JPS6310465A - Maganese dioxide battery - Google Patents
Maganese dioxide batteryInfo
- Publication number
- JPS6310465A JPS6310465A JP61153134A JP15313486A JPS6310465A JP S6310465 A JPS6310465 A JP S6310465A JP 61153134 A JP61153134 A JP 61153134A JP 15313486 A JP15313486 A JP 15313486A JP S6310465 A JPS6310465 A JP S6310465A
- Authority
- JP
- Japan
- Prior art keywords
- manganese dioxide
- amorphous
- manganese
- active material
- 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
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000007774 positive electrode material Substances 0.000 claims abstract description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052748 manganese Inorganic materials 0.000 abstract description 13
- 239000011572 manganese Substances 0.000 abstract description 13
- 239000013078 crystal Substances 0.000 abstract description 8
- 238000009792 diffusion process Methods 0.000 abstract description 8
- 239000007790 solid phase Substances 0.000 abstract description 5
- 230000004888 barrier function Effects 0.000 abstract description 3
- 239000011149 active material Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical class [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 229910016978 MnOx Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- -1 oxygen ions Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 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】
産業上の利用分野
本発明は、二酸化マンガンを正極活物質とするマンガン
乾電池、およびアルカリマンガン電池における二酸化マ
ンガンの材質に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a manganese dry battery using manganese dioxide as a positive electrode active material, and to the material of manganese dioxide in an alkaline manganese battery.
従来の技術
従来、この種のマンガン乾電池やアルカリマンガン電池
の正極活物質として電解二酸化マンガン。Conventional technology Conventionally, electrolytic manganese dioxide has been used as the positive electrode active material for this type of manganese dry battery or alkaline manganese battery.
化学二酸化マンガン、そして天然二酸化マンガンが用い
られている。その中でも高性能電池用正極活物質として
は、電解二酸化マンガンが最も優れており、現在量も多
く使用されている。Chemical manganese dioxide and natural manganese dioxide are used. Among them, electrolytic manganese dioxide is the most excellent positive electrode active material for high-performance batteries, and is currently used in large quantities.
ところで二酸化マンガンの還元反応は、次式で示される
ように電子とプロトンが結晶格子内へ拡散し進行する。Incidentally, the reduction reaction of manganese dioxide proceeds as electrons and protons diffuse into the crystal lattice, as shown by the following equation.
ＭｎＯ２＋Ｈ２０＋ｅ−＋Ｍｎ０ＯＨ＋ＯＨ−・−・・
−・−（１）従って放電特性特に高負荷特性を良好にす
るには、この電子とプロトンの拡散を遅れないようにす
ることにある。MnO2+H20+e-+Mn0OH+OH-・-・・
-.- (1) Therefore, in order to improve discharge characteristics, especially high load characteristics, it is necessary to keep up with the diffusion of electrons and protons.
このため、従来では、種々の二酸化マンガンの中からこ
の拡散速度が比較的速いといわれているガンマ型あるい
はエンスタイト型の結晶構造をもつ斜方晶形の二酸化マ
ンガンを用いてきた。For this reason, orthorhombic manganese dioxide having a gamma type or enstite type crystal structure, which is said to have a relatively fast diffusion rate among various manganese dioxides, has conventionally been used.
しかし、結晶性の二酸化マンガンを用いた場合、負荷が
大きくなると（１）式の反応が次第に遅れる。However, when crystalline manganese dioxide is used, as the load increases, the reaction of formula (1) is gradually delayed.
つまり、プロトンの二酸化マンガン固相内への拡散が遅
れ、良好な高負荷特性、即ち利用率が得られなくなる。In other words, the diffusion of protons into the solid phase of manganese dioxide is delayed, making it impossible to obtain good high-load characteristics, that is, utilization efficiency.
発明が解決しようとする問題点
このような従来の材質であるガンマ型あるいはエンスタ
イト型二酸化マンガンは、基本的には斜方晶形であるが
、他の二酸化マンガンに比べると結晶性は悪く、やや無
定形化している。これは結晶Ｃ軸方向で結晶成長に乱れ
があり、それだけ結品性が低下していることによる。Problems to be Solved by the Invention These conventional materials, gamma-type or enstite-type manganese dioxide, are basically orthorhombic, but compared to other manganese dioxides, their crystallinity is poor and they are somewhat amorphous. It is formalized. This is because the crystal growth is disordered in the crystal C-axis direction, and the crystallinity is reduced accordingly.
しかし、このように結晶性の悪い、いわば無定形化した
ガンマ二酸化マンガンを用いても充分な高負荷特性が得
られず、利用率が低くなる原因は、この二酸化マンガン
がもつ結晶性に問題がある。However, even with the use of gamma manganese dioxide, which has poor crystallinity and has become amorphous, it is not possible to obtain sufficient high-load characteristics and the utilization rate is low. be.
