JPS58137975A - Nonaqueous electrolyte secondary battery - Google Patents
Nonaqueous electrolyte secondary batteryInfo
- Publication number
- JPS58137975A JPS58137975A JP57020558A JP2055882A JPS58137975A JP S58137975 A JPS58137975 A JP S58137975A JP 57020558 A JP57020558 A JP 57020558A JP 2055882 A JP2055882 A JP 2055882A JP S58137975 A JPS58137975 A JP S58137975A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- battery
- polyacethylene
- negative electrode
- polyacetylene
- 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.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- 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
【発明の詳細な説明】 本発明は非水電解液二次電池に関するものである。[Detailed description of the invention] The present invention relates to a non-aqueous electrolyte secondary battery.
従来より貴重活物質りしてリチウム、ナトリウム、マグ
ネシウム等の軽金属を用い、王権活物質として金属の酸
化物、硫化物、へロゲン化物等を用い、電解液としてプ
ロピレンカーボネート、ｌ−ブナルラクトン、１，２ジ
メトキシエタン等の有機溶媒に過塩素酸リチウム、過塩
素酸す）ｌクム。Conventionally, light metals such as lithium, sodium, and magnesium have been used as precious active materials, metal oxides, sulfides, halide, etc. have been used as royal active materials, and propylene carbonate, l-bunarlactone, 1, 2) Lithium perchlorate, perchloric acid, etc. in an organic solvent such as dimethoxyethane.
ホワフツ化リチウム、ホヮフッ化ナトリウム等の溶質を
溶解させた非水電解液を用いる非水電解液電池が提案さ
れて８す、高エネルギー！１ｆｔ−育Ｔること、自己放
電が少ない等の利点Ｖ有するものである。A non-aqueous electrolyte battery has been proposed that uses a non-aqueous electrolyte in which solutes such as lithium fluoride and sodium fluoride are dissolved.8 High energy! It has advantages such as being 1ft thick and having little self-discharge.
さて、特に近年題二８いてはこの種電池の二次系１二つ
いて注目され、そして研究されているが非水電解液二次
電池に８いては一次系にはない新たな間層が生じる。そ
の重要な一つはリチウム等の負ａ活物質が充電の際響二
、リチウム板等で構成される負極表面に樹枝状に伍長し
て同部短ｖＩｔｌ′引起Ｔため充放電サイクルが極めて
短かいことである。Now, especially in recent years, secondary systems of this type of battery have been attracting attention and research, but in non-aqueous electrolyte secondary batteries, a new interlayer that does not exist in the primary system is created. . One of the important reasons is that during charging, the negative active material such as lithium extends like a tree on the surface of the negative electrode composed of lithium plates, causing a short vItl'T, resulting in an extremely short charge/discharge cycle. That's important.
本発明は斯る点Ｉ：鑑みなされたものであり、その要旨
とするところはｔ４はフチ９ム、ナトリウム、マグネシ
ウム等の軽金属のイオン檀をドーピングしたポリアセチ
レンで構成し、王権は二酸化マンガン活物質ｇニボリア
セチレンＶ混合した混合物な主体として構成する点１：
あり、サイクル特性Ｃ：優れ且高電位を有する非水電解
液二次電池Ｖ提供するものである。The present invention has been made in view of the above point I, and its gist is that t4 is made of polyacetylene doped with ions of light metals such as aluminum, sodium, and magnesium, and the king is made of manganese dioxide active material. Point 1: Constituting the main body of the mixture of gnibolyacetylene V:
This provides a non-aqueous electrolyte secondary battery V having excellent cycle characteristics C and high potential.
以下本発明の実施例ｉ二ついて負極活物質とじてリチウ
ムを用いた場合を例にとり晩明する。Two embodiments of the present invention will be described below, taking as an example the case where lithium is used as the negative electrode active material.
