CN107919484A - Direct borohydride fuel cell that is a kind of while handling organic wastewater - Google Patents
Direct borohydride fuel cell that is a kind of while handling organic wastewater Download PDFInfo
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- CN107919484A CN107919484A CN201711096394.5A CN201711096394A CN107919484A CN 107919484 A CN107919484 A CN 107919484A CN 201711096394 A CN201711096394 A CN 201711096394A CN 107919484 A CN107919484 A CN 107919484A
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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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
- H01M8/0245—Composites in the form of layered or coated products
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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
- H01M8/02—Details
- H01M8/0289—Means for holding the electrolyte
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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
- H01M8/08—Fuel cells with aqueous electrolytes
- H01M8/083—Alkaline fuel cells
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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 kind of while handle the direct borohydride fuel cell of organic wastewater, the fuel cell is that the Bipolar Membrane for using anion and cation exchange membrane compound assembles composition as membrane, and produce hydrogen peroxide using direct borohydride fuel cell cathodic oxygen reduction, Fenton reagent is formed by adding ferrous ion, polluter while electricity production in degradation of organic waste water, possesses effect of both production capacity and treatment of Organic Wastewater.The present invention need not the substantial amounts of H of scene addition in degradation of organic substances2O2, whole process environmental protection naturally.
Description
Technical field
It is more specifically a kind of using bipolar the present invention relates to a kind of directly with the alkaline fuel cell of full liquid feed
The direct borohydride fuel cell energy of film while the power generator of degradable organic pollutant.
Background technology
Direct borohydride fuel cell（DBFC）It is the alkali metal borohydride MBH with liquid4（NaBH4、LiBH4、
KBH4）Make fuel, aoxidized in anode-side, ejected electron, oxidant is reduced in cathode side.Boron hydride is that a kind of hydrogen content is very high
Compound.For example, NaBH4Containing 10.6%（Percentage by weight）Hydrogen, this is than hydrogen that most of alloy material storing hydrogens are stored
It is more.If it is used as fuel, NaBH by the use of boron hydride sodium4Theoretical energy density can reach 9.3Wh/g, be much higher than methanol
（6.1Wh/g）As the fuel cell of fuel, and boron hydride chemical property is stablized, easily stored, supply, it is safe to use and
It is nonflammable, so direct borohydride fuel cell most promises to be the mobile power of low temperature decentralized.
In theory, borohydride ion is unstable in acid medium, therefore the electrochemical reaction medium of DBFC should be in alkali
Carried out in property medium.Electrode reaction is as follows with cell reaction：
Anode： (1)
Cathode： (2)
Total cell reaction： (3)
It was found from electrode reaction above, eachIon can produce 8 electronics, and electromotive force reaches 2.469V, this is hydrogen-oxygen
2.01 times of proton membrane exchange fuel cell, are 2.04 times of direct methanol fuel cell；And the electrochemical reaction production of DBFC
Thing only has water and borate ion；Borate ion can be changed into as a kind of environmental-friendly material by certain approach
Boron hydride, achievees the purpose that recycling.
A borohydride fuel battery part is the anolyte in anode and highly basic medium dissolved with borohydride fuel,
The catholyte of reduction reaction occurs for cathode and oxygen in acid medium for another part.Due to borohydride fuel battery
Both sides electrolyte is respectively Strong Acid and Alkali Medium, is made so must use with solid electrolyte film of the ion selectivity through characteristic
For membrane by cell partition into two parts.The dielectric film usually selected has cation-exchange membrane（CEM）Or anion exchange
Film（AEM）Two types.
Cation permeable membrane is widely used that Nafion series --- the proton exchange membrane of E.I.Du Pont Company's production（PEM）, this
When being contacted with highly basic and strong reductant, property is highly stable after fluorination for kind film.Nafion membrane is selected as battery diaphragm
When, cation migrates the transmission for completing electric charge from anode to cathode direction.In DBFC, fuel boron hydride aoxidizes on anode
During with sodium ion through proton exchange membrane to cathode permeate, cause sodium hydroxide cathode side assemble.Due to anode
Sodium hydroxide is lost in electrolyte, causes electrode both sides chemical substance uneven.In addition, the sodium hydroxide of boron hydride anolyte
Concentration, which reduces, exacerbates borohydride hydrolytic reaction, causes fuel availability with regard to low, battery performance declines.Battery is set to stablize
Operation, must use extremely complex battery structure, and the sodium ion of cathode side is returned in anolyte.
