CN106328961B - A kind of anode material and preparation method thereof for biomass alkaline fuel cell - Google Patents

A kind of anode material and preparation method thereof for biomass alkaline fuel cell Download PDF

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CN106328961B
CN106328961B CN201610911589.XA CN201610911589A CN106328961B CN 106328961 B CN106328961 B CN 106328961B CN 201610911589 A CN201610911589 A CN 201610911589A CN 106328961 B CN106328961 B CN 106328961B
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preparation
foam
fuel cell
nickel
nickel foam
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CN106328961A (en
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刘宪华
赵杨
林青霞
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Tianjin University
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Tianjin University
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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
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • 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
    • 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
    • H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
    • 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
    • H01M4/9041—Metals or alloys
    • 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 belongs to field of fuel cell technology, disclose a kind of anode material and preparation method thereof for biomass alkaline fuel cell, graphene modified nickel foam Composite Patches roll-in is fixed with the carbon thin layer of package methyl viologen, and preparation method is to prepare graphene oxide suspension first with oxidation-reduction method；Using graphene oxide suspension as electrolyte, nickel foam is used as working electrode, platinum electrode to electrode, and on nickel foam two sides, repeated deposition graphene obtains graphene modified foam nickel composite material；The carbon thin layer of the package methyl viologen of preparation is laid in graphene modified foam nickel composite material one side above and fixes its roll-in, until reaching specified thickness.The present invention is fixed on graphene modified foam nickel composite material by preparing graphene modified nickel foam anode material, and by viologen compound, improves the performance of biomass alkaline fuel cell, preparation process is cheap, efficiently, cleaning.

Description

A kind of anode material and preparation method thereof for biomass alkaline fuel cell
Technical field
The invention belongs to field of fuel cell technology, and in particular to a kind of anode applied to biomass alkaline fuel cell Material and preparation method thereof.
Background technique
Biomass alkaline fuel cell is a kind of will to be stored in biomass fuel and oxidant in alkaline environment Chemical energy is converted into the device of electric energy by the redox reaction of anode and cathode, it have energy conversion efficiency it is high, Environmental pollution is small, can for a long time continuously power supply, it is applied widely many advantages, such as, have become the hot spot in energy research field, Receive the favor of many researchers.
Core component of the anode catalyst as biomass alkaline fuel cell has to battery performance and stability is improved Highly important effect.Although common noble metal such as gold, platinum are made, catalyst catalytic performance is good, and property is also relatively stable, It is easy to lose catalytic site by the intermediate product package of reaction process, and reduces catalytic activity even and lose catalytic activity, send out Raw catalyst poisoning phenomenon.Although current research shows that the noble metals such as palladium, ruthenium can avoid catalyst poisoning problem, electricity is improved Pond performance but still there are problems that in price.With the development of alkaline fuel cell, the catalyst for being used for anode is also obtained It greatlys improve, Cindy X.Zhao et al. (Chen JY, Zhao CX, Zhi MM, Wang KW, Deng LL, Xu G.Electrochim Acta 2012；66:133-138.) doing anode and cathode using the nickel foam that catalyst poisoning will not occur makes Battery performance improves 6 times；Jinyao Chen et al. (Chen JY, Zhao CX, Zhi MM, Wang KW, Deng LL, Xu G.Electrochim Acta 2012；66:133-138.) silver is carried in nickel foam anode is made.
