CN105789646A - Preparation method of chargeable type manganese oxide cathode material for fuel cells - Google Patents
Preparation method of chargeable type manganese oxide cathode material for fuel cells Download PDFInfo
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- CN105789646A CN105789646A CN201610264922.2A CN201610264922A CN105789646A CN 105789646 A CN105789646 A CN 105789646A CN 201610264922 A CN201610264922 A CN 201610264922A CN 105789646 A CN105789646 A CN 105789646A
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- China
- Prior art keywords
- preparation
- manganese dioxide
- electrolysis
- manganese oxide
- manganese sulfate
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- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8853—Electrodeposition
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- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
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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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a preparation method of a chargeable type manganese oxide cathode material for fuel cells, and relates to the technical field of renewable resources. The preparation method comprises the following steps: mixing manganese sulfate with concentrated sulfuric acid so as to prepare manganese sulfate electrolyte; in the manganese sulfate electrolyte, using Pt as an anode, using carbon paper as a cathode, performing constant-current constant-voltage electrolysis, and directly electrolyzing manganese oxide to the surface of the carbon so as to obtain the manganese oxide cathode material. The chargeable type manganese oxide cathode prepared according to the preparation method disclosed by the invention is suitable for microbiological fuel cells, the making technology is rapid, simple and convenient, and the chargeable type manganese oxide cathode shows stable cycled charge and discharge properties in the microbiological fuel cells.
Description
Technical field
The present invention relates to technical field of renewable energy sources, particularly the preparation method of rechargeable type cathode material in fuel cell.
Background technology
In recent years, the energy resource consumption in global range is day by day serious.The energy is divided into three classes: Fossil fuel, regenerative resource and nuclear power source, and wherein, non-renewable energy resources include a huge energy consumption part, it is possible to be divided into two big classes: nuclear energy and fossil energy.Due to the discharge of carbon dioxide, the character of Fossil fuel is had certain negative effect by it, such as global warming and atmospheric pollution.Therefore, the new forms of energy selecting a kind of environmental protection and sustainable development are most important.
Manganese dioxide is a kind of aboundresources, preparation is simple, price is cheap, have the hydrogen reduction catalysis material of good catalytic performance, is usually used in single-chamber microbial fuel cell, as the catalysis source material that air cathode is good.For expensive Pt catalyst, manganese dioxide can as the sub of Pt.
Summary of the invention
The preparation method that it is an object of the invention to provide a kind of fuel cell rechargeable type manganese dioxide cathodes material, to solve above-mentioned prior art Problems existing.
The technical scheme is that and manganese sulfate and concentrated sulphuric acid are hybridly prepared into manganese sulfate electrolyte, with Pt for anode in described manganese sulfate electrolyte, carbon paper is negative electrode, through constant current constant voltage electrolysis, by manganese dioxide Direct Electrolysis to carbon paper surface, obtain manganese dioxide cathodes material.
Electrolyzer of the present invention occurs the redox reaction equation to be on positive pole: Mn2++2H2O+2e-→MnO2+4H+。
The manganese dioxide cathodes that the present invention is prepared by direct electrolysis method, is applied in microbiological fuel cell, it may be achieved the rechargeable type electric discharge of battery system, thus reaching the application capable of circulation of battery, solves energy shortage problem.
Adopting rechargeable type manganese dioxide cathodes material prepared by the present invention to be more suitable in microbiological fuel cell, processing technology is easy rapidly, and it shows more stable charge-discharge performance capable of circulation in microbiological fuel cell.
Further, having considered properties of product and economic benefit, in manganese sulfate electrolyte of the present invention, the concentration of manganese sulfate is 60g/L, and the concentration of sulphuric acid is 20g/L sulphuric acid.
It is 98% for preparing the concentration of the described concentrated sulphuric acid of electrolyte, for the commercially available analytical reagent being easy to get.
During electrolysis, the temperature of described manganese sulfate electrolyte is 95 ± 1 DEG C.During electrolyte temperature height, it is possible to reduce the polarization of anode and negative electrode.
Voltage during electrolysis is 24V, and electric current is 50mA.Anode By Electrolysis generates the amount of manganese dioxide and is directly proportional to electric current, and electric current is more big, and the manganese dioxide content of precipitation is more many.
