JPH11154415A - Gel-like electrolyte and gel-like electrolyte battery - Google Patents
Gel-like electrolyte and gel-like electrolyte batteryInfo
- Publication number
- JPH11154415A JPH11154415A JP9320145A JP32014597A JPH11154415A JP H11154415 A JPH11154415 A JP H11154415A JP 9320145 A JP9320145 A JP 9320145A JP 32014597 A JP32014597 A JP 32014597A JP H11154415 A JPH11154415 A JP H11154415A
- Authority
- JP
- Japan
- Prior art keywords
- gel electrolyte
- plasticizer
- weight
- halogen
- gel
- 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
-
- 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、炭酸エステルを含
有するゲル状電解質及びゲル状電解質電池に関する。The present invention relates to a gel electrolyte containing a carbonate ester and a gel electrolyte battery.
【０００２】[0002]
【従来の技術】近年、カメラ一体型ビデオテープレコー
ダ、携帯電話、携帯用コンピュータ等のポータブル電子
機器が多く登場し、その小型軽量化が図られている。そ
してこれらの電子機器のポータブル電源となる電池、特
に二次電池、なかでもリチウムイオン電池について、薄
型や折り曲げ可能な電池の研究開発が活発に進められて
いる。このような電池の電解質として電解液を固体化し
た固体電解質の研究が盛んに行われており、特に、可塑
剤を含んだゲル状の固体電解質（以下、ゲル状電解質と
称する。）が注目を浴びている。2. Description of the Related Art In recent years, many portable electronic devices such as a camera-integrated video tape recorder, a mobile phone, and a portable computer have appeared and their size and weight have been reduced. Research and development of thin and bendable batteries, which are portable batteries for these electronic devices, particularly secondary batteries, especially lithium ion batteries, are being actively pursued. Research on a solid electrolyte obtained by solidifying an electrolytic solution as an electrolyte for such a battery has been actively conducted. In particular, a gel solid electrolyte containing a plasticizer (hereinafter, referred to as a gel electrolyte) has attracted attention. I'm taking a bath.
【０００３】リチウムイオン電池に使用するゲル状電解
質の可塑剤として、炭酸プロピレンなどの炭酸エステル
系非水溶媒にＬｉＰＦ6のようなリチウム塩を溶解させ
た電解液を用いると、導電率の比較的高いゲル状電解質
を得ることができる。When an electrolytic solution in which a lithium salt such as LiPF 6 is dissolved in a carbonate-based non-aqueous solvent such as propylene carbonate is used as a plasticizer for a gel electrolyte used in a lithium ion battery, the conductivity of the electrolyte is relatively low. A high gel electrolyte can be obtained.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、炭酸プ
ロピレンなど一部の炭酸エステルは電気化学的に安定で
あるにもかかわらず、グラファイトなどを負極に用いた
電池では、充電時に電解液の反応、分解が起こってしま
う。電解液の反応、分解により充放電効率が著しく悪化
するだけでなく、同時に放電容量など電池の諸特性にも
悪影響を及ぼすという問題が生じる。このような問題は
炭酸プロピレンなどを可塑剤として用いたゲル状電解質
でも同様である。However, in spite of the fact that some carbonates such as propylene carbonate are electrochemically stable, in a battery using graphite or the like for the negative electrode, the reaction and decomposition of the electrolytic solution during charging are not possible. Will happen. Not only does the charge and discharge efficiency deteriorate significantly due to the reaction and decomposition of the electrolytic solution, but also there is a problem that various characteristics of the battery such as the discharge capacity are adversely affected. Such a problem is the same in a gel electrolyte using propylene carbonate or the like as a plasticizer.
【０００５】本発明は、上述した従来の実情に鑑みて提
案されたものであり、充電時の可塑剤の反応、分解を防
止し、電池の充放電効率を向上させるゲル状電解質、及
びゲル状電解質電池を提供することを目的とする。[0005] The present invention has been proposed in view of the above-mentioned conventional circumstances, and a gel electrolyte and a gel electrolyte for preventing the reaction and decomposition of a plasticizer during charging and improving the charge and discharge efficiency of a battery. An object is to provide an electrolyte battery.
【０００６】[0006]
【課題を解決するための手段】本発明のゲル状電解質
は、可塑剤と、上記可塑剤を分散するマトリクス高分子
とを含有し、上記可塑剤が、一般式（１）で表される炭
酸エステル化合物を含有することを特徴とする。The gel electrolyte of the present invention contains a plasticizer and a matrix polymer in which the plasticizer is dispersed, and the plasticizer is a carbonate represented by the general formula (1). It is characterized by containing an ester compound.
【０００７】[0007]
【化３】 Embedded image
【０００８】（式中、Ｘ1及びＸ2はハロゲン又は水素を
表し、Ｒ1及びＲ2は同一又は異なるハロゲン化アルキル
基ＣnＸａ2n-m+1Ｘｂm又は水素を表す。Ｘａはハロゲ
ン、Ｘｂはハロゲン又は水素である。ただしＸ1，Ｘ2，
Ｒ1，Ｒ2すべてがハロゲン又は水素である場合を除
く。） 上述した本発明に係るゲル状電解質は、可塑剤が、一般
式（１）で表される炭酸エステル化合物を含有し、電気
化学的安定性を高めている。(Wherein X1 and X2 represent halogen or hydrogen, R1 and R2 represent the same or different halogenated alkyl groups C n Xa 2n-m + 1 Xb m or hydrogen. Xa is halogen, Xb is halogen Or hydrogen, provided that X1, X2,
Except when all of R1 and R2 are halogen or hydrogen. In the above-mentioned gel electrolyte according to the present invention, the plasticizer contains a carbonate compound represented by the general formula (1), and has improved electrochemical stability.
【０００９】また、本発明のゲル状電解質電池は、負極
と、正極と、ゲル状電解質とを有し、上記ゲル状電解質
は、可塑剤がマトリクス高分子中に分散されてなり、上
記可塑剤が、一般式（１）で表される炭酸エステル化合
物を含有することを特徴とする。Further, the gel electrolyte battery of the present invention has a negative electrode, a positive electrode, and a gel electrolyte, wherein the gel electrolyte is obtained by dispersing a plasticizer in a matrix polymer. Contains a carbonate compound represented by the general formula (1).
【００１０】[0010]
【化４】 Embedded image
【００１１】（式中、Ｘ1及びＸ2はハロゲン又は水素を
表し、Ｒ1及びＲ2は同一又は異なるハロゲン化アルキル
基ＣnＸａ2n-m+1Ｘｂm又は水素を表す。Ｘａはハロゲ
ン、Ｘｂはハロゲン又は水素である。ただしＸ1，Ｘ2，
Ｒ1，Ｒ2すべてがハロゲン又は水素である場合を除
く。） 上述した本発明に係るゲル状電解質電池では、ゲル状電
解質の可塑剤が一般式（１）で示される炭酸エステルを
含有しており、電気化学的安定性が高く、充電時に負極
上で可塑剤の分解が起こらない。(Wherein, X1 and X2 represent halogen or hydrogen, R1 and R2 represent the same or different halogenated alkyl groups C n Xa 2n-m + 1 Xb m or hydrogen. Xa is halogen, Xb is halogen Or hydrogen, provided that X1, X2,
Except when all of R1 and R2 are halogen or hydrogen. In the gel electrolyte battery according to the present invention described above, the plasticizer of the gel electrolyte contains the carbonate represented by the general formula (1), has high electrochemical stability, and has a high plasticity on the negative electrode during charging. No decomposition of the agent occurs.