正極：市販の電解二酸化マンガンｔ’２５０〜４３０”
（ｊＯＪ温度で熱処理して得た正極活物質Ｃニボリアセ
チレン粉末２０重量％を加えて混合した正極合剤８０重
量Ｓｔ二対して、導電剤としてのアセチレンブラック及
び黒鉛１５重量部、結着剤としてのフッ素樹脂粉末５重
量部ｔ−加え充分混合した後、約１）１の圧力で加圧成
型して径１５％、厚み１１％のペレットとし、これｖ２
５０〜３５０℃の諷ハで熱処理して正極とする。Positive electrode: Commercially available electrolytic manganese dioxide t'250~430"
(20% by weight of the positive electrode active material C obtained by heat treatment at OJ temperature and mixed with 20% by weight St of positive electrode mixture, 15 parts by weight of acetylene black and graphite as a conductive agent, and 15 parts by weight of graphite as a binder) After adding 5 parts by weight of fluororesin powder and mixing thoroughly, it was press-molded at a pressure of about 1) to form pellets with a diameter of 15% and a thickness of 11%.
A positive electrode is prepared by heat treatment at a temperature of 50 to 350°C.
負ｌ！ＩＡ：ボツアセチレン膜をアノード、リチウム教
ヲカソードとし、電解液としてプロピレンカーボネート
５二Ｑ、５〜ｔＯ七＃／２の過塩素酸リチウムイーオン
したものを用い、１０瑠Ａの定電流で通電しリチウムイ
ーオンをポリアセチレン膜にドーピングする。そしてこ
の−リチウムイオンがドーピングされたポリアセチレン
Ｉｌ’ｒ怪１５％の寸法ｇ：、ｔａ断して負極とするも
電解液：プロピレンカーボネートと１．２ジメトキシエ
タンの等体積混合溶媒に過塩素酸リチウムｖ１−溶解し
たものを用いた。Negative l! IA: Using a botuacetylene film as an anode and a lithium cathode, and using propylene carbonate 52Q, 5~tO7#/2 lithium perchlorate ion as the electrolyte, electricity was applied at a constant current of 10 A to lithium. A polyacetylene film is doped with ions. Dimensions of this 15% polyacetylene Il'r doped with lithium ions: Cut it off to make a negative electrode Electrolyte: Lithium perchlorate in an equal volume mixed solvent of propylene carbonate and 1.2 dimethoxyethane v1-dissolved material was used.
１１１図は上記各要素を組込んだ本発明電池の縦断面図
１示し、（１）は正極であって正ａ缶（２１の内底面に
圧接されている。（３）は負極であって負極缶（４）の
内底面に固着された負極集電体（２）に圧接されている
。（５）は正、負１間に介挿されたセパレータであって
ボップロピレン不繊布よりなり所定量の電解液が含浸さ
れている。（６１は正、１１Ｌ掻缶を隔鴫Ｔる絶縁バッ
キングである。Figure 111 shows a vertical cross-sectional view 1 of the battery of the present invention incorporating each of the above elements, in which (1) is the positive electrode, which is pressed against the inner bottom surface of the positive A can (21), and (3) is the negative electrode. It is pressed into contact with the negative electrode current collector (2) fixed to the inner bottom surface of the negative electrode can (4). (5) is a separator inserted between the positive and negative electrodes 1 and made of BOPP propylene nonwoven fabric. It is impregnated with a fixed amount of electrolyte. (61 is the insulating backing that separates the 11L canister.
ζζで、負極の集電方法としては、外部端子との電気＊
ＩＩｔ−より良好とするために、金属り金属ラス＠或い
はネサ膜よりなる負極集電体上にポリアセチレンｌｌｌ
を生成させて予じめポリアセチレンと負極集電体とを一
体化した負１基板とし、集電体の−ｓｖ負掻缶の一部（
二電気Ｗ７Ｉｍ’ｒる方法若しくは電池電槽を絶縁物質
で構成Ｔる場合Ｉ：は前記集電体の一部を電槽外部に露
出させて外部端子として利用Ｔることもできる。ζζ, the negative electrode current collection method is to connect the external terminal *
In order to make it better than IIt-, polyacetylene is placed on the negative electrode current collector made of metallic lath or Nesa film.