In preparation process, electrolysis time >=2 hour, can obtain, at carbon paper surface, the manganese dioxide that granule is more intensive, more.
The thickness of described carbon paper is 255 μm, and density is 0.4g/cm3。
Accompanying drawing explanation
Fig. 1 is the manganese dioxide electrode surface SEM figure obtained after electrolysis 1h in preparation technology.
Fig. 2 is the manganese dioxide electrode surface SEM figure obtained after electrolysis 2h in preparation technology.
Fig. 3 is manganese dioxide electrode XRD figure under different discharge condition.
Fig. 4 is the constant-current discharge figure of electrolysis difference manganese dioxide content.
When Fig. 5 is shallow discharge, electrode charge and discharge figure.
When Fig. 6 is deep discharge, electrode charge and discharge figure.
Detailed description of the invention
Below according to drawings and Examples, the present invention is discussed further and explanation.
One, manganese dioxide cathodes is prepared:
(1) cutting length is 3.0cm, and width is the carbon paper of 2.5cm, and this carbon paper is with carbon fiber for base material, and thickness is 255 μm, and density is 0.4g/cm3。
(2) with conductive silver glue, carbon paper is connected with copper cash, at junction point place with the epoxy sealing with good electrical insulation property.Above conductive silver glue is a kind of adhesive solidifying or having after drying certain performance.
(3) concentrated sulphuric acid of manganese sulfate and 98% being hybridly prepared into 500mL manganese sulfate solution, wherein manganese sulfate concentration is 60g/L, and the concentration of concentrated sulphuric acid is 20g/L sulphuric acid.
(4) with Pt for anode, carbon paper is negative electrode, Pt and carbon paper is placed in the manganese sulfate solution of 95 ± 1 DEG C of preparations, external 24V power supply.
(5) in addition 50mA constant current between Pt and carbon paper, carries out electrolysis with manganese sulfate solution, and manganese dioxide Direct Electrolysis, to carbon paper surface, obtains manganese dioxide cathodes material.
Two, the product that the present invention prepares application in microbiological fuel cell:
Manganese dioxide cathodes the inventive method prepared is positioned in vaccinated single-chamber microbial fuel cell, it is assembled into a single-chamber microbial fuel cell with the manganese dioxide cathodes that carbon paper electrode is biological anode with preparation, recording its initial COD is 1027mg/L, regulates pH to 7.0.Three kinds of manganese dioxide content respectively 7.6mg/cm of electrolysis gained2、13.6mg/cm2And 25.4mg/cm2Negative electrode when 5mA constant-current discharge, discharge time is 15h, 40h and 80h respectively.Afterwards the manganese dioxide cathodes obtained by electrolysis 2h is positioned in microbiological fuel cell, observes the electrode charging and discharging curve when shallow discharge and the charging and discharging curve when deep discharge.
1, the physicochemical property test of manganese dioxide cathodes:
By the structure of manganese dioxide surface topography under field emission microscopy observation difference electrolysis time.
Fig. 1 is the shape appearance figure preparing the manganese dioxide electrode surface obtained after electrolysis 1h in manganese dioxide cathodes, it is seen that be attached to substantial amounts of manganese dioxide granule on electrode carbon fiber.
Fig. 2 prepares in manganese dioxide cathodes the shape appearance figure through electrolysis 2h manganese dioxide electrode surface, compared to Figure 1, it is apparent that during electrolysis 2h, on carbon fiber, the manganese dioxide granule of attachment is more intensive, may infer that electrolysis time is more long, on electrode surface, the content of the manganese dioxide of attachment is more many.
Fig. 3 is deep discharge, shallow discharge and the XRD curve not discharged in three kinds of situations, and wherein curve 1 represents the XRD curve in shallow discharge situation, and curve 2 represents the XRD curve in deep discharge situation, and curve 3 represents the XRD curve under not discharge scenario.When not discharging, XRD figure occurs 4 obvious manganese dioxide material peaks, discharge about 25% time manganese dioxide peak position be substantially free of and change, and when electric discharge is more than 80%, the position at manganese dioxide peak changes, and fades away.
