JPH0556383B2 - - Google Patents
Info
- Publication number
- JPH0556383B2 JPH0556383B2 JP60167737A JP16773785A JPH0556383B2 JP H0556383 B2 JPH0556383 B2 JP H0556383B2 JP 60167737 A JP60167737 A JP 60167737A JP 16773785 A JP16773785 A JP 16773785A JP H0556383 B2 JPH0556383 B2 JP H0556383B2
- Authority
- JP
- Japan
- Prior art keywords
- ion
- polymer composite
- organic solvent
- present
- polyalkylene carbonate
- 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
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
-
- 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
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Conductive Materials (AREA)
- Primary Cells (AREA)
- Secondary Cells (AREA)
Description
【発明の詳細な説明】
(イ) 産業上の利用分野
本発明は、イオン伝導性高分子複合体に関する
ものであり、詳しくは安定な高いイオン伝導性を
有し且つ透明で加工性に優れ、機械的性質が任意
に調節可能なイオン伝導性高分子複合体に関する
ものである。[Detailed Description of the Invention] (a) Field of Industrial Application The present invention relates to an ion-conducting polymer composite, and more specifically, it has stable and high ion conductivity, is transparent, and has excellent processability. The present invention relates to an ion-conducting polymer composite whose mechanical properties can be arbitrarily adjusted.
(ロ) 従来の技術
イオン伝導性物質としてはLiClO4、LiAlCl4、
LiBF4、KPF6、NaPF6及びLiAsF6等をプロピレ
ンカーボネート、γ−ブチロラクトン、テトラヒ
ドロフラン及びジメトキシエタン等に溶解した電
解質溶液やRbAg4I5、Na−βAl2O3及びZrO2等の
固体電解質等が知られている。(b) Conventional technology Ionic conductive materials include LiClO 4 , LiAlCl 4 ,
Electrolyte solutions such as LiBF 4 , KPF 6 , NaPF 6 and LiAsF 6 dissolved in propylene carbonate, γ-butyrolactone, tetrahydrofuran and dimethoxyethane, solid electrolytes such as RbAg 4 I 5 , Na-βAl 2 O 3 and ZrO 2, etc. It has been known.
又、特開昭57−143356号公報では比誘電率が４
以上の有機高分子化合物、比誘電率が10以上の有
機溶媒及び金属塩からなるイオン伝導性固体組成
物が提案されている。 In addition, in Japanese Patent Application Laid-open No. 57-143356, the dielectric constant is 4.
An ion conductive solid composition comprising the above organic polymer compound, an organic solvent having a dielectric constant of 10 or more, and a metal salt has been proposed.
(ハ) 発明が解決しようとする問題点
上述の電解質溶液は、リチウム電池等で実用化
されているが、溶液を使用する為漏洩の問題は避
けられない。(c) Problems to be solved by the invention The above-mentioned electrolyte solution has been put to practical use in lithium batteries, etc., but since the solution is used, the problem of leakage is unavoidable.
固体電解質は真空蒸着法、スパツタリング法及
びCVD法等の特殊な方法で製造される為高価で
あり、無機物という性質上成形加工性に劣る欠点
がある。 Solid electrolytes are expensive because they are manufactured using special methods such as vacuum evaporation, sputtering, and CVD, and because they are inorganic, they have poor moldability.
又、固体電解質は一般に高温でのみ作動する為
用途が限定される。 Furthermore, solid electrolytes generally operate only at high temperatures, which limits their applications.
特開昭57−143356号公報の系は、有機溶媒が必
須構成要件である為有機溶媒の漏洩及び揮散によ
る導電率の変化は避けられない。 In the system disclosed in JP-A-57-143356, since an organic solvent is an essential component, changes in conductivity due to leakage and volatilization of the organic solvent are unavoidable.
又、有機溶媒濃度は導電率との兼合いから一義
的に決まる為、イオン伝導性高分子複合体の機械
的物性を有機溶媒濃度で調節する事は不可能であ
る。 Furthermore, since the organic solvent concentration is uniquely determined by the balance with the electrical conductivity, it is impossible to adjust the mechanical properties of the ion-conductive polymer composite by the organic solvent concentration.
