one kind in.
Further, bonding agent, triphen amine monomers, organic solvent mass fraction are weighed in step S1 to be respectively：1-3%、
5-15%、82-94%。
Further, the commercialization barrier film is single-layer polypropylene film, monolayer polyethylene film, polyethylene/polypropylene/poly- second
One kind in alkene three-layer membrane.
Further, barrier film carries out low temperature drying at 60 ~ 90 DEG C described in step S4.
Further, the voltage sensitivity membrane thicknesses are 12 ~ 40 microns.
The present invention uses infusion process by triphenylamine monomer coats in the both sides of barrier film, is applied in ferric phosphate lithium cell, first
Secondary charging is that electroxidation aggregates into poly-triphenylamine, then using the reversible doping/removing impurities of this electroactive polymer of poly-triphenylamine,
And its electric conductivity was carried out with the feature of the carrying out of doping/removing impurities reversible change between conductive state and insulation state to battery
Fill protection.Using the potential-sensitive separator with reversible charging protection function excessively prepared by the present invention, particularly to LiFePO4
Battery, can play effective reversible overcharging protective effect.Preparation method disclosed in this invention, it is simple to operate, it is practical.
Specific embodiment
With reference to embodiments of the invention, the invention will be further elaborated.
Embodiment 1
A kind of preparation method of voltage sensitivity barrier film, step is as follows：
S1. according to binding agent PVDF, triphen amine monomers, organic solvent-acetone mass fraction be respectively 1%, 5%, 94% requirement
PVDF, triphen amine monomers, acetone are weighed respectively；
S2. first PVDF is dissolved in acetone, is subsequently adding triphen amine monomers, the mixing of PVDF and triphen amine monomers is obtained after dissolving
Solution；
S3. in the PVDF and the mixed solution of triphen amine monomers that commercialization individual layer PP barrier films are immersed in obtained by S2, dipping every
Film；
S4. the barrier film after being impregnated to S3 carries out low temperature drying treatment under 65 DEG C of environment, you can obtain voltage sensitivity barrier film, film
Thickness is 20 μm.
The diaphragm application is overcharged in ferric phosphate lithium cell to this battery, and the degree that overcharges is 100%, its voltage clamp
Platform is 4.0V, and then battery is discharged, and discharge capacity is 1995mAh.
Embodiment 2
A kind of preparation method of voltage sensitivity barrier film, step is as follows：
S1. according to binding agent PMMA, triphen amine monomers, organic solvents, chloroform mass fraction be respectively 2%, 10%, 88% requirement
PMMA, triphen amine monomers, chloroform are weighed respectively；
S2. first PMMA is dissolved in chloroform, is subsequently adding triphen amine monomers, the mixing of PMMA and triphen amine monomers is obtained after dissolving
Solution；
S3. in the PMMA and the mixed solution of triphen amine monomers that commercialization individual layer PE barrier films are immersed in obtained by S2, dipping every
Film；
S4. the barrier film after being impregnated to S3 carries out low temperature drying treatment under 78 DEG C of environment, you can obtain voltage sensitivity barrier film, film
Thickness is 34 μm.
The diaphragm application is overcharged in ferric phosphate lithium cell to this battery, and the degree that overcharges is 100%, its voltage clamp
Platform is 3.8V, and then battery is discharged, and discharge capacity is 1990mAh.
Embodiment 3
A kind of preparation method of voltage sensitivity barrier film, step is as follows：
S1. according to binding agent PMMA, triphen amine monomers, organic solvents, chloroform mass fraction be respectively 3%, 15%, 82% requirement
PMMA, triphen amine monomers, chloroform are weighed respectively；
S2. first PMMA is dissolved in chloroform, is subsequently adding triphen amine monomers, the mixing of PMMA and triphen amine monomers is obtained after dissolving
Solution；
S3. in the PMMA and the mixed solution of triphen amine monomers that commercialization PE/PP/PE three-layer membranes are immersed in obtained by S2,
Dipping barrier film；
S4. the barrier film after being impregnated to S3 carries out low temperature drying treatment under 85 DEG C of environment, you can obtain voltage sensitivity barrier film, film
Thickness is 28 μm.
The diaphragm application is overcharged in ferric phosphate lithium cell to this battery, and the degree that overcharges is 100%, its voltage clamp
Platform is 3.6V, and then battery is discharged, and discharge capacity is 1950mAh.
Comparative example 1
By commercialization individual layer PE diaphragm applications in ferric phosphate lithium cell, first to the normal discharge and recharge of battery, the specified of battery is tested
Capacity, capacity is 2000mAh, it is then fully charged to battery after overcharge, battery does not have voltage clamp platform, on voltage is continuous
Rise, finally smolder, it is on fire.