And use anion-exchange membrane（AEM）During as membrane, OH-Electric charge is served as in the transmission in ion direction from cathode to anode
Transmission and the migration of ion, at this time, the OH of cathode side-Ion transport is to directly take part in BH on anode4 -Oxidation reaction, is conducive to
The stabilization of anode alkaline electrolyte concentration.But the anionic membrane of business does not have enough stability in highly basic medium at present, together
When, using anion-exchange membrane leakage problems there are boron hydride from anolyte to catholyte again, mixed potential is produced, seriously
Influence battery performance.For DBFC membranes there are the problem of, Chinese patent（Authorization Notice No.：CN102437348B）Propose one
Kind uses the borohydride fuel battery of macromolecular fibre film, but since anode fuel can be oozed by this macromolecular fibre film
Arrive cathode thoroughly, it is desirable to which cathod catalyst has anti-BH4 -Oxidation and the function of hydrolysis.So directly borohydride fuel is electric at present
In cell system, no matter using anion-exchange membrane or cation-exchange membrane, performance and the service life of battery, DBFC are all directly affected
Electrolyte membrance selection plays battery vital.
DBFC cathode active materials are the oxygen in air, and the electrochemical reaction of battery is occurred in air electrode and electrolysis
Liquid formed solid-liquid-gas three phase interface, so its electrochemical reaction rates be subject to oxygen diffused into from air come speed with
And the reactivity at interface is controlled.The reduction of fuel battery negative pole active material oxygen is the electrochemical reaction of a series of complex
Process, has been generally acknowledged that two electron reaction mechanism and four electron reaction mechanism two during electric discharge in catalyst surface oxygen reduction reaction
Class, is shown in reaction equation (4) and (5).
1）Direct 4 electronic channel：O2 + 4H+ + 4e → 2H2O (4)
2）2 electronic channel approach：O2 + 2H+ + 2e → H2O2 (5)
Catalyst used is different, and the reaction mechanism during hydrogen reduction also differs.When the oxygen on fuel cell oxygen cathode also
When original reaction is carried out with four electron reactions, battery can obtain optimum performance.But in acidic electrolysis bath, two electron reactions of oxygen are more
Easily occur and generate H2O2, hydrogen peroxide cannot further using will decompose release oxygen, seriously affect the output of battery
Performance.
The content of the invention
For above-mentioned direct borohydride fuel cell membrane and oxygen cathode there are the problem of, the present invention provide it is a kind of at the same time
Handle the direct borohydride fuel cell of organic wastewater.The present invention is produced using direct borohydride fuel cell cathodic oxygen reduction
Raw hydrogen peroxide, by adding ferrous ion Fe2+Fenton reagent is formed, polluter that can be effectively in degradation of organic waste water.
With reference to the characteristics of above-mentioned direct borohydride fuel cell and Fenton-like system, can build a kind of degraded based on electric Fenton-like system is had
The direct borohydride fuel cell system of organic pollutants, possesses effect of both production capacity and treatment of Organic Wastewater.
The direct borohydride fuel cell that is a kind of while handling organic wastewater of the above-mentioned offer of the present invention, its battery unit
The Bipolar Membrane being combined into by anion and cation exchange membrane is separated into two parts as membrane：A part is anode and the sun dissolved with fuel
Pole electrolyte；Another part is cathode and catholyte.One layer of the Bipolar Membrane as battery diaphragm is anode membrane, and another layer is the moon
Film, and anode membrane is placed in cathode side, and cavity block is as anode side；The anode membrane is proton exchange membrane, and cavity block is anion
Exchange membrane.The intermediate product that this battery can prevent anode fuel or anode from producing penetrates into cathode, produces mixed potential, at the same time
Also cathode product can be prevented to reach anode.
Direct borohydride fuel cell that is above-mentioned a kind of while handling organic wastewater, its anode is by nickel screen and is sprayed at nickel
Online carbon supported catalyst is made, and carbon supported catalyst is the bimetallic alloy grain of Au and a kind of composition in Cu, Ni, Co, Fe or Zn
Son is carried on Vulcan XC-72, and loading of the metal on nickel screen electrode is 0.5-2mg/ cm2。
Direct borohydride fuel cell that is above-mentioned a kind of while handling organic wastewater, its cathode are with made of carbon material
Prepared by gas-diffusion electrode, wherein gas-diffusion electrode includes the following steps：
（1）The preparation of Carbon Materials body of paste
Suitable carbon material is taken, 5-8 times of acetone is added, stirs evenly, sonic oscillation 10 minutes, is made prepared Chinese ink shape mixture,
Then the polytetrafluoroethylene (PTFE) of 10%-60% is added（PTFE）The mass ratio of lotion, PTFE and carbon carrier is 5-35: 100, is stirred, and is surpassed
After sound oscillation 70 minutes, it is placed in 60 DEG C of water-baths, until forming a kind of body of paste.
（2）The preparation of supporting layer
Suitable PTFE lotions are taken, is diluted with 4 times of deionized waters, titanium net is immersed in PTFE dilutions and has been soaked
Entirely, take out after 120 DEG C of drying, so repeatedly 3 times, most heat 10 min after 350 DEG C, make PTFE molten homogeneous to titanium net
Surface.
