CN101348920A - Electrolytic manganese dioxide and production method thereof - Google Patents
Electrolytic manganese dioxide and production method thereof Download PDFInfo
- Publication number
- CN101348920A CN101348920A CNA2008101432384A CN200810143238A CN101348920A CN 101348920 A CN101348920 A CN 101348920A CN A2008101432384 A CNA2008101432384 A CN A2008101432384A CN 200810143238 A CN200810143238 A CN 200810143238A CN 101348920 A CN101348920 A CN 101348920A
- Authority
- CN
- China
- Prior art keywords
- electrolytic manganese
- manganese dioxide
- content
- production method
- paraffin
- 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
Classifications
-
- 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
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to electrolytic manganese dioxide and a method for manufacturing the same. The content of an anionic surface active agent in the electrolytic manganese dioxide is less than 1ppm, and the content of plus strand saturated hydrocarbon is less than 10ppm. The method comprises the step that a heat-resisting acid-proof resin isolating film is used as a material used for heat dissipation protection for the liquid surface and evaporation prevention of an electrolytic bath. Because the content of the anionic surface active agent and the plus strand saturated hydrocarbon is extremely low, the electrolytic manganese dioxide can effectively improve the storage discharge performance of a dry battery when used to manufacture dry batteries. Moreover, the method not only can manufacture the electrolytic manganese dioxide in which the content of the anionic surface active agent and the plus strand saturated hydrocarbon is extremely low, but also can simplify large-sized equipment used for cleaning during post treatment; in addition, the method ensures higher yield, thereby having lower production cost.
Description
Technical field
The present invention relates to a kind of electrolytic manganese dioxide and production method thereof, especially relate to electrolytic manganese dioxide and the production method thereof of a kind of anionic surfactant concentration below 1ppm.
Background technology
After drying battery is produced, be not all can come into operation at once.In most of the cases, all be just can use after storing for some time as required, so the storge quality of drying battery is one of its very important characteristic.
The factor that influences the drying battery storge quality comprises the quality of its constitute electrolytic manganese dioxide, zinc, carbon cathode, electrolytic solution and the production method of battery etc.Wherein, the quality that is called as the electrolytic manganese dioxide of most important constitute in the drying battery is one of most important factor.
And electrolytic manganese dioxide generally includes aspects such as its crystalline structure, micro heavy content and acidity thereof to the influence factor of drying battery storge quality, these aspects, and passing had many researchs and a countermeasure.
But in existing electrolytic manganese dioxide production process, also have micro-content organism and sneak into wherein.These micro-content organisms mainly by electrolyzer insulation under high temperature (g5～98 ℃) condition, reduce and prevent that employed paraffin of solution evaporation or whipping agent from sneaking into.
Total liquid measure of electrolyzer should be kept constant substantially usually.If the electrolytic solution evaporation excessively, in order to keep total liquid measure, just need to add a lot of water to electrolyzer, this can cause thermosteresis excessive; If not evaporation fully, general total liquid measure can constantly increase, and is constant in order to keep total liquid measure, just must discharge solution outside system, and this also can cause damage.
Therefore,, all to utilize the effect of the by product hydrogen of electrolytic process, keep the foam layer of 10～30mm thickness at the electrolyzer liquid level no matter be to use paraffin or whipping agent.
The electrolyzer heat calculation result of electrolyzer (6500A, 5 groove/groups) when using paraffin and whipping agent respectively to identical geometrical dimension is as shown in table 1.The relative steam output of feed liquor amount, paraffin and whipping agent are respectively 7.5wt% and 25wt%, and promptly the steam output of whipping agent is about three times of paraffin, and therefore, the loss of the vaporization heat of whipping agent greatly also is one of its feature.
Paraffin (Parafin Wax) is the natural wax of petroleum series, is made of hydrocarbon polymer.In hydrocarbon polymer, paraffin series hydrocarbon polymer is the normal chain saturated hydrocarbon, useful molecules formula C
nH
2n+2Expression.Common n=20～37 wherein, fusing point is 37～77 ℃, floats on the surface of solution in electrolyzer after the fusion.But well-known, decomposing oxidation can take place in paraffin after heating, and metal, oxygenant and light have significant promoter action to this kinds of oxidation reaction.
