CN104900897A - Enhanced efficient-hydrogen production microbial electrolysis cell - Google Patents
Enhanced efficient-hydrogen production microbial electrolysis cell Download PDFInfo
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- CN104900897A CN104900897A CN201510217696.8A CN201510217696A CN104900897A CN 104900897 A CN104900897 A CN 104900897A CN 201510217696 A CN201510217696 A CN 201510217696A CN 104900897 A CN104900897 A CN 104900897A
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
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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
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
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Abstract
The invention relates to an enhanced efficient-hydrogen production microbial electrolysis cell, preparation methods of a microbial carbon aerogel anode and a cobalt phosphide cathode thereof, and an application of the microbial carbon aerogel anode and the cobalt phosphide cathode in the microbial electrolysis cell. A hydrogen evolution reaction is carried out on the cathode under a low voltage, and hydrogen is efficiently produced under an external voltage of 0.3-0.8V. The microbial electrolysis cell can provide a negative anode potential and a low cathode hydrogen evolution overpotential, and realizes high electricity generation ability of a microbial anode and a high current density of a cathode, so the microbial electrolysis cell has excellent hydrogen generation ability under a low voltage and a high hydrogen generation rate. A carbon aerogel electrode adhered with electricigens has the advantages of large specific surface area, rough surface, simple production, and good plasticity and conductivity, and facilitates microbial adhesion and electron transfer; and the cobalt phosphide cathode used by the microbial electrolysis cell has good hydrogen evolution catalysis ability, and the preparation method of the cobalt phosphide cathode is simple and cheap, so the cobalt phosphide cathode can be a precious metal platinum catalyst substitute, and has bright application prospect in the microbial electrolysis cell.
Description
Technical field
The present invention relates to field of microbial electromechanical technology, especially relate to a kind of microorganism electrolysis cell of highly effective hydrogen yield of enhancement mode and the preparation method of Microbial aeroge anode and phosphatization cobalt negative electrode and its thereof application in microorganism electrolysis cell.
Background technology
Due in the last few years to exhaustive exploitation and the use of fossil energy, traditional fossil energy day by day reduces, and energy shortage problem manifests, and meanwhile, the burning of fossil fuel exacerbates CO
2discharge, people generally believe that the use of fossil fuel facilitates global warming and climate change, and the element such as nitrogen, sulphur in fossil energy is discharged in air in combustion, causes the pollution such as acid rain, haze.Therefore, the exploitation of the clean energy resource of substitutability becomes hot issue day by day.Hydrogen Energy has high calorific value due to it, and the product especially after its burning only has water, thus makes Hydrogen Energy become a kind of energy with DEVELOPMENT PROSPECT.And hydrogen is also a kind of very important raw material of industry, hydrogen is made to become a kind of product with high economic value added.Therefore, to the research of the preparation method of efficient, the low cost of hydrogen, scientific research and practical application all have great importance.
Although can high-purity hydrogen be obtained by the method for brine electrolysis, but often to use noble metal catalyst, and the voltage applied is usually at more than 1.6V, although the hydrogen purity that this method obtains is higher, but its energy consumption and cost are also higher, be only applicable to small-scale production, industrial hydrogen is obtained by natural gas or water-gas usually.Microorganism electrolysis cell (MEC) be a kind of biology and electrochemistry and technology, by the metabolism of the microbe (electrogenesis bacterium) with electro-chemical activity of adhering at anode surface, organic substance in oxidative degradation water, the electronics produced is delivered to negative electrode by external circuit, can realize producing hydrogen under lower applying voltage.But the anode of traditional microorganism electrolysis cell uses the material such as carbon felt, carbon cloth, carbon paper be made up of carbon fiber usually, and its microcosmic surface is comparatively smooth structure, limits attachment and the electron transmission of microbe, has lower current density; In addition, the negative electrode of microorganism electrolysis cell uses usually containing platinum electrode, although it has good catalysis H2-producing capacity, but it is expensive, and improve the cost of hydrogen manufacturing, and some non-platinum catalysts have higher liberation of hydrogen crosses a position, make the microorganism electrolysis cell external voltage required when practical application be normally placed in about 0.6 ~ 0.8V, add energy consumption.
