JPS6230148A - Novel ion conductive high polymer complex - Google Patents
Novel ion conductive high polymer complexInfo
- Publication number
- JPS6230148A JPS6230148A JP60167738A JP16773885A JPS6230148A JP S6230148 A JPS6230148 A JP S6230148A JP 60167738 A JP60167738 A JP 60167738A JP 16773885 A JP16773885 A JP 16773885A JP S6230148 A JPS6230148 A JP S6230148A
- Authority
- JP
- Japan
- Prior art keywords
- high polymer
- polymer complex
- ion
- carbonate
- 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.)
- Granted
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
Abstract
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
加工性及び機械的性質に優れた新規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) Industrial Application Field The present invention relates to an ion-conducting polymer composite, and more specifically, it has stable and high ion-conductivity, is transparent, and has good processability and mechanical properties. This invention relates to a novel ion-conducting polymer composite with excellent properties.
（ロ）従来の技術
イオン伝導性物質としてはＬｉＣｌ０ｎ、ＬｉＡＩＣ］
４、し１ＢＦ４ 、ＫＰＦイＮａＰＦ、、及びＬｉＡ
ｓＦ６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ＲｂＡｇｔ１５ 、Ｎａ−βＡｈ（ｈ
及びＺｒ０ｚ等の固体電解質等が知られている。(b) Conventional technology: LiCl0n, LiAIC as ion conductive materials]
4, 1BF4, KPF, NaPF, and LiA
Electrolyte solutions in which sF6, etc. are dissolved in propylene carbonate, γ-butyrolactone, tetrahydrofuran, dimethoxyethane, etc., RbAgt15, Na-βAh (h
Solid electrolytes such as ZrOz and ZrOz are 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従業さ
れている。In addition, in Japanese Patent Application Laid-open No. 57-143356, the dielectric constant is 4.
Ion conductive solid compositions comprising the above organic polymer compounds, organic solvents having a dielectric constant of 10 or more, and metal salts have been used.
（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、スパッタリング法及び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 electrolyte can be used by vacuum evaporation method, sputtering method and CVD method.
It is expensive because it is manufactured using a special method such as a method such as a method, and has the disadvantage of poor moldability due to its inorganic nature.
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？容媒の漏洩及び揮散による導
電率の変化は避けられない。The system disclosed in JP-A-57-143356 is organic because an organic solvent is an essential component. Changes in conductivity due to leakage and volatilization of the medium are unavoidable.
又、有機溶媒を一定量残留させるように成膜するには、
煩雑な工程が必要となる。In addition, in order to form a film so that a certain amount of organic solvent remains,
A complicated process is required.
（ニ）問題点を解決するだめの手段
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ＣＬ）のポリアルキレンカーボネートがＬ
ｉＣＩＯ４、ＬｉＡｌＣｌ４、ＬｉＢＦ、 、にＰＦい
ＮａＰＦ、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性を発現す
る事を見出し本発明を完成するに至った。(d) Means for solving the problem The inventors of the present invention have made extensive efforts to solve the above-mentioned drawbacks, and have found that the polyalkylene carbonate of the general formula CL)
We have completed the present invention by discovering that it promotes the dissociation of metal salts such as iCIO4, LiAlCl4, LiBF, PF, NaPF, and LiAsF6, forms a stable complex, and exhibits high ionic conductivity. .
即ち、本発明は一般式（１）で表される（Ｒ，、Ｒ２、
Ｒ３、Ｒ，は水素原子、炭素数１〜５のアルキル基及び
フェ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 (1) (R,, R2,
R3, R, 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, X is a number of 0 to 1, and Y is a number of 0 to 1. And X+Y=
It is 1. ) Polyalkylene carbonate and Groups ■ and ■ of the periodic table
The present invention relates to an ion-conducting polymer composite comprising one or more metal salts selected from the group consisting of:
本発明の一般式（１）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゛Ｃ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 general formula (1) of the present invention include polyethylene carbonate having a glass transition point of 10°C and polypropylene carbonate having a glass transition point of 32°C.
本発明の周期律表第１族及び第■族から選ばれる金属塩
の具体例としては、ＬｉＣｌ０いＬｉＡｌＣｌ４、Ｌｉ
ＢＦ４、ＫＰＰ６％ ＮａＰＦ６ 、ＬＩＡＳＦイＢａ
（ＣｌＯ２）ｚ及びＺｎ１ｔ等が挙げられる。Specific examples of the metal salts selected from Groups 1 and 2 of the periodic table of the present invention include LiCl0, LiAlCl4, Li
BF4, KPP6% NaPF6, LIASF Ba
Examples include (ClO2)z and Znlt.
