CN86105859A - Particulate manganese dioxide composites and preparation method thereof - Google Patents
Particulate manganese dioxide composites and preparation method thereof Download PDFInfo
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- CN86105859A CN86105859A CN198686105859A CN86105859A CN86105859A CN 86105859 A CN86105859 A CN 86105859A CN 198686105859 A CN198686105859 A CN 198686105859A CN 86105859 A CN86105859 A CN 86105859A CN 86105859 A CN86105859 A CN 86105859A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
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- 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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- Inorganic Compounds Of Heavy Metals (AREA)
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Abstract
The invention provides a kind of particulate manganese dioxide composites, this mixture is made up of the Manganse Dioxide of the chemical method production of Manganse Dioxide matrix synsedimentary on matrix that the particulate state electrolytic process is produced.The preparation method of mixture is suspended in the Manganse Dioxide that electrolytic process is produced in certain solution, wherein contain oxidable soluble manganese salt and soluble oxidant, described solution is through heating, generates the Manganse Dioxide of chemical method production and is formed in the original place on the surface of the Manganse Dioxide that electrolytic process produces.
Description
The present invention relates to a kind of Manganse Dioxide of improvement.More particularly, the present invention relates to a kind of manganese dioxide composites and preparation method thereof, this mixture is made up of the Manganse Dioxide that chemistry and two kinds of methods of electrolysis make.
As everyone knows, in electrochemical cell especially drying battery, adopt Manganse Dioxide to make depolariser.In this respect, the source of Manganse Dioxide can be a kind of active especially natural crystal, can be a kind of activated ore, can be a kind of natural crystal through the chemical treatment modification, also can be the Manganse Dioxide that makes with chemistry or electrolysis process.Wherein, the most important with the latter again, because the battery made from their, its use properties is far better more than the battery of making from natural manganese dioxide ore.
The known chemical process of preparation Manganse Dioxide is in oxidizing atmosphere such as air and oxygen, will precipitate manganous carbonate and form through roasting.Generally only contain 80～85% the qualified Manganse Dioxide of having an appointment in the product of roasting.Though this product can directly be used for the good battery of manufacturing effect, to deal with again usually, to improve Manganse Dioxide content wherein.These treatment processs comprise that the solution of chlorate that product is added a small amount of primary manganous carbonate raw material together with the sulphuric acid soln that contains small amounts of chlorine hydrochlorate Jia Re ， And together heats together.Example is seen United States Patent (USP) 4,402,931.
Adopt manganese salt such as the manganous sulfate chemical process with alkaline metal chlorate's direct reaction in the presence of free sulfuric acid, the preparation battery electrode manganese dioxide also is known.In general, the reaction effect of this method is very poor.But, advise that in addition adding has the manganese dioxide product of katalysis in right amount in reaction mixture, reaction effect just can be improved significantly, this catalytic Manganse Dioxide be from for example under oxidizing condition roasting precipitation manganous carbonate make.Example is seen United States Patent (USP) 2,956,860.
Also know and adopt the method for the electrolytic oxidation mn ion aqueous solution to prepare battery electrode manganese dioxide.The Manganse Dioxide that electrolytic process makes, generally the product than chemical method is good as depolariser in high-capacity battery.This mainly is reasons such as available oxygen content is higher because it is compared with the product of chemical method, and the amount of manganese oxide is less at a low price, and proportion is bigger, and crystalline structure is even more ideal.But, though electrolytic process prepares Manganse Dioxide as United States Patent (USP) 3,856, shown in 576, can improve its depolarize character; The present invention finds, the Manganse Dioxide that electrolytic process makes is handled with the sulphuric acid soln that contains mn ion again, and by the battery that the Manganse Dioxide of such generation is made, performance characteristics improves.
In order further to improve the battery activity of the Manganse Dioxide that makes with electrolytic process and chemical method, constantly made effort.
Nowadays, developed a kind of new manganese dioxide product, it is used for making the negative electrode of electrochemical cell (or battery), especially the negative electrode of drying battery, make the performance characteristics of those batteries, than singly being to improve to some extent with the Manganse Dioxide of chemical method or electrolytic process preparation or the battery that its physical mixture is done negative electrode production.Manganse Dioxide of the present invention is a kind of particulate composite, and its matrix is the Manganse Dioxide that is made by electrolytic process, and the outside covers the Manganse Dioxide that makes with chemical method.The invention still further relates to the method for making this new manganese dioxide mixture.
