CN1595678A - A voltage sensitive membrane and preparation method thereof - Google Patents
A voltage sensitive membrane and preparation method thereof Download PDFInfo
- Publication number
- CN1595678A CN1595678A CNA2004100133777A CN200410013377A CN1595678A CN 1595678 A CN1595678 A CN 1595678A CN A2004100133777 A CNA2004100133777 A CN A2004100133777A CN 200410013377 A CN200410013377 A CN 200410013377A CN 1595678 A CN1595678 A CN 1595678A
- Authority
- CN
- China
- Prior art keywords
- barrier film
- voltage sensitivity
- electroactive polymer
- binding agent
- battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A voltage sensitive diaphragm and its manufacturing method is disclosed, whose basic characteristics is: diaphragm structure has electric active polymer material which can have P-typed doping under high oxidation potential, the material is electric insulator in intrinsic condition while electric conductor in P-typed doping condition, so that electric conductivity will change according to positive electric potential of battery. The diaphragm can supply reversible protection for secondary battery .
Description
Technical field
The present invention is a kind of principle of compositionality of voltage sensitivity barrier film, belongs to field of chemical power source.
Background technology
The fail safe that overcharges battery under the state is the maximum application problem that organic electrolyte secondary cell faced always.For aqueous solution secondary cell, be in when overcharging state, water produces oxygen in the anodal oxidation of battery, produces hydrogen in the negative pole reduction, and the gaseous product of generation can reversibly be combined into water again at inside battery.The reversible decomposition of this water-compound for aqueous solution secondary cell provides a kind of inner over-charge protective mechanism makes aqueous solution secondary cell possess good overcharging resisting ability.And for the non-aqueous secondary batteries system that adopts organic electrolyte solution, owing to lack similar protection mechanism, battery is particularly responsive to overcharging.Be in when overcharging state, positive electrode potential prolonged and fast rise with the charging interval, cause the irreversible change of positive active material structure and the oxidation Decomposition of electrolyte, produce a large amount of gas and emit a large amount of heat, thereby cell voltage and temperature are sharply risen, cause unsafe acts such as blast, burning.Therefore, reinforcement is particularly important to the over-charge protective of organic electrolyte secondary cell.
In order to prevent over-charging of battery, people often adopt special-purpose charging circuit to control the charging process of battery in the practical application.This method is direct, effective, but is not perfectly safe.Particularly for the battery pack that is formed by many battery combination, the difficulty of each batteries being implemented management separately is very big.Therefore, the overcharging resisting ability or the anti-overcharge ability of raising battery self are extremely important.
The content of invention
The present invention proposes a kind of voltage sensitivity barrier film and preparation method, its objective is in organic electrolyte secondary cell inside and set up a kind of over-charge protective mechanism, prevent over-charging of battery, solve the over-charging of battery safety issue.
Technical scheme of the present invention is: a kind of voltage sensitivity barrier film, it is characterized in that it by porous septum matrix and filling the filler in the hole form, described filler is electroactive polymer material, binding agent and mixtures of auxiliary materials thereof.
Aforesaid voltage sensitivity barrier film is characterized in that described electroactive polymer material is polypyrrole, polythiophene, polyaniline, polyhenylene, polyacetylene and their derivative.
Aforesaid voltage sensitivity barrier film is characterized in that described binding agent is polytetrafluoroethylene (PTFE), Kynoar (PVDF) and Kynoar-hexafluoropropylene copolymer (PVDF-HFP); Auxiliary material are nano silicon (SiO
2), nano-aluminium oxide (Al
2O
3).
Aforesaid voltage sensitivity barrier film is characterized in that the parts by weight of described filler are:
Electroactive polymer material 5～50
Binding agent 5～90
Auxiliary material 0＜～50
The voltage sensitivity barrier film can be made by following method, at first that electroactive polymer powder body material, binding agent and other auxiliary material are evenly mixed, add an amount of solvent again and make uniform sizing material, be filled in then in the porous septum matrix, perhaps adopt the coating or the mode that rolls directly to make porous septum.
