JP3036798B2 - Solid electrolyte secondary battery - Google Patents
Solid electrolyte secondary batteryInfo
- Publication number
- JP3036798B2 JP3036798B2 JP20995890A JP20995890A JP3036798B2 JP 3036798 B2 JP3036798 B2 JP 3036798B2 JP 20995890 A JP20995890 A JP 20995890A JP 20995890 A JP20995890 A JP 20995890A JP 3036798 B2 JP3036798 B2 JP 3036798B2
- Authority
- JP
- Japan
- Prior art keywords
- battery
- solid electrolyte
- negative electrode
- secondary battery
- discharge
- 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
- 239000007784 solid electrolyte Substances 0.000 title claims description 11
- 239000003575 carbonaceous material Substances 0.000 claims description 9
- 229920000767 polyaniline Polymers 0.000 claims description 5
- 229920001940 conductive polymer Polymers 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- 229920000123 polythiophene Polymers 0.000 claims description 3
- 208000028659 discharge Diseases 0.000 description 14
- 239000008151 electrolyte solution Substances 0.000 description 7
- 239000000571 coke Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 229910013063 LiBF 4 Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- -1 polypyrrol Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- Y02E60/122—
Landscapes
- Primary Cells (AREA)
Description
【発明の詳細な説明】 （イ）産業上の利用分野 本発明は固体電解質二次電池に関する。The present invention relates to a solid electrolyte secondary battery.
（ロ）従来の技術 昨今、リチウム電池は高エネルギ−密度を有するため
に注目されており、活発な研究が行われている。(B) Conventional technology In recent years, lithium batteries have attracted attention because of their high energy density, and active research has been conducted.
一般にリチウム電池は、正極集電板と負極集電板との
間に、正極と、リチウム、リチウム合金または炭素材料
からなる負極と、これらの間に介在するセパレ−タ及び
非水電解質とで構成される電池要素を封入した構造をし
ており、使用される電解質は液体電解質であった。In general, a lithium battery includes a positive electrode, a negative electrode made of lithium, a lithium alloy, or a carbon material, a separator and a nonaqueous electrolyte interposed between the positive electrode and the negative electrode current collector. The battery element was sealed, and the electrolyte used was a liquid electrolyte.
この場合、電池の封口方法としてガスケットを介した
クリンプシ−ルを用いた封口技術が主として用いられて
いるが、電池が薄くなるほど封口部材の電池容積に占め
る割合が大きくなり、電池のエネルギ−密度の低下を招
いてしまう。In this case, as a battery sealing method, a sealing technique using a crimp seal via a gasket is mainly used. However, as the battery becomes thinner, the ratio of the sealing member to the battery volume increases, and the energy density of the battery decreases. It causes a decline.
また、電解液と負極活物質が反応してしまうため、電
解液の分解が生じ電池の特性劣化を招いたり、自己放電
も大きいという問題があった。In addition, since the electrolytic solution reacts with the negative electrode active material, the electrolytic solution is decomposed to cause deterioration of battery characteristics and self-discharge is large.
（ハ）発明が解決しようとする課題 上記のように従来の電池系では電解液の分解による電
池の特性劣化や自己放電が大きいといった問題点があっ
た。(C) Problems to be Solved by the Invention As described above, in the conventional battery system, there was a problem that the characteristics of the battery deteriorated due to decomposition of the electrolytic solution and self-discharge was large.
本発明はかかる従来技術の問題点に鑑みて成されたも
のであり、負極に炭素材料を用いた電池において、電解
液と負極活物質との反応を抑えて電解液の分解を抑制
し、自己放電量を少なく抑えて電池の特性を維持するこ
とを目的とする。The present invention has been made in view of the problems of the related art, and in a battery using a carbon material for the negative electrode, the reaction between the electrolytic solution and the negative electrode active material is suppressed to suppress the decomposition of the electrolytic solution, and the self An object of the present invention is to maintain the characteristics of a battery while suppressing the amount of discharge.
（ニ）課題を解決するための手段 本発明の固体電解質二次電池は、ポリアニリン、ポリ
ピロ−ル、ポリチオフェンから選択された少なくとも一
種の導電性ポリマ−からなる正極と、炭素材料からなる
負極と、ポリエチレンオキサイドからなるリチウムイオ
ン導電性固体電解質とからなることを特徴とする。(D) Means for Solving the Problems The solid electrolyte secondary battery of the present invention comprises: a positive electrode made of at least one kind of conductive polymer selected from polyaniline, polypyrrol, and polythiophene; a negative electrode made of a carbon material; And a lithium ion conductive solid electrolyte made of polyethylene oxide.