Disclose describedly roughly as above, this new manganese dioxide product of the present invention is a kind of particulate composite.It is made up of the matrix of the particulate manganese dioxide that electrolytic process makes, and what described matrix outside covered is the Manganse Dioxide that is made by chemical method.The present invention can be the product of making and reclaiming with any known Manganse Dioxide electrolysis method for production as this Manganse Dioxide of particulate composite matrix.Usually, this method is to be equipped with in the suitable electrolyzer of anode and negative electrode, and direct current is passed through a manganese sulfate solution.When electric current passed through electrolyzer, the manganous sulfate in the solution suffered oxidation, forms Manganse Dioxide ， And and form tectum or foreskin closely on anode.When electrolytic Manganse Dioxide tectum foreskin has reached requirement, just it is stripped down from anode.Subsequently, through for example solution-treated of alkaline carbonate, alkali metal hydroxide, alkali metal hydroxide or ammonium hydroxide, make its pulverizing and neutralization.After the drying again pulverize just can be used to make battery to suitable granularity.
Cover the Manganse Dioxide that the chemical method on the Manganse Dioxide matrix that above-mentioned electrolytic process makes makes, make And in system on the spot and cover on the matrix.In general, adopt in acidic aqueous solution, make the tectum of the Manganse Dioxide that this chemical method makes by oxidable, the same oxidant reaction of soluble manganese salt.Known oxidable, soluble manganese salt for this purposes for example have manganous sulfate and manganous carbonate.Under solution condition, the oxygenant that can be used to above-mentioned soluble manganese salt is changed into desired Manganse Dioxide also is well-known.The typical case of these oxygenants and nonrestrictive example have the hypochlorite of periodictable I A family metallic element, oxymuriate, perchlorate, and persulphate.Wherein being recommended most to be used to produce the tectal soluble oxidant of Manganse Dioxide that chemical legal system gets is clorox and sodium chlorate.
Usually, this particulate manganese dioxide composites of the present invention, the Manganse Dioxide that Manganse Dioxide that will be made by the electrolytic process below about 99% weight and the chemical method below about 30% weight make is formed.Here, two kinds of shared weight percentage of Manganse Dioxide are to calculate by the gross weight of the mixture of final formation.In certain better example of the present invention, the Manganse Dioxide that the Manganse Dioxide that mixture will be made by the electrolytic process of about 92～98% weight and the chemical method of about 2～8% weight make is formed.Being stated in following example, these particulate composite with singly being that negative electrode with chemical method or electrolytic process or their physical mixture are made is compared, have obtained unpredictable consequence as the negative electrode of battery the time.
The front was said, in this new mixture of preparation the present invention, while the Manganse Dioxide that chemical method makes is generating on the spot, covering simultaneously on the electrolytic process Manganse Dioxide matrix.According to the present invention, make the reaction mixture of forming by oxidable soluble manganese salt, soluble oxidant and acidic aqueous solution, subsequently, the Manganse Dioxide that electrolytic process is made is suspended in the inside.Make mixture Sheng Wen And and constantly stir, the Manganse Dioxide that keeps electrolytic process to make has the sufficient time to be in suspended state, so that needed oxidation products, promptly the Manganse Dioxide that makes of chemical method can be completed into basically.The Manganse Dioxide that this chemical method makes is in case form, and just deposits and cover to be suspended on the Manganse Dioxide that the electrolytic process in the reaction mixture makes.So the needed mixture that obtains like this is in addition dry to remove residual reactant ， And through washing.
Usually, carry out that the used temperature of this oxidizing reaction is the highest will to reach the boiling point of about mixture when normal atmosphere.But, preferably adopt about 70 ℃ of temperature, as adopt 90～98 ℃ temperature range then more suitable to the following scope of boiling point of mixture when the normal atmosphere.
