JP3416265B2 - Solid electrolyte secondary battery - Google Patents
Solid electrolyte secondary batteryInfo
- Publication number
- JP3416265B2 JP3416265B2 JP13142494A JP13142494A JP3416265B2 JP 3416265 B2 JP3416265 B2 JP 3416265B2 JP 13142494 A JP13142494 A JP 13142494A JP 13142494 A JP13142494 A JP 13142494A JP 3416265 B2 JP3416265 B2 JP 3416265B2
- Authority
- JP
- Japan
- Prior art keywords
- terpolymer
- solid electrolyte
- polymer
- ethylene
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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
Landscapes
- Secondary Cells (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は固体電解質二次電池に係
わり、詳しくは充放電サイクル特性に優れた固体電解質
二次電池を得ることを目的とした、高分子固体電解質又
は高分子ゲル状電解質の改良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid electrolyte secondary battery, and more specifically to a solid polymer electrolyte or a polymer gel electrolyte for the purpose of obtaining a solid electrolyte secondary battery having excellent charge / discharge cycle characteristics. Regarding the improvement of.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】近年、
固体電解質電池が、漏液の心配が無いためにポジション
フリーであること、電解液の注液を必要としないために
電池の組立が容易であることなどの液体電解質電池には
無い利点があることから、注目されている。2. Description of the Related Art In recent years,
There are advantages that liquid electrolyte batteries do not have, such as solid electrolyte batteries that are position-free because there is no risk of liquid leakage, and battery assembly is easy because electrolyte injection is not required. It has been attracting attention.
【０００３】而して、その電解質としては、ＬｉＣｌＯ
4 、ＬｉＢＦ4 等の電解質塩とＰＥＯ（ポリエチレンオ
キシド）とを複合化した高分子固体電解質が提案されて
いる。As the electrolyte, LiClO is used.
A polymer solid electrolyte in which an electrolyte salt such as 4 , LiBF 4 and PEO (polyethylene oxide) is composited has been proposed.
【０００４】しかしながら、ＰＥＯを用いた高分子固体
電解質は、充放電サイクルを繰り返すと、ＰＥＯが負極
のリチウムと反応し、両者の界面に電子伝導性の無いＬ
ｉ2Ｏ等の被膜が生成するため、従来提案されている固
体電解質二次電池には、充放電サイクル特性が良くない
という問題があった。このため、現在実用化されている
固体電解質電池は、心臓ペースメーカーの電源用に使用
されているリチウム電池（一次電池）のみである。However, in the solid polymer electrolyte using PEO, when the charge / discharge cycle is repeated, PEO reacts with lithium of the negative electrode, and the interface between them has no electron conductivity.
Since a film of i 2 O or the like is formed, the conventionally proposed solid electrolyte secondary battery has a problem that the charge / discharge cycle characteristics are not good. Therefore, the only solid electrolyte battery that has been put into practical use at present is the lithium battery (primary battery) used for the power supply of the cardiac pacemaker.
【０００５】本発明は、上述の問題を解決するべくなさ
れたものであって、その目的とするところは、充放電サ
イクル特性に優れた固体電解質二次電池を提供するにあ
る。The present invention has been made to solve the above problems, and an object of the present invention is to provide a solid electrolyte secondary battery having excellent charge / discharge cycle characteristics.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するため
の請求項１記載の発明に係る固体電解質電池（以下、
「第１電池」と称する。）は、正極と、リチウムを活物
質とする負極と、電解質塩及び高分子の複合体からなる
高分子固体電解質とを備える固体電解質二次電池であっ
て、前記高分子が、エチレンオキシド−アクリロニトリ
ル−エポキシ３元共重合体、エチレンオキシド−フッ化
ビニリデン−エチレン３元共重合体、フォスファゼン−
スチレン−シロキサン３元共重合体、ウレタン−エチレ
ンオキシド−スチレン３元共重合体、エチレンオシキド
−フォスファゼン−スチレン３元共重合体、又は、エチ
レンオシキド−フォスファゼン−スルホン３元共重合体
であるものである。In order to achieve the above object, the solid electrolyte battery according to the invention of claim 1 (hereinafter,
It is referred to as the "first battery". ) Is a solid electrolyte secondary battery comprising a positive electrode, a negative electrode using lithium as an active material, and a polymer solid electrolyte composed of a composite of an electrolyte salt and a polymer, wherein the polymer is ethylene oxide-acrylonitril.