Table 1. uses paraffin and whipping agent electrolyzer heat calculation
By analyzing the used paraffin of electrolyzer, discovery is along with oxidizing reaction is carried out, and oil content wherein is near 10%, and the oil content in the new paraffin has increased by 5～30 times, total oxidation valency has also reached 10～15mgKOH/g, and new paraffin has increased more than 100 times.In the actual production operation, be to add new paraffin termly to be replaced.
The oxidation mechanism of paraffin generally is at first to generate superoxide, through ethanol, carbonyl compound (aldehyde, ketone), finally generates lipid acid, oxygen acid, polycondensation compound etc. then.
In electrolyzer, also, can infer that paraffin exists same reaction in electrolyzer because have sulfuric acid reaction heat, titanium, electrolysis to adhere to the reaction promoter action of EMD (Electricity separates Manganse Dioxide).The EMD that can cause electrolysis to be adhered to is reduced like this, makes the performance degradation of EMD.
Under the situation of using paraffin, in normal electrolytic process, have only the EMD that adheres on groove face top to contact with paraffin, when still going out groove, adhering to EMD all can the comprehensive engagement by paraffin layer.
Therefore, the laundry operation of subsequent handling must be careful, and need large-scale washing plant.
In addition, whipping agent is the foaming effect that has utilized tensio-active agent.Whipping agent is to utilize anion surfactant as hydrophilic group mostly, has monoalkyl acid structure, generally uses monoalkyl sulfonate (as ROSO
3 -Na
+).
This kind promoting agent is also the same with paraffin, belongs to the normal chain saturated hydrocarbon, and still, carbonatoms is few than paraffin, is generally C=8～18.The same with paraffin also have a reductive action.Because this reductive action, the electrolytic manganese dioxide with oxidisability can be reduced, and causes quality to worsen.
Whipping agent is different with paraffin because have water-soluble, can dissolving in electrolyzer, can be adsorbed on the inside of electrolysis dirt settling at any time.Therefore, also the same with use paraffin, the equipment that subsequent handling need be able to effectively be handled.Because its adhesion mechanism difference, the removal fully of whipping agent will be difficult to paraffin.
In addition, this whipping agent has been sneaked into chlorion in process of production, has confirmed that its content is about 0.5%～number %.Chlorine is self-evident to the deterioration of the storge quality of battery.
By gas chromatographic analysis, paraffin residual hydrochloric acid Daricon saturated hydrocarbon content in the electrolytic manganese dioxide product is 50～200ppm.
To using the electrolytic manganese dioxide product of whipping agent, analyze according to the GB7494-87 prescriptive procedure, found that its residual anionic surfactant concentration is 10～50ppm.In addition, the anionic surfactant concentration in the electrolytic solution of discovery electrolyzer is 100～300ppm.
As the method for removing residual organic matter in the electrolytic manganese dioxide, what generally at first consider is the removal efficient that improves postprocessing working procedures, promptly selects optimum parameters such as washing times, wash temperature, washing time, washing plant by trial and error method.
But there is adsorption in essence in EMD, remove quite difficulty fully, even improve washing intensity by every possible means, and the residual quantity of anion surfactant and paraffin still have an appointment respectively 5ppm and 25ppm.
Find that the concentration of chlorine is 5～10ppm in the electrolytic solution of electrolyzer when analyzing the chlorine in the whipping agent according to the GB13580.9-92 prescriptive procedure, the cl content among the EMD is 10～30ppm.As everyone knows, chlorine is the same with Pb, Cu, is very deleterious element to battery, generally all wishes to be controlled at the level that can not detect.
Sneak into the organism in the electrolytic manganese dioxide, precedingly address, generally have reductibility, can react, thereby may cause the current potential of electrolytic manganese dioxide to reduce or storge quality worsens with the electrolytic manganese dioxide surface.Up to now, in existing document, the present inventor does not see the correlative study report as yet, and the relevant method report of avoiding micro-content organism to sneak into wherein or remove.