The principle of compositionality of voltage sensitivity barrier film of the present invention is: adopting the electroactive polymer material that the doping of P type can take place under high potential is the electromotive force sensitive material, and it is joined in the battery diaphragm composition.Under normal charging condition, polymeric material is the electric insulation attitude of intrinsic.At this moment, barrier film can be isolated positive pole/negative pole effectively, and abundant ionic liquid phase transmission channel is provided, and guarantees normal charging of battery and use.But under the state of overcharging, because anodal electrode potential has surpassed the oxidation potential of electroactive polymer, the P type takes place and mixes in electroactive polymer, and polymer manifests the electronic conductance feature because of doping, barrier film changes the electron conduction attitude into by the electric insulation attitude apace, thereby causes internal short-circuit of battery.Short circuit current causes that cell voltage descends.In the time of under positive electrode potential is reduced to electroactive polymer oxidation potential value, the reversible assorted reaction of taking off takes place in polymer, and changes the electronic isolation attitude into by the electron conduction attitude.At this moment, barrier film recovers its normal function again, and battery can accept to continue charging.And after voltage surpasses set point, cause short circuit again, cause voltage to descend.This sensitiveness to electromotive force of barrier film makes the cell voltage that is under the state of overcharging not change with the charging interval.At this moment, battery has become a pure resistance in fact and has been used for consuming the external charging electric energy.Therefore, this voltage-sensitive barrier film can be secondary cell the reversible inside over-charge protective is provided, and prevents over-charging of battery.
The electromotive force sensitive material that the present invention adopts is a kind of electroactive polymer.Reversible P type assorted reaction of mixing-take off can take place in this polymeric material in battery system of living under certain electromotive force.Under the intrinsic state, polymer is an electronic body, and is the electronics good conductor in the P-dopant states.The polymeric material that meets the demands has:: polypyrrole, polythiophene, polyaniline, polyhenylene, polyacetylene etc. and their derivative.
Voltage sensitivity barrier film of the present invention can be made by following mode.At first that electroactive polymer powder body material, binding agent and other auxiliary material are evenly mixed, add an amount of solvent again and make uniform sizing material, be filled in then in the porous septum matrix.Perhaps adopt the coating or the mode that rolls directly to make porous septum.Binding agent can be polytetrafluoroethylene (PTFE), Kynoar (PVDF) and Kynoar-hexafluoropropylene copolymer (PVDF-HFP) etc.Auxiliary material can be nano silicon (SiO
2) and nano-aluminium oxide (Al
2O
3) wait powder.According to the binding agent difference of selecting for use, solvent can adopt water, N, N-dimethyl pyrrolidone, N, dinethylformamide etc. respectively.
Can be by selecting the electroactive polymer kind to adjust the responsive value of electromotive force of barrier film and being suitable for voltage range.The inner over-charge protective magnitude of voltage of battery system is by the oxidation doping electromotive force decision of the electroactive polymer that is adopted.
Description of drawings
Fig. 1, the change in voltage curve when overcharging with different electric currents for the battery of the voltage sensitivity barrier film that adopts the embodiment of the invention one.
Fig. 2, the change in voltage curve when overcharging with different electric currents for the battery of the voltage sensitivity barrier film that adopts the embodiment of the invention two.
Embodiment
It is that electromotive force sensitive material, Kynoar (PVDF) are binding agent, N that example 1. adopts polyaniline, and the N-dimethyl pyrrolidone is a solvent, makes uniform sizing material after mixing according to a certain ratio.With thickness is 50 μ m, and porosity is that 80% porous polypropylene film immerses in these slurries.Treat to take out after slurries fully soak into microporous barrier, oven dry promptly makes the voltage-sensitive barrier film.With this film is barrier film, LiTiS
2For anodal, Li sheet are negative pole, 1mol/LLiPF
6/ EC+DMC solution is that electrolyte is assembled into 2025 type button lithium batteries.In the normal charging/discharging voltage scope of 1.5V-3.0V, during with 10mA electric current constant current charge-discharge, battery capacity is 50mAh.
Fig. 1 is Li/LiTiS
2Button cell overcharge curve.As we can see from the figure, because the over-charge protective effect of barrier film, after battery was overcharged a period of time, voltage is time to time change no longer.