Ru-epoxy terpolymer, ethylene oxide-fluoride
Vinylidene-ethylene terpolymer, phosphazene-
Styrene-siloxane terpolymer, urethane-ethylene
Oxide-styrene terpolymer, ethylene oxydide
-Phosphazene-styrene terpolymer or ethylene
It is a terrenoxide-phosphazene-sulfone terpolymer .
【０００７】また、請求項２記載の発明に係る固体電解
質電池（以下、「第２電池」と称する。）は、正極と、
リチウムを活物質とする負極と、高分子に電解質塩と非
プロトン性溶媒とからなる電解液を含浸させてなる高分
子ゲル状電解質とを備える固体電解質二次電池であっ
て、前記高分子が、エチレンオキシド−アクリロニトリ
ル−エポキシ３元共重合体、エチレンオキシド−フッ化
ビニリデン−エチレン３元共重合体、フォスファゼン−
スチレン−シロキサン３元共重合体、ウレタン−エチレ
ンオキシド−スチレン３元共重合体、エチレンオシキド
−フォスファゼン−スチレン３元共重合体、又は、エチ
レンオシキド−フォスファゼン−スルホン３元共重合体
であるものである。なお、高分子ゲル状電解質を用いた
電池は、厳密にはゲル状電解質電池と称すべきかも知れ
ないが、高分子ゲル状電解質は見掛け上固形であるの
で、本明細書ではこれをも固体電解質電池に含める。ま
た、第１電池と第２電池とを本発明電池と総称すること
がある。A solid electrolyte battery (hereinafter, referred to as a "second battery") according to a second aspect of the present invention includes a positive electrode,
A solid electrolyte secondary battery comprising a negative electrode using lithium as an active material, and a polymer gel electrolyte obtained by impregnating a polymer with an electrolyte solution comprising an electrolyte salt and an aprotic solvent, wherein the polymer is , Ethylene oxide-acrylonitrile
Ru-epoxy terpolymer, ethylene oxide-fluoride
Vinylidene-ethylene terpolymer, phosphazene-
Styrene-siloxane terpolymer, urethane-ethylene
Oxide-styrene terpolymer, ethylene oxydide
-Phosphazene-styrene terpolymer or ethylene
It is a terrenocidide-phosphazene-sulfone terpolymer . The battery using the polymer gel electrolyte may be strictly called a gel electrolyte battery, but since the polymer gel electrolyte is apparently solid, this is also referred to as a solid electrolyte in this specification. Include in battery. Further, the first battery and the second battery may be collectively referred to as the battery of the present invention.
【０００８】第１電池は、電解質として電解質塩と特定
の３元共重合体との複合体からなる高分子固体電解質を
用いた固体電解質電池であり、また第２電池は、電解質
として電解質塩と非プロトン性溶媒とからなる電解液を
特定の３元共重合体に含浸させてなる高分子ゲル状電解
質を用いた固体電解質電池である。The first battery is a solid electrolyte battery using a polymer solid electrolyte composed of a composite of an electrolyte salt and a specific terpolymer as the electrolyte, and the second battery is an electrolyte salt as the electrolyte. It is a solid electrolyte battery using a polymer gel electrolyte obtained by impregnating a specific ternary copolymer with an electrolytic solution containing an aprotic solvent.
