JP2752670B2 - Alkaline manganese secondary battery - Google Patents

Alkaline manganese secondary battery

Info

Publication number
JP2752670B2
JP2752670B2 JP63297823A JP29782388A JP2752670B2 JP 2752670 B2 JP2752670 B2 JP 2752670B2 JP 63297823 A JP63297823 A JP 63297823A JP 29782388 A JP29782388 A JP 29782388A JP 2752670 B2 JP2752670 B2 JP 2752670B2
Authority
JP
Japan
Prior art keywords
secondary battery
battery
alkaline manganese
manganese
alkaline
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
Application number
JP63297823A
Other languages
Japanese (ja)
Other versions
JPH02144849A (en
Inventor
義久 日野
吉郎 原田
正典 中西
雅一 北方
秀哲 名倉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
FDK Corp
Original Assignee
FDK Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by FDK Corp filed Critical FDK Corp
Priority to JP63297823A priority Critical patent/JP2752670B2/en
Publication of JPH02144849A publication Critical patent/JPH02144849A/en
Application granted granted Critical
Publication of JP2752670B2 publication Critical patent/JP2752670B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Description

【発明の詳細な説明】 ＜産業上の利用分野＞ この発明は、アルカリマンガン二次電池に関するもの
である。Description: TECHNICAL FIELD The present invention relates to an alkaline manganese secondary battery.

＜従来の技術＞ アルカリマンガン二次電池では、一般に、アルカリ水
溶液を電解液とし、また二酸化マンガンを活物質とする
正極合剤と、粉末亜鉛をゲル状に分散させたゲル状亜鉛
負極を用いて構成される。<Conventional technology> In general, an alkaline manganese secondary battery uses an alkaline aqueous solution as an electrolyte, a positive electrode mixture containing manganese dioxide as an active material, and a gelled zinc negative electrode in which powdered zinc is dispersed in a gel form. Be composed.

従来、この種の電池の正極活物質に用いられる二酸化
マンガンとしては、所謂電解二酸化マンガン（γ形二酸
化マンガン）、250〜400℃で熱処理した二酸化マンガ
ン、あるいはMn（NO3）２・6H2Oを150〜190℃で加熱処
理して得た二酸化マンガンなどがある。Conventionally, as a manganese dioxide used as a positive electrode active material of this type of battery, so-called electrolytic manganese dioxide (γ-type manganese dioxide), manganese dioxide heat-treated at 250 to 400 ° C., or Mn (NO 3 ) 2 .6H 2 O And manganese dioxide obtained by heat treatment at 150 to 190 ° C.

＜発明が解決しようとする課題＞ しかしながら、従来より使用されている上記の二酸化
マンガンを正極活物質とするアルカリマンガン二次電池
では、放電の際に二酸化マンガン固相内に侵入した水素
イオンが内部で安定化し、続く充電によって二酸化マン
ガン外部に放出され難く、充放電による可逆性が悪い。<Problems to be solved by the invention> However, in the conventional alkaline manganese secondary battery using manganese dioxide as a positive electrode active material, hydrogen ions penetrating into the manganese dioxide solid phase at the time of discharge are internally charged. And it is difficult to be released to the outside of manganese dioxide by subsequent charging, and reversibility due to charging and discharging is poor.

このため、充電による電池容量の回復が十分でなく、
またサイクル進行に伴う放電容量の低下が大きく、十分
なサイクル数が得られないという問題がある。For this reason, the recovery of the battery capacity by charging is not sufficient,
Further, there is a problem that the discharge capacity is greatly reduced with the progress of the cycle, and a sufficient number of cycles cannot be obtained.

この発明は、充放電サイクル特性が良好なアルカリマ
ンガン二次電池を提供することを目的とする。An object of the present invention is to provide an alkaline manganese secondary battery having good charge / discharge cycle characteristics.

＜課題を解決するための手段＞ この発明のアルカリマンガン二次電池は、負極活物質
に亜鉛を、また電解液にはアルカリ水溶液をそれぞれ用
いてなるアルカリマンガン二次電池において、正極活物
質に亜マンガン酸（H2MnO3あるいはMnO2・H2O）または
亜マンガン酸塩を用いたことを要旨とする。<Means for Solving the Problems> The alkaline manganese secondary battery according to the present invention is an alkaline manganese secondary battery using zinc as a negative electrode active material and an aqueous alkaline solution as an electrolytic solution. The gist is that manganese acid (H 2 MnO 3 or MnO 2 .H 2 O) or manganate is used.

上記の亜マンガン酸塩としては、カルシウム，マグネ
シウム，亜鉛，あるいはアルミニウムなどから選ばれる
少なくとも一種の金属を含むものが挙げられる。Examples of the above manganate include those containing at least one metal selected from calcium, magnesium, zinc, aluminum and the like.

＜作用＞ 上記の亜マンガン酸は層状構造を持ち、このため水素
イオンの出入りに関し、充放電における可逆性が良好で
ある。<Action> The above-described manganic acid has a layered structure, and therefore has good reversibility in charge and discharge with respect to the entry and exit of hydrogen ions.

