JPH0525814B2 - - Google Patents
Info
- Publication number
- JPH0525814B2 JPH0525814B2 JP58195038A JP19503883A JPH0525814B2 JP H0525814 B2 JPH0525814 B2 JP H0525814B2 JP 58195038 A JP58195038 A JP 58195038A JP 19503883 A JP19503883 A JP 19503883A JP H0525814 B2 JPH0525814 B2 JP H0525814B2
- Authority
- JP
- Japan
- Prior art keywords
- mno
- manganese dioxide
- electrolytic
- electrolytic manganese
- heat
- 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.)
- Expired - Lifetime
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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
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
-
- 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)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】
本発明は固体電解コンデンサやリチウム電池、
各種触媒等に用いられるβ−二酸化マンガンの製
法に関し、特に高純度のβ−二酸化マンガンの製
法に関するものである。[Detailed Description of the Invention] The present invention provides solid electrolytic capacitors, lithium batteries,
The present invention relates to a method for producing β-manganese dioxide used in various catalysts, and particularly to a method for producing highly purified β-manganese dioxide.
マンガンの代表的な酸化物である二酸化マンガ
ン（MnO2）は、その結晶構造の違い等から、α
−二酸化マンガン（α−MnO2）、β−二酸化マ
ンガン（β−MnO2）、γ−二酸化マンガン（γ
−MnO2）等が知られている。そして、例えばリ
チウム電池の正極活物質として用いられる二酸化
マンガンとしては、従来、硫酸マンガンや塩化マ
ンガンの酸性浴からの電解酸化によつて得られる
電解二酸化マンガンや中性硫酸マンガンの沸騰溶
液に過マンガン酸アルカリ溶液を添加して得られ
る化学合成二酸化マンガン等のγ−MnO2が使用
されている。 Manganese dioxide (MnO 2 ), a typical oxide of manganese, has an α
- Manganese dioxide (α-MnO 2 ), β-manganese dioxide (β-MnO 2 ), γ-manganese dioxide (γ
-MnO 2 ), etc. are known. For example, manganese dioxide used as a positive electrode active material in lithium batteries has conventionally been prepared by adding permanganese to electrolytic manganese dioxide obtained by electrolytic oxidation from an acidic bath of manganese sulfate or manganese chloride, or a boiling solution of neutral manganese sulfate. γ-MnO 2 such as chemically synthesized manganese dioxide obtained by adding an acid-alkaline solution is used.
ところで、上述の電解酸化や化学合成で得られ
るγ−MnO2は、かなりの量の水分を含んでいる
ことが知られており、また、化学量論的にもずれ
が生じていると言われている。すなわち、上記電
解二酸化マンガンや化学合成二酸化マンガンを
MnOxとしたときに、ｘ＝2.0ではなくｘ＝1.95前
後であると言われている。そして、このｘ＝2.0
からのずれは、三酸化二マンガン（Mn2O3）等
の存在によるものと考えられる。 By the way, γ-MnO 2 obtained through the electrolytic oxidation and chemical synthesis described above is known to contain a considerable amount of water, and is also said to have a stoichiometric deviation. ing. In other words, the above-mentioned electrolytic manganese dioxide and chemically synthesized manganese dioxide
When MnO x is used, it is said that x is around 1.95, not 2.0. And this x=2.0
It is thought that the deviation from the above is due to the presence of dimanganese trioxide (Mn 2 O 3 ) and the like.
このように、γ−MnO2が水分を含んだり不純
物であるMn2O3を含んでいるために、このγ−
MnO2を使用する上で種々の欠点が問題となつて
いる。 In this way, because γ-MnO 2 contains water and Mn 2 O 3 , which is an impurity, this γ-MnO 2
Various drawbacks have been raised in the use of MnO 2 .
