JPH09180736A - Alkaline manganese battery - Google Patents
Alkaline manganese batteryInfo
- Publication number
- JPH09180736A JPH09180736A JP33913295A JP33913295A JPH09180736A JP H09180736 A JPH09180736 A JP H09180736A JP 33913295 A JP33913295 A JP 33913295A JP 33913295 A JP33913295 A JP 33913295A JP H09180736 A JPH09180736 A JP H09180736A
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- JP
- Japan
- Prior art keywords
- positive electrode
- potassium hydroxide
- negative electrode
- electrolytic solution
- weight
- 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.)
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- Y02E60/12—
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- Primary Cells (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はアルカリマンガン電
池に関する。TECHNICAL FIELD The present invention relates to an alkaline manganese battery.
【０００２】[0002]
【従来の技術】従来のアルカリマンガン電池にあって
は、図１のＬＲ６形電池の断面図に示すように、電池ケ
ースを兼ねる有底円筒形の正極缶１内に、二酸化マンガ
ン（電解二酸化マンガン：ＥＭＤ）と黒鉛等を混合して
円筒状に成形した２つの正極２，２が同心に積み重ねら
れた状態で装填されている。この正極２，２の中空部内
にはビニロンやパルプ繊維等の不織布からなる筒状のセ
パレータ３が配設され、これには水酸化カリウム（ＫＯ
Ｈ）のアルカリ電解液が含浸されている。さらにセパレ
ータ３内にはゲル状負極４が充填されており、この負極
４は、酸化亜鉛（ＺｎＯ）を含む水酸化カリウム電解液
に対して亜鉛粉末を主体としてゲル化剤および高吸水性
ポリマーを適量混合した構成となっている。2. Description of the Related Art In a conventional alkaline manganese battery, a manganese dioxide (electrolytic manganese dioxide) is placed in a bottomed cylindrical positive electrode can 1 which also serves as a battery case, as shown in the sectional view of the LR6 battery in FIG. : EMD) and graphite or the like are mixed to form two cylindrical positive electrodes 2 and 2 that are concentrically stacked. A cylindrical separator 3 made of non-woven fabric such as vinylon or pulp fiber is disposed in the hollow portion of the positive electrodes 2 and 2, and potassium hydroxide (KO
H) is impregnated with the alkaline electrolyte. Further, a gelled negative electrode 4 is filled in the separator 3, and the negative electrode 4 is mainly composed of zinc powder in a potassium hydroxide electrolytic solution containing zinc oxide (ZnO) and contains a gelling agent and a superabsorbent polymer. It has a composition in which an appropriate amount is mixed.
【０００３】この負極４の中央には集電棒５が挿入さ
れ、セパレータ３の下端開口部は、ホットメルト樹脂等
からなる絶縁材６によって閉塞され、これによって負極
４と正極缶１の内底面とが互いに絶縁している。そし
て、正極缶１の上端開口部に封口ガスケット７を介して
負極端子板８が嵌合され、正極缶１の開口端縁を内側へ
カール成形することによって密封されている。A collector rod 5 is inserted in the center of the negative electrode 4, and an opening at the lower end of the separator 3 is closed by an insulating material 6 made of hot melt resin or the like, whereby the negative electrode 4 and the inner bottom surface of the positive electrode can 1 are formed. Are insulated from each other. Then, the negative electrode terminal plate 8 is fitted into the upper end opening of the positive electrode can 1 through the sealing gasket 7, and the opening end edge of the positive electrode can 1 is curled inward to be sealed.
【０００４】このようなアルカリマンガン電池におい
て、その放電容量を大きくできるものが特公平５−１２
８２４号公報に示されており、同公報に示された電池に
あっては正極の配合比率を工夫することにより放電容量
の増大を図っている。Among such alkaline manganese batteries, the one which can increase the discharge capacity is disclosed in JP-B-5-12.
In the battery disclosed in Japanese Patent No. 824, the discharge capacity is increased by devising the compounding ratio of the positive electrode.
【０００５】具体的に説明すると、正極としては、活物
質としての二酸化マンガンと導電剤としての黒鉛とを、
重量比で９／１〜３２／１の範囲で混合した合剤が用い
られる。つまり、黒鉛の含有率を正極２の合剤固形分に
対して３〜１０重量％の範囲としている。Specifically, for the positive electrode, manganese dioxide as an active material and graphite as a conductive agent are used.
A mixture mixed in a weight ratio of 9/1 to 32/1 is used. That is, the content of graphite is set within the range of 3 to 10% by weight based on the solid mixture content of the positive electrode 2.
【０００６】即ち、黒鉛の含有率を１０％以上にする
と、二酸化マンガンの容量減少が顕著となり、放電容量
の大きな低下を招くので好ましくない。また、黒鉛の含
有率を３％以下にすると正極２中の導電性が低くなりす
ぎるため、内部抵抗の増加、短絡電流の減少が顕著にな
り、やはり好ましくない。That is, if the content of graphite is 10% or more, the capacity of manganese dioxide decreases remarkably and the discharge capacity decreases significantly, which is not preferable. Further, if the graphite content is 3% or less, the conductivity in the positive electrode 2 becomes too low, so that the internal resistance increases and the short-circuit current decreases remarkably, which is also not preferable.
【０００７】[0007]
【発明が解決しようとする課題】しかしながら、前述し
たように正極合剤の配合比率を工夫しただけでは、例え
ば１５００ｍＡ程度の極めて大きな放電電流を必要とす
る超高負荷に対しては対応できないといった問題があっ
た。However, it is not possible to cope with an ultra-high load requiring an extremely large discharge current of, for example, about 1500 mA simply by devising the mixing ratio of the positive electrode mixture as described above. was there.
【０００８】例えばノート型パソコン等の超高負荷に対
してその動作電力を供給するための電源としてアルカリ
マンガン電池を用いようとすると、ノート型パソコンの
フロッピーディスク駆動装置の動作時に１５００ｍＡ程
度の極めて大きな放電電流が必要とされる。ところが、
前述したような従来のアルカリマンガン電池にあっては
このような超高負荷に対して満足な放電容量を得ること
ができなかった。For example, when an alkaline manganese battery is used as a power source for supplying an operating power to an ultra-high load of a notebook type personal computer or the like, when the floppy disk drive of the notebook type personal computer is operating, it is extremely large, about 1500 mA. Discharge current is required. However,
In the conventional alkaline manganese battery as described above, it was not possible to obtain a satisfactory discharge capacity under such an ultrahigh load.
【０００９】そこで、前述したような正極合剤の配合比
率を工夫したアルカリマンガン電池に対して改良を施す
ことにより本発明に至ったのであり、その目的は超高負
荷に対する放電特性の優れたアルカリマンガン電池を提
供することにある。Therefore, the present invention has been accomplished by improving the alkaline manganese battery in which the compounding ratio of the positive electrode mixture is devised as described above, and the purpose thereof is to obtain an alkaline having excellent discharge characteristics against an ultrahigh load. To provide a manganese battery.
【００１０】[0010]
【課題を解決するための手段】前記目的を達成するため
請求項１に係る本発明は、正極活物質としての二酸化マ
ンガンに混合される導電剤としての黒鉛を３〜１０重量
％の範囲で含有する正極合剤固形分に対し、正極用水酸
化カリウム電解液を含浸させた正極と、酸化亜鉛を含む
負極用水酸化カリウム電解液に対して負極活物質として
の亜鉛粉末、ゲル化剤、および高吸水性ポリマーを混合
したゲル状負極とを備えたアルカリ電池において、前記
正極と前記負極との電気容量比率を１００：１０５〜１
００：１２５の範囲とした。In order to achieve the above-mentioned object, the present invention according to claim 1 comprises 3 to 10% by weight of graphite as a conductive agent mixed with manganese dioxide as a positive electrode active material. For the positive electrode mixture solid content, the positive electrode impregnated with the potassium hydroxide electrolytic solution for the positive electrode, and the zinc powder, the gelling agent, and the high water absorption as the negative electrode active material for the potassium hydroxide electrolytic solution for the negative electrode containing zinc oxide In an alkaline battery provided with a gelled negative electrode mixed with a conductive polymer, an electric capacity ratio between the positive electrode and the negative electrode is 100: 105 to 1
The range was 00: 125.
【００１１】ここで正極または負極の電気容量とは次に
示す計算式によって定まる理論容量のことである。Here, the electric capacity of the positive electrode or the negative electrode is a theoretical capacity determined by the following formula.
【００１２】〔正極の電気容量：１電子反応として〕 （二酸化マンガンの当量に対する正極に用いた二酸化マ
ンガンの質量の割合）×（９６５００／３６００） 〔負極の電気容量：２電子反応として〕 （亜鉛の当量に対する負極に用いた亜鉛粉末の質量の割
合）×（９６５００／３６００）[Electrical capacity of positive electrode: as one-electron reaction] (Ratio of mass of manganese dioxide used for positive electrode to equivalent of manganese dioxide) × (96500/3600) [Electrical capacity of negative electrode: as two-electron reaction] (Zinc Ratio of the mass of the zinc powder used for the negative electrode to the equivalent weight of x) (96500/3600)
【００１３】また、前記目的を達成するため請求項２に
係る本発明は、前記正極用水酸化カリウム電解液の水酸
化カリウム濃度を４０重量％とするとともに、前記正極
合剤固形分と前記正極用水酸化カリウム電解液との体積
比率を１００：２５〜１００：３５の範囲とした。In order to achieve the above object, the present invention according to claim 2 provides that the potassium hydroxide concentration of the potassium hydroxide electrolyte for the positive electrode is 40% by weight, and the solid content of the positive electrode mixture and the water for the positive electrode. The volume ratio with the potassium oxide electrolyte was in the range of 100: 25 to 100: 35.
【００１４】さらに、前記目的を達成するため請求項３
に係る本発明は、正極活物質としての二酸化マンガンに
混合される導電剤として平均粒径が１０〜２０μｍの黒
鉛を３〜１０重量％の範囲で含有する正極合剤固形分に
対し、正極用水酸化カリウム電解液を含浸させた正極
と、酸化亜鉛を含む負極用水酸化カリウム電解液に対し
て負極活物質としての亜鉛粉末、ゲル化剤、および高吸
水性ポリマーを混合したゲル状負極とを備えたアルカリ
マンガン電池において、前記正極と前記負極との電気容
量比率を１００：１０５〜１００：１２５の範囲とし、
且つ前記正極用水酸化カリウム電解液の水酸化カリウム
濃度を４０重量％とするとともに、前記正極合剤固形分
と前記正極用水酸化カリウム電解液との体積比率を１０
０：２５〜１００：３５の範囲とした。Furthermore, in order to achieve the above-mentioned object, claim 3
The present invention relates to a positive electrode mixture solid content containing graphite having an average particle size of 10 to 20 μm in a range of 3 to 10 wt% as a conductive agent mixed with manganese dioxide as a positive electrode active material. A positive electrode impregnated with a potassium oxide electrolytic solution, and a gelled negative electrode in which zinc powder as a negative electrode active material for a negative electrode potassium hydroxide electrolytic solution containing zinc oxide, a gelling agent, and a superabsorbent polymer are mixed In the alkaline manganese battery, the electric capacity ratio between the positive electrode and the negative electrode is in the range of 100: 105 to 100: 125,
The potassium hydroxide concentration of the positive electrode potassium hydroxide electrolytic solution is set to 40% by weight, and the volume ratio of the positive electrode mixture solid content to the positive electrode potassium hydroxide electrolytic solution is 10%.
The range was 0:25 to 100: 35.
【００１５】好ましくは、前記負極用水酸化カリウム電
解液の水酸化カリウム濃度を４０重量％とするととも
に、前記負極用水酸化カリウム電解液に対する前記酸化
亜鉛の濃度を４重量％とする。Preferably, the potassium hydroxide concentration of the negative electrode potassium hydroxide electrolytic solution is 40% by weight, and the zinc oxide concentration of the negative electrode potassium hydroxide electrolytic solution is 4% by weight.
【００１６】前述したような構成の本発明にあっては次
のような作用を奏する。The present invention having the above-described structure has the following operation.
【００１７】正極と負極との電気容量比率を１００：１
０５〜１００：１２５の範囲として負極側の電気容量を
大きくすることにより、正極および負極の放電利用率を
向上させ、例えば１５００m Ａ程度の大放電流を必要と
する超高負荷に対してその放電時間を長くすることがで
きる。The electric capacity ratio of the positive electrode and the negative electrode is 100: 1.
The discharge capacity of the positive electrode and the negative electrode is improved by increasing the electric capacity on the negative electrode side in the range of 05 to 100: 125, and the discharge is performed against an ultrahigh load that requires a large discharge current of, for example, 1500 mA. The time can be lengthened.
【００１８】前記電気容量比率において負極側が１０５
より小さいと、正極側の二酸化マンガンに対して負極側
の亜鉛粉末の量が少ないため正極および負極の活物質の
放電利用率が低下し、超高負荷に対する放電容量が小さ
くなり好ましくない。また、前記電気容量比率において
負極側が１２５より大きいと、正極側の二酸化マンガン
に対して負極側の亜鉛粉末の量が多すぎるためゲル負極
が電池の所定容積に入りきらず製造困難となり好ましく
ない。In the electric capacity ratio, the negative electrode side is 105
When it is smaller, the amount of zinc powder on the negative electrode side is smaller than the amount of manganese dioxide on the positive electrode side, so the discharge utilization factor of the active material of the positive electrode and the negative electrode decreases, and the discharge capacity under an ultrahigh load decreases, which is not preferable. Further, when the negative electrode side is larger than 125 in the above electric capacity ratio, the amount of the zinc powder on the negative electrode side is too large for the manganese dioxide on the positive electrode side, and the gel negative electrode does not fill the predetermined volume of the battery, which is difficult to manufacture, which is not preferable.
【００１９】正極合剤固形分と４０重量％正極用水酸化
カリウム電解液との体積比率を１００：２５〜１００：
３５の範囲とすることにより、正極および負極の放電利
用率を向上させ、例えば１５００ｍＡ程度の大放電流を
必要とする超高負荷に対してその放電時間を長くするこ
とができる。The volume ratio of the positive electrode mixture solid content to the 40 wt% positive electrode potassium hydroxide electrolyte is 100: 25 to 100:
By setting it in the range of 35, the discharge utilization factor of the positive electrode and the negative electrode can be improved, and the discharge time can be lengthened for an ultra-high load requiring a large discharge current of, for example, about 1500 mA.
【００２０】前記体積比率において水酸化カリウム電解
液側が２５より小さいと、イオン電導性の低下を生じて
正極合剤の放電利用率が低下するため、超高負荷に対す
る放電容量が小さくなり好ましくない。前記体積比率に
おいて水酸化カリウム電解液側が３５より大きいと、こ
の電解液が多すぎて電池として組み立てると保存条件に
よっては漏液が発生する可能性があり好ましくない。When the potassium hydroxide electrolyte solution side is less than 25 in the above volume ratio, the ion conductivity is lowered and the discharge utilization rate of the positive electrode mixture is lowered, so that the discharge capacity under an extremely high load is reduced, which is not preferable. When the potassium hydroxide electrolyte solution side is larger than 35 in the volume ratio, the electrolyte solution is too much, and there is a possibility that liquid leakage may occur depending on storage conditions when assembled into a battery, which is not preferable.
【００２１】負極用水酸化カリウム電解液の水酸化カリ
ウム濃度を４０重量％とするとともに、負極用水酸化カ
リウム電解液に対する前記酸化亜鉛の濃度を４重量％と
すれば、前述したような超高負荷の放電特性をより向上
できる。If the potassium hydroxide concentration of the negative electrode potassium hydroxide electrolyte is set to 40% by weight and the concentration of the zinc oxide to the negative electrode potassium hydroxide electrolyte is set to 4% by weight, the ultrahigh load as described above is obtained. The discharge characteristics can be further improved.
【００２２】[0022]
【発明の実施の形態】本発明の実施の形態にあっては、
正極、負極および電解液を構成する要素は前述した従来
の技術と同様であるが、これら構成要素のうち次の乃
至についてその比率または濃度を特定している。BEST MODE FOR CARRYING OUT THE INVENTION In the embodiments of the present invention,
The elements constituting the positive electrode, the negative electrode, and the electrolytic solution are the same as those in the conventional technique described above, but the ratios or concentrations of the following elements are specified.
【００２３】電池に対するゲル負極の充填量を調整す
ることにより、正極と負極との電気容量比率を１００：
１０５〜１００：１２５の範囲として負極側の電気容量
を大きくする。By adjusting the filling amount of the gel negative electrode in the battery, the electric capacity ratio between the positive electrode and the negative electrode was 100:
The electric capacity on the negative electrode side is increased in the range of 105 to 100: 125.
【００２４】正極合剤固形分と４０重量％の正極用水
酸化カリウム電解液との体積比率を１００：２５〜１０
０：３５の範囲とする。The volume ratio of the positive electrode mixture solid content to the 40% by weight positive electrode potassium hydroxide electrolyte is 100: 25 to 10
The range is 0:35.
【００２５】４０重量％の負極用水酸化カリウム電解
液に対する酸化亜鉛の濃度を４重量％とする。The concentration of zinc oxide relative to 40% by weight of the negative electrode potassium hydroxide electrolytic solution is set to 4% by weight.
【００２６】正極合剤は、電解二酸化マンガン６５．０
重量部に対して粒度分布が１〜２００μｍ、平均粒径
（５０重量％）１８μｍの膨張化黒鉛を３．２５重量部
を加えることにより正極合剤の固形分に対する黒鉛の含
有率を４．７重量％とし、前述した従来の技術と同様
に、３〜１０重量％の範囲内として放電容量の増大を図
った。この正極合剤の成形密度は３．３ｇ／cm3 とし
た。この正極合剤に対して４０重量％の水酸化カリウム
電解液を２．１０重量部含浸させた。The positive electrode mixture is electrolytic manganese dioxide 65.0.
By adding 3.25 parts by weight of expanded graphite having a particle size distribution of 1 to 200 μm and an average particle size (50% by weight) of 18 μm to parts by weight, the content ratio of graphite to the solid content of the positive electrode mixture is 4.7. In the same manner as the conventional technique described above, the discharge capacity was set to be within the range of 3 to 10% by weight to increase the discharge capacity. The molding density of this positive electrode mixture was 3.3 g / cm 3 . The positive electrode mixture was impregnated with 2.10 parts by weight of a 40% by weight potassium hydroxide electrolytic solution.
【００２７】尚、さらに放電容量の増加を図れるように
平均粒径が１０μｍより小さな膨張化黒鉛を用い、二酸
化マンガン比率を高めた正極合剤を試作したが、成形し
た正極合剤の強度が低く、製造困難となった。また、膨
張化黒鉛の平均粒径を変えた本形態の正極合剤と後述す
るゲル負極とを用いたＬＲ６形電池を試作して初度の内
部抵抗を測定した。その結果、膨張化黒鉛の平均粒径が
２０μｍ以下の場合には内部抵抗が０．１オーム以下と
なったのに対して、これが２０μｍを越えると内部抵抗
が例えば０．２オームとなったりして大きくなってしま
い、実用的ではないことが判明した。したがって、膨張
化黒鉛の平均粒径は１０〜２０μｍの範囲であることが
好ましい。In order to further increase the discharge capacity, an expansive graphite having an average particle size of less than 10 μm was used, and a positive electrode mixture having a high manganese dioxide ratio was prototyped. However, the strength of the molded positive electrode mixture was low. , Became difficult to manufacture. Further, an LR6 type battery using a positive electrode mixture of the present embodiment in which the average particle diameter of expanded graphite was changed and a gel negative electrode to be described later was prototyped and the initial internal resistance was measured. As a result, the internal resistance was 0.1 ohms or less when the average particle size of the expanded graphite was 20 μm or less, whereas the internal resistance was 0.2 ohms when it exceeded 20 μm. It turned out to be too big to be practical. Therefore, the average particle size of the expanded graphite is preferably in the range of 10 to 20 μm.
【００２８】ゲル負極は、４０重量％の水酸化カリウム
に対して酸化亜鉛を４重量％混合した電解液９２重量部
に対して、２００重量部の亜鉛粉末、ゲル化剤としてポ
リアクリル酸を０．９重量部、高吸水性ポリマーとして
ポリアクリル酸ナトリウムを０．９重量部をそれぞれ混
合することにより構成した。The gel negative electrode was prepared by mixing 200 parts by weight of zinc powder and 92 parts by weight of an electrolytic solution prepared by mixing 4% by weight of zinc oxide with 40% by weight of potassium hydroxide, and polyacrylic acid of 0 as a gelling agent. 1.9 parts by weight and 0.9 parts by weight of sodium polyacrylate as a superabsorbent polymer, respectively.
【００２９】このような構成のアルカリ電池について、
前記、で示した各比率を変えた前記図１のＬＲ６形
（Ｎｏ．１〜１２）に適用して超高負荷放電試験を行っ
た。このとき各電池は正極について体積、電気容量、成
形密度（３．３ｇ／cm3 ）および黒鉛の含有率（４．７
重量％）を一定とするとともに、前記の通り、負極に
ついて４０重量％の水酸化カリウム電解液に対する酸化
亜鉛の濃度を４重量％とし、２０℃の雰囲気中で放電終
止電圧０．９Ｖで１５００ｍＡの定電流放電時間を測定
した。この試験結果を表１に示す。Regarding the alkaline battery having such a structure,
An ultra-high load discharge test was performed by applying the above-mentioned LR6 type (No. 1 to 12) of FIG. At this time, each battery had a volume, an electric capacity, a molding density (3.3 g / cm 3 ) and a graphite content (4.7%) with respect to the positive electrode.
(% By weight), and the concentration of zinc oxide in the negative electrode was 40% by weight with respect to 40% by weight of the potassium hydroxide electrolyte as described above, and the discharge end voltage was 0.9 mA and 1500 mA at 20 ° C. in the atmosphere. The constant current discharge time was measured. Table 1 shows the test results.
【００３０】[0030]
【表１】 先ず、Ｎｏ．１〜６の電池にあっては正極と負極との電
気容量比率を変えたものであり、Ｎｏ．２〜５の負極側
の比率がそれぞれ１０５、１１４、１２０、１２５のも
のは、Ｎｏ．１の負極側の比率が１００の従来品に比
べ、放電時間が明らかに向上している。これは、正極側
の二酸化マンガンに対して負極側の亜鉛粉末の量が多い
ため正極および負極の活物質の放電利用率が向上し、超
高負荷に対する放電容量が大きくなったためと考えられ
る。Ｎｏ．６の負極側の比率が１３０のものは、正極側
の二酸化マンガンに対して負極側の亜鉛粉末の量が多す
ぎるためゲル負極が電池の所定容積に入りきらず製造困
難となった。[Table 1] First, No. In the batteries Nos. 1 to 6, the electric capacity ratios of the positive electrode and the negative electrode were changed. Nos. 2 to 5 having a negative electrode side ratio of 105, 114, 120 and 125, respectively, are No. The discharge time is clearly improved as compared with the conventional product in which the ratio of 1 on the negative electrode side is 100. It is considered that this is because the amount of zinc powder on the negative electrode side was larger than the amount of manganese dioxide on the positive electrode side, the discharge utilization rate of the active material of the positive electrode and the negative electrode was improved, and the discharge capacity under an ultrahigh load was increased. No. In the case of No. 6 having a ratio of 130 on the negative electrode side, the amount of zinc powder on the negative electrode side was too large relative to the manganese dioxide on the positive electrode side, and the gel negative electrode did not fill the predetermined volume of the battery, making manufacturing difficult.
【００３１】次に、Ｎｏ．７〜１１の電池にあっては正
極合剤固形分と４０重量％の水酸化カリウム電解液との
体積比率を変えたものであり、Ｎｏ．８〜１０の電解液
側の比率がそれぞれ２５％、３０％、３５％のものは、
Ｎｏ．７の電解液側の比率が２０のものに比し、放電時
間が明らかに向上している。これは正極合剤固形分に対
して水酸化カリウム電解液が多くなることによりイオン
導電性が向上して正極合剤の放電利用率が高くなったた
めと考えられる。Ｎｏ．１１の電解液側の比率が４０％
のものは高温多湿貯蔵試験において不具合が発生したた
め採用できない。具体的には、温度６０℃で湿度９０％
の雰囲気下で２０日間保存したところ漏液が発生した。
なお、Ｎｏ．１１以外の電池についてはこの高温多湿貯
蔵試験において不具合は発生しなかった。Next, No. In the batteries Nos. 7 to 11, the volume ratio of the solid content of the positive electrode mixture to the potassium hydroxide electrolytic solution of 40% by weight was changed. The proportions of 8 to 10 on the electrolyte side are 25%, 30%, and 35%, respectively,
No. The discharge time is obviously improved as compared with the case where the ratio of 7 on the electrolytic solution side is 20. It is considered that this is because an increase in the amount of the potassium hydroxide electrolytic solution relative to the solid content of the positive electrode mixture improved the ionic conductivity and increased the discharge utilization rate of the positive electrode mixture. No. The ratio of 11 on the electrolyte side is 40%
The ones listed above cannot be used because a problem occurred in the high temperature and high humidity storage test. Specifically, the temperature is 60 ° C and the humidity is 90%.
When it was stored for 20 days under the atmosphere described above, liquid leakage occurred.
In addition, No. For batteries other than No. 11, no trouble occurred in this high temperature and high humidity storage test.
【００３２】また、Ｎｏ．１２に示すように、正極と負
極との電気容量比率を１００：１２０とするとともに、
正極合剤固形分と４０重量％の水酸化カリウム電解液と
の体積比率を１００：３５とすると、放電時間を２５．
０分と各Ｎｏ．の電池の中で最も大きくすることができ
た。No. 12, the electric capacity ratio between the positive electrode and the negative electrode is 100: 120, and
When the volume ratio of the solid content of the positive electrode mixture to the 40 wt% potassium hydroxide electrolytic solution is 100: 35, the discharge time is 25.
0 minutes and each No. Could be the largest of all batteries.
【００３３】なお、本発明にあっては、正極および負極
に対して用いられる水酸化カリウム電解液の濃度を４０
重量％とすることが最も良く、４０重量％未満では貯蔵
後の放電性能の低下が見られて好ましくない。In the present invention, the concentration of the potassium hydroxide electrolytic solution used for the positive electrode and the negative electrode is 40%.
The content is most preferably in the range of 40% by weight, and if it is less than 40% by weight, the discharge performance after storage is deteriorated, which is not preferable.
【００３４】[0034]
【発明の効果】本発明のアルカリ電池にあっては、正極
および負極の放電利用率を向上させることにより、例え
ば１５００ｍＡ程度の大放電流を必要とする超高負荷に
対してその放電時間を長くすることができ、超高負荷放
電特性を向上させることができる。In the alkaline battery of the present invention, by improving the discharge utilization factor of the positive electrode and the negative electrode, the discharge time is extended for an ultrahigh load requiring a large discharge current of, for example, about 1500 mA. It is possible to improve the super high load discharge characteristics.
【図１】従来および本発明によるアルカリマンガン電池
の断面図である。FIG. 1 is a cross-sectional view of an alkaline manganese battery according to the related art and the present invention.
１ 正極缶 ２ 正極 ３ セパレータ ４ ゲル状負極 ５ 集電棒 ６ 絶縁材 ７ 封口ガスケット ８ 負極端子板 1 Positive Electrode Can 2 Positive Electrode 3 Separator 4 Gel Negative Electrode 5 Current Collector 6 Insulating Material 7 Sealing Gasket 8 Negative Terminal Plate
フロントページの続き (72)発明者 西田 国良 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 泉 彰英 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Front Page Continuation (72) Inventor Kuniyoshi Nishida 5-36-11 Shimbashi, Minato-ku, Tokyo Fuji Electric Chemical Co., Ltd. (72) Inventor Akihide Izumi 5-36-11 Shinbashi, Minato-ku, Tokyo Fuji Electric Chemical Co., Ltd. In the company
Claims (4)
合される導電剤としての黒鉛を３〜１０重量％の範囲で
含有する正極合剤固形分に対し、正極用水酸化カリウム
電解液を含浸させた正極（２）と、酸化亜鉛を含む負極
用水酸化カリウム電解液に対して負極活物質としての亜
鉛粉末、ゲル化剤、および高吸水性ポリマーを混合した
ゲル状負極（４）とを備えたアルカリ電池において、該
正極と該負極との電気容量比率を１００：１０５〜１０
０：１２５の範囲としてなることを特徴とするアルカリ
マンガン電池。1. A positive electrode mixture solid content containing 3 to 10% by weight of graphite as a conductive agent mixed with manganese dioxide as a positive electrode active material is impregnated with a potassium hydroxide electrolytic solution for a positive electrode. Alkali comprising a positive electrode (2) and a gelled negative electrode (4) in which zinc powder as a negative electrode active material, a gelling agent, and a superabsorbent polymer are mixed in a negative electrode potassium hydroxide electrolytic solution containing zinc oxide. In the battery, the electric capacity ratio between the positive electrode and the negative electrode is 100: 105 to 10
Alkali manganese battery characterized by having a range of 0: 125.
合される導電剤としての黒鉛を３〜１０重量％の範囲で
含有する正極合剤固形分に対し、正極用水酸化カリウム
電解液を含浸させた正極（２）と、酸化亜鉛を含む負極
用水酸化カリウム電解液に対して負極活物質としての亜
鉛粉末、ゲル化剤、および高吸水性ポリマーを混合した
ゲル状負極（４）とを備えたアルカリマンガン電池にお
いて、該正極用水酸化カリウム電解液の水酸化カリウム
濃度を４０重量％とするとともに、該正極合剤固形分と
該正極用水酸化カリウム電解液との体積比率を１００：
２５〜１００：３５の範囲としてなることを特徴とする
アルカリマンガン電池。2. A positive electrode mixture solid content containing 3 to 10% by weight of graphite as a conductive agent mixed with manganese dioxide as a positive electrode active material is impregnated with a potassium hydroxide electrolytic solution for a positive electrode. Alkali comprising a positive electrode (2) and a gelled negative electrode (4) in which zinc powder as a negative electrode active material, a gelling agent, and a superabsorbent polymer are mixed in a negative electrode potassium hydroxide electrolytic solution containing zinc oxide. In the manganese battery, the potassium hydroxide concentration of the positive electrode potassium hydroxide electrolytic solution is set to 40% by weight, and the volume ratio of the positive electrode mixture solid content to the positive electrode potassium hydroxide electrolytic solution is 100:
The alkaline manganese battery is characterized by having a range of 25 to 100: 35.
合される導電剤として平均粒径が１０〜２０μｍの黒鉛
を３〜１０重量％の範囲で含有する正極合剤固形分に対
し、正極用水酸化カリウム電解液を含浸させた正極
（２）と、酸化亜鉛を含む負極用水酸化カリウム電解液
に対して負極活物質としての亜鉛粉末、ゲル化剤、およ
び高吸水性ポリマーを混合したゲル状負極（４）とを備
えたアルカリマンガン電池において、該正極と該負極と
の電気容量比率を１００：１０５〜１００：１２５の範
囲とし、且つ該正極用水酸化カリウム電解液の水酸化カ
リウム濃度を４０重量％とするとともに、該正極合剤固
形分と該正極用水酸化カリウム電解液との体積比率を１
００：２５〜１００：３５の範囲としてなることを特徴
とするアルカリマンガン電池。3. A positive electrode mixture containing a graphite having an average particle size of 10 to 20 μm in a range of 3 to 10% by weight as a conductive agent mixed with manganese dioxide as a positive electrode active material is used as a positive electrode hydroxide. A positive electrode (2) impregnated with a potassium electrolytic solution, and a gelled negative electrode obtained by mixing a negative electrode potassium hydroxide electrolytic solution containing zinc oxide with zinc powder as a negative electrode active material, a gelling agent, and a superabsorbent polymer ( 4) In the alkaline manganese battery provided with, the electric capacity ratio between the positive electrode and the negative electrode is in the range of 100: 105 to 100: 125, and the potassium hydroxide concentration of the potassium hydroxide electrolyte solution for the positive electrode is 40% by weight. And the volume ratio of the positive electrode mixture solid content to the positive electrode potassium hydroxide electrolytic solution is 1
Alkali manganese battery having a range of 00:25 to 100: 35.
化カリウム濃度を４０重量％とするとともに、該負極用
水酸化カリウム電解液に対する前記酸化亜鉛の濃度を４
重量％としてなることを特徴とする請求項３に記載のア
ルカリマンガン電池。4. The potassium hydroxide concentration of the negative electrode potassium hydroxide electrolytic solution is set to 40% by weight, and the zinc oxide concentration of the negative electrode potassium hydroxide electrolytic solution is set to 4%.
The alkaline manganese battery according to claim 3, wherein the alkaline manganese battery is used as a weight percentage.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33913295A JP3022758B2 (en) | 1995-12-26 | 1995-12-26 | Alkaline manganese battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33913295A JP3022758B2 (en) | 1995-12-26 | 1995-12-26 | Alkaline manganese battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09180736A true JPH09180736A (en) | 1997-07-11 |
| JP3022758B2 JP3022758B2 (en) | 2000-03-21 |
Family
ID=18324553
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33913295A Expired - Fee Related JP3022758B2 (en) | 1995-12-26 | 1995-12-26 | Alkaline manganese battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3022758B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000113895A (en) * | 1998-10-06 | 2000-04-21 | Toshiba Battery Co Ltd | Cylindrical alkaline battery |
| WO2000030193A1 (en) * | 1998-11-16 | 2000-05-25 | Duracell Inc. | Alkaline cell with improved cathode |
| JP2002500417A (en) * | 1997-12-31 | 2002-01-08 | デュラセル インコーポレイテッド | Porous alkaline zinc / manganese oxide battery |
| JP2002500418A (en) * | 1997-12-31 | 2002-01-08 | デュラセル インコーポレイテッド | Electrochemical cell balance |
| JP2002008668A (en) * | 2000-06-21 | 2002-01-11 | Toshiba Battery Co Ltd | Alkaline battery |
| JP2006500742A (en) * | 2002-09-20 | 2006-01-05 | エヴァレディー バッテリー カンパニー インコーポレイテッド | Battery with increased electrode interface surface area and increased active material |
| JP5022526B1 (en) * | 2011-04-18 | 2012-09-12 | パナソニック株式会社 | Alkaline primary battery |
| WO2012143984A1 (en) * | 2011-04-18 | 2012-10-26 | パナソニック株式会社 | Alkaline primary battery |
-
1995
- 1995-12-26 JP JP33913295A patent/JP3022758B2/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002500417A (en) * | 1997-12-31 | 2002-01-08 | デュラセル インコーポレイテッド | Porous alkaline zinc / manganese oxide battery |
| JP2002500418A (en) * | 1997-12-31 | 2002-01-08 | デュラセル インコーポレイテッド | Electrochemical cell balance |
| JP2000113895A (en) * | 1998-10-06 | 2000-04-21 | Toshiba Battery Co Ltd | Cylindrical alkaline battery |
| WO2000030193A1 (en) * | 1998-11-16 | 2000-05-25 | Duracell Inc. | Alkaline cell with improved cathode |
| US6207322B1 (en) | 1998-11-16 | 2001-03-27 | Duracell Inc | Alkaline cell with semisolid cathode |
| JP2002008668A (en) * | 2000-06-21 | 2002-01-11 | Toshiba Battery Co Ltd | Alkaline battery |
| JP4503790B2 (en) * | 2000-06-21 | 2010-07-14 | 東芝電池株式会社 | Alkaline battery |
| JP2006500742A (en) * | 2002-09-20 | 2006-01-05 | エヴァレディー バッテリー カンパニー インコーポレイテッド | Battery with increased electrode interface surface area and increased active material |
| JP5022526B1 (en) * | 2011-04-18 | 2012-09-12 | パナソニック株式会社 | Alkaline primary battery |
| WO2012143984A1 (en) * | 2011-04-18 | 2012-10-26 | パナソニック株式会社 | Alkaline primary battery |
| CN102859767A (en) * | 2011-04-18 | 2013-01-02 | 松下电器产业株式会社 | Alkaline primary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3022758B2 (en) | 2000-03-21 |
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