JP2000058128A - Gel electrolyte battery - Google Patents
Gel electrolyte batteryInfo
- Publication number
- JP2000058128A JP2000058128A JP10226788A JP22678898A JP2000058128A JP 2000058128 A JP2000058128 A JP 2000058128A JP 10226788 A JP10226788 A JP 10226788A JP 22678898 A JP22678898 A JP 22678898A JP 2000058128 A JP2000058128 A JP 2000058128A
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- JP
- Japan
- Prior art keywords
- gel electrolyte
- polymer
- formula
- integer
- compound
- 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.)
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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、リチウム電池、リ
チウムイオン電池においてゲル電解質を用いた電池に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium battery and a lithium ion battery using a gel electrolyte.
【０００２】[0002]
【従来の技術】近年の携帯用電子機器の小型化に伴い、
高エネルギー密度を有するリチウム二次電池の需要が増
大している。また、電気自動車用等の大型電池への応用
も期待されており、これらの研究開発において、高エネ
ルギー密度化や大容量化の技術および安全性向上の技術
の確立は不可欠である。高分子固体電解質を用いた電池
は、従来の電解液を用いた電池に比べて液漏れがないた
め、電池の信頼性、安全性が向上するとともに薄膜化や
パッケージの簡略化、軽量化等が可能となる。しかしな
がら、高分子とリチウム塩の複合体である高分子固体電
解質のイオン伝導機構は高分子の分子運動を利用するた
め、電解液を用いた電池と比較して充放電電流密度が限
定されるなどの問題点を有する。このため、高いイオン
伝導度を有する高分子固体電解質材料の開発が要求され
ている。2. Description of the Related Art With the recent miniaturization of portable electronic devices,
Demand for lithium secondary batteries having high energy density is increasing. In addition, application to large batteries for electric vehicles and the like is also expected, and in these research and development, establishment of technologies for increasing energy density and increasing capacity and technologies for improving safety are indispensable. Batteries using solid polymer electrolytes do not leak as compared with batteries using conventional electrolytes, so battery reliability and safety are improved, as well as thinning, simplification of packages, and weight reduction. It becomes possible. However, the ion conduction mechanism of the polymer solid electrolyte, which is a composite of a polymer and a lithium salt, uses the molecular motion of the polymer, so the charge / discharge current density is limited compared to batteries using an electrolyte. Problem. Therefore, development of a solid polymer electrolyte material having high ionic conductivity is required.
【０００３】この様な中で、高橋らはポリアルキレンオ
キシドとアルカリ金属塩との複合体に有機溶媒を含有す
ることにより比較的高いイオン伝導度を達成している
（特開昭６３ー９４５６３号公報）。このような有機溶
媒を含む高分子電解質はゲル電解質と呼ばれ、現在盛ん
にリチウム電池あるいはリチウムイオン電池への応用が
検討されている。Under such circumstances, Takahashi et al. Achieved relatively high ionic conductivity by containing an organic solvent in a complex of a polyalkylene oxide and an alkali metal salt (JP-A-63-94563). Gazette). Such a polymer electrolyte containing an organic solvent is called a gel electrolyte, and its application to a lithium battery or a lithium ion battery is being studied actively.
【０００４】高分子材料としてはポリアルキレンオキシ
ド以外にも、ポリアクリロニトリル（ＰＡＮ）やポリフ
ッ化ビニリデン（ＰＶｄＦ）あるいはそれらの類似品等
が検討されている。しかしながら、ＰＡＮ系ゲル電解質
は温度の上昇に伴い高分子が流動性を示すため、高温で
はフィルム状態を維持できない。また、ＰＶｄＦ系ゲル
電解質においては、ＰＶｄＦが電解液に対して難溶性を
示すために、電解液の保持性に問題を生じる。In addition to polyalkylene oxides, polyacrylonitrile (PAN), polyvinylidene fluoride (PVdF), and similar products have been studied as polymer materials. However, the PAN-based gel electrolyte cannot maintain a film state at a high temperature because the polymer exhibits fluidity with an increase in temperature. Further, in the PVdF-based gel electrolyte, since PVdF shows poor solubility in the electrolytic solution, a problem occurs in the retention of the electrolytic solution.
