CN110295297A - A kind of preparation method of direct alcohol fuel cell cathode support body material - Google Patents

A kind of preparation method of direct alcohol fuel cell cathode support body material Download PDF

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Publication number
CN110295297A
CN110295297A CN201910558342.8A CN201910558342A CN110295297A CN 110295297 A CN110295297 A CN 110295297A CN 201910558342 A CN201910558342 A CN 201910558342A CN 110295297 A CN110295297 A CN 110295297A
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graphitized charcoal
support body
cathode support
charcoal
fuel cell
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郭峰
刘森瑞
张润泽
张媛媛
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/205—Preparation
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1005—Pretreatment of the non-metallic additives
    • C22C1/1015—Pretreatment of the non-metallic additives by preparing or treating a non-metallic additive preform
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1089—Alloys containing non-metals by partial reduction or decomposition of a solid metal compound
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/028—Sealing means characterised by their material
    • H01M8/0282—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/028—Sealing means characterised by their material
    • H01M8/0284—Organic resins; Organic polymers
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention relates to a kind of preparation methods of direct alcohol fuel cell cathode support body material.Its technical solution be the following steps are included: one, use polyvinyl chloride for raw material, through pyrolysis, charing, crushing and classification be made partial size be 5-30um easy graphitized charcoal；Two, copper chloride is added in reaction kettle, is melted using far-infrared heater heating into liquid state；Three, it is added in reaction kettle using polyvinyl chloride as easy graphitized charcoal made from raw material, is stirred, high temperature carbothermic reduction reaction is carried out, by graphitized charcoal dries pulverizing；Four, it is coated with covering, even particle size distribution is made after high temperature graphitization, classification, be direct alcohol fuel cell cathode support body material.Beneficial effect is: can substitute carbonaceous mesophase spherules and graphite completely, and manufacture craft is reliable；And having the characteristics that shrinking percentage is low, deflection is small, degree of graphitization is high, conductivity is high, mechanical property is good, the cathode support body performance of manufacture is stablized, and service life is 2-3 times of conventional cathodes supporter.

Description

A kind of preparation method of direct alcohol fuel cell cathode support body material
Technical field
The present invention relates to a kind of preparation of fuel battery negative pole support body material, in particular to a kind of direct Aalcohols fuel electricity The preparation method of pool cathode support body material.
Background technique
Fuel cell is a kind of chemical devices for chemical energy possessed by fuel being directly changed into electric energy, also known as electrochemistry Electric organ.It is the 4th kind of generation technology after hydroelectric generation, heat energy power-generating and nuclear electric power generation.Since fuel cell is The Gibbs free energy part in the chemical energy of fuel is converted into electric energy by electrochemical reaction, not by Carnot cycle effect Limitation, thus it is high-efficient;In addition, fuel cell-use fuel and oxygen are as raw material；There is no mechanical transmission component simultaneously, therefore does not have There is noise pollution, the pernicious gas given off is few.
Direct alcohol fuel cell is without intermediate reforming unit, thus system structure is simple, and volume energy density is high, also has Have that the starting time is short, load response characteristic is good, operational reliability is high, can be worked normally within the scope of larger temperature, fuel Supplement the advantages that facilitating.Wherein, the cathode support body of direct alcohol fuel cell is important product, existing conventional manufacture yin The technique of pole supporter: using Tween 80 as dispersing agent, respectively with acrylamide and N, N '-methylene-bisacrylamide be monomer and Crosslinking agent prepares carbonaceous mesophase spherules/graphite (MCMB/G) slurry, and using Gel-casting process, direct Aalcohols fuel electricity is made Pond sleeve cathode supporter biscuit, through liquid, its sample is made in the processes processing such as dry, roll-drying and ink powder of layinging of markstone sintering.Its The problem is that: carbonaceous mesophase spherules are since with self sintering matter, particle occurs to merge and forms burning during the sintering process Knot body, sintered hole merge, and fine pore merges to form macrovoid, and sintering neck occur, are easily deformed in sintering And cracking；Graphite addition is to reduce to shrink and deform, and manufactured cathode support body service life is short, it is difficult to meet market need It wants, it is therefore desirable to which a kind of new material that can substitute carbonaceous mesophase spherules and graphite prepares cathode support body.
