CN110129992A - A kind of fuel cell carbon fiber paper and preparation method thereof - Google Patents

A kind of fuel cell carbon fiber paper and preparation method thereof Download PDF

Info

Publication number
CN110129992A
CN110129992A CN201910479795.1A CN201910479795A CN110129992A CN 110129992 A CN110129992 A CN 110129992A CN 201910479795 A CN201910479795 A CN 201910479795A CN 110129992 A CN110129992 A CN 110129992A
Authority
CN
China
Prior art keywords
carbon fiber
paper
carbon
preparation
preform
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201910479795.1A
Other languages
Chinese (zh)
Other versions
CN110129992B (en
Inventor
缪梦程
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Jiazi New Material Technology Co.,Ltd.
Original Assignee
缪梦程
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 缪梦程 filed Critical 缪梦程
Priority to CN201910479795.1A priority Critical patent/CN110129992B/en
Publication of CN110129992A publication Critical patent/CN110129992A/en
Application granted granted Critical
Publication of CN110129992B publication Critical patent/CN110129992B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4209—Inorganic fibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/60—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in dry state, e.g. thermo-activatable agents in solid or molten state, and heat being applied subsequently
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
    • D06C7/00—Heating or cooling textile fabrics
    • D06C7/04—Carbonising or oxidising
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/41—Phenol-aldehyde or phenol-ketone resins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon

Abstract

The invention discloses a kind of preparation method of fuel cell carbon fiber paper, the preparation method includes the following steps: that (1) carbon fiber and graphiteization is handled；(2) carbon paper preform is prepared using dry method of paper-making method；(3) carbonization treatment is carried out to carbon paper preform；(4) carbon paper preform of carbonization treatment is subjected to chemical vapor deposition；(5) purification processes and graphitization processing are carried out to the carbon paper preform Jing Guo chemical vapor deposition process, the fuel cell carbon fiber paper is finally made.The present invention is more more environmentally friendly than conventional wet lay paper technology, technique is more simplified, cost is lower, can satisfy different fluid diffusion and requires.