It is electromotive force sensitive material, nanometer SiO that example 2. adopts polyhenylene
2Powder is that inert component additive, polytetrafluoroethylene (PTFE) emulsion are binding agent, after mixing according to a certain ratio, is rolled into the film of thick about 30 μ m.With this film is barrier film, LiCoO
2Be anodal, Li
4Ti
5O
12Sheet is negative pole, 1mol/L LiPF
6/ EC+DMC solution is that electrolyte is assembled into 2025 type buckle type lithium-ion batteries.In the normal charging/discharging voltage scope of 2.0V-2.7V, during with 5mA electric current constant current charge-discharge, battery capacity is 20mAh.
Fig. 2 is LiCoO
2/ Li
4Ti
5O
12The buckle type lithium-ion battery overcharge curve.Can see that from figure because the over-charge protective effect of barrier film, after battery was overcharged a period of time, voltage is time to time change no longer.
Claims (5)
1, a kind of voltage sensitivity barrier film, it is characterized in that it by porous septum matrix and filling the filler in the hole form, described filler is electroactive polymer material, binding agent and mixtures of auxiliary materials thereof.
2, voltage sensitivity barrier film as claimed in claim 1 is characterized in that described electroactive polymer material is one or more of polypyrrole, polythiophene, polyaniline, polyhenylene, polyacetylene and their derivative.
3, voltage sensitivity barrier film as claimed in claim 1 is characterized in that described binding agent is polytetrafluoroethylene (PTFE), Kynoar (PVDF) and Kynoar-hexafluoropropylene copolymer (PVDF-HFP); Auxiliary material are nano silicon (SiO
2), nano-aluminium oxide (Al
2O
3).
4, as claim 1 or 2 or 3 described voltage sensitivity barrier films, it is characterized in that the parts by weight of described filler are:
Electroactive polymer material 5～50
Binding agent 5～90
Auxiliary material 0＜～50
5, the preparation method of voltage sensitivity barrier film, it is characterized in that at first that electroactive polymer powder body material, binding agent and other auxiliary material are evenly mixed, add an amount of solvent again and make uniform sizing material, be filled in then in the porous septum matrix, perhaps adopt the coating or the mode that rolls directly to make porous septum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2004100133777A CN1595678A (en) | 2004-06-28 | 2004-06-28 | A voltage sensitive membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2004100133777A CN1595678A (en) | 2004-06-28 | 2004-06-28 | A voltage sensitive membrane and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1595678A true CN1595678A (en) | 2005-03-16 |
Family
ID=34662935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2004100133777A Pending CN1595678A (en) | 2004-06-28 | 2004-06-28 | A voltage sensitive membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1595678A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8379351B2 (en) | 2007-03-30 | 2013-02-19 | Kabushiki Kaisha Toshiba | Magneto-resistance effect element, and method for manufacturing the same |
| CN104916870A (en) * | 2014-03-12 | 2015-09-16 | 罗伯特·博世有限公司 | Battery cell with electrode assembly |
| CN105932207A (en) * | 2016-07-15 | 2016-09-07 | 中国工程物理研究院化工材料研究所 | Gel polymer composite diaphragm for lithium ion battery reversible overcharge protection, and production method thereof |
| CN106601969A (en) * | 2017-02-23 | 2017-04-26 | 深圳市海盈科技股份有限公司 | Voltage sensitive diaphragm preparation method |
| CN106816568A (en) * | 2017-02-23 | 2017-06-09 | 深圳市海盈科技股份有限公司 | A kind of preparation method of voltage sensitivity barrier film |
| CN109524604A (en) * | 2018-12-07 | 2019-03-26 | 银隆新能源股份有限公司 | A kind of lithium ion battery separator and lithium ion battery |
| CN109904374A (en) * | 2019-03-19 | 2019-06-18 | 北京卫蓝新能源科技有限公司 | A kind of anti-overcharge diaphragm and its preparation method and application |
| 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 |