A negative 1 substrate in which polyacetylene and a negative electrode current collector are integrated in advance by forming a
In the second electric method or when the battery case is made of an insulating material, a part of the current collector can be exposed outside the case and used as an external terminal.
尚、比較のためｇ二、正−がポリアセチレンを含まず、
二酸化マンガン活物質を主体として構成され、且負極が
リチウム板で構成された比較電池ビ）と、正極がポリア
セチレンを含まず、二酸化マンガン活物質を主体として
構成され、且負極が本発明電池の場合と同様にリチウム
イオンをドーピングしたポリアセチレン磨で構成された
比較電池（０１を作成した・
第２図及びｌＮ３図は本発明電池（Ａ）と比較電池＆（
１１０１との電池特性比較図であり、第２図は充放電サ
イクル特性比較図を示し、充放電条件は充電電池３１１
Ａ、放電電流３ｓｗム、充電終止電圧４． ＯＶ 。For comparison, g2, positive- does not contain polyacetylene,
Comparative battery B) which is composed mainly of manganese dioxide active material and whose negative electrode is composed of a lithium plate; and case where the positive electrode is composed mainly of manganese dioxide active material without polyacetylene and whose negative electrode is a battery of the present invention. A comparison battery (01 was created) made of polyacetylene polishing doped with lithium ions in the same manner as the above.
Fig. 2 shows a comparison chart of charge/discharge cycle characteristics, and the charge/discharge conditions are that of rechargeable battery 311.
A, discharge current 3swm, charge end voltage 4. OV.
敬電終止電ＦＥ２．５Ｖとした。叉第３図は１２に０足
負荷放電特性を示す。The final voltage for honoring electricity was set to FE2.5V. Figure 3 shows the 0 foot load discharge characteristics at 12.
第２図の充放電サイクル特性比較図から明白なるように
、本発明電池（ム）及び比較電池１四は比較電池ビ１（
：比して飛躍的に特性が改善されていることがわかる。As is clear from the charge/discharge cycle characteristic comparison diagram in FIG.
: It can be seen that the characteristics are dramatically improved compared to the above.
この理由は比較電池（イ）では充電時にリチウム板より
なる負極の表面上にリチウム金属が樹枝状に午長し内部
短絡が生じるのに対して本発明電池（Ａｌ及び比較電池
−ロニよれば、負極がリチウムイオンなドーピングした
ポリアセチレンで構成されているため、充電の際、リチ
ウムイオンは金属リチウムとして負ｖｈｓ面上に析出す
るのではなく、ポリアセチレンにドーピングされる挙ａ
ｔとるものであるため比較電池（イ）のようなリチウム
金属の樹枝状生長が生じず号イクル特性が改善されるも
のである。The reason for this is that in the comparative battery (A), lithium metal forms a dendritic shape on the surface of the negative electrode made of a lithium plate during charging, causing an internal short circuit, whereas the present invention battery (Al and comparative battery - according to Roni) Since the negative electrode is composed of polyacetylene doped with lithium ions, during charging, lithium ions are not deposited as metallic lithium on the negative VHS surface, but are doped into the polyacetylene.
Since the battery has a high temperature of t, dendritic growth of lithium metal does not occur as in comparative battery (a), and the cycle characteristics are improved.
一方、１１３図の放電特性比較図から明白なるように、
電池電圧及び円部抵抗に８いて本発明電池（ムｌは比較
電池呻ロ：比して優れている。On the other hand, as is clear from the discharge characteristic comparison diagram in Figure 113,
The battery of the present invention was superior in terms of battery voltage and circular resistance compared to the comparison battery.