Carbon aerogels has the very high BET specific surface area (500 ~ 600m in coarse surface due to it
2/ g), good absorption property and good conductivity and plasticity, electrochemistry and photoelectrochemical degradation pollutant have had certain application.In addition its good bio-compatibility, carbon aerogels is a kind of desirable anode material for microorganism electrolysis cell.Phosphatization cobalt is the material of a kind of wide material sources, cheap, easy preparation, the phosphatization cobalt nanowire that carbon cloth grows has high specific area and lower liberation of hydrogen overpotential, in addition its good stability, make it be suitable for alternative platinum electrode, thus can realize producing hydrogen at lower voltages by microorganism electrolysis cell.In addition, because the carbon silica aerogel electrode and phosphatization cobalt electrode being attached with electrogenesis bacterium can both reach higher current density, the microorganism electrolysis cell be therefore made up of the two can highly effective hydrogen yield.
Summary of the invention
Object of the present invention is exactly provide a kind of low anode potential, the carbon silica aerogel electrode being attached with electrogenesis bacterium of high current density and phosphatization cobalt negative electrode of low hydrogen-evolution overpotential of having both to overcome defect that above-mentioned prior art exists, can under lower applying voltage the microorganism electrolysis cell of highly effective hydrogen yield.
In order to reach above object, the present invention by the following technical solutions:
The microorganism electrolysis cell of the highly effective hydrogen yield of a kind of enhancement mode that the present invention proposes, the anode of microorganism electrolysis cell adopts the carbon silica aerogel electrode being attached with electrogenesis bacterium, the negative electrode of microorganism electrolysis cell adopts phosphatization cobalt electrode, anode chamber and cathode chamber are separated by proton exchange membrane, described microorganism electrolysis cell can under the external voltage of 0.3 ~ 0.8V highly effective hydrogen yield.
The preparation method of the microorganism electrolysis cell of the highly effective hydrogen yield of a kind of enhancement mode that the present invention proposes, concrete steps are as follows:
(1) preparation is attached with the carbon silica aerogel electrode of electrogenesis bacterium
(1.1) carbon silica aerogel electrode is prepared
(1.2) the carbon silica aerogel electrode ultrasonic 1 ~ 30min in deionized water step (1.1) obtained, to discharge the air in carbon aerogels, subsequently carbon silica aerogel electrode is placed in and solution A and sediment of pond volume ratio (0.5 ~ 2) are housed: the anode chamber of 1 mixed liquid B mixed carries out the inoculation of carbon aerogels anode, cathode chamber passes into the solution C containing the potassium ferricyanide, between carbon silica aerogel electrode and negative electrode, be connected with 500 ~ 1000 Ω resistance to form closed-loop path, carry out at the temperature of 15 ~ 37 DEG C electrogenesis bacterium on carbon silica aerogel electrode domestication and enrichment;
(1.3), after carbon silica aerogel electrode inoculation step (1.2) prepared, every 24h changes mixed once liquid B and solution C; After resistance voltage is greater than 100mV, every 48h changes and solution A and sediment of pond volume ratio (0.5 ~ 2) is once housed: 1 mixed liquid B mixed and the solution C containing the potassium ferricyanide; When resistance voltage reaches more than 600mV, think electrogenesis bacterium on carbon silica aerogel electrode domestication and enrichment complete;
(1.4) carbon silica aerogel electrode being attached with electrogenesis bacterium prepared in step (1.3) is transferred in the anode chamber of microorganism electrolysis cell, as the anode of the microorganism electrolysis cell of the highly effective hydrogen yield of enhancement mode;
Wherein: the composition of solution A is: often liter of solution A is by 1.0 ~ 3.0g CH
3cOONa, 18.30g K
2hPO
43H
2o, 2.70g KH
2pO
4, 0.5g NaCl, 0.1g NH
4cl, 0.1g MgSO
47H
2o, 10mg EDTA, 3.75mg CaCl
22H
2o, 1.5mg FeCl
36H
2o, 0.2mg KI, 0.2mg Co (NO
3)
26H
2o, 0.15mg H
3bO
3, 0.1mg MnSO
4, 0.06mg ZnCl
2, 0.05mg (NH
4)
2moO
42H
2o, 0.03mg CuSO
45H
2the deionized water composition of O and surplus; The composition of solution C is: often liter of solution C is by 4.0 ~ 20.0g K
3[Fe (CN)
6], 18.30g K
2hPO
43H
2o, 2.70g KH
2pO
4form with the deionized water of surplus; Negative electrode is carbon felt or carbon cloth;
(2) negative electrode of microorganism electrolysis cell is prepared
(2.1) with carbon cloth or carbon paper for basal electrode, with Co (NO
3)
26H
2o, NH
4f, CO (NH
2)
2and NaH
2pO
2for raw material prepares phosphatization cobalt nanowire electrode;
(2.2) prepared phosphatization cobalt electrode is put in the cathode chamber of microorganism electrolysis cell, as the negative electrode of the microorganism electrolysis cell of the highly effective hydrogen yield of enhancement mode.
In the present invention, the preparation method of step (1.1) is as follows:
With formaldehyde, resorcinol, water and sodium carbonate for organic wet gel prepared by raw material, the moisture in organic wet gel is replaced with acetone, treat the complete laggard row carbonization of acetone volatilization in organic wet gel, obtain carbon silica aerogel electrode, be polished into the carbon silica aerogel electrode being of a size of (10 ~ 50) mm × (5 ~ 40) mm × (1 ~ 5) mm.
The application of the microorganism electrolysis cell of the highly effective hydrogen yield of a kind of enhancement mode that the present invention proposes, the carbon silica aerogel electrode being attached with electrogenesis bacterium is applicable to microbiological fuel cell (Microbial Fuel Cells, MFC) or microbe photoelectrolytic cell (Microbial Photoelectrochemical Cells).
The application of the microorganism electrolysis cell of the highly effective hydrogen yield of a kind of enhancement mode that the present invention proposes, the carbon silica aerogel electrode being attached with electrogenesis bacterium can provide comparatively negative anode potential, the carbon cloth electrode of phosphatization cobalt nanowire load has less liberation of hydrogen overpotential, microorganism electrolysis cell can under low applying voltage highly effective hydrogen yield.
In the present invention, the pH value range of cathode chamber solution is 0 ~ 8.
Compared with prior art, the present invention has the following advantages:
1. compared with traditional microorganism electrolysis cell, the present invention can under lower applying voltage highly effective hydrogen yield;
2. compared with traditional carbon felt microbe anode, Microbial aeroge anode of the present invention has lower anode potential and the current density of Geng Gao, has good electricity generation ability, and preparation is comparatively simple, plasticity and good conductivity;
3. the phosphatization cobalt electrode that prepared by the present invention has good liberation of hydrogen catalytic capability, and its preparation method is simple, with low cost, can become the substitute of precious metals platinum catalyst, have considerable application prospect in microorganism electrolysis cell.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the microorganism electrolysis cell of the highly effective hydrogen yield of enhancement mode in the present invention;
Fig. 2 is the scanning electron microscope diagram being attached with the carbon silica aerogel electrode of electrogenesis bacterium prepared in the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
Be attached with the preparation method of the carbon silica aerogel electrode of electrogenesis bacterium, specifically comprise the following steps:
Be that the Homogeneous phase mixing liquid of the formaldehyde of 1:2:17.5:0.0008, resorcinol, water and sodium carbonate is poured in mould by mol ratio, sealing is placed in baking oven carries out polymerization reaction, reacts 24h, react 24h at 50 DEG C at 30 DEG C, react 72h at 90 DEG C, obtain organic wet gel; After surface finish is extremely coarse, be placed in acetone and soak 3d, every 24h changes an acetone, obtains organic aerogel after taking-up after acetone volatilization completely; Being in the tube furnace of the nitrogen protection of 50 ~ 100mL/min with being placed on flow, being warming up to 950 DEG C with the heating rate of 1 DEG C/min, after insulation 4h, Temperature fall is to room temperature, obtains carbon silica aerogel electrode.Carbon silica aerogel electrode is polished into the electrode being of a size of 28mm × 13mm × 3mm, ultrasonic 10min in deionized water, to discharge the air in carbon aerogels, carbon silica aerogel electrode is placed in the anode chamber that the mixed liquid B that solution A mixes with sediment of pond volume ratio 1:1 is housed; Cathode chamber passes into the solution C containing the potassium ferricyanide, 1000 Ω resistance are connected with to form closed-loop path between carbon silica aerogel electrode and negative electrode, when ohmically voltage changes mixed liquid B and solution C lower than during 50mV, lasting replacing mixed liquid B and solution C tame enrichment success until voltage is 600 ~ 650mV to thinking when stablizing.