従ってこの亜マンガン酸を正極活物質に用いた場合、
サイクル進行に伴う容量低下が少なく、従ってサイクル
特性の良いアルカリマンガン二次電池を得ることができ
る。Therefore, when this manganic acid is used for the positive electrode active material,
An alkaline manganese secondary battery having a small capacity reduction due to the progress of the cycle and having good cycle characteristics can be obtained.

＜実施例＞ Mn（NO3）２・4H2O〜6H2Oを70g、またLiOHを24g採
り、各々を水200mlにそれぞれ溶かし混合した水溶液
に、温度５℃にて空気を吹込んで、亜マンガン酸を合成
した。次いで、この亜マンガン酸を純水１で洗浄した
後、温度100℃で乾燥した。<Example> 70 g of Mn (NO 3 ) 2 .4H 2 O to 6H 2 O and 24 g of LiOH were taken, and each was dissolved in 200 ml of water and mixed with an aqueous solution at a temperature of 5 ° C. Manganese acid was synthesized. Next, the manganic acid was washed with pure water 1 and dried at a temperature of 100 ° C.

以上の処理で得た亜マンガン酸８重量部に、グラファ
イト，ポリエチレンディスパージョンをそれぞれ１重量
部づつ混合し、この混合物を円筒状に加圧成形してリン
グ状の正極合剤を作った。One part by weight of graphite and 8 parts by weight of polyethylene dispersion were mixed with 8 parts by weight of the manganic acid obtained by the above treatment, and the mixture was pressure-formed into a cylindrical shape to prepare a ring-shaped positive electrode mixture.

そして、第１図の通り、この正極合剤１を、有底円筒
状の電池缶２に圧入し、またこの正極合剤１の中空部に
は、セパレータ２を介して、電解液として40％KOH水溶
液を用いてなるゲル状亜鉛負極４を充填するなどして、
単３形の円筒形アルカリマンガン二次電池（本発明品）
を作製した。図中５は封口ガスケット、６は端子板,7は
集電棒である。Then, as shown in FIG. 1, this positive electrode mixture 1 was pressed into a cylindrical battery can 2 having a bottom, and a 40% electrolyte solution was inserted into the hollow portion of the positive electrode mixture 1 through a separator 2 as an electrolyte. By filling the gelled zinc negative electrode 4 using an aqueous KOH solution,
AA cylindrical alkaline manganese rechargeable battery (product of the present invention)
Was prepared. In the figure, 5 is a sealing gasket, 6 is a terminal plate, and 7 is a current collecting rod.

一方正極活物質として亜マンガン酸に代えて電解二酸
化マンガンを用いた他は同様にして、単３形の円筒形ア
ルカリマンガン二次電池（従来品）を作製した。On the other hand, an AA cylindrical alkaline manganese secondary battery (conventional product) was produced in the same manner except that electrolytic manganese dioxide was used instead of manganese oxide as the positive electrode active material.

これらの電池を、電流0.1Aで電池電圧が1.8Vになるま
で充電した後、電流0.3Aで終止電圧0.9Vまで放電すると
いうサイクルを繰返した。These batteries were repeatedly charged at a current of 0.1 A until the battery voltage reached 1.8 V, and then discharged at a current of 0.3 A to a final voltage of 0.9 V.

これらの電池のサイクル特性は第２図に示した通りで
あり、本発明品では第80サイクルをすぎても容量変化率
が80％以上であるのに対し、従来品では第25サイクル頃
から容量変化率が50％以下に低下してしまった。The cycle characteristics of these batteries are as shown in FIG. 2. The capacity change rate of the battery of the present invention is 80% or more even after the 80th cycle, whereas the capacity of the conventional battery is about 25 cycles. The rate of change has dropped below 50%.

一方、Mn（NO3）２・4H2O〜6H2Oを70g、またカルシウ
ム，マグネシウム，亜鉛，あるいはアルミニウムの硝酸
塩をマンガンに対し１〜30モル％とり、これらを水300m
lに溶かし混合した水溶液に、LiOH（24g＋上記硝酸塩の
２倍のモル比に相当する量）を200ml水溶液にしたもの
を混ぜ、またこの水溶液に温度５℃にて空気を吹き込ん
で、亜マンガン酸塩を種々合成した。次いで、これら亜
マンガン酸塩を純水１で洗浄した後、温度100℃で乾
燥した。On the other hand, 70 g of Mn (NO 3 ) 2 .4H 2 O to 6H 2 O, 1 to 30 mol% of calcium, magnesium, zinc, or aluminum nitrate based on manganese are taken, and these are mixed with 300 m of water.
The aqueous solution obtained by dissolving and mixing the mixture into a solution of LiOH (24 g + an amount corresponding to twice the molar ratio of the above nitrate) in a 200 ml aqueous solution was mixed, and air was blown into the aqueous solution at a temperature of 5 ° C. Various salts were synthesized. Next, these manganites were washed with pure water 1 and dried at a temperature of 100 ° C.

そして、上記の亜マンガン酸塩をそれぞれ正極活物質
に用いた他は、上記と同様にして、単３形の円筒形アル
カリマンガン二次電池を作製し、またこれらの電池につ
いて、上記と同じ条件で充放電サイクル試験を行った。Then, AA cylindrical alkaline manganese rechargeable batteries were manufactured in the same manner as above, except that the above manganates were used as the positive electrode active materials, respectively. A charge / discharge cycle test was performed.

これらの電池の第30サイクル目における容量変化率
（％）は第３図に示した通りで、それぞれ良好な特性を
示した。尚、図において、はカルシウムを含む亜マン
ガン酸塩を、はマグネシウムを含む亜マンガン酸塩
を、は亜鉛を含むマンガン酸塩を、またはアルミニ
ウムを含む亜マンガン酸塩をそれぞれ正極活物質とする
電池の特性である。また、この図で横軸は、上記各金属
のマンガンに対するモル（％）である。The capacity change rate (%) of these batteries in the 30th cycle was as shown in FIG. 3, and each battery showed good characteristics. In the figures, is a battery containing calcium as a positive electrode active material using calcium-containing manganate, magnesium-containing manganate, zinc-containing manganate, or aluminum-containing manganate. It is the characteristic of. In this figure, the horizontal axis is the mole (%) of each of the above metals with respect to manganese.

尚、以上は本発明を筒形電池に適用した例であるが、
この他例えばボタン形電池に適用した場合も同様な効果
が得られることは明らかである。The above is an example in which the present invention is applied to a cylindrical battery.
It is apparent that similar effects can be obtained when applied to, for example, a button-type battery.

＜発明の効果＞ 以上のようにこの発明によれば、充放電サイクル特性
が良好なアルカリマンガン二次電池を提供することがで
きる。<Effects of the Invention> As described above, according to the present invention, an alkaline manganese secondary battery having good charge / discharge cycle characteristics can be provided.

【図面の簡単な説明】[Brief description of the drawings]

第１図は実施例の電池の断面図、第２図は本発明品と従
来品の充放電サイクル特性を示したグラフ、第３図は他
の実施例の電池の第30サイクル目における容量変化率を
示したグラフである。 １……正極合剤、２……電池缶、４……ゲル状亜鉛負
極。FIG. 1 is a cross-sectional view of the battery of the embodiment, FIG. 2 is a graph showing the charge / discharge cycle characteristics of the battery of the present invention and the conventional battery, and FIG. It is the graph which showed the rate. 1 ... a positive electrode mixture, 2 ... a battery can, 4 ... a gelled zinc negative electrode.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 北方 雅一 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 名倉 秀哲 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 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masakazu Kita 5-36-11 Shimbashi, Minato-ku, Tokyo Inside Fuji Electric Chemical Co., Ltd. (72) Inventor Hidenori Nakura 5-36-11 Shimbashi, Minato-ku, Tokyo No. Fuji Electric Chemical Co., Ltd.

Claims (2)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】負極活物質に亜鉛を、また電解液にはアル
カリ水溶液をそれぞれ用いてなるアルカリマンガン二次
電池において、正極活物質に亜マンガン酸または亜マン
ガン酸塩を用いたことを特徴とするアルカリマンガン二
次電池。1. An alkaline manganese secondary battery using zinc as a negative electrode active material and an aqueous alkaline solution as an electrolyte, wherein manganic acid or manganite is used as a positive electrode active material. Alkaline manganese secondary battery. 【請求項２】前記亜マンガン酸塩が、カルシウム，マグ
ネシウム，亜鉛，あるいはアルミニウムなどの金属を含
むものであることを特徴とする請求項１記載のアルカリ
マンガン二次電池。2. The alkaline manganese secondary battery according to claim 1, wherein said manganite contains a metal such as calcium, magnesium, zinc or aluminum.
JP63297823A 1988-11-25 1988-11-25 Alkaline manganese secondary battery Expired - Fee Related JP2752670B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP63297823A JP2752670B2 (en) 1988-11-25 1988-11-25 Alkaline manganese secondary battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP63297823A JP2752670B2 (en) 1988-11-25 1988-11-25 Alkaline manganese secondary battery

Publications (2)

Publication Number Publication Date
JPH02144849A JPH02144849A (en) 1990-06-04
JP2752670B2 true JP2752670B2 (en) 1998-05-18

Family

ID=17851620

Family Applications (1)

Application Number Title Priority Date Filing Date
JP63297823A Expired - Fee Related JP2752670B2 (en) 1988-11-25 1988-11-25 Alkaline manganese secondary battery

Country Status (1)

Country Link
JP (1) JP2752670B2 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113851738B (en) * 2021-08-24 2023-03-21 深圳先进技术研究院 Rechargeable manganese ion battery and preparation method thereof

Also Published As

Publication number Publication date
JPH02144849A (en) 1990-06-04

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