JP3369920B2 - Polymer electrolyte battery - Google Patents
Polymer electrolyte batteryInfo
- Publication number
- JP3369920B2 JP3369920B2 JP23966997A JP23966997A JP3369920B2 JP 3369920 B2 JP3369920 B2 JP 3369920B2 JP 23966997 A JP23966997 A JP 23966997A JP 23966997 A JP23966997 A JP 23966997A JP 3369920 B2 JP3369920 B2 JP 3369920B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer electrolyte
- electrolyte battery
- substrate
- battery
- positive electrode
- 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]
【発明の属する技術分野】この発明は、正極と、負極
と、ポリマー電解質とを備えたポリマー電解質電池に係
り、ポリマー電解質基材に非水電解液を含浸させたポリ
マー電解質を用いるにあたって、このポリマー電解質に
おけるポリマー電解質基材を改善し、ポリマー電解質電
池における充放電サイクル特性を向上させるようにした
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer electrolyte battery provided with a positive electrode, a negative electrode and a polymer electrolyte, and in using a polymer electrolyte obtained by impregnating a polymer electrolyte substrate with a non-aqueous electrolyte, It is intended to improve a polymer electrolyte base material in an electrolyte to improve charge / discharge cycle characteristics in a polymer electrolyte battery.
【０００２】[0002]
【従来の技術】近年、高出力，高エネルギー密度の新型
電池の１つとして、電解液に非水電解液を用い、リチウ
ムの酸化，還元を利用した高起電力の非水電解質電池が
利用されるようになった。2. Description of the Related Art In recent years, as one of new type batteries with high output and high energy density, a non-aqueous electrolyte battery of high electromotive force using a non-aqueous electrolyte as an electrolyte and utilizing oxidation and reduction of lithium has been used. It became so.
【０００３】また、近年においては、上記のような電解
液の漏液や電解液による腐食等を抑制するため、上記の
ような非水電解液をポリマー電解質基材に含浸させたポ
リマー電解質を用いたポリマー電解質電池が注目される
ようになった。Further, in recent years, in order to suppress the leakage of the electrolytic solution and the corrosion due to the electrolytic solution as described above, a polymer electrolyte in which a polymer electrolyte substrate is impregnated with the nonaqueous electrolytic solution as described above is used. The polymer electrolyte battery, which had been used, has come to the fore.
【０００４】ここで、このようなポリマー電解質電池に
おけるポリマー電解質として、従来においては、一般
に、ＬｉＰＦ6 等のリチウム塩を炭酸エステル等の有機
溶媒に溶解させた非水電解液を、ポリエチレンオキシド
やポリフッ化ビニリデン等のポリマー電解質基材に含浸
させたものが用いられていた。Here, as a polymer electrolyte in such a polymer electrolyte battery, heretofore, generally, a non-aqueous electrolytic solution prepared by dissolving a lithium salt such as LiPF 6 in an organic solvent such as carbonic acid ester was used as polyethylene oxide or polyfluoride. Those impregnated with a polymer electrolyte substrate such as vinylidene chloride have been used.
【０００５】しかし、ポリマー電解質基材として従来使
用されているポリエチレンオキシドやポリフッ化ビニリ
デン等は、リチウムイオンと反応しやすく、この反応に
よってポリマー電解質電池における充放電サイクル特性
が低下するという問題があった。However, polyethylene oxide, polyvinylidene fluoride, etc., which have been conventionally used as a polymer electrolyte base material, easily react with lithium ions, and this reaction has a problem that charge / discharge cycle characteristics in a polymer electrolyte battery are deteriorated. .
【０００６】また、近年においては、特開平６−５２８
９３号公報に示されるように、ポリマー電解質基材とし
て、ポリエチレンオキシドとポリシロキサンとを用いた
ものが提案された。In recent years, Japanese Patent Laid-Open No. 6-528.
As disclosed in Japanese Patent Laid-Open No. 93, a polymer electrolyte substrate using polyethylene oxide and polysiloxane has been proposed.