Wherein the composition of solution A is: often liter of solution A is by 1.64g CH
3cOONa, 18.30g K
2hPO
43H
2o, 2.70g KH
2pO
4, 0.5g NaCl, 0.1g NH
4cl, 0.1g MgSO
47H
2o, 10mg EDTA, 3.75mg CaCl
22H
2o, 1.5mg FeCl
36H
2o, 0.2mg KI, 0.2mg Co (NO
3)
26H
2o, 0.15mg H
3bO
3, 0.1mg MnSO
4, 0.06mg ZnCl
2, 0.05mg (NH
4)
2moO
42H
2o, 0.03mg CuSO
45H
2the deionized water composition of O and surplus.The composition of solution C is: often liter of solution C is by 16.46g K
3[Fe (CN)
6], 18.30g K
2hPO
43H
2o, 2.70g KH
2pO
4form with the deionized water of surplus.
Embodiment 2
The construction method of microorganism electrolysis cell is as follows:
Proton exchange membrane is soaked 24h before use in deionized water and is activated to make it.The carbon silica aerogel electrode that domestication enrichment is successfully attached with electrogenesis bacterium is the anode chamber that anode is placed on microorganism electrolysis cell, and using the negative electrode of phosphatization cobalt electrode as microorganism electrolysis cell, anode chamber and cathode chamber proton exchange membrane are separated.The titanium silk taking diameter as 0.5mm, as wire, is exposed to outside titanium silk epoxy sealing.The preparation method of phosphatization cobalt electrode is as follows:
Carbon cloth (CC) is ultrasonic cleaning 10min in acetone, deionized water and ethanol respectively, room temperature is cooled to after the temperature lower calcination 30min of 450 DEG C, to be dipped in the autoclave of the 20mL that solution D is housed after the carbon cloth at room temperature drying after cleaning, 6h is reacted at the temperature of 120 DEG C, be cooled to room temperature subsequently, with deionized water rinsing, under room temperature, after drying, obtain Co (OH) F/CC presoma; By Co (OH) F/CC presoma and NaH
2pO
2being placed in respectively can the tube furnace of temperature programmed control, logical N in tube furnace
2gas shielded, NaH
2pO
2be positioned at the air inlet side of tube furnace, the mol ratio of Co and P is 0.2:1, at the N of static state
2under atmosphere, at 300 DEG C of temperature, continue 60min, subsequently at logical N
2room temperature is naturally cooled under atmosphere.Wherein the composition of solution D is: often liter of solution D is by 14.55g Co (NO
3)
26H
2o, 4.65g NH
4f and 15g CO (NH
2)
2form with the deionized water of surplus.
Embodiment 3
Microorganism electrolysis cell produces hydrogen.Pour the solution A in embodiment 1 in the anode compartment into, in cathode chamber, pour the PBS of the 0.1mol/L of pH=7 into.Before experiment starts be that the high pure nitrogen of 20mL/min to pass in anode chamber's solution and cathode chamber solution 30min to discharge oxygen by flow velocity.Constant-voltage DC source is used in experiment, adopt two electrode systems, the positive pole of constant-voltage DC source connects the anode of microorganism electrolysis cell, the negative pole of constant-voltage DC source connects the negative electrode of microorganism electrolysis cell, under constant voltage 0.3V, carry out microorganism electrolysis cell produce hydrogen experiment, the hydrogen gas chromatographic detection obtained.Result obtains, and when applied voltage is 0.3V, to be attached with the carbon silica aerogel electrode of electrogenesis bacterium be anode, on carbon cloth, the hydrogen-producing speed of the microorganism electrolysis cell that load has the electrode of phosphatization cobalt nanowire to be negative electrode is 0.85 μm of ol/cm
2h.
