CN109411767A - Direct alcohol fuel cell profiled porous cathode support body material and preparation method - Google Patents
Direct alcohol fuel cell profiled porous cathode support body material and preparation method Download PDFInfo
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- CN109411767A CN109411767A CN201811267467.7A CN201811267467A CN109411767A CN 109411767 A CN109411767 A CN 109411767A CN 201811267467 A CN201811267467 A CN 201811267467A CN 109411767 A CN109411767 A CN 109411767A
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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
- H01M4/8605—Porous electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention relates to a kind of direct alcohol fuel cell profiled porous cathode support body material and preparation methods.Its technical solution is: one, using sodium metasilicate and the concentrated sulfuric acid as raw material, chemical additives is added according to required aperture value, control nucleus shape and the speed of growth；Two, micro- heating by infrared heating to constent temperature heater inner cavity；Three, the gel particles of receiver being fallen by the immersion of consolidation agent solution, the gel particles that solid state is completed carry out expanding treatment by heat treatment, and four, squeeze into water washing tank, the processing of acid bubble and the processing of alkali bubble are carried out, then squeeze into surface modifier, heat is dried；Five, the material dried is obtained into final products using pulverizer crushing and classification.The beneficial effects of the present invention are: the cathode support body porosity 44.3% of manufacture, 0.0212 Ω .cm of resistivity, flexural strength is big, and compression strength is big, has the characteristics that shrinking percentage is low, deflection is small, conductivity is high, mechanical property is good.
Description
Technical field
The present invention relates to a kind of cathode for fuel cell support body material and preparation, in particular to a kind of direct Aalcohols fuel
Battery profiled porous cathode support body material and preparation method.
Background technique
Methanol, ethyl alcohol and propyl alcohol etc. can be used as the fuel of direct alcohol fuel cell, wherein direct methanol fuel electricity
Pond (Direct methanol fuel cell, DMFC) and Direct Ethanol Fuel Cell (Direct ethanol fuel
Cel1, DEFC) because used in it methanol or ethyl alcohol it is from a wealth of sources, it is cheap, and its energy utilization efficiency is high, it is environmental-friendly
The method of operation, room temperature operability and it is easy to carry the advantages that, thus become new fuel cell in outstanding person, in army
The fields such as thing, communications and transportation, telecommunications tool has a wide range of applications.
Traditional direct alcohol fuel cell is mainly by bipolar plates (mainly being prepared using graphite or metal), catalysis-expansion
It dissipates layer and polymer dielectric film to constitute, the shape of fuel cell is mostly flat, catalysis-diffusion layer of cathode and anode and poly-
Polymer electrolyte membrane is shaped to " three-in-one " membrane electrode assembly using hot pressing mode.But plate direct alcohol fuel cell is deposited
In following disadvantage: (1) using the bipolar plate structure with complex flowfield, manufacturing cost is high；(2) miniature and large-scale prepared by
DMFC weight, volume are big；(3) structure of anode is unfavorable for the discharge of byproduct of reaction (such as carbon dioxide), and the structure of cathode
Also it is unfavorable for the discharge of byproduct of reaction (such as water), influences stability of the battery under long-term work；(4) DFC therein
Subcommittee-to is all made of liquid methanol as fuel in studying carefully, and there are methanol crossover phenomenon, DMC power density substantially reduces (5) cannot be direct
Fuel is stored, complicated intake line is needed；(6) be not suitable for canned non-liquid mobile phase (fuel).
Direct alcohol fuel cell profiled porous cathode support body material is mainly used for making yin in direct alcohol fuel cell
Pole support body material, manufacturing technology require height, and existing manufacture craft is expensive, and shrinking percentage is high, deflection is big, conductance
Rate is low, mechanical property is bad.
Summary of the invention
The purpose of the present invention is to drawbacks described above of the existing technology, and it is different to provide a kind of direct alcohol fuel cell
It is complicated-shape porous can to produce direct alcohol fuel cell by this kind of method for type porous cathode support body material and preparation method
Cathode support body material product, the cathode support body porosity 44.3% manufactured using this kind of cathode support body material, resistivity
0.0212 Ω .cm, 6.52 MPa of flexural strength, 17.25 MPa of compression strength, with shrinking percentage is low, deflection is small, conductivity
High, the features such as mechanical property is good.