Graphene has good electricity-optics performance, mechanical property, heat-conductive characteristic and high charge carriers Transport factor, while there are also outstanding mechanical strengths and flexibility.It is wide that these properties have graphene in numerous areas General application value and prospect.Due to its high conductivity, big specific surface area, high chemical stability and to catalyst particles The strong adhesive force of grain is considered as a strong candidate of fuel-cell catalyst application.In addition, graphene or oxidation The a large amount of functional group of graphene surface can provide more chances for the nucleation of catalyst nano-particles and attachment.Nickel foam tool There is the features such as porosity is high, density is small, large specific surface area to be widely used in the production of electrode base materials.Although in recent years Come the nanometer material of the elctro-catalyst nickel based on nano material, nickel oxide, nickel hydroxide and the other metallic additions that are concerned Material, such as carbon nanotube, graphene and Ti/TiO2 material be used to make anode catalyst and have to improve battery performance very Effect, but its manufacture craft is more complex.In addition, researches show that one kind to be known as purpurine (1,1 '-dialkyl group -4,4 '-two pyridiniujms) Organic compound catalytic is shown in alkaline solution (PH > 10) and can be rapidly by electronics from carbohydrate It is transmitted to metal electrode.But viologen compound has toxicity, also there is very big harmfulness to ecological environment.
Summary of the invention
The present invention is to solve above-mentioned noble metal catalyst it is expensive and it is easy poisoning, graphene preparation process Complicated, viologen compound endangers the technical problems such as big to ecological environment, provides a kind of cheap, efficient, clean for biology The anode material and preparation method thereof of matter alkaline fuel cell, by preparing graphene modified nickel foam anode material, and will be purple Compounds are fixed on graphene modified foam nickel composite material, improve the performance of biomass alkaline fuel cell.
In order to solve the above-mentioned technical problem, the present invention is achieved by technical solution below:
Stone made of a kind of anode material for biomass alkaline fuel cell, including nickel foam two sides deposition graphene Black alkene modifying foam nickel composite material, the graphene modified nickel foam Composite Patches roll-in are fixed with package methyl viologen Carbon thin layer, and obtained by following preparation method:
(1) 0.8g/l~1.5g/l graphene oxide dispersion is prepared using oxidation-reduction method, takes upper layer after centrifuge separation Liquid obtains graphene oxide suspension；
(2) using the graphene oxide suspension of step (1) preparation as the electrolyte of electro-deposition, nickel foam is as work electricity Pole, platinum electrode are used as to electrode, and deposition voltage is 5V~10V, and nickel foam front deposition a period of time to electrolyte is become limpid Afterwards, nickel foam is cleaned with deionized water, replaces electrolyte and change nickel foam reverse side and continues to deposit a period of time to electrolyte change clearly It is clear, nickel foam is cleaned with deionized water；
(3) it repeats to obtain graphene modified foam nickel composite material step (2) 3~7 times；
(4) the carbon thin layer of the package methyl viologen of 2~4mm thickness is prepared；
(5) the carbon thin layer that step (4) is prepared is laid in the graphene modified nickel foam composite wood of step (3) preparation Material one side is upper and fixes its roll-in, until its thickness reaches 3~5mm, obtains this for biomass alkaline fuel cell Anode material.
A kind of preparation method of the anode material for biomass alkaline fuel cell, this method according to the following steps into Row:
(1) 0.8g/l~1.5g/l graphene oxide dispersion is prepared using oxidation-reduction method, takes upper layer after centrifuge separation Liquid obtains graphene oxide suspension；
(2) using the graphene oxide suspension of step (1) preparation as the electrolyte of electro-deposition, nickel foam is as work electricity Pole, platinum electrode are used as to electrode, and deposition voltage is 0.5V~10V, and nickel foam front deposition a period of time to electrolyte is become clear After clear, nickel foam is cleaned with deionized water, electrolyte is replaced and changes nickel foam reverse side and continue deposition a period of time to electrolyte change It is limpid, nickel foam is cleaned with deionized water；
(3) it repeats to obtain graphene modified foam nickel composite material step (2) 3~7 times；
(4) the carbon thin layer of the package methyl viologen of 2~4mm thickness is prepared；
(5) the carbon thin layer that step (4) is prepared is laid in the graphene modified nickel foam composite wood of step (3) preparation Material one side is upper and fixes its roll-in, until its thickness reaches 3~5mm, obtains this for biomass alkaline fuel cell Anode material.