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（
１）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 electrical 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 determined by the general formula (
The amount is preferably 1 to 100 parts by weight per 100 parts by weight of the polyalkylene carbonate (1).
金属塩の配合量が１重量部未満では充分な導電率が得ら
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って
は好ましくない。If the amount of the metal salt is less than 1 part by weight, sufficient electrical 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, which may be undesirable for some applications. .
本発明のイオン伝導性高分子複合体は、一般式［１）の
ポリアルキレンカーボネートと周期律表第１族及び第■
族から選ばれる１種又は２種以上の金属塩をアセトン、
テトラヒドロフラン及びプロピレンカーボネート等に溶
解後、キャスチング法で成膜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 comprises polyalkylene carbonate of general formula [1] and Group 1 and Group ① of the periodic table.
One or more metal salts selected from the group consisting of acetone,
It can be easily produced by dissolving it in tetrahydrofuran, propylene carbonate, etc. and forming a film by a casting method.
又、金属塩を溶融しポリアルキレンカーボネートと混合
する事によっても製造する事が出来る。It can also be produced by melting a metal salt and mixing it with polyalkylene carbonate.
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−次電池、二次電池、センサー及びエレクトロクロ
ミックディ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（１）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) Effects of the invention The ion-conducting polymer composite of the present invention is characterized in that the polyalkylene carbonate of the general formula (1) is a polyalkylene carbonate of group
It exhibits high ionic conductivity because it promotes the dissociation of one or more metal salts selected from the group, causes most of the metals to exist as ions, and forms a stable complex.
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、且つ有機溶媒を含有しない固体状である為、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 in a solid state that does not contain an organic solvent, the electrolyte will not leak or volatilize.
更に、高分子複合体である為、成形性及び後加工性に優
れている。Furthermore, since it is a polymer composite, it has excellent moldability and post-processability.
而も、−ｉ式ＣＩ）のポリアルキレンカーボネートの置
換基Ｒ＋ 、Ｒ２、Ｒ３、Ｒａ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機械物
性を調節する事も出来る。Moreover, the mechanical properties can be adjusted by appropriately selecting the mole fractions of the substituents R+, R2, R3, Ra, and X and Y of the polyalkylene carbonate of the formula CI) and adjusting the glass transition point, etc. I can do it.
（へ）実施例
次に実施例を挙げて本発明の詳細な説明するが、本発明
はこれらに限定されるものではない。(f) Examples The present invention will now be described in detail with reference to Examples, but the present invention is not limited thereto.
実施例１
ポリエチレンカーボネート１ ｇＸＬｉＣＩ０４０．
１ｇ及びプロピレンカーボネー）５ｇを混合撹拌し５句
−ン容？夜とした。Example 1 Polyethylene carbonate 1 gXLiCI040.
Mix and stir 1g and 5g of propylene carbonate to make 5 volumes. It was night.
このン容？（ｌをステンレス手反上にキャスチンク膏麦
、減圧下９０℃で４時間乾燥を行いプロピレンカーボネ
ートを除去し厚さ０．２龍の透明なイオン伝導性高分子
複合体を得た。This nong? (1) was cast onto a stainless steel cloth and dried under reduced pressure at 90° C. for 4 hours to remove propylene carbonate to obtain a transparent ion-conductive polymer composite with a thickness of 0.2 mm.
このイオン伝導性高分子複合体上にステンレス類の主電
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Ｃｏ１ｅ−Ｃｏｌｅプロ
ッ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, conductivity was measured by changing the frequency from 102 to 105 Hz using the impedance method to avoid ion polarization. The conductivity was calculated by plotting.
導電率は２． ３ Ｘ １０−’Ｓ ・ｃｍ−’であっ
た。The conductivity is 2. It was 3×10-'S·cm-'.
実施例２
ボリブロピレンカーポネー） １ ｇ、、ＬｉＣｌ０ｎ
０゜１ｇ及びアセトン３ｇを混合撹拌し均一溶液とした
。Example 2 Polypropylene carbonate) 1 g, LiCl0n
0.1 g and 3 g of acetone were mixed and stirred to form a homogeneous solution.
この溶液をステンレス板上にキャスチング後、室温で６
時間放置し更に減圧下５０℃で１時間乾燥を行いアセト
ンを除去し厚さ０．３１ｎ＋の透明なイオン伝導性高分
子複合体を得た。After casting this solution on a stainless steel plate, it was heated to room temperature for 6 hours.
The mixture was left to stand for an hour and then dried under reduced pressure at 50° C. for 1 hour to remove acetone, yielding a transparent ion-conductive polymer composite with a thickness of 0.31n+.
このイオン伝導性高分子複合体上に実施例１と同様にし
て電極を形成後、導電率の測定を行った。After forming an electrode on this ion-conductive polymer composite in the same manner as in Example 1, conductivity was measured.
導電率は１．２Ｘ１０−６０−６Ｓ−’であった。The conductivity was 1.2×10-60-6S-'.
Claims (1)
１〜５のアルキル基及びフェ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 I 族及び第
II族から選ばれる１種又は２種以上の金属塩からなるイ
オン伝導性高分子複合体。[Claims] There are ▲ mathematical formulas, chemical formulas, tables, etc. represented by the general formula [I] ▼ (R_1, R_2, R_3, R_4 are selected from a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a phenyl group) X and Y represent the mole fraction, X is 0 to 1, and Y is 0.
~1 and X+Y=1. ) Polyalkylene carbonates and Group I and Groups of the periodic table
An ion-conducting polymer composite consisting of one or more metal salts selected from Group II.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60167738A JPS6230148A (en) | 1985-07-31 | 1985-07-31 | Novel ion conductive high polymer complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60167738A JPS6230148A (en) | 1985-07-31 | 1985-07-31 | Novel ion conductive high polymer complex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6230148A true JPS6230148A (en) | 1987-02-09 |
| JPH0556384B2 JPH0556384B2 (en) | 1993-08-19 |
Family
ID=15855209
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60167738A Granted JPS6230148A (en) | 1985-07-31 | 1985-07-31 | Novel ion conductive high polymer complex |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6230148A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0756344A1 (en) * | 1995-07-24 | 1997-01-29 | Sumitomo Chemical Company, Limited | Non-aqueous electrolyte lithium secondary battery |
| EP1026767A1 (en) * | 1998-08-11 | 2000-08-09 | Yuasa Corporation | Lithium battery, polymer electrolyte, electrolyte material, di(meth)acrylic ester, and di(meth)acrylate polymer |
| KR100471970B1 (en) * | 2002-11-20 | 2005-03-11 | 삼성에스디아이 주식회사 | An electrolyte for a lithium ion battery and a lithium ion battery comprising the same |
| US6878492B2 (en) | 2000-07-10 | 2005-04-12 | Showa Denko Kabushiki Kaisha | Polymerizable composition and use thereof |
| WO2006051323A1 (en) * | 2004-11-15 | 2006-05-18 | The University Of Sheffield | Polymer electrolyte |
| JP2007141859A (en) * | 1995-07-24 | 2007-06-07 | Sumitomo Chemical Co Ltd | Non-aqueous electrolyte lithium secondary battery |
| JP2016126928A (en) * | 2015-01-05 | 2016-07-11 | 公立大学法人大阪府立大学 | Polycarbonate-based solid electrolyte, and magnesium ion secondary battery |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0896340A4 (en) * | 1996-12-03 | 2001-03-07 | Mitsui Chemicals Inc | Gel-form solid polymer electrolyte |
-
1985
- 1985-07-31 JP JP60167738A patent/JPS6230148A/en active Granted
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0756344A1 (en) * | 1995-07-24 | 1997-01-29 | Sumitomo Chemical Company, Limited | Non-aqueous electrolyte lithium secondary battery |
| JP2007141859A (en) * | 1995-07-24 | 2007-06-07 | Sumitomo Chemical Co Ltd | Non-aqueous electrolyte lithium secondary battery |
| JP4544250B2 (en) * | 1995-07-24 | 2010-09-15 | 住友化学株式会社 | Non-aqueous electrolyte lithium secondary battery |
| EP1026767A1 (en) * | 1998-08-11 | 2000-08-09 | Yuasa Corporation | Lithium battery, polymer electrolyte, electrolyte material, di(meth)acrylic ester, and di(meth)acrylate polymer |
| EP1026767A4 (en) * | 1998-08-11 | 2008-03-26 | Gs Yuasa Corp | Lithium battery, polymer electrolyte, electrolyte material, di(meth)acrylic ester, and di(meth)acrylate polymer |
| US6878492B2 (en) | 2000-07-10 | 2005-04-12 | Showa Denko Kabushiki Kaisha | Polymerizable composition and use thereof |
| US7022264B2 (en) | 2000-07-10 | 2006-04-04 | Showa Denko Kabushiki Kaisha | Polymerizable composition and use thereof |
| KR100471970B1 (en) * | 2002-11-20 | 2005-03-11 | 삼성에스디아이 주식회사 | An electrolyte for a lithium ion battery and a lithium ion battery comprising the same |
| WO2006051323A1 (en) * | 2004-11-15 | 2006-05-18 | The University Of Sheffield | Polymer electrolyte |
| JP2016126928A (en) * | 2015-01-05 | 2016-07-11 | 公立大学法人大阪府立大学 | Polycarbonate-based solid electrolyte, and magnesium ion secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0556384B2 (en) | 1993-08-19 |
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