JPH05234591A - Non-aqueous electrolyte battery - Google Patents
Non-aqueous electrolyte batteryInfo
- Publication number
- JPH05234591A JPH05234591A JP4037973A JP3797392A JPH05234591A JP H05234591 A JPH05234591 A JP H05234591A JP 4037973 A JP4037973 A JP 4037973A JP 3797392 A JP3797392 A JP 3797392A JP H05234591 A JPH05234591 A JP H05234591A
- Authority
- JP
- Japan
- Prior art keywords
- manganese dioxide
- aqueous electrolyte
- battery
- calcium iodide
- electrolyte battery
- 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.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
-
- 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
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
- Secondary Cells (AREA)
Abstract
(57)【要約】
【目的】 予備放電することなくガスの発生を抑制し、
また完成電池の放電容量のバラツキを小さくできるよう
にした非水電解液電池を提供する。
【構成】 二酸化マンガンを主成分とする正極を用い、
溶媒としてエチレンカーボネートないしはプロピレンカ
ーボネートを含む非水電解液を用いた非水電解液電池に
おいて、前記二酸化マンガン中にあらかじめモル比で二
酸化マンガン１００に対し、０．２〜５．０の範囲の少
量のヨウ化カルシウムを添加した。(57) [Summary] [Purpose] Suppress gas generation without pre-discharge,
Further, the present invention provides a non-aqueous electrolyte battery in which variations in discharge capacity of a completed battery can be reduced. [Configuration] Using a positive electrode containing manganese dioxide as a main component,
In a non-aqueous electrolyte battery using a non-aqueous electrolyte solution containing ethylene carbonate or propylene carbonate as a solvent, a small amount of 0.2 to 5.0 relative to 100 of manganese dioxide is previously added to the manganese dioxide in a molar ratio. Calcium iodide was added.
Description
【０００１】[0001]
【産業上の利用分野】この発明は、電池製造後の予備放
電工程を不要とした非水電解液電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte battery which does not require a pre-discharge step after battery production.
【０００２】[0002]
【従来の技術】正極に二酸化マンガン、非水電解液の溶
媒としてプロピレンカーボネートを用いた非水電解液電
池においては、電池製造後そのまま放置したのでは保存
中に多量のガスが発生し、膨脹したり、漏液したり、内
部抵抗の増大により性能が低下する欠点があった。2. Description of the Related Art In a non-aqueous electrolyte battery using manganese dioxide for the positive electrode and propylene carbonate as a solvent for the non-aqueous electrolyte, a large amount of gas is generated and swells during storage if left as it is after the battery is manufactured. However, there is a drawback that the performance deteriorates due to leakage, liquid leakage, or increase in internal resistance.
【０００３】この原因は、溶媒中のプロピレンカーボネ
ートが微量の水分の存在下で二酸化マンガンの活性部分
に接触することで分解し、一酸化炭素，二酸化炭素など
のガスを発生させるためであることがある程度解明され
ている。The cause of this is that propylene carbonate in the solvent is decomposed by contacting the active portion of manganese dioxide in the presence of a trace amount of water, and gas such as carbon monoxide and carbon dioxide is generated. It is understood to some extent.
【０００４】そこで、例えば特開昭５５−８０２７６号
公報には、電池製造後に予備放電を行い、電池容量の一
部を除くことでガス発生を抑制する方法が開示されてい
る。この方法では、電池製造後数時間以内に定電流を流
して１００〜７００mAh 程度の容量を放電し、この予備
放電工程を終了後に完成電池とする。Therefore, for example, Japanese Patent Application Laid-Open No. 55-80276 discloses a method of suppressing gas generation by preliminarily discharging after manufacturing a battery and removing a part of the battery capacity. In this method, a constant current is flown within a few hours after the battery is manufactured to discharge a capacity of about 100 to 700 mAh, and a finished battery is obtained after this preliminary discharge step is completed.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、この方
法においては、得られた電池を一つずつ所定量放電しな
ければならず、予備放電のための設備および放電処理時
間を要し、また、処理後の電池性能にも予備放電に起因
する電池容量のバラツキが生ずる欠点があった。However, in this method, the obtained batteries must be discharged one by one by a predetermined amount, which requires equipment for pre-discharge and discharge treatment time. The subsequent battery performance also had a defect that the battery capacity varied due to the preliminary discharge.