（3）The coating and hot pressing of Carbon Materials body of paste
Carbon Materials body of paste is taken uniformly to roll coated in titanium net, the load capacity of Carbon Materials body of paste is 0.1-0.5g/ cm2,
It is 110 DEG C that the titanium net of Carbon Materials body of paste, which is coated with, in temperature, and pressure is 15 min of hot pressing under 10 MPa, most after 350
DEG C calcining 10 min, 12 h are soaked after taking-up in deionized water.
Direct borohydride fuel cell that is above-mentioned a kind of while handling organic wastewater, the carbon material used in its cathode are work
Property Carbon fibe, graphite, carbon nanotubes（CNTs）, one kind in Vulcan XC-72.
Direct borohydride fuel cell that is above-mentioned a kind of while handling organic wastewater, its anolyte are alkali metal boron
The aqueous solution of hydride and alkali metal hydroxide composition, catholyte is organic used water difficult to degradate；Organic difficult drop
It is 2-5 to solve waste water and first adjust pH value with sulfuric acid or sodium hydroxide solution when entering cathode chamber, then adds FeSO4•7H2O；Institute
The Fe stated2+Concentration is 7.5-25mmol/L.
Direct borohydride fuel cell that is above-mentioned a kind of while handling organic wastewater, the gas that its cathode side is passed through are oxygen
Gas or air, the oxygen or air mass flow are 10-50 L/min.
Above-mentioned the provided direct borohydride fuel cell that is a kind of while handling organic wastewater of the present invention, its yin, yang
The electrolyte of heterogencity can be extremely used, i.e., anode-side uses alkaline electrolyte and cathode side uses acidic electrolyte bath, favorably
In the raising of cell voltage.
Above-mentioned the provided direct borohydride fuel cell that is a kind of while handling organic wastewater of the present invention, during it is formed
Bipolar Membrane including cathode, anode, anolyte, catholyte and barrier positive and negative anodes etc..The direct hydroboration of the present invention
Thing fuel cell, Bipolar Membrane used are existing product.
The technical solution adopted in the present invention is a kind of direct borohydride fuel cell that can handle organic wastewater at the same time,
It includes fuel BH4 -Oxidation reaction ejected electron occurs in anode, electronics is transported to cathode through external circuit from anode, and oxygen is in the moon
Pole surface obtain electronics and with the H in water+With reference to generation H2O2, with the Fe in water sample2+Form Fenton reagent.Electrode surface
H2O2By diffusing into organic used water difficult to degradate, in Fe2+Catalytic action under, because of H2O2Decomposition activation energy it is relatively low
(34.9kJ mol), produces substantial amounts of intermediate state active specy hydroxyl radical free radical OH in reaction process.Hydroxyl radical free radical has very
High oxidation-reduction potential (2.20V), can make the either general chemical oxidization method of many difficult for biological degradation be difficult to aoxidize it is organic
Material oxygenolysis.Its ferrous ions plays catalyst in the reaction, it with hydroperoxidation generation ferric iron from
After son, iron ion can occur reduction reaction with hydrogen peroxide and regenerate ferrous ion, continue to participate in Fenton's reaction；The iron of generation
In cathode reduction reaction generation ferrous ion can also occur for ion.It is continually fed into oxygen and ensure that the dense of dissolved oxygen in system
Degree, H2O2It is continuously generated and is supplemented, further generates the extremely strong hydroxyl radical free radical of oxidisability, oxidation operation is degraded to low
The intermediate of carbon number, final all molecular fragments are oxidized to CO2And H2O。
The direct borohydride fuel cell that is a kind of while handling organic wastewater, includes the hydroxide ion of anode
Neutralization reaction process occurs in inside battery with the hydrogen ion of cathode, during being somebody's turn to do, the hydroxide ion of anode can pass through cavity block
Layer, the hydrogen ion of cathode can be by anode membrane layer, and between two film layers, with hydroxide ion neutralization reaction, generation occur for hydrogen ion
Product water can by the modes such as scattering and permeating enter both sides electrolyte in.When the pH value of both sides electrolyte changes, bipolar
The dissociation reaction of water occurs in the interface of two film layer of film（H2O→H++OH-）, the H of generation+And OH-Respectively enter cathode and anode electricity
Solve in liquid, keep the pH value of both sides to balance.
Direct borohydride fuel cell a kind of while that handle organic wastewater of the present invention, the electricity that when its performance test uses
The effective area of pool unit electrode is 4 cm2, it is 2cm × 2cm that it, which is grown with width, and thickness is about 0.2mm.Anolyte：
1.5 M NaBH4+ 2 M NaOH.With III potentiostats of U.S. Princeton VMP, by testing organic wastewater in cathode chamber
COD and colourity, measure battery is to the degradation capability of organic matter.
Compared with prior art, advantages of the present invention and it is characterized in that：
The present invention degrades fuel cell power generation and electric Fenton oxidation two kinds of PROCESS COUPLINGs, is produced using borohydride fuel battery
H is generated while electric energy2O2Degradable organic pollutant, the H produced with electrochemical reaction2O2As the constant source of Fenton reagent,
Need not the substantial amounts of H of scene addition2O2, whole process is naturally environmentally friendly, has good development prospect.
The present invention is because setting two layers of charged electrically opposite solid electrolyte film, due to Donnan repelling effects, thus energy
Block fuel BH4 -Consume of the cathode side so as to avoid fuel is penetrated into through film layer, fuel availability is improved, reduces electricity
The polarization loss of pole, eliminates mixed potential.Meanwhile the water decomposition reaction energy in the bipolar reaction interface between yin, yang film
Supplement OH on anode-Ion, keeps anolyte alkaline environment, avoids BH4 -Hydrolysis.
The present invention uses the direct borohydride fuel cell of Bipolar Membrane, can concentrate acid and alkaline polymer membrane fuel
The respective advantage of battery, maximizes favourable factors and minimizes unfavourable ones, and by selecting the type of ionic membrane, can effectively improve the direct boron hydride combustion of Bipolar Membrane
Expect the performance of battery.Meanwhile the electrolyte membrance of excellent performance may also be constructed out using cheap anions and canons film, expand
The range of choice of membrane material.
The present invention can use the electrolyte of heterogencity, the i.e. corresponding anode in Bipolar Membrane both sides and catholyte
Acid, alkalescence are different.
The present invention is used using acid solution as the direct borohydride fuel cell of catholyte, anode-side electrolyte
Alkaline hydrated oxide, one side OH-As anode reactant, another aspect fuel BH4 -It is anti-to suppress hydrolysis in highly basic medium
Should；And in cathode side, higher output voltage can be provided using acid medium, because the pH value of cathode side electrolyte directly affects
The electrode potential of cathode.
The fuel cell of the present invention is conducive to the pH of holding electrode both sides electrolyte because separating anode and cathode using Bipolar Membrane
Value, can meet the effective pH value scope of Fenton-like system.
The present invention realizes Fe3+Recycle, reduce FeSO4•7H2The dosage of O, overcomes conventional electric Fenton and Fenton
The drawbacks of a large amount of solid waste pollution environment are produced in method processing procedure.
Brief description of the drawings
Fig. 1 is the present invention while handles the direct borohydride fuel cell structure diagram of organic wastewater.
Embodiment
The invention will be further described with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
（1）1.0 grams of Vulcan XC-72 carbon dusts are weighed, it is 1 to add volume ratio：1 water and the mixture 40mL of isopropanol, ultrasound
30min, sequentially adds 0.5 mol/L chlorauric acid solutions and CuSO4Solution, the molar ratio for controlling Au and Cu are 0.2:1, ultrasound shake
1h is swung, then adds enough sodium borohydride solution reduction, constant temperature stirs 1h at 80 DEG C, filters, and with distilled water flushing, gold is made
Category content is 40%AuCu/C catalyst.0.5g carbon supported catalyst AuCu/C are taken, add 10 mL absolute ethyl alcohols and 3 mL Nafion
Solution, 30 min of ultrasound, for even application on nickel screen, it is 1 mg/ cm to make loading of the metal on nickel screen2.Drying is institute
The anode of the battery of system.
（2）1g activated carbon fibre is taken, adds 7mL acetone, sonic oscillation 10 minutes, is made prepared Chinese ink shape mixture, Ran Houjia
Enter 0.05g 10%PTFE, stir, sonic oscillation is placed in 60 DEG C of water-baths after 70 minutes, until forming a kind of body of paste.
Suitable PTFE lotions are taken, is diluted with 4 times of deionized waters, titanium net is immersed in PTFE dilutions and is soaked
Completely, take out and be placed on 120 DEG C of drying, so repeatedly 3 times, most heat 10 min after 350 DEG C, make PTFE molten homogeneous
To titanium net surface.
Obtained activated carbon fibre body of paste is taken, is rolled coated in titanium net, making the load capacity of activated carbon fibre be 0.1g/
cm2, the titanium net of activated carbon fibre is coated with 110 DEG C of hot pressing, and pressure is 10 MPa, 15 min is suppressed, most after 350
DEG C calcining 10 min, 12 h are soaked after taking-up in deionized water.
（3）By obtained electrode and Bipolar Membrane Neosepta BP-1（Tokuyama Soda Inc., Japan）According to
Battery unit is assembled into shown in Fig. 1, anolyte is 1.5 M NaBH4+ 2 M NaOH；Catholyte is the rhodamine B of 25mg/L,
It is that 10% dilute sulfuric acid adjusting pH value is 2 with mass concentration, adds FeSO4•7H2O makes Fe in reaction solution2+Concentration is 7.5mmol/
L。
（4）Battery discharge and organic matter degradation
Battery unit is connected to III potentiostats of U.S. Princeton VMP, it is 30L/min to be passed through air mass flow.Battery
Open-circuit voltage is 1.9 V, is 110 mA/cm in current density2Continuous discharge, after battery operation 50min, measures in catholyte
Rhodamine B removal rate is 85.7%, and chroma removal rate reaches 89.8%.
Embodiment 2
（1）1.0 grams of Vulcan XC-72 carbon dusts are weighed, it is 1 to add volume ratio：1 water and the mixture 40mL of isopropanol, ultrasound
30min, sequentially adds 0.5 mol/L chlorauric acid solutions and NiCl2Solution, the molar ratio for controlling Au and Ni are 0.5:1, ultrasound shake
1h is swung, then adds enough sodium borohydride solution reduction, constant temperature stirs 1h at 80 DEG C, filters, and with distilled water flushing, gold is made
Category content is 20%AuNi/C catalyst.0.5g carbon supported catalyst AuNi/C are taken, add 10 mL absolute ethyl alcohols and 3 mL Nafion
Solution, 30 min of ultrasound, coated on nickel screen, making loading of the metal on nickel screen be 0.5 mg/ cm2.Drying is as made
Battery anode.
（2）1g graphite powders are taken, add 10mL acetone, sonic oscillation 10 minutes, is made prepared Chinese ink shape mixture, then adds
0.2g 30%PTFE, stirring, sonic oscillation are placed in 60 DEG C of water-baths after 45 minutes, until forming a kind of body of paste.
Suitable PTFE lotions are taken, is diluted with 4 times of deionized waters, titanium net is immersed in PTFE dilutions and is soaked
Completely, take out after 120 DEG C of drying, so repeatedly 3 times, most heat 10 min after 350 DEG C, arrive PTFE molten homogeneous
Titanium net surface.
Obtained graphite body of paste is taken, is rolled coated in titanium net, making the load capacity of graphite body of paste be 0.5g/cm2, will
For titanium net coated with graphite body of paste in 110 DEG C of hot pressing, pressure is 10 MPa, suppresses 15 min, most after 350 DEG C of calcinings
10 min, soak 12 h in deionized water after taking-up.
（3）By obtained electrode and Bipolar Membrane CJ-BPM（Hefei Ke Jia high molecular materials Science and Technology Ltd.）According to figure
Battery unit is assembled into shown in 1, anolyte is 1.5 M NaBH4+ 2 M NaOH；Catholyte is the polyvinyl alcohol of 450mg/L,
It is that 10% dilute sulfuric acid adjusting pH value is 4 with mass concentration, adds FeSO4•7H2O makes Fe in reaction solution2+Concentration is 12mmol/L.
（4）Battery discharge and organic matter degradation
Battery unit is connected to III potentiostats of U.S. Princeton VMP, it is 10L/min to be passed through oxygen flow.Battery
Open-circuit voltage is 2.0 V, is 110 mA/cm in current density2Continuous discharge, after battery operation 50min, measures in catholyte
Polyvinyl alcohol removal rate is 95.7%.
Embodiment 3
（1）1.0 grams of Vulcan XC-72 carbon dusts are weighed, it is 1 to add volume ratio：1 water and the mixture 40mL of isopropanol, ultrasound
30min, sequentially adds 0.5 mol/L chlorauric acid solutions and CoCl2Solution, the molar ratio for controlling Au and Co are 0.3:1, ultrasound shake
1h is swung, then adds enough sodium borohydride solution reduction, constant temperature stirs 1h at 80 DEG C, filters, and with distilled water flushing, gold is made
Category content is 30%AuCo/C catalyst.0.5g carbon supported catalyst AuCo/C are taken, add 10 mL absolute ethyl alcohols and 3 mL Nafion
Solution, 30 min of ultrasound, coated on nickel screen, making loading of the metal on nickel screen be 1.5 mg/ cm2.Drying is as made
Battery anode.
（2）Take 1g carbon nanotubes（CNTs）, 8mL acetone is added, sonic oscillation 10 minutes, is made prepared Chinese ink shape mixture, so
0.35g 50%PTFE, stirring are added afterwards, and sonic oscillation is placed in 60 DEG C of water-baths after 90 minutes, until forming a kind of body of paste.
Suitable PTFE lotions are taken, is diluted with 4 times of deionized waters, titanium net is immersed in PTFE dilutions and is soaked
Completely, take out after 120 DEG C of drying, so repeatedly 3 times, most heat 10 min after 350 DEG C, arrive PTFE molten homogeneous
Titanium net surface.
Take obtained carbon nanotubes（CNTs）Body of paste, rolls coated in titanium net, makes carbon nanotubes（CNTs）Load
Measure as 0.2g/cm2, it is coated with carbon nanotubes（CNTs）Titanium net in 110 DEG C of hot pressing, pressure is 10 MPa, compacting 15
Min, most calcines 10 min after 350 DEG C, soaks 12 h after taking-up in deionized water.
（3）By obtained electrode and Bipolar Membrane Fumasep FBM（FuMATech GmbH, Germany）According to shown in Fig. 1
Battery unit is assembled into, anolyte is 1.5 M NaBH4+ 2 M NaOH；Catholyte early period is after materialization, biochemical treatment
Dyeing waste water, the COD of the dyeing waste water is 864mg/L, colourity is 150 times, is that 10% dilute sulfuric acid adjusts pH value and is with mass concentration
3, add FeSO4•7H2O makes Fe in reaction solution2+Concentration is 20mmol/L.
（4）Battery discharge and organic matter degradation
Battery unit is connected to III potentiostats of U.S. Princeton VMP, it is 50L/min to be passed through air mass flow.Battery
Open-circuit voltage is 2.0 V, is 100 mA/cm in current density2Continuous discharge, after battery operation 50min, measures in catholyte
COD removal rates are 82.9%, and chroma removal rate reaches 85.7%.
Embodiment 4
（1）1.0 grams of Vulcan XC-72 carbon dusts are weighed, it is 1 to add volume ratio：1 water and the mixture 40mL of isopropanol, ultrasound
30min, sequentially adds 0.5 mol/L chlorauric acid solutions and FeCl2Solution, the molar ratio for controlling Au and Fe are 0.3:1, ultrasound shake
1h is swung, then adds enough sodium borohydride solution reduction, constant temperature stirs 1h at 80 DEG C, filters, and with distilled water flushing, gold is made
Category content is 20%AuFe/C catalyst.0.5g carbon supported catalyst AuFe/C are taken, add 10 mL absolute ethyl alcohols and 3 mL Nafion
Solution, 30 min of ultrasound, coated on nickel screen, making loading of the metal on nickel screen be 2 mg/ cm2.Drying is made
The anode of battery.
（2）1g Vulcan XC-72 are taken, add 9mL acetone, sonic oscillation 10 minutes, is made prepared Chinese ink shape mixture, so
After add 0.28 g 40%PTFE, stir, sonic oscillation is placed in 60 DEG C of water-baths after 30 minutes, until forming a kind of body of paste.
Suitable PTFE lotions are taken, is diluted with 4 times of deionized waters, titanium net is immersed in PTFE dilutions and is soaked
Completely, take out after 120 DEG C of drying, so repeatedly 3 times, most heat 10 min after 350 DEG C, arrive PTFE molten homogeneous
Titanium net surface.
Obtained graphite body of paste is taken, is rolled coated in titanium net, making the load capacity of activated carbon fibre be 0.3g/cm2, will
For titanium net coated with activated carbon fibre in 110 DEG C of hot pressing, pressure is 10 MPa, suppresses 15 min, most after 350 DEG C of calcinings
10 min, soak 12 h in deionized water after taking-up.
（3）By obtained electrode and Bipolar Membrane CJ-BPM（Hefei Ke Jia high molecular materials Science and Technology Ltd.）According to attached
Battery unit is assembled into shown in Fig. 1, anolyte is 1.5 M NaBH4+ 2 M NaOH；Catholyte early period is by materialization, biochemistry
Sucrose waste water after processing, the COD of the sucrose waste water is 2635mg/L, pH 7.5.Adjusted with mass concentration for 10% dilute sulfuric acid
PH value is 5, adds FeSO4•7H2O makes Fe in reaction solution2+Concentration is 25mmol/L.
（4）Battery discharge and organic matter degradation
Battery unit is connected to III potentiostats of U.S. Princeton VMP, it is 40L/min to be passed through oxygen flow.Battery
Open-circuit voltage is 2.0 V, is 100 mA/cm in current density2Continuous discharge, after battery operation 50min, measures in catholyte
COD removal rates are 75.4%, and chroma removal rate reaches 63.7%.
Embodiment 5
（1）1.0 grams of Vulcan XC-72 carbon dusts are weighed, it is 1 to add volume ratio：1 water and the mixture 40mL of isopropanol, ultrasound
30min, sequentially adds 0.5 mol/L chlorauric acid solutions and ZnCl2Solution, the molar ratio for controlling Au and Zn are 0.3:1, ultrasound shake
1h is swung, then adds enough sodium borohydride solution reduction, constant temperature stirs 1h at 80 DEG C, filters, and with distilled water flushing, gold is made
Category content is 50% AuZn/C catalyst.0.5g carbon supported catalyst AuZn/C are taken, add 10 mL absolute ethyl alcohols and 3 mL
Nafion solution, 30 min of ultrasound, coated on nickel screen, making loading of the metal on nickel screen be 2 mg/ cm2.Drying is
The anode of made battery.