In above-mentioned anode material for biomass alkaline fuel cell and preparation method thereof:
Using oxidation-reduction method preparation graphene oxide suspension specific steps are as follows: by dense nitre in step (1) Acid is added in natural flake graphite, and stirring is uniformly mixed the two, is continued to stir and be added formic acid, be reacted at room temperature 40min；It is 5~7 that the washing of gained mixture, which is filtered to pH, obtains no sulphur graphite oxide after dry；Take no sulphur graphite oxide ultrasound It is scattered in deionized water, stratification takes supernatant, and gained supernatant liquid is graphite oxide after supernatant is centrifugated Alkene suspension.
In step (4) the carbon thin layer of preparation package methyl viologen specific steps are as follows: weigh active carbon powder with The methyl viologen aqueous solution that concentration is 30mM is mixed and added into dehydrated alcohol, and ultrasonic agitation makes active carbon and methyl in 25~30 minutes Purpurine is sufficiently mixed in dehydrated alcohol；The polytetrafluoroethylene (PTFE) cream that mass percent concentration is 60% is added dropwise into above-mentioned mixed liquor Liquid then proceedes to ultrasonic agitation 25~30 minutes to mixing well；Above-mentioned remaining mixture is placed in 80~100 DEG C of water-baths Heating water bath is carried out, and is constantly stirred, until mixture becomes the sticky gunk that can be provoked with glass bar；It will Above-mentioned sticky gunk kneading is uniform, and the carbon thin layer of 2~4mm thickness is rolled on roll squeezer.
The beneficial effects of the present invention are:
Anode material applied to biomass alkaline fuel cell proposed by the invention, it is multiple in graphene modified nickel foam It is adulterated on condensation material and fixed viologen compound, one side graphene improves the electric conductivity and catalytic activity of nickel foam；It is another Aspect viologen compound is fixed on graphene modified foam nickel composite material, not only increases the dense of local viologen compound Degree, improves catalysis reaction efficiency, also realizes the recycling of viologen compound, eliminates dirt of the viologen compound to environment Dye, improves fuel battery performance.
Meanwhile compared to the method for more traditional noble metal catalyst raising battery performance, electrode system used in the present invention Standby technique can reduce production cost, and shorten the reaction time, improve battery performance.On the one hand make graphite using electrochemical reducing Alkene is stronger in conjunction with nickel foam, is on the other hand created using polar active carbon and nonpolar polytetrafluoroethylene (PTFE) micro- Environment is fixed on methyl viologen in nickel foam, nickel foam, graphene, active carbon and methyl viologen aoxidizes biomass anti- The catalytic action answered combines, and improves the chemical property of carbohydrate battery.
Detailed description of the invention
Fig. 1 is the flow diagram of anode material preparation method provided by the present invention；
Fig. 2 is the power density curve graph of biomass alkaline fuel cell corresponding to three kinds of different anodes；
Fig. 3 is the polarization curve of biomass alkaline fuel cell corresponding to three kinds of different anodes；
Fig. 4 is the cell power density curvilinear motion figure of same anode stability test；
Fig. 5 is that deposition voltage is anode material polarization curve obtained under the conditions of 5V, 7V and 10V.
Specific embodiment
Below by specific embodiment, the present invention is described in further detail:
Following embodiment can make those skilled in the art that the present invention be more completely understood, but not limit this in any way Invention.