Oxidable soluble manganese salt, soluble oxidant contains acidic aqueous solution, and is suspended in the electrolytic process Manganse Dioxide in the reaction mixture, and the consumption of these materials will change with the concrete composition of needed last mixture.In general, be longer than the composition that this passerby will make reaction mixture, have the mixture of the present invention that particular requirement is formed thereby be used for making, he can determine the consumption of each composition like a dream.
When preparation was used for making the reaction mixture of mixture of the present invention, soluble manganese salt and oxygenant can add reaction mixture in solution or the solid mode that is made in advance.But, for the purpose of easy to operate, the solution that preferably adopts these compositions to prepare in advance, like this since removed that these compositions needed originally in the original place dissolved time, thereby reduced total activity duration.
One works as reaction finishes, and then just the mixture that obtains is separated the water washing of ， And with the band alkaline ph value in mother liquor.The purpose that mixture is isolated in washing is to remove the mother liquor of any trace, unreacted manganese salt and oxygenant, and any other reaction by product, otherwise these by products may have a negative impact to the performance of the drying battery made thus.The last drying of mixture product just promptly can be used to make battery.
Following example only supplies illustrative purposes, scope that is not intended to limit the present invention and aim.
Example 1
The particulate manganese dioxide composites of forming by the Manganse Dioxide of the electrolytic process preparation of the Manganse Dioxide of the chemical method of 4% weight preparation and 96.0% weight of the present invention, its preparation method is as follows: one liter round-bottomed flask, nitrogen inlet and outlet are housed, and an inlet is used for adding reagent and sets up whipping appts in addition.The Manganse Dioxide that adds 100 gram particulate state electrolytic process preparations in the bottle, 50 milliliters of 1.2M(molconcentration) sulphuric acid soln.So the mixture heating up of Manganse Dioxide and acidic solution is constantly stirred to about 96 ℃ ， And, ceaselessly in bottle, feeds N
2Gas, tail gas is discharged by outlet, is in N to keep top of mixture
2Under the gas shiled; Simultaneously, after remaining reagent adds flask, N
2Gas can be used to remove by product chlorine and the dioxide peroxide in the bottle falling.
When top mixture arrives desired temperature, in reaction flask, add 17 milliliters of manganous sulfates and the 28 milliliters of sodium chlorate solutions that prepare in advance simultaneously immediately.Both concentration respectively is 3.1M and 3.7M.Add 24 ml waters more in addition, the cumulative volume that makes bottle interior liquid is 119 milliliters.These reagents added in one hour.
After reagent manganous sulfate, sodium chlorate all added, the reacting by heating mixture made temperature be maintained at about 96 ℃, continued to react 20 to 21 hours again.After this, the particulate composite product that obtains is separated the cold water washing of ， And with alkaline ph value in mother liquor.Product just can be used to make drying battery subsequently through super-dry.The data of the drying battery that makes from this particulate manganese dioxide composites are shown in following table.
Example 2
Example 1 uses above adopting same device, step and solution are made particulate manganese dioxide composites of the present invention, and the Manganse Dioxide that Manganse Dioxide that this thing is made by the chemical method of 8.0% weight and 92.0% electrolytic process make is formed.This examples preparation mixture with the difference of example 1 only in the solution usage difference that is used to prepare chemical method Manganse Dioxide.Like this, adopt 100 milliliters of sulphuric acid solns in this example, 36 milliliters of manganese sulfate solutions and 59 milliliters of sodium chlorate solutions as being narrated in the example 1.In addition, also add 52 ml waters, make that the cumulative volume of liquid reaches 247 milliliters in the flask.The data of the drying battery that makes from the mixture of this example are shown in following table.
Example 3
The same device that example 1 uses above adopting, step and solution are made particulate manganese dioxide composites of the present invention, and the Manganse Dioxide that Manganse Dioxide that this product is made by the chemical method of 8.0% weight and 92.0% electrolytic process make is formed.This examples preparation mixture with the difference of example 1 only in the solution usage difference that is used to prepare chemical method Manganse Dioxide.Like this, adopt 295 milliliters of sulphuric acid solns in this example, 36 milliliters of manganese sulfate solutions, 170 milliliters of sodium chlorate solutions as being narrated in the example 1.In addition, also add 141 ml waters, make that the cumulative volume of liquid reaches 709 milliliters in the flask.The data of the drying battery that makes from the mixture of this example are shown in following table.