【０００５】我々はこれまで、保液性およびフィルム形
成性の点より架橋性ポリアルキレンオキシドを用いたゲ
ル電解質について、リチウム電池あるいはリチウムイオ
ン電池への応用を検討してきた。このタイプのゲル電解
質においてはポリアルキレンオキシドが電解液と相溶性
を示すため高い液保持性を示し、架橋構造を有すること
により幅広い温度範囲においてフィルム状態を維持する
ことが可能である。そのため、信頼性および安全性に優
れたリチウム電池あるいはリチウムイオン電池を提供で
きる。[0005] We have studied the application of a gel electrolyte using a crosslinkable polyalkylene oxide to a lithium battery or a lithium ion battery from the viewpoints of liquid retention and film forming properties. In this type of gel electrolyte, the polyalkylene oxide exhibits high liquid retention because it is compatible with the electrolytic solution, and can maintain a film state in a wide temperature range by having a crosslinked structure. Therefore, a lithium battery or a lithium ion battery excellent in reliability and safety can be provided.
【０００６】[0006]
【発明が解決しようとする課題】しかし、ポリアルキレ
ンオキシド系ゲル電解質を用いた電池では、他の高分子
を用いたゲル電解質電池に比べ、充放電における低温特
性あるいはハイレート特性が優れず、電池性能が問題で
あった。However, batteries using a polyalkylene oxide-based gel electrolyte do not have excellent low-temperature characteristics or high-rate characteristics in charge / discharge compared to gel electrolyte batteries using other polymers, and the battery performance is poor. Was a problem.
【０００７】ポリアルキレンオキシド系ゲル電解質は、
アルキレンオキシド／リチウム塩複合体である高分子固
体電解質の有機溶媒による可塑化より発展した材料であ
り、ポリアルキレンオキシド自体がリチウム塩を溶解で
きる。さらに、ポリアルキレンオキシドと同様の構造を
有するエーテル系溶媒は、リチウム電池あるいはリチウ
ムイオン電池用電解液溶媒として一般的に用いれる環状
炭酸エステルおよび鎖状炭酸エステルに比べ、ドナー数
が高いため、優先的にリチウムイオンと配位する可能性
がある。The polyalkylene oxide gel electrolyte is
It is a material developed by plasticizing a polymer solid electrolyte, which is an alkylene oxide / lithium salt composite, with an organic solvent. Polyalkylene oxide itself can dissolve a lithium salt. Furthermore, ether solvents having a structure similar to that of polyalkylene oxide have a higher number of donors than cyclic carbonates and chain carbonates generally used as electrolyte solvents for lithium batteries or lithium ion batteries. May potentially coordinate with lithium ions.
【０００８】このため、ポリアルキレンオキシド系ゲル
電解質において、リチウムイオンはポリアルキレンオキ
シド、有機溶媒あるいはその両方と錯体を形成する可能
性があるが、優先的にポリアルキレンオキシドと錯体を
形成していると予想される。有機溶媒に比べ極端に運動
性の低いポリアルキレンオキシドにリチウムイオンが配
位することにより、ポリアルキレンオキシド系ゲル電解
質ではリチウムイオンの移動性が低下していると考えら
れる。For this reason, in the polyalkylene oxide-based gel electrolyte, lithium ions may form a complex with the polyalkylene oxide, the organic solvent, or both, but the lithium ions are preferentially complexed with the polyalkylene oxide. It is expected to be. It is considered that the mobility of lithium ions is reduced in the polyalkylene oxide-based gel electrolyte due to the coordination of lithium ions to the polyalkylene oxide having extremely low mobility as compared with the organic solvent.
【０００９】これに対し、ＰＡＮ系あるいはＰＶｄＦ系
ゲル電解質において、リチウム塩は高分子自体には難溶
あるいは不溶性を示す。このため、リチウムイオンは高
分子に拘束されず、リチウムイオンの移動性の低下が抑
えられていると考えられる。しかし、ＰＡＮ系ゲル電解
質では高温安定性、ＰＶｄＦ系においては液保持性とい
った問題点がある。本発明は、保液性およびフィルム形
成性に優れ、電池の充放電における低温特性およびハイ
レート特性に優れるゲル電解質を用い、信頼性、安全性
および充放電特性に優れたた電池を提供することを目的
とする。On the other hand, in the PAN-based or PVdF-based gel electrolyte, the lithium salt is hardly soluble or insoluble in the polymer itself. For this reason, it is considered that the lithium ions are not restricted by the polymer, and a decrease in the mobility of the lithium ions is suppressed. However, PAN-based gel electrolytes have problems such as high-temperature stability, and PVdF-based gel electrolytes have problems such as liquid retention. The present invention provides a battery excellent in reliability, safety and charge / discharge characteristics by using a gel electrolyte having excellent liquid retention properties and film forming properties, and excellent low temperature characteristics and high rate characteristics in charge / discharge of the battery. Aim.
【００１０】[0010]
【課題を解決するための手段】上記問題を解決するため
に、本発明は、リチウイオンを吸蔵・放出可能な正極
と、リチウムイオンを吸蔵・放出あるいは析出・溶解可
能な負極、およびゲル電解質を有する電池において、該
ゲル電解質が少なくとも溶媒、溶質および高分子で構成
されており、該高分子が化１および／または化２の化合
物の重合体であることを特徴とするものである。SUMMARY OF THE INVENTION In order to solve the above problems, the present invention comprises a positive electrode capable of inserting and extracting lithium ions, a negative electrode capable of inserting and extracting lithium ions or depositing and dissolving lithium ions, and a gel electrolyte. In the battery, the gel electrolyte is composed of at least a solvent, a solute, and a polymer, and the polymer is a polymer of the compound of Formula 1 and / or Formula 2.
【００１１】[0011]
【化１】 Embedded image
【００１２】[0012]
【化２】 Embedded image
【００１３】ここで、ｌは０あるいは１以上の数、ｍは
１以上の数、Ｒ1 ＝Ｃp Ｈ2p、Ｒ2=Cq Ｈ2q、ｐ≠ｑ、
ｐおよびｑは１以上の整数、ＡはＣＨ2 ＝ＣＨ−ＣＯ−
あるいはＣＨ2 ＝Ｃ（ＣＨ3 ）−ＣＯ−，Ｘはｎ価の連
結基（ｎは１〜４の整数）であり、ｒは０あるいは１以
上の数、ｓは１以上の数、Ｒ3 ＝Ｃt Ｈ2t、Ｒ4 ＝Ｃu
Ｈ2u、ｔ≠ｕ、ｔおよびｕは１以上の整数である。Ｘの
例としては以下のものが挙げられるが、これに限定され
るものではない。[0013] Here, l is 0 or a number of 1 or more, m is a number of 1 or more, R 1 = C p H 2p , R 2 = C q H 2q, p ≠ q,
p and q are integers of 1 or more, and A is CH 2 ＣＨCH—CO—
Alternatively, CH 2 ＣC (CH 3 ) —CO—, X is an n-valent linking group (n is an integer of 1 to 4), r is 0 or 1 or more, s is 1 or more, R 3 = C t H 2t , R 4 = C u
H 2u , t ≠ u, t and u are integers of 1 or more. Examples of X include, but are not limited to:
【００１４】[0014]
【化３】 Embedded image
【００１５】[0015]
【化４】 Embedded image
【００１６】[0016]
【化５】 Embedded image
【００１７】[0017]
【化６】 Embedded image
【００１８】[0018]
【化７】 Embedded image
【００１９】[0019]
【化８】 Embedded image
【００２０】[0020]
【化９】 Embedded image
【００２１】[0021]
【化１０】 Embedded image
【００２２】[0022]
【化１１】 Embedded image
【００２３】化１および化２は、リチウム電池あるいは
リチウムイオン電池で用いられる有機溶媒と類似する構
造であり、リチウムイオンの選択的配位性は有機溶媒と
同程度であると予想される。リチウムイオンが高分子に
選択的に配位しないため、化１および／または化２の重
合体からなるゲル電解質は、ポリアルキレンオキシド系
ゲル電解質に比べ、高いリチウムイオン移動性を有す
る。また、化１および／または化２の重合体は電池用有
機溶媒と相溶性も良好であるため、保液性の優れたゲル
電解質を形成可能である。本発明では、化１および／ま
たは化２の重合体からなるゲル電解質をポリカーボネー
ト系ゲル電解質と呼ぶ。Chemical formulas 1 and 2 have structures similar to organic solvents used in lithium batteries or lithium ion batteries, and the selective coordination of lithium ions is expected to be similar to that of organic solvents. Since lithium ions do not selectively coordinate to the polymer, the gel electrolyte composed of the polymer of Chemical Formula 1 and / or Chemical Formula 2 has higher lithium ion mobility than a polyalkylene oxide gel electrolyte. In addition, the polymer of Chemical Formula 1 and / or Chemical Formula 2 has good compatibility with the organic solvent for batteries, and thus can form a gel electrolyte having excellent liquid retention properties. In the present invention, a gel electrolyte composed of the polymer of Chemical Formula 1 and / or Chemical Formula 2 is referred to as a polycarbonate-based gel electrolyte.
【００２４】ゲル電解質に用いる有機溶媒にはエチレン
カーボネートやプロピレンカーボネート等の環状炭酸エ
ステル、γーブチロラクトン等の環状カルボン酸エステ
ル、テトラヒドロフランや１，３−ジオキソラン等の環
状エーテル、１，２−ジメトキシエタン等の鎖状エーテ
ル、ジメチルカーボネートやエチルメチルカーボネート
等の鎖状炭酸エステル、プロピオン酸メチル等の鎖状カ
ルボン酸エステルなどが挙げられるが、これに限定され
るものではなく、また、２種類以上の混合溶媒を用いる
ことも可能である。また、リチウム塩としては、ＬｉＰ
Ｆ6 、ＬｉＢＦ4 、ＬｉＮ（ＳＯ2 ＣＦ3 ）、ＬｉＯＳ
Ｏ2 ＣＦ3 等が挙げられるが、これに限定されるもので
はない。Examples of the organic solvent used for the gel electrolyte include cyclic carbonates such as ethylene carbonate and propylene carbonate, cyclic carboxylic esters such as γ-butyrolactone, cyclic ethers such as tetrahydrofuran and 1,3-dioxolan, and 1,2-dimethoxyethane. Chain ethers such as dimethyl carbonate and ethyl methyl carbonate, and chain carboxylic esters such as methyl propionate, but are not limited thereto. It is also possible to use a mixed solvent. As the lithium salt, LiP
F 6 , LiBF 4 , LiN (SO 2 CF 3 ), LiOS
O 2 CF 3 and the like, but are not limited thereto.
【００２５】化１および化２の分子量は、化１で１６０
〜１０００００、化２で２２８〜１０００００が適当で
ある。分子量が低すぎると重合体である高分子の架橋密
度が高くなり、高分子膜の柔軟性が低くなる。また、分
子量が高くなりすぎると重合後の高分子の架橋密度が低
くなり、高分子膜の強度が低下する。The molecular weight of Chemical Formula 1 and Chemical Formula 2 is 160
１００100,000, and 228０００100,000 in Chemical Formula 2 are suitable. If the molecular weight is too low, the crosslinking density of the polymer, which is a polymer, becomes high, and the flexibility of the polymer film becomes low. On the other hand, if the molecular weight is too high, the crosslink density of the polymer after polymerization will be low, and the strength of the polymer film will be low.
【００２６】化１および／または化２と共重合体を形成
する他のモノマーとしては以下の化合物等が挙げられる
が、これに限定されるものではない。Other monomers forming a copolymer with Chemical Formula 1 and / or Chemical Formula 2 include, but are not limited to, the following compounds.
【００２７】[0027]
【化１２】 Embedded image
【００２８】[0028]
【化１３】 Embedded image
【００２９】[0029]
【化１４】 Embedded image
【００３０】[0030]
【化１５】 Embedded image
【００３１】[0031]
【化１６】 Embedded image
【００３２】[0032]
【化１７】 Embedded image
【００３３】ここで、ｖおよびｗは１以上の整数を示
す。含有率については、化１および／または化２が共重
合体に対し重量部で５０％以上含有することにより本発
明の効果が得られる。Here, v and w each represent an integer of 1 or more. Regarding the content, the effect of the present invention can be obtained by containing 50% by weight or more of Chemical Formula 1 and / or Chemical Formula 2 with respect to the copolymer.
【００３４】化１および／または化２の重合体とポリマ
ーアロイを形成する他の高分子としてはポリフッ化ビニ
リデン、ポリアクリロニトリル、ポリビニルアルコー
ル、シリコーン樹脂、メタクリル樹脂等が挙げられる
が、これに限定されるものではない。また、含有率にお
いては化１および／または化２がポリマーアロイに対し
重量部で５０％以上含有することにより本発明の効果が
得られる。Other polymers that form a polymer alloy with the polymer of Chemical Formula 1 and / or Chemical Formula 2 include, but are not limited to, polyvinylidene fluoride, polyacrylonitrile, polyvinyl alcohol, silicone resin, methacrylic resin and the like. Not something. Further, with respect to the content, the effect of the present invention can be obtained by containing 50% or more by weight of Chemical Formula 1 and / or Chemical Formula 2 with respect to the polymer alloy.