【０００９】本発明電池におけるリチウムを活物質とす
る負極としては、金属リチウム又はリチウムを吸蔵放出
可能な、合金、酸化物、炭素材料が例示される。リチウ
ムを吸蔵放出可能な合金としては、リチウム−アルミニ
ウム合金、リチウム−インジウム合金、リチウム−錫合
金、リチウム−鉛合金、リチウム−ビスマス合金、リチ
ウム−ガリウム合金、リチウム−亜鉛合金、リチウム−
カドミウム合金、リチウム−珪素合金、リチウム−カル
シウム合金、リチウム−バリウム合金、リチウム−スト
ロンチウム合金が、リチウムを吸蔵放出可能な酸化物と
しては、酸化鉄、酸化錫、酸化ニオビウム、酸化タング
ステン、酸化チタンが、またリチウムを吸蔵放出可能な
炭素材料としては、コークス、黒鉛、有機物焼成体が、
それぞれ例示される。Examples of the negative electrode using lithium as an active material in the battery of the present invention include metallic lithium or alloys, oxides and carbon materials capable of inserting and extracting lithium. As an alloy capable of inserting and extracting lithium, lithium-aluminum alloy, lithium-indium alloy, lithium-tin alloy, lithium-lead alloy, lithium-bismuth alloy, lithium-gallium alloy, lithium-zinc alloy, lithium-
Cadmium alloys, lithium-silicon alloys, lithium-calcium alloys, lithium-barium alloys, lithium-strontium alloys, as oxides capable of occluding and releasing lithium, iron oxide, tin oxide, niobium oxide, tungsten oxide, titanium oxide. As the carbon material capable of occluding and releasing lithium, coke, graphite, and a fired organic material are
Each is illustrated.
【００１０】本発明電池における正極の活物質は特に制
限されず、例えばマンガン、コバルト、ニッケル、バナ
ジウム及びニオブから選ばれた少なくとも１種の金属を
含有する金属酸化物が挙げられる。The active material for the positive electrode in the battery of the present invention is not particularly limited, and examples thereof include metal oxides containing at least one metal selected from manganese, cobalt, nickel, vanadium and niobium.
【００１１】本発明電池における３元共重合体は、エチ
レンオキシド−アクリロニトリル−エポキシ３元共重合
体、エチレンオキシド−フッ化ビニリデン−エチレン３
元共重合体、フォスファゼン−スチレン−シロキサン３
元共重合体、ウレタン−エチレンオキシド−スチレン３
元共重合体、エチレンオシキド−フォスファゼン−スチ
レン３元共重合体、又は、エチレンオシキド−フォスフ
ァゼン−スルホン３元共重合体である。 The ternary copolymer in the battery of the present invention is ethylene oxide-acrylonitrile-epoxy terpolymer, ethylene oxide-vinylidene fluoride-ethylene 3
Original copolymer, phosphazene-styrene-siloxane 3
Original copolymer, urethane-ethylene oxide-styrene 3
It is a terpolymer, an ethylene osquid-phosphazene-styrene terpolymer, or an ethylene osquid-phosphazene-sulfone terpolymer .
【００１２】本発明電池における電解質塩としては、過
塩素酸リチウム（ＬｉＣｌＯ4 ）、トリフルオロメタン
スルホン酸リチウム（ＬｉＣＦ3 ＳＯ3 ）、六フッ化リ
ン酸リチウム（ＬｉＰＦ6 ）、四フッ化ホウ酸リチウム
（ＬｉＢＦ4 ）、六フッ化ヒ酸リチウム（ＬｉＡｓ
Ｆ6 ）、六フッ化アンチモン酸リチウム（ＬｉＳｂ
Ｆ6 ）、リチウムトリフルオロメタンスルホン酸イミド
〔ＬｉＮ（ＣＦ3 ＳＯ2 ）2 〕が例示される。The electrolyte salt in the battery of the present invention includes lithium perchlorate (LiClO 4 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate. (LiBF 4 ), lithium hexafluoroarsenate (LiAs
F 6 ), lithium hexafluoroantimonate (LiSb
F 6), lithium trifluoromethanesulfonate imide [LiN (CF 3 SO 2) 2] are exemplified.