Example 4
The Manganse Dioxide that the Manganse Dioxide that same device, step, the manufacturing particulate manganese dioxide composites of the present invention that example 1 uses above adopting, this mixture are made by the chemical method of 4.0% weight and the electrolytic process of 96.0% weight make is formed.But, electrolytic process Manganse Dioxide heats with the sulphuric acid soln Xiang Hun He And of 100 milliliters of 2.2M earlier.When mixture temperature arrived about 96 ℃, the 60 milliliters of 1.8M sulphuric acid solns and the 68 milliliters of 3.7M sodium chlorate solutions that prepare in advance that will be used for example 1 added reaction flask simultaneously.Total liquid volume is 224 milliliters in the bottle, and remaining preparation process is identical with example 1.The data of the drying battery that makes from the mixture of this example are shown in following table.
Except being made the drying battery by the mixture of example 1-4, also single Manganse Dioxide that makes with electrolytic process is made drying battery (comparison test A and B); The physical mixture of the Manganse Dioxide that And employing chemical method and electrolytic process make is made drying battery (comparison test C); Also single Manganse Dioxide that makes with chemical method is made drying battery (comparison test D).The data of these batteries equally also are shown in following table.
Table
Test number Manganse Dioxide, weight % cell container
Chemical method electrolytic process Milliampere Hour/gram (MAh/g)
1 4.0 96.0 221
2 8.0 92.0 224
3 20.0 80.0 228
4 8.0 92.0 241
Comparison test A(a) 0 100.0 210
Comparison test B(b) 0 100.0 231
Comparison test C(c) 8.0 92.0 212
Comparison test D(d) 100.0 0 232
(a) the used electrolytic process Manganse Dioxide of test examples 1-3 is to make on graphite cathode.
(b) the used electrolytic process Manganse Dioxide of test examples 4 is to make on the titanium negative electrode.
(c) the electrolytic process MnO that on graphite cathode, makes
2Together by MnSo
4With NaClO
3The chemical method MnO that reaction makes
2The physical mixture that constitutes.
(d) be used for making the chemical method MnO of the physical mixture of comparison test C
2
As can be seen from the above table, with the battery that particulate manganese dioxide composites of the present invention is made, its capacity will be higher than the battery that single Manganse Dioxide that makes with chemical method or electrolytic process or their physical mixture are made.This essence of it seems is that the capacity that is caused by synergy increases, the especially physical mixture of the Manganse Dioxide that makes from chemical method and electrolytic process or the capability value of blend, be exceed fully unexpected.
Though according to the example of thinking at present to be recommended, the invention has been described, certainly the inventive method made changes and improvements, only otherwise violate aim of the present invention and scope above-mentioned and following claim defined.
Claims (20)
1, a kind of particulate state tantalum dioxide mixture, it comprises the Manganse Dioxide matrix that a kind of particulate state electrolytic process is produced; And a kind of Manganse Dioxide tectum that is added in the chemical method production on the described matrix, the latter is that the acidic aqueous solution that will contain oxidable soluble manganese salt and soluble oxidant heats and forms, and is suspended with the Manganse Dioxide that electrolytic process is produced in the described solution.
2, according to the mixture of claim 1, it is about 99% to it is characterized in that described matrix shared weight percentage in described mixture gross weight reaches as high as, and tectum shared weight percentage in described mixture gross weight reaches as high as about 30%.
3, according to the mixture of claim 1, it is characterized in that being used for forming the employed oxidable soluble manganese salt of Manganse Dioxide tectum that chemical method is produced, be selected from by manganous sulfate and manganous carbonate one class and form.
4, according to the mixture of claim 1, it is characterized in that being used for forming the employed soluble oxidant of Manganse Dioxide tectum that chemical method is produced, be selected from by alkali-metal oxymuriate and hypochlorite one class and form.
5,, it is characterized in that the highest described acidic aqueous solution boiling point under atmospheric pressure that reaches approximately of Heating temperature scope of acidic aqueous solution according to the mixture of claim 1.
