CN106549170A - A kind of porous carbon fiber for Proton Exchange Membrane Fuel Cells and preparation method thereof - Google Patents
A kind of porous carbon fiber for Proton Exchange Membrane Fuel Cells and preparation method thereof Download PDFInfo
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- CN106549170A CN106549170A CN201611116485.6A CN201611116485A CN106549170A CN 106549170 A CN106549170 A CN 106549170A CN 201611116485 A CN201611116485 A CN 201611116485A CN 106549170 A CN106549170 A CN 106549170A
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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
- H01M8/0234—Carbonaceous material
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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
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Abstract
The present invention is applied to electrochemical energy source domain, there is provided a kind of porous carbon fiber suitable for Proton Exchange Membrane Fuel Cells and preparation method thereof.The preparation method is comprised the following steps：High-voltage electrostatic spinning process is carried out to PAN/PLA mixed liquors, spinning fibre is obtained；The spinning fibre is placed in chloroform carries out ultrasonic solvent extraction processing；Heat treatment is carried out to the spinning fibre through ultrasonic solvent extraction processing, porous carbon fiber is obtained.The preparation method of the porous carbon fiber that the present invention is provided, the features such as with quick, simple, inexpensive, controlled diameter.Prepared porous carbon fiber can be directly used as gas diffusion layers, be not required to extra hydrophobic and process and coat microporous layers, advantageously reduce the cost of manufacture of the resistance to mass tranfer and gas diffusion layers of gas.
Description
Technical field
The invention belongs to electrochemical energy source domain, more particularly to a kind of porous carbon fibre for Proton Exchange Membrane Fuel Cells
Dimension and preparation method thereof.
Background technology
In numerous renewable and clean energy resource technologies, Proton Exchange Membrane Fuel Cells has energy conversion efficiency because of which
The advantage of high, no pollution discharge, in recent years by countries in the world enterprise and the extensive concern of research institution.Pem fuel
The core of battery system is membrane electrode (MEA), and film needs water to remove to maintain high proton conductivity so that it is guaranteed that sufficiently high
Battery performance, but water excessive in the electrodes may cause electrode water logging, the generation for preventing electrochemical reaction, reduce performance,
Therefore need to maintain appropriate water balance.The gas diffusion layers contacted with catalyst are the passes for affecting fuel cell system performance
One of key member, its basic function are, from runner reactant transport gas to Catalytic Layer, aqueous water to be discharged from runner, conduct electronics
Deng.
However, Proton Exchange Membrane Fuel Cells is in its commercialization road, and there are the following problems：Cost of manufacture is high, catalyst
Poisoning, hydrogen storage difficulty and waterflooding electrode prevent reaction gas entrance etc..In Proton Exchange Membrane Fuel Cells, gas diffusion layers
A very important role is played in water management and reaction gas transmission, it makes reacting gas be evenly distributed, and manages battery
Middle water content, supports Catalytic Layer, collected current to provide electron channel, gas passage and drainage channel for electrochemical reaction.Cause
This, the material of gas diffusion layers selects most important.At present, gas diffusion layers mainly include the porous material such as carbon paper and carbon cloth.
The features such as porous carbon materials are due to stablizing with good conductivity, chemistry and electrochemical properties relatively, is widely used as proton exchange
The gas diffusion layers of membrane cell.Conventional carbon paper or carbon cloth needs Jing hydrophobics to process to reduce the water logging in gas diffusion layers,
But after hydrophobic process, the aperture of carbon paper or carbon cloth can reduce, and adds somewhat to the resistance of oxygen transmission.Additionally, in order to
Loss of the catalyst in spraying process and reinforcing water management are reduced, conventional carbon paper or carbon cloth surfaces can also coat one layer by carbon
The microporous layers (about 1 μm of average pore size) that powder and politef (PTFE) are formed, adds somewhat to gas diffusion layers
Manufacturing process and cost.Therefore, new gas diffusion layers are developed, is fabricated to improving its oxygen mass transfer ability and reducing which
This, is the main development direction of the current technology.
The content of the invention
The technical problem to be solved there are provided a kind of porous carbon for Proton Exchange Membrane Fuel Cells
Fiber and preparation method thereof.Prepared porous carbon fiber can be directly used as the gas diffusion layers of Proton Exchange Membrane Fuel Cells,
It is not required to extra hydrophobic and processes and coat microporous layers, the resistance to mass tranfer and gas diffusion layers for advantageously reducing gas is fabricated to
This.
The present invention is achieved in that a kind of preparation method of porous carbon fiber, comprises the following steps：
High-voltage electrostatic spinning process is carried out to PAN/PLA mixed liquors, spinning fibre is obtained；
The spinning fibre is placed in chloroform carries out ultrasonic solvent extraction processing；
Heat treatment is carried out to the spinning fibre through ultrasonic solvent extraction processing, porous carbon fiber is obtained.
Further, the PAN/PLA mixed liquors are mixed with PLA solution by PAN solution；The PAN solution and PLA
The solvent of solution is DMF.
Further, the mass concentration of the PAN solution is 5%-11%, and the mass concentration of the PLA solution is 3%-
5%；The PAN solution is 0.5-4 with the mass ratio of PLA solution:1.
Further, in -1-3KV, over-pressure control is in 8-16KV for the spinning vacuum cavitations that the high-voltage electrostatic spinning is processed.
Further, the charging rate that the high-voltage electrostatic spinning is processed is 1-3mL/h, and spinning distance is 8-20cm.
Further, the time of the ultrasonic solvent extraction processing is 20-50min, and supersonic frequency is 6-9Hz.
Further, the heat treatment process includes：
Pre-oxidation treatment is carried out under air conditionses, then carbonization treatment is carried out under argon protection.
Further, the pre-oxidation treatment includes：
By temperature in 2h from room temperature to 250-300 DEG C, be incubated 0.5-2.5h；
The carbonization treatment includes：
Temperature is warming up to into 800-1100 DEG C in 2h under argon protection, 2h is incubated.
Present invention also offers a kind of porous carbon fiber for Proton Exchange Membrane Fuel Cells, the porous carbon fiber is adopted
Made with preparation method described above.
Present invention also offers a proton exchanging film fuel battery, including porous carbon fiber described above.
Compared with prior art, beneficial effect is the present invention：The preparation of porous carbon fiber provided in an embodiment of the present invention
Method, using polyacrylonitrile (PAN) and polylactic acid (PLA) mixed liquor as spinning liquid, carries out electrostatic spinning process, using electrostatic field
High voltage power supply is loaded on the spinning liquid by effect, makes the molecule of spinning liquid with the electrostatic of certain density, when electrostatic repulsion foot
When enough, solution is drawn into fiber, fiber solidifying molding while solvent volatilizees, and spinning liquid is stretched under electrostatic constantly
Split, with preferably into fine type.Then by chloroform ultrasonic solvent extraction is carried out to spinning fibre, make on the spinning fibre
Make porous.
The preparation method of porous carbon fiber provided in an embodiment of the present invention, quick, simple low cost, and controllable standby nanometer
Fiber.Prepared porous carbon fiber can be directly used as the gas diffusion layers of Proton Exchange Membrane Fuel Cells, be not required to extra
Hydrophobic process and coating microporous layers, advantageously reduce the cost of manufacture of the resistance to mass tranfer and gas diffusion layers of gas.
Description of the drawings
Fig. 1 is electron scanning imaging figure (SEM of the 10KV voltages spinning fibre Jing after chloroform process in the embodiment of the present invention 1
Figure)；
Fig. 2 is SEM figure of the 12KV voltages spinning fibre Jing after chloroform process in the embodiment of the present invention 2；
Fig. 3 is the volt-ampere of the Proton Exchange Membrane Fuel Cells of 12KV voltage spinning carbon fiber preparation in the embodiment of the present invention 2
Performance diagram.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, it is below in conjunction with drawings and Examples, right
The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only to explain the present invention, and
It is not used in the restriction present invention.
A kind of preparation method of porous carbon fiber is embodiments provided, is comprised the following steps：
High-voltage electrostatic spinning process is carried out to polyacrylonitrile/polylactic acid (PAN/PLA) mixed liquor, spinning fibre is obtained；
The spinning fibre is placed in chloroform carries out ultrasonic solvent extraction processing；
Heat treatment is carried out to the spinning fibre through ultrasonic solvent extraction processing, porous carbon fiber is obtained.
The preparation method of porous carbon fiber provided in an embodiment of the present invention, using polyacrylonitrile and polylactic acid mixed liquor as spinning
Silk liquid, carries out electrostatic spinning process, high voltage power supply is loaded on the spinning liquid using electrostatic field, make the molecule of spinning liquid
Electrostatic with certain density, when electrostatic repulsion is enough, solution is drawn into fiber, fiber solidifying while solvent volatilizees
Molding, and spinning liquid is stretched under electrostatic and do not rupture, with preferably into fine type.Then by carrying out chloroform to spinning fibre
Ultrasonic solvent is extracted, and the PLA on chloroform soluble solution fiber manufactures porous on the spinning fibre.
The preparation method of porous carbon fiber provided in an embodiment of the present invention, quick, simple low cost, and controllable standby nanometer
Fiber.Prepared porous carbon fiber, with big surface-to-volume ratio and diameter is adjustable, a diameter of 200～600nm.
Specifically, the PAN/PLA mixed liquors are mixed with PLA solution by PAN solution；The PAN solution is molten with PLA
The solvent of liquid is dimethylformamide (DMF).The mass concentration of the PAN solution be 5%-11%, preferably 9%, the PLA
The mass concentration of solution be 3%-5%, preferably 5%；The PAN solution is 0.5～4 with the mass ratio of PLA solution:1, preferably
80:20 or 70:30.By the concentration and mass ratio that control PAN solution and PLA solution, electrostatic repulsion is made to be drawn into solution
The time of fiber reach with the time that solvent volatilizees it is consistent, so as to quickly obtain porous carbon fiber.
Specifically, in -1-3KV, over-pressure control is in 8-16KV for the spinning vacuum cavitations that the high-voltage electrostatic spinning is processed.Institute
The charging rate for stating high-voltage electrostatic spinning process is 1-3mL/h, and spinning distance is 8-20cm.By adjusting positive and negative pressure and charging
Speed, it is ensured that solution is drawn into fiber when electrostatic repulsion is enough, fiber solidifying molding while solvent volatilizees, and spinning liquid
It is stretched under electrostatic and does not rupture, with preferably into fine type.
Specifically, the time of the ultrasonic solvent extraction processing is 20-50min, and supersonic frequency is 6-9Hz.
Specifically, the heat treatment process includes：
Pre-oxidation treatment is carried out under air conditionses, then carbonization treatment is carried out under argon protection.
The pre-oxidation treatment includes：
By temperature in 2h from room temperature to 250～300 DEG C, be incubated 0.5～2.5h；
The carbonization treatment includes：
Temperature is warming up to into 800-1100 DEG C in 2h under argon protection, 2h is incubated.
The embodiment of the present invention additionally provides a kind of porous carbon fiber for Proton Exchange Membrane Fuel Cells, the porous carbon
Fiber is made using above-mentioned preparation method.Porous carbon fiber prepared by the embodiment of the present invention, by carrying out chlorine to spinning fibre
The extraction of imitative ultrasonic solvent, manufactures porous on fiber, for Proton Exchange Membrane Fuel Cells gas diffusion layers when, with preferable
Oxygen transmission, and need not additionally coat microporous layers, so as to effectively alleviate Proton Exchange Membrane Fuel Cells in prior art
Exist at higher current densities and concentration polarization phenomenon that is not enough and causing is supplied due to oxygen.
The embodiment of the present invention additionally provides the preparation method of above-mentioned membrane electrode of fuel batter with proton exchange film, and activated carbon is born
The platinum catalyst (Pt/C) of load is coated on smooth politef (PTFE) thin slice using ultrasonic spray technique, has been sprayed
Anode, PEM and the PTFE thin slices for being sprayed with catalyst are carried out hot pressing, hot pressing in the pressure of 135 DEG C and 4MPa by Cheng Hou
Again PTFE thin slices are slowly torn after good, the catalyst on former PTFE thin slices is completely transferred on PEM, finally with
Carbon fiber forms complete membrane electrode when assembled battery.
Specifically, the consumption of the catalyst is 2mg/cm2, the pad is 8cm × 8cm PTFE thin slices.
Specifically, the preparation method includes：
Pt/C and perfluoro sulfonic acid membrane (Nafion) are dissolved in 100-140mL dehydrated alcohol, supersound process；The ultrasound
The frequency of process is 6-9Hz；
Solution after ultrasound is carried out into ultrasonic spraying.When the frequency of ultrasound spraying is 40kHz, atomizing particle average diameter is
40 microns, be 20 microns during 95kHz.
Wherein, the consumption of Pt/C is the 0.1%～0.2% of ultrasonic spray solution quality.It is described ultrasound spraying temperature be
40～60 DEG C.
The embodiment of the present invention additionally provides a proton exchanging film fuel battery, including above-mentioned porous carbon fiber.This
The Proton Exchange Membrane Fuel Cells that bright embodiment is provided, the porous carbon fiber is used to prepare Proton Exchange Membrane Fuel Cells
Gas diffusion layers.The gas diffusion layers for being used have preferable oxygen transporting, thus with preferably performance, in high humility
Can use with low-humidity environment.The Proton Exchange Membrane Fuel Cells is 0～300mA/cm in current density range2Condition
Under, its power density is 70～90mW/cm2。
Technical scheme is described further below in conjunction with specific embodiment.
Embodiment 1
The handling process of spinning fibre：
Prepare PAN solution：0.189g PAN are taken in the small beaker of 25mL, 1.911g DMF is added, is positioned over magnetic force and stirs
Mix；Prepare PLA solution：0.045g PLA are taken in the small beaker of 25mL, 0.855g DMF is added, is positioned over
24h is stirred on magnetic stirring apparatuss；Then by PAN/PLA=70:30 are mixed, and are positioned on magnetic stirring apparatuss and are stirred 12h, obtain
To the spinning liquid of clear.Aluminium foil is attached on collection cylinder, then spinning mixture is poured in 2.5mL syringes, assembling is spun
Silk instrument, adjusts flow velocity 1-3mL/h, spinning apart from 12cm, spinning voltage (negative pressure -2KV, malleation 8KV, voltage difference are 10KV),
Carry out spinning.
Chloroform solvent supersound process is carried out to spinning fibre：
Fiber after spinning is placed in 250mL beakers, pours 20-40mL chloroforms, chloroform ultrasonic time 20min, supersonic frequency into
Rate 8Hz, carries out ultrasonic extraction.Under ultrasound, Jing extractions can dissolve the PLA on fiber, form porous shape.Treat that ultrasound is completed
Afterwards, deionized water is cleaned repeatedly, dries 24h.
Spinning fibre after chloroform is processed carries out heat treatment：
Fiber after drying is placed in tube furnace and is pre-oxidized and carbonization treatment, the pre-oxidation extraction under air conditionses
Fiber afterwards, pretreatment temperature are warming up to 280 DEG C in 2h, be incubated 2h, then carbonization treatment is carried out under argon protection, carbonization temperature
Degree is warming up to 1100 DEG C in 2h, is incubated 2h, obtains porous carbon fiber.
Ultrasound spraying and assembling membrane electrode：
First PTFE pads are placed on ultrasonic flush coater, spray solution is mounted in 20mL syringes, remaining solution enters
Row supersound process so as to disperse evenly, 40 DEG C of ultrasonic spraying temperature.Under the promotion of automatic spraying machine, with 0.4mL per minute
Speed carry out even application, catalyst is dispersed in its surface, after the completion of spraying, puts it in baking oven, at 20-40 DEG C
Under the conditions of, drying.Finally, the size that can be used can be cut into according to the model of Proton Exchange Membrane Fuel Cells.Spray
PTFE pads afterwards should be preserved in the case where room temperature sealed environment is dried.The sample for having sprayed is cut into into 2.24cm × 2.24cm
Size, is down followed successively by as under：Anode, PEM, the order of the PTFE pads for being sprayed with catalyst are placed, then are entered
Row hot pressing treats its cooling, slowly by PTFE pads for membrane electrode, 135 DEG C of hot pressing temperature, hot pressing time 4min after the completion of hot pressing
Piece is taken off, then by anode and PEM together next, being finally cut into the cathode porous carbon fiber for preparing
2.24cm × 2.24cm sizes, are placed on the negative electrode of membrane electrode, and assembled battery carries out performance test.
What is obtained in the present embodiment is the spinning fibre of chloroform supersound process under 10KV voltages, and its SEM figure is as shown in Figure 1.
The porous carbon fiber prepared by the use of under 10KV voltages as cathode gas diffusion layer, current density range be 0～
300mA/cm2Under conditions of, maximum power density is 75mW/cm in atmosphere2。
Embodiment 2
The handling process of spinning fibre is：
Prepare PAN solution：0.189g PAN are taken in the small beaker of 25mL, 1.911g DMF is added, is positioned over magnetic force and stirs
Mix；Prepare PLA solution：0.045g PLA are taken in the small beaker of 25mL, 0.855g DMF is added, is positioned over
24h is stirred on magnetic stirring apparatuss；Then by PAN/PLA=70:30 are mixed, and are positioned on magnetic stirring apparatuss and are stirred 12h, obtain
To the spinning liquid of clear.Aluminium foil is attached on collection cylinder, then spinning mixture is poured in 2.5mL syringes, assembling is spun
Silk instrument, adjusts flow velocity 1-3mL/h, spinning apart from 12cm, spinning voltage (negative pressure -2KV, malleation 10KV, voltage difference are 12KV),
Carry out spinning.
Chloroform solvent supersound process is carried out to spinning fibre：
Fiber after spinning is placed in 250mL beakers, pours 20-40mL chloroforms, chloroform ultrasonic time 20min, supersonic frequency into
Rate 8Hz, carries out ultrasonic extraction.Under ultrasound, Jing extractions can dissolve the PLA on fiber, form porous shape.Treat that ultrasound is completed
Afterwards, deionized water is cleaned repeatedly, dries 24h.
Spinning fibre after chloroform is processed carries out heat treatment：
Fiber after drying is placed in tube furnace and is pre-oxidized and carbonization treatment, the pre-oxidation extraction under air conditionses
Fiber afterwards, pretreatment temperature are warming up to 280 DEG C in 2h, be incubated 2h, then carbonization treatment is carried out under argon protection, carbonization temperature
Degree is warming up to 1100 DEG C in 2h, is incubated 2h, obtains porous carbon fiber.
Ultrasound spraying and assembling membrane electrode：
First PTFE pads are placed on ultrasonic flush coater, spray solution is mounted in 20mL syringes, remaining solution enters
Row supersound process so as to disperse evenly, 40 DEG C of ultrasonic spraying temperature.Under the promotion of automatic spraying machine, with 0.4mL per minute
Speed carry out even application, catalyst is dispersed in its surface, after the completion of spraying, puts it in baking oven, at 20-40 DEG C
Under the conditions of, drying.Finally, the size that can be used can be cut into according to the model of Proton Exchange Membrane Fuel Cells.Spray
PTFE pads afterwards should be preserved in the case where room temperature sealed environment is dried.The sample for having sprayed is cut into into 2.24cm × 2.24cm
Size, is down followed successively by as under：Anode, PEM, the order of the PTFE pads for being sprayed with catalyst are placed, then are entered
Row hot pressing treats its cooling, slowly by PTFE pads for membrane electrode, 135 DEG C of hot pressing temperature, hot pressing time 4min after the completion of hot pressing
Piece is taken off, then by anode and PEM together next, being finally cut into the cathode porous carbon fiber for preparing
2.24cm × 2.24cm sizes, are placed on the negative electrode of membrane electrode, and assembled battery carries out performance test.
The rear spinning fibre for being chloroform supersound process under 12KV voltages, its SEM image such as Fig. 2 institutes are obtained in the present embodiment
Show.I-V characteristic curve of cell such as Fig. 3 institute of the porous carbon fiber being prepared into using under 12KV voltages as cathode gas diffusion layer
Show, be 0～300mA/cm in current density range2Under conditions of, maximum power density is 81mW/cm in atmosphere2。
Embodiment 3
The handling process of spinning fibre is：
Prepare PAN solution：0.189g PAN are taken in the small beaker of 25mL, 1.911g DMF is added, is positioned over magnetic force and stirs
Mix；Prepare PLA solution：0.045g PLA are taken in the small beaker of 25mL, 0.855g DMF is added, is positioned over
24h is stirred on magnetic stirring apparatuss；Then by PAN/PLA=70:30 are mixed, and are positioned on magnetic stirring apparatuss and are stirred 12h, obtain
To the spinning liquid of clear.Aluminium foil is attached on collection cylinder, then spinning mixture is poured in 2.5mL syringes, assembling is spun
Silk instrument, adjusts flow velocity 1-3mL/h, spinning apart from 12cm, spinning voltage (negative pressure -2KV, malleation 12KV, voltage difference are 14KV),
Carry out spinning.
Chloroform solvent supersound process is carried out to spinning fibre：
Fiber after spinning is placed in 250mL beakers, pours 20-40mL chloroforms, chloroform ultrasonic time 20min, supersonic frequency into
Rate 8Hz, carries out ultrasonic extraction.Under ultrasound, Jing extractions can dissolve the PLA on fiber, form porous shape.Treat that ultrasound is completed
Afterwards, deionized water is cleaned repeatedly, dries 24h.
Spinning fibre after chloroform is processed carries out heat treatment：
Fiber after drying is placed in tube furnace and is pre-oxidized and carbonization treatment, the pre-oxidation extraction under air conditionses
Fiber afterwards, pretreatment temperature are warming up to 280 DEG C in 2h, be incubated 2h, then carbonization treatment is carried out under argon protection, carbonization temperature
Degree is warming up to 1100 DEG C in 2h, is incubated 2h, obtains porous carbon fiber.
Ultrasound spraying and assembling membrane electrode：
First PTFE pads are placed on ultrasonic flush coater, spray solution is mounted in 20mL syringes, remaining solution enters
Row supersound process so as to disperse evenly, 40 DEG C of ultrasonic spraying temperature.Under the promotion of automatic spraying machine, with 0.4mL per minute
Speed carry out even application, catalyst is dispersed in its surface, after the completion of spraying, puts it in baking oven, at 20-40 DEG C
Under the conditions of, drying.Finally, the size that can be used can be cut into according to the model of Proton Exchange Membrane Fuel Cells.Spray
PTFE pads afterwards should be preserved in the case where room temperature sealed environment is dried.The sample for having sprayed is cut into into 2.24cm × 2.24cm
Size, is down followed successively by as under：Anode, PEM, the order of the PTFE pads for being sprayed with catalyst are placed, then are entered
Row hot pressing treats its cooling, slowly by PTFE pads for membrane electrode, 135 DEG C of hot pressing temperature, hot pressing time 4min after the completion of hot pressing
Piece is taken off, then by anode and PEM together next, being finally cut into the cathode porous carbon fiber for preparing
2.24cm × 2.24cm sizes, are placed on the negative electrode of membrane electrode, and assembled battery carries out performance test.
It is the spinning fibre prepared under 14KV voltages to obtain in the present embodiment.Using the porous prepared under 12KV voltages
Carbon fiber, as cathode gas diffusion layer, is 0～300mA/cm in current density range2Under conditions of, highest work(in atmosphere
Rate density is 78mW/cm2。
Embodiment 4
The handling process of spinning fibre is：
Prepare PAN solution：0.189g PAN are taken in the small beaker of 25mL, 1.911g DMF is added, is positioned over magnetic force and stirs
Mix；Prepare PLA solution：0.045g PLA are taken in the small beaker of 25mL, 0.855g DMF is added, is positioned over
24h is stirred on magnetic stirring apparatuss；Then by PAN/PLA=70:30 are mixed, and are positioned on magnetic stirring apparatuss and are stirred 12h, obtain
To the spinning liquid of clear.Aluminium foil is attached on collection cylinder, then spinning mixture is poured in 2.5mL syringes, assembling is spun
Silk instrument, adjusts flow velocity 1-3mL/h, spinning apart from 12cm, spinning voltage (negative pressure -2KV, malleation 14KV, voltage difference are 16KV),
Carry out spinning.
Chloroform solvent supersound process is carried out to spinning fibre：
Fiber after spinning is placed in 250mL beakers, pours 20-40mL chloroforms, chloroform ultrasonic time 20min, supersonic frequency into
Rate 8Hz, carries out ultrasonic extraction.Under ultrasound, Jing extractions can dissolve the PLA on fiber, form porous shape.Treat that ultrasound is completed
Afterwards, deionized water is cleaned repeatedly, dries 24h.
Spinning fibre after chloroform is processed carries out heat treatment：
Fiber after drying is placed in tube furnace and is pre-oxidized and carbonization treatment, the pre-oxidation extraction under air conditionses
Fiber afterwards, pretreatment temperature are warming up to 280 DEG C in 2h, be incubated 2h, then carbonization treatment is carried out under argon protection, carbonization temperature
Degree is warming up to 1100 DEG C in 2h, is incubated 2h, obtains porous carbon fiber.
Ultrasound spraying and assembling membrane electrode：
First PTFE pads are placed on ultrasonic flush coater, spray solution is mounted in 20mL syringes, remaining solution enters
Row supersound process so as to disperse evenly, 40 DEG C of ultrasonic spraying temperature.Under the promotion of automatic spraying machine, with 0.4mL per minute
Speed carry out even application, catalyst is dispersed in its surface, after the completion of spraying, puts it in baking oven, at 20-40 DEG C
Under the conditions of, drying.Finally, the size that can be used can be cut into according to the model of Proton Exchange Membrane Fuel Cells.Spray
PTFE pads afterwards should be preserved in the case where room temperature sealed environment is dried.The sample for having sprayed is cut into into 2.24cm × 2.24cm
Size, is down followed successively by as under：Anode, PEM, the order of the PTFE pads for being sprayed with catalyst are placed, then are entered
Row hot pressing treats its cooling, slowly by PTFE pads for membrane electrode, 135 DEG C of hot pressing temperature, hot pressing time 4min after the completion of hot pressing
Piece is taken off, then by anode and PEM together next, being finally cut into the cathode porous carbon fiber for preparing
2.24cm × 2.24cm sizes, are placed on the negative electrode of membrane electrode, and assembled battery carries out performance test.
It is the spinning fibre prepared under 16KV voltages to obtain in the present embodiment.Using the porous prepared under 16KV voltages
Carbon fiber, as cathode gas diffusion layer, is 0～300mA/cm in current density range2Under conditions of, highest work(in atmosphere
Rate density is 73mW/cm2。
Embodiment 5
The handling process of spinning fibre is：
Prepare PAN solution：0.189g PAN are taken in the small beaker of 25mL, 1.911g DMF is added, is positioned over magnetic force and stirs
Mix；Prepare PLA solution：0.045g PLA are taken in the small beaker of 25mL, 0.855g DMF is added, is positioned over
24h is stirred on magnetic stirring apparatuss；Then by PAN/PLA=70:30 are mixed, and are positioned on magnetic stirring apparatuss and are stirred 12h, obtain
To the spinning liquid of clear.Aluminium foil is attached on collection cylinder, then spinning mixture is poured in 2.5mL syringes, assembling is spun
Silk instrument, adjusts flow velocity 1-3mL/h, spinning apart from 12cm, spinning voltage (negative pressure -2KV, malleation 16KV, 18KV), is spun
Silk.
Chloroform solvent supersound process is carried out to spinning fibre：
Fiber after spinning is placed in 250mL beakers, pours 20-40mL chloroforms, chloroform ultrasonic time 20min, supersonic frequency into
Rate 8Hz, carries out ultrasonic extraction.Under ultrasound, Jing extractions can dissolve the PLA on fiber, form porous shape.Treat that ultrasound is completed
Afterwards, deionized water is cleaned repeatedly, dries 24h.
Spinning fibre after chloroform is processed carries out heat treatment：
Fiber after drying is placed in tube furnace and is pre-oxidized and carbonization treatment, the pre-oxidation extraction under air conditionses
Fiber afterwards, pretreatment temperature are warming up to 280 DEG C in 2h, be incubated 2h, then carbonization treatment is carried out under argon protection, carbonization temperature
Degree is warming up to 1100 DEG C in 2h, is incubated 2h, obtains porous carbon fiber.
Ultrasound spraying and assembling membrane electrode：
First PTFE pads are placed on ultrasonic flush coater, spray solution is mounted in 20mL syringes, remaining solution enters
Row supersound process so as to disperse evenly, 40 DEG C of ultrasonic spraying temperature.Under the promotion of automatic spraying machine, with 0.4mL per minute
Speed carry out even application, catalyst is dispersed in its surface, after the completion of spraying, puts it in baking oven, at 20-40 DEG C
Under the conditions of, drying.Finally, the size that can be used can be cut into according to the model of Proton Exchange Membrane Fuel Cells.Spray
PTFE pads afterwards should be preserved in the case where room temperature sealed environment is dried.The sample for having sprayed is cut into into 2.24cm × 2.24cm
Size, is down followed successively by as under：Anode, PEM, the order of the PTFE pads for being sprayed with catalyst are placed, then are entered
Row hot pressing treats its cooling, slowly by PTFE pads for membrane electrode, 145 DEG C of hot pressing temperature, hot pressing time 4min after the completion of hot pressing
Piece is taken off, then by anode and PEM together next, being finally cut into the cathode porous carbon fiber for preparing
2.24cm × 2.24cm sizes, are placed on the negative electrode of membrane electrode, and assembled battery carries out performance test.