Chinese patent literature publication number 101546832B, the invention discloses " a kind of direct alcohol fuel cell is special-shaped more Hole cathode support body material ", by carbonaceous mesophase spherules powder, powdered graphite and zinc oxide, calcium oxide, carbonic acid ammonia, calcium carbonate, oxygen After changing magnesium or silica mixing, using gel injection-moulding or compression molding, then product is being made through carbon burial sintering.It is obtained with the present invention The direct alcohol fuel cell profiled porous cathode support body obtained makes special-shaped direct alcohol fuel cell, light-weight, small in size, It can store fuel, it is easy to carry；But its there are the problem of use carbonaceous mesophase spherules powder, powdered graphite for primary raw material Cathode support body is made, shrinking percentage is big, deflection is big, and service life is short.
Chinese patent literature publication number 109873173A, patent name are a kind of " direct alcohol fuel cell cathode support The preparation method of body material ", technical solution is to use phenolic resin for raw material, and additive is added, and mixture is placed in and is carbonized It is carbonized under vacuum conditions in furnace, carbonization temperature is 600-800 DEG C, carbonizes good resulting pyrolytic carbon and passes through pulverizing grading machine After crushing and classification, the material of gained 5-30um is handed over covering in pyrolysis carbon surface by the way that covering cladding is added, then using 300 DEG C Connection forms encasement.Material after the cladding pyrolytic carbon size distribution obtained after 700 DEG C of charings, 2800 DEG C of high temperature graphitizations Uniformly.Foregoing invention also may be implemented the substitution to carbonaceous mesophase spherules and graphite, the present invention provide a kind of different technique and Preparation method realizes the substitution to carbonaceous mesophase spherules and graphite.
Summary of the invention
The purpose of the present invention is to drawbacks described above of the existing technology, provide a kind of direct alcohol fuel cell yin The preparation method of pole support body material, the present invention use polyvinyl chloride and copper chloride for raw material, can substitute carbonaceous mesophase spherules With graphite to prepare cathode support body, with preferable size distribution, tap density, powder compacted density, real density are higher, The features such as specific surface area is smaller, and resistivity is low is a kind of preferable cathode support body material, the contraction of manufactured cathode support body Rate is low, deflection is small, and the service life substantially extends.
Its technical solution be the following steps are included:
One, it uses 900-950 parts of polyvinyl chloride for raw material, the easy stone that partial size is 5-30um is made through pyrolysis, charing, crushing and classification Inkization charcoal；
Two, 500-520 parts of copper chlorides are added in reaction kettle, 550-600 DEG C and constant temperature, chlorine are heated to using far-infrared heater Change copper to melt into liquid state；
Three, stirring by easy graphitized charcoal, opening made from raw material of polyvinyl chloride for 100-110 parts of 5-30um is added in reaction kettle Motor is mixed, is sufficiently mixed easy graphitized charcoal with copper chloride, copper chloride penetrates into easy graphitized charcoal；Later, by reaction kettle Material is filtered, and is the easy graphitized charcoal for penetrating into copper chloride on filter cloth, and the easy graphitized charcoal for penetrating into copper chloride is placed in retort It is interior, 2-3 hours progress high temperature carbothermic reduction reactions are kept the temperature using vacuumizing, after being heated to 2800 DEG C, easy graphitized charcoal is as also Former agent restores copper chloride, and the Nanometer Copper after reduction is adsorbed in the lamellar structure of graphitized charcoal, by high temperature carbothermic reduction reaction institute Graphitized charcoal to entering in water washing tank, copper chloride is washed off in addition distilled water washing, later by graphitized charcoal to entering retort It is interior, 300 DEG C of drying are carried out under vacuum state, the graphitized charcoal after drying is classified out the material of 5-30um using pulverizing grading machine；
Four, the material of classification gained 5-30um is coated with covering, then uses 300 DEG C of temperature by covering on graphitized charcoal surface Crosslinking forms encasement；Granularity point is made in graphitized charcoal after cladding after 700 DEG C of charings, 2800 DEG C of high temperature graphitizations, classifications Cloth is uniform, is direct alcohol fuel cell cathode support body material.
Preferably, above-mentioned covering is n-hexane, naphthalene one or two, and the mass ratio of covering and material is 1:100.