さらに本発明の負極の炭素材料としてはグラファイ
ト、カ−ボンブラック、コークス等が挙げられる。Examples of the carbon material of the negative electrode of the present invention include graphite, carbon black, coke, and the like.
（ホ）作用 上記の構成を持ってすれば、負極が炭素材料であって
も、電解質が固体なので漏液や電解液の分解の心配がな
く、自己放電量も少なくすることができる。(E) Function With the above configuration, even if the negative electrode is made of a carbon material, the electrolyte is solid, so there is no risk of liquid leakage or decomposition of the electrolyte, and the amount of self-discharge can be reduced.
（ヘ）実施例 以下に実施例を挙げ、本発明を具体的に説明する。(F) Examples Hereinafter, the present invention will be described specifically with reference to Examples.
まず、LiBF4N−メチル−２−ピロリドンに溶解し、こ
れにリチウムイオン導電性固体電解質としてのポリエチ
レンキサイドを加え、均一になるまで振り混ぜた。この
液をガラス基板上にキャストし、80℃で真空乾燥し、厚
み30μｍの高分子固体電解質フィルムを得た。First, it was dissolved in LiBF 4 N-methyl-2-pyrrolidone, and polyethylene oxide as a lithium ion conductive solid electrolyte was added thereto, followed by shaking until uniform. This liquid was cast on a glass substrate and vacuum dried at 80 ° C. to obtain a 30 μm thick polymer solid electrolyte film.
そして、正極には導電性ポリマ−であるポリアニリ
ン、負極には炭素材料としてのコ−クスを用いて、本発
明電池Ａを作製した。The battery A of the present invention was produced using polyaniline as a conductive polymer for the positive electrode and coke as a carbon material for the negative electrode.
このようにして作製した本発明電池の断面図を、第１
図に示す。コ−クスからなる負極１は、負極集電体２の
内面に圧着されており、この負極集電体２はフェライト
系ステンレス鋼（SUS430）からなる断面コ字状の負極缶
３の内定面に固着されている。上記負極缶３の周端は、
ポリプロピレン製の絶縁パッキング４の内部に固定され
ている。この絶縁パッキング４の外周には、上記負極缶
３とは反対方向に、フェライト系ステンレス鋼（SUS43
0）から構成された断面コ字状をなす正極缶５が固定さ
れている。The cross-sectional view of the battery of the present invention thus produced is shown in FIG.
Shown in the figure. A negative electrode 1 made of coke is pressed against the inner surface of a negative electrode current collector 2. It is fixed. The peripheral end of the negative electrode can 3
It is fixed inside the insulating packing 4 made of polypropylene. On the outer periphery of the insulating packing 4, a ferritic stainless steel (SUS43)
0), a positive electrode can 5 having a U-shaped cross section is fixed.
この正極缶５の内底面には、正極集電体６が固定され
ており、この正極集電体６の内面に、ポリアニリンから
なる正極７が固定されている。そして、この正極７と負
極１との間には、固体電解質フィルムのセパレ−タ８が
介挿されている。A positive electrode current collector 6 is fixed to the inner bottom surface of the positive electrode can 5, and a positive electrode 7 made of polyaniline is fixed to the inner surface of the positive electrode current collector 6. A separator 8 of a solid electrolyte film is interposed between the positive electrode 7 and the negative electrode 1.
一方、比較例として、前記固体電解質フィルムのセパ
レ−タ８に代えて、LiBF4が溶解されたプロピレンカ−
ボネ−ト溶液を電解液として含浸させたセパレ−タを使
用した。この点以外は、前記本発明電池Ａと同様にし
て、比較電池Ｂを作製した。On the other hand, as a comparative example, instead of the separator 8 of the solid electrolyte film, a propylene carrier in which LiBF 4 was dissolved was used.
A separator impregnated with a carbonate solution as an electrolyte was used. Except for this point, a comparative battery B was produced in the same manner as the battery A of the present invention.
次にこれらの電池Ａ、Ｂについて充放電試験を行なっ
た。充電は充電電流1mAで、3.6Vまで、放電は放電電流1
mAで2.5Vまでとした。Next, these batteries A and B were subjected to a charge / discharge test. Charge is 1mA charge current, up to 3.6V, discharge is 1 discharge current
Up to 2.5 V in mA.
