CN1115323A - Gel electrolyte film and its prepn. method - Google Patents
Gel electrolyte film and its prepn. method Download PDFInfo
- Publication number
- CN1115323A CN1115323A CN94108795A CN94108795A CN1115323A CN 1115323 A CN1115323 A CN 1115323A CN 94108795 A CN94108795 A CN 94108795A CN 94108795 A CN94108795 A CN 94108795A CN 1115323 A CN1115323 A CN 1115323A
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- gel electrolyte
- film
- electrolyte film
- polyacrylonitrile
- mixture
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- Y02E60/122—
Abstract
The gel film material as electrolyte used in solid-state cell, sensor and other solid electronic devices is made of polyacrylonitrile, mixed plasticizer and lithium salt. A thermal extruder for making said film is disclosed. Said gel film has a certain mechanical strength and very high electric conductivity (0.004S/cm).
Description
The present invention relates to a kind of gel electrolyte film material and its preparation method, particularly be applied in solid state battery, the free-standing gel electrolyte film material on transmitter and other solid ionic device.
Common solid polymeric electrolyte is that an alkali metal salt is (as lithium perchlorate LiCLO
4) being dissolved in the formed complex compound in polyoxyethylene (PEO) back, the ionic conductivity under the room temperature has only
Because ionic conductivity is too low, so limited its practical application greatly.For satisfy all solid state high energy serondary lithium battery to the requirement of the high ionic conductivity of solid polymeric electrolyte (
), (for example its ionic conductivity just can reach 100 ℃ the time so common solid polymeric electrolyte must operate at 80-120 ℃
), obviously this is very disadvantageous for practical application.
Gel electrolyte, particularly polyacrylonitrile (PAN) are basic gel electrolyte, are a kind of very promising materials, as can be used on high energy serondary lithium battery, transmitter or other solid ionic device.But, when preparing this type of material, because matrix polyacrylonitrile and an alkali metal salt are (as LiCLO in the past
4) the content height and the content of solvent is few, so viscosity is big.Again because the polyacrylonitrile molecular polarity is bigger, be difficult to find lower boiling good solvent, make solvent evaporates behind the system film, remove, so be difficult to prepare gel electrolyte film with the casting of common solid polymeric electrolyte, even prepare, also easily produce transudate on the film and bubble occurs, so the poor quality of film is difficult to practical value.
Reference:
I.K.M.Abraham?and?M.?Alamgir，J.?Electrochem.?Soc.，137(1990)1657.
2.M.Watanabe，M.Kanba，K.Nagaoka?and?J.Shinob-ara，J.polym.Sci.：polym.phys.，21(1983)939.
The objective of the invention is to overcome the shortcoming and defect of above-mentioned prior art, a kind of hot extrusion preparation method of free-standing gel electrolyte film is provided;
Two of purpose is: provide a kind of conductivity at room temperature that utilizes hot extrusion method preparation can up to
Free-standing polyacrylonitrile (PAN) be that (this kind film is with support substrate polyacrylonitrile (PAN) to basic gel electrolyte film, mixes plastification solvent vinyl carbonate (EC) and propylene carbonate (PC), and lithium salts lithium perchlorate (LiCLO
4) form).
The objective of the invention is to finish like this:
The invention provides a kind of free-standing gel electrolyte film material, be made up of supporter polyacrylonitrile and plastic binder and lithium salts, its proportioning is: (1)
Propylene carbonate with
The ethene carbonic ether be mixed into softening agent, replace single softening agent with it, be easy to film and form.(2) supporter polyacrylonitrile
(3) lithium salts, as: lithium perchlorate
Film thickness is the thinnest can be about 50um-200um.