Preferably, the manufacturing process of the easy graphitized charcoal of step 1 is as follows:
900-950 parts of polyvinyl chloride are that raw material is squeezed into polymeric kettle, opening stirring motor, stirring rate 160-180r/min, It is heated to 400-420 DEG C by 10-15 DEG C/min heating rate under nitrogen protection, is pyrolyzed within constant temperature 2-3 hours, corresponding HCl Abjection；Later, 700 DEG C are heated to by 8-10 DEG C/min heating rate under nitrogen protection, are carbonized within constant temperature 3-3.5 hours, The process is cyclisation and aromatization process, and it is molten to become pitch shape for the release of simultaneous ethylene, butylene, ethane, benzene small molecule Body undergoes the interphase stage, forms easy graphitized charcoal, and grain is made using pulverizing grading machine crushing and classification in easy graphitized charcoal obtained Diameter is the easy graphitized charcoal of 5-30um.
Preferably, in step 3, it will penetrate into the easy graphitized charcoal merging retort of copper chloride, using vacuumizing, heat 10-15 DEG C of rate/min keeps the temperature 2-3 hours progress high temperature carbothermic reduction reactions after being heated to 2800 DEG C.
Preferably, in step 3, addition 40-50 DEG C of distilled water of temperature is washed 5 times, washes off copper chloride.
In step 4, the graphitized charcoal after cladding is heated to 700 by 10-15 DEG C/min heating rate under vacuum conditions DEG C, constant temperature 2-3 hours, the material after charing was heated to 2800 DEG C by 10-15 DEG C/min heating rate under evacuated state, perseverance 2-3 hours warm, the material of wherein 5-30um is classified out after classification is handled by resulting material again.
The beneficial effects of the present invention are: the present invention uses polyvinyl chloride for raw material, it is made through pyrolysis, charing, crushing and classification Partial size is the easy graphitized charcoal of 5-30um；Copper chloride is added in reaction kettle, is heated to 550-600 DEG C using far-infrared heater And constant temperature, copper chloride are melted into liquid state.Toward the interior addition 5-30um of reaction kettle using polyvinyl chloride as easy graphite made from raw material Change charcoal, stirring is sufficiently mixed easy graphitized charcoal with copper chloride, copper chloride penetrates into easy graphitized charcoal.Later, by reaction kettle Material filtered, on filter cloth for penetrate into copper chloride easy graphitized charcoal, will penetrate into copper chloride easy graphitized charcoal merging charing In furnace, using vacuumizing, 10-15 DEG C of the rate of heat addition/min keeps the temperature progress high temperature carbon thermal reduction in 2-3 hours after being heated to 2800 DEG C Reaction, carbon material restore copper chloride as reducing agent, and the Nanometer Copper after reduction is adsorbed in the lamellar structure of graphitized charcoal；Pass through The different methods mentioned from documents produce direct alcohol fuel cell cathode support body material product, almost without It shrinks and deformation, the cathode support body performance produced is stablized, service life is 2-3 times of conventional cathodes supporter, can be complete Carbonaceous mesophase spherules and graphite are substituted, and there is shrinking percentage using the cathode support body that this kind of cathode support body material manufactures Low, the features such as deflection is small, degree of graphitization is high, conductivity is high, mechanical property is good.
Specific embodiment
Hereinafter, preferred embodiments of the present invention will be described, it should be understood that preferred embodiment described herein is only used In the description and interpretation present invention, it is not intended to limit the present invention.
Embodiment 1, a kind of preparation method for direct alcohol fuel cell cathode support body material that the present invention mentions, system Preparation Method is specific as follows:
Weighing 900 kilograms of polyvinyl chloride is that raw material is squeezed into polymeric kettle, opens stirring motor, stirring rate 170r/min, in nitrogen 410 DEG C are heated to by 12 DEG C/min heating rate under gas shielded, is pyrolyzed within constant temperature 2.5 hours, corresponding HCl abjection.Later, 700 DEG C are heated to by 9 DEG C/min heating rate under nitrogen protection, is carbonized within constant temperature 3 hours, which is cyclisation and aromatization Change process, the release of the small molecules such as simultaneous ethylene, butylene, ethane, benzene become pitch shape melt, undergo interphase rank Section, forms easy graphitized charcoal.Easy graphitized charcoal obtained uses pulverizing grading machine crushing and classification that partial size is made as the easy of 5-30um Graphitized charcoal；
500 kilograms of copper chloride is added in reaction kettle, 580 DEG C and constant temperature are heated to using far-infrared heater, copper chloride is molten Solution is at liquid state；
Toward the interior 5-30um for being added 100 kilograms of reaction kettle using polyvinyl chloride as easy graphitized charcoal made from raw material, stirring is opened Motor, stirring rate 120r/min mixing time 6 hours, are sufficiently mixed easy graphitized charcoal with copper chloride, copper chloride penetrates into In easy graphitized charcoal.Later, be heated to using far-infrared heater in the suction filtration kettle of 580 DEG C and constant temperature by the material of reaction kettle into Row filters, and is the easy graphitized charcoal for penetrating into copper chloride on filter cloth, will penetrate into the easy graphitized charcoal merging retort of copper chloride, adopts With vacuumizing, 12 DEG C/min of the rate of heat addition keeps the temperature 2.5 hours progress high temperature carbothermic reduction reactions, carbon materials after being heated to 2800 DEG C Material restores copper chloride as reducing agent, and the Nanometer Copper after reduction is adsorbed in the lamellar structure of graphitized charcoal.Also by pyrocarbon heat Original reacts resulting graphitized charcoal to entering in water washing tank, and addition temperature 45 C distilled water is washed 5 times, and copper chloride is washed off, and later will Graphitized charcoal carries out 300 DEG C of drying to entering in retort, under vacuum state, and the graphitized charcoal after drying is using pulverizing grading machine point Grade goes out the material of 5-30um.
Classification gained 5-30um material in 100:1.2(mass ratio) ratio add n-hexane stirred as after covering Stirring 3 hours in kettle are mixed, kettle temperature is controlled at 95 DEG C, later, resulting mixture is placed in baking oven and presses 8 DEG C/min heating rate 300 DEG C are heated to, constant temperature 3 hours, covering is surface-crosslinked in graphitized charcoal, formation encasement coats stone by covering Inkization charcoal makes graphitized charcoal structure in charge and discharge process more stable, is not pulverized easily, and charge and discharge cycles stability is more preferable.Packet Graphitized charcoal after covering is heated to 700 DEG C by 12 DEG C/min heating rate under vacuum conditions, and constant temperature 3 hours, the object after charing Material is heated to 2800 DEG C by 12 DEG C/min heating rate under evacuated state, and constant temperature 3 hours, resulting material was handled through classification again The material of wherein 5-30um is classified out afterwards, even particle size distribution, high mechanical strength is made, the good graphitized charcoal of heat resistance is A kind of excellent direct alcohol fuel cell cathode support body material.
The technical indicator for the graphitized charcoal that the embodiment obtains is as follows:
D50(um) Tap density (g/cm3) Powder compacted density (g/cm3) Real density (g/cm3) Specific surface area (m2/ g) Resistivity (Ω .cm)
18±2.0 ≥1.38 ≥1.96 2.45±0.03 0.75±0.5 0.0202
Wherein, D50: being measured using Particle Size Analyzer, obtain accumulative 50% point of the cathode support body material of diameter be 18 ± 2.0um.(2) tap density: being measured using tap density meter, and the tap density for obtaining the cathode support body material is >=1.38g/ cm3.(3) powder compacted density: being tested using powder compacted density tester, obtains the powder compacting of the cathode support body material Density is >=1.96g/cm3.(4) it real density: is tested using real density analyzer, obtains the real density of the cathode support body material For 2.45 ± 0.03g/cm3.(5) it specific surface area: is tested using specific surface area analysis instrument, obtains the ratio of the cathode support body material Surface area is 0.75 ± 0.5m2/g.(6) resistivity: being measured by Instrument Measuring Resistivity of Carbon Products, is obtained through measurement, the cathode support body The resistivity of material is 0.0202 Ω .cm.
Direct alcohol fuel cell cathode support body material product can be produced by this kind of method, uses this kind of cathode The performance testing index of the cathode support body of support body material manufacture is as follows:
(1) porosity: being measured using Archimedes's drainage, and the porosity for obtaining the cathode support body material is 41.2%, hole It is uniformly distributed；(2) resistivity: being measured by Instrument Measuring Resistivity of Carbon Products, is obtained through measurement, the resistivity of the cathode support body material is 0.0202Ω.cm；(3) mechanical property: flexural strength is measured using the three point bending test of universal testing machine, compression strength uses It presses deficient test to measure, is obtained through measurement, the flexural strength 20.52MPa of cathode support body material, compression strength 17.26MPa.(4) Through limit test, service life is 2 times of conventional cathodes supporter；(5) shrinking percentage is tested by shrinking percentage tester, passes through change Shape tester tests deflection, and both shrinking percentage and deflection are respectively less than carbonaceous mesophase spherules/graphite shrinking percentage and deformation Amount.In addition have the characteristics that degree of graphitization is high, conductivity is high, mechanical property is good, carbonaceous mesophase spherules/stone can be substituted completely Ink.
Embodiment 2, a kind of preparation method for direct alcohol fuel cell cathode support body material that the present invention mentions, preparation side Method is specific as follows:
Weighing 900 kilograms of polyvinyl chloride is that raw material is squeezed into polymeric kettle, opens stirring motor, stirring rate 160r/min, in nitrogen 400 DEG C are heated to by 10 DEG C/min heating rate under gas shielded, is pyrolyzed within constant temperature 3 hours, corresponding HCl abjection.Later, exist 700 DEG C are heated to by 8 DEG C/min heating rate under nitrogen protection, is carbonized within constant temperature 3.5 hours, which is cyclisation and aromatization Change process, the release of the small molecules such as simultaneous ethylene, butylene, ethane, benzene become pitch shape melt, undergo interphase rank Section, forms easy graphitized charcoal.Easy graphitized charcoal obtained uses pulverizing grading machine crushing and classification that partial size is made as the easy graphite of 5um Change charcoal；
500 kilograms of copper chloride is added in reaction kettle, 550 DEG C and constant temperature are heated to using far-infrared heater, copper chloride is molten Solution is at liquid state；
Toward the interior 5um for being added 100 kilograms of reaction kettle using polyvinyl chloride as easy graphitized charcoal made from raw material, stirring electricity is opened Machine, stirring rate 120r/min mixing time 5 hours, are sufficiently mixed easy graphitized charcoal with copper chloride, and copper chloride penetrates into easily In graphitized charcoal.Later, in the material progress filtered in kettle by reaction kettle for being heated to 550 DEG C and constant temperature using far-infrared heater It filters, is the easy graphitized charcoal for penetrating into copper chloride on filter cloth, will penetrate into the easy graphitized charcoal merging retort of copper chloride, use It vacuumizes, 10 DEG C/min of the rate of heat addition, 3 hours progress high temperature carbothermic reduction reactions is kept the temperature after being heated to 2800 DEG C, carbon material is made Copper chloride is restored for reducing agent, the Nanometer Copper after reduction is adsorbed in the lamellar structure of graphitized charcoal.High temperature carbon thermal reduction is anti- Answer resulting graphitized charcoal to entering in water washing tank, addition 40 DEG C of distilled water of temperature are washed 5 times, copper chloride are washed off, later by graphite Change charcoal to entering in retort, 300 DEG C of drying are carried out under vacuum state, the graphitized charcoal after drying is classified out using pulverizing grading machine 5 material.
Classification gained 5um material in 100:1(mass ratio) ratio add naphthalene stirred in stirred tank as after covering It mixes 3 hours, kettle temperature is controlled at 90 DEG C, later, resulting mixture is placed in baking oven and is heated to by 5 DEG C/min heating rate It is 300 DEG C, constant temperature 3 hours, covering is surface-crosslinked in graphitized charcoal, encasement is formed, covering coated graphite charcoal is passed through So that graphitized charcoal structure in charge and discharge process is more stable, it is not pulverized easily, charge and discharge cycles stability is more preferable.After cladding Graphitized charcoal is heated to 700 DEG C by 10 DEG C/min heating rate under vacuum conditions, and constant temperature 2 hours, the material after charing was being taken out 2800 DEG C are heated to by 10 DEG C/min heating rate under vacuum state, constant temperature 2 hours, resulting material was again by it after classification is handled The material of middle 5um is classified out, and even particle size distribution, high mechanical strength is made, and the good graphitized charcoal of heat resistance is a kind of excellent Direct alcohol fuel cell cathode support body material.
The technical indicator for the graphitized charcoal that the embodiment obtains is as follows:
D50(um) Tap density (g/cm3) Powder compacted density (g/cm3) Real density (g/cm3) Specific surface area (m2/ g) Resistivity (Ω .cm)
17±2.0 ≥1.39 ≥1.99 2.48±0.03 0.71±0.5 0.0229
Wherein, D50: being measured using Particle Size Analyzer, obtain accumulative 50% point of the cathode support body material of diameter be 17 ± 2.0um.(2) tap density: being measured using tap density meter, and the tap density for obtaining the cathode support body material is >=1.39g/ cm3.(3) powder compacted density: being tested using powder compacted density tester, obtains the powder compacting of the cathode support body material Density is >=1.99g/cm3.(4) it real density: is tested using real density analyzer, obtains the real density of the cathode support body material For 2.48 ± 0.03g/cm3.(5) it specific surface area: is tested using specific surface area analysis instrument, obtains the ratio of the cathode support body material Surface area is 0.71 ± 0.5m2/g.(6) resistivity: being measured by Instrument Measuring Resistivity of Carbon Products, is obtained through measurement, the cathode support body The resistivity of material is 0.0229 Ω .cm.
Direct alcohol fuel cell cathode support body material product can be produced by this kind of method, uses this kind of cathode The performance testing index of the cathode support body of support body material manufacture is as follows:
(1) porosity: being measured using Archimedes's drainage, and the porosity for obtaining the cathode support body material is 41.7%, hole It is uniformly distributed；(2) resistivity: being measured by Instrument Measuring Resistivity of Carbon Products, is obtained through measurement, the resistivity of the cathode support body material is 0.0229Ω.cm；(3) mechanical property: flexural strength is measured using the three point bending test of universal testing machine, compression strength uses It presses deficient test to measure, is obtained through measurement, the flexural strength 21.20MPa of cathode support body material, compression strength 16.21MPa；(4) Through limit test, service life is 2.6 times of conventional cathodes supporter；(5) shrinking percentage is tested by shrinking percentage tester, passed through Deflection tester tests deflection, and both shrinking percentage and deflection are respectively less than carbonaceous mesophase spherules/graphite shrinking percentage and change Shape amount.In addition have the characteristics that degree of graphitization is high, conductivity is high, mechanical property is good, carbonaceous mesophase spherules/stone can be substituted completely Ink.
Embodiment 3, a kind of preparation method for direct alcohol fuel cell cathode support body material that the present invention mentions, system Preparation Method is specific as follows:
Weighing 950 kilograms of polyvinyl chloride is that raw material is squeezed into polymeric kettle, opens stirring motor, stirring rate 180r/min, in nitrogen 420 DEG C are heated to by 15 DEG C/min heating rate under gas shielded, is pyrolyzed within constant temperature 2 hours, corresponding HCl abjection.Later, exist 700 DEG C are heated to by 10 DEG C/min heating rate under nitrogen protection, is carbonized within constant temperature 3.5 hours, which is cyclisation and virtue Structure process, the release of the small molecules such as simultaneous ethylene, butylene, ethane, benzene become pitch shape melt, undergo interphase Stage forms easy graphitized charcoal.Easy graphitized charcoal obtained uses pulverizing grading machine crushing and classification that partial size is made as the easy of 30um Graphitized charcoal；
520 kilograms of copper chloride is added in reaction kettle, 600 DEG C and constant temperature are heated to using far-infrared heater, copper chloride is molten Solution is at liquid state；
Toward the interior 30um for being added 110 kilograms of reaction kettle using polyvinyl chloride as easy graphitized charcoal made from raw material, stirring electricity is opened Machine, stirring rate 120r/min mixing time 6 hours, are sufficiently mixed easy graphitized charcoal with copper chloride, and copper chloride penetrates into easily In graphitized charcoal.Later, in the material progress filtered in kettle by reaction kettle for being heated to 600 DEG C and constant temperature using far-infrared heater It filters, is the easy graphitized charcoal for penetrating into copper chloride on filter cloth, will penetrate into the easy graphitized charcoal merging retort of copper chloride, use It vacuumizes, 15 DEG C/min of the rate of heat addition, 2 hours progress high temperature carbothermic reduction reactions is kept the temperature after being heated to 2800 DEG C, carbon material is made Copper chloride is restored for reducing agent, the Nanometer Copper after reduction is adsorbed in the lamellar structure of graphitized charcoal.High temperature carbon thermal reduction is anti- Answer resulting graphitized charcoal to entering in water washing tank, addition temperature 50 C distilled water is washed 5 times, copper chloride is washed off, later by graphite Change charcoal to entering in retort, 300 DEG C of drying are carried out under vacuum state, the graphitized charcoal after drying is classified out using pulverizing grading machine The material of 30um.
The material of classification gained 30um is in 100:1.5(mass ratio) ratio addition covering (covering is using n-hexane Mixed with naphthalene 1:1 in mass ratio) after stirred 2 hours in stirred tank, kettle temperature control at 100 DEG C, later, by resulting mixture 300 DEG C are heated to by 10 DEG C/min heating rate in merging baking oven, it is constant temperature 2 hours, covering is surface-crosslinked in graphitized charcoal, Encasement is formed, makes graphitized charcoal structure in charge and discharge process more stable by covering coated graphite charcoal, is not easy Dusting, charge and discharge cycles stability are more preferable.Graphitized charcoal after cladding presses the heating of 15 DEG C/min heating rate under vacuum conditions To 700 DEG C, constant temperature 2 hours, the material after charing is heated to 2800 DEG C by 15 DEG C/min heating rate under evacuated state, perseverance Temperature 2 hours, the material of wherein 30um is classified out after classification is handled by resulting material again, and even particle size distribution, mechanical strength is made Height, the good graphitized charcoal of heat resistance are a kind of excellent direct alcohol fuel cell cathode support body materials.
The technical indicator for the graphitized charcoal that the embodiment obtains is as follows:
D50(um) Tap density (g/cm3) Powder compacted density (g/cm3) Real density (g/cm3) Specific surface area (m2/ g) Resistivity (Ω .cm)
16±2.0 ≥1.40 ≥1.87 2.49±0.03 0.69±0.5 0.0243
Wherein, D50: being measured using Particle Size Analyzer, obtain accumulative 50% point of the cathode support body material of diameter be 16 ± 2.0um.(2) tap density: being measured using tap density meter, and the tap density for obtaining the cathode support body material is >=1.40g/ cm3.(3) powder compacted density: being tested using powder compacted density tester, obtains the powder compacting of the cathode support body material Density is >=1.87g/cm3.(4) it real density: is tested using real density analyzer, obtains the real density of the cathode support body material For 2.49 ± 0.03g/cm3.(5) it specific surface area: is tested using specific surface area analysis instrument, obtains the ratio of the cathode support body material Surface area is 0.69 ± 0.5m2/g.(6) resistivity: being measured by Instrument Measuring Resistivity of Carbon Products, is obtained through measurement, the cathode support body The resistivity of material is 0.0243 Ω .cm.
Direct alcohol fuel cell cathode support body material product can be produced by this kind of method, uses this kind of cathode The performance testing index of the cathode support body of support body material manufacture is as follows:
(1) porosity: being measured using Archimedes's drainage, and the porosity for obtaining the cathode support body material is 42.1%, hole It is uniformly distributed；(2) resistivity: being measured by Instrument Measuring Resistivity of Carbon Products, is obtained through measurement, the resistivity of the cathode support body material is 0.0243Ω.cm；(3) mechanical property: flexural strength is measured using the three point bending test of universal testing machine, compression strength uses It presses deficient test to measure, is obtained through measurement, the flexural strength 16.22MPa of cathode support body material, compression strength 17.15MPa；(4) Through limit test, service life is 3 times of conventional cathodes supporter；(5) shrinking percentage is tested by shrinking percentage tester, passes through change Shape tester tests deflection, and both shrinking percentage and deflection are respectively less than carbonaceous mesophase spherules/graphite shrinking percentage and deformation Amount.In addition have the characteristics that degree of graphitization is high, conductivity is high, mechanical property is good, carbonaceous mesophase spherules/stone can be substituted completely Ink.
The above, is only part preferred embodiment of the invention, and anyone skilled in the art may benefit Equivalent technical solution is modified or is revised as with the technical solution of above-mentioned elaboration.Therefore, technology according to the present invention Any simple modification or substitute equivalents that scheme is carried out, belong to the greatest extent the scope of protection of present invention.

Claims (6)

1. a kind of preparation method of direct alcohol fuel cell cathode support body material, it is characterized in that the following steps are included:
One, it uses 900-950 parts of polyvinyl chloride for raw material, the easy stone that partial size is 5-30um is made through pyrolysis, charing, crushing and classification Inkization charcoal；
Two, 500-520 parts of copper chlorides are added in reaction kettle, 550-600 DEG C and constant temperature, chlorine are heated to using far-infrared heater Change copper to melt into liquid state；
Three, stirring by easy graphitized charcoal, opening made from raw material of polyvinyl chloride for 100-110 parts of 5-30um is added in reaction kettle Motor is mixed, is sufficiently mixed easy graphitized charcoal with copper chloride, copper chloride penetrates into easy graphitized charcoal；Later, by reaction kettle Material is filtered, and is the easy graphitized charcoal for penetrating into copper chloride on filter cloth, and the easy graphitized charcoal for penetrating into copper chloride is placed in retort It is interior, 2-3 hours progress high temperature carbothermic reduction reactions are kept the temperature using vacuumizing, after being heated to 2800 DEG C, easy graphitized charcoal is as also Former agent restores copper chloride, and the Nanometer Copper after reduction is adsorbed in the lamellar structure of graphitized charcoal, by high temperature carbothermic reduction reaction institute Graphitized charcoal to entering in water washing tank, copper chloride is washed off in addition distilled water washing, later by graphitized charcoal to entering retort It is interior, 300 DEG C of drying are carried out under vacuum state, the graphitized charcoal after drying is classified out the material of 5-30um using pulverizing grading machine；
Four, the material of classification gained 5-30um is coated with covering, then uses 300 DEG C of temperature by covering on graphitized charcoal surface Crosslinking forms encasement；Granularity point is made in graphitized charcoal after cladding after 700 DEG C of charings, 2800 DEG C of high temperature graphitizations, classifications Cloth is uniform, is direct alcohol fuel cell cathode support body material.
2. the preparation method of direct alcohol fuel cell cathode support body material according to claim 1, it is characterized in that: institute Stating covering is n-hexane, naphthalene one or two, and the mass ratio of covering and material is 1:100.
3. the preparation method of direct alcohol fuel cell cathode support body material according to claim 1, it is characterized in that: step The manufacturing process of rapid one easy graphitized charcoal is as follows:
900-950 parts of polyvinyl chloride are that raw material is squeezed into polymeric kettle, opening stirring motor, stirring rate 160-180r/min, It is heated to 400-420 DEG C by 10-15 DEG C/min heating rate under nitrogen protection, is pyrolyzed within constant temperature 2-3 hours, corresponding HCl Abjection；Later, 700 DEG C are heated to by 8-10 DEG C/min heating rate under nitrogen protection, are carbonized within constant temperature 3-3.5 hours, The process is cyclisation and aromatization process, and it is molten to become pitch shape for the release of simultaneous ethylene, butylene, ethane, benzene small molecule Body undergoes the interphase stage, forms easy graphitized charcoal, and grain is made using pulverizing grading machine crushing and classification in easy graphitized charcoal obtained Diameter is the easy graphitized charcoal of 5-30um.
4. the preparation method of direct alcohol fuel cell cathode support body material according to claim 1, it is characterized in that: step In rapid three, it will penetrate into the easy graphitized charcoal merging retort of copper chloride, using vacuumizing, 10-15 DEG C of the rate of heat addition/min adds Heat is to keeping the temperature 2-3 hours progress high temperature carbothermic reduction reactions after 2800 DEG C.
5. the preparation method of direct alcohol fuel cell cathode support body material according to claim 1, it is characterized in that: step In rapid three, addition 40-50 DEG C of distilled water of temperature is washed 5 times, washes off copper chloride.
6. the preparation method of direct alcohol fuel cell cathode support body material according to claim 1, it is characterized in that: step In rapid four, the graphitized charcoal after cladding is heated to 700 DEG C by 10-15 DEG C/min heating rate under vacuum conditions, and constant temperature 2-3 is small When, material after charing is heated to 2800 DEG C by 10-15 DEG C/min heating rate under evacuated state, and constant temperature 2-3 hours, institute Material is obtained again to be classified out the material of wherein 5-30um after classification is handled.
CN201910558342.8A 2019-06-26 2019-06-26 A kind of preparation method of direct alcohol fuel cell cathode support body material Pending CN110295297A (en)

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