CN208753439U - A kind of fuel cell based on biomass pyrolysis product - Google Patents
A kind of fuel cell based on biomass pyrolysis product Download PDFInfo
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- CN208753439U CN208753439U CN201821393843.2U CN201821393843U CN208753439U CN 208753439 U CN208753439 U CN 208753439U CN 201821393843 U CN201821393843 U CN 201821393843U CN 208753439 U CN208753439 U CN 208753439U
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The application belongs to field of fuel cell technology, more particularly to a kind of fuel cell based on biomass pyrolysis product.Existing fuel cell, fuel cost is high, electrode structure complexity, higher cost.The application provides a kind of fuel cell based on biomass pyrolysis product, including several concatenated battery units, the battery unit successively includes the first fixture, plate, membrane electrode, cathode plate and the second fixture from top to bottom, the plate includes first surface, several first grooves are provided on the first surface, the cathode plate includes second surface, and several second grooves are provided on the second surface；The membrane electrode includes anion-exchange membrane and catalyst layer, and pyrolytic carbon bisque is provided on the anion-exchange membrane.The fuel cell manufactured using biomass pyrolysis products such as agriculture and forestry organic waste materials, concise production process, it is easily stored transport, it is cheap and green renewable.
Description
Technical field
The application belongs to field of fuel cell technology, more particularly to a kind of fuel electricity based on biomass pyrolysis product
Pond.
Background technique
Fuel cell is a kind of power generator for directly converting chemical energy to electric energy, and fuel cell has so far from invention
More than 100 years history nowadays has been considered as one of most promising electrochemical energy power generator, it is that one kind passes through electrochemistry
Reaction, is directly translated into the chemical energy being stored in fuel and oxidant in the device of electric energy, it is sent out after hydroelectric generation, thermal energy
The 4th kind of generation technology after electricity and nuclear electric power generation has the advantages that high conversion efficiency, operating cost be low, green cleaning.
The fuel of existing fuel cell is the fossil fuels such as the fuel containing hydrogen atom, such as natural gas, petroleum, coal, Huo Zhezhao
The bio-fuels such as gas, alcohol, methanol, then electrode catalyst is done with the inertia noble metal such as platinum.However, either increasingly exhaustion, valence
The bio-fuel of the constantly soaring fossil fuel of lattice or complex production process, price are all more expensive.In addition, noble metal
Expensive, in the cost of fuel cell, platinum catalyst has accounted for 40% of total cost or so.Therefore, fuel cell is because making
Valence is too high, chemical energy source is exhausted and reasons such as hydrogen storage technology etc. limit its commercialized development application.
Biomass energy is directly or indirectly from solar energy, by plant photosynthesis carbon solidification effect, with the shape of chemical energy
Formula is contained in one of biomass clean energy resource, has the characteristics that rich reserves, green are renewable.Biomass pyrolytic liquid produces
Product-pyrolysis oil is a kind of emerging green novel energy source, and main component includes acid, alcohol, ketone, phenol, ether, ester, sugar, furans, nitrogen
Object and polyfunctional group organic compound etc. are closed, has many advantages, such as that renewable, environmentally friendly, storage transport is convenient, rich reserves.Pyrolysis oil
It can be used for liquid fuel was prepared, or extract chemicals and synthesis chemical products, be a kind of petroleum base for having very much development prospect
Substitute and green material.
And during existing pyrolysis oil recovery energy, when directly burning, utilization efficiency is lower, while needing to pyrolysis
Oil use after catalytic hydrogenation, catalytic pyrolysis etc. further refine as liquid fuel, so that technique is very complicated, is produced into
This is higher.
Summary of the invention
1. technical problems to be solved
Based on existing conventional fuel cell, fuel cost is high, electrode structure complexity, higher cost.Meanwhile pyrolysis oil
During recovery energy, utilization efficiency is lower when directly burning, added value is not high, at the same need to carry out pyrolysis oil catalysis plus
Hydrogen, catalytic pyrolysis etc. use after further refining as liquid fuel, so that technique is very complicated, production cost is higher to be asked
Topic, this application provides the preparation methods of a kind of fuel cell based on biomass pyrolysis product and membrane electrode.