【００１３】第２電池における非プロトン性溶媒として
は、エチレンカーボネート（ＥＣ）、プロピレンカーボ
ネート（ＰＣ）、ブチレンカーボネート（ＢＣ）、γ−
ブチロラクトン（γ−ＢＬ）、スルホラン（ＳＬ）、
１，２−ジメトキシエタン（ＤＭＥ）、１，２−ジエト
キシエタン（ＤＥＥ）、エトキシメトキシエタン（ＥＭ
Ｃ）、テトラヒドロフラン（ＴＨＦ）、２−メチルテト
ラヒドロフラン（２Ｍ−ＴＨＦ）、１，３−ジオキソラ
ン（ＤＯＸＬ）、４−メチル−１，３−ジオキソラン
（４Ｍ−ＤＯＸＬ）が例示される。As the aprotic solvent in the second battery, ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), γ-
Butyrolactone (γ-BL), sulfolane (SL),
1,2-dimethoxyethane (DME), 1,2-diethoxyethane (DEE), ethoxymethoxyethane (EM
C), tetrahydrofuran (THF), 2-methyltetrahydrofuran (2M-THF), 1,3-dioxolane (DOXL) and 4-methyl-1,3-dioxolane (4M-DOXL) are exemplified.
【００１４】[0014]
【作用】充放電サイクルを繰り返しても内部抵抗が上昇
しにくいので、従来の固体電解質電池と比較して、放電
容量が低下しにくい。負極と高分子固体電解質又は高分
子ゲル状電解質とが反応しにくく、それゆえ両者の界面
に電子伝導性の無いＬｉ2 Ｏ等の被膜が生成しにくいた
めと推察される。[Function] Since the internal resistance is unlikely to increase even if the charge / discharge cycle is repeated, the discharge capacity is less likely to decrease as compared with the conventional solid electrolyte battery. It is presumed that the negative electrode and the polymer solid electrolyte or the polymer gel electrolyte are less likely to react with each other, and thus a film of Li 2 O or the like having no electron conductivity is less likely to be formed at the interface between the both.
【００１５】[0015]
【実施例】以下、本発明を実施例に基づいてさらに詳細
に説明するが、本発明は下記実施例に何ら限定されるも
のではなく、その要旨を変更しない範囲において適宜変
更して実施することが可能なものである。EXAMPLES The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to the following examples, and various modifications may be made without departing from the scope of the invention. Is possible.
【００１６】（実施例１〜６：第１電池）
〔正極〕正極活物質としての二酸化マンガンと、導電剤
としての黒鉛粉末と、ＰＴＦＥ（ポリテトラフルオロエ
チレン）とを重量比８：１：１で混合して正極合剤を調
製し、これを円板状に成形し、１００°Ｃで真空乾燥し
て、正極を作製した。(Examples 1 to 6) First battery [Positive electrode] Manganese dioxide as a positive electrode active material, graphite powder as a conductive agent, and PTFE (polytetrafluoroethylene) in a weight ratio of 8: 1: 1. Was mixed to prepare a positive electrode mixture, which was molded into a disk shape and vacuum dried at 100 ° C. to prepare a positive electrode.
【００１７】〔負極〕リチウム−アルミニウム合金を用
いた。[Anode] A lithium-aluminum alloy was used.
【００１８】〔高分子固体電解質〕化１〜化６に構造式
を示す平均分子量約６万の各種の３元共重合体９３重量
部を、アセトニトリルに溶かして溶液を調製し、この溶
液にＬｉＣｌＯ4 ７重量部を加えて混合し、これをステ
ンレス製のシャーレ上にキャストし、減圧乾燥してアセ
トニトリルを除去した後、１００°Ｃで加熱乾燥して、
高分子固体電解質を作製した。実施例１〜６で使用した
３元共重合体は化１〜化６中のｎとｍとｌが１：１：１
の比率のものである。[Polymer Solid Electrolyte] 93 parts by weight of various terpolymers having an average molecular weight of about 60,000, whose structural formulas are shown in Chemical formulas 1 to 6, are dissolved in acetonitrile to prepare a solution, and LiClO is added to the solution. 4 7 parts by weight was added and it was cast on a stainless steel dish, after removing the acetonitrile and dried under reduced pressure, and dried by heating at 100 ° C,
A polymer solid electrolyte was prepared. In the terpolymers used in Examples 1 to 6, n, m and l in Chemical Formulas 1 to 6 are 1: 1: 1.
It is the ratio of.
【００１９】[0019]
【化１】 [Chemical 1]
【００２０】[0020]
【化２】 [Chemical 2]
【００２１】[0021]
【化３】 [Chemical 3]
【００２２】[0022]
【化４】 [Chemical 4]
【００２３】[0023]
【化５】 [Chemical 5]
【００２４】[0024]
【化６】 [Chemical 6]
【００２５】〔固体電解質電池〕上記の正極、負極及び
各高分子固体電解質を用いて、順に、扁平型の固体電解
質電池Ａ１〜Ａ６（第１電池；理論容量：３０ｍＡｈ／
ｇ−電池重量；電池寸法：直径２０ｍｍ、厚さ１．６ｍ
ｍ）を組み立てた。[Solid Electrolyte Battery] Flat type solid electrolyte batteries A1 to A6 (first battery; theoretical capacity: 30 mAh /
g-Battery weight; Battery dimensions: diameter 20 mm, thickness 1.6 m
m) was assembled.
【００２６】（実施例７〜１２：第２電池）表２に示す
各種の３元共重合体フィルムを、プロピレンカーボネー
トにＬｉＣｌＯ4 を１モル／リットル溶かした溶液（電
解液）に浸漬して膨潤させ、高分子ゲル状電解質を作製
した。なお、含浸せる電解液と各フィルムとの重量比は
全て４：１とした。次いで、これらの高分子ゲル状電解
質を用いたこと以外は実施例１〜６と同様にして、固体
電解質電池Ａ７〜Ａ１２（第２電池）を組み立てた。(Examples 7 to 12: Second battery) Various terpolymer films shown in Table 2 were swollen by immersing them in a solution (electrolytic solution) in which 1 mol / liter of LiClO 4 was dissolved in propylene carbonate. Then, a polymer gel electrolyte was prepared. The weight ratio of the electrolyte to be impregnated and each film was 4: 1. Next, solid electrolyte batteries A7 to A12 (second battery) were assembled in the same manner as in Examples 1 to 6 except that these polymer gel electrolytes were used.
【００２７】（比較例１）平均分子量約６万のポリエチ
レンオキシド〔−（ＣＨ2 −ＣＨ2 −Ｏ）n −〕９３重
量部を、アセトニトリルに溶かして溶液を調製し、この
溶液にＬｉＣｌＯ4 ７重量部を加え、これをステンレス
製のシャーレ上にキャストし、減圧乾燥してアセトニト
リルを除去した後、１００°Ｃで加熱乾燥して、高分子
固体電解質を作製した。この高分子固体電解質を用いた
こと以外は実施例１〜６と同様にして、固体電解質電池
Ｂ１を組み立てた。Comparative Example 1 93 parts by weight of polyethylene oxide [— (CH 2 —CH 2 —O) n −] having an average molecular weight of about 60,000 was dissolved in acetonitrile to prepare a solution, and LiClO 4 7 was added to this solution. Parts by weight were added, and this was cast on a stainless petri dish, dried under reduced pressure to remove acetonitrile, and then dried by heating at 100 ° C. to prepare a polymer solid electrolyte. A solid electrolyte battery B1 was assembled in the same manner as in Examples 1 to 6 except that this polymer solid electrolyte was used.
【００２８】（比較例２〜４）ＬｉＣｌＯ4 を、エチレ
ンカーボネートと１，２−ジメトキシエタンとの体積比
３：２の混合溶媒（比較例２）、エチレンカーボネート
とテトラヒドロフランとの体積比３：２の混合溶媒（比
較例３）又はエチレンカーボネートと１，２−ジメトキ
シエタンとテトラヒドロフランとの体積比３：１：１の
混合溶媒（比較例４）に１モル／リットル溶かした溶液
を電解液として用いて、順に液体電解質電池Ｂ２〜Ｂ４
を組み立てた。セパレータとしては、ポリプロピレン製
の不織布を用いた。(Comparative Examples 2 to 4) LiClO 4 was mixed with ethylene carbonate and 1,2-dimethoxyethane in a volume ratio of 3: 2 (Comparative Example 2), and ethylene carbonate and tetrahydrofuran in a volume ratio of 3: 2. 1 mol / liter of a mixed solvent (Comparative Example 3) or a mixed solvent (Comparative Example 4) of ethylene carbonate, 1,2-dimethoxyethane and tetrahydrofuran in a volume ratio of 3: 1: 1 was used as an electrolytic solution. , In order, liquid electrolyte batteries B2 to B4
Assembled. A polypropylene non-woven fabric was used as the separator.
【００２９】（比較例５）ポリエチレンオキシドフィル
ムを、プロピレンカーボネートにＬｉＣｌＯ4 を１モル
／リットル溶かした溶液（電解液）に浸漬して膨潤さ
せ、高分子ゲル状電解質を作製した。なお、含浸せる電
解液とポリエチレンオキシドフィルムとの重量比は全て
４：１とした。次いで、この高分子ゲル状電解質を用い
たこと以外は実施例１〜６と同様にして、固体電解質電
池Ｂ５を組み立てた。Comparative Example 5 A polyethylene oxide film was prepared by immersing a polyethylene oxide film in a solution (electrolyte) of LiClO 4 dissolved in propylene carbonate at 1 mol / l to swell it. The weight ratio of the electrolytic solution to be impregnated and the polyethylene oxide film was 4: 1. Then, a solid electrolyte battery B5 was assembled in the same manner as in Examples 1 to 6 except that this polymer gel electrolyte was used.
【００３０】〈分解電流〉各電解質と、作用極としての
白金電極と、対極及び参照極としてのリチウム電極とを
用いて、試験セルを組み立て、次いで白金電極の電位を
０Ｖ対参照極（Ｌｉ／Ｌｉ+ ）に設定したときの還元電
流（分解電流μＡ／ｃｍ2 ）を測定して、各電解質の分
解性の難易を調べた。分解電流が大きいほど、電解質が
分解し易いことを表す。結果を表１及び表２に示す。<Decomposition current> A test cell was assembled using each electrolyte, a platinum electrode as a working electrode, and a lithium electrode as a counter electrode and a reference electrode, and then the potential of the platinum electrode was set to 0 V vs. the reference electrode (Li / The reduction current (decomposition current μA / cm 2 ) when set to Li + ) was measured to examine the difficulty of the decomposability of each electrolyte. The larger the decomposition current, the easier the electrolyte is to decompose. The results are shown in Tables 1 and 2.
【００３１】[0031]
【表１】 [Table 1]
【００３２】[0032]
【表２】 [Table 2]
【００３３】表１より、実施例１〜６で作製した高分子
固体電解質は、比較例２〜４で作製した液体電解質はも
とより、比較例１で作製した従来の高分子固体電解質と
比較して、分解電流が小さいことから、分解しにくいこ
とが分かる。また、表２より、実施例７〜１２で作製し
た高分子ゲル状電解質は、比較例５で作製した従来の高
分子ゲル状電解質と比較して、分解電流が小さいことか
ら、分解しにくいことが分かる。From Table 1, the polymer solid electrolytes prepared in Examples 1 to 6 are compared with the liquid polymer electrolytes prepared in Comparative Examples 2 to 4 as well as the conventional polymer solid electrolytes prepared in Comparative Example 1. It can be seen that the decomposition current is small, which makes it difficult to decompose. In addition, from Table 2, the polymer gel electrolytes produced in Examples 7 to 12 are less likely to be decomposed as compared with the conventional polymer gel electrolytes produced in Comparative Example 5 because the decomposition current is smaller. I understand.
【００３４】〈５０サイクル目の放電容量〉各電池につ
いて、室温（２５°Ｃ）下にて、０．５ｍＡ／ｃｍ2 で
３．２０Ｖまで充電した後、０．５ｍＡ／ｃｍ2 で２．
００Ｖまで放電する工程を１サイクルとする充放電サイ
クル試験を行い、５０サイクル目の放電容量を求めた。
結果を先の表１及び表２に示す。<Discharge Capacity at 50th Cycle> Each battery was charged at room temperature (25 ° C.) at 0.5 mA / cm 2 to 3.20 V, and then at 0.5 mA / cm 2 2.
A charging / discharging cycle test in which the step of discharging to 00 V was defined as one cycle was performed, and the discharge capacity at the 50th cycle was obtained.
The results are shown in Tables 1 and 2 above.
【００３５】表１及び表２より、分解電流が小さい高分
子固体電解質又は高分子ゲル状電解質を用いた固体電解
質電池Ａ１〜Ａ１２（本発明電池）は、分解電流が大き
い高分子固体電解質、液体電解質又は高分子ゲル状電解
質を用いた電池Ｂ１〜Ｂ５（比較電池）に比し、５０サ
イクル目の放電容量が大きく、充放電サイクル特性に優
れていることが分かる。From Tables 1 and 2, solid electrolyte batteries A1 to A12 (invention batteries) using polymer solid electrolytes or polymer gel electrolytes having small decomposition currents are polymer solid electrolytes and liquids having large decomposition currents. It can be seen that the discharge capacity at the 50th cycle is large and the charge / discharge cycle characteristics are excellent as compared with the batteries B1 to B5 (comparative batteries) using the electrolyte or the polymer gel electrolyte.
【００３６】[0036]
【発明の効果】使用せる高分子固体電解質又は高分子ゲ
ル状電解質が負極と反応しにくく、充放電サイクルを繰
り返しても内部抵抗が上昇しにくいので、充放電サイク
ル特性に優れる。The polymer solid electrolyte or polymer gel electrolyte to be used is less likely to react with the negative electrode, and the internal resistance is unlikely to rise even after repeated charge / discharge cycles, so that the charge / discharge cycle characteristics are excellent.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 西尾 晃治 大阪府守口市京阪本通２丁目５番５号 三洋電機株式会社内 (72)発明者 斎藤 俊彦 大阪府守口市京阪本通２丁目５番５号 三洋電機株式会社内 (56)参考文献 特開 平５−299119（ＪＰ，Ａ) 特開 平６−52893（ＪＰ，Ａ) 特開 平６−124728（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 10/40 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Koji Nishio 2-5-5 Keihanhondori, Moriguchi-shi, Osaka Sanyo Denki Co., Ltd. (72) Toshihiko Saito 2-5-5 Keihanhondori, Moriguchi-shi, Osaka No. 5 within Sanyo Electric Co., Ltd. (56) Reference JP-A-5-299119 (JP, A) JP-A-6-52893 (JP, A) JP-A-6-124728 (JP, A) (58) Field (Int.Cl. 7 , DB name) H01M 10/40
Claims (2)
電解質塩及び高分子の複合体からなる高分子固体電解質
とを備える固体電解質二次電池であって、前記高分子
が、エチレンオキシド−アクリロニトリル−エポキシ３
元共重合体、エチレンオキシド−フッ化ビニリデン−エ
チレン３元共重合体、フォスファゼン−スチレン−シロ
キサン３元共重合体、ウレタン−エチレンオキシド−ス
チレン３元共重合体、エチレンオシキド−フォスファゼ
ン−スチレン３元共重合体、又は、エチレンオシキド−
フォスファゼン−スルホン３元共重合体であることを特
徴とする固体電解質二次電池。1. A positive electrode, a negative electrode using lithium as an active material,
What is claimed is: 1. A solid electrolyte secondary battery comprising a polymer solid electrolyte comprising a composite of an electrolyte salt and a polymer, wherein the polymer is ethylene oxide-acrylonitrile-epoxy 3
Original copolymer, ethylene oxide-vinylidene fluoride-E
Tylene terpolymer, phosphazene-styrene-silo
Xan terpolymer, urethane-ethylene oxide
Tylene terpolymer, ethylene osquid-phosphase
-Styrene terpolymer or ethylene oxide
A solid electrolyte secondary battery comprising a phosphazene-sulfone terpolymer .