The invention provides a kind of method that is exclusively used in the free-standing gel electrolyte film material of preparation: earlier the said ratio raw material is weighed up, propylene carbonate with after the ethene carbonic ether mixes, with LiCLO
4Put into and stir evenly, add polyacrylonitrile again and stir, be placed in the glove box 1-10 days, take out 110-140 ℃ of heating to transparent, bubble-free mixtures.The system film is a kind of brand-new hot extrusion method: with two slick flat boards, as: glass, metal sheet etc. all can, scribble the mixture of the gel electrolyte that stirs on plate, two flat boards are put into baking oven toast 0.5～3.0 hour (storing temperature, time decide on the kind of gel electrolyte), take out two flat boards while hot, one is pressed in another piece and has on the flat board of gel electrolyte and carry out hot extrusion, makes it the film of extruding, and placing it in gloves is desirable film after 1-5 days in box.The size of film and thickness can be controlled with different pressures, and pressure is 0.1～2.0kg/cm usually
2
We replace single plastification solvent EC or PC with mixing plastification solvent EC+PC, and select proper supporting matrix PAN for use, adopt the hot extrusion method of original creation to prepare gel electrolyte film.
Plastification solvent EC, PC are high-k, high boiling point and low viscous organic compound.Their adding makes the second-order transition temperature Tg (=107 ℃) of PAN reduce a lot, thereby makes the ionic conductivity of film increase.But the adding of mixing plastification solvent EC+PC is disadvantageous to the physical strength of film.Therefore ionic conductivity and the physical strength that will take into account electrolytic thin-membrane change the add-on of considering plastification solvent.
When EC+PC one timing, increase LiCLO
4Amount ionic conductivity is increased, but on the contrary, this may be because Tg raises.So, the ionic conductivity of film and add-on (EC+PC/LiCLO
4) be directly proportional.
The effect of PAN is dual: at first be to make it to become the stable film of physical strength as support substrate; Next is to help to make LiCLO
4Solubleness in PAN+EC+PC surpasses its solubleness in EC+PC, and obviously this performance to film plays a part crucial.
We have certain mechanical strength with the free-standing gel electrolyte film of hot extrusion method preparation, and moisture-sensitive not.Its conductivity at room temperature up to
Higher by 10 than the ionic conductivity of common polymer dielectric
4Doubly, this is the highest a kind of ionic conductive polymer of lithium ion conductivity so far.
It is that the specific embodiments of basic gel electrolyte film preparation is as follows that hot extrusion method is used for PAN:
Embodiment 1:
1. weighing at first respectively
EC,
PC and
LiCLO
4, put into a bottle with cover, treat LiCLO
4After the dissolving, slowly add fully
PAN stirs;
2. said mixture was placed in the glove box ten days, stirred first and second every day;
3. treat that PAN dissolves substantially, when mixture is even, places it on the sheet glass, and place baking oven, cover mixture with a glass beaker simultaneously, be heated to 110 ℃.Simultaneously or after a while another piece sheet glass is also put into baking oven;
4. when treating that said mixture presents transparent, no bubble, two sheet glass are taken out from baking oven.The first sheet glass upper glass beaker of taking away slowly is flat on second sheet glass above first sheet glass mixture, imposes 0.4kg/cm
2Pressure and put it in the glove box;
5. take off sheet glass after one day, just can obtain freestanding gel electrolyte film.
Embodiment 2:
1. first weighing
EC and
PC, back weighing
LiCLO
4, put into a bottle with cover, treat LiCLO
4After the dissolving, slowly add fully
PAN stirs;
2. said mixture is placed on one day and often stirring in the glove box;
3. treat that PAN dissolves substantially, when mixture is even, places it on the sheet glass, and place baking oven, cover mixture with a glass beaker simultaneously, be heated to 140 ℃.Also second sheet glass also to be put into baking oven;
4. it is transparent to treat that said mixture presents, during no bubble, first beaker that glass is pulled of taking away, and it is taken out from baking oven, then second sheet glass also taken out from baking oven and slowly be placed on above the mixture of first sheet glass, impose 2.0kg/cm
2Pressure and put it in the glove box;
5. separate two sheet glass after five days and just can obtain freestanding gel electrolyte film.
Simple, the easy row of the method that hot extrusion prepares gel electrolyte film, applied widely, it is applicable to that not only with PAN be in the preparation of basic gel electrolyte film, and is applicable in the preparation of other gel electrolyte film and composite cathode material film.
Utilize the gel electrolyte film of hot extrusion method preparation to have broad application prospects, can be used on all solid state high energy secondary cell, transmitter and other solid ionic device.