Summary of the invention
The object of the present invention is to provide a kind of anionic surfactant concentration is following electrolytic manganese dioxide and production method thereof of 1ppm.
It is following electrolytic manganese dioxide and production method thereof of 10ppm that further aim of the present invention is to provide a kind of normal chain saturated hydrocarbon content.
The objective of the invention is to be achieved through the following technical solutions:
Studies show that for improving, improve the storge quality of drying battery as far as possible, the anionic surfactant concentration in the constitute electrolytic manganese dioxide of drying battery should be below 1ppm.
Preferred version is that the normal chain saturated hydrocarbon content in the described electrolytic manganese dioxide also should be below 10ppm.
The present invention's production method is; in electrolytic process; use heat-resisting acid-proof resin film to replace existing whipping agent anion surfactant or/and the material that paraffin is used as electrolyzer liquid level heat radiation protection vaporization prevention; like this; owing to avoided using the paraffin and the whipping agent anion surfactant of sneaking into easily in the electrolytic manganese dioxide to make the material that electrolyzer liquid level heat radiation protection vaporization prevention is used; the content of the anion surfactant in the electrolytic manganese dioxide product just can be reduced to about 0.5ppm, and the content of hydrochloric acid Daricon saturated hydrocarbon can be reduced to about 7ppm.But, carry out repeatedly along with electrolytic, also may be because of there being the pollution of equipment aspect, this parameter can not reduce to zero fully.
Use above-mentioned sample that current potential reduction situation is detected: anionic surfactant concentration is 0.5ppm, and hydrochloric acid Daricon saturated hydrocarbon content is that the electrolytic manganese dioxide of 7ppm is containing the anion surfactant (C of 300ppm
13H
25SO
4Na) neutralize in the aqueous solution, soak the 1Hr after-filtration at normal temperatures, the current potential of washing back working sample.
Found that, be 267mV～259mV, reduced 8mV with respect to the alkaline current potential of the Hg/HgO electrode that uses 40%KOH solution.With respect to using 20%NH
4The Hg of CI solution
2CI
2The current potential of electrode (CHCP) is 704mV～687mV, has reduced 17mV.Can infer also that thus anion surfactant is to the detrimentally affect of alkaline dry battery, carbon zinc drying battery discharge performance.
In electrolytic process, do not use under the situation of paraffin and whipping agent without exception, the steam output of feed liquor amount is 35% relatively, the heat of needed heat exchanger is as shown in table 1, and the steam output of its solution is for using about 1.3 times under the whipping agent situation, for using about 2.1 times under the paraffin situation.
Calculated example: with under the situation of using paraffin relatively-
(doubly)
Calculating under the situation of use whipping agent too.
For reducing the steam output of electrolyzer, the present invention uses needn't worry that the heat-resisting acid-proof resin film that organic impurities is sneaked into prevents the electrolytic solution materials evaporated as electrolyzer liquid level heat radiation protection.
Because the proportion of electrolytic solution is 1.1～1.2g/ml; service temperature is 85～98 ℃; so; described heat-resisting acid-proof resin film can be selected polypropylene (PP for use; proportion 0.90～0.91; heat-resisting 120 ℃) film or polyethylene (PE, proportion 0.92～0.96, heat-resisting 100 ℃) film be as electrolysis liquid surface heat radiation protection vaporization prevention barrier film.
The shape of described barrier film, rectangle, square, circle or spherically all can.Recently, a kind of material of inner hollow is arranged on the market, also can use.If the coverage of tank liquor face is 80%, steam output can be controlled at about 120% under the whipping agent situation of using.
According to the heat calculation of table 1, can also increase the joule heating of electrolyzer, reduce the heat exchange amount of heat exchanger.
Generally, the current density of titanium plate electrode generally is controlled at 0.4～0.8A/dm
2
Preferred version of the present invention is: current density is brought up to 0.9～1.8A/dm
2, the groove under this current density is pressed and can be improved about 1.5 times, and therefore, relative joule heating can increase, and can reduce the heat exchange amount of heat exchanger.