高分子に電解質塩と非プロトン性溶媒とからなる電解液
を含浸させてなる高分子ゲル状電解質とを備える固体電
解質二次電池であって、前記高分子が、エチレンオキシ
ド−アクリロニトリル−エポキシ３元共重合体、エチレ
ンオキシド−フッ化ビニリデン−エチレン３元共重合
体、フォスファゼン−スチレン−シロキサン３元共重合
体、ウレタン−エチレンオキシド−スチレン３元共重合
体、エチレンオシキド−フォスファゼン−スチレン３元
共重合体、又は、エチレンオシキド−フォスファゼン−
スルホン３元共重合体であることを特徴とする固体電解
質二次電池。2. A positive electrode, a negative electrode using lithium as an active material,
A solid electrolyte secondary battery comprising a polymer gel electrolyte obtained by impregnating a polymer with an electrolyte solution comprising an electrolyte salt and an aprotic solvent, wherein the polymer is ethyleneoxy
Do-acrylonitrile-epoxy terpolymer, ethylene
Oxide-vinylidene fluoride-ethylene terpolymer
Body, phosphazene-styrene-siloxane terpolymer
Body, urethane-ethylene oxide-styrene terpolymer
Body, ethylene oxykid-phosphazene-styrene ternary
Copolymer or ethylene osquid-phosphazene-
A solid electrolyte secondary battery, which is a sulfone terpolymer .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13142494A JP3416265B2 (en) | 1994-05-20 | 1994-05-20 | Solid electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13142494A JP3416265B2 (en) | 1994-05-20 | 1994-05-20 | Solid electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07320782A JPH07320782A (en) | 1995-12-08 |
| JP3416265B2 true JP3416265B2 (en) | 2003-06-16 |
Family
ID=15057644
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13142494A Expired - Fee Related JP3416265B2 (en) | 1994-05-20 | 1994-05-20 | Solid electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3416265B2 (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999026308A1 (en) * | 1997-11-19 | 1999-05-27 | Mitsubishi Denki Kabushiki Kaisha | Bonding agent for cells and cell using the same |
| KR100644850B1 (en) * | 1998-11-30 | 2006-11-10 | 소니 가부시키가이샤 | Non-Aqueous Electrolyte Secondary Cell |
| KR100502321B1 (en) * | 1998-12-16 | 2005-09-26 | 삼성에스디아이 주식회사 | Composition for forming polymer matrix for lithium secondary battery, lithium secondary battery employing polymer matrix formed using said composition and method for manufacturing said battery |
| KR100382069B1 (en) * | 2000-09-05 | 2003-04-26 | 삼성에스디아이 주식회사 | Manufacturing method for lithium secondary battery |
| US7695860B2 (en) | 2002-03-22 | 2010-04-13 | Quallion Llc | Nonaqueous liquid electrolyte |
| US7498102B2 (en) | 2002-03-22 | 2009-03-03 | Bookeun Oh | Nonaqueous liquid electrolyte |
| US6887619B2 (en) | 2002-04-22 | 2005-05-03 | Quallion Llc | Cross-linked polysiloxanes |
| US7008564B2 (en) * | 2002-07-11 | 2006-03-07 | Battelle Energy Alliance, Llc | Cured composite materials for reactive metal battery electrolytes |
| US7588859B1 (en) | 2004-02-11 | 2009-09-15 | Bookeun Oh | Electrolyte for use in electrochemical devices |
| US8076032B1 (en) | 2004-02-04 | 2011-12-13 | West Robert C | Electrolyte including silane for use in electrochemical devices |
| US20070065728A1 (en) | 2003-03-20 | 2007-03-22 | Zhengcheng Zhang | Battery having electrolyte with mixed solvent |
| US8076031B1 (en) | 2003-09-10 | 2011-12-13 | West Robert C | Electrochemical device having electrolyte including disiloxane |
| US7718321B2 (en) | 2004-02-04 | 2010-05-18 | Quallion Llc | Battery having electrolyte including organoborate salt |
| US7473491B1 (en) | 2003-09-15 | 2009-01-06 | Quallion Llc | Electrolyte for electrochemical cell |
| US9786954B2 (en) | 2004-02-04 | 2017-10-10 | Robert C. West | Electrolyte including silane for use in electrochemical devices |
| US8153307B1 (en) | 2004-02-11 | 2012-04-10 | Quallion Llc | Battery including electrolyte with mixed solvent |
| KR101309161B1 (en) | 2009-11-17 | 2013-09-17 | 삼성에스디아이 주식회사 | Polymer composition for rechargeable lithium battery, method of preparing same and rechargeable lithium battery including same |
| KR102217108B1 (en) * | 2017-11-30 | 2021-02-18 | 주식회사 엘지화학 | Composition for gel polymer electrolyte, gel polymer electrolyte and lithium secondary battery comprising the same |
-
1994
- 1994-05-20 JP JP13142494A patent/JP3416265B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07320782A (en) | 1995-12-08 |
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