【０００６】本発明者らは、前記反応によるガス発生を
抑制できる方法を種々検討した結果、少量のヨウ化カル
シウムをあらかじめ二酸化マンガン中に添加しておくこ
とにより、二酸化マンガンの分解能が低下し、ガス発生
を抑制できることを見出だした。本発明は以上の知見に
基づきなされたものであって、その目的は、予備放電す
ることなくガスの発生を抑制し、また完成電池の放電容
量のバラツキを小さくできるようにした非水電解液電池
を提供するものである。As a result of various studies on the method of suppressing the gas generation due to the above reaction, the present inventors have found that adding a small amount of calcium iodide to manganese dioxide in advance lowers the resolution of manganese dioxide. It has been found that gas generation can be suppressed. The present invention has been made based on the above findings, and an object thereof is to suppress generation of gas without performing preliminary discharge, and to make it possible to reduce variations in discharge capacity of completed batteries. Is provided.
【０００７】[0007]
【課題を解決するための手段】前記目的を達成するた
め、この発明は、二酸化マンガンを主成分とする正極を
用い、溶媒としてエチレンカーボネートないしはプロピ
レンカーボネートを含む非水電解液を用いた非水電解液
電池において、前記二酸化マンガン中にあらかじめ少量
のヨウ化カルシウムを添加したものである。In order to achieve the above object, the present invention provides a non-aqueous electrolysis using a positive electrode containing manganese dioxide as a main component and a non-aqueous electrolytic solution containing ethylene carbonate or propylene carbonate as a solvent. In the liquid battery, a small amount of calcium iodide is previously added to the manganese dioxide.
【０００８】より詳しくは、前記ヨウ化カルシウムの前
記二酸化マンガンに対する添加量が、モル比で二酸化マ
ンガン１００に対し０．２〜５の範囲となるような量の
ヨウ化カルシウムを添加するものである。前記ヨウ化カ
ルシウムの前記二酸化マンガンに対する添加量が０．２
を下回った場合、例えば０．１のときには、ガス発生抑
止効果が小さく製造後の電池に膨れが発生する。添加量
が５を上回った場合、例えば６のときには、主活物質で
ある二酸化マンガンの容量が小さくなり放電容量が減少
する。More specifically, calcium iodide is added in an amount such that the addition amount of calcium iodide to manganese dioxide is in the range of 0.2 to 5 with respect to 100 of manganese dioxide in a molar ratio. .. The addition amount of the calcium iodide to the manganese dioxide is 0.2.
When it is less than 0.1, for example, when the value is 0.1, the gas generation suppressing effect is small, and the battery after manufacturing is swollen. When the amount added exceeds 5, for example, when the amount is 6, the capacity of manganese dioxide, which is the main active material, decreases and the discharge capacity decreases.
【０００９】また、製造方法としては、ヨウ化カルシウ
ム水和物を前述の範囲内で二酸化マンガンに混合し、乾
燥後導電材およびバインダとともに混合して正極合剤と
し、その後は通常の方法で造形し、セパレータ、リチウ
ム，ナトリウムなどの軽金属と組合わせ、エチレンカー
ボネートないしはプロピレンカーボネートおよびこれと
エーテル類を溶媒とする非水電解液を注液した状態で電
池を形成する手法が取られる。As a manufacturing method, calcium iodide hydrate is mixed with manganese dioxide within the above-mentioned range, dried and then mixed with a conductive material and a binder to form a positive electrode mixture, and thereafter, a normal method is used for shaping. However, a battery is formed by combining a separator, a light metal such as lithium and sodium, and injecting ethylene carbonate or propylene carbonate and a non-aqueous electrolytic solution containing this and ether as a solvent.