A kind of preparation method for direct alcohol fuel cell profiled porous cathode support body material that the present invention mentions, skill
Art scheme be include following procedure:
One, it using sodium metasilicate and the concentrated sulfuric acid as raw material, is diluted after sodium metasilicate is carried out material, being diluted to mass percent concentration is 25
± 2%, the sodium silicate solution after dilution is squeezed into alkali tank, and alkali tank temperature control is 35 ± 3 DEG C, stirring；The concentrated sulfuric acid is diluted with softened water
It is 35 ± 2% to percent concentration, the sulfuric acid solution after dilution is squeezed into sour tank, and sour tank temperature control is 35 ± 3 DEG C, stirring；It will dilution
Chemical additives are added according to required aperture value in sulfuric acid solution afterwards, later mix the sulfuric acid in sour tank with chemical additives
It closes liquid to squeeze into reaction kettle, until, by infrared heating reaction kettle, being kept for 45 ± 3 DEG C of temperature of reaction kettle after proper height；Using
Centrifugal pump squeezes into sodium silicate solution in alkali tank in reaction kettle by fog-spray nozzle, stirring, sulfuric acid and chemical additives mixed liquor and
Sodium silicate solution starts to react, and controls reaction time 1-1.3 hours, and the additive amount by controlling chemical additives controls nucleus shape
Shape and the speed of growth；
Two, the reaction time arrive after open reaction kettle discharge gate, synthesize resulting gel particles and heated by constent temperature heater inner cavity
After drop in receiver, constent temperature heater using infrared heating as heat source, the constent temperature heater inner cavity temperature of control is
55 ± 5 DEG C, constent temperature heater cavity length is adjusted according to required partial size；By infrared heating to constent temperature heater inner cavity
Micro- heat effect, gel particles nucleus nucleation rate in dropping process is accelerated, while liquid water in nucleus is heated slight
Expansion overcomes the deformation for causing nucleus to generate due to gravity, ensure that the uniformity of gel particles pore-size distribution；
Three, the gel particles of receiver are fallen by the immersion of consolidation agent solution, soaking time is 3-3.5 hours, completes gel particles
Solid state；Later, it bleeding off and consolidates agent solution in receiver, receiver is passed through using 90-95 DEG C of saturated vapor, heat is dried 5-6 hours,
The gel particles that solid state is completed carry out expanding treatment by being heat-treated, after steam expanding treatment；
Four, the gel particles after above-mentioned reaming are squeezed into water washing tank later, adds sour infusion and carry out sour bubble processing, acid bubble temperature is
35-45 DEG C, the acid bubble processing time is 3-3.5 hours, and acid bubble bleeds off sour infusion solution after having handled, and addition alkali infusion carries out alkali bubble
Processing, it is 35-50 DEG C that alkali, which steeps temperature, and the alkali bubble processing time is 3.5-4 hours, and alkali bubble solution is bled off after the processing of alkali bubble, squeezes into 70-
80 DEG C of pure water washing, bleeds off washing water after washing, squeezes into surface modifier, and surface modification temperature is 30-45 DEG C, and surface is modified
Handling the time is 2.5-3 hours, after surface modification treatment is complete, gel particles merging drying roller is dried, using 120 DEG C of heat
It dries 2.5 hours；
Five, the material dried is put into water washing tank, uses compressed air for power, material in water washing tank is mixed,
Incorporation time is 6.5-7.5 hours, and the material mixed is reached in drying roller using conveyer belt, controls drying roller temperature
450 DEG C, reaction time 4.5-5 hour；The crushing material dried is classified to obtain the complicated-shape porous yin of direct alcohol fuel cell
Pole support body material.
Preferably, above-mentioned chemical additives use diallyl dimethyl ammoniumchloride, diallyl dimethyl chlorination
The mass ratio of ammonium and sulfuric acid are as follows: 0.5-3.0:100.
Preferably, above-mentioned consolidation agent solution uses concentration for 0.3-2.2%, and temperature is 65 ± 5 DEG C of hydroxylamine hydrochloride solutions.
Preferably, sour infusion uses formic acid solution or acetic acid solution, and addition concentration is 0.5-1:100, in mass ratio.
Preferably, alkali infusion uses triethanolamine solution, and addition concentration is 0.5-1.0:100, in mass ratio.
Preferably, surface modifier use sodium hexametaphosphate solution, concentration 0.2-0.8:100, in mass ratio.
Preferably, in step 5, N-Methyl pyrrolidone, dioctyl phthalate, γ-are squeezed into respectively in water washing tank
Aminopropyl triethoxysilane, ethyl orthosilicate；Material and N-Methyl pyrrolidone, dioctyl phthalate, γ-aminopropyl
Triethoxysilane, ethyl orthosilicate mix in proportion；
The N-Methyl pyrrolidone: dioctyl phthalate: gamma-aminopropyl-triethoxy-silane: ethyl orthosilicate: object
The mixed volume ratio of material are as follows: 750:750:500:500:500.