(ニ) 問題点を解決するための手段
本発明者らは、上述の欠点を解決すべく鋭意努
力検討の結果、一般式〔〕のポリアルキレンカ
ーボネートがLiClO4、LiAlCl4、LiBF4、KPF6、
NaPF6及びLiAsF6等の金属塩の解離を促進し且
つ安定な複合体を形成して高いイオン伝導を発現
する事並びにポリアルキレンカーボネート及び上
記金属塩を溶解する有機溶媒を配合するとイオン
伝導性高分子複合体の機械物性を任意に調節出来
る事を見出し本発明を完成するに至つた。(d) Means for Solving the Problems The present inventors have made extensive efforts to solve the above-mentioned drawbacks and have found that polyalkylene carbonates of the general formula [] are LiClO 4 , LiAlCl 4 , LiBF 4 , KPF 6 ,
It promotes the dissociation of metal salts such as NaPF 6 and LiAsF 6 and forms stable complexes to exhibit high ionic conductivity, and when combined with polyalkylene carbonate and an organic solvent that dissolves the metal salts mentioned above, high ionic conductivity can be achieved. The inventors discovered that the mechanical properties of molecular complexes can be adjusted arbitrarily and completed the present invention.
即ち、本発明は一般式〔〕で表される
（R1、R2、R3、R4は水素原子、炭素数１〜５の
アルキル基及びフエニル基から選ばれる置換基で
あり、Ｘ及びＹはモル分率を示しＸは０〜１、Ｙ
は０〜１の数で且つＸ＋Ｙ＝１である。）
ポリアルアルキレンカーボネートと周期律表第
族及び第族から選ばれる１種又は２種以上の
金属塩並びに上記ポリアルキレンカーボネート及
び金属塩を溶解する有機溶媒からなるイオン伝導
性高分子複合体に関するものである。 That is, the present invention is represented by the general formula [] (R 1 , R 2 , R 3 , R 4 are substituents selected from a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a phenyl group, X and Y represent a mole fraction, and X is 0 to 1, Y
is a number from 0 to 1, and X+Y=1. ) Regarding an ion-conducting polymer composite consisting of a polyalkylene carbonate, one or more metal salts selected from Groups 1 and 3 of the periodic table, and an organic solvent that dissolves the polyalkylene carbonate and metal salt. It is.
本発明の一般式〔〕のポリアルキレンカーボ
ネートの具体例としては、ガラス転移点が10℃の
ポリエチレンカーボネート及びガラス転移点が32
℃のポリプロピレンカーボネート等が挙げられ
る。 Specific examples of the polyalkylene carbonate of the general formula [] of the present invention include polyethylene carbonate with a glass transition point of 10°C and glass transition point of 32°C.
℃ polypropylene carbonate and the like.
本発明の周期律表第族及び第族から選ばれ
る金属塩の具体例としては、LiClO4、LiAlCl4、
LiBF4、KPF6、NaPF6、LiAsF6、Ba（ClO4）2及
びZnI2等が挙げられる。 Specific examples of the metal salts selected from Groups and Groups of the Periodic Table of the present invention include LiClO 4 , LiAlCl 4 ,
Examples include LiBF 4 , KPF 6 , NaPF 6 , LiAsF 6 , Ba(ClO 4 ) 2 and ZnI 2 .
本発明のイオン伝導性高分子複合体の導電率は
金属塩配合量に比例して高くなるが、金属塩の配
合量は一般式〔〕のポリアルキレンカーボネー
ト100重量部に対して１〜100重量部が望ましい。 The conductivity of the ion-conductive polymer composite of the present invention increases in proportion to the amount of metal salt blended, but the amount of metal salt blended is 1 to 100 parts by weight per 100 parts by weight of polyalkylene carbonate of general formula []. part is preferable.
金属塩の配合量が１重量部未満であると充分な
導電性は得られず、又金属塩の配合量が100重量
部を越えると得られるイオン伝導性高分子複合体
が脆くなり用途によつて好ましくない。 If the amount of the metal salt is less than 1 part by weight, sufficient conductivity cannot be obtained, and if the amount of the metal salt is more than 100 parts by weight, the resulting ion-conductive polymer composite becomes brittle and may be difficult to use depending on the application. I don't like it.
本発明の一般式〔〕のポリアルキレンカーボ
ネート及び周期律表第族及び第族から選ばれ
る金属塩を溶解する有機溶媒の具体例としては、
アセトン、酢酸エチル、テトラヒドロフラン及び
プロピレンカーボネート等が挙げられる。 Specific examples of the organic solvent for dissolving the polyalkylene carbonate of the general formula [] of the present invention and the metal salt selected from Groups and Groups of the Periodic Table include:
Examples include acetone, ethyl acetate, tetrahydrofuran and propylene carbonate.
有機溶媒の配合量は、一般式〔〕のポリアル
キレンカーボネート100重量部に対して１〜100重
量部が望ましい。 The amount of the organic solvent to be blended is preferably 1 to 100 parts by weight per 100 parts by weight of the polyalkylene carbonate of the general formula [].
有機溶媒の配合量が１重量部未満であると顕著
な機械物性の向上は認められず、無添加の場合と
差はあまりない。 When the amount of the organic solvent is less than 1 part by weight, no significant improvement in mechanical properties is observed, and there is not much difference from the case where no additive is added.
又、有機溶媒の配合量が100重量部を越えると
得られるイオン伝導性高分子複合体は液体状とな
つてしまう。 Furthermore, if the amount of the organic solvent exceeds 100 parts by weight, the resulting ion-conductive polymer composite will be in a liquid state.
本発明のイオン伝導性高分子複合体は、例えば
一般式〔〕のポリアルキレンカーボネートと周
期律表第族及び第族から選ばれる１種又は２
種以上の金属塩の上記ポリアルキレンカーボネー
ト及び金属塩を溶解する有機溶媒に均一に溶解
し、キヤスチング法で成膜後有機溶媒含有量を所
定量に調節する事により容易に製造する事が出来
る。 The ion-conducting polymer composite of the present invention is composed of, for example, a polyalkylene carbonate of the general formula [] and one or two selected from Groups 1 and 2 of the periodic table.
It can be easily produced by uniformly dissolving one or more metal salts in an organic solvent that dissolves the polyalkylene carbonate and the metal salt, and adjusting the organic solvent content to a predetermined amount after film formation by a casting method.
本発明のイオン伝導性高分子複合体の用途とし
ては、例えば一次電池、二次電池、センサー及び
エレクトロクロミツクデイスプレイ等が挙げられ
る。 Applications of the ion-conductive polymer composite of the present invention include, for example, primary batteries, secondary batteries, sensors, electrochromic displays, and the like.
(ホ) 発明の効果
本発明のイオン伝導性高分子複合体は、一般式
〔〕のポリアルキレンカーボネートが周期律表
第族及び第族から選ばれる１種又は２種以上
の金属塩の解離を促進し大部分の金属をイオンと
して存在させ且つ安定な複合体を形成する為、高
いイオン伝導性を示す。(E) Effect of the invention The ion-conducting polymer composite of the present invention is characterized in that the polyalkylene carbonate of the general formula [] is capable of dissociating one or more metal salts selected from Groups and Groups of the Periodic Table. Because most of the metals exist as ions and form stable complexes, it exhibits high ionic conductivity.
又、本発明のイオン伝導性高分子複合体は高い
透明性を有し且つ固体状である為、電解質が漏
洩、揮散する事はない。 Furthermore, since the ion-conducting polymer composite of the present invention has high transparency and is solid, the electrolyte will not leak or volatilize.
更に、有機溶媒を含有する高分子複合体である
為、特に賦形性に優れ成形性及び後加工性も良
い。 Furthermore, since it is a polymer composite containing an organic solvent, it has particularly excellent shapeability and good moldability and post-processability.
例えば、本発明のイオン伝導性高分子複合体上
に電極を形成する場合、電極との接触状態が非常
に良好であり界面に起因する抵抗が低滅する利点
がある。 For example, when an electrode is formed on the ion-conducting polymer composite of the present invention, there is an advantage that the contact state with the electrode is very good and the resistance due to the interface is reduced.
本発明のイオン伝導性高分子複合体の機械物性
は、一般式〔〕のポリアルキレンカーボネート
の置換基R1、R2、R3、R4及びＸ及びＹのモル分
率を適宜選択しガラス転移点等を調節する事によ
り或る程度調節する事も出来るが、一般式〔〕
のポリアルキレンカーボネート及び周期律表第
族及び第族から選ばれる金属塩を溶解する有機
溶媒を含有させる事により機械物性を容易、且つ
任意に調節する事が出来る。 The mechanical properties of the ion-conductive polymer composite of the present invention are determined by appropriately selecting the mole fractions of substituents R 1 , R 2 , R 3 , R 4 and X and Y of the polyalkylene carbonate of the general formula []. It can be adjusted to some extent by adjusting the transition point, etc., but the general formula []
By containing an organic solvent that dissolves polyalkylene carbonate and a metal salt selected from Groups 1 and 3 of the periodic table, mechanical properties can be easily and arbitrarily adjusted.