【００１２】[0012]
【発明の実施の形態】以下、本発明の実施の形態につい
て説明する。Embodiments of the present invention will be described below.
【００１３】本発明のゲル状電解質は、リチウム塩を含
有する可塑剤がマトリクス高分子中に溶解されてなる。The gel electrolyte of the present invention comprises a plasticizer containing a lithium salt dissolved in a matrix polymer.
【００１４】上記可塑剤には、エステル類、エーテル
類、炭酸エステル類などを、単独又は可塑剤の一成分と
して用いることができる。As the above-mentioned plasticizer, esters, ethers, carbonates and the like can be used alone or as one component of the plasticizer.
【００１５】本発明のゲル状電解質の可塑剤は、一般式
（１）で示される炭酸エステルを含有する。[0015] The plasticizer of the gel electrolyte of the present invention contains a carbonate represented by the general formula (1).
【００１６】[0016]
【化５】 Embedded image
【００１７】（式中、Ｘ1及びＸ2はハロゲン又は水素を
表し、Ｒ1及びＲ2は同一又は異なるハロゲン化アルキル
基ＣnＸａ2n-m+1Ｘｂm又は水素を表す。Ｘａはハロゲ
ン、Ｘｂはハロゲン又は水素である。ただしＸ1，Ｘ2，
Ｒ1，Ｒ2すべてがハロゲン又は水素である場合を除
く。） 好ましくは、あまり分子量が大きくなると導電率が下が
るので、一般式（１）において、Ｒ1及びＲ2は、Ｃ
Ｆ3、ＣＦ2ＣＦ3、ＣＨＦ2など炭素群ｎ＝１〜３の群か
ら選択されるハロゲン化アルキル基であることが好まし
い。[0017] (wherein, X1 and X2 represent a halogen or hydrogen, .Xa R1 and R2 represent the same or different halogenated alkyl group C n Xa 2n-m + 1 Xb m or hydrogen halogen, Xb is halogen Or hydrogen, provided that X1, X2,
Except when all of R1 and R2 are halogen or hydrogen. Preferably, when the molecular weight is too large, the conductivity decreases. Therefore, in the general formula (1), R 1 and R 2 are
It is preferably a halogenated alkyl group selected from the group of carbon groups n = 1 to 3 , such as F 3 , CF 2 CF 3 and CHF 2 .
【００１８】一般式（１）で示される炭酸エステルをゲ
ル状電解質の可塑剤に含有させると、充電時に、グラフ
ァイト負極上で可塑剤の分解が起こらず、充放電効率が
向上する。When the carbonate represented by the general formula (1) is contained in the plasticizer of the gel electrolyte, the plasticizer does not decompose on the graphite negative electrode during charging, and the charge / discharge efficiency is improved.
【００１９】可塑剤は炭酸エチレンのような高誘電率溶
媒と混合して用いるのが好ましいので、一般式（１）で
示される炭酸エステルの含有量は、可塑剤の１０重量％
以上、８０重量％以下が望ましい。炭酸エステルの含有
量が可塑剤の１０重量％より少ないと、グラファイト負
極上で充電時の可塑剤の分解を抑制することができず、
充放電効率を向上させることができない。また、炭酸エ
ステルの含有量が可塑剤の８０重量％より多いと、高誘
電率溶媒の量が少なくなり、導電率が低下してしまう。Since the plasticizer is preferably used in a mixture with a high dielectric constant solvent such as ethylene carbonate, the content of the carbonate represented by the general formula (1) is 10% by weight of the plasticizer.
At least 80% by weight is desirable. If the content of the carbonate is less than 10% by weight of the plasticizer, the decomposition of the plasticizer at the time of charging on the graphite negative electrode cannot be suppressed,
The charge / discharge efficiency cannot be improved. On the other hand, when the content of the carbonate is more than 80% by weight of the plasticizer, the amount of the high dielectric constant solvent is reduced, and the conductivity is reduced.
【００２０】また、上記可塑剤は、リチウム塩を含有す
る。本発明に係るゲル状電解質に用いられるリチウム塩
として、通常、電池電解液に用いられる公知のリチウム
塩を使用することができる。具体的には、ＬｉＰＦ6、
ＬｉＢＦ4、ＬｉＡｓＦ6、ＬｉＣｌＯ4、ＬｉＣＦ3ＳＯ
3、ＬｉＮ（ＳＯ2ＣＦ3）2、ＬｉＣ（ＳＯ2ＣＦ3）3、
ＬｉＡｌＣｌ4、ＬｉＳｉＦ6などを挙げることができ
る。その中でも特にＬｉＰＦ6、ＬｉＢＦ4が酸化安定性
の点から望ましい。リチウム塩の濃度は、可塑剤の０．
１ｍｏｌ／ｌ以上、３．０ｍｏｌ／ｌが好ましく、より
好ましくは、０．５ｍｏｌ／ｌ以上、２．０ｍｏｌ／ｌ
以下である。The plasticizer contains a lithium salt. As the lithium salt used in the gel electrolyte according to the present invention, a known lithium salt usually used in a battery electrolyte can be used. Specifically, LiPF 6 ,
LiBF 4 , LiAsF 6 , LiClO 4 , LiCF 3 SO
3 , LiN (SO 2 CF 3 ) 2 , LiC (SO 2 CF 3 ) 3 ,
LiAlCl 4 , LiSiF 6 and the like can be given. Among them, LiPF 6 and LiBF 4 are particularly desirable from the viewpoint of oxidation stability. The concentration of the lithium salt is 0.1% of the plasticizer.
1 mol / l or more, preferably 3.0 mol / l, more preferably 0.5 mol / l or more, 2.0 mol / l
It is as follows.
【００２１】上述したような可塑剤の含有量は、ゲル状
電解質の３０重量％以上、８５重量％以下とすることが
好ましい。可塑剤の含有量が８５重量％より多ければイ
オン導電率は高いが、機械強度は保てない。可塑剤の含
有量が３０重量％より少ないと機械強度は大きいが、イ
オン導電率は低くなってしまう。可塑剤の含有量を、ゲ
ル状電解質の３０重量％以上、８５重量％以下とするこ
とで、イオン導電率と機械強度とを両立することができ
る。The content of the above-mentioned plasticizer is preferably 30% by weight or more and 85% by weight or less of the gel electrolyte. If the content of the plasticizer is more than 85% by weight, the ionic conductivity is high, but the mechanical strength cannot be maintained. If the content of the plasticizer is less than 30% by weight, the mechanical strength is high, but the ionic conductivity is low. By setting the content of the plasticizer to 30% by weight or more and 85% by weight or less of the gel electrolyte, both ionic conductivity and mechanical strength can be achieved.
【００２２】上述したような可塑剤をゲル化するマトリ
クス高分子としては、ゲル状電解質を構成するのに使用
されている種々の高分子が使用できる。具体的には、ポ
リビニリデンフルオライドや、ビニリデンフルオライド
とヘキサフルオロプロピレンとの共重合体などのフッ素
系高分子、ポリエチレンオキサイドや、ポリエチレンオ
キサイド架橋体などのエーテル系高分子、その他、ポリ
アクリロニトリルなどを単独、又は混合して使用でき
る。その中でも特に、フッ素系高分子を用いることが望
ましい。フッ素系高分子を用いることで、酸化還元安定
性を高めることができる。As the matrix polymer for gelling the plasticizer as described above, various polymers used for forming a gel electrolyte can be used. Specifically, fluorine-based polymers such as polyvinylidene fluoride and a copolymer of vinylidene fluoride and hexafluoropropylene, ether-based polymers such as polyethylene oxide and cross-linked polyethylene oxide, and other materials such as polyacrylonitrile Can be used alone or as a mixture. Among them, it is particularly desirable to use a fluoropolymer. By using a fluorine-based polymer, the redox stability can be increased.
【００２３】マトリクス高分子は、ゲル状電解質の１０
重量％以上、５０重量％以下とすることが好ましい。The matrix polymer is composed of 10
It is preferable that the content be not less than 50% by weight and not more than 50% by weight.
【００２４】上述したようなゲル状電解質を用いた、本
発明に係るゲル状電解質電池１の一構成例を図１に示
す。FIG. 1 shows a configuration example of the gel electrolyte battery 1 according to the present invention using the above-mentioned gel electrolyte.
【００２５】このゲル状電解質電池１は、集電体上に正
極活物質層が形成された正極板２と、集電体上に負極活
物質層が形成された負極板３と、セパレータ４と、正極
板２を収容する正極外装材５と、負極板３を収容する負
極外装材６とを有する。The gel electrolyte battery 1 has a positive electrode plate 2 having a positive electrode active material layer formed on a current collector, a negative electrode plate 3 having a negative electrode active material layer formed on a current collector, and a separator 4. And a positive electrode exterior material 5 that accommodates the positive electrode plate 2 and a negative electrode exterior material 6 that accommodates the negative electrode plate 3.
【００２６】上記正極板２は、正極活物質と結着剤とを
含有する正極合剤を集電体上に塗布、乾燥することによ
り作製される。集電体には例えばアルミニウム箔等の金
属箔が用いられる。The positive electrode plate 2 is manufactured by applying a positive electrode mixture containing a positive electrode active material and a binder on a current collector and drying the mixture. A metal foil such as an aluminum foil is used for the current collector.
【００２７】正極活物質には、目的とする電池の種類に
応じて金属酸化物、金属硫化物又は特定の高分子を用い
ることができる。As the positive electrode active material, a metal oxide, a metal sulfide, or a specific polymer can be used depending on the type of the intended battery.
【００２８】例えばリチウムイオン電池を構成する場
合、正極活物質としては、ＴｉＳ2、ＭｏＳ2、ＮｂＳｅ
2、Ｖ2Ｏ5等の金属硫化物あるいは酸化物を使用するこ
とができる。また、ＬｉＭxＯ2（式中Ｍは一種以上の遷
移金属を表し、ｘは電池の充放電状態によって異なり、
通常０．０５以上、１．１０以下である。）を主体とす
るリチウム複合酸化物等を使用することができる。この
リチウム複合酸化物を構成する遷移金属Ｍとしては、Ｃ
ｏ、Ｎｉ、Ｍｎ等が好ましい。このようなリチウム複合
酸化物の具体例としてはＬｉＣｏＯ2、ＬｉＮｉＯ2、Ｌ
ｉＮｉｙＣｏ1-yＯ2（式中、０＜ｙ＜１である。）、Ｌ
ｉＭｎ2Ｏ4等を挙げることができる。これらのリチウム
複合酸化物は、高電圧を発生でき、エネルギー密度的に
優れた正極活物質となる。正極には、これらの正極活物
質の複数種をあわせて使用してもよい。For example, when forming a lithium ion battery, TiS 2 , MoS 2 , NbSe may be used as the positive electrode active material.
2 , metal sulfides or oxides such as V 2 O 5 can be used. LiM x O 2 (where M represents one or more transition metals, x varies depending on the charge / discharge state of the battery,
Usually, it is 0.05 or more and 1.10 or less. ) Can be used. As the transition metal M constituting this lithium composite oxide, C
o, Ni, Mn and the like are preferable. Specific examples of such a lithium composite oxide include LiCoO 2 , LiNiO 2 , L
iNiyCo 1-y O 2 (where 0 <y <1), L
iMn 2 O 4 and the like can be mentioned. These lithium composite oxides can generate a high voltage and become positive electrode active materials excellent in energy density. A plurality of these positive electrode active materials may be used in combination for the positive electrode.
【００２９】また、上記正極合剤の結着剤としては、通
常リチウムイオン電池の正極合剤に用いられている公知
の結着剤を用いることができるほか、上記正極合剤に導
電剤等、公知の添加剤を添加することができる。As the binder for the positive electrode mixture, a known binder which is usually used for a positive electrode mixture of a lithium ion battery can be used. Known additives can be added.
【００３０】上記負極板３は、負極活物質と結着剤とを
含有する負極合剤を、集電体上に塗布、乾燥することに
より作製される。上記集電体には、例えば銅箔等の金属
箔が用いられる。The negative electrode plate 3 is manufactured by applying a negative electrode mixture containing a negative electrode active material and a binder on a current collector and drying the mixture. For the current collector, for example, a metal foil such as a copper foil is used.
【００３１】リチウムイオン電池を構成する場合、負極
材料としては、リチウムをドープ、脱ドープできる材料
を使用することが好ましい。リチウムをドープ、脱ドー
プできる材料として具体的には、熱分解炭素類、コーク
ス類、黒鉛類、ガラス状炭素繊維、有機高分子化合物焼
成体、炭素繊維、活性炭等の炭素材料を使用することが
できる。上記コークス類には、ピッチコークス、ニート
ルコークス、石油コークス等がある。また、上記有機高
分子化合物焼成体とは、フェノール樹脂、フラン樹脂等
を適当な温度で焼成し炭素化したものを示す。In constructing a lithium ion battery, it is preferable to use a material capable of doping and undoping lithium as a negative electrode material. Specific examples of the material capable of doping and undoping lithium include carbon materials such as pyrolytic carbons, cokes, graphites, glassy carbon fibers, organic polymer compound fired bodies, carbon fibers, and activated carbon. it can. Examples of the coke include pitch coke, needle coke, and petroleum coke. The fired organic polymer compound is obtained by firing a phenol resin, a furan resin or the like at an appropriate temperature and carbonizing the same.
【００３２】上述した炭素材料のほか、リチウムをドー
プ、脱ドープできる材料として、ポリアセチレン、ポリ
ピロール等の高分子やＳｎＯ2等の酸化物を使用するこ
ともできる。In addition to the above-mentioned carbon materials, polymers such as polyacetylene and polypyrrole and oxides such as SnO 2 can also be used as materials capable of doping and undoping lithium.
【００３３】また、上記負極合剤の結着剤としては、通
常リチウムイオン電池の負極合剤に用いられている公知
の結着剤を用いることができるほか、上記負極合剤に公
知の添加剤等を添加することができる。As the binder for the negative electrode mixture, a known binder which is usually used for a negative electrode mixture of a lithium ion battery can be used, and a known additive for the negative electrode mixture can be used. Etc. can be added.
【００３４】このゲル状電解質電池１では、可塑剤とマ
トリクス高分子とを含有する電解質溶液を正極活物質層
又は負極活物質層上に塗布し、電解質溶液を正極活物質
層又は負極活物質層中に浸透させた後に溶媒を除去して
電解質をゲル化することにより、正極活物質層又は負極
活物質層中にゲル状電解質を含浸させている。活物質層
中にゲル状電解質を含浸させることで、ゲル状電解質電
池１の内部抵抗を減少させ、かつ、活物質とゲル状電解
質との接触状態を改善することができる。In the gel electrolyte battery 1, an electrolyte solution containing a plasticizer and a matrix polymer is applied on the positive electrode active material layer or the negative electrode active material layer, and the electrolyte solution is applied to the positive electrode active material layer or the negative electrode active material layer. The gel electrolyte is impregnated in the positive electrode active material layer or the negative electrode active material layer by gelling the electrolyte by removing the solvent after infiltrating into the inside. By impregnating the gel electrolyte in the active material layer, the internal resistance of the gel electrolyte battery 1 can be reduced, and the contact state between the active material and the gel electrolyte can be improved.