It is the spinning fibre prepared under 18KV voltages to obtain in the present embodiment.Using the porous prepared under 18KV voltages
Carbon fiber, as cathode gas diffusion layer, is 0～300mA/cm in current density range2Under conditions of, highest work(in atmosphere
Rate density is 70mW/cm2。
Presently preferred embodiments of the present invention is the foregoing is only, not to limit the present invention, all essences in the present invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of porous carbon fiber, it is characterised in that comprise the following steps：
High-voltage electrostatic spinning process is carried out to PAN/PLA mixed liquors, spinning fibre is obtained；
The spinning fibre is placed in chloroform carries out ultrasonic solvent extraction processing；
Heat treatment is carried out to the spinning fibre through ultrasonic solvent extraction processing, porous carbon fiber is obtained.
2. preparation method as claimed in claim 1, it is characterised in that the PAN/PLA mixed liquors are molten with PLA by PAN solution
Liquid is mixed；The PAN solution is DMF with the solvent of PLA solution.
3. preparation method as claimed in claim 2, it is characterised in that the mass concentration of the PAN solution is 5%-11%, institute
The mass concentration for stating PLA solution is 3%-5%；The PAN solution is 0.5-4 with the mass ratio of PLA solution:1.
4. preparation method as claimed in claim 1, it is characterised in that the spinning vacuum cavitations that the high-voltage electrostatic spinning is processed
In -1-3KV, over-pressure control is in 8-16KV.
5. preparation method as claimed in claim 1, it is characterised in that the charging rate that the high-voltage electrostatic spinning is processed is 1-
3mL/h, spinning distance are 8-20cm.
6. preparation method as claimed in claim 1, it is characterised in that the time of the ultrasonic solvent extraction processing is 20-
50min, supersonic frequency are 6-9Hz.
7. preparation method as claimed in claim 1, it is characterised in that the heat treatment process includes：
Pre-oxidation treatment is carried out under air conditionses, then carbonization treatment is carried out under argon protection.
8. preparation method as claimed in claim 7, it is characterised in that the pre-oxidation treatment includes：
By temperature in 2h from room temperature to 250-300 DEG C, be incubated 0.5-2.5h；
The carbonization treatment includes：
Temperature is warming up to into 800-1100 DEG C in 2h under argon protection, 2h is incubated.
9. a kind of porous carbon fiber for Proton Exchange Membrane Fuel Cells, it is characterised in that the porous carbon fiber is using power
Profit requires that the preparation method described in 1 to 8 any one is made.
10. a proton exchanging film fuel battery, it is characterised in that including the porous carbon fiber described in claim 9.
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| CN107978768A (en) * | 2017-11-10 | 2018-05-01 | 新奥科技发展有限公司 | A kind of fuel cell module and preparation method thereof |
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| CN113878835A (en) * | 2021-12-08 | 2022-01-04 | 国家电投集团氢能科技发展有限公司 | Polytetrafluoroethylene/carbon fiber composite release film and preparation method and application thereof |
| CN114824298A (en) * | 2022-04-12 | 2022-07-29 | 安徽枡水新能源科技有限公司 | Preparation method of microporous layer in gas diffusion layer of hydrogen fuel cell |
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| CN107978768A (en) * | 2017-11-10 | 2018-05-01 | 新奥科技发展有限公司 | A kind of fuel cell module and preparation method thereof |
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| CN113878835A (en) * | 2021-12-08 | 2022-01-04 | 国家电投集团氢能科技发展有限公司 | Polytetrafluoroethylene/carbon fiber composite release film and preparation method and application thereof |
| CN114824298A (en) * | 2022-04-12 | 2022-07-29 | 安徽枡水新能源科技有限公司 | Preparation method of microporous layer in gas diffusion layer of hydrogen fuel cell |
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