【０００７】ここで、同公報において使用されているポ
リシロキサンは、ガラス転移点が低い粘ちょうな液体で
あって、固体電解質のガラス転移点を低下させる目的で
使用されており、このようなポリシロキサンをポリエチ
レンオキシドと一緒に使用した場合、電極との密着性が
優れるが、ポリマー電解質としての機械的強度が低くな
り、充放電時にこのポリマー電解質が破損する等によ
り、充放電サイクル特性が低下するという問題があっ
た。The polysiloxane used in this publication is a viscous liquid having a low glass transition point and is used for the purpose of lowering the glass transition point of a solid electrolyte. When siloxane is used together with polyethylene oxide, the adhesion with the electrode is excellent, but the mechanical strength as a polymer electrolyte is low, and the polymer electrolyte is damaged during charge / discharge, etc., resulting in deterioration of charge / discharge cycle characteristics. There was a problem.
【０００８】[0008]
【発明が解決しようとする課題】この発明は、正極と、
負極と、ポリマー電解質とを備えるポリマー電解質電池
おいて、ポリマー電解質基材に非水電解液が含浸された
ポリマー電解質を使用した場合における上記のような問
題を解決することを課題とするものであり、ポリマー電
解質の機能を低下させることなく、このポリマー電解質
の機械的強度を向上させて、充放電時におけるポリマー
電解質の破損等を抑制し、充放電サイクル特性に優れた
ポリマー電解質電池が得られるようにすることを課題と
するものである。SUMMARY OF THE INVENTION The present invention comprises a positive electrode,
In a polymer electrolyte battery comprising a negative electrode and a polymer electrolyte, it is an object to solve the above problems in the case of using a polymer electrolyte impregnated with a non-aqueous electrolyte solution to the polymer electrolyte substrate. In order to obtain a polymer electrolyte battery having excellent charge / discharge cycle characteristics, it is possible to improve the mechanical strength of the polymer electrolyte without deteriorating the function of the polymer electrolyte, suppress damage to the polymer electrolyte during charge / discharge, etc. The task is to
【０００９】[0009]
【課題を解決するための手段】この発明におけるポリマ
ー電解質電池においては、上記のような課題を解決する
ため、正極と、負極と、ポリマー電解質とを備えたポリ
マー電解質電池において、ポリマー電解質基材に非水電
解液が含浸されたポリマー電解質を用いるにあたり、こ
のポリマー電解質基材として、少なくともシリコーンゴ
ムとポリオレフィンとが共重合されたものを用いると共
に、このポリマー電解質基材中に、シリコーンゴムを５
０重量％以上、ポリオレフィンを２０重量％〜４０重量
％の範囲で含有させるようにしたのである。In order to solve the above problems, in a polymer electrolyte battery according to the present invention, a polymer electrolyte battery comprising a positive electrode, a negative electrode and a polymer electrolyte is used as a polymer electrolyte substrate. When using a polymer electrolyte impregnated with a non-aqueous electrolyte , at least a silicone rubber is used as the polymer electrolyte substrate.
When a copolymer of polyolefin and polyolefin is used,
In this polymer electrolyte substrate , 5
0% by weight or more , 20% by weight to 40% by weight of polyolefin
It was made to contain in the range of% .
【００１０】ここで、ポリマー電解質基材に用いる上記
のシリコーンゴムは、オルガノポリシロキサンに硬化剤
等を加えて架橋させたものであり、Ｓｉに結合したメチ
ル基の一部が相互に結合してメチレン架橋されたものと
考えられており、このようなシリコーンゴムを少なくと
もポリオレフィンと共重合させて、ポリマー電解質基材
中に５０重量％以上含有させると、このシリコーンゴム
によってポリマー電解質の機械的強度が増大し、充放電
時におけるポリマー電解質の破損等が抑制されて、ポリ
マー電解質電池における充放電サイクル特性が向上す
る。なお、上記のシリコーンゴムの主成分は、ジメチル
ポリシロキサンであるが、そのメチル基の一部を、フェ
ニル基，水素原子，ビニル基等で置換したものであって
もよい。Here, the above used for the polymer electrolyte substrate
The silicone rubber is made by adding a curing agent or the like to organopolysiloxane and cross-linked, and it is considered that some of the methyl groups bonded to Si are mutually bonded and cross-linked with methylene. With less silicone rubber
When 50% by weight or more is also copolymerized with the polyolefin and contained in the polymer electrolyte substrate, the silicone rubber increases the mechanical strength of the polymer electrolyte and suppresses damage to the polymer electrolyte during charging and discharging, Charge / discharge cycle characteristics in the polymer electrolyte battery are improved. Although the main component of the above silicone rubber is dimethylpolysiloxane, a part of the methyl group may be replaced with a phenyl group, a hydrogen atom, a vinyl group or the like.
【００１１】また、上記のように少なくともシリコーン
ゴムとポリオレフィンとが共重合されたポリマー電解質
基材中に、ポリオレフィンを２０重量％〜４０重量％の
範囲で含有させると、ポリマー電解質の機械的強度がさ
らに増大して、充放電時におけるポリマー電解質の破損
等がさらに抑制され、ポリマー電解質電池における充放
電サイクル特性がさらに向上する。Further , as described above, at least silicone
When the polyolefin is contained in the range of 20% by weight to 40% by weight in the polymer electrolyte substrate in which rubber and polyolefin are copolymerized, the mechanical strength of the polymer electrolyte is further increased, and the polymer electrolyte during charge / discharge is increased. The damage and the like are further suppressed, and the charge / discharge cycle characteristics in the polymer electrolyte battery are further improved.
【００１２】また、ポリマー電解質基材中に含有させる
上記のポリオレフィンとして、請求項２に示すように、
ポリエチレンとポリプロピレンとから選択される少なく
とも１種を用いると、ポリマー電解質の機械的強度がよ
り増大して、ポリマー電解質電池における充放電サイク
ル特性がより向上する。As the above-mentioned polyolefin to be contained in the polymer electrolyte substrate, as described in claim 2 ,
By using at least one selected from polyethylene and polypropylene, the mechanical strength of the polymer electrolyte is further increased, and the charge / discharge cycle characteristics in the polymer electrolyte battery are further improved.
【００１３】また、この発明におけるポリマー電解質電
池において、上記のポリマー電解質基材に含浸させる非
水電解液としては、従来より一般に使用されている公知
のものを使用することができ、この非水電解液における
溶媒としては、例えば、プロピレンカーボネート、エチ
レンカーボネート、γ−ブチロラクトン、ブチレンカー
ボネート、１，２−ジメトキシエタン、ジメチルカーボ
ネート、ジエチルカーボネート等の有機溶媒を１種又は
２種以上組み合わせて使用することができ、また溶質と
しては、例えば、ヘキサフルオロリン酸リチウムＬｉＰ
Ｆ6 、過塩素酸リチウムＬｉＣｌＯ4 、テトラフルオロ
ホウ酸リチウムＬｉＢＦ4 、トリフルオロメタンスルホ
ン酸リチウムＬｉＣＦ3 ＳＯ3 、トリフルオロメタンス
ルホン酸イミドリチウムＬｉＮ（ＣＦ3 ＳＯ2 ）2 等の
リチウム化合物を用いることができる。Further, in the polymer electrolyte battery according to the present invention, as the non-aqueous electrolytic solution with which the above-mentioned polymer electrolyte substrate is impregnated, known ones which have been generally used can be used. As the solvent in the liquid, for example, organic solvents such as propylene carbonate, ethylene carbonate, γ-butyrolactone, butylene carbonate, 1,2-dimethoxyethane, dimethyl carbonate and diethyl carbonate may be used alone or in combination of two or more. As a solute, for example, lithium hexafluorophosphate LiP
It is possible to use lithium compounds such as F 6 , lithium perchlorate LiClO 4 , lithium tetrafluoroborate LiBF 4 , lithium trifluoromethanesulfonate LiCF 3 SO 3 , and lithium trifluoromethanesulfonate imide LiN (CF 3 SO 2 ) 2. it can.