2. technical solution
To achieve the above object, this application provides a kind of fuel cells based on biomass pyrolysis product, including
Several concatenated battery units, the battery unit successively include the first fixture, plate, membrane electrode, cathode from top to bottom
Pole plate and the second fixture, the plate include first surface, and several first grooves are provided on the first surface, described
Cathode plate includes second surface, and several second grooves are provided on the second surface；
The membrane electrode includes anion-exchange membrane and catalyst layer, and pyrolysis carbon dust is provided on the anion-exchange membrane
Layer.
Optionally, the first groove is oxygen channel, and the second groove is pyrolysis oil fuel channel.
Optionally, the anion-exchange membrane includes chitosan series anion-exchange membrane, polysulfones series anion-exchange membrane, benzene
Ethers anion-exchange membrane or vinyl fluoride series anion-exchange membrane.
Optionally, it is provided with threaded hole on first fixture and second fixture, the battery unit passes through screw
It is fastened.
Optionally, first fixture, plate, membrane electrode, cathode plate and the second fixture are by stainless steel
Material is made.
3. beneficial effect
Compared with prior art, the beneficial effect of a kind of fuel cell based on biomass pyrolysis product provided by the present application
It is:
A kind of fuel cell based on biomass pyrolysis product provided by the present application, passes through the anion exchange in membrane electrode
Pyrolytic carbon bisque is set on film, biomass pyrolytic processing technology and pyrolysis byproducts are sufficiently applied into fuel cell, guaranteed
Its production cost is reduced while battery performance and improves the green environmental protection of fuel cell.It is fired pyrolysis oil as fuel cell
Material, not only raw material sources are extensive, concise production process, easily stored transport, but also cheap, green renewable, facilitate
Dependence of the fuel cell to fossil fuel is reduced, therefore provides a kind of good renewable cheap fuel for fuel cell.Meanwhile
The new way for opening biomass economy realizes the full constituent higher value application of agriculture and forestry organic waste material.
Detailed description of the invention
Fig. 1 is a kind of structural schematic diagram of fuel cell based on biomass pyrolysis product of the application；
Fig. 2 is a kind of fuel cell structure decomposition diagram based on biomass pyrolysis product of the application；
In figure: the first fixture of 1-, 2- plate, 3- membrane electrode, 4- cathode plate, the second fixture of 5-, 6- first surface,
7- first groove, 8- second surface, 9- second groove.
Specific embodiment
Hereinafter, specific embodiment of the reference attached drawing to the application is described in detail, it is detailed according to these
Description, one of ordinary skill in the art can implement the application it can be clearly understood that the application.Without prejudice to the application principle
In the case where, the feature in each different embodiment can be combined to obtain new embodiment, or be substituted certain
Certain features in embodiment, obtain other preferred embodiments.
Since fuel cell is that the Gibbs free energy part in the chemical energy of fuel is converted by electrochemical reaction
Electric energy is not limited by Carnot cycle effect, and generating efficiency is high；In addition, fuel cell structure is simple, moving component is few, work
When noise it is very low, the pernicious gas given off is few.It can be seen that from energy saving and from the perspective of preserving the ecological environment,
Fuel cell is most promising generation technology.It is mainly made of four parts, i.e. anode, cathode, electrolyte and dispatch from foreign news agency
Road.In operation of fuel cells, fuel occurs oxidation reaction in anode (also known as fuel electrodes) and loses electronics, and the oxidants such as oxygen
Reduction reaction occurs in cathode (also known as air pole) and obtains electronics, conductive ion migrates in the electrolyte for separating anode and cathode,
Electronics migrates by external circuit and constitutes the circuit of electricity, generates electric current.