Description

A kind of fuel cell carbon fiber paper and preparation method thereof
Technical field
The present invention relates to the preparation technical fields of high-performance carbon fibre paper, expand more particularly, to a kind of different fluid that meets Dissipate desired fuel cell carbon fiber paper and preparation method thereof.
Background technique
Proton Exchange Membrane Fuel Cells (PEMFC) be it is a kind of without burning directly with electrochemical reaction continuously combustion Chemical energy in material and oxidant is directly changed into the power generator of electric energy.As the nova of 21 century fuel cell, proton is handed over The inherent characteristics that membrane cell has not only had both fuel cell are changed, more because it is using Hydrogen Energy as main power source, and there is energy High conversion efficiency, the advantages that pollution-free, starting is fast, battery life length, specific power, high specific energy, in the energy and power-saving technology neck Domain has a wide range of applications.
Carbon fiber paper is Proton Exchange Membrane Fuel Cells core component --- the body portion of diffusion layer electrode, quality It is directly related to the performance of fuel cell.Diffusion layer substrates as fuel cell, it is desirable that hole characteristic (aperture, hole of carbon paper Rate, pore size distribution, hole surface characteristic), resistivity, thermal conductivity, mechanical strength, purity, corrosion resistance etc. reach and meet proton friendship Change membrane cell technical property requirements.Carbon fiber paper manufacturer mainly has German SGL company, toray in the world at present (Toray) company, Ballard company, Canada.The country starts late about the research of carbon fiber paper, has with foreign countries biggish Gap.There is more research in recent years, also there is relevant patent.By patent and correlative theses retrieval discovery, carbon is prepared at present The method of fibrous paper generallys use conventional wet lay paper process (also referred to as copy paper method), that is, uses carbon fiber material, copied using pattern Piece device makes carbon fiber sheet forming, through the drying of plate drier, obtains carbon fiber body paper (carbon paper presoma), is then soaked Stain is prepared into satisfactory carbon fiber paper in resin solution, through techniques such as solidification, carbonization, graphitizations.
However, carbon fiber most distinct issues in wet process is manufactured paper with pulp are dispersion and molding.Carbon fiber is not easy point in mashing It dissipates, generally first passes through high-speed cutting machine them and prescind suitable length.If fiber Qie get Tai is short, often it is easier to disperse, It can be ferreted out the preferable page of evenness, but its intensity is lower.If fiber on the contrary is cut too long, dispersion is more difficult, and being easy to wad a quilt with cotton is polymerized to Group, it is also difficult to be ferreted out the good page of evenness.Meanwhile water-soluble polymer dispersant must be added in dispersion process, keep carbon fiber outstanding It is floating to be uniformly dispersed, then it is sent to copy paper.Macromolecule dispersing agent is added excessively, and carbon fiber slurry concentration is too low, and drainage is too fast, can not It manufactures paper with pulp on common fourdrinier machine and cylinder mould machine；Macromolecule dispersing agent is very little, and fiber is not easy to disperse, and slurry Concentration is too high, and drainage is too slow, is unfavorable for large-scale production.In addition, there is also liquid in production process to arrange for wet papermaking technology The environmental issues such as put.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, the applicant provides a kind of fuel cell carbon fiber papers And preparation method thereof.The present invention is more more environmentally friendly than conventional wet lay paper technology, technique is more simplified, cost is lower, can satisfy difference Fluid diffusion requires.
Technical scheme is as follows:
A kind of fuel cell carbon fiber paper, the carbon fiber paper with a thickness of 0.10-0.30mm, bulk density is 0.30-0.60g/cm3, porosity 60-90%；The resistivity of thickness direction≤0.16 Ω cm, the resistivity of in-plane ≤0.01Ω·cm；Thermal coefficient at room temperature: vertical direction >=1.7W/ (mK), parallel direction >=21W/ (mK)；Gas Transmitance≤50mmH2O/mm。
A kind of preparation method of fuel cell carbon fiber paper, the preparation method include the following steps:
(1) carbon fiber and graphiteization is handled；
(2) carbon paper preform is prepared using dry method of paper-making method；
(3) carbonization treatment is carried out to carbon paper preform；
(4) carbon paper preform of carbonization treatment is subjected to chemical vapor deposition；
(5) purification processes and graphitization processing are carried out to the carbon paper preform Jing Guo chemical vapor deposition process, it is final to make Obtain the fuel cell carbon fiber paper.
The condition of graphitization processing described in step (1) are as follows: by carbon fiber under argon atmosphere, 1800-3000 DEG C Carry out graphitization processing；While removing photoresist, the degree of graphitization of carbon fiber is improved.
The preparation method of carbon paper preform described in step (2) includes the following steps:
1. the carbon fiber of graphitization processing is cut into the carbon fiber that length is 10-100mm；
It is decentralized medium using air, using high speed 2. carrying out shredding to chopped carbon fiber using double roller fibre opening machine Fibrous raw material is separated into single fiber state, then brings chopped carbon fiber into air-flow by the defeated fine machine of air-flow by the roller of revolution Carbon fiber is further combed in carding machine, then by net-forming process, forms nonwoven page；
3. being bonded to nonwoven page at 100-150 DEG C using hot melt adhesive, and it is dried at 80-120 DEG C, at Volume batches, and obtains carbon paper preform.
Step (2) 2. described in roller revolving speed be 3000-7500 revs/min；The air stream transportation fibre machine and air-flow are combed Reason machine uses compressed air for medium, gas flow rate 5-40m/s；The net-forming process is inhaled using vibration to fine machine and vacuum Heavy lapping machine is used cooperatively, and forces chopped carbon fiber sedimentation, and wherein vibration frequency is 800-1200r/min, and pull of vacuum is 800-2000Pa；The nonwoven page with a thickness of 0.01-0.3mm.
Step (2) 3. described in hot melt adhesive be one or both of LDPE, HDPE powder mixing；Pass through dusting Mode is evenly distributed on nonwoven page, is 100-150 DEG C in temperature and is bonded.