例えば、リチウム電池においては、負極活物質
として金属リチウムを用いているので水分を極端
に嫌い、もしも上記γ−MnO2中に水分が存在す
ると、この水が上記金属リチウムと反応して電池
罐の腐蝕や漏液を引き起こし保存特性が悪くなつ
てしまう。また、γ−MnO2の不純物である
Mn2O3はリチウム電池においては活物質ではな
いので、利用できるγ−MnO2の量がかなり少な
くなつて電池の寿命を低下してしまう。あるい
は、上記γ−MnO2を固体電解コンデンサに使用
した場合には、このγ−MnO2中の水分により耐
電圧、漏電流、経時変化等の問題が生じ、また不
純物であるMn2O3により電気抵抗の増加、耐圧
信頼性、周波数特性等に問題が生じている。さら
に、上記γ−MnO2を触媒として用いる場合に
も、上記Mn2O3の存在は好ましいものでない。 For example, in lithium batteries, metal lithium is used as the negative electrode active material, so moisture is extremely disliked. If moisture is present in the γ-MnO 2 , this water will react with the metal lithium and cause the battery case to deteriorate. This will cause corrosion and leakage, resulting in poor storage properties. Also, it is an impurity of γ-MnO 2
Since Mn 2 O 3 is not an active material in lithium batteries, the amount of γ-MnO 2 available is significantly reduced, reducing battery life. Alternatively, when the above γ-MnO 2 is used in a solid electrolytic capacitor, the moisture in this γ-MnO 2 causes problems such as withstand voltage, leakage current, and aging, and the impurity Mn 2 O 3 Problems have arisen with increased electrical resistance, withstand voltage reliability, frequency characteristics, etc. Furthermore, even when the above-mentioned γ-MnO 2 is used as a catalyst, the presence of the above-mentioned Mn 2 O 3 is not preferable.
このため、水分をほとんど含まず熱力学的に安
定なβ−MnO2が注目されている。このβ−
MnO2の製法としては、通常は硝酸マンガン
（Mn（NO3）2・6H2O）を熱分解するという方法が
知られており、例えば固体電解コンデンサにおい
ては、タンタルTaやアルミニウムAl等のバルブ
金属上にホウ酸、ホウ酸アンモニウム、リン酸ア
ンモニウム等の電解質溶液から陽極酸化法により
金属酸化物被膜を形成させて、さらにこの上に硝
酸マンガンを浸漬（デイツピング）やスプレーに
よる吹付け等の手段により付着し、熱分解してβ
−MnO2層を形成している。 For this reason, β-MnO 2, which contains almost no water and is thermodynamically stable, is attracting attention. This β-
The commonly known method for producing MnO 2 is to thermally decompose manganese nitrate (Mn(NO 3 ) 2 6H 2 O). For example, in solid electrolytic capacitors, tantalum Ta, aluminum Al, etc. Methods such as forming a metal oxide film on metal by anodizing from an electrolyte solution such as boric acid, ammonium borate, or ammonium phosphate, and then dipping or spraying manganese nitrate on top of this. It adheres to the metal and thermally decomposes into β
- Forms two MnO layers.
しかしながら、上述のような硝酸マンガンの熱
分解によつて得られるβ−MnO2においても
Mn2O3の混入はさけられず、このβ−MnO2の品
質を低下してしまつている。 However, even in β-MnO 2 obtained by thermal decomposition of manganese nitrate as mentioned above,
The contamination of Mn 2 O 3 is unavoidable and degrades the quality of this β-MnO 2 .
さらに、上記硝酸マンガンは出発原料として大
量に入手することが難かしく価格も高いので、上
記電解二酸化マンガンや化学合成二酸化マンガン
を原料として用い、これら原料を350〜450℃で熱
処理しγ−MnO2をβ−MnO2に相転移させると
いう方法も知られているが、この方法においては
上記熱処理温度が高温であるために生成するβ−
MnO2がさらに分解し酸素を放出してMn2O3の如
き不純物を生成してしまうという虞れがある。例
えば電解二酸化マンガンを350〜450℃で熱処理し
た生成物について本発明者等が熱分析によりその
組成を解析したところ、残存水分が1.2〜1.8重量
％、不純物が少なくとも７〜18重量％存在するこ
とが判明した。 Furthermore, since the manganese nitrate is difficult to obtain in large quantities as a starting material and is expensive, the electrolytic manganese dioxide and chemically synthesized manganese dioxide are used as raw materials, and these raw materials are heat-treated at 350 to 450°C to form γ-MnO 2 A method is also known in which the phase transition of MnO2 to β-MnO 2 is carried out, but in this method, the β-
There is a risk that MnO 2 may further decompose and release oxygen, producing impurities such as Mn 2 O 3 . For example, when the present inventors analyzed the composition of a product obtained by heat-treating electrolytic manganese dioxide at 350 to 450°C by thermal analysis, it was found that residual moisture was 1.2 to 1.8% by weight and impurities were at least 7 to 18% by weight. There was found.