【００３５】ゲル状電解質電池１は、例えば次のように
して製造される。The gel electrolyte battery 1 is manufactured, for example, as follows.
【００３６】正極板２は、正極活物質と結着剤とを含有
する正極合剤を、集電体となる例えばアルミニウム箔等
の金属箔上に均一に塗布、乾燥して正極活物質層を形成
することにより作製される。The positive electrode plate 2 is uniformly coated with a positive electrode mixture containing a positive electrode active material and a binder on a metal foil such as an aluminum foil serving as a current collector, and dried to form a positive electrode active material layer. It is produced by forming.
【００３７】負極板３は、負極活物質と結着剤とを含有
する負極合剤を、集電体となる例えば銅箔等の金属箔上
に均一に塗布、乾燥して負極活物質層を形成することに
より作製される。The negative electrode plate 3 is uniformly coated with a negative electrode mixture containing a negative electrode active material and a binder on a metal foil such as a copper foil, which serves as a current collector, and dried to form a negative electrode active material layer. It is produced by forming.
【００３８】電解質溶液は、リチウム塩を含有する可塑
剤と、マトリクス高分子とを溶媒中に溶解させて調製さ
れる。本発明では、上記可塑剤が、一般式（１）で表さ
れる炭酸エステル化合物を含有する。The electrolyte solution is prepared by dissolving a plasticizer containing a lithium salt and a matrix polymer in a solvent. In the present invention, the plasticizer contains a carbonate compound represented by the general formula (1).
【００３９】まず、上記電解質溶液を、正極活物質層及
び負極活物質層上に均一に塗布する。次に、電解質溶液
を正極活物質層又は負極活物質層中に含浸させ、最後に
溶媒を除去して電解質をゲル化させることにより、活物
質中にゲル状電解質を含浸させる。First, the above-mentioned electrolyte solution is uniformly applied on the positive electrode active material layer and the negative electrode active material layer. Next, the electrolyte solution is impregnated into the positive electrode active material layer or the negative electrode active material layer, and finally, the solvent is removed to gel the electrolyte, whereby the active material is impregnated with the gel electrolyte.
【００４０】最後に、以上のようにして作製された正極
板２、負極板３をそれぞれ正極外装材５、負極外装材６
に収容し、正極板２が収容された正極外装材５と、負極
板３が収容された負極外装材５とを、セパレータ４を介
して、正極板２と負極板３とが対向するように積層す
る。最後に正極外装材５、負極外装材６の外周縁部をホ
ットメルト材７を介して熱融着することで接合、密閉し
てゲル状電解質電池１が完成する。Lastly, the positive electrode plate 2 and the negative electrode plate 3 manufactured as described above were respectively combined with the positive electrode sheath material 5 and the negative electrode sheath material 6.
The negative electrode package 5 containing the positive electrode plate 2 and the negative electrode package 3 containing the negative electrode plate 3 are placed such that the positive plate 2 and the negative plate 3 face each other with the separator 4 interposed therebetween. Laminate. Lastly, the outer peripheral edges of the positive electrode packaging material 5 and the negative electrode packaging material 6 are thermally fused via a hot melt material 7 to join and seal, thereby completing the gel electrolyte battery 1.
【００４１】本発明のゲル状電解質電池１は、円筒型、
角型、コイン型、ボタン型等、その形状については特に
限定されることはなく、また、薄型、大型等の種々の大
きさにすることができる。The gel electrolyte battery 1 of the present invention has a cylindrical shape,
The shape such as a square shape, a coin shape, and a button shape is not particularly limited, and the shape can be various sizes such as a thin shape and a large size.
【００４２】[0042]
【実施例】図１に示すような平板型ゲル状電解質電池を
作製した。EXAMPLE A flat gel electrolyte battery as shown in FIG. 1 was produced.
【００４３】〈実施例１〉負極を次のように作製した。<Example 1> A negative electrode was produced as follows.
【００４４】まず、粉砕した黒鉛粉末９０重量部と、結
着剤としてポリビニリデンフルオライド１０重量部とを
混合して負極合剤を調製し、さらにこれをＮ−メチル−
２−ピロリドンに分散させスラリー状とした。First, 90 parts by weight of pulverized graphite powder and 10 parts by weight of polyvinylidene fluoride as a binder were mixed to prepare a negative electrode mixture.
It was dispersed in 2-pyrrolidone to form a slurry.
【００４５】そして、このスラリーを負極集電体である
厚さ１０μｍの帯状銅箔の片面に均一に塗布し、乾燥
後、ロールプレス機で圧縮成形し、負極を作製した。This slurry was uniformly applied to one side of a 10 μm-thick strip-shaped copper foil as a negative electrode current collector, dried, and then compression-molded with a roll press to produce a negative electrode.
【００４６】正極を次のように作製した。A positive electrode was produced as follows.
【００４７】まず、正極活物質を得るために、炭酸リチ
ウムと炭酸コバルトとを０．５ｍｏｌ対１ｍｏｌの比率
で混合し、空気中９００℃で５時間焼成した。次に、得
られたＬｉＣｏＯ2を９１重量部と、導電剤として黒鉛
６重量部と、結着剤として、ビニリデンフルオライドと
ヘキサフルオロプロピレンとの共重合体１０重量部とを
混合して正極合剤を調製し、さらにこれをＮ−メチル−
２−ピロリドンに分散させスラリー状とした。First, in order to obtain a positive electrode active material, lithium carbonate and cobalt carbonate were mixed at a ratio of 0.5 mol to 1 mol, and fired in air at 900 ° C. for 5 hours. Next, 91 parts by weight of the obtained LiCoO 2 , 6 parts by weight of graphite as a conductive agent, and 10 parts by weight of a copolymer of vinylidene fluoride and hexafluoropropylene as a binder were mixed to form a positive electrode. And N-methyl-
It was dispersed in 2-pyrrolidone to form a slurry.
【００４８】そして、このスラリーを正極集電体である
厚さ２０μｍのアルミニウム箔の片面に均一に塗布し、
乾燥後、ロールプレス機で圧縮成形し、正極を作製し
た。Then, this slurry was uniformly applied to one side of a 20 μm thick aluminum foil as a positive electrode current collector,
After drying, compression molding was performed using a roll press machine to produce a positive electrode.
【００４９】ゲル状電解質を次のようにして得た。A gel electrolyte was obtained as follows.
【００５０】可塑剤を３０ｇと、マトリクス高分子を１
０ｇと、テトラヒドロフラン（以下、ＴＨＦと称す
る。）を６０ｇとを混合溶解させてゲル状電解質溶液を
調製した。30 g of plasticizer and 1 part of matrix polymer
0 g and 60 g of tetrahydrofuran (hereinafter, referred to as THF) were mixed and dissolved to prepare a gel electrolyte solution.
【００５１】ここで、上記可塑剤には、炭酸エチレン
（以下、ＥＣと称する。）を７６．５重量％と、トリフ
ルオロ化炭酸プロピレン（以下、ＴＦＰＣと称する。）
を８．５重量％と、ＬｉＰＦ6を１５重量％との混合物
を用いた。また、上記マトリクス高分子には、ビニリデ
ンフルオライドとヘキサフルオロプロピレンとの共重合
体を用いた。Here, the plasticizer contains 76.5% by weight of ethylene carbonate (hereinafter, referred to as EC) and trifluorocarbonized propylene carbonate (hereinafter, referred to as TFPC).
Was used, and a mixture of 8.5 wt% of LiPF 6 and 15 wt% of LiPF 6 was used. Further, as the matrix polymer, a copolymer of vinylidene fluoride and hexafluoropropylene was used.
【００５２】正極上及び負極上に、上記ゲル状電解質溶
液を均一に塗布し、常温で８時間放置してゲル状電解質
溶液を正極中及び負極中に含浸させた。最後にＴＨＦを
気化させて除去した。The gel electrolyte solution was uniformly applied on the positive electrode and the negative electrode, and allowed to stand at room temperature for 8 hours to impregnate the gel electrolyte solution in the positive electrode and the negative electrode. Finally, the THF was vaporized and removed.
【００５３】ゲル状電解質を塗布した負極、及び正極を
ゲル状電解質側を合わせ、圧着することで面積２．５ｃ
ｍ×４．０ｃｍ、厚さ０．３ｍｍの平板型ゲル状電解質
電池を作製した。The negative electrode coated with the gel electrolyte and the positive electrode were brought into contact with the gel electrolyte side and pressed to obtain an area of 2.5 c.
A flat gel electrolyte battery having a size of mx 4.0 cm and a thickness of 0.3 mm was prepared.
【００５４】〈実施例２〉可塑剤の組成を、ＥＣを６８
重量％と、ＴＦＰＣを１７重量％と、ＬｉＰＦ6を１５
重量％としたこと以外は、実施例１と同様にしてゲル状
電解質電池を作製した。Example 2 The composition of the plasticizer was changed to an EC of 68.
And weight%, and 17% by weight of TFPC, the LiPF 6 15
A gel electrolyte battery was produced in the same manner as in Example 1, except that the content was changed to% by weight.
【００５５】〈実施例３〉可塑剤の組成を、ＥＣを５１
重量％と、炭酸プロピレン（以下、ＰＣと称する）を
８．５重量％と、ＴＦＰＣを２５．５重量％と、ＬｉＰ
Ｆ6を１５重量％としたこと以外は、実施例１と同様に
してゲル状電解質電池を作製した。Example 3 The composition of the plasticizer was changed to EC of 51.
% By weight, 8.5% by weight of propylene carbonate (hereinafter referred to as PC), 25.5% by weight of TFPC, LiP
A gel electrolyte battery was produced in the same manner as in Example 1, except that F 6 was 15% by weight.
【００５６】〈実施例４〉可塑剤の組成を、ＥＣを４
２．５重量％と、ＰＣを１７重量％と、ＴＦＰＣを２
５．５重量％と、ＬｉＰＦ6を１５重量％としたこと以
外は、実施例１と同様にしてゲル状電解質電池を作製し
た。Example 4 The composition of the plasticizer was changed to EC of 4
2.5% by weight, 17% by weight of PC and 2% of TFPC
A gel electrolyte battery was produced in the same manner as in Example 1 except that 5.5 wt% and LiPF 6 were 15 wt%.
【００５７】〈実施例５〉可塑剤の組成を、ＥＣを４
２．５重量％と、ＰＣを８．５重量％と、ＴＦＰＣを３
４重量％と、ＬｉＰＦ6を１５重量％とし、可塑剤の量
を３．３ｇとしたこと以外は、実施例１と同様にしてゲ
ル状電解質電池を作製した。Example 5 The composition of the plasticizer was changed to EC of 4
2.5% by weight, 8.5% by weight of PC and 3% of TFPC
A gel electrolyte battery was produced in the same manner as in Example 1, except that 4 wt%, LiPF 6 was 15 wt%, and the amount of the plasticizer was 3.3 g.
【００５８】〈実施例６〉可塑剤の組成を、ＥＣを４
２．５重量％と、ＰＣを８．５重量％と、ＴＦＰＣを３
４重量％と、ＬｉＰＦ6を１５重量％とし、可塑剤の量
を４．２９ｇとしたこと以外は、実施例１と同様にして
ゲル状電解質電池を作製した。Example 6 The composition of the plasticizer was changed to EC of 4
2.5% by weight, 8.5% by weight of PC and 3% of TFPC
A gel electrolyte battery was produced in the same manner as in Example 1 except that 4 wt%, LiPF 6 was 15 wt%, and the amount of the plasticizer was 4.29 g.
【００５９】〈実施例７〉可塑剤の組成を、ＥＣを５１
重量％と、ＴＦＰＣを３４重量％と、ＬｉＰＦ6を１５
重量％としたこと以外は、実施例１と同様にしてゲル状
電解質電池を作製した。Example 7 The composition of the plasticizer was changed to EC of 51.
And weight%, and a 34 wt% TFPC, the LiPF 6 15
A gel electrolyte battery was produced in the same manner as in Example 1, except that the content was changed to% by weight.
【００６０】〈実施例８〉可塑剤の組成を、ＥＣを４
２．５重量％と、ＰＣを８．５重量％と、ＴＦＰＣを３
４重量％と、ＬｉＰＦ6を１５重量％としたこと以外
は、実施例１と同様にしてゲル状電解質電池を作製し
た。Example 8 The composition of the plasticizer was changed to EC of 4
2.5% by weight, 8.5% by weight of PC and 3% of TFPC
A gel electrolyte battery was produced in the same manner as in Example 1, except that 4 wt% and LiPF 6 were 15 wt%.
【００６１】〈実施例９〉可塑剤の組成を、ＥＣを３４
重量％と、ＰＣを１７重量％と、ＴＦＰＣを３４重量％
と、ＬｉＰＦ6を１５重量％としたこと以外は、実施例
１と同様にしてゲル状電解質電池を作製した。Example 9 The composition of the plasticizer was changed to EC of 34.
% By weight, 17% by weight of PC and 34% by weight of TFPC
A gel electrolyte battery was produced in the same manner as in Example 1, except that LiPF 6 was changed to 15% by weight.
【００６２】〈実施例１０〉可塑剤の組成を、ＥＣを４
２．５重量％と、ＰＣを８．５重量％と、ＴＦＰＣを３
４重量％と、ＬｉＰＦ6を１５重量％とし、可塑剤の量
を５６．７ｇとしたこと以外は、実施例１と同様にして
ゲル状電解質電池を作製した。Example 10 The composition of the plasticizer was changed to EC of 4
2.5% by weight, 8.5% by weight of PC and 3% of TFPC
A gel electrolyte battery was produced in the same manner as in Example 1 except that 4 wt%, LiPF 6 was 15 wt%, and the amount of the plasticizer was 56.7 g.
【００６３】〈実施例１１〉可塑剤の組成を、ＥＣを４
２．５重量％と、ＰＣを８．５重量％と、ＴＦＰＣを３
４重量％と、ＬｉＰＦ6を１５重量％とし、可塑剤の量
を７０ｇとしたこと以外は、実施例１と同様にしてゲル
状電解質電池を作製した。Example 11 The composition of the plasticizer was changed to EC of 4
2.5% by weight, 8.5% by weight of PC and 3% of TFPC
A gel electrolyte battery was produced in the same manner as in Example 1 except that 4 wt%, LiPF 6 was 15 wt%, and the amount of the plasticizer was 70 g.