The process of carbonization described in step (3) are as follows: phenolic resin or asphaltic resin are used, to single-layer or multi-layer lamination Carbon paper precast body is impregnated, and is solidified 2-8 hours at 180-220 DEG C；Then under nitrogen protection atmosphere, temperature is It is carbonized at 600-1000 DEG C；The performance requirement of fuel cell, control dipping-solidification-carbonization cycle number are 1-5 It is secondary.
The process of chemical vapor deposition described in step (4) are as follows: the carbon paper preform of carbonization treatment is placed on chemical gaseous phase In cvd furnace, to being vacuumized in reacting furnace, when pressure is less than 1000Pa, start to warm up, after temperature is to 900-1150 DEG C, It is passed through propylene and nitrogen mixed gas, the flow of propylene is 2-3L/min, and the flow-rate ratio of propylene and nitrogen is 1:2, deposition pressure For 1000Pa, the final densities and porosity of composite material are controlled by control soaking time 10-100h.
The method of purification processes described in step (5) are as follows: immerse the carbon paper preform Jing Guo chemical vapor deposition process In fluorine-containing or chemical reagent containing chlorine, to purification processes 2-30min is carried out under the conditions of temperature is 20-80 DEG C, eliminate in carbon paper Existing metal and nonmetalloid, then under argon atmosphere, 1800-2700 DEG C of high temperature is graphitized carbon paper Processing, further increases the performance of carbon paper.
Chemical reagent described fluorine-containing or containing chlorine are as follows: one of freon, hydrofluoric acid, hypochlorous acid, hydrochloric acid are a variety of； The mass concentration of the reagent is 0.01-5%.
The present invention is beneficial to be had the technical effect that
(1) it is longer to improve length using dry technique for the manufacturing method relative to traditional carbon fiber paper prefabricated component The dispersibility of chopped carbon fiber.
(2) manufacturing method relative to traditional carbon fiber paper prefabricated component, is improved in carbon fiber paper using dry technique The length of carbon fiber is more advantageous to and obtains high-intensitive carbon paper intensity.
(3) using the carbon fiber paper precast body internal carbon fibers and even pore distribution of dry technique preparation, so that The carbon fiber paper performance of acquisition is uniform.
(4) dipping-solidification-carbonization and chemical vapour deposition technique are used simultaneously, and the performance for being conducive to fuel cell is wanted Seek the performance of adjustment carbon fiber paper.
(5) chemical purification and high temperature graphitization method are used, the performance of carbon fiber paper can be further promoted.
(6) fuel cell prepared by the present invention has excellent electric property, heating conduction with carbon fiber paper, simultaneously also With the series of advantages such as intensity is good, modulus is high.
Specific embodiment
Below with reference to embodiment, the present invention is specifically described.
Embodiment 1:
A kind of preparation method of fuel cell carbon fiber paper, the preparation method include the following steps:
(1) using mass ratio for T700-48K the and T300-48K carbon fiber of 3:7 is raw material, passes through 2400 DEG C of high temperature After graphitization processing, the staple fiber of 50mm is cut into；
(2) using double roller fibre opening machine to chopped carbon fiber carry out shredding, using air be decentralized medium, using turn Fibrous raw material is separated into single fiber state by the revolution at a high speed roller that speed is 6000 revs/min, then passing through flow velocity is 20m/s Air-flow defeated fine machine chopped carbon fiber is brought into air-flow carding machine carbon fiber is further combed, then use vibration frequency Cooperate the vacuum lapping machine that pull of vacuum is 1000Pa to fine machine for the vibration of 960r/min, forces chopped carbon fiber sedimentation, shape At 0.080mm nonwoven page；Finally, bonded to nonwoven page at 120 DEG C using LDPE hot melt adhesive, and at 80 DEG C into Row drying, is batched in rolls, obtains carbon paper preform.
(3) 3 layers of carbon paper preform are impregnated using phenolic resin, and solidified 4 hours at 180 DEG C, then in nitrogen Under protective atmosphere, temperature is carbonized when being 900 DEG C；Repeated impregnations-solidification-carbonization technique is primary.
(4) it will be then placed in chemical vapor deposition stove by the carbon paper preform of step (3) processing, in reacting furnace It vacuumizes, when pressure is less than 1000Pa, starts to warm up, after temperature is to 1050 DEG C, be passed through propylene and nitrogen mixed gas, The flow of propylene is 7L/min, and the flow-rate ratio of propylene and nitrogen is 1:2, deposition pressure 1000Pa, and chemical vapor deposition 10 is small When.
(5) it uses concentration to carry out purification processes 5min to carbon paper at room temperature for 0.1% hydrochloric acid, eliminates and deposited in carbon paper Metal and nonmetalloid, then under argon atmosphere, 2700 DEG C of high temperature to carbon paper carry out graphitization processing 0.5 Hour, further increase the performance of carbon paper.
The performance of made carbon fiber paper: with a thickness of 0.23mm, bulk density is in 0.42g/cm3, porosity 82%；It is flat Face direction resistivity 3.5m Ω cm；Tensile strength is 53N/cm.
Embodiment 2:
A kind of preparation method of fuel cell carbon fiber paper, the preparation method include the following steps:
(1) using mass ratio for the T700-12K carbon fiber of 5:5 and T300-12K carbon fiber is raw material, is passed through After 2500 DEG C of high temperature graphitization processing, the staple fiber of 30mm is cut into.
(2) using double roller fibre opening machine to chopped carbon fiber carry out shredding, using air be decentralized medium, using turn Fibrous raw material is separated into single fiber state by the revolution at a high speed roller that speed is 4000 revs/min, then passing through flow velocity is 15m/s Air-flow defeated fine machine chopped carbon fiber is brought into air-flow carding machine carbon fiber is further combed, then use vibration frequency Cooperate the vacuum lapping machine that pull of vacuum is 800Pa to fine machine for the vibration of 1050r/min, forces chopped carbon fiber sedimentation, shape At 0.2mm nonwoven page；Finally, being bonded to nonwoven page at 120 DEG C using LDPE hot melt adhesive, and carried out at 80 DEG C It is dry, it batches in rolls, obtains carbon paper preform.
(3) single layer carbon paper precast body is impregnated using phenolic resin, and solidified 6 hours at 200 DEG C, then in nitrogen Under gas shielded atmosphere, temperature is carbonized when being 900 DEG C, and repeated impregnations-solidification-carbonization technique is primary.
(4) then by by step (3) processing carbon paper preform temperature be 1050 DEG C, pressure 1000Pa, propylene Flow be 3L/min, when the flow-rate ratio of propylene and nitrogen is 1:2, chemical vapor deposition 15 hours.
