CN116732817A - Carbon paper prepared by phenolic resin slurry internal addition method and preparation method thereof - Google Patents
Carbon paper prepared by phenolic resin slurry internal addition method and preparation method thereof Download PDFInfo
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- CN116732817A CN116732817A CN202310653062.1A CN202310653062A CN116732817A CN 116732817 A CN116732817 A CN 116732817A CN 202310653062 A CN202310653062 A CN 202310653062A CN 116732817 A CN116732817 A CN 116732817A
- Authority
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- China
- Prior art keywords
- phenolic resin
- carbon
- carbon fiber
- paper
- carbon paper
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 139
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 139
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 117
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000002002 slurry Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 108
- 239000004917 carbon fiber Substances 0.000 claims abstract description 108
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 97
- 239000000725 suspension Substances 0.000 claims abstract description 62
- 239000000835 fiber Substances 0.000 claims abstract description 47
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 36
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000011268 mixed slurry Substances 0.000 claims abstract description 19
- 238000007731 hot pressing Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000010000 carbonizing Methods 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 230000010355 oscillation Effects 0.000 claims abstract description 8
- 238000009792 diffusion process Methods 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 6
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 6
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 6
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 229920001187 thermosetting polymer Polymers 0.000 claims description 5
- 229920005614 potassium polyacrylate Polymers 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 229920000297 Rayon Polymers 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 claims description 2
- 239000004416 thermosoftening plastic Substances 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 11
- 239000012467 final product Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 23
- 239000000446 fuel Substances 0.000 description 20
- 239000007789 gas Substances 0.000 description 20
- 239000006185 dispersion Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000012528 membrane Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000003912 environmental pollution Methods 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
- D21H13/12—Organic non-cellulose fibres from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/16—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/36—Inorganic fibres or flakes
- D21H13/46—Non-siliceous fibres, e.g. from metal oxides
- D21H13/50—Carbon fibres
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/47—Condensation polymers of aldehydes or ketones
- D21H17/48—Condensation polymers of aldehydes or ketones with phenols
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Paper (AREA)
Abstract
The application relates to a phenolic resin slurry internal addition method carbon paper and a preparation method thereof. Adding phenolic resin and a dispersing agent into water, carrying out ultrasonic oscillation, and mechanically stirring to obtain phenolic resin suspension; stirring and dispersing the carbon fiber in water, adding the polyvinyl alcohol fiber and the polyethylene oxide, and uniformly mixing to obtain a carbon fiber/polyvinyl alcohol fiber suspension. And pouring the prepared phenolic resin suspension into the carbon fiber/polyvinyl alcohol fiber suspension, uniformly mixing to obtain mixed slurry, forming by papermaking, squeezing and drying to obtain the carbon paper base paper. Hot pressing and carbonizing to obtain the final product. The carbon paper prepared by the application has high mechanical strength, low resistivity, easy adjustment of porosity and air permeability, simple preparation process and controllable quality.
Description
Technical Field
The application belongs to the technical field of fuel cell preparation, and particularly relates to carbon paper prepared by a phenolic resin slurry internal addition method and a preparation method thereof.
Background
A fuel cell is an energy conversion device that converts chemical energy directly into electrical energy, with proton exchange membrane fuel cells (i.e., hydrogen fuel cells) being the most widely used fuel cell at present. The proton exchange membrane fuel cell works without involving a surplus energy conversion process and being limited by the Carnot cycle, so that the energy conversion efficiency is very high. The energy conversion efficiency of a general fuel cell is between 50% and 60%, while the energy conversion efficiency of a proton exchange membrane fuel cell is as high as 90% (working below 100 ℃). In addition, no harmful gas is discharged in the operation process of the proton exchange membrane fuel cell. Therefore, the proton exchange membrane fuel cell has the advantages of high power generation efficiency, no environmental pollution and the like.
Proton exchange membrane fuel cells are currently the most promising fuel cell, but the development thereof is limited by high manufacturing cost, so that optimization and improvement of key materials are needed. The proton exchange membrane fuel cell consists of a bipolar plate, a gas diffusion layer, a catalyst layer and a proton exchange membrane, wherein the gas diffusion layer consists of a basal layer and a microporous layer. The gas diffusion layer plays a role of supporting a catalyst layer, stabilizing an electrode structure, conducting water, gas, electrons and the like in the fuel cell, and is one of key components affecting the performance of the cell.