そこで本発明は、上述の従来の方法の有する欠
点を解消するために提案されたものであり、安価
で入手の容易な電解二酸化マンガンや化学合成二
酸化マンガンを原料として高純度なβ−MnO2を
得ることが可能なβ−MnO2の製法を提供するこ
とを目的とする。 Therefore, the present invention was proposed in order to eliminate the drawbacks of the above-mentioned conventional methods . The purpose of the present invention is to provide a method for producing β-MnO 2 that can be obtained.
本発明者等は、上記目的を達成せんものと鋭意
検討の結果、電解二酸化マンガンや化学合成二酸
化マンガンの如きγ−MnO2に硝酸を加えて加熱
することにより低温で速やかにβ−MnO2に相転
移することを見出し本発明を完成したものであつ
て、電解二酸化マンガンあるいは化学合成二酸化
マンガンに硝酸を加えて熱処理することを特徴と
するものである。 As a result of intensive study to achieve the above object, the present inventors quickly converted β-MnO 2 at low temperature by adding nitric acid to γ-MnO 2 such as electrolytic manganese dioxide or chemically synthesized manganese dioxide and heating it. The present invention was completed by discovering that a phase transition occurs, and is characterized by adding nitric acid to electrolytic manganese dioxide or chemically synthesized manganese dioxide and heat-treating it.
すなわち、本発明においては、電解二酸化マン
ガンあるいは化学合成二酸化マンガンを出発原料
として用意し、これら原料に硝酸を加えて熱処理
する。 That is, in the present invention, electrolytic manganese dioxide or chemically synthesized manganese dioxide is prepared as a starting material, nitric acid is added to these materials, and heat treatment is performed.
上記熱処理温度としては、170℃以上であれば
γ−MnO2からβ−MnO2への相転移が進行する
が、できるだけ低温で行なうことが好ましい。上
記熱処理温度を高くしすぎると生成するβ−
MnO2が分解し酸素を放出してMn2O3を生じてし
まう虞れがある。 As for the heat treatment temperature, if it is 170° C. or higher, the phase transition from γ-MnO 2 to β-MnO 2 will proceed, but it is preferable to carry out the heat treatment at a temperature as low as possible. β- produced when the above heat treatment temperature is too high
There is a risk that MnO 2 will decompose and release oxygen to produce Mn 2 O 3 .
また、上記熱処理時に加える硝酸の量は、上記
電解二酸化マンガンあるいは化学合成二酸化マン
ガン1.00gに対して13規定の硝酸0.4ml以上、すな
わち0.52グラム当量以上であることが好ましい。
さらに、上記熱処理は必要に応じて複数回繰り返
し行なつてもよい。 Further, the amount of nitric acid added during the heat treatment is preferably 0.4 ml or more of 13N nitric acid, ie, 0.52 gram equivalent or more, per 1.00 g of the electrolytic manganese dioxide or chemically synthesized manganese dioxide.
Furthermore, the above heat treatment may be repeated multiple times as necessary.
このように硝酸を加えて熱処理することによ
り、上記電解二酸化マンガンあるいは化学合成二
酸化マンガンは熱分解による不純物を生成するこ
となく速やかに相転移して純度が高く極めて粒径
の小さなβ−MnO2が得られる。 By adding nitric acid and heat-treating, the electrolytic manganese dioxide or chemically synthesized manganese dioxide undergoes a rapid phase transition without producing impurities due to thermal decomposition, resulting in β-MnO 2 with high purity and extremely small particle size. can get.