（2）Take 1g carbon nanotubes（CNTs）, 8mL acetone is added, sonic oscillation 10 minutes, is made prepared Chinese ink shape mixture, so
0.2g 20%PTFE, stirring are added afterwards, and sonic oscillation is placed in 60 DEG C of water-baths after 30 minutes, until forming a kind of body of paste.
Suitable PTFE lotions are taken, is diluted with 4 times of deionized waters, titanium net is immersed in PTFE dilutions and is soaked
Completely, take out after 120 DEG C of drying, so repeatedly 3 times, most heat 10 min after 350 DEG C, arrive PTFE molten homogeneous
Titanium net surface.
Obtained graphite body of paste is taken, rolls coated in titanium net, makes carbon nanotubes（CNTs）Load capacity be 0.25g/
cm2, it is coated with carbon nanotubes（CNTs）Titanium net in 110 DEG C of hot pressing, pressure is 10 MPa, suppress 15 min, most after
350 DEG C of 10 min of calcining, soak 12 h in deionized water after taking-up.
（3）By obtained electrode and Bipolar Membrane Neosepta BP-1（Tokuyama Soda Inc., Japan）According to
Battery unit is assembled into shown in Fig. 1, anolyte is 1.5 M NaBH4+ 2 M NaOH；Catholyte early period is by materialization, biochemistry
The waste water of starch factory production after processing, the COD of the starch wastewater is 5146mg/L, pH 4.5.Add FeSO4•7H2O makes instead
Answer Fe in liquid2+Concentration is 25mmol/L.
（4）Battery discharge and organic matter degradation
Battery unit is connected to III potentiostats of U.S. Princeton VMP, it is 20L/min to be passed through oxygen flow.Battery
Open-circuit voltage is 2.0 V, is 100 mA/cm in current density2Continuous discharge, after battery operation 50min, measures in catholyte
COD removal rates are 86.2%, and chroma removal rate reaches 75.9%.
Claims (8)
1. direct borohydride fuel cell that is a kind of while handling organic wastewater, it is characterised in that：The direct boron hydride
Fuel cell is to be combined into Bipolar Membrane by anion and cation exchange membrane to be separated into two parts as membrane：It is a part of for anode and its molten
There is the anolyte of fuel；Another part is formed for cathode and its catholyte.
2. direct borohydride fuel cell that is according to claim 1 a kind of while handling organic wastewater, its feature exist
In：One layer of the Bipolar Membrane is anode membrane, and another layer is cavity block, and anode membrane is placed in cathode side；Cavity block is as anode side.
3. direct borohydride fuel cell that is according to claim 2 a kind of while handling organic wastewater, the anode membrane
For proton exchange membrane, the cavity block is anion-exchange membrane.
4. direct borohydride fuel cell that is according to claim 1 a kind of while handling organic wastewater, its feature exist
In：The anode is made of nickel screen and the carbon supported catalyst that is sprayed on nickel screen, carbon supported catalyst be Au and Cu, Ni, Co, Fe,
A kind of composition bimetallic alloy particle in Zn, and be carried on Vulcan XC-72, loading of the metal on nickel screen electrode
For 0.5-2mg/ cm2。
5. direct borohydride fuel cell that is according to claim 1 a kind of while handling organic wastewater, its feature exist
In：The cathode is prepared and included the following steps with gas-diffusion electrode made of carbon material, wherein gas-diffusion electrode：
（1）The preparation of Carbon Materials body of paste
Suitable carbon material is taken, 5-8 times of acetone is added, stirs evenly, sonic oscillation 10 minutes, is made prepared Chinese ink shape mixture,
Then the polytetrafluoroethylene (PTFE) of 10%-60% is added（PTFE）The mass ratio of lotion, PTFE and carbon material is 5-35: 100, is stirred, and is surpassed
After sound oscillation 70 minutes, it is placed in 60 DEG C of water-baths, until forming a kind of body of paste；
（2）The preparation of supporting layer
Suitable PTFE lotions are taken, is diluted with 4 times of deionized waters, titanium net is immersed in PTFE dilutions and has been soaked
Entirely, take out after 120 DEG C of drying, so repeatedly 3 times, most heat 10 min after 350 DEG C, make PTFE molten homogeneous to titanium
Net surface；
（3）The coating and hot pressing of Carbon Materials body of paste
Carbon Materials body of paste is taken uniformly to roll coated in titanium net, the load capacity of Carbon Materials body of paste is 0.1-0.5g/cm2, will
Titanium net coated with Carbon Materials body of paste is 110 DEG C in temperature, and pressure is 15 min of hot pressing under 10 MPa, is most forged after 350 DEG C
10 min are burnt, soak 12 h after taking-up in deionized water.
6. direct borohydride fuel cell that is according to claim 5 a kind of while handling organic wastewater, its feature exist
In：The carbon material is activated carbon fibre, graphite, carbon nanotubes（CNTs）, one kind in Vulcan XC-72.