(5) it uses concentration to carry out purification processes 15min to carbon paper at room temperature for 0.5% hydrofluoric acid, eliminates in carbon paper Existing metal and nonmetalloid, then under argon atmosphere, 2300 DEG C of high temperature carry out graphitization processing 1 to carbon paper Hour, further increase the performance of carbon paper.
The performance of made carbon fiber paper: thickness is in 0.205mm, and bulk density is in 0.44g/cm3, porosity 80%；It is flat Face direction resistivity 9.8m Ω cm；Tensile strength is 25N/cm.
Embodiment 3:
A kind of preparation method of fuel cell carbon fiber paper, the preparation method include the following steps:
(1) using mass ratio for the T700-24K carbon fiber of 6:4 and T300-24K carbon fiber is raw material, is passed through After 2700 DEG C of high temperature graphitization processing, the staple fiber of 80mm is cut into.
(2) using double roller fibre opening machine to chopped carbon fiber carry out shredding, using air be decentralized medium, using turn Fibrous raw material is separated into single fiber state by the revolution at a high speed roller that speed is 5000 revs/min, then passing through flow velocity is 30m/s Air-flow defeated fine machine chopped carbon fiber is brought into air-flow carding machine carbon fiber is further combed, then use vibration frequency Cooperate the vacuum lapping machine that pull of vacuum is 1500Pa to fine machine for the vibration of 1200r/min, force chopped carbon fiber sedimentation, Form 0.12mm nonwoven page；Finally, bonded to nonwoven page at 120 DEG C using HDPE hot melt adhesive, and at 80 DEG C into Row drying, is batched in rolls, obtains carbon paper preform.
(3) 2 layers of carbon paper precast body are impregnated using phenolic resin, and solidified 4 hours at 200 DEG C.Then in nitrogen Under protective atmosphere, temperature is carbonized when being 900 DEG C, and repeated impregnations-solidification-carbonization technique is primary.
(4) then by by step (3) processing carbon paper preform temperature be 1100 DEG C, pressure 1000Pa, propylene Flow be 4L/min, when the flow-rate ratio of propylene and nitrogen is 1:2, chemical vapor deposition 10 hours.
(5) it uses concentration to carry out purification processes 10min to carbon paper at room temperature for 1% freon, eliminates and deposited in carbon paper Metal and nonmetalloid, then under argon atmosphere, 2500 DEG C of high temperature to carbon paper carry out graphitization processing 1 it is small When, further increase the performance of carbon paper.
The performance of made carbon fiber paper: thickness is in 0.25mm, and bulk density is in 0.40g/cm3, porosity 84%；It is flat Face direction resistivity 6.3m Ω cm；Tensile strength is 35N/cm.
Embodiment 4:
A kind of preparation method of fuel cell carbon fiber paper, the preparation method include the following steps:
(1) using mass ratio for the T700-50K carbon fiber of 4:6 and T300-50K carbon fiber is raw material, is passed through After 2300 DEG C of high temperature graphitizations are handled 1 hour, the staple fiber of 50mm is cut into.
(2) using double roller fibre opening machine to chopped carbon fiber carry out shredding, using air be decentralized medium, using turn Fibrous raw material is separated into single fiber state by the revolution at a high speed roller that speed is 6500 revs/min, then passing through flow velocity is 35m/s The defeated fine machine of air-flow carbon fiber will further be combed in chopped carbon fiber band popularity stream carding machine, then use vibration frequency Cooperate the vacuum lapping machine that pull of vacuum is 1500Pa to fine machine for the vibration of 1200r/min, force chopped carbon fiber sedimentation, Form 0.25mm nonwoven page；Finally, bonded to nonwoven page at 120 DEG C using LDPE hot melt adhesive, and at 80 DEG C into Row drying, is batched in rolls, obtains carbon paper preform.
(3) single layer carbon paper precast body is impregnated using phenolic resin, and solidified 6 hours at 200 DEG C.Then in nitrogen Under gas shielded atmosphere, temperature is carbonized when being 900 DEG C.Repeated impregnations-solidification-carbonization technique is twice.
(4) then by by step (3) processing carbon paper preform temperature be 1100 DEG C, pressure 1000Pa, propylene Flow be 5L/min, when the flow-rate ratio of propylene and nitrogen is 1:2, chemical vapor deposition 10 hours.
(5) it uses concentration to carry out purification processes 15min to carbon paper at room temperature for 1% hydrochloric acid, eliminates and exist in carbon paper Metal and nonmetalloid；Then under argon atmosphere, 2500 DEG C of high temperature carry out carbon paper graphitization processing 1 hour, Further increase the performance of carbon paper.
The performance of made carbon fiber paper: thickness is in 0.25mm, and bulk density is in 0.48g/cm3, porosity 76%；It is flat Face direction resistivity 9.5m Ω cm；Tensile strength is 42N/cm.
Embodiment 5:
A kind of preparation method of fuel cell carbon fiber paper, the preparation method include the following steps:
(1) using mass ratio for the T700-12K carbon fiber of 7:3 and T300-12K carbon fiber is raw material, is passed through After 2300 DEG C of high temperature graphitizations are handled 0.5 hour, the staple fiber of 40mm is cut into.
(2) using double roller fibre opening machine to chopped carbon fiber carry out shredding, using air be decentralized medium, using turn Fibrous raw material is separated into single fiber state by the revolution at a high speed roller that speed is 4500 revs/min, then passing through flow velocity is 20m/s Air-flow defeated fine machine chopped carbon fiber is brought into air-flow carding machine carbon fiber is further combed, then use vibration frequency Cooperate the vacuum lapping machine that pull of vacuum is 950Pa to fine machine for the vibration of 1000r/min, forces chopped carbon fiber sedimentation, shape At 0.10mm nonwoven page；Finally, being bonded to nonwoven page at 120 DEG C using hot melt adhesive, and done at 80 DEG C It is dry, it batches in rolls, obtains carbon paper preform.
(3) 2 layers of carbon paper precast body are impregnated using phenolic resin, and solidified 3 hours at 180 DEG C.Then in nitrogen Under protective atmosphere, temperature is carbonized when being 900 DEG C.
(4) then by by step (3) processing carbon paper preform temperature be 1050 DEG C, pressure 1000Pa, propylene Flow be 3L/min, when the flow-rate ratio of propylene and nitrogen is 1:2, chemical vapor deposition 5 hours.
(5) it uses concentration to carry out purification processes 10min to carbon paper at room temperature for 0.5% hydrochloric acid, eliminates and deposited in carbon paper Metal and nonmetalloid；Then under argon atmosphere, it is small that 2700 DEG C of high temperature carry out graphitization processing 1 to carbon paper When, further increase the performance of carbon paper.
The performance of made carbon fiber paper: thickness is in 0.20mm, and bulk density is in 0.34g/cm3, porosity 88%；It is flat Face direction resistivity 5.8m Ω cm；Tensile strength is 18N/cm.