Embodiment 1:
(1) concentrated nitric acid (analysis is pure) is added in the natural flake graphite of 325 mesh by the mass ratio of 1:1, stirring makes two Person is uniformly mixed, and after natural flake graphite reacts 20min by concentrated nitric acid oxidation, formic acid is added under conditions of being stirred continuously (analysis is pure), makes the ratio 4:5 of formic acid and natural flake graphite, and react 40min at room temperature；
(2) filtering the washing of mixture obtained by (1) to pH is 5~7, by gained washing product in 70 DEG C of dry 5h, is made Without sulphur graphite oxide；
(3) it takes no sulphur graphite oxide ultrasonic disperse in deionized water, after ultrasound removing 4h, the dispersion of 1.25g/l is made Liquid is stood overnight, and supernatant is taken to be centrifugated 20min under the conditions of 10000r/min, and gained supernatant liquid is graphite oxide Alkene suspension；
(4) take appropriate graphene oxide suspension as the electrolyte of electro-deposition, nickel foam is as working electrode, platinum electrode As to electrode, deposition voltage 10V is cleaned after nickel foam front deposition 20min is become limpid to electrolyte with deionized water Nickel foam, replace electrolyte and change nickel foam reverse side continue deposit 20min to electrolyte become it is limpid, clean foam with deionized water Nickel；
(5) it repeats to obtain graphene modified foam nickel composite material step (4) 5 times；
(6) active carbon powder and methyl viologen aqueous solution are weighed by the mass ratio of 1:3, methyl viologen concentration of aqueous solution is 30mM；Dehydrated alcohol is added in the two mixture, until dehydrated alcohol submerges mixture and is higher by the height of 1~2cm of mixture Degree, then ultrasound, stirring 25~30 minutes, are sufficiently mixed active carbon and methyl viologen in dehydrated alcohol；
(7) ptfe emulsion is added dropwise in Xiang Shangshu solution, makes the mass ratio of active carbon and ptfe emulsion 1:0.5~0.8 then proceedes to ultrasonic agitation 25~30 minutes to mixing well；The mass percent of ptfe emulsion is dense Degree is 60%；
(8) above-mentioned remaining mixture is placed in 80~100 DEG C of water-baths and carries out heating water bath, and constantly stirred It mixes, until the sticky gunk that mixture can be provoked with glass bar；
(9) above-mentioned sticky gunk kneading is uniform, the carbon thin layer of 2~4mm thickness is rolled on roll squeezer；
(10) after making carbon thin layer, it is laid in the graphene modified foam nickel composite material one of step (5) preparation In layer surface, then its roll-in is fixed on roll squeezer, until final thickness be 3~5mm, can be prepared by the alkali of the present embodiment Property anode of fuel cell.
Embodiment 2:
The power density curve comparison of biomass alkaline fuel cell corresponding to three kinds of different anodes:
Fig. 2 show the power density curve of battery corresponding to three kinds of different anodes.Square indicates galvanic anode in figure For foam nickel surface electro-deposition graphene (making step with for (1) of embodiment 1, (2), (3), (4), (5) step identical)；Figure Marking circle indicates that galvanic anode is that simultaneously (making step is not in addition to depositing stone in nickel foam for immobilization methyl viologen for doping in nickel foam Black alkene, with for (6) of embodiment 1, (7), (8), (9), (10) step it is identical)；Triangle indicates that galvanic anode is by embodiment 1 The anode that methyl viologen obtains is adulterated and fixed on the graphene modified foam nickel composite material of preparation.Hollow icon representation in figure The variation tendency of voltage, corresponding filled icons indicate the variation tendency of current density and power density.Battery used is single chamber Glucose fuel cell, concentration of glucose is 1M in battery, and KOH concentration is 3M.
The result shows that corresponding to different anodes as shown in Figure 2, power density is 8.9W/m respectively2、12.07W/m2、 14.84W/m2.As can be seen that implementing compared with the nickel foam for having graphene modified and anode without graphene modified nickel foam Example 1 prepare graphene modified foam nickel composite material adulterate and fix methyl viologen anode can increase substantially it is cell performance Energy.Its reason is compared with other anodes, and graphene is deposited on foam nickel surface, not only contributes to the electronics for improving electrode Transmission efficiency also advantageously improves the catalytic activity of electrode.Therefore, there is larger effect to raising battery performance.
The polarization curve comparison of biomass alkaline fuel cell corresponding to 3: three kinds of embodiment different anodes:
Fig. 3 show the polarization curve of battery corresponding to three kinds of different anodes.Square indicates that galvanic anode is bubble in figure Foam nickel surface electro-deposition graphene (making step with for (1) of example 1, (2), (3), (4), (5) step identical)；Icon circle Indicate galvanic anode be doping and immobilization methyl viologen in nickel foam (making step in addition to not depositing graphene in nickel foam, With for (6) of example 1, (7), (8), (9), (10) step it is identical)；Triangle indicates that galvanic anode prepares embodiment 1 The anode that methyl viologen obtains is adulterated and fixed on graphene modified foam nickel composite material.Battery used is the combustion of single chamber glucose Expect battery, concentration of glucose is 1M in battery, and KOH concentration is 3M.
The result shows that the open-circuit voltage of three kinds of different anodes is respectively 0.6574V, 0.7135V, 0.7918V.The pole of battery The quality of battery can be indicated by changing curve, and the polarization curve slope of battery is smaller, i.e., curve is gentler, shows the pole of battery electrode Change degree is smaller, and the obstruction that corresponding electrode is subject to is also smaller, and battery performance is more superior, figure it is seen that embodiment 1 is made Standby graphene modified foam nickel composite material adulterates and fixes the galvanic anode of methyl viologen, the polarization with other two anodes Dependence Results comparison shows that homemade anode can reduce the polarization curve slope of battery, that is, the anode compared with other two kinds Anode can effectively improve battery performance.
Embodiment 4:
The stability test of same anode.
Anode used in the power density curve that Fig. 4 is measured is as obtained by embodiment 1, with this anode test glucose fuel electricity The power density curve in pond, wherein the concentration of glucose and KOH solution is respectively 1M and 3M.
The result shows that as shown in figure 4, the open-circuit voltage of test battery and maximum power density are respectively for the first time 0.7957V and 14.83W/m2；Second and third, four test results show the open-circuit voltage and maximum power density difference of battery It is 0.7705V, 0.7636V, 0.7568V and 14.63W/m2、14.33W/m2And 14.24W/m2.It can from above-mentioned experimental result Out, the anodic stabilization performance of production is good, and practicability is higher.
Embodiment 5:
The anodic polarization curves of the anode material prepared under different deposition voltages:
The anode material obtained under three kinds of different deposition voltages is made, by step (1) (2) (3) preparation oxidation in embodiment 1 Graphene suspension, deposition voltage takes 5V, 7V, 10V respectively in step (4)；It is subsequent to press 1 step of embodiment (5) (6) (7) (8) (9) (10) make anode material.Fig. 5 show the pole that deposition voltage is respectively the anode material prepared under the conditions of 5V, 7V and 10V Change curve, the anode material that square expression deposition voltage is prepared under the conditions of being 5V in figure；Icon circle indicates that deposition voltage is 7V Under the conditions of the anode material for preparing；Icon triangle indicates deposition voltage as the anode material prepared under the conditions of 10V.Battery used For single chamber glucose fuel cell, concentration of glucose is 1M in battery, and KOH concentration is 3M.
The result shows that electrolyte becomes limpid after depositing 50min when deposition voltage is 5V；When deposition voltage is 7V, sink Electrolyte becomes limpid after product 40min；When deposition voltage is 10V, after depositing 20min, electrolyte becomes limpid.Its open-circuit voltage point It Wei not 0.7435V, 0.7652V and 0.7918V.The polarization curve of battery can indicate the quality of battery, the polarization curve of battery Slope is smaller, i.e., curve is gentler, shows that the degree of polarization of battery electrode is smaller, and the obstruction that corresponding electrode is subject to is also smaller, Battery performance is more superior.From fig. 5, it can be seen that the cell polarization curves for the anode material that deposition voltage is prepared under the conditions of being 10V Slope is minimum, that is, deposition voltage can effectively improve battery performance for the anode material prepared under the conditions of 10V.
