JPH0470746B2 - - Google Patents
Info
- Publication number
- JPH0470746B2 JPH0470746B2 JP61220014A JP22001486A JPH0470746B2 JP H0470746 B2 JPH0470746 B2 JP H0470746B2 JP 61220014 A JP61220014 A JP 61220014A JP 22001486 A JP22001486 A JP 22001486A JP H0470746 B2 JPH0470746 B2 JP H0470746B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- solid electrolyte
- polyether
- present
- diacrylate
- 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.)
- Expired - Lifetime
Links
- 229920000642 polymer Polymers 0.000 claims description 14
- 239000007784 solid electrolyte Substances 0.000 claims description 12
- 229920000570 polyether Polymers 0.000 claims description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000004386 diacrylate group Chemical group 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 6
- -1 isocyanate salt Chemical class 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000005518 polymer electrolyte Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 238000006845 Michael addition reaction Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- JMMVHMOAIMOMOF-UHFFFAOYSA-N (4-prop-2-enoyloxyphenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=C(OC(=O)C=C)C=C1 JMMVHMOAIMOMOF-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
- Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Primary Cells (AREA)
- Secondary Cells (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、全固体形二次電池の電解質に関する
もので、特に高分子固体電解質の改良に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an electrolyte for an all-solid-state secondary battery, and in particular to improvement of a polymer solid electrolyte.
従来技術とその問題点
リチウムのイオン導電性固体電解質として、
LiCO4等のLi塩を溶解させたポリエチレンオキ
シド（PEO）に代表される高分子固体電解質が
ある。このものは薄膜への加工が容易であるこ
と、強度が大でしかも柔軟性があること等の長所
を有する。Conventional technology and its problems As an ion conductive solid electrolyte for lithium,
There is a polymer solid electrolyte represented by polyethylene oxide (PEO) in which Li salt such as LiCO 4 is dissolved. This material has advantages such as being easy to process into a thin film, having high strength and flexibility.
しかしながら、従来のPEOにおいては、直鎖
形（二官能）を用いてLi塩を溶解させる段階で
PEOの結晶化が起こり、イオンの移動度が低下
する。このために、高い導電率が得られないとい
う欠点があつた。 However, in conventional PEO, a linear type (bifunctional) is used at the stage of dissolving Li salt.
Crystallization of PEO occurs, reducing ion mobility. For this reason, there was a drawback that high conductivity could not be obtained.
この改良として、三官能性ポリエーテルをイソ
シアナート塩で架橋した三次元架橋体が提案され
ている。これは、ポリマーの結晶化が抑制されて
いるために、従来より高いイオン導電性が得られ
た。しかしながら、これらのイオン導電性は室温
で10-5Sm-1であり、電池が一般に使用される室
温において、充分な性能が発揮できないという欠
点があつた。 As an improvement on this, a three-dimensionally crosslinked product in which a trifunctional polyether is crosslinked with an isocyanate salt has been proposed. This is because the crystallization of the polymer is suppressed, resulting in higher ionic conductivity than before. However, their ionic conductivity was 10 −5 Sm −1 at room temperature, and they had the drawback that they could not exhibit sufficient performance at room temperature, where batteries are generally used.
発明の目的
本発明は上記従来の欠点に鑑みなされたもので
あり、イオン導電性の高い、高分子固体電解質を
提供することを目的とする。OBJECTS OF THE INVENTION The present invention was made in view of the above-mentioned conventional drawbacks, and an object of the present invention is to provide a solid polymer electrolyte with high ionic conductivity.
発明の構成
本発明は上記目的を達成するべく、ポリエーテ
ルを架橋した高分子化合物に金属塩を溶解した固
体電解質において、該高分子化合物が多官能性水
酸基を有するポリエーテルとジアクリレートによ
つてエーテル結合することにより架橋したことを
特徴とする高分子固体電解質である。Structure of the Invention In order to achieve the above object, the present invention provides a solid electrolyte in which a metal salt is dissolved in a polymer compound crosslinked with polyether, in which the polymer compound is composed of a polyether having a polyfunctional hydroxyl group and a diacrylate. This is a solid polymer electrolyte characterized by being crosslinked by ether bonding.