The base layer needs to have a uniform void structure, low resistivity, sufficient mechanical strength, suitable hydrophilicity/hydrophobicity, good thermal conductivity, and excellent chemical stability. At present, the material of the base layer mainly comprises carbon fiber paper (carbon paper for short), carbon fiber cloth, carbon black paper and the like, and the carbon paper is the most commonly used material of the base layer, and has the advantages of high mechanical strength, high air permeability, low resistivity, high production efficiency, low manufacturing cost and the like.
The current carbon paper production flow is as follows: carbon fiber, other fiber (such as plant fiber, polyvinyl alcohol fiber, polyacrylonitrile fiber, etc.) and dispersant (such as polyethylene oxide, polyacrylamide, sodium dodecyl benzene sulfonate, etc.) are mixed and dispersed in water, and are manufactured and formed in a machine, pressed, dried (moisture removed), impregnated with phenolic resin/ethanol solution, dried (ethanol solution removed), cured by hot pressing, graphitized by high temperature carbonization, and made into carbon paper.
The Chinese patent with the grant publication No. CN103556543B and the grant publication No. 2016.04.20 uses chopped carbon fiber, plant fiber, thermal bonding fiber, carbon black and other raw materials, and uses wet papermaking technology to manufacture wet paper web after fluffing, pulping and pulp blending, and then the wet paper web is dried, hot pressed and hydrophobic treated to prepare the carbon paper. However, the carbon paper is not carbonized, contains a large amount of plant fibers and thermally bonded fibers, and has a high electrical resistivity.
The Chinese patent with the authority of publication No. CN113774720B and the authority of publication No. 2022.07.12 carries out hydrophilic surface treatment on the chopped polyacrylonitrile carbon fiber, then the chopped polyacrylonitrile carbon fiber is placed in water for dispersion, a wet paper web is manufactured by paper making, drying is carried out, carbon paper base paper is manufactured, and then the carbon paper base paper is manufactured by soaking in thermosetting phenolic resin ethanol solution, drying, hot pressing, solidification and carbonization. However, the raw materials of the carbon paper base paper are only one carbon fiber, so that the mechanical strength, the porosity and the conductivity of the carbon paper are difficult to adjust, in addition, the process and the operation for dipping the thermosetting phenolic resin ethanol solution are complex, uneven resin distribution can be caused, and the volatilization of ethanol can cause environmental pollution.
The chinese patent of grant publication No. CN114808536B and grant publication No. 2023.02.28 puts the carbon paper skeleton layer (including carbon fiber base paper, carbon fiber mat, etc.) into the boron-containing thermosetting resin/alcohol impregnating solution, and then performs rolling, drying, hot press curing, carbonization and graphitization to obtain the carbon paper. In order to prepare the boron-containing carbon paper with good performance, the carbon fiber still needs to be bonded by a method of dipping resin/ethanol solution and boron-containing substances are added, so the preparation method still has the problems of complex process and operation, environmental pollution and the like.
In summary, the existing carbon paper preparation method has the problems of multiple process links, high production cost, high energy consumption, high environmental pollution and the like. In addition, the resin impregnation method using ethanol as a solvent can influence the distribution uniformity of the resin in the carbon paper, so that the pore diameter and the porosity of the carbon paper are not easy to control, and the strength of the carbon paper is also influenced. Therefore, there is a need to develop a novel carbon paper preparation method with simple process, easy operation and controllable quality.
Disclosure of Invention
The application aims to solve the technical problems that: aiming at the problems that the prior carbon paper preparation needs to prepare carbon paper base paper first and then impregnate phenolic resin ethanol solution, the process operation is complex, the porosity of the carbon paper is not easy to control, the mechanical strength is low, the environmental pollution is large, and the like, the application provides the carbon paper prepared by the phenolic resin internal addition method and the preparation method thereof, and the impregnation and drying procedures of the phenolic resin ethanol solution are eliminated, thereby simplifying the process operation, improving the product quality, reducing the production cost and reducing the environmental pollution.