Claims (3)
1. a gel electrolyte film is characterised in that; Form and comprise polyacrylonitrile, plastic binder, lithium salts, its proportioning is as follows:
2. by the described gel electrolyte film of claim 1, it is characterized in that: said lithium salts is a lithium perchlorate.
3. one kind is exclusively used in the method for preparing the described gel electrolyte film of claim 1, it is characterized in that: earlier propylene carbonate is mixed with the ethene carbonic ether, add lithium perchlorate afterwards and stir, add polyacrylonitrile again and stir and put into drying receptacle 1-10 days; Take out and heat 110-140 ℃ to transparent, bubble-free mixture; Get two flat boards then, scribble mixture above one, two flat boards are put into baking oven simultaneously, toasted 0.5-3.0 hours down at 110-140 ℃, take out two flat boards while hot, one is pressed on the flat board that scribbles the gel electrolyte mixture, imposes 0.1～2.0kg/cm
2Pressure carries out the hot extrusion film forming, puts into drying receptacle again and gets film in 1-5 days.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94108795A CN1044484C (en) | 1994-07-22 | 1994-07-22 | Gel electrolyte film and its prepn. method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94108795A CN1044484C (en) | 1994-07-22 | 1994-07-22 | Gel electrolyte film and its prepn. method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1115323A true CN1115323A (en) | 1996-01-24 |
| CN1044484C CN1044484C (en) | 1999-08-04 |
Family
ID=5033644
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94108795A Expired - Fee Related CN1044484C (en) | 1994-07-22 | 1994-07-22 | Gel electrolyte film and its prepn. method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1044484C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091306C (en) * | 1998-02-18 | 2002-09-18 | 中国科学院化学研究所 | Solid electrolyte and preparation and uses thereof |
| CN101577349B (en) * | 2009-06-19 | 2011-08-31 | 哈尔滨工业大学 | All-solid-state composite polymer electrolyte and preparation method thereof |
| CN1934657B (en) * | 2003-03-31 | 2012-04-25 | 托雷金恩株式会社 | Composite polymer electrolyte composition |
| CN103222100A (en) * | 2010-09-24 | 2013-07-24 | 积水化学工业株式会社 | Manufacturing method for electrolyte, electrolyte solution, gel electrolyte, electrolyte membrane and gel electrolyte battery, and lithium-on secondary battery |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1293126C (en) * | 2001-06-19 | 2007-01-03 | 三星Sdi株式会社 | Polymer electrolyte and lithium secondary battery containing the polymer electrolyte |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9121117D0 (en) * | 1991-10-03 | 1991-11-13 | Nat Res Dev | Ionically conductive polymer gels |
| US5240790A (en) * | 1993-03-10 | 1993-08-31 | Alliant Techsystems Inc. | Lithium-based polymer electrolyte electrochemical cell |
-
1994
- 1994-07-22 CN CN94108795A patent/CN1044484C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091306C (en) * | 1998-02-18 | 2002-09-18 | 中国科学院化学研究所 | Solid electrolyte and preparation and uses thereof |
| CN1934657B (en) * | 2003-03-31 | 2012-04-25 | 托雷金恩株式会社 | Composite polymer electrolyte composition |
| CN101577349B (en) * | 2009-06-19 | 2011-08-31 | 哈尔滨工业大学 | All-solid-state composite polymer electrolyte and preparation method thereof |
| CN103222100A (en) * | 2010-09-24 | 2013-07-24 | 积水化学工业株式会社 | Manufacturing method for electrolyte, electrolyte solution, gel electrolyte, electrolyte membrane and gel electrolyte battery, and lithium-on secondary battery |
| CN103222100B (en) * | 2010-09-24 | 2017-09-08 | 积水化学工业株式会社 | Electrolyte, electrolyte, gel electrolyte, dielectric film, the manufacture method of gel electrolyte battery and lithium rechargeable battery |
| US10256497B2 (en) | 2010-09-24 | 2019-04-09 | Sekisui Chemical Co., Ltd. | Electrolyte, electrolyte solution, gel electrolyte, electrolyte membrane, method for manufacturing gel electrolyte battery, and lithium ion secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1044484C (en) | 1999-08-04 |
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