7. direct borohydride fuel cell that is according to claim 1 a kind of while handling organic wastewater, its feature exist
In：The anolyte is the aqueous solution of alkali metal borohydride and alkali metal hydroxide composition；Catholyte is that have
Machine used water difficult to degradate；It is 2-5 that organic used water difficult to degradate first adjusts pH value when entering cathode chamber with sulfuric acid or sodium hydroxide solution,
Then FeSO is added4•7H2O, makes Fe2+Concentration is 7.5-25mmol/L.
8. direct borohydride fuel cell that is according to claim 1 a kind of while handling organic wastewater, its feature exist
In：It is oxygen or air that the cathode side, which is passed through gas, and the flow of the oxygen or air is 10-50 L/min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108693230A (en) * | 2018-05-25 | 2018-10-23 | 西安交通大学 | The device and method of sulphion concentration in a kind of quick detection strong alkali solution |
| CN110306203A (en) * | 2019-07-09 | 2019-10-08 | 郑州大学 | A kind of cathode generates the electrochemical appliance and method of the hydrogen peroxide organic wastewater of anode processing simultaneously |
| CN113270621A (en) * | 2021-03-23 | 2021-08-17 | 西安交通大学 | Acid-base type direct liquid fuel cell |
| US11339483B1 (en) | 2021-04-05 | 2022-05-24 | Alchemr, Inc. | Water electrolyzers employing anion exchange membranes |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201072787Y (en) * | 2007-06-19 | 2008-06-11 | 汉能科技有限公司 | Portable fuel cell system |
| CN102104151A (en) * | 2009-12-16 | 2011-06-22 | 中国科学院大连化学物理研究所 | Application of membrane electrode in basic anion exchange membrane fuel cell |
| WO2011100732A2 (en) * | 2010-02-13 | 2011-08-18 | Mcalister Roy E | System and method for renewable resource production, for example, hydrogen production by microbial electrolysis, fermentation, and/or photosynthesis |
| CN102324542A (en) * | 2011-07-28 | 2012-01-18 | 西安交通大学 | Device for coprocessing heavy metal waste water and organic waste water and generating electric power |
| CN103151547A (en) * | 2013-03-18 | 2013-06-12 | 天津大学 | Composite fuel cell |
| CN203300747U (en) * | 2013-03-18 | 2013-11-20 | 天津大学 | Hybrid fuel cell |
| CN103739161A (en) * | 2013-12-26 | 2014-04-23 | 江南大学 | Low-energy-consumption degradation-resistant organic wastewater recycling method |
-
2017
- 2017-11-09 CN CN201711096394.5A patent/CN107919484A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201072787Y (en) * | 2007-06-19 | 2008-06-11 | 汉能科技有限公司 | Portable fuel cell system |
| CN102104151A (en) * | 2009-12-16 | 2011-06-22 | 中国科学院大连化学物理研究所 | Application of membrane electrode in basic anion exchange membrane fuel cell |
| WO2011100732A2 (en) * | 2010-02-13 | 2011-08-18 | Mcalister Roy E | System and method for renewable resource production, for example, hydrogen production by microbial electrolysis, fermentation, and/or photosynthesis |
| CN102324542A (en) * | 2011-07-28 | 2012-01-18 | 西安交通大学 | Device for coprocessing heavy metal waste water and organic waste water and generating electric power |
| CN103151547A (en) * | 2013-03-18 | 2013-06-12 | 天津大学 | Composite fuel cell |
| CN203300747U (en) * | 2013-03-18 | 2013-11-20 | 天津大学 | Hybrid fuel cell |
| CN103739161A (en) * | 2013-12-26 | 2014-04-23 | 江南大学 | Low-energy-consumption degradation-resistant organic wastewater recycling method |
Non-Patent Citations (1)
| Title |
|---|
| PAATA NIKOLEISHVILI ET AL.: ""Waste Water Treatment in Direct Borohydride Fuel Cell with Bipolar Membrane"", 《OPEN JOURNAL OF ECOLOGY》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108693230A (en) * | 2018-05-25 | 2018-10-23 | 西安交通大学 | The device and method of sulphion concentration in a kind of quick detection strong alkali solution |
| CN110306203A (en) * | 2019-07-09 | 2019-10-08 | 郑州大学 | A kind of cathode generates the electrochemical appliance and method of the hydrogen peroxide organic wastewater of anode processing simultaneously |
| CN110306203B (en) * | 2019-07-09 | 2021-08-06 | 郑州大学 | Electrochemical device and method for generating hydrogen peroxide at cathode and simultaneously carrying out anodic treatment on organic wastewater |
| CN113270621A (en) * | 2021-03-23 | 2021-08-17 | 西安交通大学 | Acid-base type direct liquid fuel cell |
| US11339483B1 (en) | 2021-04-05 | 2022-05-24 | Alchemr, Inc. | Water electrolyzers employing anion exchange membranes |
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