The technical scheme adopted for solving the technical problems is as follows:
the application provides a preparation method of carbon paper by an internal addition method of phenolic resin slurry, which comprises the following steps:
(1) Adding phenolic resin into water, and adding a dispersing agent to obtain phenolic resin suspension;
placing the phenolic resin suspension in an ultrasonic cleaner for ultrasonic vibration to obtain a uniformly dispersed phenolic resin suspension;
stirring the phenolic resin suspension by using a stirrer for standby;
(2) Adding carbon fiber into water to obtain carbon fiber slurry;
adding polyvinyl alcohol fibers and polyethylene oxide;
stirring in a stirrer to obtain a uniformly mixed carbon fiber/polyvinyl alcohol fiber suspension;
(3) Slowly pouring the phenolic resin suspension prepared in the step (1) into the carbon fiber/polyvinyl alcohol fiber suspension prepared in the step (2), and uniformly mixing to obtain mixed slurry;
forming, squeezing and drying the mixed slurry in a paper machine to obtain carbon paper base paper;
and (3) hot-pressing the carbon paper base paper in a hot press, and carbonizing after hot-pressing to obtain the target carbon paper.
Further, the phenolic resin in the step (1) is thermosetting phenolic resin or thermoplastic phenolic resin, and is in powder form, and the particle size of the phenolic resin is 0.01-200 mu m.
Further, placing the phenolic resin suspension in the step (1) in an ultrasonic cleaner for ultrasonic oscillation for 5-30min at an ultrasonic frequency of 50-500kHz to obtain a uniformly dispersed phenolic resin suspension; the phenolic resin suspension is stirred using a stirrer with a rotational speed of 30-300 revolutions per minute.
Further, the dispersing agent in the step (1) is sodium polyacrylate or potassium polyacrylate.
Further, the carbon fiber in the step (2) is one or more of polyacrylonitrile-based carbon fiber, pitch-based carbon fiber and viscose-based carbon fiber;
the diameter of the carbon fiber is 1-15 mu m or a plurality of carbon fibers with different diameters are compounded;
the length of the carbon fiber is 1-12mm or the carbon fiber with various lengths is compounded.
Further, the mass concentration of the carbon fiber slurry is 0.05% -0.5%; the addition amount of the polyvinyl alcohol fiber is 0-15% of the mass of the carbon fiber; the addition amount of the polyethylene oxide is 0.05-5% of the mass of the phenolic resin.
Further, the drying temperature in the step (3) is 80-110 ℃ and the drying time is 5-40min; the hot pressing temperature is 140-200deg.C, the pressure is 2-15MPa, and the time is 20-120min; the temperature of the atmosphere furnace is 600-1600 ℃, and the carbonization time is 30-120min.
The application also provides a piece of carbon paper, which is prepared by the preparation method of the carbon paper and has the quantitative ratio of 30-150g/m 2 。
The application provides a gas diffusion layer, which comprises the carbon paper.
The application provides a battery comprising the gas diffusion layer.
The application has the beneficial effects that:
(1) The adhesive used in the application is phenolic resin, and the problems of agglomeration and agglomeration in water are solved by adding the dispersing agent and ultrasonic pretreatment, so that the wettability of water is improved, and uniform dispersion in water is realized.
(2) The polyvinyl alcohol fiber is beneficial to improving the strength of the carbon paper base paper and enhancing the operability of the production process.
(3) The application uses polyethylene oxide to promote the carbon fiber to disperse in the water body, and solves the problems that the carbon fiber is easy to agglomerate in the water and the paper is uneven. The other remarkable effect is that the polyethylene oxide and the phenolic resin form network flocculation, so that the phenolic resin is promoted to be retained, the phenomenon that the phenolic resin runs off along with the water body in the papermaking process is avoided, and the double functions of dispersion and retention are realized.
(4) The application adopts the phenolic resin slurry internal adding method to realize the one-step forming of the carbon paper base paper, omits the phenolic resin dipping step, removes organic solvents such as ethanol and the like and the use of related dipping and drying equipment, saves energy consumption, and reduces production cost and environmental pollution. The carbon paper production process is clean and efficient, and the raw materials are economical and easy to obtain, so that continuous and large-scale production can be realized.
(5) The carbon paper has good mechanical strength, excellent conductivity and uniform pore structure.
Drawings
FIG. 1 is a flow chart of the carbon paper production process of the present application;
FIG. 2 is a diagram of the carbon paper base paper according to example 2 of the present application;
FIG. 3 is a diagram of a carbon paper according to example 2 of the present application;
FIG. 4 is a chart of a carbon paper Scanning Electron Microscope (SEM) of example 2 of the present application, magnification 100.
Detailed Description
The technical scheme of the application is as follows:
(1) Phenolic resin is added into water, and then dispersing agent (sodium polyacrylate or potassium polyacrylate) accounting for 0-1.0% of the mass of the phenolic resin is added, so that phenolic resin suspension is obtained. And then placing the phenolic resin suspension in an ultrasonic cleaner for ultrasonic oscillation for 5-30min at an ultrasonic frequency of 50-500kHz to obtain the uniformly dispersed phenolic resin suspension. The phenolic resin suspension is then stirred using a stirrer with a rotational speed of 30-300 revolutions per minute for further use.
(2) Adding carbon fiber with the diameter of 1-15 mu m and the length of 1-12mm into water to obtain carbon fiber slurry with the mass concentration of 0.05% -0.5%. Then adding 0-15% polyvinyl alcohol fiber relative to the mass of the carbon fiber and 0.05-5% polyethylene oxide relative to the mass of the phenolic resin. And then stirring for 1-5 minutes in a stirrer with the rotating speed of 30-300 rpm to obtain the uniformly mixed carbon fiber/polyvinyl alcohol fiber suspension.
(3) And slowly pouring the prepared phenolic resin suspension into the carbon fiber/polyvinyl alcohol fiber suspension (the phenolic resin accounts for 50-400% of the mass of the carbon fiber), and uniformly mixing to obtain mixed slurry. And (3) forming the mixed slurry in a paper making machine, squeezing, and drying at 80-110 ℃ for 5-40min to obtain the carbon paper base paper. And then hot-pressing the carbon paper base paper in a hot press with the temperature of 140-200 ℃ and the pressure of 2-15MPa for 20-120min. Finally carbonizing for 30-120min in an atmosphere furnace at 600-1600 ℃ to obtain the product with the quantitative value of 30-150g/m 2 A carbon paper is added in phenolic resin slurry.
The principle of the method of the application is as follows:
phenolic resin is prepared by polycondensation of phenol and formaldehyde as main raw materials under the action of a catalyst, is a linear or body type polycondensate organic matter and contains a large amount of benzene ring structures and phenolic hydroxyl groups. Phenolic resins are insoluble in water and have poor hydrophilic properties. According to the application, phenolic resin blocks are crushed under the ultrasonic action, the surface tension of phenolic resin is reduced by the dispersing agent, the wettability of the phenolic resin in water is improved, and uniform stable phenolic resin dispersion liquid is formed by mechanical stirring.
The carbon fiber is composed of more than 90% of carbon elements, has a graphite-like structure, and has sp between the carbon elements 2 The hybridized covalent bond is connected, so that the surface of the carbon fiber lacks active functional groups, and is not easy to combine and react with other compounds. Meanwhile, because the length-diameter ratio of the carbon fiber is large, the carbon fiber is easy to agglomerate in water, so that the carbon fiber is difficult to uniformly disperse in water, and the uniformity of the carbon paper is poor. According to the application, polyethylene oxide is added into the carbon fiber slurry, so that a wetting film is formed on the surface of the carbon fiber, the sliding energy efficiency among the carbon fibers is enhanced, and the carbon fiber is dispersed in water. In addition, the polyvinyl alcohol fiber has rich hydroxyl groups, has excellent dispersion performance in water,therefore, the addition of the polyvinyl alcohol fibers can effectively enhance the barrier effect among the carbon fibers and promote the dispersion of the carbon fibers.
When only the phenolic resin and the carbon fiber form slurry, the phenolic resin has small particle size, so the loss in the papermaking forming process is serious. However, when phenolic resin is added into the slurry composed of carbon fiber, polyvinyl alcohol fiber and polyethylene oxide, as the polyethylene oxide contains ether oxygen non-shared electron pairs, the polyethylene oxide has strong affinity with hydroxyl groups of the phenolic resin, hydrogen bond association is generated mutually, a network structure is formed, and the fine fiber and the filler in the paper stock are coagulated together, so that the retention rate of the paper stock is greatly improved. Therefore, the application utilizes the ether bond oxygen atom of polyethylene oxide to generate hydrogen bond association with the hydroxyl of phenolic resin to form a network structure, and captures the phenolic resin in the mixed slurry, thereby greatly improving the retention rate of the phenolic resin. Therefore, the polyethylene oxide not only can effectively disperse the carbon fibers, but also can form a network structure with the phenolic resin through hydrogen bond association, thereby providing possibility for the retention and uniform distribution of the phenolic resin in the carbon paper.