Preferably, in step 5, N-Methyl pyrrolidone, dioctyl phthalate, γ-are squeezed into respectively in water washing tank
Aminopropyl triethoxysilane, ethyl orthosilicate；Material and N-Methyl pyrrolidone, dioctyl phthalate, γ-aminopropyl
Triethoxysilane, ethyl orthosilicate mix in proportion；
The N-Methyl pyrrolidone: dioctyl phthalate: gamma-aminopropyl-triethoxy-silane: ethyl orthosilicate: object
The mixed volume ratio of material are as follows: 750:700:600:500:600.
Preferably, above-mentioned chemical additives use sodium tripolyphosphate, the mass ratio of sodium tripolyphosphate and sulfuric acid are as follows: 0.6-
4.0:100.
Preferably, in step 3, after steam expanding treatment, then ultrasonic oscillator is opened, ultrasonic frequency 35KHz,
Power 0.6w/cm2, through-hole and reaming are carried out to gel particles by ultrasonic wave again, get through the micropore of gel particles, and mutually
Connection.
The beneficial effects of the present invention are:
The present invention is synthesized after resulting gel particles are heated by constent temperature heater inner cavity and is drop in receiver, and constent temperature heater is adopted
Use infrared heating as heat source, the constent temperature heater inner cavity temperature of control is 55 ± 5 DEG C, constent temperature heater cavity length according to
Required partial size is adjusted.By infrared heating to micro- heat effect of constent temperature heater inner cavity, gel particles are in dropping process
Middle nucleus nucleation rate is accelerated, while the heated slight expansion of liquid water in nucleus, overcomes since gravity causes nucleus to produce
Raw deformation ensure that the uniformity of gel particles pore-size distribution；
The present invention is passed through receiver using 90-95 DEG C of saturated vapor, and heat is dried 5-6 hours, and the gel particles that solid state is completed are passed through
It is heat-treated and carries out expanding treatment, after steam expanding treatment；It can also open ultrasonic oscillator again, ultrasonic frequency 35KHz,
Power 0.6w/cm2, through-hole and reaming are carried out to gel particles by ultrasonic wave again, get through the micropore of gel particles, and mutually
Connection；
The present invention squeezes into N-Methyl pyrrolidone, dioctyl phthalate, gamma-aminopropyl-triethoxy respectively in water washing tank
Silane, ethyl orthosilicate, then use compressed air for power, material in water washing tank is mixed, the material mixed is adopted
It is reached in drying roller with conveyer belt, the material dried is obtained into even aperture distribution, aperture using pulverizer crushing and classification
Adjustable (5-120nm), high mechanical strength, the good direct alcohol fuel cell profiled porous cathode support body material of heat resistance
Material；Direct alcohol fuel cell profiled porous cathode support body material product can be produced by this kind of method, uses this kind
The cathode support body porosity 44.3% of cathode support body material manufacture, resistivity 0.0212 Ω .cm, 6.52 MPa of flexural strength,
17.25 MPa of compression strength has the characteristics that shrinking percentage is low, deflection is small, 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 for direct alcohol fuel cell profiled porous cathode support body material that the present invention mentions
Method specifically includes as follows:
One, with modulus for 3.3 ± 0.02, the high-quality sodium metasilicate and purity of iron content≤0.02 are 98.5%, and impurity content is lower than
The concentrated sulfuric acid of 50ppm is raw material, is diluted after sodium metasilicate is carried out material, and dilution mass percent concentration is 26%, the silicon after dilution
Acid sodium solution is squeezed into alkali tank, and alkali tank temperature control is 36 DEG C, mixing speed 250r/min.The concentrated sulfuric acid is diluted to matter with softened water
Measuring percent concentration is 34%, and the sulfuric acid solution after dilution is squeezed into sour tank, and sour tank temperature control is 34 DEG C, mixing speed 150r/
min.Chemical additives diallyl dimethyl ammoniumchloride is added according to required aperture value in sulfuric acid solution after dilution
(mass ratio: additive amount 2:100) later squeezes into the sulfuric acid in sour tank instead with diallyl dimethyl ammoniumchloride mixed liquor
It answers in kettle, until after proper height, by infrared heating reaction kettle, is kept for 46 DEG C of temperature of reaction kettle, using centrifugal pump by alkali tank
Interior sodium silicate solution is squeezed into reaction kettle by fog-spray nozzle, is stirred, and sulfuric acid is mixed with diallyl dimethyl ammoniumchloride
Liquid and sodium silicate solution start to react, and control reaction time 1-1.3 hours, due to using chemical additives, by controlling crystal form
The additive amount control nucleus shape and the speed of growth of controlling agent.
Two, the reaction time arrive after open reaction kettle discharge gate, synthesize resulting gel particles by constent temperature heater inner cavity
It is drop in receiver after heating, constent temperature heater is using infrared heating as heat source, the constent temperature heater inner cavity temperature of control
Degree is 57 DEG C, and constent temperature heater cavity length is adjusted according to required partial size.By infrared heating in constent temperature heater
Micro- heat effect of chamber, gel particles nucleus nucleation rate in dropping process is accelerated, while the liquid water in nucleus is heated light
Microdilatancy overcomes the deformation for causing nucleus to generate due to gravity, ensure that the uniformity of gel particles pore-size distribution.
Three, falling into the gel particles of receiver, (adjustable as needed, concentration is by a certain concentration consolidation agent solution
1.8%, temperature be 67 DEG C of hydroxylamine hydrochloride solutions) immersion, soaking time be 3-3.5 hour, completion gel particles solid state.Later,
It bleeds off and consolidates agent solution in receiver, receiver is passed through using 90-95 DEG C of saturated vapor, heat dries 5-6 hours, solid state is completed
Gel particles expanding treatment is carried out by heat treatment, after steam expanding treatment；
Four, the gel particles after expanding treatment are squeezed into water washing tank later, addition concentration is 0.7:100(mass ratio) acid infusion first
Acid solution carries out sour bubble processing, and acid bubble temperature is 40 DEG C, and the acid bubble processing time is 3-3.5 hours, and acid bubble bleeds off acid after having handled
Infusion solution, addition concentration be 0.8:100(mass ratio) alkali infusion triethanolamine solution carry out the processing of alkali bubble, alkali bubble temperature be
35-50 DEG C, the alkali bubble processing time is 3.5-4 hours, and alkali bubble solution is bled off after the processing of alkali bubble, squeezes into 70-80 DEG C of pure water by string
Four mode is washed 5 times, and washing water is bled off after washing, squeeze into concentration be 0.5:100(mass ratio) the inclined phosphorus of surface modifier six
Acid sodium solution, surface modification temperature are 30-45 DEG C, and the surface modification treatment time is 2.5-3 hours, after surface modification treatment is complete,
Gel particles merging drying roller is dried, is dried 2.5 hours using 120 DEG C of heat.
Five, the material dried is put into water washing tank, squeezes into N-Methyl pyrrolidone, adjacent benzene two respectively in water washing tank
Formic acid dioctyl ester, gamma-aminopropyl-triethoxy-silane, ethyl orthosilicate.Material and N-Methyl pyrrolidone, phthalic acid two
Monooctyl ester, gamma-aminopropyl-triethoxy-silane, ethyl orthosilicate are mixed in a certain ratio；Specific mixed proportion is as follows:
N-Methyl pyrrolidone: dioctyl phthalate: gamma-aminopropyl-triethoxy-silane: ethyl orthosilicate: material
=750l:750l:500l:500l:500l；
It uses compressed air for power, material in water washing tank is mixed, incorporation time is 6.5-7.5 hours, will be mixed
Material reached in drying roller using conveyer belt, control 450 DEG C of drying roller temperature, reaction time 4.5-5 hour.It will drying
Good material obtains even aperture distribution using pulverizer crushing and classification, and aperture is adjustable (5-120nm), high mechanical strength,
The good direct alcohol fuel cell profiled porous cathode support body material of heat resistance.
Embodiment 2, a kind of preparation for direct alcohol fuel cell profiled porous cathode support body material that the present invention mentions
Method,
One, with modulus for 3.3 ± 0.02, the high-quality sodium metasilicate and purity of iron content≤0.02 are 98.5%, and impurity content is lower than
The concentrated sulfuric acid of 50ppm is raw material, is diluted after sodium metasilicate is carried out material, and dilution mass percent concentration is 25%, the silicon after dilution
Acid sodium solution is squeezed into alkali tank, and alkali tank temperature control is 35 DEG C, mixing speed 250r/min.The concentrated sulfuric acid is diluted to matter with softened water
Measuring percent concentration is 35%, and the sulfuric acid solution after dilution is squeezed into sour tank, and sour tank temperature control is 35 DEG C, mixing speed 150r/
min.Chemical additives diallyl dimethyl ammoniumchloride is added according to required aperture value in sulfuric acid solution after dilution
(mass ratio: additive amount 2:100) later squeezes into the sulfuric acid in sour tank instead with diallyl dimethyl ammoniumchloride mixed liquor
It answers in kettle, until after proper height, by infrared heating reaction kettle, is kept for 45 DEG C of temperature of reaction kettle, using centrifugal pump by alkali tank
Interior sodium silicate solution is squeezed into reaction kettle by fog-spray nozzle, is stirred, and sulfuric acid is mixed with diallyl dimethyl ammoniumchloride
Liquid and sodium silicate solution start to react, and control reaction time 1-1.3 hours, due to using chemical additives, by controlling crystal form
The additive amount control nucleus shape and the speed of growth of controlling agent.