Biomass pyrolytic refers under conditions of isolation or a small amount of supply oxidant, in certain temperature range, utilizes thermal energy
The chemical bond in biomass macromolecular is cut off, is allowed to be converted into the conversion process of lower-molecular substance.Biomass pyrolysis product is main
Including solid (pyrolytic carbon), liquid (pyrolysis oil), gas (combustible gas) three classes product.After pyrolysis oil is agricultural-forestry biomass thermal cracking
Obtained liquid product is condensed, energy density height, easily stored transport are that have very much the green energy resource of development potentiality and chemical industry former
Material；Carbon element content height, chemical structure are abundant in pyrolytic carbon, can be used as the raw materials for production such as active carbon, electrode, without condensable
Gas then can be used as the heat source for reaction of pyrolytic process and process carrier gas is recycled.Pyrolysis oil is a kind of dark brown, with cigarette
Smoked or tart flavour the liquid that can be flowed naturally, origin are answered derived from what the depolymerization such as cellulose, hemicellulose and lignin generated
Miscellaneous mixture is constituted.Chemically said on ingredient, pyrolysis oil by a part of water, a small amount of solid particle and acid, alcohol, ketone, aldehyde, phenol,
Hundreds of organic compound compositions such as ester, ether, sugar, furans, nitrogen oxides.Biomass pyrolysis oil is in acidity, and chemical component is very
Abundant, energy density height.
Therefore, there is an urgent need to a green, cleaning, efficient recovery energy modes, and utilize in pyrolysis oil rich in sugar
The characteristics of reducing substances such as class, can generate electricity directly as fuel-cell fuel.
Biomass-based Carbon Materials have big specific surface area, good corrosion resistance, chemical stability and thermal stability and
Electric conductivity has the potentiality as production electrode material.
Battery stack is for fuel cell, when the single cell operation being made of one group of electrode and electrolyte panel
Output voltage is lower, and current density is about smaller.To obtain high voltage and power, usually by multiple cells in series, electricity is constituted
Chi Dui.It is separated between adjacent single cells with bipolar plates, bipolar plates play cells in series up and down and provide gas flow path.Battery
Heap is mounted in round or rectangle pressure apparatus.
Referring to Fig. 1~2, the application provides a kind of fuel cell based on biomass pyrolysis product, including several concatenated
Battery unit, the battery unit successively include the first fixture 1, plate 2, membrane electrode 3,4 and of cathode plate from top to bottom
Second fixture 5, the plate 1 include first surface 6, are provided with several first grooves 7 on the first surface 6, described
Cathode plate 4 includes second surface 8, is provided with several second grooves 9 on the second surface 8；
The membrane electrode 3 includes anion-exchange membrane and catalyst layer, is provided with pyrolytic carbon on the anion-exchange membrane
Bisque.
Optionally, the first groove 7 is oxygen channel, and the second groove 9 is pyrolysis oil fuel channel.Here heat
Solution oil is the preparation method is as follows: molten for 4~8mol/L KOH by the crude pyrolysis oil and concentration obtained by biomass fast pyrogenation
Liquid is formulated, wherein biomass pyrolysis oil accounting 30%~60%.
Optionally, the anion-exchange membrane includes chitosan series anion-exchange membrane, polysulfones series anion-exchange membrane, benzene
Ethers anion-exchange membrane or vinyl fluoride series anion-exchange membrane.
Optionally, it is provided with threaded hole on first fixture 1 and second fixture 5, the battery unit passes through spiral shell
Nail is fastened.
Optionally, first fixture 1, plate 2, membrane electrode 3, cathode plate 4 and the second fixture 5 are by stainless
Steel material is made.
The application also provides a kind of preparation method of membrane electrode, and described method includes following steps:
1) pyrolysis carbon dust is taken, after sequentially adding platinum, ion exchange resin, acetylene black and binder, is mixed；Here
Ion exchange resin includes that perhaps polyacrylic binder includes polytetrafluoroethylene (PTFE) or Kynoar to polystyrene type.
2) mixture in step 1) is added in dispersing agent, is sufficiently mixed by ultrasonic vibration；Here point
Powder includes water, glycerine or isopropanol.
3) mixture in step 2) is coated on anion-exchange membrane two sides, is put into hot press, 120 DEG C of temperature~
150 DEG C, 2~8min of hot pressing is carried out under 0.5~5MPa of pressure.
Optionally, the preparation method of pyrolysis carbon dust includes the following steps: in the step 1)
A. biomass pyrolytic carbon dust is impregnated in alcohol, after cleaning for 24 hours in natural air drying；
B. under an inert atmosphere in tube furnace with 1~5 DEG C/min heating rate be heated to 500~700 DEG C and keep the temperature 2~
4h is carried out after being once carbonized, cooled to room temperature；
C. under an inert atmosphere in tube furnace 5~10 DEG C/min heating rate be heated to 900~1100 DEG C and keep the temperature 1~
3h carries out secondary purification carbonization, further refines biomass carbon dust, increases molecule micropore quantity, prepares the fine carbon dust of biomass,
Specific surface area reaches 700m2/ g or more.
Optionally, in the step a biomass pyrolytic carbon dust the preparation method comprises the following steps: biological material is taken to be dried to containing
Water rate 10% is hereinafter, be crushed to 40~60 mesh of partial size, after thermal cracking liquefaction reaction then occurs in fast pyrogenation equipment, carries out
Gas solid separation is form biomass pyrolysis carbon dust after solid product collection, and the part of condensable collection is heat in gas-phase product
Solution oil, uncondensable part may be used as pyrolytic process heat source and circulating carried.
Optionally, the amount of the pyrolysis carbon dust is 1~5mg/cm of membrane electrode area2, the amount of the platinum is the pyrolysis
The 0.3%~3% of carbon dust quality, the amount of the ion exchange resin be the membrane electrode catalyst layer quality 20%~
50%, the amount of the acetylene black is the 3%~5% of the membrane electrode catalyst layer quality, and the amount of the binder is the film
The 5%~10% of electrode catalyst layer quality.
Optionally, the thermal cracking liquefaction reaction temperature is 450~550 DEG C, wherein gas phase residence time < 2s.
Embodiment 1
(1) industrial wood waste of solid wood and furniture processing factory is taken --- sawdust carries out biomass fast pyrogenation: first
The sawdust particle that screening obtains 40 mesh first is carried out to sawdust, heated-air drying or solar energy drying are then used, by its moisture content
It dries to 5~8%；It is small in 500~520 DEG C of pyrolysis reaction temperature, meteorological residence time in fluidized bed type fast pyrogenation equipment
Fast pyrogenation reaction is carried out under conditions of 2s, gas solid separation is carried out to thermal decomposition product, respectively obtain 60% after condensation is collected~
65% pyrolysis oil and 20~25% pyrolytic carbon, residue 10%~20% non-condensable gas be recycled as pyrolytic process
Heat source and carrier gas, wherein pyrolysis oil and pyrolytic carbon are spare.
(2) carbon dust of membrane electrode 3 is prepared using thermal decomposition of wood carbon dust: using biomass pyrolytic carbon as raw material, in alcohol
Raw material is impregnated, after cleaning for 24 hours in natural air drying, then under an inert atmosphere in tube furnace with 3 DEG C/min heating rate
It is heated to 650 DEG C and keeps the temperature 3h to be carbonized, then cooled to room temperature；Then again under an inert atmosphere 6 DEG C in tube furnace/
Min heating rate is heated to 1000 DEG C and keeps the temperature 3h to carry out purification carbonization, further refines biomass carbon dust, increases molecule micropore
Quantity, prepares the fine carbon dust of biomass, and specific surface area reaches 750~850m2/ g or more.
(3) further, membrane electrode 3 is prepared using thermal decomposition of wood carbon dust and amberplex: being taken relative to membrane electrode
Area 3mg/cm2Biomass pyrolytic carbon dust, then be added carbon dust quality 1.5% platinum, add relative catalytic oxidant layer quality
For 30% polystyrene type, about 3% acetylene black and about 8% polytetrafluoroethylene (PTFE) are added, is added to after preliminary mixing different
In propyl alcohol, catalyst pulp is thoroughly mixed to form by ultrasonic vibration；Further, catalyst pulp is coated on chitosan respectively
Series anion-exchange membrane two sides, are put into hot press, and hot pressing 6min is carried out at 140 DEG C of temperature and pressure 4MPa and is made.
(4) pyrolysis oil cell fuel solution is prepared using wood pyrolysis oil: being 6mol/L using wood pyrolysis oil and concentration
KOH solution is formulated, wherein biomass pyrolysis oil accounting 40-50%, is configured and is protected from light low-temperature storage, spare.
(5) according to shown in attached drawing 2 by the first fixture 1 of battery unit, plate 2, membrane electrode 3, cathode plate 4 and
Two fixtures 5 connect, and wherein membrane electrode 3 is between plate 2, cathode plate 4.
(6) oxygen is each led into several permeability grooves in one side surface of the cathode plate or plate
With pyrolysis oil fuel, battery operation exports current work after stablizing, and the voltage by testing every group of battery unit can achieve
0.56~0.65V.Anion-exchange membrane fuel cells generally become fuel using multiple battery cells in series when working together
Battery stack, for industrial actual power.
Embodiment 2
(1) corn stover on farmland or farm is taken to carry out biomass fast pyrogenation: corn stover is crushed first,
Screening obtains the stalk particle of 60 mesh, then uses heated-air drying or solar energy drying, by its moisture content it is dry to 8~
10%；In fluidized bed type fast pyrogenation equipment, the item of 2s is less than in 460~480 DEG C of pyrolysis reaction temperature, meteorological residence time
Fast pyrogenation reaction is carried out under part, and 55%~60% heat is respectively obtained after collecting to thermal decomposition product progress gas solid separation, condensation
The oily pyrolytic carbon with 15~20% of solution, the non-condensable gas of residue 20%~30% are recycled as the heat source and load of pyrolytic process
Gas, wherein pyrolysis oil and pyrolytic carbon are spare.
(2) carbon dust is pyrolyzed using corn stover to prepare the carbon dust of membrane electrode 3: using stalk pyrolytic carbon as raw material, in alcohol
Middle immersion raw material, after cleaning for 24 hours in natural air drying, then under an inert atmosphere in tube furnace with 2 DEG C/min heating speed
Rate is heated to 600 DEG C and keeps the temperature 2.5h to be carbonized, then cooled to room temperature；Then again under an inert atmosphere in tube furnace
8 DEG C/min heating rate is heated to 950 DEG C and keeps the temperature 2h to carry out purification carbonization, further refines biomass carbon dust, increases molecule
Micropore quantity, prepares the fine carbon dust of biomass, and specific surface area reaches 700~800m2/ g or more.
(3) further, membrane electrode 3 is prepared using thermal decomposition of wood carbon dust and amberplex: being taken relative to membrane electrode
Then the platinum of carbon dust quality 2% is added in the biomass pyrolytic carbon dust of area 4mg/cm2, adding relative catalytic oxidant layer quality is
25% polystyrene type adds about 4% acetylene black and about 6% polytetrafluoroethylene (PTFE), and the third three are added to after preliminary mixing
In alcohol, catalyst pulp is thoroughly mixed to form by ultrasonic vibration；Further, catalyst pulp is coated on chitosan class respectively
Anion-exchange membrane two sides, are put into hot press, and hot pressing 4min is carried out at 130 DEG C of temperature and pressure 3MPa and is made.
(4) pyrolysis oil cell fuel solution is prepared using wood pyrolysis oil: being 5mol/L using wood pyrolysis oil and concentration
KOH solution is formulated, wherein biomass pyrolysis oil accounting 50%-60%, is configured and is protected from light low-temperature storage, spare.
(5) according to shown in attached drawing 2 by the first fixture 1 of battery unit, plate 2, membrane electrode 3, cathode plate 4 and
Two fixtures 5 connect, and wherein membrane electrode 3 is between plate 2, cathode plate 4.
(6) oxygen is each led into several permeability grooves in one side surface of the cathode plate or plate
It is pyrolyzed oil fuel with stalk, battery operation exports current work after stablizing, and the voltage by testing every group of battery unit can reach
To 0.45-0.58V.Anion-exchange membrane fuel cells generally become fuel using multiple battery cells in series when working together
Battery stack, for industrial actual power.
A kind of fuel cell based on biomass pyrolysis product provided by the present application, passes through the anion exchange in membrane electrode
Pyrolytic carbon bisque is set on film, biomass pyrolytic processing technology and pyrolysis byproducts are sufficiently applied into fuel cell, guaranteed
Its production cost is reduced while battery performance and improves the green environmental protection of fuel cell.It is fired pyrolysis oil as fuel cell
Material, not only raw material sources are extensive, concise production process, easily stored transport, but also cheap, green renewable, facilitate
Dependence of the fuel cell to fossil fuel is reduced, therefore provides a kind of good renewable cheap fuel for fuel cell.Meanwhile
The new way for opening biomass economy realizes the full constituent higher value application of agriculture and forestry organic waste material.
Although the application is described above by referring to specific embodiment, one of ordinary skill in the art are answered
Work as understanding, in principle disclosed in the present application and range, many modifications can be made for configuration disclosed in the present application and details.
The protection scope of the application is determined by the attached claims, and claim is intended to technical characteristic in claim
Equivalent literal meaning or range whole modifications for being included.
Claims (5)
1. a kind of fuel cell based on biomass pyrolysis product, it is characterised in that: described including several concatenated battery units
Battery unit is from top to bottom successively
Including the first fixture, plate, membrane electrode, cathode plate and the second fixture, the plate includes first surface,
Several first grooves are provided on the first surface, the cathode plate includes second surface, is arranged on the second surface
There are several second grooves；
The membrane electrode includes anion-exchange membrane and catalyst layer, and pyrolytic carbon bisque is provided on the anion-exchange membrane.
2. as described in claim 1 based on the fuel cell of biomass pyrolysis product, it is characterised in that: the first groove is
Oxygen channel, the second groove are pyrolysis oil fuel channel.
3. as described in claim 1 based on the fuel cell of biomass pyrolysis product, it is characterised in that: the anion exchange
Film includes chitosan series anion-exchange membrane, polysulfones series anion-exchange membrane, phenylate series anion-exchange membrane or vinyl fluoride class
Anion-exchange membrane.
4. the fuel cell according to any one of claims 1 to 3 based on biomass pyrolysis product, it is characterised in that: institute
It states and is provided with threaded hole on the first fixture and second fixture, the battery unit is fastened by screw.
5. as described in claim 1 based on the fuel cell of biomass pyrolysis product, it is characterised in that: first fixture,
Plate, membrane electrode, cathode plate and the second fixture are made of stainless steel material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109119664A (en) * | 2018-08-28 | 2019-01-01 | 北京林业大学 | A kind of preparation method of fuel cell and membrane electrode based on biomass pyrolysis product |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109119664A (en) * | 2018-08-28 | 2019-01-01 | 北京林业大学 | A kind of preparation method of fuel cell and membrane electrode based on biomass pyrolysis product |
| CN109119664B (en) * | 2018-08-28 | 2023-12-12 | 北京林业大学 | Fuel cell based on biomass pyrolysis product and preparation method of membrane electrode |
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