この理由は本発明電池Ｉ＝ｓいては正極Ｃ：ポリアセチ
レンが混合されているため、放電に伴ってリチウムイオ
ンがポリアセチレンジニド−ピングされボ；アセチレン
自身の電導「が同上し、その結果として正極の電導度が
同上すること口起因するものである。The reason for this is that in the battery I of the present invention, positive electrode C: polyacetylene is mixed, and as a result of discharging, lithium ions are doped with polyacetylene, and the conductivity of acetylene itself is the same as above, and as a result, the positive electrode This is due to the fact that the conductivity is the same as above.
又１本発明電池では特に活物質として二酸化マンガンを
用いているため電池電圧が高く、充電反応、即ち負極活
物質の金属イオンがポリアセチレンジニドープされるド
ーピング反応が円滑Ｃ二進むという利点を有し優れた充
電特性を示すものである更に、二酸化マンガンの放電反
応は次式の如（貴重活物質としてのリチウムのイオンが
二酸化マンガンの結晶構造内に固相拡散により入り込む
反応であると提唱されて８す、且可逆性を有することが
確認されて寞り、高電圧の二次電池用正極活物質として
楊めて有益なるものである。In addition, the battery of the present invention particularly uses manganese dioxide as the active material, so the battery voltage is high, and the charging reaction, that is, the doping reaction in which the metal ions of the negative electrode active material are doped with polyacetylene dini, has the advantage of proceeding smoothly. In addition, the discharge reaction of manganese dioxide is proposed to be a reaction in which lithium ions, a valuable active material, enter the crystal structure of manganese dioxide by solid-phase diffusion, as shown in the following equation: Furthermore, it has been confirmed that it has reversibility, making it extremely useful as a positive electrode active material for high-voltage secondary batteries.
Ｌｉ＋Ｍｎｆ’） Ｏｘ→ Ｍｎ’置） ０ｘ（Ｌ
ｉ”）上述した如く１本発明は非水電解液二次電池ｉ：
係り、リチウム、ナトリウム、マグネシウム等の軽金属
のイオン種なドーピングしたポリアセチレンで構成され
た負極と、二酸化マンガン活物質にポリアセチレンｔ’
／ｊ！合した混合物を主体として構成された王権と１用
いることによりサイクル特性に優れ且高電位を有する非
水電解液二次電池を提供するものであり、その工業的価
値は極めて大である。Li+Mnf') Ox→ Mn' position) 0x(L
i'') As mentioned above, the present invention provides a non-aqueous electrolyte secondary battery i:
The negative electrode is composed of polyacetylene doped with ionic species of light metals such as lithium, sodium, and magnesium, and polyacetylene t' is used as a manganese dioxide active material.
/j! By using the mixture as a main component and a non-aqueous electrolyte secondary battery having excellent cycle characteristics and a high potential, the industrial value thereof is extremely large.
第１図は本発明の一実施例にｇける扁平型電池の縦断面
図、第２図及び第３図は本発明電池と比較電池との電池
特性比較図であり、第２図は充放電管イクル特性、Ｗ＆
３図は放電特性を夫々示す。
（１）・・・正１に、 （２１−・・王権缶、（３）
・・・負極、（４）・・・負１に缶、＋５１・・・セパ
レータ、（６１・・・絶縁バッキング、（Ａ）・・・本
発明電池、 （イ）（ロ）・・・比較電池。
７１ｇ−−ＩＩ４＼ ― ？
製 ν 袈 湖 ９FIG. 1 is a longitudinal cross-sectional view of a flat battery according to an embodiment of the present invention, FIGS. 2 and 3 are comparison diagrams of battery characteristics between the battery of the present invention and a comparative battery, and FIG. Tube cycle characteristics, W&
Figure 3 shows the discharge characteristics. (1)...Sho 1, (21-...Kingen Can, (3)
... Negative electrode, (4) ... Negative 1 can, +51 ... Separator, (61 ... Insulating backing, (A) ... Invention battery, (A) (B) ... Comparison Battery. 71g--II4＼ - ? Manufactured by ν Keiko 9
Claims (1)
イオン檀をドーピングしたポリアセチレンで構成された
負ａと、少（とも一つの溶媒と少くとも一つの溶質とか
らなる非水電解液と、二酸化マンガン活物質Ｉ：ポリア
セチレンＶ混合した混合物を主体として構成された王権
とを備えることを特徴とする非水電解液二次電池。■ Negative a made of polyacetylene doped with ion powders of the @sparrow genus such as Lidewam, Sodiumwum, and Maggyo νwam; and a non-aqueous electrolyte consisting of at least one solvent and at least one solute; 1. A non-aqueous electrolyte secondary battery comprising: a mixture consisting mainly of manganese dioxide active material I: polyacetylene V;
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57020558A JPS58137975A (en) | 1982-02-09 | 1982-02-09 | Nonaqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57020558A JPS58137975A (en) | 1982-02-09 | 1982-02-09 | Nonaqueous electrolyte secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS58137975A true JPS58137975A (en) | 1983-08-16 |
Family
ID=12030483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57020558A Pending JPS58137975A (en) | 1982-02-09 | 1982-02-09 | Nonaqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58137975A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6154164A (en) * | 1984-08-24 | 1986-03-18 | Hoxan Corp | Plastic secondary battery |
| EP0199175A2 (en) * | 1985-04-19 | 1986-10-29 | AlliedSignal Inc. | Negative electrodes for non-aqueous secondary batteries composed of conjugated polymer and alkali metal alloying or inserting material |
| EP0205913A2 (en) * | 1985-06-27 | 1986-12-30 | AlliedSignal Inc. | Conjugated polymer as substrate for the plating of alkali metal in a nonaqueous secondary battery |
| JPS63102162A (en) * | 1986-10-17 | 1988-05-07 | Showa Denko Kk | Secondary battery |
| JPS63202858A (en) * | 1987-02-18 | 1988-08-22 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte battery |
| EP0600718A3 (en) * | 1992-11-30 | 1995-11-15 | Canon Kk | Secondary battery. |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5580271A (en) * | 1978-12-12 | 1980-06-17 | Matsushita Electric Ind Co Ltd | Organic electrolyte cell |
| JPS56136469A (en) * | 1980-03-11 | 1981-10-24 | University Patents Inc | Secondary cell and method of charging same |
| JPS5711476A (en) * | 1980-06-24 | 1982-01-21 | Yuasa Battery Co Ltd | Secondary organic electrolyte battery |
-
1982
- 1982-02-09 JP JP57020558A patent/JPS58137975A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5580271A (en) * | 1978-12-12 | 1980-06-17 | Matsushita Electric Ind Co Ltd | Organic electrolyte cell |
| JPS56136469A (en) * | 1980-03-11 | 1981-10-24 | University Patents Inc | Secondary cell and method of charging same |
| JPS5711476A (en) * | 1980-06-24 | 1982-01-21 | Yuasa Battery Co Ltd | Secondary organic electrolyte battery |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6154164A (en) * | 1984-08-24 | 1986-03-18 | Hoxan Corp | Plastic secondary battery |
| EP0199175A2 (en) * | 1985-04-19 | 1986-10-29 | AlliedSignal Inc. | Negative electrodes for non-aqueous secondary batteries composed of conjugated polymer and alkali metal alloying or inserting material |
| EP0205913A2 (en) * | 1985-06-27 | 1986-12-30 | AlliedSignal Inc. | Conjugated polymer as substrate for the plating of alkali metal in a nonaqueous secondary battery |
| JPS63102162A (en) * | 1986-10-17 | 1988-05-07 | Showa Denko Kk | Secondary battery |
| JPS63202858A (en) * | 1987-02-18 | 1988-08-22 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte battery |
| EP0600718A3 (en) * | 1992-11-30 | 1995-11-15 | Canon Kk | Secondary battery. |
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