【００６４】〈実施例１２〉可塑剤の組成を、ＥＣを４
２．５重量％と、ＴＦＰＣを４２．５重量％と、ＬｉＰ
Ｆ6を１５重量％としたこと以外は、実施例１と同様に
してゲル状電解質電池を作製した。Example 12 The composition of the plasticizer was changed to EC of 4
2.5% by weight, 42.5% by weight of TFPC, LiP
A gel electrolyte battery was produced in the same manner as in Example 1, except that F 6 was 15% by weight.
【００６５】〈実施例１３〉可塑剤の組成を、ＥＣを４
２．５重量％と、ＴＦＰＣを４２．５重量％と、ＬｉＰ
Ｆ6を１５重量％とし、マトリクス高分子にポリビニリ
デンフルオライドを用いたこと以外は、実施例１と同様
にしてゲル状電解質電池を作製した。Example 13 The composition of the plasticizer was changed to EC of 4
2.5% by weight, 42.5% by weight of TFPC, LiP
A gel electrolyte battery was produced in the same manner as in Example 1 except that F 6 was 15% by weight and polyvinylidene fluoride was used as a matrix polymer.
【００６６】〈実施例１４〉可塑剤の組成を、ＥＣを３
４重量％と、ＴＦＰＣを５１重量％と、ＬｉＰＦ6を１
５重量％としたこと以外は、実施例１と同様にしてゲル
状電解質電池を作製した。Example 14 The composition of the plasticizer was changed to EC of 3
4% by weight, 51% by weight of TFPC, 1 part of LiPF 6
A gel electrolyte battery was produced in the same manner as in Example 1 except that the content was 5% by weight.
【００６７】〈実施例１５〉可塑剤の組成を、ＥＣを２
５．５重量％と、ＴＦＰＣを５９．５重量％と、ＬｉＰ
Ｆ6を１５重量％としたこと以外は、実施例１と同様に
してゲル状電解質電池を作製した。Example 15 The composition of the plasticizer was changed to EC of 2
5.5% by weight, 59.5% by weight of TFPC, LiP
A gel electrolyte battery was produced in the same manner as in Example 1, except that F 6 was 15% by weight.
【００６８】〈実施例１６〉可塑剤の組成を、ＥＣを１
７重量％と、ＴＦＰＣを６８重量％と、ＬｉＰＦ6を１
５重量％としたこと以外は、実施例１と同様にしてゲル
状電解質電池を作製した。Example 16 The composition of the plasticizer was changed to 1 for EC.
7% by weight, 68% by weight of TFPC, 1 part of LiPF 6
A gel electrolyte battery was produced in the same manner as in Example 1 except that the content was 5% by weight.
【００６９】〈実施例１７〉可塑剤の組成を、ＥＣを
８．５重量％と、ＴＦＰＣを７６．５重量％と、ＬｉＰ
Ｆ6を１５重量％としたこと以外は、実施例１と同様に
してゲル状電解質電池を作製した。Example 17 The composition of the plasticizer was 8.5% by weight of EC, 76.5% by weight of TFPC, LiP
A gel electrolyte battery was produced in the same manner as in Example 1, except that F 6 was 15% by weight.
【００７０】〈実施例１８〉可塑剤の組成を、ＴＦＰＣ
を８５重量％と、ＬｉＰＦ6を１５重量％としたこと以
外は、実施例１と同様にしてゲル状電解質電池を作製し
た。Example 18 The composition of the plasticizer was TFPC
, And a gel electrolyte battery was produced in the same manner as in Example 1 except that LiPF 6 was 15% by weight.
【００７１】〈比較例〉負極を次のように作製した。<Comparative Example> A negative electrode was manufactured as follows.
【００７２】粉砕した黒鉛粉末９０重量部と、結着剤と
してポリビニリデンフルオライド１０重量部とを混合し
て負極合剤を調製し、さらにこれをＮ−メチル−２−ピ
ロリドンに分散させスラリー状とした。そして、このス
ラリーを負極集電体である厚さ１０μｍの帯状銅箔の片
面に均一に塗布し、乾燥後、ロールプレス機で圧縮成形
し、負極を作製した。90 parts by weight of the ground graphite powder and 10 parts by weight of polyvinylidene fluoride as a binder were mixed to prepare a negative electrode mixture, which was further dispersed in N-methyl-2-pyrrolidone to form a slurry. And Then, this slurry was uniformly applied to one surface of a 10 μm-thick strip-shaped copper foil as a negative electrode current collector, dried, and then compression-molded with a roll press to produce a negative electrode.
【００７３】正極を次のように作製した。A positive electrode was produced as follows.
【００７４】正極活物質を得るために、炭酸リチウムと
炭酸コバルトとを０．５ｍｏｌ対１ｍｏｌの比率で混合
し、空気中９００℃で５時間焼成した。次に、得られた
ＬｉＣｏＯ2を９１重量部、導電剤として黒鉛６重量
部、結着剤として、ビニリデンフルオライドとヘキサフ
ルオロプロピレンとの共重合体１０重量部を混合して正
極合剤を調製し、さらにこれをＮ−メチル−２−ピロリ
ドンに分散させスラリー状とした。そして、このスラリ
ーを正極集電体である厚さ２０μｍのアルミニウム箔の
片面に均一に塗布し、乾燥後、ロールプレス機で圧縮成
形し、正極を作製した。To obtain a positive electrode active material, lithium carbonate and cobalt carbonate were mixed at a ratio of 0.5 mol to 1 mol, and fired at 900 ° C. in air for 5 hours. Next, 91 parts by weight of the obtained LiCoO 2 , 6 parts by weight of graphite as a conductive agent, and 10 parts by weight of a copolymer of vinylidene fluoride and hexafluoropropylene as a binder were mixed to prepare a positive electrode mixture. This was further dispersed in N-methyl-2-pyrrolidone to form a slurry. Then, this slurry was uniformly applied on one side of a 20 μm-thick aluminum foil serving as a positive electrode current collector, dried, and then compression-molded with a roll press to produce a positive electrode.
【００７５】ゲル状電解質を次のようにして得た。A gel electrolyte was obtained as follows.
【００７６】可塑剤を３０ｇと、マトリクス高分子を１
０ｇと、ＴＨＦを６０ｇとを混合溶解させてゲル状電解
質溶液を調製した。30 g of a plasticizer and 1 part of a matrix polymer
0 g and 60 g of THF were mixed and dissolved to prepare a gel electrolyte solution.
【００７７】ここで、上記可塑剤には、ＥＣを４２．５
重量％と、ＰＣを４２．５重量％と、ＬｉＰＦ6を１５
重量％との混合物を用いた。また、上記マトリクス高分
子には、ビニリデンフルオライドとヘキサフルオロプロ
ピレンとの共重合体を用いた。Here, EC is 42.5 to the above plasticizer.
% Of PC, 42.5% by weight of PC, and 15% of LiPF 6 .
% By weight. Further, as the matrix polymer, a copolymer of vinylidene fluoride and hexafluoropropylene was used.
【００７８】正極上及び負極上に、上記ゲル状電解質溶
液を均一に塗布し、常温で８時間放置してゲル状電解質
溶液を正極中及び負極中に含浸させた。最後にＴＨＦを
気化させて除去した。The gel electrolyte solution was uniformly applied on the positive electrode and the negative electrode, and allowed to stand at room temperature for 8 hours to impregnate the gel electrolyte solution in the positive electrode and the negative electrode. Finally, the THF was vaporized and removed.