即ち、二酸化マンガンがもつ結晶粒界あるいは異語晶子
間における拡散障壁がプロトンの固相的拡散を阻害させ
ていると考えらｎる。That is, it is considered that the diffusion barrier between the crystal grain boundaries or the crystallites of manganese dioxide inhibits the solid phase diffusion of protons.
本発明は、このような問題を解決するもので、優れた放
電利用率を有する正極活物質としての二酸化マンガンを
提供することを目的とするものである。The present invention solves these problems and aims to provide manganese dioxide as a positive electrode active material having excellent discharge utilization.
問題点を解決するための手段
この問題点を解決するために本発明は、マンガン乾電池
およびアルカリ・マンガン電池の正極活物質として非晶
質二酸化マンガンを用いたものである。Means for Solving the Problem In order to solve this problem, the present invention uses amorphous manganese dioxide as a positive electrode active material for manganese dry batteries and alkaline manganese batteries.
作 用
このような非晶質二酸化マンガンを正極活物質として用
いると、プロトンの二酸化マンガン固相内への拡散は結
晶粒界や異語晶子間による拡散障壁をもたないと考えら
れるため速やかに進行し、高負荷印加時の利用率はマン
ガン電池、アルカリマンガン電池のいずれにおいても向
上させることができた。Effect When such amorphous manganese dioxide is used as a positive electrode active material, protons can be rapidly diffused into the solid phase of manganese dioxide because it is thought that there are no diffusion barriers such as grain boundaries or intercrystallites. As a result, the utilization rate under high load conditions was improved for both manganese and alkaline manganese batteries.
本発明は、このような事実に基づいて提案されたもので
あシ、以下その実施例について説明する。The present invention has been proposed based on such facts, and examples thereof will be described below.
実施例１
まず、用いた非晶質の二酸化マンガンは、有効二酸化マ
ンガン量が９４％ 、ＭｎＯｘのＸ値は１．９６で結晶
形はＸ線回折図からほぼ無定形と判断される非常にブロ
ードなピークが観察された。また比導電率は無定形酸化
物特有のかなり低い値を示した。通常の電解二酸化マン
ガンの比導電率は１（） −３（Ｓ／ｃｒｎ）のオーダ
であったのに対し、非晶質二酸化マンガンのそれは、１
０〜１０ （Ｓ／ｃｍ）となった。これは４価のマンガ
ンイオンを中心として６個の酸素イオンが配置してでき
る八面体構造において、互いの八面体セグメントの配向
が乱れたこと、および４価のマンガンイオン同志間の島
構造がより無秩序な状態、即ち無定形化していることを
意味する。Example 1 First, the amorphous manganese dioxide used had an effective amount of manganese dioxide of 94%, an X value of MnOx of 1.96, and a very broad crystal form judged to be almost amorphous from the X-ray diffraction diagram. A peak was observed. In addition, the specific conductivity showed a fairly low value, which is typical of amorphous oxides. The specific conductivity of ordinary electrolytic manganese dioxide was on the order of 1()-3(S/crn), whereas that of amorphous manganese dioxide was on the order of 1()-3(S/crn).
0 to 10 (S/cm). This is because the orientation of the octahedral segments is disordered in the octahedral structure formed by arranging six oxygen ions around a tetravalent manganese ion, and the island structure between the tetravalent manganese ions becomes more It means a disordered state, that is, an amorphous state.
また、結晶水は、通常の二酸化マンガンが１．７〜１．
８％である０（７）し非晶質二酸化マンガンのそれは２
〜３％に達し、結晶性の乱れに応じ、水酸基が増大した
ことを反映している。In addition, the crystal water contains ordinary manganese dioxide of 1.7 to 1.
8% is 0(7) and that of amorphous manganese dioxide is 2
It reached ~3%, reflecting an increase in the number of hydroxyl groups in response to disordered crystallinity.
このような特性をもつ非晶質二酸化マンガンを正極活物
質、亜鉛を負極活物質とし、電解液に塩化亜鉛を主とし
だ中性溶液を用いて第１図に示すマンガン乾電池のモデ
ルセルを組み放電特性、特に二酸化マンガンの利用率を
検討した。A model cell of a manganese dry battery as shown in Figure 1 was assembled using amorphous manganese dioxide, which has these characteristics, as a positive electrode active material, zinc as a negative electrode active material, and a neutral solution mainly containing zinc chloride as an electrolyte. The discharge characteristics, especially the utilization rate of manganese dioxide, were investigated.
第１図において、１は本発明に二る非晶質二酸化マンガ
ンとアセチレンプラックを５：１の重量比で混合した正
極合剤である。なお、通常の電解二酸化マンガンとアセ
チレンプラックを同比率で混合した合剤と上記合剤の比
導率は両方とも１００のオーダとなり、はぼ同様であっ
た。２は正極集電体で白金板を用いている。３はセパレ
ータである。４は負極活物質である亜鉛板、５は正負極
のリード線、６はセルを固定するためのネジである。In FIG. 1, reference numeral 1 is a positive electrode mixture in which amorphous manganese dioxide and acetylene plaque according to the present invention are mixed at a weight ratio of 5:1. The specific conductivities of the ordinary mixture of electrolytic manganese dioxide and acetylene plaque in the same ratio and the above mixture were both on the order of 100, and were almost the same. 2 is a positive electrode current collector using a platinum plate. 3 is a separator. 4 is a zinc plate which is a negative electrode active material, 5 is a lead wire of the positive and negative electrodes, and 6 is a screw for fixing the cell.
７．８は樹脂製のセル容器である。放電実験を行う前に
は単位体積あたりの正極合剤重量が全ての試験において
必ず一定になるように考慮した。放電条件は、電流密度
が５ｍＡ／ｆｆｌ、７ｍＡ／ｃｆｆｌ、９ｍＡ／、７の
各定電流連続放電試験とし、環境温度は２０℃とした。7.8 is a resin cell container. Before conducting the discharge experiment, consideration was given to ensuring that the weight of the positive electrode mixture per unit volume remained constant in all tests. The discharge conditions were constant current continuous discharge tests with current densities of 5 mA/ffl, 7 mA/cffl, 9 mA/, and 7, and the environmental temperature was 20°C.
評価方法としては、従来の電解二酸化マンガンの正極利
用率に対する非晶質二酸化マンガンのそれの比率で検討
した。The evaluation method was based on the ratio of the positive electrode utilization rate of amorphous manganese dioxide to that of conventional electrolytic manganese dioxide.
電流密度を５．ア、 ９ ｍＡ／ｃｎｌ とした時の
利用率比較結果を第２図に示す。図から判るように、５
ｍＡ／ｉでは従来の二酸化マンガンとほぼ同様の利用率
を示すのに対して、９ｍＡ／ｃｎでは従来品よりも約２
６係の改善がみられる。このことから、非晶質二酸化マ
ンガンを用いると、軽負荷印加時での利用率は従来品と
ほぼ同様で、もっばら二酸化マンガンの充填量に依存す
るが、重負荷印加時では利用率を大福に改善できる。こ
れは、プロトンの固相内への拡散が非晶質状態でより速
やかに行われることばよると考えられ、（１）Ｅの反応
速度が速くなるに伴ってその効果がより顕著に現れる。The current density is 5. A. Figure 2 shows the comparison results of the utilization rate when it was set to 9 mA/cnl. As you can see from the figure, 5
At mA/i, the utilization rate is almost the same as that of conventional manganese dioxide, while at 9 mA/cn, it is about 2 times lower than the conventional product.
There is an improvement in Section 6. From this, when amorphous manganese dioxide is used, the utilization rate when applying a light load is almost the same as that of conventional products, and depends mostly on the amount of manganese dioxide filled, but when applying a heavy load, the utilization rate is much lower than that of conventional products. can be improved. This is thought to be due to the fact that protons diffuse more quickly into the solid phase in the amorphous state, and (1) this effect becomes more pronounced as the reaction rate of E becomes faster.
実施例２
次に実施例１で示したモデルセルを用いてアルカリ電解
液中で同様の試験を行った。Example 2 Next, a similar test was conducted in an alkaline electrolyte using the model cell shown in Example 1.
ここで用いた正極合剤は、非晶質二酸化マンガンと人造
黒鉛を９：１の重量比で混合した合剤である。なお、通
常の電解二酸化マンガンと人造黒鉛を同比率で混合した
合剤と前記合剤の比導電率は両者とも１ｏ０のオーダで
あった。The positive electrode mixture used here was a mixture of amorphous manganese dioxide and artificial graphite at a weight ratio of 9:1. Note that the specific conductivities of the mixture and the mixture of ordinary electrolytic manganese dioxide and artificial graphite in the same ratio were both on the order of 100.
電流密度をｓ 、 ７ 、９ ｍＡ／ｃＪとした時の利
用率比較結果を第３図に示す。図から判るように、実施
例１の如く軽負荷印加時よりも９ ｍＡ／、ｆｆｌのよ
うな重負荷印加時の方に改善がみられ、利用率は従来品
よりも約２６％向上した。FIG. 3 shows the comparison results of the utilization rates when the current densities were set to s, 7, and 9 mA/cJ. As can be seen from the figure, an improvement was seen when a heavy load such as 9 mA/ffl was applied than when a light load was applied as in Example 1, and the utilization rate was improved by about 26% compared to the conventional product.
以上のことかられかるように、マンガン乾電池、アルカ
リマンガン電池の正極活物質として非晶質二酸化マンガ
ンを用いると、正極利用率は改善される。特に重負荷印
加時には利用率が従来品よりも約２５係も改善された。As can be seen from the above, when amorphous manganese dioxide is used as the positive electrode active material of manganese dry batteries and alkaline manganese batteries, the positive electrode utilization rate is improved. Especially when applying heavy loads, the utilization rate was improved by about 25 factors compared to the conventional product.
発明の効果
以上のように、本発明によれば、アルカリ電解液、中性
電解液いずれにおいても正極利用率は改善され、特に重
負荷特性に優れた二酸化マンガン電池を提供し得るもの
である。Effects of the Invention As described above, according to the present invention, the positive electrode utilization rate is improved in both alkaline electrolyte and neutral electrolyte, and it is possible to provide a manganese dioxide battery particularly excellent in heavy load characteristics.
第１図は、本発明の実施例におけるモデルセルの断面略
図、第２図は中性電解液中における従来品と本発明の非
晶質二酸化マンガンの正極利用率を比較した図、第３図
はアルカリ電解液中における従来品と本発明の非晶質二
酸化マンガンの正極利用率を比較した図である。
１・・・・・・正極合剤、３・・・・・・セパレータ、
４・・・・・・負極。
代理人の氏名 弁理士 中 尾 敏 男 ほか１名第１
図
第 ２ 図 （中・と電解永）Ｒ茸晶
貫二酸イ巳マン刀′ンのオ］届率夕 ｊ
７ デ ／ｌｔうＬ客演（ａ、Ｚ声′）Fig. 1 is a schematic cross-sectional view of a model cell in an example of the present invention, Fig. 2 is a comparison of the positive electrode utilization rate of the conventional product and the amorphous manganese dioxide of the present invention in a neutral electrolyte, and Fig. 3 FIG. 2 is a diagram comparing the positive electrode utilization rates of the conventional product and the amorphous manganese dioxide of the present invention in an alkaline electrolyte. 1... Positive electrode mixture, 3... Separator,
4...Negative electrode. Name of agent: Patent attorney Toshio Nakao and 1 other person No. 1
Figure 2 (Middle and Electron Era) R Mushroom Crystal Kanji Acid Imi Manto'n'o] Notification Rate Yu j
7 De/ltU L guest performance (a, Z voice')
Claims (1)
ことを特徴とする二酸化マンガン電池。A manganese dioxide battery characterized in that manganese dioxide, which is a positive electrode active material, is in an amorphous state.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61153134A JPH067484B2 (en) | 1986-06-30 | 1986-06-30 | Manganese dioxide battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61153134A JPH067484B2 (en) | 1986-06-30 | 1986-06-30 | Manganese dioxide battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6310465A true JPS6310465A (en) | 1988-01-18 |
| JPH067484B2 JPH067484B2 (en) | 1994-01-26 |
Family
ID=15555741
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61153134A Expired - Lifetime JPH067484B2 (en) | 1986-06-30 | 1986-06-30 | Manganese dioxide battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH067484B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5969341A (en) * | 1996-10-11 | 1999-10-19 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Optical integrated voltage sensor for optically measuring the magnitude of a voltage |
| JP2006139973A (en) * | 2004-11-11 | 2006-06-01 | Hitachi Maxell Ltd | Alkaline cell |
| WO2019090422A1 (en) * | 2017-11-09 | 2019-05-16 | The University Of British Columbia | Electrolytic manganese dioxide and a method of preparing thereof |
| CN113921804A (en) * | 2021-10-11 | 2022-01-11 | 燕山大学 | Electrochemical preparation method of monatomic manganese catalyst |
-
1986
- 1986-06-30 JP JP61153134A patent/JPH067484B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5969341A (en) * | 1996-10-11 | 1999-10-19 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Optical integrated voltage sensor for optically measuring the magnitude of a voltage |
| JP2006139973A (en) * | 2004-11-11 | 2006-06-01 | Hitachi Maxell Ltd | Alkaline cell |
| WO2019090422A1 (en) * | 2017-11-09 | 2019-05-16 | The University Of British Columbia | Electrolytic manganese dioxide and a method of preparing thereof |
| CN113921804A (en) * | 2021-10-11 | 2022-01-11 | 燕山大学 | Electrochemical preparation method of monatomic manganese catalyst |
| CN113921804B (en) * | 2021-10-11 | 2022-12-27 | 燕山大学 | Electrochemical preparation method of monatomic manganese catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH067484B2 (en) | 1994-01-26 |
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