【００１０】また、前記二酸化マンガンとヨウ化カルシ
ウムとの反応によって遊離したヨウ素を水洗分離後に正
極合剤を作り、その後電池に組立てる手法も取られる。Another method is also available in which iodine liberated by the reaction between manganese dioxide and calcium iodide is washed and separated to prepare a positive electrode mixture, and then assembled into a battery.
【００１１】ボタン形，円筒形などの電池形状その他各
種の規格については、通常の非水電解液電池に応じたも
のとすればよい。The battery shape such as the button shape and the cylindrical shape and various other standards may be adapted to those of ordinary non-aqueous electrolyte batteries.
【００１２】[0012]
【作用】以上の構成によれば、予備放電をしなくてもガ
ス発生がなく、また予備放電した場合に比べて放電容量
のバラツキが小さい。これはヨウ化カルシウムの添加に
より二酸化マンガン活物質の分解成分である活性部分が
電池形成以前に均一な状態で失活するため、前記カーボ
ネート類の分解を阻止するものと推定される。According to the above structure, no gas is generated even if the preliminary discharge is not performed, and the variation of the discharge capacity is smaller than that in the case of the preliminary discharge. It is presumed that this is because the addition of calcium iodide deactivates the active component, which is a decomposition component of the manganese dioxide active material, in a uniform state before the formation of the battery, and thus prevents the decomposition of the carbonates.
【００１３】[0013]
【発明の効果】本発明では、次の効果がある。すなわ
ち、あらかじめ二酸化マンガン中に含まれる活性部分を
取り除いておくことによって、予備放電することなくガ
ス発生を未然に防止できるため、予備放電のための装置
および時間を要することなく電池製造後直ちに製品とし
て出荷できる。The present invention has the following effects. In other words, by removing the active portion contained in manganese dioxide in advance, it is possible to prevent gas generation without performing preliminary discharge, so that a product can be produced immediately after battery production without requiring a device and time for preliminary discharge. Can be shipped.
【００１４】また、予備放電に起因する電池容量のバラ
ツキが生ずることがなく、個々の電池の容量バラツキを
小さく押さえることができる。Further, variation in battery capacity due to preliminary discharge does not occur, and variation in capacity of individual batteries can be suppressed to a small level.
【００１５】[0015]
【実施例】次に実施例について説明する。ただし本発明
は以下の実施例に限定されるものではない。EXAMPLES Next, examples will be described. However, the present invention is not limited to the following examples.
【００１６】実施例１．ヨウ化カルシウムの水和物Ｃａ
Ｉ2 ・n Ｈ2 Ｏ（n は約３．３）０．７ｇを水５０ccに
溶解し、これを二酸化マンガン８７ｇとよく混合し１１
０℃で乾燥した。添加混合比率はモル比で二酸化マンガ
ン１００に対し、ヨウ化カルシウム０．２である。次い
でこの混合物を導電材であるグラファイト１０ｇ，バイ
ンダとしてのＰＴＦＥ２ｇと混合して正極合剤とし、こ
の正極合剤１０００ｍｇをディスク状にプレスし、ＣＲ
２０３２形電池（ボタン形電池）の正極とした。また、
負極としては金属リチウムを用い、セパレータとしては
ＰＰ不織布とＰＰポーラスフィルムラミネート品とを用
い、さらに非水電解液としては溶媒としてプロピレンカ
ーボネートとジメトキシエタンの１：１の混合溶剤に過
塩素酸リチウムを溶質として溶解したものを用いた。Example 1. Calcium iodide hydrate Ca
0.7 g of I 2 · n H 2 O (n is about 3.3) was dissolved in 50 cc of water and mixed well with 87 g of manganese dioxide.
It was dried at 0 ° C. The molar ratio of addition is 100 parts of manganese dioxide and 0.2 parts of calcium iodide. Next, this mixture was mixed with 10 g of graphite, which is a conductive material, and 2 g of PTFE, which was a binder, to prepare a positive electrode mixture, and 1000 mg of this positive electrode mixture was pressed into a disk shape to form a CR film.
It was used as the positive electrode of the 2032 type battery (button type battery). Also,
Lithium metal is used as the negative electrode, a PP nonwoven fabric and a PP porous film laminate are used as the separator, and lithium perchlorate is used as a non-aqueous electrolyte in a 1: 1 mixed solvent of propylene carbonate and dimethoxyethane. What was melt | dissolved was used as a solute.
【００１７】実施例２．ヨウ化カルシウムの水和物Ｃａ
Ｉ2 ・n Ｈ2 Ｏ（n は約３．３）１７．７ｇを水１５０
ccに溶解し、これを二酸化マンガン８７ｇとよく混合し
６０℃に加熱して反応させた後、遊離したヨウ素を水洗
して除去し、その後１１０℃で乾燥した。添加混合比率
はモル比で二酸化マンガン１００に対し、ヨウ化カルシ
ウム５である。次いでこの混合物を用いて実施例１．と
同様な手順および組合せでＣＲ２０３２形電池を完成し
た。Embodiment 2. Calcium iodide hydrate Ca
I 2 · n H 2 O (n is about 3.3) 17.7 g of water 150
It was dissolved in cc, mixed well with 87 g of manganese dioxide, heated at 60 ° C. to react, and then free iodine was removed by washing with water, followed by drying at 110 ° C. The molar ratio of addition is 100 parts of manganese dioxide and 5 parts of calcium iodide. This mixture is then used in Example 1. A CR2032 type battery was completed by the same procedure and combination.
【００１８】実施例３．ヨウ化カルシウムの水和物Ｃａ
Ｉ2 ・n Ｈ2 Ｏ（n は約３．３）０．３５ｇを水５０cc
に溶解し、これを二酸化マンガン８７ｇとよく混合し６
０℃に加熱して反応させた後、遊離したヨウ素を水洗し
て除去し、その後１１０℃で乾燥した。添加混合比率は
モル比で二酸化マンガン１００に対し、ヨウ化カルシウ
ム０．１である。次いでこの混合物を用いて実施例１．
と同様な手順および組合せでＣＲ２０３２形電池を完成
した。Example 3. Calcium iodide hydrate Ca
I 2 · n H 2 O (n is about 3.3) 0.35 g with water 50 cc
It was dissolved in and mixed well with 87 g of manganese dioxide 6
After heating to 0 ° C. for reaction, the released iodine was removed by washing with water, and then dried at 110 ° C. The molar ratio of addition is 100 parts of manganese dioxide and 0.1 parts of calcium iodide. This mixture is then used in Example 1.
A CR2032 type battery was completed by a procedure and a combination similar to.
【００１９】実施例４．ヨウ化カルシウムの水和物Ｃａ
Ｉ2 ・n Ｈ2 Ｏ（n は約３．３）２１．１ｇを水２００
ccに溶解し、これを二酸化マンガン８７ｇとよく混合し
６０℃に加熱して反応させた後、遊離したヨウ素を水洗
して除去し、その後１１０℃で乾燥した。添加混合比率
はモル比で二酸化マンガン１００に対し、ヨウ化カルシ
ウム６である。次いでこの混合物を用いて実施例１．と
同様な手順および組合せでＣＲ２０３２形電池を完成し
た。Example 4. Calcium iodide hydrate Ca
I 2 · n H 2 O (n is about 3.3) 21.1 g of water 200
It was dissolved in cc, mixed well with 87 g of manganese dioxide, heated at 60 ° C. to react, and then free iodine was removed by washing with water, followed by drying at 110 ° C. The molar ratio of addition is 100 parts of manganese dioxide and 6 parts of calcium iodide. This mixture is then used in Example 1. A CR2032 type battery was completed by the same procedure and combination.
【００２０】比較例１． 実施例１．において、ヨウ化カルシウムを添加せずに同
様の手順および組合せで完成したＣＲ２０３２形電池を
放電処理しないまま放置した。Comparative Example 1. Example 1. In, the CR2032 type battery completed by the same procedure and combination without adding calcium iodide was left without being discharged.
【００２１】比較例２． 比較例１．において電池完成後、６mAh 分の容量を予備
放電した。Comparative Example 2. Comparative Example 1. After completion of the battery, the capacity of 6 mAh was pre-discharged.
【００２２】次に、以上の構成の電池各１０個ずつを６
０℃で２０日間保存した後、２０℃２．７ＫΩの負荷で
放電したところ、以下の表に一括して示すように、それ
ぞれの放電容量およびバラツキ（標準偏差）に差異が生
じることが確認された。Next, each of the 10 batteries having the above structure is replaced with 6 batteries.
When stored at 0 ° C for 20 days and then discharged at a load of 20 ° C and 2.7 KΩ, it was confirmed that there was a difference in each discharge capacity and variation (standard deviation), as shown in the table below. It was
【００２３】[0023]
【表１】 以上の表から明らかなように、本発明にあっては、放電
容量が予備放電を施したものよりも高く、またバラツキ
（標準偏差）も小さい。またこのことは、ヨウ化カルシ
ウムの添加により二酸化マンガン活物質の分解成分であ
る活性部分が電池形成以前に均一な状態で失活するた
め、カーボネート類の分解を阻止することを示唆するも
のである。[Table 1] As is clear from the above table, in the present invention, the discharge capacity is higher than that in the case of performing the preliminary discharge, and the variation (standard deviation) is small. This also suggests that the addition of calcium iodide deactivates the active components, which are the decomposition components of the manganese dioxide active material, in a uniform state before the formation of the battery, thus preventing the decomposition of carbonates. ..
───────────────────────────────────────────────────── フロントページの続き (72)発明者 野末 智久 東京都港区新橋５丁目36番11号 富士電気 化学株式会社内 (72)発明者 吉岡 吾恵 東京都港区新橋５丁目36番11号 富士電気 化学株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tomohisa Nozue 5-36-1 Shimbashi, Minato-ku, Tokyo Fuji Electric Chemical Co., Ltd. (72) Inventor Goe Yoshioka 5-36-11 Shinbashi, Minato-ku, Tokyo Fuji Electric Chemical Co., Ltd.
Claims (2)
い、溶媒としてエチレンカーボネートないしはプロピレ
ンカーボネートを含む非水電解液を用いた非水電解液電
池において、前記二酸化マンガン中にあらかじめ少量の
ヨウ化カルシウムを添加したことを特徴とする非水電解
液電池。1. A non-aqueous electrolyte battery using a positive electrode containing manganese dioxide as a main component and a non-aqueous electrolyte solution containing ethylene carbonate or propylene carbonate as a solvent, wherein a small amount of calcium iodide is previously contained in the manganese dioxide. A non-aqueous electrolyte battery comprising the addition of:
ガンに対する添加量がモル比で二酸化マンガン１００に
対し、０．２〜５．０であることを特徴とする請求項１
に記載の非水電解液電池。2. The addition amount of the calcium iodide to the manganese dioxide is 0.2 to 5.0 with respect to 100 of manganese dioxide in a molar ratio.
The non-aqueous electrolyte battery described in.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04037973A JP3115080B2 (en) | 1992-02-25 | 1992-02-25 | Non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04037973A JP3115080B2 (en) | 1992-02-25 | 1992-02-25 | Non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05234591A true JPH05234591A (en) | 1993-09-10 |
| JP3115080B2 JP3115080B2 (en) | 2000-12-04 |
Family
ID=12512511
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04037973A Expired - Lifetime JP3115080B2 (en) | 1992-02-25 | 1992-02-25 | Non-aqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3115080B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2141109A4 (en) | 2007-04-26 | 2013-10-30 | Mitsubishi Electric Corp | ELEVATOR DEVICE |
-
1992
- 1992-02-25 JP JP04037973A patent/JP3115080B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP3115080B2 (en) | 2000-12-04 |
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