【００３５】[0035]
【実施例】以下、本発明の実施例について説明する。図
１にゲル電解質におけるリチウムイオン移動性評価用セ
ルの断面図を示す。１および５はステンレス綱集電体で
あり、２および４は４ｃｍ2 のリチウム箔である。３は
評価するゲル電解質であり、６は外装である。２と４の
間に電流値の異なる電流を流した場合の二極間電圧の変
化を測定することにより、ゲル電解質中のリチウムイオ
ンの移動性を評価する。測定は２０℃雰囲気で行った。Embodiments of the present invention will be described below. FIG. 1 shows a cross-sectional view of a cell for evaluating lithium ion mobility in a gel electrolyte. 1 and 5 are stainless steel current collectors, and 2 and 4 are 4 cm 2 lithium foils. Reference numeral 3 denotes a gel electrolyte to be evaluated, and reference numeral 6 denotes an exterior. The mobility of lithium ions in the gel electrolyte is evaluated by measuring the change in the voltage between the two electrodes when a current having a different current value flows between 2 and 4. The measurement was performed in a 20 ° C. atmosphere.
【００３６】（実施例１）化１８で示される平均分子量
約４６００のマクロモノマー、エチレンカーボネート
（ＥＣ）およびγーブチロラクトン（γＢＬ）を重量比
２１．２：３４．８：４４．０の割合で混合した後、１
ｍｏｌ／リットルとなるようにＬｉＢＦ4 を溶解した。(Example 1) A macromonomer having an average molecular weight of about 4600, ethylene carbonate (EC) and γ-butyrolactone (γBL) represented by Chemical Formula 18 were mixed at a weight ratio of 21.2: 34.8: 44.0. After mixing, 1
LiBF 4 was dissolved so as to be mol / liter.
【００３７】[0037]
【化１８】 Embedded image
【００３８】このマクロモノマー／ＥＣ／γＢＬ／Ｌｉ
ＢＦ4 混合溶媒を不織布に含浸し、２枚のＰＥＴフィル
ムで挟んだ後、電子線照射することによりマクロモノマ
ーを重合してゲル電解質を調製した。ゲル電解質の厚み
は１５０μｍとした。今回、ゲル電解質の支持体として
不織布を用いたが、必ずしも不織布や微多孔性膜等を用
いる必要はない。また、ＰＶｄＦ等の高分子をブレンド
することも可能である。 （比較例１）化１９で示される平均分子量約８０００の
マクロモノマー、ＥＣおよびγＢＬを重量比２１．２：
３４．８：４４．０の割合で混合した後、１ｍｏｌ／ｌ
となるようにＬｉＢＦ4 を溶解した。This macromonomer / EC / γBL / Li
The non-woven fabric was impregnated with the BF 4 mixed solvent, sandwiched between two PET films, and irradiated with an electron beam to polymerize the macromonomer to prepare a gel electrolyte. The thickness of the gel electrolyte was 150 μm. In this case, a nonwoven fabric was used as a support for the gel electrolyte, but it is not always necessary to use a nonwoven fabric or a microporous membrane. It is also possible to blend polymers such as PVdF. (Comparative Example 1) A macromonomer having an average molecular weight of about 8000 represented by Chemical Formula 19, EC and γBL were mixed at a weight ratio of 21.2:
After mixing at a ratio of 34.8: 44.0, 1 mol / l
LiBF 4 was dissolved such that
【００３９】[0039]
【化１９】 Embedded image
【００４０】このマクロモノマー／ＥＣ／γＢＬ／Ｌｉ
ＢＦ4 混合溶媒を不織布に含浸し、２枚のＰＥＴフィル
ムで挟んだ後、電子線照射することによりマクロモノマ
ーを重合してゲル電解質を調製した。ゲル電解質の厚み
は１５０μｍとした。This macromonomer / EC / γBL / Li
The non-woven fabric was impregnated with the BF 4 mixed solvent, sandwiched between two PET films, and irradiated with an electron beam to polymerize the macromonomer to prepare a gel electrolyte. The thickness of the gel electrolyte was 150 μm.