以下、本発明の具体的な実施例について説明す
る。なお、本発明がこの実施例に限定されるもの
でないことは言うまでもない。 Hereinafter, specific examples of the present invention will be described. It goes without saying that the present invention is not limited to this embodiment.
実施例
電解二酸化マンガン10gを磁製るつぼに取り、
濃硝酸４mlを加えて電気炉中で１時間当り12℃の
割合で260℃まで昇温して熱処理した。Example: Place 10g of electrolytic manganese dioxide in a porcelain crucible.
4 ml of concentrated nitric acid was added and the mixture was heated to 260°C at a rate of 12°C per hour in an electric furnace for heat treatment.
さらに、上記熱処理による生成物に対して濃硝
酸４mlを加え、再び電気炉中で１時間当り12℃の
割合で260℃まで昇温して再熱処理を行なつた。 Furthermore, 4 ml of concentrated nitric acid was added to the product resulting from the above heat treatment, and the temperature was again raised to 260°C at a rate of 12°C per hour in an electric furnace for reheating.
得られた生成物の走査型電子顕微鏡写真を第１
図に示す。第１図は拡大倍率10000倍での電子顕
微鏡写真であり、得られた生成物の粒径は0.1〜
0.3μm程度に観察される。そして、上記生成物の
粒子には結晶の成長面等が見られず、結晶粒子は
さらに小さいものと推定される。 The first scanning electron micrograph of the obtained product is
As shown in the figure. Figure 1 is an electron micrograph at a magnification of 10,000 times, and the particle size of the obtained product is 0.1~
Observed at around 0.3 μm. Further, no crystal growth surface or the like was observed in the particles of the above product, and the crystal particles are presumed to be even smaller.
また、得られた生成物の回折Ｘ線スペクトルを
第２図に示す。この回折Ｘ線スペクトルをハナワ
ルト法により解析したところ、ASTM（The
American Society for Testing Materials）カ
ード24−735と−致し、β―MnO2単相であるこ
とが確認された。 Moreover, the diffraction X-ray spectrum of the obtained product is shown in FIG. When this diffraction X-ray spectrum was analyzed using the Hanawalt method, ASTM (The
American Society for Testing Materials) card 24-735, and it was confirmed that it was β-MnO 2 single phase.
これに対し、電解二酸化マンガンを400℃で２
時間熱処理したものの回折Ｘ線スペクトルは第３
図に示す如きものであり、この第３図より上記電
解二酸化マンガンを単に熱処理したものにおいて
はβ−MnO2の回折線が観察されるが各回折線が
ブロードとなつており、結晶性が悪く不純物や水
分等を含んでいるものと考えられる。 In contrast, electrolytic manganese dioxide was heated to 2
The diffraction X-ray spectrum of the heat-treated product is
As shown in Fig. 3, the diffraction lines of β-MnO 2 are observed in the electrolytic manganese dioxide simply heat-treated, but each diffraction line is broad and the crystallinity is poor. It is thought that it contains impurities and moisture.
さらに、本実施例により得られた生成物を熱重
量分析した。結果を第４図に示す。第４図中、ａ
は本実施例による生成物の熱分解曲線、ｂは市販
の電解二酸化マンガン（γ−MnO2）の熱分解曲
線をそれぞれ示す。なお、この第４図において、
縦軸はMnO2の熱分解により得られるMn2O3の量
から逆算して求められるMnO2の理論量を100％
としたときの相対重量を示す。すなわち、本実施
例により得られた生成物（β−MnO2）は、市販
の電解二酸化マンガン（γ−MnO2）と比較する
と、高温で安定なものとなつていることが分か
る。 Furthermore, the product obtained in this example was subjected to thermogravimetric analysis. The results are shown in Figure 4. In Figure 4, a
b shows the thermal decomposition curve of the product according to this example, and b shows the thermal decomposition curve of commercially available electrolytic manganese dioxide (γ-MnO 2 ). In addition, in this Figure 4,
The vertical axis is 100% of the theoretical amount of MnO 2 calculated by back calculation from the amount of Mn 2 O 3 obtained by thermal decomposition of MnO 2
It shows the relative weight when . That is, it can be seen that the product (β-MnO 2 ) obtained in this example is stable at high temperatures when compared with commercially available electrolytic manganese dioxide (γ-MnO 2 ).
比較例
電解二酸化マンガン（γ―MnO2）を400℃で
20時間熱処理してβ―MnO2に相転移させたもの
と磁製るつぼ中に10g取り、濃硝酸４mlを加えて
電気炉中に入れ、１時間当り12℃の昇温速度で
280℃まで温度を上げて熱処理した。得られた生
成物をＸ線回折により分析したところ、先の第３
図に示す電解二酸化マンガンが単に熱処理したも
のと同様の回折Ｘ線スペクトルが観測された。し
たがつて、本発明においては、出発原料として電
解二酸化マンガンや化学合成二酸化マンガンの如
きγ−MnO2を用いる必要があるものと考えられ
る。Comparative example Electrolytic manganese dioxide (γ-MnO 2 ) at 400℃
10g of the material heat-treated for 20 hours to undergo a phase transition to β-MnO 2 was placed in a porcelain crucible, 4ml of concentrated nitric acid was added, and the mixture was placed in an electric furnace at a heating rate of 12°C per hour.
The temperature was raised to 280°C for heat treatment. When the obtained product was analyzed by X-ray diffraction, it was found that
A diffraction X-ray spectrum similar to that of the electrolytic manganese dioxide shown in the figure that was simply heat-treated was observed. Therefore, in the present invention, it is considered necessary to use γ-MnO 2 such as electrolytic manganese dioxide or chemically synthesized manganese dioxide as a starting material.
第１図は本発明を適用した実施例により得られ
るβ―MnO2の粒を写真で示す図であり、拡大倍
率10000倍の電子顕微鏡写真である。第２図はそ
の回折Ｘ線スペクトルを示す図である。第３図は
市販の電解二酸化マンガンを400℃、20時間熱処
理したものの回折Ｘ線スペクトルを示す図であ
る。第４図は本発明を適用した実施例により得ら
れるβ−MnO2の熱分解曲線を市販の電解二酸化
マンガンの熱分解曲線と比較して示すグラフであ
る。
FIG. 1 is a photograph showing β-MnO 2 grains obtained in an example to which the present invention is applied, and is an electron micrograph at a magnification of 10,000 times. FIG. 2 is a diagram showing the diffraction X-ray spectrum. FIG. 3 is a diagram showing the diffraction X-ray spectrum of commercially available electrolytic manganese dioxide heat-treated at 400° C. for 20 hours. FIG. 4 is a graph showing a comparison between the thermal decomposition curve of β-MnO 2 obtained in an example to which the present invention is applied and the thermal decomposition curve of commercially available electrolytic manganese dioxide.
Claims (1)
マンガンに硝酸を加えて熱処理することを特徴と
するβ−二酸化マンガンの製法。1. A method for producing β-manganese dioxide, which is characterized by adding nitric acid to electrolytic manganese dioxide or chemically synthesized manganese dioxide and heat-treating it.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58195038A JPS6086028A (en) | 1983-10-18 | 1983-10-18 | Production method of β-manganese dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58195038A JPS6086028A (en) | 1983-10-18 | 1983-10-18 | Production method of β-manganese dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6086028A JPS6086028A (en) | 1985-05-15 |
| JPH0525814B2 true JPH0525814B2 (en) | 1993-04-14 |
Family
ID=16334503
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58195038A Granted JPS6086028A (en) | 1983-10-18 | 1983-10-18 | Production method of β-manganese dioxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6086028A (en) |
-
1983
- 1983-10-18 JP JP58195038A patent/JPS6086028A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6086028A (en) | 1985-05-15 |
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