Conventional carbon paper employs a phenolic resin/ethanol solution impregnation method of carbon paper base paper in order to improve the bonding strength between carbon fibers and the conductivity of the carbon paper. The application utilizes the dispersion in water, the addition in slurry and the retention technology of phenolic resin, introduces the phenolic resin into water and uniformly adsorbs and retains the phenolic resin on fibers, regulates the glass transition temperature of the phenolic resin to make the phenolic resin become a high-elasticity state and further become a viscous state, and is inlaid at the intersection point of carbon fibers and solidified. Therefore, the phenolic resin is added into the slurry to improve the bonding strength of the carbon fiber, the conductivity and the porosity of the carbon paper. Compared with the traditional carbon paper, the application optimizes the carbon paper preparation process, regulates and controls the pores of the carbon paper, and improves the strength and the conductivity of the carbon paper.
Example 1
The first step: phenolic resin was added to water, and then sodium polyacrylate was added in an amount of 0.01% relative to the mass of the phenolic resin to obtain a phenolic resin suspension. And then placing the phenolic resin suspension in an ultrasonic cleaner for ultrasonic oscillation for 5min at an ultrasonic frequency of 50kHz to obtain the uniformly dispersed phenolic resin suspension. The phenolic resin suspension was then stirred using a stirrer at a speed of 30 revolutions per minute for further use.
And a second step of: adding carbon fiber into water to obtain carbon fiber slurry with mass concentration of 0.05%. Then, 5% of polyvinyl alcohol fiber relative to the mass of the carbon fiber and 0.1% of polyethylene oxide relative to the mass of the phenolic resin were added, and stirred in a stirrer at a rotation speed of 30 rpm for 1 minute, to obtain a uniformly mixed carbon fiber/polyvinyl alcohol fiber suspension.
And a third step of: and slowly pouring the prepared phenolic resin suspension into the carbon fiber/polyvinyl alcohol fiber suspension (phenolic resin accounts for 50% of the mass of the carbon fiber), and uniformly mixing to obtain the carbon fiber mixed slurry. And (3) forming the mixed slurry in a paper making machine, squeezing, and drying at 80 ℃ for 40min to obtain the carbon paper base paper. And then the carbon paper base paper is hot pressed for 120min in a hot press with the temperature of 140 ℃ and the pressure of 13 MPa. Finally carbonizing for 120min in an atmosphere furnace at 800 ℃ to obtain the quantitative 80g/m 2 A carbon paper for a gas diffusion layer of a fuel cell.
Example 2
The first step: phenolic resin was added to water, followed by addition of 0.25% dispersant sodium polyacrylate relative to the mass of the phenolic resin to give a phenolic resin suspension. And then placing the phenolic resin suspension in an ultrasonic cleaner for ultrasonic oscillation for 10min at an ultrasonic frequency of 100kHz to obtain the uniformly dispersed phenolic resin suspension. The phenolic resin suspension was then stirred using a stirrer at a speed of 100 revolutions per minute for further use.
And a second step of: adding carbon fiber into water to obtain carbon fiber slurry with mass concentration of 0.15%. Then 10% of polyvinyl alcohol fiber relative to the mass of the carbon fiber and 2% of polyethylene oxide relative to the mass of the phenolic resin are added and stirred for 3 minutes in a stirrer with the rotating speed of 100 revolutions per minute, so as to obtain a uniformly mixed carbon fiber/polyvinyl alcohol fiber suspension.
And a third step of: and slowly pouring the prepared phenolic resin suspension into the carbon fiber/polyvinyl alcohol fiber suspension (phenolic resin accounts for 200% of the mass of the carbon fiber), and uniformly mixing to obtain the carbon fiber mixed slurry. The mixed slurry is manufactured and formed in a paper machine and pressed,drying at 100deg.C for 20min to obtain carbon paper base paper. And then the carbon paper base paper is hot pressed for 60min in a hot press with the temperature of 170 ℃ and the pressure of 10 MPa. Finally carbonizing for 60min in an atmosphere furnace at 1200 ℃ to obtain the quantitative 80g/m 2 A carbon paper for a gas diffusion layer of a fuel cell.
The carbon paper base paper prepared by the embodiment is shown in fig. 2, the target carbon paper is shown in fig. 3, and in addition, the carbon fibers in the carbon paper are randomly distributed as shown in fig. 4, so that the overall uniformity of the carbon paper matrix can be effectively ensured. The phenolic resin of the conventional phenolic resin impregnation method carbon paper is unevenly distributed, and a large amount of phenolic resin is accumulated on one side of the carbon paper in the drying process, so that gaps are blocked. The phenolic resin of this example was uniformly distributed in the carbon paper (both inside and on the surface), especially at the points of contact between the carbon fibers. The bonding strength between the carbon fibers is increased by the hot pressing and carbonization processes, so that the strength of the carbon paper is also improved. In addition, the carbon paper of the embodiment has good porosity and air permeability, and can ensure that gas passes smoothly.
Example 3
The first step: phenolic resin was added to water, followed by 0.8% potassium polyacrylate relative to the mass of the phenolic resin, to give a phenolic resin suspension. And then placing the phenolic resin suspension in an ultrasonic cleaner for ultrasonic oscillation for 30min at an ultrasonic frequency of 500kHz to obtain the uniformly dispersed phenolic resin suspension. The phenolic resin suspension was then stirred using a stirrer at a speed of 300 revolutions per minute for further use.
And a second step of: adding carbon fiber into water to obtain carbon fiber slurry with mass concentration of 0.4%. Then adding 15% of polyvinyl alcohol fiber relative to the mass of the carbon fiber and 5% of polyethylene oxide relative to the mass of the phenolic resin, and stirring for 5 minutes in a stirrer with the rotating speed of 300 revolutions per minute to obtain a uniformly mixed carbon fiber/polyvinyl alcohol fiber suspension.
And a third step of: and slowly pouring the prepared phenolic resin suspension into the carbon fiber/polyvinyl alcohol fiber suspension (phenolic resin accounts for 400% of the mass of the carbon fiber), and uniformly mixing to obtain the carbon fiber mixed slurry. Forming the mixed slurry in a paper machine, squeezing, and drying at 110deg.CDrying for 40min to obtain the carbon paper base paper. And then the carbon paper base paper is hot pressed for 20min in a hot press with the temperature of 200 ℃ and the pressure of 15 MPa. Finally carbonizing for 30min in an atmosphere furnace at 1600 ℃ to obtain the quantitative 80g/m 2 A carbon paper for a gas diffusion layer of a fuel cell.
Comparative example 1
The first step: adding carbon fiber into water to obtain carbon fiber slurry with mass concentration of 0.15%. Then 10% of polyvinyl alcohol fiber and 1% of polyethylene oxide relative to the mass of the carbon fiber are added, and stirred for 3 minutes in a stirrer with the rotating speed of 100 revolutions per minute, so as to obtain a uniformly mixed carbon fiber/polyvinyl alcohol fiber suspension.
And a second step of: and (3) carrying out papermaking forming on the mixed slurry in a paper machine, squeezing, and drying at 100 ℃ for 20min to obtain the carbon paper base paper. And then the carbon paper base paper is hot pressed for 60min in a hot press with the temperature of 170 ℃ and the pressure of 10 MPa. Finally carbonizing for 60min in an atmosphere furnace at 1200 ℃ to obtain the quantitative 80g/m 2 A carbon paper for a gas diffusion layer of a fuel cell.
Comparative example 2
The first step: adding carbon fiber into water to obtain carbon fiber slurry with mass concentration of 0.15%. Then 10% of polyvinyl alcohol fiber relative to the mass of the carbon fiber and 2% of polyethylene oxide relative to the mass of the phenolic resin are added and stirred for 3 minutes in a stirrer with the rotating speed of 100 revolutions per minute, so as to obtain a uniformly mixed carbon fiber/polyvinyl alcohol fiber suspension.
And a second step of: adding the phenolic resin which is not subjected to dispersion treatment into the carbon fiber/polyvinyl alcohol fiber suspension (the phenolic resin accounts for 200% of the mass of the carbon fiber), and uniformly mixing to obtain the carbon fiber mixed slurry. And (3) carrying out papermaking forming on the mixed slurry in a paper machine, squeezing, and drying at 100 ℃ for 20min to obtain the carbon paper base paper. And then the carbon paper base paper is hot pressed for 60min in a hot press with the temperature of 170 ℃ and the pressure of 10 MPa. Finally carbonizing for 60min in an atmosphere furnace at 1200 ℃ to obtain the carbon paper for the fuel cell gas diffusion layer.
Comparative example 3
(1) Phenolic resin was added to water, and then sodium polyacrylate was added at 0.25% relative to the mass of the phenolic resin to obtain a phenolic resin suspension. And then placing the phenolic resin suspension in an ultrasonic cleaner for ultrasonic oscillation for 10min at an ultrasonic frequency of 100kHz to obtain the uniformly dispersed phenolic resin suspension. The phenolic resin suspension was then stirred using a stirrer at a speed of 100 revolutions per minute for further use.
(2) Adding carbon fiber into water to obtain carbon fiber slurry with mass concentration of 0.15%. Then adding 10% of polyvinyl alcohol fiber relative to the mass of the carbon fiber, and stirring for 3 minutes in a stirrer with the rotating speed of 100 revolutions per minute to obtain a uniformly mixed carbon fiber/polyvinyl alcohol fiber suspension.
(3) And slowly pouring the prepared phenolic resin suspension into the carbon fiber/polyvinyl alcohol fiber suspension (the phenolic resin accounts for 200% of the mass of the carbon fiber), and uniformly mixing to obtain the carbon fiber mixed slurry. And (3) carrying out papermaking forming on the mixed slurry in a paper machine, squeezing, and drying at 100 ℃ for 20min to obtain the carbon paper base paper. And then the carbon paper base paper is hot pressed for 60min in a hot press with the temperature of 170 ℃ and the pressure of 10 MPa. Finally carbonizing for 60min in an atmosphere furnace at 1200 ℃ to obtain the carbon paper for the fuel cell gas diffusion layer.
And (3) testing the performance of the carbon paper with the gas diffusion layer:
the carbon papers prepared in the above examples and comparative examples were subjected to performance tests of tensile strength, resistivity, air permeability, porosity, and the like, respectively. The measurement results are shown in Table 1.
TABLE 1 comparison of gas diffusion layer carbon paper Performance
The comparison of the examples in table 1 with comparative example 1 (no phenolic resin added) shows that the addition of phenolic resin can significantly improve the tensile strength, reduce the resistivity, the air permeability and the porosity of the carbon paper, mainly because the presence of phenolic resin increases the bonding sites between the carbon fibers, so that the carbon paper forms a space network structure, thereby increasing the tensile strength and the conductivity of the carbon paper. The mesh structure impedes the passage of a portion of the gas and therefore the gas permeability is slightly reduced.
Example 2 and comparative example 2 (added with non-dispersed phenolic resin) are compared, and the addition of the dispersed phenolic resin can improve the tensile strength, reduce the resistivity, improve the air permeability and the porosity of the carbon paper, so that the performance of the carbon paper can be effectively improved by adding the pre-dispersed phenolic resin (compared with the non-dispersed phenolic resin) in the preparation process of the carbon paper. This is mainly because the pretreatment can effectively disperse the phenolic resin, so that the phenolic resin can be more uniformly combined with the polyethylene oxide, and the generation of the high-uniformity carbon paper is promoted. While uneven uniformity of the carbon paper can reduce the tensile strength, the resistivity and the air permeability and the porosity of the carbon paper.
Comparison of example 2 and comparative example 3 (without polyethylene oxide added) shows that the presence of polyethylene oxide can significantly increase the tensile strength and conductivity of the carbon paper and the air permeability and porosity can be reduced. This is mainly because polyethylene oxide can improve the retention of the phenolic resin and the uniformity of slurry dispersion, promoting close bonding of the phenolic resin with the fibers. The lack of phenolic resin in carbon paper without polyethylene oxide results in weak binding force among fibers, so that the carbon paper has low tensile strength, and loose structure is a main reason for high air permeability and porosity.
The embodiment of the application also provides a carbon paper prepared by the preparation method of the carbon paper, and more technical details can be found in the related description of the preparation method of the carbon paper, which is not repeated herein.
Embodiments of the present application further provide a battery including the foregoing gas diffusion layer, and for further technical details, reference may be made to the foregoing description of the gas diffusion layer, which is not repeated herein.
In conclusion, the carbon paper prepared by the method has the advantages of high mechanical strength, low resistivity, easiness in adjustment of porosity and air permeability, simple preparation process, controllable quality and practical application value.
The above description is only a preferred embodiment of the present application, and is not intended to limit the application in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to equivalent embodiments without departing from the technical content of the present application, and any simple modification, equivalent changes and modification to the above embodiments according to the technical substance of the present application still fall within the scope of the technical solution of the present application.
Claims (10)
1. A preparation method of carbon paper by an internal addition method of phenolic resin slurry is characterized by comprising the following steps:
(1) Adding phenolic resin into water, and adding a dispersing agent to obtain phenolic resin suspension;
placing the phenolic resin suspension in an ultrasonic cleaner for ultrasonic vibration to obtain a uniformly dispersed phenolic resin suspension;
stirring the phenolic resin suspension by using a stirrer for standby;
(2) Adding carbon fiber into water to obtain carbon fiber slurry;
adding polyvinyl alcohol fibers and polyethylene oxide;
stirring in a stirrer to obtain a uniformly mixed carbon fiber/polyvinyl alcohol fiber suspension;
(3) Slowly pouring the phenolic resin suspension prepared in the step (1) into the carbon fiber/polyvinyl alcohol fiber suspension prepared in the step (2), and uniformly mixing to obtain mixed slurry;
forming, squeezing and drying the mixed slurry in a paper machine to obtain carbon paper base paper;
and (3) hot-pressing the carbon paper base paper in a hot press, and carbonizing after hot-pressing to obtain the target carbon paper.
2. The method for preparing carbon paper by the phenolic resin slurry internal addition method according to claim 1, which is characterized in that: the phenolic resin in the step (1) is thermosetting phenolic resin or thermoplastic phenolic resin, is powdery and has the particle size of 0.01-200 mu m.
3. The method for preparing carbon paper by the phenolic resin slurry internal addition method according to claim 2, which is characterized in that: placing the phenolic resin suspension in the step (1) in an ultrasonic cleaner for ultrasonic oscillation for 5-30min at an ultrasonic frequency of 50-500kHz to obtain a uniformly dispersed phenolic resin suspension; the phenolic resin suspension is stirred using a stirrer with a rotational speed of 30-300 revolutions per minute.
4. The method for preparing carbon paper by the phenolic resin slurry internal addition method according to claim 1, which is characterized in that: the dispersing agent in the step (1) is sodium polyacrylate or potassium polyacrylate.
5. The method for preparing carbon paper by the phenolic resin slurry internal addition method according to claim 1, which is characterized in that: the carbon fiber in the step (2) is one or more of polyacrylonitrile-based carbon fiber, pitch-based carbon fiber and viscose-based carbon fiber;
the diameter of the carbon fiber is 1-15 mu m or a plurality of carbon fibers with different diameters are compounded;
the length of the carbon fiber is 1-12mm or the carbon fiber with various lengths is compounded.
6. The method for preparing carbon paper by the phenolic resin slurry internal addition method according to claim 5, which is characterized in that: the mass concentration of the carbon fiber slurry is 0.05% -0.5%; the addition amount of the polyvinyl alcohol fiber is 0-15% of the mass of the carbon fiber; the addition amount of the polyethylene oxide is 0.05-5% of the mass of the phenolic resin.
7. The method for preparing carbon paper by the phenolic resin slurry internal addition method according to claim 1, which is characterized in that: the drying temperature in the step (3) is 80-110 ℃ and the drying time is 5-40min; the hot pressing temperature is 140-200deg.C, the pressure is 2-15MPa, and the time is 20-120min; the temperature of the atmosphere furnace is 600-1600 ℃, and the carbonization time is 30-120min.
8. A carbon paper characterized by being produced by the carbon paper production method of any one of claims 1 to 7, having a basis weight of 30 to 150g/m 2 。
9. A gas diffusion layer comprising the carbon paper of claim 8.
10. A battery comprising the gas diffusion layer of claim 9.
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