【００４１】実施例１および比較例１で調製したゲル電
解質を図１のセルを用いて評価した結果を図２に示す。
横軸は電流密度、縦軸は二極間電圧である。比較例１で
用いたポリアルキレンオキシド系ゲル電解質に比べ、実
施例１で用いたポリカーボネート系ゲル電解質では高い
電流密度においても二極間電圧は低い。このような二極
間電圧変化の違いはリチウムイオンの移動性を反映して
おり、ポリアルキレンオキシド系ゲル電解質に比べ、ポ
リカーボネート系ゲル電解質の高いリチウムイオン移動
性を示唆している。よって、ポリカーボネート系ゲル電
解質を用いた電池ではより高い電流密度での充放電が可
能であると予想される。FIG. 2 shows the results of evaluating the gel electrolytes prepared in Example 1 and Comparative Example 1 using the cell shown in FIG.
The horizontal axis represents the current density, and the vertical axis represents the voltage between the two electrodes. Compared with the polyalkylene oxide gel electrolyte used in Comparative Example 1, the polycarbonate gel electrolyte used in Example 1 has a lower voltage between the two electrodes even at a high current density. Such a difference in the voltage change between the two electrodes reflects the mobility of lithium ions, and suggests a higher lithium ion mobility of the polycarbonate gel electrolyte than the polyalkylene oxide gel electrolyte. Therefore, it is expected that a battery using a polycarbonate gel electrolyte can be charged and discharged at a higher current density.
【００４２】（実施例２）実施例１で調製したゲル電解
質を用いて電池（電池容量約９．４５ｍＡｈ）を作製
し、放電特性を評価した。ゲル電解質の厚みは３０μｍ
とした。この時用いた電池の断面図を図３に示す。ここ
で、７はＡｌ集電体、８は正極活物質であり、１１はＣ
ｕ集電体、１０は負極活物質である。９は評価するゲル
電解質であり、１２は外装である。正極はＬｉＣｏＯ2
活物質、アセチレンブラック（ＡＢ）導電剤およびＰＶ
ｄＦ結着剤からなり、負極はカーボンおよび結着剤から
なる。ここでは電極中に実施例１と異なるゲル電解質を
用いたが、実施例１と同じゲル電解質を用いても良い。Example 2 Using the gel electrolyte prepared in Example 1, a battery (battery capacity: 9.45 mAh) was manufactured, and the discharge characteristics were evaluated. Gel electrolyte thickness is 30μm
And FIG. 3 shows a sectional view of the battery used at this time. Here, 7 is an Al current collector, 8 is a positive electrode active material, and 11 is C
The u current collector 10 is a negative electrode active material. 9 is a gel electrolyte to be evaluated, and 12 is an exterior. The positive electrode is LiCoO 2
Active material, acetylene black (AB) conductive agent and PV
It consists of a dF binder, and the negative electrode consists of carbon and a binder. Here, a gel electrolyte different from that of Example 1 was used in the electrode, but the same gel electrolyte as that of Example 1 may be used.
【００４３】（比較例２）図３で示される電池を用い
て、比較例１で調製したゲル電解質を用いた電池（電池
容量約９．４５ｍＡｈ）の放電特性を評価した。ゲル電
解質の厚みは３０μｍとした。正極はＬｉＣｏＯ2 活物
質、アセチレンブラック（ＡＢ）導電剤およびＰＶｄＦ
結着剤からなり、負極はカーボンおよび結着剤からな
る。電極中には実施例１と同じゲル電解質を用いた。Comparative Example 2 Using the battery shown in FIG. 3, the discharge characteristics of a battery (battery capacity: about 9.45 mAh) using the gel electrolyte prepared in Comparative Example 1 were evaluated. The thickness of the gel electrolyte was 30 μm. The positive electrode is made of LiCoO 2 active material, acetylene black (AB) conductive agent and PVdF
It consists of a binder, and a negative electrode consists of carbon and a binder. The same gel electrolyte as in Example 1 was used in the electrode.
【００４４】実施例２および比較例２で作製した電池を
用いて行った放電試験結果を図４に示す。横軸に放電電
流値、縦軸に放電容量を示す。５ｍＡまでの放電電流値
においては実施例２、比較例２ともに同程度の放電容量
が得られたのに対し、１０ｍＡ放電では放電容量に差が
見られ、ポリカーボネート系ゲル電解質がポリアルキレ
ンオキシド系ゲル電解質に比べハイレート放電に適して
いることがわかる。FIG. 4 shows the results of a discharge test performed using the batteries prepared in Example 2 and Comparative Example 2. The horizontal axis shows the discharge current value, and the vertical axis shows the discharge capacity. At a discharge current value of up to 5 mA, the same discharge capacity was obtained in both Example 2 and Comparative Example 2, whereas a difference was observed in the discharge capacity at 10 mA discharge, and the polycarbonate-based gel electrolyte was replaced with a polyalkylene oxide-based gel. It turns out that it is more suitable for high-rate discharge than the electrolyte.