即ち、アクレートのようなα，β−不飽和カル
ボニル化合物は、水酸基、アミノ基、メルカプト
基などの活性水素を有する官能基と反応して付加
化合物を作ることは、Michael付加反応として知
られている。 In other words, α,β-unsaturated carbonyl compounds such as acrylates react with functional groups containing active hydrogen such as hydroxyl groups, amino groups, and mercapto groups to form addition compounds, which is known as the Michael addition reaction. .
この反応を三官能以上の多官能性水酸基を有す
るポリオールとジアクリレートの反応に応用する
ならば、Michael付加反応の結果としてエーテル
結合によつて架橋した三次元ポリマーが得られる
ことになる。 If this reaction is applied to the reaction of a diacrylate with a polyol having trifunctional or higher functional hydroxyl groups, a three-dimensional polymer crosslinked by ether bonds will be obtained as a result of the Michael addition reaction.
多官能性水酸基を有するポリエーテルとジアク
リレートとの反応で得られた三次元ポリエーテル
とは、その架橋構造の中にアルカリ金属塩などの
金属塩を溶解させることができ、しかもエーテル
結合によつて生成した架橋ポリマーであるため
に、分子間水素結合のない、ガラス転移温度の低
い構造となり、溶解した金属塩イオンの泳動が極
めて容易になる特徴がある。 A three-dimensional polyether obtained by the reaction of a polyether with polyfunctional hydroxyl groups and a diacrylate is capable of dissolving metal salts such as alkali metal salts in its crosslinked structure. Because it is a cross-linked polymer produced by a process of oxidation, it has a structure with no intermolecular hydrogen bonds and a low glass transition temperature, making it extremely easy for dissolved metal salt ions to migrate.
多官能性水酸基を有するポリエーテルとして
は、例えばグリセリンとエチレンオキシドあるい
はプロピレンオキシドとの反応で得られたポリエ
ーテルが例示されるが、これに限定されるもので
はない。 Examples of polyethers having polyfunctional hydroxyl groups include, but are not limited to, polyethers obtained by reacting glycerin with ethylene oxide or propylene oxide.
ジアクリレートとしてはジエチレングリコール
ジアクリレート、トリエチレングリコールジアク
リレート、あるいはハイドロキノンジアクリレー
トなどのようにグリコールあるいは二価フエノー
ルから誘導される脂肪族、芳香族ジアクリレート
が用いられる。 As the diacrylate, aliphatic or aromatic diacrylates derived from glycol or dihydric phenol such as diethylene glycol diacrylate, triethylene glycol diacrylate, or hydroquinone diacrylate are used.
実施例
以下に本発明の詳細について、一実施例により
説明する。アセトニトリル10部、三官能性ポリエ
ーテル10部、当量のエチレングリコールジアクリ
レート、少量のカリウムメトキシドを数時間混合
攪拌した。EXAMPLE The details of the present invention will be explained below by way of an example. 10 parts of acetonitrile, 10 parts of trifunctional polyether, an equivalent amount of ethylene glycol diacrylate, and a small amount of potassium methoxide were mixed and stirred for several hours.
この混合物をガラスシヤーレ上に流延し、40℃
の不活性ガス雰囲気中で放置し、架橋体フイルム
を得た。フイルムの未反応物を除去した後、80℃
にて真空乾燥した。次に、トリフロロメタンサル
ホン酸リチウム−アセトン溶液中にフイルムを浸
漬させることにより、トリフロロメタンサルホン
酸リチウムを溶解させた。80℃において真空乾燥
し、本発明の固体電解質を得た。 This mixture was cast on a glass shear dish and heated to 40°C.
The film was left to stand in an inert gas atmosphere to obtain a crosslinked film. After removing unreacted substances from the film, heat to 80℃
It was vacuum dried. Next, the lithium trifluoromethanesulfonate was dissolved by immersing the film in a lithium trifluoromethanesulfonate-acetone solution. The solid electrolyte of the present invention was obtained by vacuum drying at 80°C.