(ヘ) 実施例
次に実施例を挙げて本発明を詳細に説明する
が、本発明はこれらに限定されるものではない。(f) Examples Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto.
実施例 １
ポリプロピレンカーボネート１ｇ、LiClO40.1
ｇ及びプロピレンカーボネート５ｇを混合撹拌し
均一溶液とした。Example 1 1 g of polypropylene carbonate, LiClO 4 0.1
g and 5 g of propylene carbonate were mixed and stirred to form a homogeneous solution.
この溶液をステンレス板上にキヤスチング後、
減圧下90℃で４時乾燥を行い、プロピレンカーボ
ネート配合量が0.5ｇで厚さ1.3mmの透明な固体状
イオン伝導性高分子複合体を得た。 After casting this solution on a stainless steel plate,
Drying was carried out under reduced pressure at 90° C. for 4 hours to obtain a transparent solid ion-conductive polymer composite containing 0.5 g of propylene carbonate and having a thickness of 1.3 mm.
このイオン伝導性高分子複合体上にステンレス
製の主電極及びガード電極を形成後、イオンの分
極を避ける為インピーダンス法を採用し周波数を
102〜105Hzまで変化させ導電率の測定を行いCole
−Coleプロツトにより導電率を算出した。 After forming stainless steel main electrodes and guard electrodes on this ion-conducting polymer composite, we adopted the impedance method to avoid polarization of the ions and set the frequency.
The conductivity was measured by varying the frequency from 102 to 105 Hz.
- Electrical conductivity was calculated by Cole plot.
導電率は5.6×10-5S・cm-1であつた。 The electrical conductivity was 5.6×10 −5 S·cm −1 .
Claims (1)
アルキル基及びフエニル基から選ばれる置換基で
あり、Ｘ及びＹはモル分率を示しＸは０〜１、Ｙ
は０〜１の数で且つＸ＋Ｙ＝１である。） ポリアルキレンカーボネートと周期律表第族
及び第族から選ばれる１種又は２種以上の金属
塩並びに上記ポリアルキレンカーボネート及び金
属塩を溶解する有機溶媒からなるイオン伝導性高
分子複合体。[Claims] 1 Represented by the general formula [] (R 1 , R 2 , R 3 , R 4 are substituents selected from a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a phenyl group, X and Y represent a mole fraction, and X is 0 to 1, Y
is a number from 0 to 1, and X+Y=1. ) An ion-conducting polymer composite comprising a polyalkylene carbonate, one or more metal salts selected from Groups 1 and 3 of the periodic table, and an organic solvent that dissolves the polyalkylene carbonate and metal salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60167737A JPS6230147A (en) | 1985-07-31 | 1985-07-31 | Ion-conducting polymer composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60167737A JPS6230147A (en) | 1985-07-31 | 1985-07-31 | Ion-conducting polymer composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6230147A JPS6230147A (en) | 1987-02-09 |
| JPH0556383B2 true JPH0556383B2 (en) | 1993-08-19 |
Family
ID=15855193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60167737A Granted JPS6230147A (en) | 1985-07-31 | 1985-07-31 | Ion-conducting polymer composite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6230147A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998025275A1 (en) * | 1996-12-03 | 1998-06-11 | Mitsui Chemicals, Inc. | Gel-form solid polymer electrolyte |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4544250B2 (en) * | 1995-07-24 | 2010-09-15 | 住友化学株式会社 | Non-aqueous electrolyte lithium secondary battery |
| US6878492B2 (en) | 2000-07-10 | 2005-04-12 | Showa Denko Kabushiki Kaisha | Polymerizable composition and use thereof |
| CN1319204C (en) | 2002-04-15 | 2007-05-30 | 日立麦克赛尔株式会社 | Ion-conductive electrolyte and cell employing the same |
| JP4902884B2 (en) | 2006-09-11 | 2012-03-21 | 旭化成株式会社 | POLYMER ELECTROLYTE, PROCESS FOR PRODUCING THE SAME, AND ELECTROCHEMICAL DEVICE |
| RU2388088C1 (en) | 2006-09-11 | 2010-04-27 | Асахи Касеи Кабусики Кайся | New polymer electrolyte and electrochemical device |
-
1985
- 1985-07-31 JP JP60167737A patent/JPS6230147A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998025275A1 (en) * | 1996-12-03 | 1998-06-11 | Mitsui Chemicals, Inc. | Gel-form solid polymer electrolyte |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6230147A (en) | 1987-02-09 |
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