2, the checking of manganese dioxide cathodes charge-discharge performance:
Fig. 4 is electrode discharge curve in 5mA constant current situation, and electrolysis different time makes the manganese dioxide of electrode surface absorption different content.It is 7.6 ± 0.9mg/cm that curve A represents the content of negative electrode By Electrolysis MnO22Discharge curve, curve B represents negative electrode By Electrolysis MnO2Content 13..6 ± 0.4mg/cm2Discharge curve, curve C represents negative electrode By Electrolysis MnO2Content 25.4 ± 0.7mg/cm2Discharge curve.Choose the manganese dioxide cathodes of electrolysis 2h as object of study, investigate its charge-discharge performance when shallow discharge and deep discharge.
Fig. 5 is electrode charge status of (about 15h discharge time) when shallow discharge, it can be seen that manganese dioxide cathode gesture changes within the scope of 0.2-0.5V, each cycle 10h, until electrode still shows good electric discharge trend during 400h.
Fig. 6 is electrode charge status of (about 25h discharge time) when deep discharge, it can be seen that manganese dioxide cathode gesture changes within the scope of 0-1V, each cycle 30h, along with the increase of discharge time, about 70h starts electrode performance and presents downward trend.Therefore, showing good charge-discharge performance when battery is in shallow discharge, cycle period is longer, it is possible to achieve the recycling of electrode.
Claims (7)
1. the preparation method of a rechargeable type manganese dioxide cathodes material, it is characterized in that manganese sulfate and concentrated sulphuric acid are hybridly prepared into manganese sulfate electrolyte, with Pt for anode in described manganese sulfate electrolyte, carbon paper is negative electrode, through constant current constant voltage electrolysis, by manganese dioxide Direct Electrolysis to carbon paper surface, obtain manganese dioxide cathodes material.
2. preparation method according to claim 1, it is characterised in that in described manganese sulfate electrolyte, the concentration of manganese sulfate is 60g/L, and the concentration of sulphuric acid is 20g/L sulphuric acid.
3. preparation method according to claim 1 and 2, it is characterised in that the concentration of described concentrated sulphuric acid is 98%.
4. preparation method according to claim 1, it is characterised in that during electrolysis, the temperature of described manganese sulfate electrolyte is 95 ± 1 DEG C.
5. preparation method according to claim 1, it is characterised in that voltage during electrolysis is 24V, electric current is 50mA.
6. preparation method according to claim 1, it is characterised in that electrolysis time >=2 hour.
7. the preparation method according to claim 1 or 2 or 4 or 5 or 6, it is characterised in that the thickness of described carbon paper is 255 μm, and density is 0.4g/cm3。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5456248A (en) * | 1977-10-12 | 1979-05-07 | Hitachi Ltd | Electrode for water treatment apparatus |
| CN101237049A (en) * | 2008-01-22 | 2008-08-06 | 重庆大学 | Making method for anti-drowning gas multi-hole pole in alkalescent medium |
| CN102796880A (en) * | 2012-09-10 | 2012-11-28 | 毛耀辉 | Method and equipment for extracting manganese from manganese alloy smelting slag |
| CN103560241A (en) * | 2013-11-07 | 2014-02-05 | 广西桂柳化工有限责任公司 | Preparation method of electrolytic manganese dioxide special for button type alkaline zinc/manganese dioxide battery |
| CN105448531A (en) * | 2015-11-13 | 2016-03-30 | 哈尔滨工业大学 | Method for preparing needle-like manganese dioxide/graphene composite electrode material |
-
2016
- 2016-04-26 CN CN201610264922.2A patent/CN105789646A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5456248A (en) * | 1977-10-12 | 1979-05-07 | Hitachi Ltd | Electrode for water treatment apparatus |
| CN101237049A (en) * | 2008-01-22 | 2008-08-06 | 重庆大学 | Making method for anti-drowning gas multi-hole pole in alkalescent medium |
| CN102796880A (en) * | 2012-09-10 | 2012-11-28 | 毛耀辉 | Method and equipment for extracting manganese from manganese alloy smelting slag |
| CN103560241A (en) * | 2013-11-07 | 2014-02-05 | 广西桂柳化工有限责任公司 | Preparation method of electrolytic manganese dioxide special for button type alkaline zinc/manganese dioxide battery |
| CN105448531A (en) * | 2015-11-13 | 2016-03-30 | 哈尔滨工业大学 | Method for preparing needle-like manganese dioxide/graphene composite electrode material |
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