Use the formula identical to calculate with aforementioned calculating formula, use the steam output under the paraffin situation to become 1.9 times relatively by about 2.1 times, steam output under the whipping agent situation becomes 1.2 times by 1.3 times relatively, simultaneously, can also expect that the heat-shift of heat exchanger reduces about 1 one-tenth.
The subsidiary effect of this raising current density improves the benefit of unit output in addition.
For improving current density, both can use existing titanium plate electrode, also can utilize the carbon plate electrode of titanium plate electrode, different shapes and the material of different shapes and material, or use known suspension electrolysis method (referring to: 1. Japan's special Xu bulletin on January 27th, 1992 flat 4-4252; 2. the special Xu of Japan announces flat 5-49757 on July 27th, 1993; 3. Japan's special Xu bulletin on August 24th, 1994 flat 6-65754), and the concentration by control sulfuric acid concentration, manganese and electrolyte temperature or the like are realized.
The present invention's electrolytic manganese dioxide because anionic surfactant concentration and normal chain saturated hydrocarbon content are extremely low, is used to produce drying battery, can effectively improve the storage discharge performance of drying battery.Use the present invention's production method, not only can produce anionic surfactant concentration and the extremely low electrolytic manganese dioxide of normal chain saturated hydrocarbon content, simultaneously, can also simplify the main equipment of aftertreatment washing usefulness, output is also higher, thereby production cost is also lower.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but these embodiment must not be interpreted as limiting the scope of the invention.
Embodiment 1
The single electrolyzer of anode titanium plate and negative carbon is being housed (among 5.2m * 1.8m * 1.9m), covering inner aperture on the electrolyzer liquid level is that 10mm, thickness are the hollow acrylic resin of 20～30mm, the steam output of feed liquor is 28% relatively, uses the steam output of whipping agent (steam output 25%) to increase about 12%; Current density is controlled at 0.8A/dm
2, decompose the production electrolytic manganese dioxide by the current electroanalysis of 9000A; Electrolysis process control condition: the sulfuric acid concentration in the electrolyzer is that 0.45mol/L, manganese concentration are that 0.7mol/L, electrolytic cell solution temperature are controlled at 95 ± 0.5 ℃; The production scene existing installation is used in aftertreatment.
The Fe content 35ppm of present embodiment product is below other heavy metal content 2ppm; The crystalline structure of product is the γ type, BET30m
2The mean particle size 25 μ m that/g, carbon-zine cell use, the mean particle size that alkaline Mn cell is used is 40 μ m.Neutral pH control: carbon-zine cell pH (JIS)=4.5, alkaline Mn cell pH (JIS)=3.5.
The anionic surfactant concentration of present embodiment product is 0.5ppm, and strand saturated hydrocarbon content is 7ppm, and CI content is not for detecting.
Embodiment 2
The product electrolytic manganese dioxide that utilizes embodiment 1 to produce is made alkaline dry battery.EMD wherein: carbon powder=20: 1, adding concentration is the KOH 5wt% of 40wt%, mix back compressed moulding, fragmentation, granulation, make anode ring (about 3.50g * 3), barrier film is inserted in the assembling back, insert Zn gel 5.05g/ again after injecting electrolytic solution, involution is made the LR-6 drying battery behind the insertion carbon-point.
Table 2 is depicted as the initial stage discharge characteristic of present embodiment product alkaline Mn cell, and table 3 is depicted as the discharge characteristic that stores under 60 ℃ of temperature of present embodiment product alkaline Mn cell after 20 days.Generally speaking, storge quality is improved, and particularly with under the situation of using whipping agent contrasts, and the continuous discharge of 2 Ω and 10 Ω all has a more substantial increase, and has improved 6% and 11% respectively, and the initial stage discharge has also improved 4～7%.
Table 2 embodiment 2 product alkaline Mn cell initial stage discharge characteristics
(LR-6) each discharge time n=3, other discharge times n=10 initial stage discharge characteristic
| The characteristic project | Product of the present invention | Use the product of paraffin | Use the product of whipping agent |
| OCV SCC RAC 2 Ω connect to be put EPV 0.9V 10 Ω and connects and put EPV 0.9V 75 Ω and connect and put EPV0.9V 3.9 Ω and connect and put EPV 0.9V 10 Ω and connect and put-10 ℃ of EPV0.9V | 1.616V 15.4A 0.104Ω 2.15Hr 18.5Hr 152.0Hr 6.50Hr 4.62Hr | 1.615V 15.4A 0.105Ω 2.12Hr 17.8Hr 147.5Hr 6.29Hr 4.02H | 1.623V 15.3A 0.107Ω 2.01Hr 17.8Hr 150.1Hr 6.23Hr 3.72H |
Discharge characteristic after storing 20 days under 60 ℃ of temperature of table 3 embodiment 2 product alkaline Mn cells
| The characteristic project | Product of the present invention | Use the product of paraffin | Use the product of whipping agent |
| OCV SCC RAC 2 Ω connect to be put EPV 0.9V 10 Ω and connects and put EPV 0.9V 75 Ω and connect and put EPV 0.9V 3.9 Ω and connect and put 30 minutes/day EPV 0.9V 10 Ω and connect and put-10 ℃ of EPV 0.9V | 1.607V 12.1A 0.120Ω 1.93Hr(90％) 17.7Hr(96％) 149Hr(98％) 152Hr (100％) 3.88Hr (84％) | 1.606V 12.0A 0.128Ω 1.78Hr(84％) 16.5Hr(93％) 144.5Hr(98％) 6.23Hr(99％) 3.18Hr(79％) | 1.604V 11.3A 0.130Ω 1.69Hr(84％) 15.1Hr(85％) 139.7Hr(93％) 6.24Hr(100) 2.84Hr(76％) |
Embodiment 3
The product electrolytic manganese dioxide that utilizes embodiment 1 to produce is made into carbon zinc drying battery.Formula rate (weight percent) is: EMD49%, carbon dust 8%, electrolytic solution 42.5% (25%ZnCI
2-2%NH
4CI), ZnO0.5% (adding up to 100%), be large size R20-P battery.In addition, formulation weight is a 60.0 ± 0.05g/ battery.Exert pressure during filling to guarantee that space, cadmia upper edge is 6～7mm.
Be respectively the initial stage discharge characteristic of present embodiment product carbon-zine cell and the discharge characteristic after the storage shown in table 4 and the table 5.The same with alkaline Mn cell, whole storage characteristics is improved, and particularly with under the situation of using whipping agent contrasts, and 2 Ω continuous discharges have all improved 8%, 2 Ω indirect discharge in 30 minutes * 2/ day and also improved 3～4%.
The 3 product carbon-zine cell initial stages of table 4 embodiment discharge and store the back discharge characteristic
(R-20P) each discharge time n=3, other discharge times n=10 initial stage discharge characteristic
| The characteristic project | Product of the present invention | Use the product of paraffin | Use the product of whipping agent |
| OCV SCC Rac 2 Ω are even put EPV 0.9V 4 Ω and are even put 30 minutes * 2/ day EPV0.9V 10 Ω 4Hr/ day EPV 0.9V of EPV 0.85V 2 Ω, 20 Ω 4Hr/ day EPV0.9V | 1.665V 9.6A 0.157Ω 430min 1200min 670min 56Hr 135Hr | 1.664V 9.6A 0.160Ω 422min 1170min 666min 55.0Hr 132Hr | 1.662V 9.6A 0.158Ω 416min 1174min 659min 53.7Hr 126Hr |
Discharge characteristic after storing 20 days under 60 ℃ of temperature of table 5 embodiment 3 product carbon-zine celies
| The characteristic project | Product of the present invention | Use the product of paraffin | Use the product of whipping agent |
| OCV SCC Rac 2 Ω are even put EPV0.9V 4 Ω and are even put 30 minutes * 2/ day EPV 0.9V 10 Ω 4Hr/ day EPV 0.9V of EPV 0.85V 2 Ω, 20 Ω 4Hr/ day EPV 0.9V | 1.609V 7.2A 0.235Ω 409min(95％) 1176min(98％) 603min(90％) 55.4Hr(99％) 132Hr(98％) | 1.602V 6.8A 0.245Ω 386min(95％) 1112min(96％) 525min(79％) 54.6Hr(99％) 122Hr(92％) | 1.605V 7.1A 0.234Ω 369min(87％) 1131min(97％) 555min(84％) 53.1Hr(99％) 121Hr(96％) |
Embodiment 4
Current density is 1.6A/dm
2, improved 0.8A/dm than embodiment 1
2Adopt the suspension electrolysis method, in the Particle Manganese Dioxide (add-on is 0.03g/L) that adds in the electrolytic solution below the 1.5 μ m; Electrolytic groove is pressed and is 3.31V, has improved 0.81V than embodiment 1, and the steam output of feed liquor has brought up to 28% by 25% of use whipping agent relatively.Other condition is with embodiment 1.
The joule heating increasing amount is:
The vaporization heat increasing amount is:
350L/Hr×(28％÷25％)×600kcal/kg＝6300kcal/Hr
The two basically identical is substantially equal to the exchanging heat of heat exchanger.In addition, increase production 1 times, its effect is more remarkable.
The Fe content 40ppm of present embodiment product is below other heavy metal content 5ppm; The crystalline structure of product is the γ type, BET 28m
2The mean particle size 25 μ m that/g, carbon-zine cell use, the mean particle size that alkaline Mn cell is used is 40 μ m.
The anionic surfactant concentration of present embodiment product is 0.2ppm, and strand saturated hydrocarbon content is 3ppm, and CI content is not for detecting.
Claims (8)
1, a kind of electrolytic manganese dioxide is characterized in that, anionic surfactant concentration is below 1ppm.
2, electrolytic manganese dioxide according to claim 1 is characterized in that, normal chain saturated hydrocarbon content is below 10ppm.
3, the production method of electrolytic manganese dioxide according to claim 1 and 2 is characterized in that, the material that uses heat-resisting acid-proof resin barrier film to use as electrolyzer liquid level heat radiation protection vaporization prevention.
4, the production method of electrolytic manganese dioxide according to claim 3 is characterized in that, described heat-resisting acid-proof resin barrier film is polypropylene screen or polyethylene film.
According to the production method of claim 3 or 4 described electrolytic manganese dioxides, it is characterized in that 5, the coverage of described electrolyzer liquid level is 80%.
6, according to the production method of claim 3 or 4 described electrolytic manganese dioxides, it is characterized in that, described heat-resisting acid-proof resin barrier film be shaped as rectangle, square, circle or spherical.
According to the production method of claim 3 or 4 described electrolytic manganese dioxides, it is characterized in that 7, the used current density of electrolysis is 0.9～1.8A/dm
2
8, the production method of electrolytic manganese dioxide according to claim 5 is characterized in that, the used current density of electrolysis is 0.9～1.8A/dm
2
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101432384A CN101348920A (en) | 2008-09-18 | 2008-09-18 | Electrolytic manganese dioxide and production method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101432384A CN101348920A (en) | 2008-09-18 | 2008-09-18 | Electrolytic manganese dioxide and production method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101348920A true CN101348920A (en) | 2009-01-21 |
Family
ID=40267885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008101432384A Pending CN101348920A (en) | 2008-09-18 | 2008-09-18 | Electrolytic manganese dioxide and production method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101348920A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102031532A (en) * | 2010-12-03 | 2011-04-27 | 北京科技大学 | Energy-saving electrolytic manganese dioxide preparation method |
| CN101545112B (en) * | 2009-05-04 | 2014-04-23 | 湖南阳光电化有限公司 | An electrolytic method of electrolytic manganese dioxide |
| CN106044862A (en) * | 2016-06-02 | 2016-10-26 | 湘潭大学 | Method for preparing nano-manganese oxide through low-temperature electrolysis |
| CN109112569A (en) * | 2018-09-19 | 2019-01-01 | 兰州交通大学 | A kind of ion-exchange film method prepares the production method of manganese metal and manganese dioxide simultaneously |
-
2008
- 2008-09-18 CN CNA2008101432384A patent/CN101348920A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101545112B (en) * | 2009-05-04 | 2014-04-23 | 湖南阳光电化有限公司 | An electrolytic method of electrolytic manganese dioxide |
| CN102031532A (en) * | 2010-12-03 | 2011-04-27 | 北京科技大学 | Energy-saving electrolytic manganese dioxide preparation method |
| CN106044862A (en) * | 2016-06-02 | 2016-10-26 | 湘潭大学 | Method for preparing nano-manganese oxide through low-temperature electrolysis |
| CN109112569A (en) * | 2018-09-19 | 2019-01-01 | 兰州交通大学 | A kind of ion-exchange film method prepares the production method of manganese metal and manganese dioxide simultaneously |
| CN109112569B (en) * | 2018-09-19 | 2023-07-25 | 兰州交通大学 | Production method for simultaneously preparing manganese metal and manganese dioxide by ion exchange membrane electrolysis method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ma et al. | Homogeneous metal nitrate hydroxide nanoarrays grown on nickel foam for efficient electrocatalytic oxygen evolution | |
| EP3222754B1 (en) | Apparatus for producing organic hydride and method for producing organic hydride using same | |
| Zhang et al. | Selenate promoted stability improvement of nickel selenide nanosheet array with an amorphous NiOOH layer for seawater oxidation | |
| Yu et al. | Advancing direct seawater electrocatalysis for green and affordable hydrogen | |
| US20190055657A1 (en) | Oxygen evolution electrocatalysts with carbon coated cobalt (ii, iii) oxide layers | |
| RU2413795C2 (en) | Installation for electrolysis of water | |
| US20160141694A1 (en) | Cathodes capable of operating in an electrochemical reaction, and related cells, devices, and methods | |
| CN101348920A (en) | Electrolytic manganese dioxide and production method thereof | |
| EP2876717B1 (en) | Redox flow battery including an electrolyte and the use of an electroylte in a redox flow battery | |
| FR3079530A1 (en) | ELECTROCHEMICAL PROCESS FOR THE PRODUCTION OF HYDROGEN GAS UNDER PRESSURE BY ELECTROLYSIS THEN BY ELECTROCHEMICAL CONVERSION | |
| Lima et al. | Energy loss in electrochemical diaphragm process of chlorine and alkali industry–A collateral effect of the undesirable generation of chlorate | |
| Saji | Corrosion and materials degradation in electrochemical energy storage and conversion devices | |
| WO2022067377A1 (en) | Catalyst and electrolyser for the synthesis of hydrogen peroxide | |
| Chu et al. | Super‐fast Charging Biohybrid Batteries through a Power‐to‐formate‐to‐bioelectricity Process by Combining Microbial Electrochemistry and CO2 Electrolysis | |
| Lhostis et al. | Promoting Selective CO2 Electroreduction to Formic Acid in Acidic Medium with Low Potassium Concentrations under High CO2 Pressure | |
| FR3079529A1 (en) | ELECTROCHEMICAL PROCESS FOR THE PRODUCTION OF GASEOUS HYDROGEN UNDER PRESSURE BY ELECTROLYSIS AND BY DEPOLARIZATION | |
| CN111378979B (en) | Arsenic nano-particles, preparation method thereof, system and method for preparing arsine through electrolysis | |
| KR20160019743A (en) | A process of reducing carbon dioxide by using a cathode comprising metal oxide | |
| FR3079510A1 (en) | METHOD AND DEVICE FOR ELECTROCHEMICALLY COMPRESSING GASEOUS HYDROGEN | |
| CN109234760A (en) | A kind of activated cathode and its preparation method and application | |
| EP0694632B1 (en) | Electrolysis cell diaphragm reclamation | |
| US10818951B2 (en) | Method and molten salt electrolytic cell for implementing a hydrogen fuel, sustainable, closed clean energy cycle on a large scale | |
| US7128824B2 (en) | Method for electrolysis of aqueous solutions of hydrogen chloride | |
| US20230095656A1 (en) | Vanadium-based solution, its manufacturing method and a battery thereof | |
| Kulkarni et al. | Tailoring hybrid CrCoSb-B nano-needles via Ar plasma: A path to sustainable water splitting and urea oxidation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20090121 |