JPS62295354A - Manufacture of manganese dioxide for alkaline manganic cell - Google Patents
Manufacture of manganese dioxide for alkaline manganic cellInfo
- Publication number
- JPS62295354A JPS62295354A JP61136181A JP13618186A JPS62295354A JP S62295354 A JPS62295354 A JP S62295354A JP 61136181 A JP61136181 A JP 61136181A JP 13618186 A JP13618186 A JP 13618186A JP S62295354 A JPS62295354 A JP S62295354A
- Authority
- JP
- Japan
- Prior art keywords
- manganese dioxide
- alkaline
- manganese
- cell
- dioxide
- 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
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 21
- 229910052748 manganese Inorganic materials 0.000 claims description 21
- 239000011572 manganese Substances 0.000 claims description 21
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract 2
- 239000013543 active substance Substances 0.000 abstract 1
- 240000007320 Pinus strobus Species 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- OZOAXHQNOFIFGD-UHFFFAOYSA-N manganese(2+) oxygen(2-) Chemical compound [O-2].[O-2].[Mn+2].[Mn+2] OZOAXHQNOFIFGD-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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
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)
Abstract
Description
【発明の詳細な説明】
３、発明の詳細な説明
［発明の属する分野］
本発明はアルカリマンガン電池において、正極活物質と
して使用される二酸化マンガンの製造法に関するもので
ある。Detailed Description of the Invention 3. Detailed Description of the Invention [Field to which the invention pertains] The present invention relates to a method for producing manganese dioxide used as a positive electrode active material in an alkaline manganese battery.
［発明の背ｒＡ］
アルカリマンガン電池はマンガン乾電池に比べ、重負荷
での放電性能において優れていることからカメラの自動
ワインダー、ストロボ並びに携帯用テープレコーダーな
どに使用され、近年急速にその需要が伸びてきている。[Background of the invention] Alkaline manganese batteries have superior discharge performance under heavy loads compared to manganese dry batteries, so they are used in automatic camera winders, strobes, portable tape recorders, etc., and demand for them has increased rapidly in recent years. It's coming.
しかし、アルカリマンガン電池に使用される二酸化マン
ガンについては、アルカリマンガン電池がマンガン乾電
池に比べて歴史が浅いことから、どのような特性をもつ
二酸化マンガンが適しているのか、まだ充分に検討され
ていないのが現状である。However, since alkaline manganese batteries have a shorter history than manganese dry batteries, the characteristics of manganese dioxide that are suitable for use in alkaline manganese batteries have not yet been fully investigated. is the current situation.
マンガン乾電池の電解液としては、中性溶液が用いられ
るため、二酸化マンガン自身のｐＨも電解液に近い値に
調整されている。Since a neutral solution is used as the electrolyte for manganese dry batteries, the pH of manganese dioxide itself is also adjusted to a value close to that of the electrolyte.
一方、アルカリマンガン電池おいては、電解液として強
アルカリ性（例えば４０％ＫＯＨ溶液）のものが使用さ
れているため、使用する二酸化マンガンの０１−１に拘
わらず、電池内に組込まれると、強アルカリ性の電解液
とほぼ同一となるため、アルカリマンガン電池に関して
は、二酸化マンガン自身のｐＨなどは考慮されていなか
った。On the other hand, in alkaline manganese batteries, a strongly alkaline electrolyte (e.g. 40% KOH solution) is used. Since it is almost the same as an alkaline electrolyte, the pH of manganese dioxide itself has not been taken into consideration in alkaline manganese batteries.
［発明の目的］
本発明は、上記のような状況に鑑み、アルカリマンガン
Ｔｉ池の正極活物質として用いられる二ｌ′ｉグ化マン
ガンの高性能化を図り、ひいてはアルカリマンガン電池
の電池性能の向上を図ることを目的としたものである。[Objective of the Invention] In view of the above-mentioned circumstances, the present invention aims to improve the performance of manganese di-l'i-glyde used as a positive electrode active material of an alkaline manganese Ti battery, and thereby improve the battery performance of an alkaline manganese battery. The purpose of this is to improve the performance.
［発明の経緯］
本発明者らは上記目的を達成するために、鋭意研究を行
なったところ、−二酸化マンガン製造工程の後処理工程
である中和処理において、二酸化マンガンのｐＨを特定
範囲に調！１することにより、アルカリマンガン°市池
の放電性能、特に−２０℃のような低温領域での放電性
能が著しく向上するという知見を得て本発明に至ったも
のである。[Background of the invention] In order to achieve the above object, the present inventors conducted extensive research and found that - the pH of manganese dioxide was adjusted to a specific range in the neutralization treatment, which is a post-treatment step in the manganese dioxide production process; ! The present invention was developed based on the finding that the discharge performance of an alkali manganese city pond, especially in a low temperature region such as -20°C, can be significantly improved by doing the following.
［発明の構成］
すなわち、本発明はＪＩＳＫ１４６７で規定する二酸化
マンガンのｐＨを２．５〜４．０に調整することを特徴
とする二酸化マンガンの製造法にある。[Structure of the Invention] That is, the present invention resides in a method for producing manganese dioxide, which is characterized by adjusting the pH of manganese dioxide defined by JIS K1467 to 2.5 to 4.0.
上述のように、従来、アルカリマンガン電池においては
、使用される電解液が強アルカリ性であるため、二酸化
マンガン自身のＥＩＨがどのような値であっても電池内
に組込まれると強アルカリ性の電解液のＤＨとほとんど
同じとなり、電池性能には二酸化マンガン自身のｐＨな
どは無関係であると考えられていた。As mentioned above, conventionally, in alkaline manganese batteries, the electrolyte used is strongly alkaline, so no matter what the EIH of manganese dioxide itself is, when incorporated into the battery, the electrolyte is strongly alkaline. It was thought that the pH of manganese dioxide itself had nothing to do with battery performance.
しかし、二酸化マンガンのｐＨを６．０以上にした場合
、電池性能が低下したことに着目し、同じ二酸化マンガ
ンを用いて各種１）Ｈｌ、：調整し電池性能を調べた結
果、二酸化マンガンのｐＨを高くすることにより、常温
での放電性能は低下する傾向にあり、特に低温領域、例
えば−２０°Ｃでの放電性能の低下が署しいことが認め
られた。However, when the pH of manganese dioxide was increased to 6.0 or higher, battery performance decreased.As a result of adjusting the battery performance using the same manganese dioxide, we found that the pH of manganese dioxide It has been found that by increasing the temperature, the discharge performance at room temperature tends to decrease, and the decrease in discharge performance is particularly significant in the low temperature region, for example, -20°C.
この原因については明白ではないが、各種ｐＨに調整し
たニー酸化マンガンの比表面積をＢＥＴ法で測定した結
果、ｐＨを高めることによって二酸化マンガンの比表面
積は低下する傾向が見られた。The cause of this is not clear, but as a result of measuring the specific surface area of di-manganese oxide adjusted to various pH values using the BET method, it was found that the specific surface area of manganese dioxide tends to decrease as the pH increases.
各種ｐＨに調整した元の二酸化マンガンは同一のもので
あるのに拘わらず、中和剤を多く使用し１）Ｈを高める
と二酸化マンガンの比表面積が小さくなることから考え
て、中和剤により二酸化マンガンの活性点が被覆され、
このことにより電池付能の低下を１３いているのではな
いかと想定される。Even though the original manganese dioxide adjusted to various pH values is the same, it is possible to use a large amount of neutralizing agent.1) Considering that increasing the H content reduces the specific surface area of manganese dioxide, The active sites of manganese dioxide are coated,
It is assumed that this causes a decrease in battery performance.
一方、二酸化マンガンのｐ（（を逆に低くした場合は、
ｐＨ２，５〜４．０の範囲内で電池の低温特性およびス
トロボ特性が向上することが確認された。On the other hand, if p(() of manganese dioxide is lowered,
It was confirmed that the low temperature characteristics and strobe characteristics of the battery were improved within the pH range of 2.5 to 4.0.
ざらに、二酸化マンガンのＤＨが極端に低下する、例え
ば２．５未満とするとカメラのストロボに使用された時
の電池性能の低下が見られた。In general, when the DH of manganese dioxide is extremely reduced, for example, less than 2.5, the battery performance deteriorates when used in a camera strobe.
以上のことよりアルカリマンガン電池に使用される二酸
化マンガンのｐＨには電池性能を高める最適ＤＩ−１が
あることが判明し、その範囲はＩ）ｌ−１２，５〜４．
０であることが判った。From the above, it has been found that the pH of manganese dioxide used in alkaline manganese batteries has an optimum DI-1 that improves battery performance, and the range is I) l-12,5 to 4.
It turned out to be 0.
本発明に用いられる二酸化マンガンとしては特に制限は
なく、例えば電解二酸化マンガン、化学二酸化マンガン
等が挙げられている。The manganese dioxide used in the present invention is not particularly limited, and examples thereof include electrolytic manganese dioxide, chemical manganese dioxide, and the like.
また、本発明によりｉｒＩられるｌ）Ｈを調整した二酸
化マンガンはアルカリマンガン電池の正極活物質として
用いられるが、ここでいうアルカリマンガン電池は亜鉛
を負極活物質とする通常のもので、形状も円筒型、ボタ
ン型（薄型）のいずれでもよく特に制限はない。Furthermore, the manganese dioxide prepared by adjusting irI (l)H according to the present invention is used as a positive electrode active material of an alkaline manganese battery, but the alkaline manganese battery referred to here is a normal type that uses zinc as a negative electrode active material and has a cylindrical shape. There is no particular restriction, and it may be either type or button type (thin).
［実施例］
以下、本発明を実施例および比較例に基づき具体的に説
明する。[Examples] The present invention will be specifically described below based on Examples and Comparative Examples.
・を例１〜４および 較例１〜４
二酸化マンガンとして電解二酸化マンガンを用い、中和
剤としての水酸化ナトリウム添加量を変量することによ
って、二酸化マンガンのＤＨが１．８から６．１までの
試料を作成した（実施例１〜４および比較例１〜４）。Examples 1 to 4 and Comparative Examples 1 to 4 By using electrolytic manganese dioxide as manganese dioxide and varying the amount of sodium hydroxide added as a neutralizing agent, the DH of manganese dioxide was increased from 1.8 to 6.1. Samples were prepared (Examples 1 to 4 and Comparative Examples 1 to 4).
この作成試料のｒｌＨ及びすトリウム添加（１は第１表
に示すごとくであり、ｐＨとナトリウム添加量との間に
は明らかに相関関係が見られた。The rlH and sthorium addition (1) of this prepared sample were as shown in Table 1, and there was a clear correlation between the pH and the amount of sodium added.
第１表
これらの各種のｐＨに調整した二酸化マンガンを用いて
、単３形アルカリマンガン電池を作成し、その放電特性
の評価を行なった。Table 1 Using manganese dioxide adjusted to various pH values, AA alkaline manganese batteries were prepared and their discharge characteristics were evaluated.
なお、評価項目は、 （１）２Ω連続、２０℃ （２）２Ω連続、−２０℃ （３）ストロボ特性 の３項目とした。The evaluation items are: (1) 2Ω continuous, 20℃ (2) 2Ω continuous, -20℃ (3) Strobe characteristics There were three items:
このようにして得られた放電特性の評価結果を第１〜４
図に示す。The evaluation results of the discharge characteristics obtained in this way are
As shown in the figure.
第１図は、２Ω連続、２０℃にＪ３ける二酸化マンガン
のｐＨと放電持続時間との関係を示すグラフであり、第
２図は、２Ω連続、−２０℃における二酸化マンガンの
ｐＨと放電持続時間との関係を示ずグラフである。Figure 1 is a graph showing the relationship between the pH of manganese dioxide and the discharge duration at J3 at 2Ω continuous and 20°C, and Figure 2 is a graph showing the relationship between the pH and discharge duration of manganese dioxide at -20°C and 2Ω continuous. It is a graph that does not show the relationship between
また、第３図および第４図は、市販のストロボ（ガイド
ナンバー３２）を用いた実機試験にてスト［１ボ性能を
評価したときのグラフであり、第３図において、縦軸は
２回目の発光が起るまでのチャージアップ時間、第４図
において、縦軸はストロボの発光回数を示し、横軸は二
酸化マンガンのｐＨをそれぞれ示す。In addition, Figures 3 and 4 are graphs when the flash performance was evaluated in an actual test using a commercially available strobe (guide number 32). In Figure 3, the vertical axis is the second In FIG. 4, the vertical axis shows the number of strobe flashes, and the horizontal axis shows the pH of manganese dioxide.
第１〜４図に示されるように、二酸化マンガンのｐＨが
３．０近傍で全般に電池性能が最も良くなっており、ｐ
Ｈが４．０より大きくなると電池性能の低下が大きく
なる。As shown in Figures 1 to 4, the battery performance is generally best when the pH of manganese dioxide is around 3.0, and the pH of manganese dioxide is around 3.0.
If H is greater than 4.0, the battery performance will deteriorate significantly.
この傾向は特に−２０℃のような低温領域での電池性能
に顕著で、二酸化マンガンのｐＨが３．０と５．０で比
較するとｐＨが約５．０の二酸化マンガンの放電持続時
間が３．５分に対しｐＨ約３．０の二酸化マンガンでは
４．４分となり約２５％の性能向上が見られる。This tendency is particularly noticeable in battery performance at low temperatures such as -20°C, and when comparing manganese dioxide with a pH of 3.0 and 5.0, the discharge duration of manganese dioxide with a pH of about 5.0 is 3. .5 minutes, compared to 4.4 minutes for manganese dioxide with a pH of about 3.0, which is an improvement in performance of about 25%.
二酸化マンガンのｐ）−１が２．０近傍では、低温領域
での放電性能は二酸化マンガンのＩＩＨ３，０近傍と比
べ余り低下は見られないが、ストロボ性能においてコン
デンサーのチャージアップ時間、発光回数共に低下が見
られる。When the p)-1 of manganese dioxide is around 2.0, the discharge performance in the low temperature region does not deteriorate much compared to the IIH around 3.0 of manganese dioxide, but in terms of strobe performance, both the capacitor charge-up time and the number of flashes are A decline is seen.
［発明の効果］
以上説明のごとく、アルカリマンガン電池の正極活物質
としで用いられる二酸化マンガンのｐＨを２．５から４
．０の範囲に調！することにより、電池性能を大幅に向
上させることができる。[Effect of the invention] As explained above, the pH of manganese dioxide used as the positive electrode active material of alkaline manganese batteries is 2.5 to 4.
．． Key in the 0 range! By doing so, battery performance can be significantly improved.
従って、本発明により得られるｐＨが特定範囲にある二
酸化マンガンは、アルカリマンガン電池の正極活物質と
して好適に用いられる。Therefore, the manganese dioxide obtained by the present invention and having a pH within a specific range is suitably used as a positive electrode active material for alkaline manganese batteries.
第１図は、２０℃における放電持続時間を示すグラフ、
第２図は、−２０℃における放電持続時間を示ずグラフ
、
第３図は、ストロボを用いた実機試験における２回目の
発光が起るまでのチャージアップ時間を示すグラフ、お
よび
第４図は、ストロボを用いた実機試験におけるストロボ
の発光回数を示すグラフである。
特許出願人 三井金属鉱業株式会社
代理人 弁理士 伊 東 辰 雄
代理人 弁理士 伊 東 哲 也
二１吏イしマン力゛ンリｐＨ
第１図
二ｔｌ勤しマン力゛ンつｐＨ
第２図Figure 1 is a graph showing the discharge duration at 20°C, Figure 2 is a graph not showing the discharge duration at -20°C, and Figure 3 is a graph showing the second light emission in an actual test using a strobe. FIG. 4 is a graph showing the charge-up time until the strobe is activated, and FIG. 4 is a graph showing the number of flashes of the strobe in an actual test using the strobe. Patent applicant Mitsui Kinzoku Mining Co., Ltd. Agent Patent attorney Tatsuo Ito Agent Patent attorney Satoshi Ito
Claims (1)
７で規定する二酸化マンガンのｐＨを２．５〜４．０の
範囲に調整することを特徴とするアルカリマンガン電池
用二酸化マンガンの製造法。In the neutralization treatment of manganese dioxide, JIS K146
7. A method for producing manganese dioxide for use in alkaline manganese batteries, which comprises adjusting the pH of manganese dioxide to a range of 2.5 to 4.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61136181A JPS62295354A (en) | 1986-06-13 | 1986-06-13 | Manufacture of manganese dioxide for alkaline manganic cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61136181A JPS62295354A (en) | 1986-06-13 | 1986-06-13 | Manufacture of manganese dioxide for alkaline manganic cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62295354A true JPS62295354A (en) | 1987-12-22 |
Family
ID=15169232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61136181A Pending JPS62295354A (en) | 1986-06-13 | 1986-06-13 | Manufacture of manganese dioxide for alkaline manganic cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62295354A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008013427A (en) * | 2006-06-07 | 2008-01-24 | Tosoh Corp | Electrolytic manganese dioxide |
| JP2009043547A (en) * | 2007-08-08 | 2009-02-26 | Fdk Energy Co Ltd | Electrolytic manganese dioxide for battery, positive electrode mix, and alkaline battery |
-
1986
- 1986-06-13 JP JP61136181A patent/JPS62295354A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008013427A (en) * | 2006-06-07 | 2008-01-24 | Tosoh Corp | Electrolytic manganese dioxide |
| JP2009043547A (en) * | 2007-08-08 | 2009-02-26 | Fdk Energy Co Ltd | Electrolytic manganese dioxide for battery, positive electrode mix, and alkaline battery |
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