本発明の高分子固体電解質は、室温で10-4
Sm-1を示し、ガラス転移点は従来の−60℃に対
し、−70℃と低く良好な充放電性能を示し、十分
に実用に供し得るものであることが判つた。第１
図に本発明の高分子固体電解質と従来品（上記実
施例において、エチレングリコールジアクリレー
トに替えて、ヘキサメチレンジイソシアナートを
用いたもの。）とのイオン導電率と温度との関係
を示した。 The solid polymer electrolyte of the present invention has a temperature of 10 -4 at room temperature.
Sm -1 , and the glass transition point was -70°C, lower than the conventional -60°C, showing good charge and discharge performance, and was found to be fully usable for practical use. 1st
The figure shows the relationship between ionic conductivity and temperature between the polymer solid electrolyte of the present invention and a conventional product (in the above example, hexamethylene diisocyanate was used instead of ethylene glycol diacrylate). .
固体電解質の導電性を決定する要素として、高
分子構造の柔らかさが挙げられる。固い構造の高
分子を用いた固体電解質では、金属イオン移動度
が低下する。イソシアナート塩によるウレタン結
合は、
であり、（架橋剤にヘキサメチレンジイソシアナ
ートを用いた従来品）結合部分の構造が固い上、
近隣する結合同志が水素結合するため、イオンの
移動度は低く抑えられる。 The softness of the polymer structure is one of the factors that determines the conductivity of solid electrolytes. In solid electrolytes using polymers with a rigid structure, metal ion mobility decreases. Urethane bonding by isocyanate salt is (Conventional product using hexamethylene diisocyanate as a crosslinking agent) In addition to the rigid structure of the bonding part,
Because neighboring bonds form hydrogen bonds, the mobility of ions is suppressed to a low level.
本発明では、エチレングリコールジアクリレー
トを架橋剤に用い、エーテル結合を導入すること
により、
の柔らかい高分子構造の固体電解質を得る。これ
によつてイオン伝導度が改良できた。 In the present invention, by using ethylene glycol diacrylate as a crosslinking agent and introducing an ether bond, A solid electrolyte with a soft polymer structure is obtained. This improved the ionic conductivity.
発明の効果
上述した如く、本発明はイオン導電性の高い高
分子固体電解質を提供することが出来るので、そ
の工業的価値は極めて大である。Effects of the Invention As described above, the present invention can provide a solid polymer electrolyte with high ionic conductivity, and therefore has extremely great industrial value.
第１図は本発明の高分子固体電解質と従来品と
のイオン導電率を比較した図である。
FIG. 1 is a diagram comparing the ionic conductivity of the polymer solid electrolyte of the present invention and a conventional product.
Claims (1)
塩を溶解した固体電解質において、該高分子化合
物が多官能性水酸基を有するポリエーテルとジア
クリレートとの反応によつてエーテル結合するこ
とにより架橋したことを特徴とする高分子固体電
解質。1. In a solid electrolyte in which a metal salt is dissolved in a polymer compound cross-linked with polyether, it is confirmed that the polymer compound is cross-linked by ether bonding through the reaction between a polyether having a polyfunctional hydroxyl group and a diacrylate. Characteristic polymer solid electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61220014A JPS6376273A (en) | 1986-09-18 | 1986-09-18 | Polymer solid electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61220014A JPS6376273A (en) | 1986-09-18 | 1986-09-18 | Polymer solid electrolyte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6376273A JPS6376273A (en) | 1988-04-06 |
| JPH0470746B2 true JPH0470746B2 (en) | 1992-11-11 |
Family
ID=16744579
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61220014A Granted JPS6376273A (en) | 1986-09-18 | 1986-09-18 | Polymer solid electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6376273A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02253571A (en) * | 1989-03-27 | 1990-10-12 | Japan Storage Battery Co Ltd | Polymer electrolyte secondary battery |
| WO1993020594A1 (en) * | 1992-04-06 | 1993-10-14 | Yuasa Corporation | Cell |
| EP0603793A3 (en) * | 1992-12-25 | 1995-11-08 | Yoshida Kogyo Kk | Organic solid electrolyte and coloring-discoloring device using the same. |
| JP4894083B2 (en) * | 2000-09-28 | 2012-03-07 | 日産自動車株式会社 | All-solid polymer battery and method for producing the same |
-
1986
- 1986-09-18 JP JP61220014A patent/JPS6376273A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6376273A (en) | 1988-04-06 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |