CN102738426A - Preparation method of high-temperature-resisting lithium battery - Google Patents
Preparation method of high-temperature-resisting lithium battery Download PDFInfo
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- CN102738426A CN102738426A CN2012102230329A CN201210223032A CN102738426A CN 102738426 A CN102738426 A CN 102738426A CN 2012102230329 A CN2012102230329 A CN 2012102230329A CN 201210223032 A CN201210223032 A CN 201210223032A CN 102738426 A CN102738426 A CN 102738426A
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- lithium battery
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- polyimide resin
- polymer electrolyte
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- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention relates to a preparation method of a high-temperature-resisting lithium battery. The method comprises the steps that: (1) soluble polyimide resin is selected; (2) the soluble polyimide resin and polycarbosilane powder are mixed according to a mass ratio of 70-100:0-30; the mixture is dissolved in an organic solvent, such that a solution B is formed; (3) lithium ion salt is dissolved in the solution B, such that a polymer electrolyte solution is formed, wherein the molar concentration ratio of the lithium ion to imide rings in polyimide resin is 0.5-1:1; (4) the polymer electrolyte solution is molded on a cathode; the solvent in the polymer electrolyte solution is removed by volatilization under a high-temperature vacuum condition, such that a polymer electrolyte film is formed; and (5) an anode is prepared on the polymer electrolyte film, and a lithium battery is obtained after packaging. With the method provided by the invention, a problem of application limitation of existing solid-state condensate lithium batteries is solved. With the method provided by the invention, the polymer ion conductivity is effectively improved, the mechanical strength of the electrolyte film is improved, and the ion conductivity of the film is improved. The battery can be applied within a wider temperature range.
Description
Technical field
The present invention relates to a kind of preparation method of high temperature resistant lithium battery.
Background technology
Lithium battery is made up of both positive and negative polarity, electrolyte and polymeric barrier films.To different electrolytes; Barrier material also is not quite similar, and present modal lithium battery adopts liquid electrolyte, and the barrier film that is adopted is polypropylene (PP), polyethylene (PE) individual layer microporous barrier; And by the compound multilayer microporous film of PP and PE as barrier film; This type of barrier film production technology can be divided into two big types according to dry method and wet method, and dry method can be subdivided into simple tension technology and stretch processes again simultaneously, and this type of barrier film is one type that has the call.But the liquid electrolyte lithium battery has some intrinsic shortcomings, like high price and lower fail safe.Usually, the metallic cover that this class I liquid I electrolyte need seal, this can reduce the energy density of battery.In addition, because security reason, lithium battery is typically designed to the automatic vent structure, avoids because the inner or outside overheated increase that causes internal pressure, otherwise will cause the blast or the burning of battery.These drawbacks limit the application of this type of battery in high performance demands fields such as cleaning power and small flexibilities.
See that from structure the liquid electrolyte in the lithium ion battery might leak and have potential safety hazard, solid polymer electrolyte replaces the fail safe that liquid electrolyte can improve lithium battery.Common solid polymer electrolyte is a gel polymer, is that lithium solution and solvent are dispersed in the hole of polymeric barrier films and form.Typical case's representative of this base polymer barrier film comprises PEO, PAN, and PMMA, and PVDF etc.Because this type electrolyte barrier film is a non-volatile type of material, does not have problems such as leakage in normal working conditions, and is more safer than liquid electrolyte from essence; And this type of solid electrolyte eliminated automatic vent mechanism and encapsulating structure, makes the preparation flexible battery become possibility, also can reduce battery weight and thickness.All solid state gelatin polymer lithium battery has indicated the main direction of following lithium battery development, and the barrier film that exploitation can be satisfied the use of all solid state lithium ion polymer battery will be trend of the times.
Though gel polymer electrolyte has had large increase than liquid electrolyte at aspects such as fail safe and manufacturabilitys; Its fail safe remains one of potential problem; This is owing to have solution in the polymeric barrier films hole, under extreme conditions can leak and causes battery to damage.In addition, this type of polymeric barrier films can not use in wider temperature range, and this is because gelatin polymer exists under lower temperature, and high temperature descends to understand other components or the metal reaction with battery.The unsteadiness of electrode and relatively poor cycle specificity have limited its application.
Summary of the invention
Be prone to exist solution can cause battery to damage in the polymeric barrier films space of existing solid-state condensation product class lithium battery; And polymeric barrier films can react with other components of battery under hot conditions; The limitation that causes solid-state condensation product class lithium battery to use; Based on solving the problems of the technologies described above, the present invention provides a kind of preparation method of high temperature resistant lithium battery.
Technical solution of the present invention:
A kind of preparation method of high temperature resistant lithium battery, its special character is: may further comprise the steps: 1] select soluble polyimide resin for use, wherein the molecular weight of polyimides ring is controlled between the 200-350; Select the solid-state Polycarbosilane powder of solubility, the Polycarbosilane molecular weight is controlled between the 1000-2000;
2] polyimides and Polycarbosilane powder are pressed mass ratio 70 ~ 100:0 ~ 30 and mix, and be dissolved in and form solution B in the organic solvent; Lithium concentration is the corresponding 1mol imide ring of 0.5-1mol lithium ion;
4] polymer dielectric solution is molded on the negative electrode, and under high-temperature vacuum, vapors away solvent, form polymer electrolyte film;
5] on polymer electrolyte film, prepare anode, be prepared into lithium battery after the encapsulation.The ionic conductivity of polymer dielectric is greater than 1*10
-4S/cm, step 3] in lithium ion salt be LiCl, LiBr, LiI, LiClO
4, LiAsF
6, LiCF
3SO
3, LiBF
4, LiPF
6, one or more the mixing among the LiTFSi.
The main thin technology of common system that adopts of polymer dielectric film preparation, like print process, lacquering technique, brushing method etc.
Organic solvent is one or more the mixing in N-methyl pyrrolidone (NMP), dimethylacetylamide (DMAc) and the dimethyl formamide (DMF).
The advantage that the present invention had:
1, polyimides has the good temperature resistance ability; The adding of Polycarbosilane has further improved the high-temperature behavior of battery; The present invention adopts soluble polyimide resin and the solid-state Polycarbosilane mixed powder of solubility; Preparation novel polymer lithium ion barrier film, and compound lithium ion electrolyte form novel full solid state polymer barrier film.On the basis that has kept the gel polymer electrolyte advantage; Overcome relevant shortcoming effectively; And effectively improved the polymer ions conductivity, and improved the mechanical strength of dielectric film and the ionic conducting property of film simultaneously, guarantee that battery uses in wider temperature range.As shown in table 1, be the conductance of lithium battery of the present invention under different temperatures.
2, lithium ion battery of the present invention prepares easily, in wide temperature range, has good reliability and storage and cycle characteristics, can satisfy the demand of lithium battery in high-end demand fields such as cleaning power and small flexibilities.
3, because polyimides and Polycarbosilane adopt thermoset forming, the structure of complicated abnormal shape can be prepared, therefore hull cell and special-shaped battery can be prepared.
Embodiment
Embodiment: select the PMDA/ODA polyimide resin for use, molecular weight is 1100 solid-state Polycarbosilane;
Polyimides and Polycarbosilane powder are pressed mass ratio 80:20 mixing, be dissolved among the N-methyl pyrrolidone NMP; Add LiTFSi salt, with the ratio of polyimides and Polycarbosilane mixed powder be 70:30, and be dissolved in the nmp solution of polyimides and Polycarbosilane; Adopt LiFePO
4Cathode material adopts typography to be coated on the negative electrode above-mentioned solution, and volatilization forms film under 120 ℃ of vacuum conditions, and its thickness is about 10 μ m.The preparation anode forms lithium ion battery.
Polyimides mixes with the Polycarbosilane powder, and the Polycarbosilane powder influences the hardness of lithium battery, and the content of Polycarbosilane powder can not be too high, and crisp if too high lithium battery is not just named, toughness is not enough; If very little, hardness is not enough.When so polyimides and Polycarbosilane powder are 80:20 by mass ratio, the best.But because require different, also addition polymerization carbon silane powder not.
Table 1 is the conductance of the lithium ion battery of employing preparation method's preparation of the present invention.
| Temperature (° C) | Conductance (S/cm) |
| -20 | 5.6×10 -6 |
| 0 | 5.4×10 -5 |
| 20 | 1.1×10 -4 |
| 40 | 3.2×10 -4 |
| 60 | 7.6×10 -4 |
Claims (5)
1. the preparation method of a high temperature resistant lithium battery is characterized in that: may further comprise the steps:
1] select soluble polyimide resin, wherein the molecular weight of imide ring is controlled between the 200-350 in the polyimide resin; Select the solid-state Polycarbosilane powder of solubility, the Polycarbosilane molecular weight is controlled between the 1000-2000;
2] polyimide resin and Polycarbosilane powder are pressed mass ratio 70 ~ 100:0 ~ 30 and mix, and be dissolved in and form solution B in the organic solvent;
3] lithium ion salt is dissolved in formation polymer dielectric solution in the solution B, wherein, the molar concentration rate of the imide ring in lithium ion molar concentration and the polyimide resin is 05-1:1
4] polymer dielectric solution is molded on the negative electrode, and under high-temperature vacuum, vapors away the solvent of polymer dielectric solution, form polymer electrolyte film;
5] on polymer electrolyte film, prepare anode, be prepared into lithium battery after the encapsulation.
2. the preparation method of high temperature resistant lithium battery according to claim 1 is characterized in that: said step 3] in lithium ion salt be LiCl, LiBr, LiI, LiClO
4, LiAsF
6, LiCF
3SO
3, LiBF
4, LiPF
6Or one or more the mixing among the LiTFSi.
3. the preparation method of high temperature resistant lithium battery according to claim 1 and 2 is characterized in that: said step 4] in polymer dielectric solution is molded on the negative electrode the concrete following method that adopts: print process, lacquering technique or brushing method.
4. the preparation method of high temperature resistant lithium battery according to claim 3 is characterized in that: said organic solvent is one or more the mixing in N-methyl pyrrolidone (NMP), dimethylacetylamide (DMAc) and the dimethyl formamide (DMF).
5. the preparation method of high temperature resistant lithium battery according to claim 4 is characterized in that: said polyimides and Polycarbosilane powder are pressed mass ratio 80:20 and are mixed.
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| CN2012102230329A CN102738426A (en) | 2012-06-29 | 2012-06-29 | Preparation method of high-temperature-resisting lithium battery |
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| CN2012102230329A CN102738426A (en) | 2012-06-29 | 2012-06-29 | Preparation method of high-temperature-resisting lithium battery |
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| CN102738426A true CN102738426A (en) | 2012-10-17 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014186980A1 (en) * | 2013-05-24 | 2014-11-27 | Basf Corporation | Ge1 polymer electrolyte and lithium-ion batteries employing the ge1 polymer electrolyte |
| CN109786849A (en) * | 2019-03-05 | 2019-05-21 | 中复新水源科技有限公司 | A kind of preparation method of high-temperature-reslithium lithium battery |
| CN114079081A (en) * | 2020-08-18 | 2022-02-22 | 厦门大学 | Polymer electrolyte and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1147953C (en) * | 1997-02-12 | 2004-04-28 | 太空实验技术集团有限公司 | Polyimide battery |
| CN100386912C (en) * | 2003-05-13 | 2008-05-07 | 瑟利寇公司 | Polyimide based electrolyte and improved batteries therefrom |
| JP2008204845A (en) * | 2007-02-21 | 2008-09-04 | Hitachi Ltd | Polymer electrolyte membrane membrane-electrode assembly using it, and fuel cell |
-
2012
- 2012-06-29 CN CN2012102230329A patent/CN102738426A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1147953C (en) * | 1997-02-12 | 2004-04-28 | 太空实验技术集团有限公司 | Polyimide battery |
| CN100386912C (en) * | 2003-05-13 | 2008-05-07 | 瑟利寇公司 | Polyimide based electrolyte and improved batteries therefrom |
| JP2008204845A (en) * | 2007-02-21 | 2008-09-04 | Hitachi Ltd | Polymer electrolyte membrane membrane-electrode assembly using it, and fuel cell |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014186980A1 (en) * | 2013-05-24 | 2014-11-27 | Basf Corporation | Ge1 polymer electrolyte and lithium-ion batteries employing the ge1 polymer electrolyte |
| CN109786849A (en) * | 2019-03-05 | 2019-05-21 | 中复新水源科技有限公司 | A kind of preparation method of high-temperature-reslithium lithium battery |
| CN114079081A (en) * | 2020-08-18 | 2022-02-22 | 厦门大学 | Polymer electrolyte and preparation method thereof |
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Application publication date: 20121017 |