【００４５】[0045]
【発明の効果】以上のように本発明によれば、電解液用
溶媒に対し相溶性を示し、さらにリチウムイオンの移動
性を抑制しにくい高分子からなるゲル電解質を用いるこ
とにより、信頼性、安全性および充放電特性に優れたた
電池を提供できる。As described above, according to the present invention, the use of a gel electrolyte made of a polymer which is compatible with a solvent for an electrolytic solution and which hardly suppresses the mobility of lithium ions makes it possible to improve reliability and reliability. A battery excellent in safety and charge / discharge characteristics can be provided.
【図１】本発明の実施例および比較例で用いた、ゲル電
解質におけるリチウムイオンの移動性を評価するための
セルの断面図である。FIG. 1 is a cross-sectional view of a cell for evaluating the mobility of lithium ions in a gel electrolyte used in Examples and Comparative Examples of the present invention.
【図２】本発明の実施例および比較例の各種電流密度の
電流を流したときの二極間電圧をプロットした図であ
る。FIG. 2 is a diagram in which voltages between two electrodes are plotted when currents of various current densities are applied in Examples and Comparative Examples of the present invention.
【図３】本発明の実施例および比較例で用いた電池の断
面図である。FIG. 3 is a sectional view of a battery used in Examples of the present invention and Comparative Examples.
【図４】本発明の実施例および比較例の電池における放
電容量を放電電流値に対してプロットした図である。FIG. 4 is a diagram in which discharge capacities of batteries of Examples and Comparative Examples of the present invention are plotted against discharge current values.
１ ステンレス集電体 ２ リチウム箔 ３ ゲル電解質 ４ リチウム箔 ５ ステンレス綱集電体 ６ 外装 ７ Ａｌ集電体 ８ 正極活物質 ９ ゲル電解質 １０ 負極活物質 １１ Ｃｕ集電体 １２ 外装 REFERENCE SIGNS LIST 1 stainless steel current collector 2 lithium foil 3 gel electrolyte 4 lithium foil 5 stainless steel current collector 6 exterior 7 Al current collector 8 positive electrode active material 9 gel electrolyte 10 negative electrode active material 11 Cu current collector 12 exterior
───────────────────────────────────────────────────── フロントページの続き (72)発明者 井土 秀一 大阪府高槻市城西町６番６号 株式会社ユ アサコーポレーション内 Ｆターム(参考） 4J002 CG011 FD206 GQ00 5H029 AJ02 AJ12 AK03 AL06 AL08 AM00 AM03 AM04 AM05 AM07 AM16 BJ04 EJ14 HJ01 HJ02 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shuichi Ido 6-6 Josaicho, Takatsuki-shi, Osaka F-term in Yuasa Corporation (reference) 4J002 CG011 FD206 GQ00 5H029 AJ02 AJ12 AK03 AL06 AL08 AM00 AM03 AM04 AM05 AM07 AM16 BJ04 EJ14 HJ01 HJ02
Claims (5)
と、リチウムイオンを吸蔵・放出あるいは析出・溶解可
能な負極、およびゲル電解質を有する電池において、該
ゲル電解質が少なくとも溶媒、溶質および高分子で構成
されており、該高分子が化１および／または化２の化合
物の重合体であることを特徴とするゲル電解質電池。 【化１】 【化２】 （ここで、ｌは０あるいは１以上の数、ｍは１以上の
数、Ｒ1 ＝Ｃp Ｈ2p、Ｒ2＝Ｃq Ｈ2q、ｐ≠ｑ、ｐおよ
びｑは１以上の整数、ＡはＣＨ2 ＝ＣＨ−ＣＯ−あるい
はＣＨ2 ＝Ｃ（ＣＨ3 ）−ＣＯ−，Ｘはｎ価の連結基
（ｎは１〜４の整数）であり、ｒは０あるいは１以上の
数、ｓは１以上の数、Ｒ3 ＝Ｃt Ｈ2t、Ｒ4 ＝Ｃ
u Ｈ2u、ｔ≠ｕ、ｔおよびｕは１以上の整数である。）1. A battery having a positive electrode capable of occluding / releasing lithium ions, a negative electrode capable of occluding / releasing or depositing / dissolving lithium ions, and a gel electrolyte, wherein the gel electrolyte comprises at least a solvent, a solute and a polymer. A gel electrolyte battery, which is constituted, wherein the polymer is a polymer of the compound of Chemical Formula 1 and / or Chemical Formula 2. Embedded image Embedded image (Where, l is 0 or a number of 1 or more, m is a number of 1 or more, R 1 = C p H 2p , R 2 = C q H 2q, p ≠ q, p and q is an integer of 1 or more, A Is CH 2 ＣＨCH—CO— or CH 2 ＣC (CH 3 ) —CO—, X is an n-valent linking group (n is an integer of 1 to 4), r is 0 or a number of 1 or more, and s Is a number of 1 or more, R 3 = C t H 2t , R 4 = C
u H 2u , t ≠ u, t and u are integers of 1 or more. )
１０００００であることを特徴とする請求項１記載のゲ
ル電解質電池。2. The compound of formula 1 having a molecular weight of 160 to
The gel electrolyte battery according to claim 1, wherein the number is 100,000.