Claims (10)

1. a kind of fuel cell carbon fiber paper, which is characterized in that the carbon fiber paper with a thickness of 0.10-0.30mm, volume Density is 0.30-0.60g/cm3, porosity 60-90%；The resistivity of thickness direction≤0.16 Ω cm, in-plane Resistivity≤0.01 Ω cm；Thermal coefficient at room temperature: vertical direction >=1.7W/ (mK), parallel direction >=21W/ (mK)； Gas permeation rate≤50mmH2O/mm。
2. the preparation method of fuel cell carbon fiber paper described in a kind of claim 1, which is characterized in that the preparation method packet Include following steps:
(1) carbon fiber and graphiteization is handled；
(2) carbon paper preform is prepared using dry method of paper-making method；
(3) carbonization treatment is carried out to carbon paper preform；
(4) carbon paper preform of carbonization treatment is subjected to chemical vapor deposition；
(5) purification processes and graphitization processing are carried out to the carbon paper preform Jing Guo chemical vapor deposition process, institute is finally made State fuel cell carbon fiber paper.
3. preparation method according to claim 2, which is characterized in that the condition of graphitization processing described in step (1) are as follows: By carbon fiber under argon atmosphere, 1800-3000 DEG C of progress graphitization processing；While removing photoresist, the stone of carbon fiber is improved Mo Huadu.
4. preparation method according to claim 2, which is characterized in that the preparation side of carbon paper preform described in step (2) Method includes the following steps:
1. the carbon fiber of graphitization processing is cut into the carbon fiber that length is 10-100mm；
It is decentralized medium using air, using revolution at a high speed 2. carrying out shredding to chopped carbon fiber using double roller fibre opening machine Roller, fibrous raw material is separated into single fiber state, then air-flow combing into is brought chopped carbon fiber by the defeated fine machine of air-flow Carbon fiber is further combed in machine, then by net-forming process, forms nonwoven page；
3. being bonded to nonwoven page at 100-150 DEG C using hot melt adhesive, and it is dried at 80-120 DEG C, it is coiled to roll up It takes, obtains carbon paper preform.
5. the preparation method according to claim 4, which is characterized in that step (2) 2. described in roller revolving speed be 3000- 7500 revs/min；The air stream transportation fibre machine and air-flow carding machine use compressed air for medium, gas flow rate 5-40m/s； The net-forming process is inhaled heavy lapping machine to fine machine and vacuum using vibration and is used cooperatively, and chopped carbon fiber sedimentation is forced, wherein shaking Dynamic frequency is 800-1200r/min, pull of vacuum 800-2000Pa；The nonwoven page with a thickness of 0.01-0.3mm.
6. the preparation method according to claim 4, which is characterized in that step (2) 3. described in hot melt adhesive be LDPE, HDPE The mixing of one or both of powder；Nonwoven page is evenly distributed on by way of dusting, temperature be 100-150 DEG C into Row bonding.
7. preparation method according to claim 2, which is characterized in that the process of carbonization described in step (3) are as follows: use phenol Urea formaldehyde or asphaltic resin impregnate carbon paper precast body, and solidify 2-8 hours at 180-220 DEG C；Then in nitrogen Under protective atmosphere, temperature is carbonized when being 600-1000 DEG C；The performance requirement of fuel cell controls dipping-solidification-carbon Changing cycle-index is 1-5 times.
8. preparation method according to claim 2, which is characterized in that the process of chemical vapor deposition described in step (4) Are as follows: the carbon paper preform of carbonization treatment is placed in chemical vapor deposition stove, to being vacuumized in reacting furnace, when pressure is less than It when 1000Pa, starts to warm up, after temperature is to 900-1150 DEG C, is passed through propylene and nitrogen mixed gas, the flow of propylene is 2- The flow-rate ratio of 3L/min, propylene and nitrogen is 1:2, deposition pressure 1000Pa, is controlled by control soaking time 10-100h The final densities and porosity of composite material.
9. preparation method according to claim 2, which is characterized in that the method for purification processes described in step (5) are as follows: will Carbon paper preform by chemical vapor deposition process immerses in fluorine-containing or chemical reagent containing chlorine, is 20-80 DEG C of item in temperature To purification processes 2-30min is carried out under part, metal and nonmetalloid present in carbon paper are eliminated, then in argon atmosphere Under, 1800-2700 DEG C of high temperature carries out graphitization processing to carbon paper, further increases the performance of carbon paper.
10. preparation method according to claim 9, which is characterized in that chemical reagent described fluorine-containing or containing chlorine are as follows: fluorine benefit One of high, hydrofluoric acid, hypochlorous acid, hydrochloric acid are a variety of；The mass concentration of the reagent is 0.01-5%.
CN201910479795.1A 2019-06-04 2019-06-04 Carbon fiber paper for fuel cell and preparation method thereof Active CN110129992B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910479795.1A CN110129992B (en) 2019-06-04 2019-06-04 Carbon fiber paper for fuel cell and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910479795.1A CN110129992B (en) 2019-06-04 2019-06-04 Carbon fiber paper for fuel cell and preparation method thereof

Publications (2)

Publication Number Publication Date
CN110129992A true CN110129992A (en) 2019-08-16
CN110129992B CN110129992B (en) 2021-04-27

Family

ID=67580202

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910479795.1A Active CN110129992B (en) 2019-06-04 2019-06-04 Carbon fiber paper for fuel cell and preparation method thereof

Country Status (1)

Country Link
CN (1) CN110129992B (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111900417A (en) * 2020-07-31 2020-11-06 齐鲁工业大学 Preparation method of carbon paper for high-carbon-content fuel cell gas diffusion layer
CN112761025A (en) * 2019-11-04 2021-05-07 广州汽车集团股份有限公司 Carbon paper for gas diffusion layer, preparation method thereof and fuel cell
CN113136737A (en) * 2021-02-23 2021-07-20 上海嘉资新材料有限公司 Ultrathin carbon fiber paper, preparation method and equipment thereof, and preparation method and equipment of corresponding carbon fiber paper blank
CN113135000A (en) * 2021-03-08 2021-07-20 上海嘉资新材料有限公司 High-flux carbon paper for fuel cell and preparation method thereof
CN113147135A (en) * 2020-11-18 2021-07-23 上海嘉资新材料有限公司 Carbon fiber paper, flexible curlable carbon paper made of carbon fiber base paper and preparation method and system thereof
CN113258081A (en) * 2021-06-15 2021-08-13 长沙理工大学 Modified electrode for flow battery, preparation method of modified electrode and flow battery
CN114256475A (en) * 2021-12-15 2022-03-29 上海嘉资新材料科技有限公司 Substrate layer of fuel cell gas diffusion layer, and preparation method and device thereof
CN114597428A (en) * 2022-03-10 2022-06-07 湖南金博氢能科技有限公司 Flexible carbon paper, preparation method thereof, gas diffusion layer and fuel cell

Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2190728A1 (en) * 1972-07-03 1974-02-01 Kureha Chemical Ind Co Ltd
CA981326A (en) * 1970-11-18 1976-01-06 Kipp G. Pearson Catalytic anode for fuel cell
CN1109844A (en) * 1993-11-01 1995-10-11 大阪瓦斯株式会社 Porous carbonaceous material and a method for producing the same
CN101083330A (en) * 2006-03-17 2007-12-05 通用汽车环球科技运作公司 Gas diffusion media and fuel cell
CN101462716A (en) * 2008-05-05 2009-06-24 陈怀军 Preparation technique for purifying graphite by high temperature method
CN101492895A (en) * 2009-02-18 2009-07-29 程显军 Carbon fibre cloth for gaseous diffusion layer of fuel cell electrode
CN101613100A (en) * 2008-06-25 2009-12-30 中国科学院大连化学物理研究所 The biomass-based graphitized carbon and the microwave preparation of carbon-carbon composite
CN101798774A (en) * 2010-04-01 2010-08-11 东华大学 Carbon fiber paper and preparation method thereof
CN102361090A (en) * 2010-05-20 2012-02-22 株式会社协进I&C Method of preparing carbon substrate for gas diffusion layer of polymer electrolyte fuel cell, carbon substrate prepard by using the method, and system for manufacturing the same
CN103556543A (en) * 2013-10-24 2014-02-05 浙江科技学院 Special high-performance carbon paper for gas diffusion layer of fuel cell and preparation method of carbon paper
CN104230368A (en) * 2014-09-26 2014-12-24 辽宁奥亿达新材料有限公司 Pitch-based carbon fiber nonwoven felt insulation board and manufacturing method thereof
CN104313937A (en) * 2014-09-29 2015-01-28 陈嗳 Carbon paper
CN105110794A (en) * 2015-08-07 2015-12-02 常州富烯科技股份有限公司 Graphene film and preparation method therefor
CN105439607A (en) * 2015-11-17 2016-03-30 安徽弘昌新材料有限公司 Hard carbon fiber insulating felt and preparation method thereof
CN106436439A (en) * 2016-09-22 2017-02-22 天津工业大学 Preparation method of carbon fiber paper
CN106560944A (en) * 2015-09-25 2017-04-12 中国科学院大连化学物理研究所 Porous carbon fiber paper electrode material for all-vanadium redox flow battery, and preparation and application thereof
CN108610080A (en) * 2018-05-16 2018-10-02 湖南世鑫新材料有限公司 A kind of preparation method of the carbon carbon composite with endoporus and carbon ceramic composite material
CN108914681A (en) * 2018-07-06 2018-11-30 天津工业大学 A kind of preparation method of carbon fiber paper