第３図に充電して室温３ヶ月保存後の放電におけるこ
れらの電池Ａ、Ｂの保存特性を示す。いずれの電池も初
期の放電容量では4mAhを示したが、充電して室温３ヶ月
保存後の放電では、電池Ａは初期と同じく放電時間４時
間（放電容量4mAh）であるのに対し、電池Ｂは2.8時間
（2.8mAh）と減少している。これは電解液にLiBF4−PC
を用いた比較電池Ｂの場合、電極活物質が電解液と反応
してしまうが本発明電池Ａではそのような反応がないた
めと考えられる。FIG. 3 shows the storage characteristics of these batteries A and B when discharged after storage at room temperature for 3 months. All batteries showed an initial discharge capacity of 4 mAh, but after charging and discharging after storage at room temperature for 3 months, battery A had a discharge time of 4 hours (discharge capacity of 4 mAh), whereas battery B had a discharge time of 4 hours. Has decreased to 2.8 hours (2.8 mAh). This is because LiBF 4 -PC
In the case of the comparative battery B using the battery, the electrode active material reacts with the electrolytic solution, but it is considered that such a reaction does not occur in the battery A of the present invention.
さらに本発明の負極の炭素材料としては前記コークス
の他に、グラファイト、カ−ボンブラッック、コ−クス
等を用いることが可能である。Further, as the carbon material of the negative electrode of the present invention, graphite, carbon black, coke, or the like can be used in addition to the coke.
（ト）発明の効果 以上述べた如く、ポリアニリン、ポリピロ−ル、ポリ
チオフェンから選択された少なくとも一種の導電性ポリ
マ−からなる正極と、炭素材料からなる負極とを用いた
二次電池において、電解質として固体電解質を用いるこ
とにより、電解質が固体なので漏液や電解液の分解の心
配なく、自己放電も少なくすることが可能となり、放電
初期の電池特性を維持できるとともに、その工業的価値
は非常に大きい。(G) Effect of the Invention As described above, in a secondary battery using a positive electrode made of at least one kind of conductive polymer selected from polyaniline, polypyrrol, and polythiophene and a negative electrode made of a carbon material, By using a solid electrolyte, since the electrolyte is solid, self-discharge can be reduced without fear of liquid leakage or decomposition of the electrolytic solution, and the battery characteristics at the initial stage of discharge can be maintained, and its industrial value is very large .
第１図は本発明電池の構成を示す半断面図、第２図
は、電池Ａ、Ｂの保存後の放電特性を示す図である。 Ａ……本発明電池、 Ｂ……比較電池、 １……負極、 ７……正極、 ８……セパレータ。FIG. 1 is a half sectional view showing the structure of the battery of the present invention, and FIG. 2 is a view showing the discharge characteristics of batteries A and B after storage. A: battery of the present invention, B: comparative battery, 1 ... negative electrode, 7 ... positive electrode, 8 ... separator.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭59−143280（ＪＰ，Ａ) 特開 平１−311561（ＪＰ，Ａ) 特開 平１−241767（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 10/40 H01M 4/60 H01M 6/18 ────────────────────────────────────────────────── (5) References JP-A-59-143280 (JP, A) JP-A-1-311561 (JP, A) JP-A-1-241767 (JP, A) (58) Field (Int.Cl. 7 , DB name) H01M 10/40 H01M 4/60 H01M 6/18
Claims (1)
ェンから選択された少なくとも一種の導電性ポリマ−か
らなる正極と、炭素材料からなる負極と、ポリエチレン
オキサイドからなるリチウムイオン導電性固体電解質と
からなることを特徴とする固体電解質二次電池。A positive electrode comprising at least one conductive polymer selected from polyaniline, polypyrrol and polythiophene, a negative electrode comprising a carbon material, and a lithium ion conductive solid electrolyte comprising polyethylene oxide. Characteristic solid electrolyte secondary battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20995890A JP3036798B2 (en) | 1990-08-07 | 1990-08-07 | Solid electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20995890A JP3036798B2 (en) | 1990-08-07 | 1990-08-07 | Solid electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0492366A JPH0492366A (en) | 1992-03-25 |
| JP3036798B2 true JP3036798B2 (en) | 2000-04-24 |
Family
ID=16581488
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20995890A Expired - Fee Related JP3036798B2 (en) | 1990-08-07 | 1990-08-07 | Solid electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3036798B2 (en) |
-
1990
- 1990-08-07 JP JP20995890A patent/JP3036798B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0492366A (en) | 1992-03-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |