JPH08176871A - Production of electrolytic manganese dioxide - Google Patents
Production of electrolytic manganese dioxideInfo
- Publication number
- JPH08176871A JPH08176871A JP31842891A JP31842891A JPH08176871A JP H08176871 A JPH08176871 A JP H08176871A JP 31842891 A JP31842891 A JP 31842891A JP 31842891 A JP31842891 A JP 31842891A JP H08176871 A JPH08176871 A JP H08176871A
- Authority
- JP
- Japan
- Prior art keywords
- electrolytic
- soln
- mno2
- produced
- contg
- 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 20
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000008151 electrolyte solution Substances 0.000 claims description 11
- 238000006277 sulfonation reaction Methods 0.000 claims description 5
- 239000006230 acetylene black Substances 0.000 abstract description 5
- 229940099596 manganese sulfate Drugs 0.000 abstract description 5
- 235000007079 manganese sulphate Nutrition 0.000 abstract description 5
- 239000011702 manganese sulphate Substances 0.000 abstract description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 abstract description 5
- 238000007613 slurry method Methods 0.000 abstract description 5
- 229910002804 graphite Inorganic materials 0.000 abstract description 3
- 239000010439 graphite Substances 0.000 abstract description 3
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 abstract description 3
- 229910045601 alloy Inorganic materials 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 2
- 229910004337 Ti-Ni Inorganic materials 0.000 abstract 1
- 229910011209 Ti—Ni Inorganic materials 0.000 abstract 1
- 150000001721 carbon Chemical class 0.000 abstract 1
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 239000000725 suspension Substances 0.000 description 8
- 238000007796 conventional method Methods 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電解二酸化マンガンの
製造法であって、粉砕性がよく、かつ放電性能の高い電
解二酸化マンガンの製造法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing electrolytic manganese dioxide, which has good pulverizability and high discharge performance.
【０００２】[0002]
【従来の技術】従来一般に電解二酸化マンガン（以下Ｅ
ＭＤという）は、チタン、鉛、黒鉛を陽極とし、硫酸マ
ンガン溶液を電解液として製造しており、特に、近年は
乾電池特性の良いＥＭＤを得るため、チタン電極による
製造が増加している。2. Description of the Related Art Conventionally, electrolytic manganese dioxide (hereinafter referred to as E
MD) is manufactured by using titanium, lead, and graphite as an anode and a manganese sulfate solution as an electrolytic solution. In particular, in recent years, in order to obtain EMD having good dry battery characteristics, the production by a titanium electrode is increasing.
【０００３】チタン電極を使用してＥＭＤを製造する場
合、その電流密度は、０．８〜１．０Ａ／ｄｍ2程度が
上限であり、電流密度を大きくすると、チタン電極表面
に不伝導性の不導体皮膜が生成し、その結果電解電圧の
急上昇が惹起し、操業困難になるという問題がある。When an EMD is manufactured using a titanium electrode, its current density has an upper limit of about 0.8 to 1.0 A / dm 2 , and when the current density is increased, the titanium electrode surface becomes non-conductive. There is a problem that a non-conductive film is formed, and as a result, a rapid increase in electrolysis voltage occurs, which makes operation difficult.
【０００４】これを克服するため、電解槽内の電解液に
マンガン酸化物を懸濁させて電解する方法（特公昭４７
ー４２７１１号公報）、また、アセチレンブラック、カ
ーボンブラック等の炭素粒子を懸濁して電解する方法
（特公昭６１ー４７９１１号公報）（以下スラリー法と
いう）等が提案されている。In order to overcome this, a method of suspending manganese oxide in an electrolytic solution in an electrolytic cell and electrolyzing it (Japanese Patent Publication No. Sho 47).
No. 42711), and a method of suspending and electrolyzing carbon particles such as acetylene black and carbon black (Japanese Patent Publication No. 61-47911) (hereinafter referred to as slurry method).
【０００５】[0005]
【発明が解決しようとする課題】前記スラリ法は、炭素
粒子が撥水性を有し、そのままでは、炭素粒子を電解液
中に懸濁させるのはきわめて困難である。In the above-mentioned slurry method, the carbon particles have water repellency, and it is extremely difficult to suspend the carbon particles in the electrolytic solution as they are.
【０００６】本発明は、前述欠点を改善し、スラリー法
における炭素粒子の電解液中の懸濁を改善し、高い放電
性能で、かつ粉砕性のよいＥＭＤを確実に製造できる方
法を提案することにある。The present invention proposes a method for improving the above-mentioned drawbacks, improving the suspension of carbon particles in an electrolytic solution in a slurry method, and reliably producing an EMD having high discharge performance and good grindability. It is in.
【０００７】[0007]
【課題を解決するための手段】本発明は、ＥＭＤを製造
するに当り、表面をスルフォン化処理した炭素粒子を、
電解液中に０．１〜１．０ｇ／ｌ懸濁させて電解するＥ
ＭＤの製造法という構成のものである。According to the present invention, in producing EMD, carbon particles whose surface is sulfonated are
Electrolyze by suspending 0.1 to 1.0 g / l in an electrolytic solution E
This is the structure of the MD manufacturing method.
【０００８】茲に、使用する炭素粒子はアセチレンブラ
ック、カーボンブラック等の公知の炭素粒子が使用でき
るが、好ましくはアセチレンブラックを使用する。As the carbon particles to be used, well-known carbon particles such as acetylene black and carbon black can be used, but acetylene black is preferably used.
【０００９】また、炭素粒子の表面のスルフォン化処理
は、例えば、炭素粒子６７部に発煙硫酸３３部を混合し
（発熱反応７０℃）、放冷の後、濾過、水洗して簡単に
スルフォン化せしめることができる。The sulfonation treatment of the surface of the carbon particles is carried out, for example, by mixing 67 parts of carbon particles with 33 parts of fuming sulfuric acid (exothermic reaction 70 ° C.), allowing to cool, filtering, and washing with water for sulfonation. It can be done.
【００１０】[0010]
【作用】本発明は、以上の如き構成のものであって、ス
ルフォン化処理された炭素粒子の懸濁物は、電解液中に
容易に懸濁し、かつ均一に分散せしめることができる。
従って、本発明によるときは、特に、アルカリ放電性能
に優れており、しかも得られたＥＭＤは粉砕性も良く、
処理能率を改善せしめることができる。The present invention has the above-mentioned structure, and the suspension of the sulfonation-treated carbon particles can be easily suspended and uniformly dispersed in the electrolytic solution.
Therefore, according to the present invention, particularly, the alkaline discharge performance is excellent, and the obtained EMD has good pulverizability,
The processing efficiency can be improved.
【００１１】[0011]
【実施例】以下、実施例を参照して本発明を具体的に説
明する。アセチレンブラック（以下ＡＢという）６７部
に、発煙硫酸３３部を混合し、放冷の後、濾過、水洗し
てスルフォン化アセチレンブラックを得た（以下Ｓ−Ａ
Ｂという）。EXAMPLES The present invention will be described in detail below with reference to examples. 67 parts of acetylene black (hereinafter referred to as AB) was mixed with 33 parts of fuming sulfuric acid, allowed to cool, filtered and washed with water to obtain a sulfonated acetylene black (hereinafter referred to as S-A).
B).
【００１２】他方、電解槽は、加温装置を設けた内容積
１０リットルのもので、陽極としてチタニウム・ニッケ
ル（ニッケル含有量５％）合金板を用い、また陰極とし
て黒鉛板を夫々交互に懸吊せしめ、さらに、電解液とし
て硫酸マンガンの水溶液中に、懸濁物として前記Ｓ−Ａ
Ｂを添加した懸濁液を用いた。On the other hand, the electrolytic cell has a heating device and has an internal volume of 10 liters. A titanium-nickel (nickel content 5%) alloy plate is used as an anode, and graphite plates are alternately suspended as cathodes. The suspension was suspended, and the suspension was suspended in an aqueous solution of manganese sulfate as an electrolyte.
The suspension to which B was added was used.
【００１３】電解するに際して、前記電解槽中の電解液
の組成が、硫酸マンガン０．６５モル／ｌ、Ｈ2ＳＯ
4０．４モル／ｌ、及びＳ−ＡＢが０．１〜１．０ｇ／
ｌとなるように調整した懸濁液を、電解槽に注入しなが
ら連続的に電解を行った。In electrolysis, the composition of the electrolytic solution in the electrolytic cell is such that manganese sulfate is 0.65 mol / l, H 2 SO
4 0.4 mol / l and S-AB 0.1-1.0 g /
The electrolysis was continuously performed while pouring the suspension adjusted to 1 into the electrolytic cell.
【００１４】尚、電解時の電解浴の温度を９０℃±１℃
に保ち、電流密度は２．０Ａ／ｄｍ2で行った。７２時
間電解した後、ＥＭＤが電着した陽極板を取り出して、
常法により洗浄、粉砕、中和、乾燥を行い、次の表１の
如き結果を得た。尚、比較のため従来法の結果を併記し
た。The temperature of the electrolytic bath during electrolysis is 90 ° C. ± 1 ° C.
The current density was 2.0 A / dm 2 . After electrolysis for 72 hours, take out the anode plate on which EMD was electrodeposited,
Washing, pulverization, neutralization and drying were carried out by a conventional method, and the results shown in Table 1 below were obtained. The results of the conventional method are also shown for comparison.
【００１５】[0015]
【表１】 [Table 1]
【００１６】尚、アルカリ放電容量は、ＥＭＤと黒鉛粉
とを合剤となし、９モルＫＯＨ中にて１ｍＡ／ｃｍ2の
定電流放電を行った。この場合の電圧は、Ｈｇ／ＨｇＯ
比較電極により測定し、−４００ｍＶまでの放電容量で
示した。表１から明らかなように、本発明では懸濁粒子
濃度Ｓ−ＡＢ ０．５ｇ／ｌが、粉砕性及びアルカリ放
電性能が共に優れており、懸濁粒子濃度が高くても或は
低くても低下する傾向を示している。Regarding the alkaline discharge capacity, a constant current discharge of 1 mA / cm 2 was performed in 9 mol KOH using EMD and graphite powder as a mixture. The voltage in this case is Hg / HgO
The discharge capacity measured up to -400 mV was measured by a reference electrode. As is clear from Table 1, in the present invention, the suspended particle concentration S-AB of 0.5 g / l is excellent in both pulverizability and alkaline discharge performance, and the suspended particle concentration is high or low. It shows a downward trend.
【００１７】また、図１に本発明と従来法（ＥＭＤ微
粉、粒度５μ、０．２ｇ／ｌ懸濁）とのアルカリ放電容
量の比較結果を示す。その結果、本発明は従来法と比較
して優れた特性を示し、良好な結果を得た。Further, FIG. 1 shows a comparison result of the alkaline discharge capacities of the present invention and the conventional method (EMD fine powder, particle size 5 μ, 0.2 g / l suspension). As a result, the present invention showed excellent characteristics as compared with the conventional method and obtained good results.
【００１８】[0018]
【発明の効果】以上の如く本発明は、電解液中に懸濁せ
しめる炭素粒子表面をスルフォン化処理することによ
り、電解液中の懸濁物の濡れを改善でき、電解液中に懸
濁粒子を均一に分散せしめることができ、従って放電性
能に優れ、かつ粉砕性の良いＥＭＤを簡単に、かつ確実
に得ることができる。INDUSTRIAL APPLICABILITY As described above, the present invention can improve the wetting of the suspension in the electrolytic solution by subjecting the surface of the carbon particles to be suspended in the electrolytic solution to the sulfonation treatment, and the suspended particles in the electrolytic solution can be improved. It is possible to uniformly disperse, and therefore it is possible to easily and surely obtain an EMD having excellent discharge performance and good pulverizability.
【図１】本発明と従来法とのアルカリ放電容量に対する
電位のグラフである。FIG. 1 is a graph of potential against alkaline discharge capacity for the present invention and a conventional method.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 松木 建三 山形県米沢市城南４丁目３ー16 山形大学 内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kenzo Matsuki 4-3-16 Jonan, Yonezawa City, Yamagata Prefecture Yamagata University
Claims (1)
をスルフォン化処理した炭素粒子を、電解液中に０．１
〜１．０ｇ／ｌ懸濁させて電解することを特徴とする電
解二酸化マンガンの製造法。1. In the production of electrolytic manganese dioxide, carbon particles whose surface is subjected to sulfonation are added to an electrolytic solution in an amount of 0.1.
A method for producing electrolytic manganese dioxide, which comprises suspending at about 1.0 g / l and electrolyzing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31842891A JPH08176871A (en) | 1991-11-06 | 1991-11-06 | Production of electrolytic manganese dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31842891A JPH08176871A (en) | 1991-11-06 | 1991-11-06 | Production of electrolytic manganese dioxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08176871A true JPH08176871A (en) | 1996-07-09 |
Family
ID=18099044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31842891A Pending JPH08176871A (en) | 1991-11-06 | 1991-11-06 | Production of electrolytic manganese dioxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08176871A (en) |
-
1991
- 1991-11-06 JP JP31842891A patent/JPH08176871A/en active Pending
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