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA981326A (en) * 1970-11-18 1976-01-06 Kipp G. Pearson Catalytic anode for fuel cell
FR2190728A1 (en) * 1972-07-03 1974-02-01 Kureha Chemical Ind Co Ltd
CN1109844A (en) * 1993-11-01 1995-10-11 大阪瓦斯株式会社 Porous carbonaceous material and a method for producing the same
CN101083330A (en) * 2006-03-17 2007-12-05 通用汽车环球科技运作公司 Gas diffusion media and fuel cell
CN101462716A (en) * 2008-05-05 2009-06-24 陈怀军 Preparation technique for purifying graphite by high temperature method
CN101613100A (en) * 2008-06-25 2009-12-30 中国科学院大连化学物理研究所 The biomass-based graphitized carbon and the microwave preparation of carbon-carbon composite
CN101492895A (en) * 2009-02-18 2009-07-29 程显军 Carbon fibre cloth for gaseous diffusion layer of fuel cell electrode
CN101798774A (en) * 2010-04-01 2010-08-11 东华大学 Carbon fiber paper and preparation method thereof
CN102361090A (en) * 2010-05-20 2012-02-22 株式会社协进I&C Method of preparing carbon substrate for gas diffusion layer of polymer electrolyte fuel cell, carbon substrate prepard by using the method, and system for manufacturing the same
CN103556543A (en) * 2013-10-24 2014-02-05 浙江科技学院 Special high-performance carbon paper for gas diffusion layer of fuel cell and preparation method of carbon paper
CN104230368A (en) * 2014-09-26 2014-12-24 辽宁奥亿达新材料有限公司 Pitch-based carbon fiber nonwoven felt insulation board and manufacturing method thereof
CN104313937A (en) * 2014-09-29 2015-01-28 陈嗳 Carbon paper
CN105110794A (en) * 2015-08-07 2015-12-02 常州富烯科技股份有限公司 Graphene film and preparation method therefor
CN106560944A (en) * 2015-09-25 2017-04-12 中国科学院大连化学物理研究所 Porous carbon fiber paper electrode material for all-vanadium redox flow battery, and preparation and application thereof
CN105439607A (en) * 2015-11-17 2016-03-30 安徽弘昌新材料有限公司 Hard carbon fiber insulating felt and preparation method thereof
CN106436439A (en) * 2016-09-22 2017-02-22 天津工业大学 Preparation method of carbon fiber paper
CN108610080A (en) * 2018-05-16 2018-10-02 湖南世鑫新材料有限公司 A kind of preparation method of the carbon carbon composite with endoporus and carbon ceramic composite material
CN108914681A (en) * 2018-07-06 2018-11-30 天津工业大学 A kind of preparation method of carbon fiber paper

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
于樹等: "以丙烯为碳源气的化学气相沉积模型", 《炭素技术》 *
朱相丽等: "燃料电池用碳材料的研究进展", 《电源技术》 *
肖勇等: "CVD法制备质子交换膜燃料电池用炭纤维纸", 《中南大学学报（自然科学版）》 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112761025A (en) * 2019-11-04 2021-05-07 广州汽车集团股份有限公司 Carbon paper for gas diffusion layer, preparation method thereof and fuel cell
CN112761025B (en) * 2019-11-04 2022-11-11 广州汽车集团股份有限公司 Carbon paper for gas diffusion layer, preparation method thereof and fuel cell
CN111900417A (en) * 2020-07-31 2020-11-06 齐鲁工业大学 Preparation method of carbon paper for high-carbon-content fuel cell gas diffusion layer
CN111900417B (en) * 2020-07-31 2022-03-29 齐鲁工业大学 Preparation method of carbon paper for high-carbon-content fuel cell gas diffusion layer
WO2022105688A1 (en) * 2020-11-18 2022-05-27 上海嘉资新材料科技有限公司 Carbon fiber paper, flexible and rollable carbon paper prepared from carbon fiber base paper, and preparation method therefor and system thereof
CN113147135A (en) * 2020-11-18 2021-07-23 上海嘉资新材料有限公司 Carbon fiber paper, flexible curlable carbon paper made of carbon fiber base paper and preparation method and system thereof
CN113147135B (en) * 2020-11-18 2023-07-28 上海嘉资新材料科技有限公司 Carbon fiber paper, flexible and crimpable carbon paper made of carbon fiber raw paper, and preparation method and system thereof
CN113136737A (en) * 2021-02-23 2021-07-20 上海嘉资新材料有限公司 Ultrathin carbon fiber paper, preparation method and equipment thereof, and preparation method and equipment of corresponding carbon fiber paper blank
CN113136737B (en) * 2021-02-23 2023-07-28 上海嘉资新材料科技有限公司 Preparation method and equipment of carbon fiber paper blank and ultrathin carbon fiber paper
CN113135000A (en) * 2021-03-08 2021-07-20 上海嘉资新材料有限公司 High-flux carbon paper for fuel cell and preparation method thereof
WO2022188891A1 (en) * 2021-03-08 2022-09-15 上海嘉资新材料科技有限公司 High-throughput carbon paper for fuel cell, and preparation method therefor
CN113258081B (en) * 2021-06-15 2021-11-19 长沙理工大学 Modified electrode for flow battery, preparation method of modified electrode and flow battery
CN113258081A (en) * 2021-06-15 2021-08-13 长沙理工大学 Modified electrode for flow battery, preparation method of modified electrode and flow battery
CN114256475A (en) * 2021-12-15 2022-03-29 上海嘉资新材料科技有限公司 Substrate layer of fuel cell gas diffusion layer, and preparation method and device thereof
CN114597428A (en) * 2022-03-10 2022-06-07 湖南金博氢能科技有限公司 Flexible carbon paper, preparation method thereof, gas diffusion layer and fuel cell

Also Published As

Publication number Publication date
CN110129992B (en) 2021-04-27

Similar Documents

Publication Publication Date Title
CN110129992A (en) A kind of fuel cell carbon fiber paper and preparation method thereof
US9825304B2 (en) Porous electrode substrate, method for manufacturing same, precursor sheet, membrane electrode assembly, and polymer electrolyte fuel cell
CN102361090B (en) Method of preparing carbon substrate for gas diffusion layer of polymer electrolyte fuel cell, carbon substrate prepard by using the method, and system for manufacturing the same
CN105870383B (en) A kind of battery capacitor barrier film and preparation method thereof
CN111900418B (en) Preparation method of carbon paper precursor for gas diffusion layer of fuel cell
CN107086311B (en) Utilize the method for graphene carbon cellulose fiber conductive paper production fuel cell porous diffusion layer electrode plate
Fan et al. MXene enhanced 3D needled waste denim felt for high-performance flexible supercapacitors
JP4669610B2 (en) Water transfer plate and method of use
JP2004511672A (en) Conductive non-woven fabric
CN101591178A (en) The manufacturing of rigid carbon-fiber heat-insulation material and surface treatment method
CA2767204C (en) Porous electrode substrate and method for producing the same
US20020058179A1 (en) Electrical conducting, non-woven textile fabric
CN105576255B (en) A kind of high power density pemfc stack Special polar board fabrication method
JP4051714B2 (en) Electrode substrate for polymer electrolyte fuel cell and method for producing the same
JP4266699B2 (en) Porous electrode substrate for polymer electrolyte fuel cell and method for producing the same
CN110485191A (en) Wet process is manufactured paper with pulp gas diffusing layer of fuel cell electrode carbon fiber paper and preparation method thereof
CN113774720B (en) Carbon fiber paper and preparation method thereof
CN113544888B (en) Carbon electrode material and redox cell
CN110247065B (en) Low-cost continuous industrial production process of gas diffusion layer of fuel cell
CN104313937A (en) Carbon paper
CN112038654A (en) Graphene composite slurry, bipolar plate preparation method and bipolar plate
WO2022105688A1 (en) Carbon fiber paper, flexible and rollable carbon paper prepared from carbon fiber base paper, and preparation method therefor and system thereof
JP2685365B2 (en) Manufacturing method of porous carbon plate
CN113026412B (en) Method for preparing heat-conducting graphite film by utilizing artificial graphite film leftover material
JPH01253164A (en) Fuel cell board resistant against corrosion and its manufacture

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20210720

Address after: 200131 building 10, No. 860, Xinyang Road, Lingang xinpian District, pilot Free Trade Zone, Pudong New Area, Shanghai

Patentee after: Shanghai Jiazi New Material Technology Co.,Ltd.

Address before: 214200 No. 15, Gehu livestock and poultry breeding farm, Yixing, HeQiao Town, Wuxi City, Jiangsu Province

Patentee before: Miao Mengcheng

TR01 Transfer of patent right