Embodiment 6:
Influence of the graphene oxide dispersion concentration to anode material open-circuit voltage:
Three kinds of anode materials obtained using various concentration graphene oxide dispersion are made, by step system in embodiment 1 Make anode material (in addition to step (3)), it is respectively 0.8g/l, 1.25g/l that the quality of step (3) control graphite oxide, which obtains concentration, With the graphene oxide dispersion of 1.5g/l.
The result shows that concentration is respectively anode made from the graphene oxide dispersion of 0.8g/l, 1.25g/l and 1.5g/l Material open-circuit voltage is respectively 0.7382V, 0.7918V, 0.7903V.It is made when graphene oxide dispersion concentration is 1.25g/l Anode material performance it is best.
Embodiment 7:
Influence of the electro-deposition number to anode material open-circuit voltage:
The anode material that three kinds of electro-deposition difference numbers obtain is made, by step production anode material in embodiment 1 (except step Suddenly (5) outside), it is 3 times, 5 times, 7 times that step (5) control, which repeats number of steps,.
The result shows that it is anode material open-circuit voltage made from 3 times, 5 times, 7 times point that step (5) control, which repeats number of steps, It Wei not 0.7196V, 0.7952V, 0.7946V.Step (5) control repeats anode material performance obtained when number of steps is 5 times It is best.
Embodiment 8:
Wrap up influence of the methyl viologen carbon thickness of thin layer to anode material open-circuit voltage:
The anode material that the package methyl viologen carbon thin layer of three kinds of different-thickness obtains is made, by step system in embodiment 1 Make anode material (in addition to step (9)), step (9) control package methyl viologen carbon thickness of thin layer is 2mm, 3mm, 4mm.
The result shows that wrapping up anode material open-circuit voltage obtained when methyl viologen carbon thickness of thin layer is 2mm, 3mm, 4mm Respectively 0.7682V, 0.7927V, 0.7704.Wrap up anode material performance obtained when methyl viologen carbon thickness of thin layer is 3mm It is best.

Claims (6)

1. a kind of anode material for biomass alkaline fuel cell, which is characterized in that deposit graphite including nickel foam two sides Graphene modified foam nickel composite material made of alkene, the graphene modified nickel foam Composite Patches roll-in are fixed with packet The carbon thin layer of methyl viologen is wrapped up in, and is obtained by following preparation method:
(1) 0.8g/l~1.5g/l graphene oxide dispersion is prepared using oxidation-reduction method, centrifuge separation takes supernatant liquid to obtain To graphene oxide suspension；
(2) using the graphene oxide suspension of step (1) preparation as the electrolyte of electro-deposition, nickel foam as working electrode, Platinum electrode is used as to electrode, and deposition voltage is 5V~10V, after nickel foam front deposition a period of time is become limpid to electrolyte, Nickel foam is cleaned with deionized water, is replaced electrolyte and is changed nickel foam reverse side and continue deposition a period of time to electrolyte and becomes limpid, Nickel foam is cleaned with deionized water；
(3) it repeats to obtain graphene modified foam nickel composite material step (2) 3~7 times；
(4) the carbon thin layer of the package methyl viologen of 2~4mm thickness is prepared；
(5) the carbon thin layer that step (4) is prepared is laid in the graphene modified foam nickel composite material one of step (3) preparation It is fixed on face and by its roll-in, until its thickness reaches 3~5mm, obtains the anode for biomass alkaline fuel cell Material.
2. a kind of anode material for biomass alkaline fuel cell according to claim 1, which is characterized in that step (1) using oxidation-reduction method preparation graphene oxide suspension specific steps are as follows: concentrated nitric acid is added to naturally in In crystalline flake graphite, stirring is uniformly mixed the two, continues to stir and be added formic acid, reacts 40min at room temperature；Gained mixture It is 5~7 that washing, which is filtered to pH, obtains no sulphur graphite oxide after dry；Take no sulphur graphite oxide ultrasonic disperse in deionized water, Stratification takes supernatant, and gained supernatant liquid is graphene oxide suspension after supernatant is centrifugated.
3. a kind of anode material for biomass alkaline fuel cell according to claim 1, which is characterized in that step (4) the carbon thin layer of preparation package methyl viologen specific steps are as follows: weighing active carbon powder and concentration is 30mM's in Methyl viologen aqueous solution is mixed and added into dehydrated alcohol, and ultrasonic agitation makes active carbon and methyl viologen in anhydrous second in 25~30 minutes It is sufficiently mixed in alcohol；The ptfe emulsion that mass percent concentration is 60% is added dropwise into above-mentioned mixed liquor, then proceedes to Ultrasonic agitation 25~30 minutes to mixing well；Said mixture is placed in 80~100 DEG C of water-baths and carries out heating water bath, and It is constantly stirred, until mixture becomes the sticky gunk that can be provoked with glass bar；By above-mentioned sticky purees Matter kneading is uniform, and the carbon thin layer of 2~4mm thickness is rolled on roll squeezer.
4. a kind of preparation method of the anode material for biomass alkaline fuel cell, which is characterized in that this method according to Lower step carries out:
(1) 0.8g/l~1.5g/l graphene oxide dispersion is prepared using oxidation-reduction method, takes supernatant liquid after centrifuge separation Obtain graphene oxide suspension；
(2) using the graphene oxide suspension of step (1) preparation as the electrolyte of electro-deposition, nickel foam as working electrode, Platinum electrode is used as to electrode, and deposition voltage is 5V~10V, after nickel foam front deposition a period of time is become limpid to electrolyte, Nickel foam is cleaned with deionized water, is replaced electrolyte and is changed nickel foam reverse side and continue deposition a period of time to electrolyte and becomes limpid, Nickel foam is cleaned with deionized water；
(3) it repeats to obtain graphene modified foam nickel composite material step (2) 3~7 times；
(4) the carbon thin layer of the package methyl viologen of 2~4mm thickness is prepared；
(5) the carbon thin layer that step (4) is prepared is laid in the graphene modified foam nickel composite material one of step (3) preparation It is fixed on face and by its roll-in, until its thickness reaches 3~5mm, obtains the anode for biomass alkaline fuel cell Material.
5. a kind of preparation method of anode material for biomass alkaline fuel cell according to claim 4, special Sign is, using oxidation-reduction method preparation graphene oxide suspension specific steps are as follows: by concentrated nitric acid in step (1) It is added in natural flake graphite, stirring is uniformly mixed the two, continues to stir and be added formic acid, reacts 40min at room temperature； It is 5~7 that the washing of gained mixture, which is filtered to pH, obtains no sulphur graphite oxide after dry；Take no sulphur graphite oxide ultrasonic disperse in In deionized water, stratification takes supernatant, and gained supernatant liquid is that graphene oxide suspends after supernatant is centrifugated Liquid.
6. a kind of preparation method of anode material for biomass alkaline fuel cell according to claim 4, special Sign is, in step (4) the carbon thin layer of preparation package methyl viologen specific steps are as follows: weigh active carbon powder with it is dense The methyl viologen aqueous solution that degree is 30mM is mixed and added into dehydrated alcohol, and ultrasonic agitation makes active carbon and crystal violet in 25~30 minutes Essence is sufficiently mixed in dehydrated alcohol；The polytetrafluoroethylene (PTFE) cream that mass percent concentration is 60% is added dropwise into above-mentioned mixed liquor Liquid then proceedes to ultrasonic agitation 25~30 minutes to mixing well；Said mixture is placed in 80~100 DEG C of water-baths and is carried out Heating water bath, and be constantly stirred, until mixture becomes the sticky gunk that can be provoked with glass bar；It will be above-mentioned Sticky gunk kneading is uniform, and the carbon thin layer of 2~4mm thickness is rolled on roll squeezer.
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