6,, it is characterized in that oxidable manganese salt is selected from by manganous sulfate and manganous carbonate one class to form, and oxygenant is selected from by alkali-metal oxymuriate and hypochlorite one class and forms according to the mixture of claim 2.
7, according to the mixture of claim 1, the tectal oxidable soluble manganese salt of Manganse Dioxide that it is characterized in that being used for forming chemical method production is manganous sulfate.
8, according to the mixture of claim 1, it is characterized in that being used for forming the tectal soluble oxidant of Manganse Dioxide that chemical method is produced, be a kind of alkaline metal chlorate.
9, according to the mixture of claim 6, the Heating temperature scope that it is characterized in that acidic aqueous solution from about 70 ℃ up to described approximately acidic aqueous solution boiling point under atmospheric pressure.
10, according to the mixture of claim 6, it is characterized in that described matrix shared weight percentage in described mixture gross weight is about 92～98%, tectum shared weight percentage in described mixture gross weight is about 2～8%.
11, according to the mixture of claim 6, can in battery, form negative electrode as depolariser ， And.
12, a kind of method for preparing particulate manganese dioxide composites, the Manganse Dioxide matrix that this mixture is produced by the particulate state electrolytic process with the Manganse Dioxide its preparation method that tectum is formed that is attached to the chemical method production on the described matrix is:
(a) prepare a kind of acidic aqueous solution, it is made up of mineral acid, soluble manganese salt and oxygenant, in addition, also is suspended with the Manganse Dioxide that the particulate state electrolytic process is produced in the described solution;
(b) heat described solution at a certain temperature, this temperature will be enough to make described manganese salt generation oxidation, generates chemical method Manganse Dioxide ， And and is deposited on the Manganse Dioxide surface of described particles suspended shape electrolytic process production, so that above-mentioned settling to be provided;
(c) Fen Li And reclaims described mixture in the described solution.
13,, it is characterized in that described oxidable soluble manganese salt is selected from by manganous sulfate and manganous carbonate one class to form according to the method for claim 12.
14,, it is characterized in that described oxidable soluble manganese salt is manganous sulfate according to the method for claim 13.
15, according to the method for claim 12, it is characterized in that described oxygenant is a kind of oxygenant of solubility, it is selected from by alkaline metal chlorate and hypochlorite one class forms.
16,, it is characterized in that described soluble oxidant is a kind of alkaline metal chlorate according to the method for claim 15.
17,, it is characterized in that the alkaline metal chlorate is a sodium chlorate according to the method for claim 16.
18,, it is characterized in that the highest described solution boiling point under atmospheric pressure that reaches approximately of Heating temperature scope of described acidic aqueous solution according to the method for claim 12.
19, according to the method for claim 18, the Heating temperature scope that it is characterized in that described acidic aqueous solution be from about 70 ℃ to described solution boiling point under atmospheric pressure.
20, according to the method for claim 12, the mixture of also stipulating to separate in the solution and reclaiming will be through handling, to remove acidic aqueous solution residual in the settling.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US75918785A | 1985-07-26 | 1985-07-26 | |
| US759187 | 1985-07-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN86105859A true CN86105859A (en) | 1987-02-25 |
Family
ID=25054713
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN198686105859A Pending CN86105859A (en) | 1985-07-26 | 1986-07-18 | Particulate manganese dioxide composites and preparation method thereof |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS6227332A (en) |
| KR (1) | KR870001117A (en) |
| CN (1) | CN86105859A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03148525A (en) * | 1989-11-06 | 1991-06-25 | Ig Tech Res Inc | Heating structure for mud room |
| JPH0478409U (en) * | 1990-11-20 | 1992-07-08 | ||
| CN102560526B (en) * | 2011-12-23 | 2015-03-25 | 苏州大学 | Preparation method of high-power electrolytic manganese dioxide |
-
1986
- 1986-07-18 CN CN198686105859A patent/CN86105859A/en active Pending
- 1986-07-25 JP JP61175438A patent/JPS6227332A/en active Pending
- 1986-07-26 KR KR1019860006143A patent/KR870001117A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| KR870001117A (en) | 1987-03-11 |
| JPS6227332A (en) | 1987-02-05 |
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