Embodiment 1,2,3 and comparative example experiment condition and results contrast such as table 1：
| Experimental group | Overcharge Clamping voltages platform | Discharge capacity after overcharge |
| Embodiment 1 | 4.0V | 1995mAh |
| Embodiment 2 | 3.8V | 1990mAh |
| Embodiment 3 | 3.6V | 1950mAh |
| Comparative example 1 | Nothing | Smolder, it is on fire |
Result shows that a kind of voltage sensitivity barrier film prepared by the present invention is applied in ferric phosphate lithium cell, can be to battery
Play and effective reversible overcharge protective effect.
Embodiments above describes general principle of the invention and preparation method, and the technical staff of the industry should
Solution, the present invention is not limited to the above embodiments, merely illustrating the principles of the invention described in above-described embodiment and specification,
Various changes and modifications of the present invention are possible without departing from the spirit and scope of the present invention, and these changes and improvements all fall
Enter in claimed scope.
Claims (7)
1. a kind of preparation method of voltage sensitivity barrier film, it is characterised in that step is as follows：
S1. weigh：Parts by weights another name takes bonding agent, triphenylamine, organic solvent；
S2. first the bonding agent that S1 is weighed is dissolved in organic solvent, is subsequently adding triphenylamine, bonding agent and three are obtained after dissolving
The mixed solution of aniline；
S3. commercialization barrier film is invaded in the mixed solution of the bonding agent and triphenylamine obtained by S2, impregnates barrier film；
S4. dry：Barrier film after being impregnated to S3 is dried treatment, you can obtain voltage sensitivity barrier film.
2. preparation method according to claim 1, it is characterised in that bonding agent, triphenylamine, You Jirong are weighed in step S1
Agent mass fraction is respectively：1-3%、5-15%、82-94%.
3. preparation method according to claim 2, it is characterised in that the organic solvent is acetone, chloroform, dimethyl formyl
One kind in amine (DMF), 1-METHYLPYRROLIDONE (NMP).
4. preparation method according to claim 1 or claim 2, it is characterised in that the bonding agent is Kynoar (PVDF), poly-
One or more in methyl methacrylate (PMMA).
5. preparation method according to claim 1, it is characterised in that the commercialization barrier film is single-layer polypropylene film, individual layer
One kind in polyethylene film, polyethylene/polypropylene/polyethylene three-layer membrane.
6. preparation method according to claim 1, it is characterised in that barrier film carries out low temperature at 60 ~ 90 DEG C described in step S4
Dry.
7. preparation method according to claim 1, it is characterised in that the voltage sensitivity membrane thicknesses are 12 ~ 40 microns.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710099502.8A CN106816568A (en) | 2017-02-23 | 2017-02-23 | A kind of preparation method of voltage sensitivity barrier film |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710099502.8A CN106816568A (en) | 2017-02-23 | 2017-02-23 | A kind of preparation method of voltage sensitivity barrier film |
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| CN106816568A true CN106816568A (en) | 2017-06-09 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110048062A (en) * | 2019-03-25 | 2019-07-23 | 惠州锂威电子科技有限公司 | A kind of anti-overcharge battery diaphragm and the lithium ion battery using the diaphragm |
| CN111312971A (en) * | 2020-03-02 | 2020-06-19 | 荣盛盟固利新能源科技有限公司 | Diaphragm, secondary battery and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1595678A (en) * | 2004-06-28 | 2005-03-16 | 武汉大学 | A voltage sensitive membrane and preparation method thereof |
-
2017
- 2017-02-23 CN CN201710099502.8A patent/CN106816568A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1595678A (en) * | 2004-06-28 | 2005-03-16 | 武汉大学 | A voltage sensitive membrane and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李素丽: "电势敏感隔膜的制备及其在锂离子电池中的应用", 《中国博士学位论文全文数据库工程科技Ⅱ辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110048062A (en) * | 2019-03-25 | 2019-07-23 | 惠州锂威电子科技有限公司 | A kind of anti-overcharge battery diaphragm and the lithium ion battery using the diaphragm |
| CN110048062B (en) * | 2019-03-25 | 2022-04-15 | 惠州锂威电子科技有限公司 | Overcharge-preventing battery diaphragm and lithium ion battery using same |
| CN111312971A (en) * | 2020-03-02 | 2020-06-19 | 荣盛盟固利新能源科技有限公司 | Diaphragm, secondary battery and preparation method thereof |
| CN111312971B (en) * | 2020-03-02 | 2022-06-28 | 荣盛盟固利新能源科技有限公司 | Diaphragm, secondary battery and preparation method thereof |
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