Embodiment 4
Microorganism electrolysis cell produces hydrogen.The constant voltage that be constant-voltage DC source apply different from embodiment 3 is 0.6V.Result obtains, and when applied voltage is 0.6V, to be attached with the carbon silica aerogel electrode of electrogenesis bacterium be anode, on carbon cloth, the hydrogen-producing speed of the microorganism electrolysis cell that load has the electrode of phosphatization cobalt nanowire to be negative electrode is 5.39 μm of ol/cm
2h.
Embodiment 5
Microorganism electrolysis cell produces hydrogen.Differently from embodiment 3 be that cathode chamber solution is the PBS of the 0.1mol/L of pH=5.
Embodiment 6
Microorganism electrolysis cell produces hydrogen.Differently from embodiment 3 be that cathode chamber solution is the PBS of the 0.1mol/L of pH=5, the constant voltage that constant-voltage DC source applies is 0.6V.
Above-mentioned is can understand and apply the invention for the ease of those skilled in the art to the description of embodiment.Be familiar with three those skilled in the art and obviously easily can make various amendment to these examples, and General Principle described herein to be applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art are according to announcement of the present invention, and the improvement made for the present invention and amendment all should within protection scope of the present invention.
Claims (5)
1. the microorganism electrolysis cell of the highly effective hydrogen yield of an enhancement mode, it is characterized in that, the anode of microorganism electrolysis cell adopts the carbon silica aerogel electrode being attached with electrogenesis bacterium, the negative electrode of microorganism electrolysis cell adopts phosphatization cobalt electrode, anode chamber and cathode chamber are separated by proton exchange membrane, described microorganism electrolysis cell can under the external voltage of 0.3 ~ 0.8V highly effective hydrogen yield.
2. a preparation method for the microorganism electrolysis cell of the highly effective hydrogen yield of a kind of enhancement mode as claimed in claim 1, is characterized in that concrete steps are as follows:
(1) preparation is attached with the carbon silica aerogel electrode of electrogenesis bacterium
(1.1) carbon silica aerogel electrode is prepared
(1.2) the carbon silica aerogel electrode ultrasonic 1 ~ 30min in deionized water step (1.1) obtained, to discharge the air in carbon aerogels, subsequently carbon silica aerogel electrode is placed in and solution A and sediment of pond volume ratio (0.5 ~ 2) are housed: the anode chamber of 1 mixed liquid B mixed carries out the inoculation of carbon aerogels anode, cathode chamber passes into the solution C containing the potassium ferricyanide, between carbon silica aerogel electrode and negative electrode, be connected with 500 ~ 1000 Ω resistance to form closed-loop path, at the temperature of 15 ~ 37 DEG C, carry out domestication and the enrichment of electrogenesis bacterium on carbon silica aerogel electrode;
(1.3), after carbon silica aerogel electrode inoculation step (1.2) prepared, every 24h changes mixed once liquid B and solution C; After resistance voltage is greater than 100mV, every 48h changes and solution A and sediment of pond volume ratio (0.5 ~ 2) is once housed: 1 mixed liquid B mixed and the solution C containing the potassium ferricyanide; When resistance voltage reaches more than 600mV, think electrogenesis bacterium on carbon silica aerogel electrode domestication and enrichment complete;
(1.4) carbon silica aerogel electrode being attached with electrogenesis bacterium prepared in step (1.3) is transferred in the anode chamber of microorganism electrolysis cell, as the anode of the microorganism electrolysis cell of the highly effective hydrogen yield of enhancement mode;
Wherein: the composition of solution A is: often liter of solution A is by 1.0 ~ 3.0g CH
3cOONa, 18.30g K
2hPO
43H
2o, 2.70g KH
2pO
4, 0.5g NaCl, 0.1g NH
4cl, 0.1g MgSO
47H
2o, 10mg EDTA, 3.75mg CaCl
22H
2o, 1.5mg FeCl
36H
2o, 0.2mg KI, 0.2mg Co (NO
3)
26H
2o, 0.15mg H
3bO
3, 0.1mg MnSO
4, 0.06mg ZnCl
2, 0.05mg (NH
4)
2moO
42H
2o, 0.03mg CuSO
45H
2the deionized water composition of O and surplus; The composition of solution C is: often liter of solution C is by 4.0 ~ 20.0g K
3[Fe (CN)
6], 18.30g K
2hPO
43H
2o, 2.70g KH
2pO
4form with the deionized water of surplus; Negative electrode is carbon felt or carbon cloth;
(2) negative electrode of microorganism electrolysis cell is prepared
(2.1) with carbon cloth or carbon paper for basal electrode, with Co (NO
3)
26H
2o, NH
4f, CO (NH
2)
2and NaH
2pO
2for raw material prepares phosphatization cobalt nanowire electrode;
(2.2) prepared phosphatization cobalt electrode is put in the cathode chamber of microorganism electrolysis cell, as the negative electrode of the microorganism electrolysis cell of the highly effective hydrogen yield of enhancement mode.
3. an application for the microorganism electrolysis cell of the highly effective hydrogen yield of a kind of enhancement mode as claimed in claim 1, is characterized in that, the carbon silica aerogel electrode being attached with electrogenesis bacterium is applicable to microbiological fuel cell or microbe photoelectrolytic cell.
4. the application of the microorganism electrolysis cell of the highly effective hydrogen yield of a kind of enhancement mode according to claim 1, it is characterized in that, the carbon silica aerogel electrode being attached with electrogenesis bacterium can provide comparatively negative anode potential, the carbon cloth electrode of phosphatization cobalt nanowire load has less liberation of hydrogen overpotential, microorganism electrolysis cell can under low applying voltage highly effective hydrogen yield.
5. the preparation method of the microorganism electrolysis cell of the highly effective hydrogen yield of a kind of enhancement mode according to claim 2, is characterized in that, the pH value range of cathode chamber solution is 0 ~ 8.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105403606A (en) * | 2015-11-10 | 2016-03-16 | 西安建筑科技大学 | Preparation method for carbon cloth electrode based on cobalt phosphide/hemoglobin modification |
| CN105817240A (en) * | 2016-04-15 | 2016-08-03 | 华中科技大学 | Pt doped phosphatizing cobalt bead catalyst carried by methanol carbon dioxide and preparation method of Pt doped phosphatizing cobalt bead catalyst |
| CN106630177A (en) * | 2016-10-19 | 2017-05-10 | 太原理工大学 | Method and device for treating coking wastewater and producing hydrogen gas by microbial electrolysis cell |
| CN109904471A (en) * | 2019-01-30 | 2019-06-18 | 天津大学 | A kind of preparation method of all-solid-state flexible metal-air battery |
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| CN101550551A (en) * | 2009-04-08 | 2009-10-07 | 哈尔滨工业大学 | Method for generating hydrogen in microorganism electrolysis cell with protein |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105403606A (en) * | 2015-11-10 | 2016-03-16 | 西安建筑科技大学 | Preparation method for carbon cloth electrode based on cobalt phosphide/hemoglobin modification |
| CN105817240A (en) * | 2016-04-15 | 2016-08-03 | 华中科技大学 | Pt doped phosphatizing cobalt bead catalyst carried by methanol carbon dioxide and preparation method of Pt doped phosphatizing cobalt bead catalyst |
| CN106630177A (en) * | 2016-10-19 | 2017-05-10 | 太原理工大学 | Method and device for treating coking wastewater and producing hydrogen gas by microbial electrolysis cell |
| CN106630177B (en) * | 2016-10-19 | 2019-09-06 | 太原理工大学 | A kind of method and device handling coking wastewater using microorganism electrolysis cell and produce hydrogen |
| CN109904471A (en) * | 2019-01-30 | 2019-06-18 | 天津大学 | A kind of preparation method of all-solid-state flexible metal-air battery |
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