【００７９】ゲル状電解質を塗布した負極、及び正極を
ゲル状電解質側を合わせ、圧着することで面積２．５ｃ
ｍ×４．０ｃｍ、厚さ０．３ｍｍの平板型ゲル状電解質
電池を作製した。The negative electrode coated with the gel electrolyte and the positive electrode were brought into contact with the gel electrolyte side and pressed to obtain an area of 2.5 c.
A flat gel electrolyte battery having a size of mx 4.0 cm and a thickness of 0.3 mm was prepared.
【００８０】特性評価 上述のようにして作製された各電池について、初期放電
容量、２サイクル目及び１００サイクル目における充放
電効率、３０ｍＡ放電時容量と６ｍＡ放電時容量との比
（以下、３０ｍＡ放電時容量／６ｍＡ放電時容量と称す
る。）をそれぞれ評価した。 Evaluation of Characteristics For each of the batteries produced as described above, the initial discharge capacity, the charge / discharge efficiency at the second cycle and the 100th cycle, and the ratio of the capacity at 30 mA discharge to the capacity at 6 mA discharge (hereinafter referred to as 30 mA discharge) Hour capacity / 6 mA discharge capacity).
【００８１】初期放電容量は次のようにして評価した。
まず、２３℃の条件下で、６ｍＡの定電流定電圧充電を
上限４．２Ｖまで１０時間行った。次に、６ｍＡの定電
流放電を終止電圧２．５Ｖ間で行った。The initial discharge capacity was evaluated as follows.
First, under the condition of 23 ° C., a constant current and constant voltage charge of 6 mA was performed for 10 hours to an upper limit of 4.2 V. Next, a constant current discharge of 6 mA was performed at a final voltage of 2.5 V.
【００８２】充放電効率は次のようにして評価した。初
期放電容量の評価実験と同じ条件で、充放電を１００サ
イクル行った。２サイクル目と１００サイクル目の充放
電効率を決定した。The charge / discharge efficiency was evaluated as follows. Under the same conditions as in the initial discharge capacity evaluation experiment, charge and discharge were performed 100 cycles. The charge and discharge efficiencies at the second cycle and the 100th cycle were determined.
【００８３】３０ｍＡ放電時容量／６ｍＡ放電時容量は
次のようにして評価した。まず初期放電容量の評価実験
と同じ条件で充放電を行った。つぎに、３０ｍＡの定電
流で同様に充放電を行った。そして、３０ｍＡ放電時
と、６ｍＡ放電時での放電容量とを決定し、３０ｍＡ放
電時容量／６ｍＡ放電時容量を決定した。The discharge capacity at 30 mA / 6 discharge capacity was evaluated as follows. First, charging and discharging were performed under the same conditions as in the initial discharge capacity evaluation experiment. Next, charging and discharging were similarly performed at a constant current of 30 mA. Then, the discharge capacity at the time of 30 mA discharge and the discharge capacity at the time of 6 mA discharge were determined, and the capacity at the time of 30 mA discharge / 6 mA discharge capacity was determined.
【００８４】各電池についての初期容量、２サイクル目
及び１００サイクル目の充放電効率、及び３０ｍＡ放電
時容量／６ｍＡ放電時容量の評価結果を表１に示す。Table 1 shows the evaluation results of the initial capacity, the charge / discharge efficiency at the second cycle and the 100th cycle, and the capacity at discharge of 30 mA / 6 mA at discharge of each battery.
【００８５】[0085]
【表１】 [Table 1]
【００８６】表１から明らかなように、可塑剤中にＴＦ
ＰＣを含有しない比較例１の電池に比べて、可塑剤中に
ＴＦＰＣを含有させた実施例１〜実施例１８の電池で
は、初期容量、充放電効率、放電容量比のいずれも優れ
た特性を示した。As is clear from Table 1, TF was contained in the plasticizer.
Compared with the battery of Comparative Example 1 containing no PC, the batteries of Examples 1 to 18 in which TFPC was contained in the plasticizer exhibited excellent characteristics in all of the initial capacity, charge / discharge efficiency, and discharge capacity ratio. Indicated.
【００８７】そして、可塑剤中のＴＦＰＣ濃度が１０重
量％以上、８０重量％以下の範囲で初期容量、充放電効
率が特に優れていることがわかった。It was found that the initial capacity and charge / discharge efficiency were particularly excellent when the TFPC concentration in the plasticizer was in the range of 10% by weight or more and 80% by weight or less.
【００８８】また、実施例５〜実施例１１では、ゲル状
電解質中の可塑剤含有量をそれぞれ変化させたが、ゲル
状電解質中の可塑剤含有量を２５重量％とした実施例５
では容量比が悪化してしまった。一方、ゲル状電解質中
の可塑剤含有量を８７．１重量％とした実施例１１では
容量比は優れているが、充放電効率が悪化してしまっ
た。In Examples 5 to 11, the content of the plasticizer in the gel electrolyte was changed, but the content of the plasticizer in the gel electrolyte was changed to 25% by weight.
Then the capacity ratio has deteriorated. On the other hand, in Example 11 in which the content of the plasticizer in the gel electrolyte was 87.1% by weight, the capacity ratio was excellent, but the charge / discharge efficiency was deteriorated.
【００８９】従って、ゲル状電解質中の可塑剤含有量を
３０重量％以上、８５重量％以下とすることで、初期容
量、充放電効率、容量比に優れたゲル状電解質電池を得
られることがわかった。Therefore, by setting the content of the plasticizer in the gel electrolyte to 30% by weight or more and 85% by weight or less, it is possible to obtain a gel electrolyte battery having excellent initial capacity, charge / discharge efficiency and capacity ratio. all right.
【００９０】[0090]
【発明の効果】本発明のゲル状電解質は、可塑剤に炭酸
エステル化合物を含有させることで、電気化学的安定性
を高めることができる。According to the gel electrolyte of the present invention, electrochemical stability can be enhanced by adding a carbonate compound to the plasticizer.
【００９１】また、本発明のゲル状電解質電池では、ゲ
ル状電解質の可塑剤に炭酸エステル化合物を含有させる
ことで、電気化学的安定性を高め、充電時に負極上での
可塑剤の分解を防ぎ、充放電効率を向上させることがで
きる。Further, in the gel electrolyte battery of the present invention, by adding a carbonate compound to the plasticizer of the gel electrolyte, the electrochemical stability is enhanced and the decomposition of the plasticizer on the negative electrode during charging is prevented. In addition, charging and discharging efficiency can be improved.
【図１】本発明のゲル状電解質電池の一構成例を示す断
面図である。FIG. 1 is a cross-sectional view showing one configuration example of a gel electrolyte battery of the present invention.
１ ゲル状電解質電池、 ２ 正極板、 ３ 負極板、
４ セパレータ、５ 正極外装材、 ６ 負極外装
材、 ７ ホットメルト材1 gel electrolyte battery, 2 positive electrode plate, 3 negative electrode plate,
4 Separator, 5 cathode exterior material, 6 negative electrode exterior material, 7 hot melt material
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０８Ｌ 101/00 Ｃ０８Ｌ 101/00 Ｈ０１Ｍ 6/18 Ｈ０１Ｍ 6/18 Ｅ 6/22 6/22 Ｃ 10/40 10/40 Ｂ ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI C08L 101/00 C08L 101/00 H01M 6/18 H01M 6/18 E 6/22 6/22 C 10/40 10/40 B
Claims (16)
合物を含有することを特徴とするゲル状電解質。 【化１】 （式中、Ｘ1及びＸ2はハロゲン又は水素を表し、Ｒ1及
びＲ2は同一又は異なるハロゲン化アルキル基ＣnＸａ
2n-m+1Ｘｂm又は水素を表す。Ｘａはハロゲン、Ｘｂは
ハロゲン又は水素である。ただしＸ1，Ｘ2，Ｒ1，Ｒ2す
べてがハロゲン又は水素である場合を除く。）1. A gel comprising: a plasticizer; and a matrix polymer in which the plasticizer is dispersed, wherein the plasticizer contains a carbonate compound represented by the general formula (1). Electrolytes. Embedded image (Wherein X 1 and X 2 represent halogen or hydrogen, and R 1 and R 2 are the same or different halogenated alkyl groups C n Xa
Represents 2n-m + 1 Xb m or hydrogen. Xa is halogen, Xb is halogen or hydrogen. However, the case where X1, X2, R1, and R2 are all halogen or hydrogen is excluded. )
を１０重量％以上、８０重量％以下の割合で含有するこ
とを特徴とする請求項１記載のゲル状電解質。2. The gel electrolyte according to claim 1, wherein the plasticizer contains the carbonate compound at a ratio of 10% by weight or more and 80% by weight or less.
％以下の割合で含有することを特徴とする請求項１記載
のゲル状電解質。3. The gel electrolyte according to claim 1, wherein the plasticizer is contained in a proportion of 30% by weight or more and 85% by weight or less.
子であることを特徴とする請求項１記載のゲル状電解
質。4. The gel electrolyte according to claim 1, wherein the matrix polymer is a fluorine-based polymer.
フルオライドであることを特徴とする請求項４記載のゲ
ル状電解質。5. The gel electrolyte according to claim 4, wherein the fluorine-containing polymer is polyvinylidene fluoride.
オライドとヘキサフルオロプロピレンとの共重合体であ
ることを特徴とする請求項４記載のゲル状電解質。6. The gel electrolyte according to claim 4, wherein said fluoropolymer is a copolymer of vinylidene fluoride and hexafluoropropylene.
し、 上記ゲル状電解質は、可塑剤がマトリクス高分子中に分
散されてなり、上記可塑剤が、一般式（１）で表される
炭酸エステル化合物を含有することを特徴とするゲル状
電解質電池。 【化２】 （式中、Ｘ1及びＸ2はハロゲン又は水素を表し、Ｒ1及
びＲ2は同一又は異なるハロゲン化アルキル基ＣnＸａ
2n-m+1Ｘｂm又は水素を表す。Ｘａはハロゲン、Ｘｂは
ハロゲン又は水素である。ただしＸ1，Ｘ2，Ｒ1，Ｒ2す
べてがハロゲン又は水素である場合を除く。）7. A gel electrolyte comprising a negative electrode, a positive electrode, and a gel electrolyte, wherein the plasticizer is dispersed in a matrix polymer, and the plasticizer is represented by the general formula (1). A gel electrolyte battery comprising a carbonate compound to be used. Embedded image (Wherein X 1 and X 2 represent halogen or hydrogen, and R 1 and R 2 are the same or different halogenated alkyl groups C n Xa
Represents 2n-m + 1 Xb m or hydrogen. Xa is halogen, Xb is halogen or hydrogen. However, the case where X1, X2, R1, and R2 are all halogen or hydrogen is excluded. )
炭酸エステル化合物を、１０重量％以上、８０重量％以
下の割合で含有することを特徴とする請求項７記載のゲ
ル状電解質電池。8. The gel according to claim 7, wherein the plasticizer contains the carbonate compound represented by the general formula (1) at a ratio of 10% by weight or more and 80% by weight or less. Electrolyte battery.
重量％以上、８５重量％以下の割合で含有することを特
徴とする請求項７記載のゲル状電解質電池。9. The gel electrolyte comprises 30 parts of the plasticizer.
The gel electrolyte battery according to claim 7, which is contained in a ratio of not less than 85% by weight and not more than 85% by weight.
分子であることを特徴とする請求項７記載のゲル状電解
質電池。10. The gel electrolyte battery according to claim 7, wherein the matrix polymer is a fluorine-based polymer.
ンフルオライドであることを特徴とする請求項１０記載
のゲル状電解質電池。11. The gel electrolyte battery according to claim 10, wherein the fluorine-based polymer is polyvinylidene fluoride.
ルオライドとヘキサフルオロプロピレンとの共重合体で
あることを特徴とする請求項１０記載のゲル状電解質。12. The gel electrolyte according to claim 10, wherein the fluoropolymer is a copolymer of vinylidene fluoride and hexafluoropropylene.
又は脱ドープできる材料を含有していること。を特徴と
する請求項７記載のゲル状電解質電池。13. The method according to claim 13, wherein the negative electrode is doped with lithium and / or
Or contain a material that can be dedoped. The gel electrolyte battery according to claim 7, characterized in that:
ープできる材料が、炭素材料であることを特徴とする請
求項１３記載のゲル状電解質電池。14. The gel electrolyte battery according to claim 13, wherein the material capable of doping and / or undoping lithium is a carbon material.
徴とする請求項１４記載のゲル状電解質電池。15. The gel electrolyte battery according to claim 14, wherein the carbon material is graphite.
複合酸化物を含有していることを特徴とする請求項７記
載のゲル状電解質電池。16. The gel electrolyte battery according to claim 7, wherein the positive electrode contains a composite oxide of lithium and a transition metal.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32014597A JP3775022B2 (en) | 1997-11-20 | 1997-11-20 | Gel electrolyte and gel electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32014597A JP3775022B2 (en) | 1997-11-20 | 1997-11-20 | Gel electrolyte and gel electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11154415A true JPH11154415A (en) | 1999-06-08 |
| JP3775022B2 JP3775022B2 (en) | 2006-05-17 |
Family
ID=18118219
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32014597A Expired - Lifetime JP3775022B2 (en) | 1997-11-20 | 1997-11-20 | Gel electrolyte and gel electrolyte battery |
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| Country | Link |
|---|---|
| JP (1) | JP3775022B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6372386B1 (en) * | 1998-11-05 | 2002-04-16 | Samsung Display Devices Co., Ltd. | Electrode active material and polymer electrolyte matrix composition for lithium ion polymer battery |
| CN117384330A (en) * | 2023-12-12 | 2024-01-12 | 蓝固(淄博)新能源科技有限公司 | Preparation method of fluoro-1, 3-dioxolane heterocyclic compound, in-situ solid electrolyte, preparation method and application thereof |
-
1997
- 1997-11-20 JP JP32014597A patent/JP3775022B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6372386B1 (en) * | 1998-11-05 | 2002-04-16 | Samsung Display Devices Co., Ltd. | Electrode active material and polymer electrolyte matrix composition for lithium ion polymer battery |
| CN117384330A (en) * | 2023-12-12 | 2024-01-12 | 蓝固(淄博)新能源科技有限公司 | Preparation method of fluoro-1, 3-dioxolane heterocyclic compound, in-situ solid electrolyte, preparation method and application thereof |
| CN117384330B (en) * | 2023-12-12 | 2024-02-23 | 蓝固(淄博)新能源科技有限公司 | Preparation method of fluoro-1, 3-dioxolane heterocyclic compound, in-situ solid electrolyte, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3775022B2 (en) | 2006-05-17 |
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