１０００００であることを特徴とする請求項１記載のゲ
ル電解質電池。3. The compound of formula 2 having a molecular weight of 228 to
The gel electrolyte battery according to claim 1, wherein the number is 100,000.
化合物と他のモノマーとの共重合体であり、化１および
／または化２の該高分子中における含有率が重量部で５
０％以上であることを特徴とする請求項１記載のゲル電
解質電池。4. The polymer is a copolymer of a compound of the formula 1 and / or 2 with another monomer, and the content of the compound 1 and / or 2 in the polymer is 5 parts by weight.
The gel electrolyte battery according to claim 1, wherein the content is 0% or more.
化合物と他の高分子とのポリマーアロイであり、化１お
よび／または化２の該高分子中における含有率が重量部
で５０％以上であることを特徴とする請求項１記載のゲ
ル電解質電池。5. The polymer is a polymer alloy of a compound of the formula 1 and / or 2 and another polymer, and the content of the compound of the formula 1 and / or 2 in the polymer is 50 parts by weight. % Or more.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22678898A JP4238386B2 (en) | 1998-08-11 | 1998-08-11 | Gel electrolyte battery |
| EP99937020A EP1026767A4 (en) | 1998-08-11 | 1999-08-11 | Lithium battery, polymer electrolyte, electrolyte material, di(meth)acrylic ester, and di(meth)acrylate polymer |
| PCT/JP1999/004339 WO2000010213A1 (en) | 1998-08-11 | 1999-08-11 | Lithium battery, polymer electrolyte, electrolyte material, di(meth)acrylic ester, and di(meth)acrylate polymer |
| US09/529,273 US6569572B1 (en) | 1998-08-11 | 1999-08-11 | Lithium battery, polymer electrolyte, electrolyte material, di(meth)acrylic ester, and di(meth)acrylate polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22678898A JP4238386B2 (en) | 1998-08-11 | 1998-08-11 | Gel electrolyte battery |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2000058128A true JP2000058128A (en) | 2000-02-25 |
| JP2000058128A5 JP2000058128A5 (en) | 2004-08-19 |
| JP4238386B2 JP4238386B2 (en) | 2009-03-18 |
Family
ID=16850634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22678898A Expired - Fee Related JP4238386B2 (en) | 1998-08-11 | 1998-08-11 | Gel electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4238386B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100428977B1 (en) * | 2001-11-24 | 2004-04-29 | 삼성에스디아이 주식회사 | Polymer electrolyte composition for improving overcharge safety and lithium battery using the same |
| WO2022181460A1 (en) * | 2021-02-25 | 2022-09-01 | 三菱瓦斯化学株式会社 | Resin composition, coating film using same, and electrolyte |
-
1998
- 1998-08-11 JP JP22678898A patent/JP4238386B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100428977B1 (en) * | 2001-11-24 | 2004-04-29 | 삼성에스디아이 주식회사 | Polymer electrolyte composition for improving overcharge safety and lithium battery using the same |
| WO2022181460A1 (en) * | 2021-02-25 | 2022-09-01 | 三菱瓦斯化学株式会社 | Resin composition, coating film using same, and electrolyte |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4238386B2 (en) | 2009-03-18 |
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