-
2004
- 2004-06-28 CN CNA2004100133777A patent/CN1595678A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8379351B2 (en) | 2007-03-30 | 2013-02-19 | Kabushiki Kaisha Toshiba | Magneto-resistance effect element, and method for manufacturing the same |
| US8542466B2 (en) | 2007-03-30 | 2013-09-24 | Kabushiki Kaisha Toshiba | Magneto-resistance effect element, and method for manufacturing the same |
| CN104916870A (en) * | 2014-03-12 | 2015-09-16 | 罗伯特·博世有限公司 | Battery cell with electrode assembly |
| CN104916870B (en) * | 2014-03-12 | 2019-04-30 | 罗伯特·博世有限公司 | Battery list pond with electrode assembly |
| CN105932207B (en) * | 2016-07-15 | 2018-10-19 | 中国工程物理研究院化工材料研究所 | Lithium ion battery is reversible to overcharge protection gelatin polymer composite diaphragm and preparation method thereof |
| CN105932207A (en) * | 2016-07-15 | 2016-09-07 | 中国工程物理研究院化工材料研究所 | Gel polymer composite diaphragm for lithium ion battery reversible overcharge protection, and production method thereof |
| CN106816568A (en) * | 2017-02-23 | 2017-06-09 | 深圳市海盈科技股份有限公司 | A kind of preparation method of voltage sensitivity barrier film |
| CN106601969A (en) * | 2017-02-23 | 2017-04-26 | 深圳市海盈科技股份有限公司 | Voltage sensitive diaphragm preparation method |
| CN109524604A (en) * | 2018-12-07 | 2019-03-26 | 银隆新能源股份有限公司 | A kind of lithium ion battery separator and lithium ion battery |
| CN109904374A (en) * | 2019-03-19 | 2019-06-18 | 北京卫蓝新能源科技有限公司 | A kind of anti-overcharge diaphragm and its preparation method and application |
| CN109904374B (en) * | 2019-03-19 | 2022-07-12 | 北京卫蓝新能源科技有限公司 | Anti-overcharging diaphragm and preparation method and application thereof |
| 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kim et al. | Effects of capacity ratios between anode and cathode on electrochemical properties for lithium polymer batteries | |
| Xiao et al. | Electrochemical behavior of biphenyl as polymerizable additive for overcharge protection of lithium ion batteries | |
| Yesibolati et al. | High performance Zn/LiFePO4 aqueous rechargeable battery for large scale applications | |
| US10862160B2 (en) | All-solid-state lithium-sulfur battery and production method for same | |
| JP5303857B2 (en) | Nonaqueous electrolyte battery and battery system | |
| US8487630B2 (en) | Battery pack and method for detecting degradation of battery | |
| CN1933232B (en) | Charge accumulating system and charge accumulating method | |
| CA2792747C (en) | Lithium secondary battery using ionic liquid | |
| US8257847B2 (en) | Lithium secondary battery | |
| Song et al. | Composite polymer electrolytes reinforced by non-woven fabrics | |
| CN101111954A (en) | Positive electrode material for lithium secondary cell | |
| KR20040014910A (en) | A rechargeable lithium electrochemical cell | |
| WO2011001666A1 (en) | Positive electrode for nonaqueous electrolyte secondary battery, method for producing same, and nonaqueous electrolyte secondary battery | |
| CN100373682C (en) | Lithium ion secondary battery and charging method therefor | |
| Xiao et al. | A composite polymer membrane with reversible overcharge protection mechanism for lithium ion batteries | |
| Park et al. | Variables study for the fast charging lithium ion batteries | |
| JP2010123331A (en) | Nonaqueous electrolyte secondary battery | |
| Chen et al. | Gel electrolyte for lithium-ion batteries | |
| CN1595678A (en) | A voltage sensitive membrane and preparation method thereof | |
| Guy et al. | Novel architecture of composite electrode for optimization of lithium battery performance | |
| Sannier et al. | Room temperature lithium metal batteries based on a new gel polymer electrolyte membrane | |
| Ito et al. | Carbon anodes for solid polymer electrolyte lithium-ion batteries | |
| JP4989985B2 (en) | battery | |
| CN1610146A (en) | Voltage blocked diaphragm and producing method thereof | |
| JP4433021B2 (en) | Non-aqueous electrolyte battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |