JPH0675400B2 - Activated chemically treated manganese dioxide for dry batteries and method for producing the same - Google Patents
Activated chemically treated manganese dioxide for dry batteries and method for producing the sameInfo
- Publication number
- JPH0675400B2 JPH0675400B2 JP61147063A JP14706386A JPH0675400B2 JP H0675400 B2 JPH0675400 B2 JP H0675400B2 JP 61147063 A JP61147063 A JP 61147063A JP 14706386 A JP14706386 A JP 14706386A JP H0675400 B2 JPH0675400 B2 JP H0675400B2
- Authority
- JP
- Japan
- Prior art keywords
- manganese dioxide
- weight
- chemically treated
- alkaline earth
- earth metal
- 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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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］ 本発明は乾電池の正極活物質として用いる二酸化マンガ
ン（MnO2）とその製造方法に関し、更に詳しくは活性化
化学処理されており、高負荷連続放電特性に優れた二酸
化マンガンとその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to manganese dioxide (MnO 2 ) used as a positive electrode active material of a dry battery and a method for producing the same. More specifically, it is subjected to activation chemical treatment and continuously under high load. TECHNICAL FIELD The present invention relates to manganese dioxide having excellent discharge characteristics and a method for producing the same.
［従来の技術］ いわゆるマンガン乾電池の正極活物質には二酸化マンガ
ンの粉末が使用されている。[Prior Art] Manganese dioxide powder is used as a positive electrode active material for so-called manganese dry batteries.
この二酸化マンガンには、大別して電解二酸化マンガ
ン，化学合成二酸化マンガン，天然二酸化マンガンと活
性化化学処理二酸化マンガンの４種類のものが使用され
ている。This manganese dioxide is roughly classified into four types: electrolytic manganese dioxide, chemically synthesized manganese dioxide, natural manganese dioxide, and activated chemically treated manganese dioxide.
このうちの電解二酸化マンガンは、例えば、菱マンガン
鉱を硫酸で浸出して硫酸マンガン水溶液とし、この中の
鉄分などの不純物を沈澱せしめて除去し、約80℃以上の
温度で硬鉛または金属チタニウムを陽極として直流電解
することにより陽極上に析出せしめて製造されている。Of these, electrolytic manganese dioxide is, for example, leaching rhodochrosite ore with sulfuric acid to form an aqueous solution of manganese sulfate, and removing impurities such as iron by precipitating and removing it, and hard lead or metallic titanium at a temperature of about 80 ° C or higher. Is manufactured by depositing on the anode by direct current electrolysis.
一方、活性化化学処理二酸化マンガンは、上記方法とは
全く異なり、各種のマンガン酸化物鉱石を例えば自成雰
囲気中で焙焼して熱分解せしめ三二酸化マンガン，四三
酸化マンガンにし、これを硫酸，硝酸，塩酸のような鉱
酸で処理して活性化された二酸化マンガンである。例え
ば、その方法を開示する文献としては特開昭53−88696
号公報，特開昭60−221324号公報をあげることができ
る。On the other hand, activated chemically treated manganese dioxide is completely different from the above method, and various manganese oxide ores are roasted in, for example, an autogenous atmosphere to be thermally decomposed into manganese sesquioxide and manganese tetroxide. , Manganese dioxide activated by treatment with mineral acids such as nitric acid and hydrochloric acid. For example, as a document disclosing the method, there is JP-A-53-88696.
And Japanese Patent Application Laid-Open No. 60-221324.
［発明が解決しようとする問題点］ 上記した電解二酸化マンガンは、たしかに高品位，高活
性であり、乾電池に組込まれたときその電池は優れた重
負荷放電，軽負荷放電特性を発現するが、しかし、製造
時の電流密度は0.8〜2.0A/dm2と小さいのでその生産性
は低く、使用電力量も膨大となり全体が高コストになる
という問題がある。[Problems to be Solved by the Invention] The electrolytic manganese dioxide described above is certainly of high quality and high activity, and when incorporated into a dry battery, the battery exhibits excellent heavy load discharge and light load discharge characteristics. However, since the current density at the time of manufacturing is as small as 0.8 to 2.0 A / dm 2 , the productivity is low, the amount of power used is enormous, and the overall cost is high.
一方、従来から知られている活性化化学処理二酸化マン
ガンはそれを乾電池に充填したとき電池の重負荷放電特
性は比較的良好であるが、一般にそのタップ密度は1.1
〜1.4g/cm3程度と小さく、非常にポーラスな充填状態と
なる。したがって、その電池における活物質たる二酸化
マンガンの量は少なく、電池の軽負荷放電が著しく低下
する。On the other hand, the conventionally known activated chemically treated manganese dioxide has a relatively good heavy load discharge characteristic when the dry cell is filled with the manganese dioxide, but its tap density is generally 1.1.
It is as small as ~ 1.4g / cm 3 and has a very porous filling state. Therefore, the amount of manganese dioxide as the active material in the battery is small, and the light load discharge of the battery is significantly reduced.
この問題を解決するために、活性化化学処理二酸化マン
ガンをロールプレスして平板状の圧縮成形体としたの
ち、これを所望の粒度に粉砕して重質化する試みがなさ
れている（前出の特開昭60−221324号公報参照）。In order to solve this problem, it has been attempted to roll-press activated chemically treated manganese dioxide into a flat-plate compression-molded body and then grind it into a desired particle size to make it heavier (see above). JP-A-60-221324).
しかしながら、上記方法によってタップ密度で1.6g/cm3
以上となる圧縮成形粉を製造し、これを用いて例えばR1
4型乾電池を組立て、２Ω連続放電のような超重負荷放
電を行なうとその放電持続時間は著しく短くなるという
問題を生じている。However, the tap density is 1.6 g / cm 3 by the above method.
The compression-molded powder as described above is produced, and using this, for example, R1
When a 4-type dry battery is assembled and a super heavy load discharge such as a 2Ω continuous discharge is performed, the discharge duration becomes extremely short.
本発明は、この超重負荷放電特性を低下させることのな
い活性化化学処理二酸化マンガンとその製造方法の提供
を目的とする。An object of the present invention is to provide an activated chemically treated manganese dioxide and a method for producing the same, which does not deteriorate the super heavy load discharge characteristics.
［問題点を解決するための手段］ 本発明者らは上記目的を達成するために、活性化化学処
理二酸化マンガンの成分組成と超重負荷放電特性との関
係を鋭意調査したところ、活性化化学処理二酸化マンガ
ン中に含有されているアルカリ土類金属の量によって上
記特性が相違してくることを見出し、本発明の二酸化マ
ンガンとその製造方法を開発するに致った。[Means for Solving the Problems] In order to achieve the above-mentioned object, the inventors of the present invention have diligently investigated the relationship between the component composition of the activated chemical treatment manganese dioxide and the super heavy load discharge characteristics. It was found that the above characteristics differ depending on the amount of alkaline earth metal contained in manganese dioxide, and it was successful in developing the manganese dioxide of the present invention and a method for producing the same.
すなわち、本発明の活性化化学処理二酸化マンガンは、
周期律表のアルカリ土類金属が0.5〜6.0重量％含有され
ていることを特徴とし、その製造方法は、後述するよう
なマンガン酸化物鉱石を焙焼し、得られた焙焼物を鉱酸
で処理したのち、水洗，乾燥することを特徴とする。That is, the activated chemically treated manganese dioxide of the present invention is
The alkaline earth metal of the periodic table is characterized by containing 0.5 to 6.0% by weight, the manufacturing method is roasting manganese oxide ore as described below, the obtained roasted product with a mineral acid. After treatment, it is characterized by being washed with water and dried.
［作用］ まず、本発明の二酸化マンガンは後述の方法で製造され
た活性化化学処理二酸化マンガンである。[Operation] First, the manganese dioxide of the present invention is an activated chemically treated manganese dioxide produced by the method described below.
この二酸化マンガンには、周期律表のアルカリ土類金属
が合計量として0.5〜6.0重量％含有されている。This manganese dioxide contains 0.5 to 6.0% by weight of alkaline earth metal in the periodic table as a total amount.
これらアルカリ土類金属は二酸化マンガンの製造過程ま
たは製造後に単体の形にしろ化合物の形でにしろ外部か
ら二酸化マンガンに配合されるものではなく、原料たる
鉱石の中に不純物として予め含有されているものであ
る。These alkaline earth metals are not blended with manganese dioxide from the outside, whether in the form of a compound or in the form of a compound, either in the process of manufacturing manganese dioxide or after the manufacturing process, but are contained as impurities in the ore as a raw material in advance. It is a thing.
この含有量が0.5重量％より少ない場合は、二酸化マン
ガンの純度がたとえ同じであったとしても超重負荷放電
特性の低下がみられ、また逆に6.0重量％より多い場合
は、得られた二酸化マンガンの結晶構造は高活性なγ型
が少なく電気化学的な活性の低いα型が多く混在し同じ
く特性低下を招く。好ましくは、0.5〜３重量％であ
る。When the content is less than 0.5% by weight, the super heavy load discharge characteristics are deteriorated even if the purity of manganese dioxide is the same. On the contrary, when the content is more than 6.0% by weight, the obtained manganese dioxide is obtained. In the crystal structure of, the highly active γ-type is less, and the electrochemically less active α-type is more mixed, and similarly, the characteristics are deteriorated. It is preferably 0.5 to 3% by weight.
アルカリ土類金属のうち、カルシウム，ストロンチウ
ム，バリウムは好ましいものであり、とくにバリウムは
好適である。Among the alkaline earth metals, calcium, strontium and barium are preferable, and barium is particularly preferable.
本発明の二酸化マンガンは次のようにして製造すること
ができる。The manganese dioxide of the present invention can be manufactured as follows.
まず、マンガン酸化物鉱石を焙焼する。鉱石としては、
上記アルカリ土類金属を全体で0.5〜3.5重量％含有して
いるものが選定される。カルシウム，ストロンチウム，
バリウムの１種または２種以上を含有する鉱石が好適で
ある。このような鉱石としては、各地で産出される軟マ
ンガン鉱，菱マンガン鉱などをあげることができるが、
これらのうちとくに、二酸化マンガン75.0〜88.0重量
％，カルシウム0.01〜0.50重量％，ストロンチウム0.01
〜0.30重量％，バリウム0.40〜3.50重量％，その他結合
水，酸化鉄，酸化アルミニウム，酸化カリ，酸化ナトリ
ウム，酸化ケイ素などを総量で5.0〜25.0重量％含有す
る軟マンガン鉱は好適である。First, manganese oxide ore is roasted. As an ore,
A material containing 0.5 to 3.5% by weight of the above alkaline earth metal is selected. Calcium, strontium,
Ore containing one or more of barium is suitable. Examples of such ores include soft manganese ore and rhodomanganese ore produced in various places.
Of these, manganese dioxide 75.0 to 88.0% by weight, calcium 0.01 to 0.50% by weight, strontium 0.01
A soft manganese ore containing .about.0.30% by weight, barium 0.40 to 3.50% by weight, other combined water, iron oxide, aluminum oxide, potassium oxide, sodium oxide, silicon oxide in a total amount of 5.0 to 25.0% by weight is suitable.
このような鉱石を粉砕して例えば粒度60メッシュ（タイ
ラー篩）以下の細粉とし、この細粉を焙焼炉により自成
雰囲気中で焙焼する。焙焼温度は鉱石の種類によって変
動するが、通常は550〜1000℃である。この焙焼過程
で、鉱石中の二酸化マンガンは400〜500℃付近から三二
酸化マンガンに転化し、更に800〜1000℃付近の温度か
ら四三酸化マンガンに転化する。焙焼する時間は格別限
定されるものではないが、通常、0.5〜５時間であれば
よい。Such an ore is crushed into fine powder having a particle size of 60 mesh (Tyler sieve) or less, and the fine powder is roasted in a self-made atmosphere in a roasting furnace. The roasting temperature varies depending on the type of ore, but is usually 550 to 1000 ° C. In this roasting process, manganese dioxide in the ore is converted to manganese trioxide at around 400 to 500 ° C, and further converted to trimanganese tetraoxide at a temperature around 800 to 1000 ° C. The time for roasting is not particularly limited, but it is usually 0.5 to 5 hours.
このようにして得られた焙焼物を、つぎに鉱酸で処理す
る。用いる鉱酸としては、例えば、硫酸，硝酸，塩酸な
どをあげることができる。The roasted product thus obtained is then treated with a mineral acid. Examples of the mineral acid used include sulfuric acid, nitric acid, hydrochloric acid and the like.
この処理により、下記のように例えば鉱酸として硫酸を
用いたときの反応式でみられるように、二酸化マンガン
が生成する。This treatment produces manganese dioxide, as can be seen in the reaction equation below when using sulfuric acid as the mineral acid, for example.
Mn2O3＋H2SO4→MnO2＋MnSO4＋H2O Mn3O4＋2H2SO4→MnO2＋2MnSO4＋2H2O このとき、用いる鉱酸の濃度および処理時間は生成した
二酸化マンガン中のアルカリ土類金属の含有量に影響を
与える。例えば、前記した軟マンガン鉱石を２規定の硫
酸で１時間処理した場合、処理前に比べて若干減少して
カルシウムは0.005〜0.30重量％，ストロンチウムは0.0
2〜0.40重量％，バリウムは増加し0.80〜6.00重量％の
含有量になる。Mn 2 O 3 ＋ H 2 SO 4 → MnO 2 ＋ MnSO 4 ＋ H 2 O Mn 3 O 4 ＋ 2H 2 SO 4 → MnO 2 ＋ 2MnSO 4 ＋ 2H 2 O At this time, the concentration of the mineral acid used and the treatment time were Affects the alkaline earth metal content. For example, when the above-mentioned soft manganese ore is treated with 2N sulfuric acid for 1 hour, it is slightly reduced as compared with that before the treatment, calcium is 0.005 to 0.30% by weight, and strontium is 0.0
2 to 0.40% by weight, barium increases to 0.80 to 6.00% by weight.
原料としての鉱酸の種類によっても変化するが、鉱酸が
硫酸であった場合は、その濃度１〜４規定，処理時間0.
5〜５時間であることが好ましく、硝酸であった場合
は、その濃度１〜６規定，処理時間0.5〜５時間である
ことが好ましく，また塩酸であった場合は、その濃度0.
5〜３規定，処理時間0.1〜１時間であることが好まし
い。When the mineral acid is sulfuric acid, its concentration is 1 to 4 N and the treatment time is 0.
It is preferably 5 to 5 hours, the concentration of nitric acid is 1 to 6 N, the treatment time is preferably 0.5 to 5 hours, and the concentration of hydrochloric acid is 0.
It is preferable that the treatment time is 5 to 3 N and the treatment time is 0.1 to 1 hour.
処理時の鉱酸の液温も生成した二酸化マンガンの特性に
影響を与えるが、通常は60〜95℃であることが好適であ
る。The liquid temperature of the mineral acid at the time of treatment also affects the characteristics of the produced manganese dioxide, but it is usually preferably 60 to 95 ° C.
上記した鉱石の焙焼過程，鉱酸による処理過程で、当初
から鉱石中に含有されていたアルカリ土類金属はどのよ
うな挙動をするのかという問題は必ずしも明確ではない
が、推定するに、カルシウム，ストロンチウム，バリウ
ムなどはそのイオン半径が比較的大きいので、上記した
過程で二酸化マンガンに大きな結晶歪を与え、その結
果、生成二酸化マンガンはその活性度が高まるのではな
いかと考えられる。It is not clear that the behavior of the alkaline earth metal contained in the ore from the beginning during the roasting process of the ore and the treatment process with the mineral acid described above, but it is estimated that calcium Since strontium, barium, and the like have relatively large ionic radii, it is considered that manganese dioxide is subjected to a large crystal strain in the above process, and as a result, the activity of the produced manganese dioxide is increased.
最後に、得られた二酸化マンガンのケーキを例えば流水
中で充分に洗浄して鉱酸を除去し、ついで60〜110℃の
温度で乾燥して水を除去すれば本発明の活性化化学処理
二酸化マンガンを得ることができる。Finally, the obtained manganese dioxide cake is thoroughly washed, for example, in running water to remove the mineral acid, and then dried at a temperature of 60 to 110 ° C. to remove the water. Manganese can be obtained.
［発明の実施例］ 実施例１〜6,比較例１〜３ 表示した成分組成のマンガン酸化物鉱石を粉砕して粒度
60メッシュ（タイラー篩）以下の粉末とした。この粉末
を約850℃の自成雰囲気中で焙焼した。主成分はα−Mn2
O3であった。焙焼後の粉末を、90℃の３規定硫酸溶液に
投入して２時間反応させた。ついで、反応処理物を充分
に水洗・過したのちアンモニア水で中和処理し、更に
水洗し、最後に乾燥して活性化化学処理に二酸化マンガ
ン粉末を得た。[Examples of the Invention] Examples 1 to 6 and Comparative Examples 1 to 3
The powder was 60 mesh (Tyler sieve) or smaller. This powder was roasted in an autogenous atmosphere at about 850 ° C. Main component is α-Mn 2
It was O 3 . The powder after roasting was put into a 3N sulfuric acid solution at 90 ° C and reacted for 2 hours. Next, the reaction-treated product was thoroughly washed with water, passed through a neutralization treatment with aqueous ammonia, further washed with water, and finally dried to obtain a manganese dioxide powder for activation chemical treatment.
これら粉末をそれぞれロールプレス機にかけ5ton/cm2の
圧力で圧縮成形したのち、この成形体を粉砕し100メッ
シュ（タイラー篩）以下の粉末とした。これら粉末の成
分組成，タップ密度を表に示した。Each of these powders was applied to a roll press machine and compression-molded at a pressure of 5 ton / cm 2 , and then this molded body was crushed to obtain a powder of 100 mesh (Tyler sieve) or smaller. The composition of these powders and tap density are shown in the table.
これら粉末を正極活物質としてR14型の乾電池を組立
て、電池の２Ω連続放電特性を測定した。その結果を表
に示した。Using these powders as a positive electrode active material, an R14 type dry battery was assembled and the 2Ω continuous discharge characteristics of the battery were measured. The results are shown in the table.
比較例４ 比較例１に用いた鉱石を粒度60メッシュ（タイラー篩）
以下の粉末とした。この粉末に水酸化バリウム粉末を鉱
石に対し1.0重量％加えたのち充分に混合した。この混
合物を850℃の自成雰囲気中で焙焼し、以下実施例１と
同様に操作して得た活性化化学処理二酸化マンガンを用
いて同様の電池を組立て、その２Ω連続放電特性を測定
した。その結果を表に併記した。Comparative Example 4 The ore used in Comparative Example 1 had a particle size of 60 mesh (Tyler sieve).
The following powder was used. Barium hydroxide powder was added to this powder in an amount of 1.0% by weight based on the ore, and the mixture was thoroughly mixed. This mixture was roasted in an autogenous atmosphere at 850 ° C., and a similar battery was assembled using activated chemically treated manganese dioxide obtained by the same operation as in Example 1 below, and its 2Ω continuous discharge characteristic was measured. . The results are also shown in the table.
比較例５ 実施例３で用いた鉱石をそのまま正極活物質として実施
例と同様の電池を組立て、その２Ω連続放電特性を測定
した。その結果を表に併記した。Comparative Example 5 The same ore as in Example was assembled using the ore used in Example 3 as it was as a positive electrode active material, and its 2Ω continuous discharge characteristic was measured. The results are also shown in the table.
［発明の効果］ 以上の説明で明らかなように、本発明の二酸化マンガン
は、それを正極活物質とした乾電池の重負荷連続放電特
性を著しく向上せしめる。これは、アルカリ土類金属を
所定量含有する鉱石を本発明方法のような化学処理をす
ることによって得られる効果であることは、実施例１の
データと比較例５のデータを比較することによって歴然
としている。すなわち、比較例５の二酸化マンガンを用
いたときの２Ω連続放電持続時間は60分であるが、しか
しこの二酸化マンガンに本発明の方法を適用して活性化
した場合は、その値が約2.4倍となるのである。 [Effect of the Invention] As is clear from the above description, the manganese dioxide of the present invention remarkably improves the heavy load continuous discharge characteristics of a dry battery using the manganese dioxide as a positive electrode active material. This is the effect obtained by chemically treating the ore containing a predetermined amount of alkaline earth metal by the chemical treatment according to the method of the present invention. By comparing the data of Example 1 with the data of Comparative Example 5, It is clear. That is, the 2Ω continuous discharge duration when the manganese dioxide of Comparative Example 5 was used was 60 minutes, but when activated by applying the method of the present invention to this manganese dioxide, the value was about 2.4 times. It becomes.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 宮坂 幸次郎 東京都品川区南品川３丁目４番10号 東芝 電池株式会社内 (72)発明者 山村 和昭 新潟県中頚城郡妙高高原町大字田口272 中央電気工業株式会社内 (72)発明者 宮下 孝洋 新潟県中頚城郡妙高高原町大字田口272 中央電気工業株式会社内 (72)発明者 重松 達彦 兵庫県尼崎市西長州本通１丁目３番地 住 友金属工業株式会社中央技術研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Kojiro Miyasaka, 3-4-10 Minami-Shinagawa, Shinagawa-ku, Tokyo, Toshiba Battery Co., Ltd. Electric Industry Co., Ltd. (72) Inventor Takahiro Miyashita Taguchi 272, Myokokogen-cho, Nakakubiki-gun, Niigata Chuo Electric Industry Co., Ltd. Central Research Institute of Industry Co., Ltd.
Claims (7)
ていることを特徴とする乾電池用の活性化化学処理二酸
化マンガン。1. An activated chemically treated manganese dioxide for a dry battery, which contains 0.5 to 6.0% by weight of an alkaline earth metal.
トロンチウム、バリウムの群から選ばれる少なくとも１
種である特許請求の範囲第１項記載の乾電池用の活性化
化学処理二酸化マンガン。2. The alkaline earth metal is at least one selected from the group consisting of calcium, strontium and barium.
Activated chemically treated manganese dioxide for dry cells according to claim 1, which is a seed.
特許請求の範囲第１項又は第２項記載の乾電池用の活性
化化学処理二酸化マンガン。3. The activated chemically treated manganese dioxide for a dry battery according to claim 1 or 2, wherein the alkaline earth metal is barium.
物鉱石を焙焼し、得られた焙焼物を鉱酸で処理したの
ち、水洗、乾燥することを特徴とするアルカリ土類金属
を0.5〜6.0重量％含有する乾電池用の活性化化学処理二
酸化マンガンの製造方法。4. A manganese oxide ore containing an alkaline earth metal is roasted, the obtained roasted product is treated with a mineral acid, washed with water, and then dried. Method for producing activated chemically treated manganese dioxide for dry cell containing 6.0% by weight.
金属を0.5〜3.50重量％含有している鉱石である特許請
求の範囲第４項記載の製造方法。5. The production method according to claim 4, wherein the manganese oxide ore is an ore containing 0.5 to 3.50% by weight of an alkaline earth metal.
トロンチウム、バリウムの群から選ばれる少なくとも１
種である特許請求の範囲第４項又は第５項記載の製造方
法。6. The alkaline earth metal is at least one selected from the group consisting of calcium, strontium and barium.
The manufacturing method according to claim 4 or 5, which is a seed.
01〜0.50重量％、ストロンチウム0.01〜0.30重量％、バ
リウム0.40〜3.50重量％、二酸化マンガン75.0〜88.0重
量％を含有する鉱石である特許請求の範囲第４項〜第６
項記載の製造方法。7. The manganese oxide ore is calcium 0.
Claims 4 to 6 which are ores containing 01 to 0.50% by weight, strontium 0.01 to 0.30% by weight, barium 0.40 to 3.50% by weight, and manganese dioxide 75.0 to 88.0% by weight.
The manufacturing method according to the item.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61147063A JPH0675400B2 (en) | 1986-06-25 | 1986-06-25 | Activated chemically treated manganese dioxide for dry batteries and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61147063A JPH0675400B2 (en) | 1986-06-25 | 1986-06-25 | Activated chemically treated manganese dioxide for dry batteries and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS634555A JPS634555A (en) | 1988-01-09 |
| JPH0675400B2 true JPH0675400B2 (en) | 1994-09-21 |
Family
ID=15421647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61147063A Expired - Fee Related JPH0675400B2 (en) | 1986-06-25 | 1986-06-25 | Activated chemically treated manganese dioxide for dry batteries and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0675400B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5300371A (en) * | 1990-03-23 | 1994-04-05 | Battery Technologies Inc. | Manganese dioxide positive electrode for rechargeable cells, and cells containing the same |
| US5504560A (en) * | 1993-10-01 | 1996-04-02 | Minolta Co., Ltd. | Photosensitive member-protective shutter |
| US7754386B2 (en) * | 2005-11-28 | 2010-07-13 | Pure Energy Visions Corporation | Rechargeable alkaline manganese cell having reduced capacity fade and improved cycle life |
| JP4850619B2 (en) * | 2006-08-14 | 2012-01-11 | キヤノン株式会社 | Image forming apparatus |
| JP4921601B2 (en) * | 2011-06-02 | 2012-04-25 | キヤノン株式会社 | Charging device and image forming apparatus having the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5388696A (en) * | 1977-01-14 | 1978-08-04 | Kinsei Kogyo | Method of making manganese dioxide for dry battery |
-
1986
- 1986-06-25 JP JP61147063A patent/JPH0675400B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5388696A (en) * | 1977-01-14 | 1978-08-04 | Kinsei Kogyo | Method of making manganese dioxide for dry battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS634555A (en) | 1988-01-09 |
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