【００１４】また、この発明におけるポリマー電解質電
池において、その正極に使用する正極材料としても、従
来より一般に使用されている公知の正極材料を用いるこ
とができ、例えば、マンガン、コバルト、ニッケル、バ
ナジウム、ニオブの少なくとも１種を含む金属酸化物等
のリチウムイオンの吸蔵，放出が可能な遷移金属化合物
を使用することができる。Further, in the polymer electrolyte battery according to the present invention, as the positive electrode material used for the positive electrode, a known positive electrode material generally used conventionally can be used. For example, manganese, cobalt, nickel, vanadium, A transition metal compound capable of inserting and extracting lithium ions such as a metal oxide containing at least one kind of niobium can be used.
【００１５】また、その負極に使用する正極材料として
も、従来より一般に使用されている公知の負極材料を用
いることができ、例えば、リチウムイオンの吸蔵，放出
が可能な黒鉛等の炭素材料、金属リチウム、リチウム合
金、Ｌｉ4 Ｔｉ5 Ｏ12、ＴｉＳ2 等を用いることができ
る。As the positive electrode material used for the negative electrode, a known negative electrode material that has been generally used can be used. For example, a carbon material such as graphite or a metal capable of inserting and extracting lithium ions, a metal Lithium, a lithium alloy, Li 4 Ti 5 O 12 , TiS 2 or the like can be used.
【００１６】[0016]
【実施例】以下、この発明に係るポリマー電解質電池に
ついて実施例を挙げて具体的に説明すると共に、この実
施例におけるポリマー電解質電池において、充放電サイ
クル特性が向上されることを比較例を挙げて明らかにす
る。なお、この発明におけるポリマー電解質電池は下記
の実施例に示したものに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できる
ものである。EXAMPLES Hereinafter, the polymer electrolyte battery according to the present invention will be specifically described with reference to examples, and the polymer electrolyte battery in this example will be improved in charge / discharge cycle characteristics by a comparative example. Make it clear. The polymer electrolyte battery according to the present invention is not limited to the ones shown in the following examples, and can be implemented by appropriately changing it without departing from the scope of the invention.
【００１７】
（実施例１〜３，参考例１〜５及び比較例１〜４）
これらの実施例１〜３，参考例１〜５及び比較例１〜４
においては、下記のようにして作製した正極と負極とポ
リマー電解質とを用い、図１に示すような扁平なコイン
形になったポリマー電解質電池を作製した。(Examples 1 to 3, Reference Examples 1 to 5 and Comparative Examples 1 to 4) These Examples 1 to 3, Reference Examples 1 to 5 and Comparative Examples 1 to 4
In, the positive electrode, the negative electrode, and the polymer electrolyte produced as described below were used to produce a flat coin-shaped polymer electrolyte battery as shown in FIG.
【００１８】［正極の作製］
正極１を作製するにあたっては、正極材料としてリチウ
ム含有二酸化コバルトＬｉＣｏＯ2 を用い、このＬｉＣ
ｏＯ2 と、導電剤としての人造黒鉛と、結着剤としての
ポリフッ化ビニリデンとを９０：５：５の重量比で混合
し、この混合物にＮ−メチル−２−ピロリドンを加えて
スラリー化させ、このスラリーをアルミニウム箔で構成
された正極集電体の上にドクターブレード法により塗布
した後、これを１５０℃で２時間真空乾燥させて正極１
を作製した。[Production of Positive Electrode] In producing the positive electrode 1, lithium-containing cobalt dioxide LiCoO 2 was used as a positive electrode material, and this LiC was used.
oO 2 , artificial graphite as a conductive agent, and polyvinylidene fluoride as a binder were mixed in a weight ratio of 90: 5: 5, and N-methyl-2-pyrrolidone was added to this mixture to form a slurry. The slurry was applied onto a positive electrode current collector made of aluminum foil by a doctor blade method, and then dried at 150 ° C. for 2 hours under vacuum to obtain a positive electrode 1.
Was produced.
【００１９】［負極の作製］
負極２を作製するにあたっては、負極材料に人造黒鉛を
用い、この人造黒鉛と結着剤としてのポリフッ化ビニリ
デンとを９５：５の重量比で混合し、この混合物にＮ−
メチル−２−ピロリドンを加えてスラリー化させ、この
スラリーを銅箔で構成された負極集電体上にドクターブ
レード法によって塗布した後、これを１５０℃で２時間
真空乾燥させて負極２を作製した。[Preparation of Negative Electrode] In preparing the negative electrode 2, artificial graphite was used as a negative electrode material, and the artificial graphite and polyvinylidene fluoride as a binder were mixed at a weight ratio of 95: 5 to prepare a mixture. N-
Methyl-2-pyrrolidone was added to make a slurry, and this slurry was applied on a negative electrode current collector composed of a copper foil by a doctor blade method, and then this was vacuum dried at 150 ° C. for 2 hours to prepare a negative electrode 2. did.
【００２０】［ポリマー電解質の作製］
ポリマー電解質基材に非水電解液が含浸されたポリマー
電解質３を作製するにあたっては、ポリマー電解質基材
を構成する材料として、下記の表１に示すように、実施
例１〜３，参考例１〜５及び比較例１〜３においては、
シリコーンゴムＳｉＲとポリプロピレンＰＰとポリエチ
レンオキシドＰＥＯとを用い、これらをそれぞれ同表に
示す割合（重量比）で共重合化させたものを、また比較
例４においては、シリコーン樹脂を用い、それぞれ１０
０μｍの厚みに成形して各ポリマー電解質基材を得た。[Preparation of Polymer Electrolyte] In preparing the polymer electrolyte 3 in which the non-aqueous electrolytic solution is impregnated in the polymer electrolyte substrate, as a material constituting the polymer electrolyte substrate, as shown in Table 1 below, In Examples 1 to 3, Reference Examples 1 to 5 and Comparative Examples 1 to 3,
Silicone rubber SiR, polypropylene PP, and polyethylene oxide PEO were used, each of which was copolymerized at the ratio (weight ratio) shown in the table, and in Comparative Example 4, a silicone resin was used.
Each polymer electrolyte substrate was obtained by molding to a thickness of 0 μm.
【００２１】一方、非水電解液としては、エチレンカー
ボネートとジメチルカーボネートとを１：１の体積比で
混合させた混合溶媒に、ヘキサフルオロリン酸リチウム
ＬｉＰＦ6 を１ｍｏｌ／ｌの割合で溶解させたものを用
いた。On the other hand, as the non-aqueous electrolyte, lithium hexafluorophosphate LiPF 6 was dissolved at a ratio of 1 mol / l in a mixed solvent in which ethylene carbonate and dimethyl carbonate were mixed at a volume ratio of 1: 1. I used one.
【００２２】そして、上記の各ポリマー電解質基材を上
記の非水電解液中にそれぞれ１５分間漬浸させて、各ポ
リマー電解質基材に上記の非水電解液を含浸させて各ポ
リマー電解質３を作製した。Then, each of the above-mentioned polymer electrolyte base materials is immersed in the above-mentioned non-aqueous electrolyte solution for 15 minutes, and each polymer electrolyte base material is impregnated with the above-mentioned non-aqueous electrolyte solution to form each polymer electrolyte 3. It was made.
【００２３】［電池の作製］
電池を作製するにあたっては、図１に示すように、上記
のようにして作製した正極１と負極２との間にそれぞれ
上記の各ポリマー電解質３を介在させ、これらをそれぞ
れ正極缶４ａと負極缶４ｂとで形成される電池ケース４
内に収容させ、正極集電体５を介して正極１を正極缶４
ａに接続させる一方、負極集電体６を介して負極２を負
極缶４ｂに接続させ、この正極缶４ａと負極缶４ｂとを
絶縁パッキン７により電気的に絶縁させて、コイン型に
なった各ポリマー電解質電池を得た。[Preparation of Battery] In preparing a battery, as shown in FIG. 1, each of the above-mentioned polymer electrolytes 3 was interposed between the positive electrode 1 and the negative electrode 2 prepared as described above, and A battery case 4 formed of a positive electrode can 4a and a negative electrode can 4b, respectively.
The positive electrode 1 is housed in the positive electrode current collector 5 and the positive electrode 1 is connected to the positive electrode can 4.
On the other hand, while being connected to a, the negative electrode 2 was connected to the negative electrode can 4b via the negative electrode current collector 6, and the positive electrode can 4a and the negative electrode can 4b were electrically insulated by the insulating packing 7 to form a coin type. Each polymer electrolyte battery was obtained.
【００２４】そして、上記の実施例１〜３，参考例１〜
５及び比較例１〜４の各ポリマー電解質電池を、それぞ
れ充電電流２ｍＡで充電終止電圧４．２Ｖまで充電した
後、放電電流１ｍＡで放電終止電圧２．５Ｖまで放電を
行ない、これを１サイクルとして、２００サイクルまで
の充放電試験を行ない、１サイクル目と２００サイクル
目とにおける放電容量を測定すると共に、１サイクル当
たりの放電容量の劣化率を示すサイクル劣化率（％／サ
イクル）を求め、その結果を下記の表１に合わせて示し
た。The above Examples 1 to 3 and Reference Examples 1 to
Each of the polymer electrolyte batteries of Example 5 and Comparative Examples 1 to 4 was charged to a charge end voltage of 4.2 V at a charge current of 2 mA, and then discharged to a discharge end voltage of 2.5 V at a discharge current of 1 mA, which is defined as one cycle. , A charge / discharge test up to 200 cycles was performed, the discharge capacities at the first cycle and the 200th cycle were measured, and a cycle deterioration rate (% / cycle) showing the deterioration rate of the discharge capacity per cycle was calculated. The results are shown in Table 1 below.
【００２５】[0025]
【表１】 [Table 1]
【００２６】この結果から明らかなように、ポリマー電
解質３におけるポリマー電解質基材に、シリコーンゴム
が５０重量％以上含有されたポリマー電解質基材を用い
た実施例１〜３及び参考例１〜５の各ポリマー電解質電
池は、シリコーンゴムの含有量が５０重量％未満の４０
重量％になったポリマー電解質基材を用いた比較例１，
２の各ポリマー電解質電池や、ポリエチレンオキシドか
らなるポリマー電解質基材を用いた比較例３のポリマー
電解質電池や、シリコーン樹脂からなるポリマー電解質
基材を用いた比較例４のポリマー電解質電池に比べてサ
イクル劣化率が大幅に低下し、充放電サイクル特性が著
しく向上していた。特に、シリコーンゴムが５０重量％
以上含有されると共にポリプロピレンが２０〜４０重量
％の範囲で含有されたポリマー電解質基材を用いた実施
例１〜３の各ポリマー電解質電池においては、ポリプロ
ピレンの量が上記の範囲外になった参考例１〜５の各ポ
リマー電解質電池に比べて充放電サイクル特性がさらに
向上していた。As is clear from these results, the polymer electrolyte substrate of Polymer Electrolyte 3 was a polymer electrolyte substrate containing 50% by weight or more of silicone rubber, and the polymer electrolyte substrate of Examples 1 to 3 and Reference Examples 1 to 5 were used. Each polymer electrolyte battery has a silicone rubber content of less than 40% by weight.
Comparative Example 1 using a polymer electrolyte substrate having a weight% of 1
Cycles as compared with the polymer electrolyte batteries of Comparative Example 3 using the polymer electrolyte battery of 2 and the polymer electrolyte substrate of polyethylene oxide, and the polymer electrolyte battery of Comparative Example 4 using the polymer electrolyte substrate of silicone resin. The deterioration rate was significantly reduced, and the charge / discharge cycle characteristics were significantly improved. Especially 50% by weight of silicone rubber
In each polymer electrolyte batteries of Examples 1 to 3 using the polymer electrolyte base polypropylene is contained in a range of 20 to 40 wt% with the weight or more, polypropylene
The amount of pyrene was out of the above range.
The charge / discharge cycle characteristics were further improved compared to the limmer electrolyte battery .
【００２７】（実施例４，５）
これらの実施例４，５においては、上記の実施例３にお
いて、ポリマー電解質基材を構成する材料として使用し
たポリプロピレンの代わりに、実施例４ではポリエチレ
ンＰＥを、実施例５ではポリブチレンＰＢを用いるよう
にし、それ以外については、上記の実施例３の場合と同
様にして、各ポリマー電解質電池を得た。(Examples 4 and 5 ) In these Examples 4 and 5 , instead of the polypropylene used as the material constituting the polymer electrolyte substrate in Example 3 above, polyethylene PE was used in Example 4. In Example 5 , polybutylene PB was used, and other than that, in the same manner as in Example 3 above, each polymer electrolyte battery was obtained.
【００２８】そして、これらの実施例４，５の各ポリマ
ー電解質電池についても、上記の場合と同様にして、１
サイクル目と２００サイクル目とにおける放電容量を測
定すると共に、１サイクル当たりの放電容量の劣化率を
示すサイクル劣化率（％／サイクル）を求め、その結果
を上記の実施例３のポリマー電解質電池と合わせて下記
の表２に示した。Then, for each of the polymer electrolyte batteries of Examples 4 and 5 , the same procedure as described above was performed.
The discharge capacities at the second cycle and the 200th cycle were measured, and at the same time, the cycle deterioration rate (% / cycle) showing the deterioration rate of the discharge capacity per cycle was determined, and the result was evaluated as the polymer electrolyte battery of Example 3 above. The results are shown in Table 2 below.
【００２９】[0029]
【表２】 [Table 2]
【００３０】この結果、実施例４，５の各ポリマー電解
質電池も、上記の比較例１〜４の各ポリマー電解質電池
に比べてサイクル劣化率が大幅に低下し、充放電サイク
ル特性が著しく向上していた。As a result, the polymer electrolyte batteries of Examples 4 and 5 also had a significantly lower cycle deterioration rate and significantly improved charge / discharge cycle characteristics as compared with the polymer electrolyte batteries of Comparative Examples 1 to 4 described above. Was there.
【００３１】また、実施例３〜５の各ポリマー電解質電
池を比較した場合、ポリマー電解質基材中に、ポリプロ
ピレンやポリエチレンを含有させた実施例３，４の各ポ
リマー電解質電池は、ポリブチレンを含有させた実施例
５のポリマー電解質電池に比べて、充放電サイクル特性
がさらに向上していた。When the polymer electrolyte batteries of Examples 3 to 5 were compared, the polymer electrolyte batteries of Examples 3 and 4 in which polypropylene or polyethylene was contained in the polymer electrolyte substrate contained polybutylene. Example
The charge / discharge cycle characteristics were further improved as compared with the polymer electrolyte battery of No. 5 .
【００３２】なお、上記の各実施例のポリマー電解質電
池においては、扁平なコイン形になったポリマー電解質
電池の例を示しただけであるが、この発明におけるポリ
マー電解質電池は、このような形状のものに限定される
ものではなく、円筒形、角形等の各種の形状になったポ
リマー電解質電池に適用し得るものである。In the polymer electrolyte battery of each of the above embodiments, only a flat coin-shaped polymer electrolyte battery is shown, but the polymer electrolyte battery of the present invention has such a shape. The present invention is not limited to the above, but can be applied to polymer electrolyte batteries having various shapes such as a cylindrical shape and a rectangular shape.
【００３３】[0033]
【発明の効果】以上詳述したように、この発明に係るポ
リマー電解質電池においては、ポリマー電解質基材に非
水電解液が含浸されたポリマー電解質を用いるにあた
り、このポリマー電解質基材として、少なくともシリコ
ーンゴムとポリオレフィンとが共重合されたものを用い
ると共に、このポリマー電解質基材中に、シリコーンゴ
ムを５０重量％以上、ポリオレフィンを２０重量％〜４
０重量％の範囲で含有させるようにしたため、このポリ
マー電解質の機械的強度がシリコーンゴム及びポリオレ
フィンによって増大した。As described in detail above, in the polymer electrolyte battery according to the present invention, when the polymer electrolyte in which the non-aqueous electrolyte solution is impregnated in the polymer electrolyte substrate is used, at least the silicon electrolyte is used as the polymer electrolyte substrate.
Made of a copolymer of rubber and polyolefin
In this polymer electrolyte substrate , 50% by weight or more of silicone rubber and 20% by weight to 4% of polyolefin are contained.
0 due to so as to in a weight percent range, the mechanical strength of silicone rubber and Poriore of the polymer electrolyte
Increased by fins .
【００３４】この結果、この発明におけるポリマー電解
質電池においては、充放電時におけるポリマー電解質の
破損等が抑制され、ポリマー電解質電池における充放電
サイクル特性が著しく向上した。As a result, in the polymer electrolyte battery of the present invention, breakage of the polymer electrolyte during charging / discharging was suppressed, and the charge / discharge cycle characteristics of the polymer electrolyte battery were remarkably improved.
【図１】この発明の実施例及び比較例において作製した
各ポリマー電解質電池の内部構造を示した断面説明図で
ある。FIG. 1 is a cross-sectional explanatory view showing the internal structure of each polymer electrolyte battery produced in Examples and Comparative Examples of the present invention.
１ 正極 ２ 負極 ３ ポリマー電解質 1 positive electrode 2 Negative electrode 3 Polymer electrolyte
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 (56)参考文献 特開 平２−291603（ＪＰ，Ａ) 特開 平７−99060（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 10/40 Front Page Continuation (72) Inventor Koji Nishio 2-5-5 Keihan Hondori, Moriguchi City, Osaka Sanyo Electric Co., Ltd. (56) References JP-A-2-291603 (JP, A) JP-A-7- 99060 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) H01M 10/40
Claims (2)
えたポリマー電解質電池において、上記のポリマー電解
質がポリマー電解質基材に非水電解液が含浸されてな
り、上記のポリマー電解質基材として、少なくともシリ
コーンゴムとポリオレフィンとが共重合されたものが用
いられると共に、このポリマー電解質基材中に、シリコ
ーンゴムが５０重量％以上、ポリオレフィンが２０重量
％〜４０重量％の範囲で含有されていることを特徴とす
るポリマー電解質電池。1. A polymer electrolyte battery comprising a positive electrode, a negative electrode, and a polymer electrolyte, wherein the polymer electrolyte is obtained by impregnating a polymer electrolyte substrate with a non-aqueous electrolyte solution, and the polymer electrolyte substrate comprises: At least Siri
Uses a copolymer of corn rubber and polyolefin
In this polymer electrolyte substrate, 50% by weight or more of silicone rubber and 20 % by weight of polyolefin are contained.
% To 40% by weight of the polymer electrolyte battery.
において、前記のポリマー電解質基材中に含有されるポ
リオレフィンが、ポリエチレンとポリプロピレンとから
選択される少なくとも１種であることを特徴とするポリ
マー電解質電池。2. The polymer electrolyte battery according to claim 1, wherein a polymer contained in the polymer electrolyte substrate is used.
Liolefin from polyethylene and polypropylene
A polymer electrolyte battery comprising at least one selected .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23966997A JP3369920B2 (en) | 1997-09-04 | 1997-09-04 | Polymer electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23966997A JP3369920B2 (en) | 1997-09-04 | 1997-09-04 | Polymer electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1186908A JPH1186908A (en) | 1999-03-30 |
| JP3369920B2 true JP3369920B2 (en) | 2003-01-20 |
Family
ID=17048155
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23966997A Expired - Fee Related JP3369920B2 (en) | 1997-09-04 | 1997-09-04 | Polymer electrolyte battery |
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| Country | Link |
|---|---|
| JP (1) | JP3369920B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113131103B (en) * | 2021-04-08 | 2022-09-16 | 惠州市超聚电池有限公司 | Circular tab and button cell |
-
1997
- 1997-09-04 JP JP23966997A patent/JP3369920B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH1186908A (en) | 1999-03-30 |
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