JP2001200125A - Ionically conductive composition - Google Patents
Ionically conductive compositionInfo
- Publication number
- JP2001200125A JP2001200125A JP2000007268A JP2000007268A JP2001200125A JP 2001200125 A JP2001200125 A JP 2001200125A JP 2000007268 A JP2000007268 A JP 2000007268A JP 2000007268 A JP2000007268 A JP 2000007268A JP 2001200125 A JP2001200125 A JP 2001200125A
- Authority
- JP
- Japan
- Prior art keywords
- conductive composition
- electrolyte
- weight
- ion
- component
- 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.)
- Pending
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Classifications
-
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は一次電池、二次電
池、電気二重層コンデンサ、エレクトロクロミック表示
素子等の電解質として使用することができるイオン伝導
性組成物に関する。The present invention relates to an ion conductive composition which can be used as an electrolyte for primary batteries, secondary batteries, electric double layer capacitors, electrochromic display devices and the like.
【０００２】[0002]
【従来の技術】近年、電子工業の分野では、電子機器の
高性能・小型化とともに、電子部品の高性能、小型薄形
化はもちろん、部品としての高い信頼性が要求されてい
る。信頼性の高い電子部品としての必要条件に、まず部
品に使用されている材料が固形体、つまり部品の使用条
件下で見掛け上固体状態を呈し、液体のように流れる物
体（以下これを流体と呼称する）の状態ではない物体
（以下これを固形体と呼称する）であることが要求され
る。これは、流体の材料を電子部品に使用した場合、部
品内部から部品外部への液漏れが頻出し、電子部品の性
能劣化を招くとともに、その電子部品の近くにある他の
電子部品に悪影響を及ぼしてしまい、ついには電子機器
を故障に至らしめるという理由による。したがって、イ
オン導電性材料を電子部品に利用する場合、流体より固
形体のイオン導電性材料を使用した電子部品の方が信頼
性が高い。一方、流体のイオン導電性材料を使用して、
高い信頼性の部品を得るために、部品を完全気密にする
手段もあるが、結局高価な電子部品となって実用に供し
得ない場合が多い。2. Description of the Related Art In recent years, in the field of the electronics industry, not only high performance and miniaturization of electronic devices, but also high performance and miniaturization of electronic components, as well as high reliability as components are required. The requirements for a highly reliable electronic component include the following: First, the material used for the component is a solid, that is, an object that appears to be in a solid state under the conditions of use of the component, and flows like a liquid (hereinafter referred to as a fluid). (Hereinafter referred to as “solid body”). This is because, when a fluid material is used for an electronic component, liquid leaks frequently from the inside of the component to the outside of the component, causing performance degradation of the electronic component and adversely affecting other electronic components near the electronic component. And eventually cause the electronic device to fail. Therefore, when an ion conductive material is used for an electronic component, an electronic component using a solid ion conductive material has higher reliability than a fluid. On the other hand, using a fluid ionic conductive material,
In order to obtain a highly reliable component, there is a means for completely sealing the component. However, in many cases, the component is expensive and cannot be put to practical use.
【０００３】固形体のイオン導電性材料としては、セラ
ミック材料または高分子材料が提案されているが、前者
のイオン導電性セラミック材料はもろい性質を有するた
め、任意の形に成形、成膜できず加工性などの機械的性
質に劣る欠点がある。一方、イオン導電性高分子材料は
加工性に優れている利点を持つ。As the solid ion conductive material, a ceramic material or a polymer material has been proposed. However, the former ion conductive ceramic material has fragile properties and cannot be formed or formed into an arbitrary shape. There is a disadvantage that mechanical properties such as workability are inferior. On the other hand, ionic conductive polymer materials have the advantage of being excellent in workability.
【０００４】しかし、高分子をマトリックスとして金属
塩を含有させ固溶させたイオン伝導性高分子材料のイオ
ン伝導度は電解液のイオン伝導度に比較してかなり小さ
いという問題を有している。However, there is a problem that the ion conductivity of an ion-conductive polymer material containing a polymer as a matrix and containing a metal salt to form a solid solution is considerably smaller than the ion conductivity of an electrolytic solution.
【０００５】現在、固形体のイオン導電性材料に電解液
を含有させたゲル型のイオン導電性材料の研究が盛んに
行われている。これは固形体のイオン導電性材料中に含
有される電解液が多いほどイオンの移動度を増大し、伝
導度が増大するためである。しかし、含有する電解液の
量が多いほど、固形体のイオン導電性材料は軟化し、最
終的には流体になってしまう。このため、大量の電解液
を含有させても軟化することがないイオン導電性高分子
材料が要求されている。[0005] At present, research on gel-type ionic conductive materials in which an electrolyte is contained in a solid ionic conductive material has been actively conducted. This is because the greater the amount of the electrolyte contained in the solid ionic conductive material, the higher the ion mobility and the higher the conductivity. However, as the amount of the contained electrolytic solution increases, the solid ionic conductive material softens and eventually becomes a fluid. For this reason, an ionic conductive polymer material that does not soften even when a large amount of electrolyte is contained is required.
【０００６】ポリビニルアセタールを用いた電解質につ
いては、特開昭５７−１４３３５５号公報および同５７
−１４３３５６号公報に、ポリビニルブチラールと有機
溶剤とを用いたイオン導電性固形体組成物が記載されて
いる。また、特開平３−４３９０９号公報にはポリビニ
ルアセタールと有機溶剤とを含んだ高分子固体電解質
が、同３−４３９１０号公報には、ポリビニルブチラー
ルと有機溶剤とを含んだ高分子固体電解質が記載されて
いる。さらに、特開平１０−５０１４１号公報には、ポ
リビニルアセタールとイオン解離性塩とを含んだ高分子
固体電解質が記載されている。しかし、上記公報記載の
電解質は、いずれも電解液の含有率が低いため、イオン
の移動度が小さく、十分なイオン伝導度が得られない。An electrolyte using polyvinyl acetal is disclosed in JP-A-57-143355 and JP-A-57-143355.
JP-A-143356 describes an ion-conductive solid composition using polyvinyl butyral and an organic solvent. JP-A-3-43909 describes a polymer solid electrolyte containing polyvinyl acetal and an organic solvent, and JP-A-3-43910 describes a polymer solid electrolyte containing polyvinyl butyral and an organic solvent. Have been. Furthermore, JP-A-10-50141 describes a polymer solid electrolyte containing polyvinyl acetal and an ion dissociable salt. However, all of the electrolytes described in the above publications have a low content of the electrolytic solution, so that the mobility of ions is small and sufficient ion conductivity cannot be obtained.
【０００７】また、米国特許第３，９８５，５７４号明
細書にはゲル型高分子電解質を用いた電池が記載されて
いる。しかし、上記明細書記載のゲル型高分子電解質
は、電解質として過塩素酸アンモニウムが例示されてい
るが、アンモニウム塩は電解質として電気化学的、熱化
学的安定性および、導電率がリチウム塩と比較して小さ
い点で好ましくない。またこれら電解質を用いたときの
ゲル型高分子電解質の液漏れや機械的強度についても問
題がある。Further, US Pat. No. 3,985,574 describes a battery using a gel-type polymer electrolyte. However, in the gel-type polymer electrolyte described in the above specification, ammonium perchlorate is exemplified as the electrolyte, but the ammonium salt is compared with the lithium salt in electrochemical, thermochemical stability and conductivity as the electrolyte. It is not preferable because it is small. There are also problems with respect to liquid leakage and mechanical strength of the gel polymer electrolyte when using these electrolytes.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、大量の電解
液が含浸した状態においても、固形体を維持し高いイオ
ン伝導度を有し、加工性、柔軟性に優れたイオン伝導性
組成物を提供するものである。SUMMARY OF THE INVENTION The present invention provides an ion conductive composition which maintains a solid body, has a high ionic conductivity, is excellent in processability and flexibility even in a state where a large amount of electrolyte is impregnated. Is provided.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、以上の諸
問題点を考慮し解決すべく鋭意研究を重ねた結果、本発
明に至った。すなわち本発明は以下の通りである。 (１)(a)重合度８００以上のポリビニルアセタール１０
〜２０重量％、(b)LiBF4、LiPF6または(CF3SO2)2NLiの
少なくとも一種からなる電解質４〜１８重量％、および
(c)アルキルカーボネート６３〜８６重量％からなるイ
オン伝導性組成物。 (２)アルキルカーボネートが、プロピレンカーボネー
ト、またはエチレンカーボネートである請求項１記載の
イオン伝導性組成物。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems in consideration of the above problems, and as a result, have reached the present invention. That is, the present invention is as follows. (1) (a) Polyvinyl acetal 10 having a degree of polymerization of 800 or more
20 wt%, (b) LiBF 4, LiPF 6 or (CF 3 SO 2) 2 of at least one consisting of electrolyte NLi 4 to 18 wt%, and
(c) An ion conductive composition comprising 63 to 86% by weight of an alkyl carbonate. (2) The ion conductive composition according to claim 1, wherein the alkyl carbonate is propylene carbonate or ethylene carbonate.
【００１０】[0010]
【発明の実施の形態】以下、詳細にわたって本発明を説
明する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
【００１１】本発明のイオン伝導性組成物の（a）成分
であるポリビニルアセタールは、一般式（１）のように
アセタール基、アセチル基、水酸基を有するそれぞれ３
種の繰り返し単位からなる高分子化合物である。 一般式(1)The polyvinyl acetal which is the component (a) of the ion conductive composition of the present invention has an acetal group, an acetyl group, and a hydroxyl group each having 3 as shown in the general formula (1).
It is a polymer compound composed of various kinds of repeating units. General formula (1)
【００１２】[0012]
【化１】 Embedded image
【００１３】(ただし、Ｒはの炭素数１から３アルキル
基を表す。ｐ、ｑ、ｒは正の整数を表す。) 本発明のイオン伝導性組成物の（a）成分であるポリビ
ニルアセタールは、アセタール基を有する繰り返し単位
の少なくとも１つを含んでいれば良い。アセタール基を
有する繰り返し単位を６０〜８０mol％、好ましくは６
５〜７０ mol％、水酸基を有する繰り返し単位を５〜３
６mol％、好ましくは２０〜３３mol％を含むポリビニル
アセタールが好ましい。なお、一般式(1)のＲは炭素数
が１から３のアルキル基、つまりメチル基、エチル基、
プロピル基、イソプロピル基が挙げられ、特にＲがプロ
ピル基の場合が好ましい。(However, R represents an alkyl group having 1 to 3 carbon atoms. P, q, and r represent positive integers.) The polyvinyl acetal which is the component (a) of the ion conductive composition of the present invention is And at least one repeating unit having an acetal group. The repeating unit having an acetal group has a content of 60 to 80 mol%, preferably 6 to 80 mol%.
5 to 70 mol%, 5 to 3 repeating units having a hydroxyl group
Polyvinyl acetal containing 6 mol%, preferably 20-33 mol%, is preferred. In the general formula (1), R represents an alkyl group having 1 to 3 carbon atoms, that is, a methyl group, an ethyl group,
Examples thereof include a propyl group and an isopropyl group, and a case where R is a propyl group is particularly preferable.
【００１４】本発明における（a）成分の組成比は組成
物全体の１０〜２０重量％である。特に、１２〜１７重
量％が好ましい。（a）成分が全体の１０重量％未満で
は、イオン伝導性組成物が非常にもろいものとなる。ま
た(a)成分の重合度は８００以上、特に１７００以上の
ものが好ましい。重合度が８００より小さいものでは、
イオン伝導性組成物が非常にもろいものとなる。The composition ratio of the component (a) in the present invention is 10 to 20% by weight of the whole composition. Particularly, 12 to 17% by weight is preferable. When the component (a) is less than 10% by weight of the whole, the ion conductive composition becomes very brittle. The polymerization degree of the component (a) is preferably 800 or more, particularly preferably 1700 or more. If the degree of polymerization is less than 800,
The ion conductive composition becomes very brittle.
【００１５】次に本発明の（b）成分である電解質とし
ては、特にリチウム二次電池として使用する場合、広い
電位窓を示す電気化学的に安定なリチウム塩が用いられ
る。この例としてLiBF4、LiPF6、(CF3SO2)2NLiを挙げる
ことができる。本発明における（b）成分の組成比は組
成物全体の４〜１８重量％である。特に６〜１７重量％
が好ましい。（b）成分が４重量％未満では十分なイオ
ン伝導性が得られない。Next, as the electrolyte which is the component (b) of the present invention, an electrochemically stable lithium salt showing a wide potential window is used particularly when used as a lithium secondary battery. Examples of this are LiBF 4 , LiPF 6 , and (CF 3 SO 2 ) 2 NLi. The composition ratio of the component (b) in the present invention is 4 to 18% by weight of the whole composition. Especially 6 to 17% by weight
Is preferred. If the component (b) is less than 4% by weight, sufficient ionic conductivity cannot be obtained.
【００１６】本発明の（c）成分の組成比は組成物全体
の６３〜８６重量％である。特に、６８〜７８重量％が
好ましい。(c）成分が８６重量％を越えると、イオン伝
導性組成物が非常にもろいものとなる。また、(c）成分
が６３重量％未満では十分なイオン伝導性が得られな
い。The composition ratio of the component (c) of the present invention is from 63 to 86% by weight of the whole composition. In particular, 68 to 78% by weight is preferable. When component (c) exceeds 86% by weight, the ion conductive composition becomes very brittle. If the component (c) is less than 63% by weight, sufficient ion conductivity cannot be obtained.
【００１７】以上、説明した（a）、（b）、（c）成分
を用いてイオン伝導性組成物を製造する場合、様々な製
造方法が考えられるが、主な製造方法として以下の方法
が挙げられる。しかし、なんらこれらに限定されるもの
ではない。In the case of producing an ion conductive composition using the components (a), (b) and (c) described above, various production methods are conceivable, but the following methods are the main production methods. No. However, it is not limited to these.
【００１８】第一の方法は、(a)成分を有機溶剤に溶解
させたものに、(b)、(c)成分を加えた後、有機溶剤を蒸
発させて取り除く方法である。この(a)成分を溶解する
有機溶剤としては、メタノール、エタノール、プロパノ
ール等のアルコール類、アセトン、メチルエチルケト
ン、シクロヘキサノン等のケトン類、N、Nージメチルア
セトアミド、N、Nージメチルホルムアミド等のアミド
類、ジオキサン、テトラヒドロフラン等のエーテル類、
メチレンクロライド、クロロホルム等の塩素化炭化水
素、トルエン、キシレン、スチレン、ピリジン等の芳香
族系溶剤、ジメチルスルホキシド、酢酸等が挙げられる
が、(a)成分を溶解するものであれば、上記の有機溶剤
に限定されるものではない。The first method is to add the components (b) and (c) to a solution of the component (a) in an organic solvent, and then remove the organic solvent by evaporation. Examples of the organic solvent for dissolving the component (a) include alcohols such as methanol, ethanol, and propanol; ketones such as acetone, methyl ethyl ketone and cyclohexanone; and amides such as N, N-dimethylacetamide, N, N-dimethylformamide. , Dioxane, ethers such as tetrahydrofuran,
Chlorinated hydrocarbons such as methylene chloride and chloroform, aromatic solvents such as toluene, xylene, styrene and pyridine, dimethyl sulfoxide, acetic acid and the like can be mentioned. It is not limited to a solvent.
【００１９】第二の方法は（a）、（b）、（c）成分の
混合物として、所定形状に成形加工する方法である。こ
こで成形加工する方法としては、（a）、（b）、（c）
成分の混合物を基盤上に塗布してシート上に形成する方
法、加熱溶融状態で成形したのち冷却加工する方法など
が使用可能である。The second method is a method of forming a mixture of the components (a), (b) and (c) into a predetermined shape. Here, the forming method includes (a), (b), and (c)
A method in which a mixture of the components is applied on a substrate to form a sheet, a method in which the mixture is molded in a heated and molten state and then cooled, and the like can be used.
【００２０】第三の方法は（a）成分をキャスト法また
は加熱溶融などの処理により、フィルムを作製し、この
フィルムを（b）、（c）成分から調製した電解質溶液に
含浸する方法である。The third method is a method of producing a film by subjecting the component (a) to a process such as a casting method or heat melting, and impregnating the film with an electrolyte solution prepared from the components (b) and (c). .
【００２１】さらに必要があれば、他のポリマー、セラ
ミック、金属を機械的強度、耐熱性、イオン導電率向上
のため添加させることができる。If necessary, other polymers, ceramics and metals can be added to improve mechanical strength, heat resistance and ionic conductivity.
【００２２】[0022]
【実施例】以下、実施例にて本発明を具体的に説明する
が、本発明は下記の実施例になんら限定されるものでは
ない。 実施例１ LiBF4１１重量部をプロピレンカーボネート７４重量部
に溶解した電解質溶液と一般式(1)のＲがプロピル基で
ある重合度が８５０のポリビニルアセタール１５重量部
をテトラヒドロフラン１６６重量部に溶解した高分子溶
液とを別々に調製した。調製した電解質溶液と高分子溶
液とを混合し、均一になるまで充分攪拌した。次に、あ
らかじめ準備したテフロン製の容器中にこの混合液の全
量を注ぎ込み、５０℃で５時間加熱乾燥し、その後真空
乾燥機中で７０℃で３時間減圧下加熱乾燥してテトラヒ
ドロフランを取り除き、イオン伝導性組成物を作製し
た。 実施例２〜８，比較例１〜６ 表１に示す(a)、(b)、(c)成分とテトラヒドロフランと
を表１に示す組成比で、実施例１と同様の方法によりイ
オン伝導性組成物を作製した。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. Example 1 An electrolyte solution obtained by dissolving 11 parts by weight of LiBF 4 in 74 parts by weight of propylene carbonate and 15 parts by weight of polyvinyl acetal having a polymerization degree of 850 in which R is a propyl group in the general formula (1) were dissolved in 166 parts by weight of tetrahydrofuran. And a polymer solution were prepared separately. The prepared electrolyte solution and polymer solution were mixed and sufficiently stirred until they became uniform. Next, the whole amount of the mixed solution was poured into a Teflon container prepared in advance, and dried by heating at 50 ° C. for 5 hours, and then dried by heating under reduced pressure at 70 ° C. for 3 hours in a vacuum dryer to remove tetrahydrofuran. An ion conductive composition was prepared. Examples 2 to 8 and Comparative Examples 1 to 6 The components (a), (b) and (c) shown in Table 1 and tetrahydrofuran were used in the composition ratio shown in Table 1 in the same manner as in Example 1 to obtain an ion conductive material. A composition was made.
【００２３】上記の方法により製造したイオン伝導性組
成物について表１に示す。ここで強度とは、イオン伝導
性組成物をテフロン製の容器から剥離する際、イオン伝
導性組成物が破断した場合に機械的強度不十分、破断し
ない場合に機械的強度十分として表す。また液漏れあり
とは、イオン伝導性組成物の表面が湿潤している場合を
表す。表１の結果から明らかなように、ポリビニルアセ
タールの重合度が８００より小さい場合(比較例１，
２)、得られる組成物は、非常にもろく機械的強度が十
分でなかった。また、LiBF4、LiPF6、(CF3SO2)2NLi以外
の電解質を用いた場合(比較例３〜６)、得られる組成物
は非常にもろく機械的強度が十分でなかった。Table 1 shows the ion conductive composition produced by the above method. Here, the strength is expressed as insufficient mechanical strength when the ion conductive composition breaks when peeling the ion conductive composition from the Teflon-made container, and sufficient mechanical strength when the ion conductive composition does not break. In addition, the presence of liquid leakage indicates a case where the surface of the ion conductive composition is wet. As is clear from the results in Table 1, when the degree of polymerization of polyvinyl acetal is less than 800 (Comparative Example 1,
2) The composition obtained was very brittle and had insufficient mechanical strength. When an electrolyte other than LiBF 4 , LiPF 6 , and (CF 3 SO 2 ) 2 NLi was used (Comparative Examples 3 to 6), the resulting composition was very brittle and had insufficient mechanical strength.
【００２４】[0024]
【表１】 [Table 1]
【００２５】実施例９〜１６、比較例７ 表２に示す(a)、(b)、(c)成分とテトラヒドロフランと
を表２に示す組成比で、実施例１と同様の方法により作
製したイオン伝導性組成物についてイオン伝導度の測定
を行った。Examples 9 to 16 and Comparative Example 7 Components (a), (b) and (c) shown in Table 2 and tetrahydrofuran were prepared by the same method as in Example 1 at a composition ratio shown in Table 2. The ion conductivity of the ion conductive composition was measured.
【００２６】イオン伝導性組成物の入ったテフロン容器
をアルゴンガスで充満させたグローブボックス内に移し
入れ、イオン伝導性組成物をテフロン容器から剥離した
のち直径１cmの円状に切断し測定用試料片を得た。この
測定用試料片をステンレス電極に挟みこみセルを作製し
た。このセルをリード線でインピーダンスアナライザー
につなぎ、交流インピーダンス法により２０℃にて試料
の抵抗値を測定した。測定は、アルゴン雰囲気中で行
い、測定用試料片の抵抗値、厚み(１００〜３００μm)
および、ステンレス電極の面積からイオン伝導性組成物
の導電率σを算出した。上記の方法で測定したイオン伝
導性組成物のイオン導電率σの測定結果を表２に示し
た。表２の結果から明らかなように、アルキルカーボネ
ートが組成物全体の６５重量％よりも少ない場合(比較
例３)、十分なイオン導電率は得られないことがわかっ
た。The Teflon container containing the ion-conductive composition was transferred into a glove box filled with argon gas, and the ion-conductive composition was peeled off from the Teflon container and cut into a circle having a diameter of 1 cm. I got a piece. This measurement sample piece was sandwiched between stainless steel electrodes to produce a cell. This cell was connected to an impedance analyzer with a lead wire, and the resistance value of the sample was measured at 20 ° C. by the AC impedance method. The measurement is performed in an argon atmosphere, and the resistance and thickness (100 to 300 μm) of the measurement sample piece are measured.
In addition, the conductivity σ of the ion-conductive composition was calculated from the area of the stainless steel electrode. Table 2 shows the measurement results of the ionic conductivity σ of the ionic conductive composition measured by the above method. As is clear from the results in Table 2, it was found that when the amount of the alkyl carbonate was less than 65% by weight of the whole composition (Comparative Example 3), sufficient ionic conductivity could not be obtained.
【００２７】[0027]
【表２】 [Table 2]
【００２８】実施例１７ 一般式(1)のＲがプロピル基である重合度が８５０のポ
リビニルアセタール２０重量部と、LiBF4１１重量部、
プロピレンカーボネート６９重量部からなる混合物をテ
フロン製の容器に注ぎ込み、６０℃で２日間加熱溶融
し、その後冷却加工してイオン伝導性組成物を作製し
た。実施例９〜１６と同様の方法でイオン導電率を測定
したところ、１．００×１０-4Scm-1であった。このこ
とから、実施例９と同様のイオン導電性組成物が製造で
きた。 実施例１８ 一般式(1)のＲがプロピル基である重合度が８５０のポ
リビニルアセタール２０重量部をテトラヒドロフラン１
６６重量部に溶解した高分子溶液をテフロン製の容器に
注ぎ込み、５０℃で５時間加熱乾燥し、その後真空乾燥
機中で７０℃で３時間減圧下加熱乾燥することでテトラ
ヒドロフランを取り除き、ポリマーフィルムを作製し
た。このポリマーフィルムをLiBF4１１重量部、プロピ
レンカーボネート６９重量部からなる電解質溶液に１２
時間浸し、イオン伝導性組成物を作製した。実施例９〜
１６と同様の方法でイオン導電率を測定したところ、
０．９９×１０-4Scm-1であった。このことから、実施
例９と同様のイオン導電性組成物が製造できた。Example 17 20 parts by weight of a polyvinyl acetal having a degree of polymerization of 850 in which R in the general formula (1) is a propyl group, 11 parts by weight of LiBF 4 ,
A mixture consisting of 69 parts by weight of propylene carbonate was poured into a Teflon container, heated and melted at 60 ° C. for 2 days, and then cooled to prepare an ion conductive composition. When the ionic conductivity was measured in the same manner as in Examples 9 to 16, it was 1.00 × 10 −4 Scm −1 . From this, the same ionic conductive composition as in Example 9 could be produced. Example 18 20 parts by weight of a polyvinyl acetal having a polymerization degree of 850 in which R in the general formula (1) is a propyl group was added to tetrahydrofuran 1
The polymer solution dissolved in 66 parts by weight was poured into a Teflon container, dried by heating at 50 ° C. for 5 hours, and then dried by heating under reduced pressure at 70 ° C. for 3 hours in a vacuum dryer to remove tetrahydrofuran. Was prepared. This polymer film was added to an electrolyte solution comprising 11 parts by weight of LiBF 4 and 69 parts by weight of propylene carbonate.
It was soaked for a time to prepare an ion conductive composition. Example 9 ~
When the ionic conductivity was measured by the same method as in 16,
0.99 × 10 −4 Scm −1 . From this, the same ionic conductive composition as in Example 9 could be produced.
【００２９】[0029]
【発明の効果】上述した如く、本発明はイオン伝導性が
高く、かつ柔軟性、加工性に優れたイオン伝導性組成物
であることから、一次電池、二次電池、電気二重層コン
デンサ、エレクトロクロミック表示素子等の電解質とし
ての利用は充分実用に供し得ることが可能である。As described above, the present invention is an ion conductive composition having high ion conductivity, excellent flexibility, and excellent workability. Therefore, primary batteries, secondary batteries, electric double layer capacitors, The use as an electrolyte of a chromic display element or the like can be sufficiently practical.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０１Ｂ 1/06 Ｈ０１Ｂ 1/06 Ａ Ｈ０１Ｇ 9/038 Ｈ０１Ｍ 10/40 Ｂ Ｈ０１Ｍ 10/40 6/18 Ｅ // Ｈ０１Ｍ 6/18 Ｈ０１Ｇ 9/00 ３０１Ｄ Ｆターム(参考） 4J002 BE061 DK006 EL107 GQ02 5G301 CA16 CA30 CD01 5H024 FF23 5H029 AM03 AM07 AM12 HJ01 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) H01B 1/06 H01B 1/06 A H01G 9/038 H01M 10/40 B H01M 10/40 6/18 E / / H01M 6/18 H01G 9/00 301D F term (reference) 4J002 BE061 DK006 EL107 GQ02 5G301 CA16 CA30 CD01 5H024 FF23 5H029 AM03 AM07 AM12 HJ01
Claims (2)
ール１０〜２０重量％、(b)LiBF4、LiPF6または(CF3S
O2)2NLiの少なくとも一種からなる電解質４〜１８重量
％、および(c)アルキルカーボネート６３〜８６重量％
からなるイオン伝導性組成物。(1) 10-20% by weight of (a) polyvinyl acetal having a degree of polymerization of 800 or more, (b) LiBF 4 , LiPF 6 or (CF 3 S
4 to 18% by weight of an electrolyte comprising at least one of O 2 ) 2 NLi, and (c) 63 to 86% by weight of an alkyl carbonate
An ion conductive composition comprising:
ボネート、またはエチレンカーボネートである請求項１
記載のイオン伝導性組成物。2. The method according to claim 1, wherein the alkyl carbonate is propylene carbonate or ethylene carbonate.
The ion-conductive composition according to the above.
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|---|---|---|---|
| JP2000007268A JP2001200125A (en) | 2000-01-17 | 2000-01-17 | Ionically conductive composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000007268A JP2001200125A (en) | 2000-01-17 | 2000-01-17 | Ionically conductive composition |
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| Publication Number | Publication Date |
|---|---|
| JP2001200125A true JP2001200125A (en) | 2001-07-24 |
Family
ID=18535665
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|---|---|---|---|---|
| JP2005050808A (en) * | 2003-07-16 | 2005-02-24 | Mitsui Chemicals Inc | Nonaqueous electrolyte, electrochemical element and its manufacturing method |
| WO2006075392A1 (en) * | 2005-01-14 | 2006-07-20 | Mitsui Chemicals, Inc. | Polyvinyl acetal resin varnish, gelling agent, nonaqueous electrolyte and electrochemical element |
| JP2006253088A (en) * | 2005-03-14 | 2006-09-21 | Sony Corp | Polymer electrolyte and battery using it |
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2000
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2005050808A (en) * | 2003-07-16 | 2005-02-24 | Mitsui Chemicals Inc | Nonaqueous electrolyte, electrochemical element and its manufacturing method |
| JP4647948B2 (en) * | 2003-07-16 | 2011-03-09 | 三井化学株式会社 | Electrochemical element and method for producing the same |
| EP1619743A3 (en) * | 2004-07-21 | 2011-03-02 | Sony Corporation | Electrolyte for battery |
| US8124272B2 (en) | 2005-01-14 | 2012-02-28 | Mitsui Chemicals, Inc. | Polyvinyl acetal resin varnish gelling agent, nonaqueous electrolyte solution, and electrochemical device |
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| JPWO2006075392A1 (en) * | 2005-01-14 | 2008-06-12 | 三井化学株式会社 | Polyvinyl acetal resin varnish, gelling agent, non-aqueous electrolyte and electrochemical device |
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| WO2006098240A1 (en) * | 2005-03-14 | 2006-09-21 | Sony Corporation | Polymer electrolyte and battery |
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| KR100856955B1 (en) * | 2007-07-26 | 2008-09-04 | 미쓰이 가가쿠 가부시키가이샤 | Polyvinyl acetal resin varnish, gelling agent, nonaqueous electrolyte solution, and electrochemical device |
| JP2010267630A (en) * | 2010-07-27 | 2010-11-25 | Sony Corp | Method of manufacturing battery |
| JP2014192074A (en) * | 2013-03-28 | 2014-10-06 | Kuraray Co Ltd | Polymer electrolyte gel composition for secondary battery use, and method for manufacturing the same |
| US11018378B2 (en) | 2017-09-19 | 2021-05-25 | Kabushiki Kaisha Toshiba | Secondary battery, battery pack, and vehicle |
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