Two, the reaction time arrive after open reaction kettle discharge gate, synthesize resulting gel particles by constent temperature heater inner cavity
It is drop in receiver after heating, constent temperature heater is using infrared heating as heat source, the constent temperature heater inner cavity temperature of control
Degree is 55 DEG C, and constent temperature heater cavity length is adjusted according to required partial size.By infrared heating in constent temperature heater
Micro- heat effect of chamber, gel particles nucleus nucleation rate in dropping process is accelerated, while the liquid water in nucleus is heated light
Microdilatancy overcomes the deformation for causing nucleus to generate due to gravity, ensure that the uniformity of gel particles pore-size distribution.
Three, falling into the gel particles of receiver, (adjustable as needed, concentration is by a certain concentration consolidation agent solution
0.3-2.2%, temperature be 65 DEG C of hydroxylamine hydrochloride solutions) immersion, soaking time be 3-3.5 hour, completion gel particles solid state.
Later, it bleeds off and consolidates agent solution in receiver, be passed through receiver using 90 DEG C of saturated vapors, heat is dried 5-6 hours, and solid state is complete
At gel particles expanding treatment is carried out by heat treatment, after steam expanding treatment；Ultrasonic oscillator is opened, ultrasonic frequency is
35KHz, power 0.6w/cm2, through-hole and reaming are carried out to gel particles by ultrasonic wave again, get through the micropore of gel particles,
And it is connected with each other；
Four, gel particles are squeezed into water washing tank later, addition concentration is 0.8:100(mass ratio) acid infusion formic acid solution progress acid
Bubble processing, acid bubble temperature is 35-45 DEG C, and the acid bubble processing time is 3-3.5 hours, and acid bubble bleeds off sour infusion solution after having handled,
Addition concentration is 0.7:100(mass ratio) the progress alkali bubble processing of alkali infusion triethanolamine solution, it is 35-50 DEG C that alkali, which steeps temperature, alkali
The bubble processing time is 3.5-4 hour, and alkali bubble solution is bled off after the processing of alkali bubble, squeezes into 70-80 DEG C of pure water by going here and there water in the way of four
Wash 5 times, washing water bled off after washing, squeeze into concentration be 0.8:100(mass ratio) surface modifier sodium hexametaphosphate solution, table
Face modification temperature is 30-45 DEG C, and the surface modification treatment time is 2.5-3 hours, and after surface modification treatment is complete, gel particles are placed in
Drying roller is dried, and is dried 2.5 hours using 120 DEG C of heat.
Five, the material dried is put into water washing tank, squeezes into N-Methyl pyrrolidone, adjacent benzene two respectively in water washing tank
Formic acid dioctyl ester, gamma-aminopropyl-triethoxy-silane, ethyl orthosilicate.Material and N-Methyl pyrrolidone, phthalic acid two
Monooctyl ester, gamma-aminopropyl-triethoxy-silane, ethyl orthosilicate are mixed in a certain ratio；Specific mixed proportion is as follows:
N-Methyl pyrrolidone: dioctyl phthalate: gamma-aminopropyl-triethoxy-silane: ethyl orthosilicate: material
=750l:750l:500l:500l:500l；
It uses compressed air for power, material in water washing tank is mixed, incorporation time is 6.5-7.5 hours, will be mixed
Material reached in drying roller using conveyer belt, control 450 DEG C of drying roller temperature, reaction time 4.5-5 hour.It will drying
Good material obtains even aperture distribution using pulverizer crushing and classification, and aperture is adjustable (5-120nm), high mechanical strength,
The good direct alcohol fuel cell profiled porous cathode support body material of heat resistance.
Embodiment 3, the present invention mention a kind of direct alcohol fuel cell profiled porous cathode support body that the present invention mentions
The preparation method of material,
One, with modulus for 3.3 ± 0.02, the high-quality sodium metasilicate and purity of iron content≤0.02 are 98.5%, and impurity content is lower than
The concentrated sulfuric acid of 50ppm is raw material, is diluted after sodium metasilicate is carried out material, and dilution mass percent concentration is 23%, the silicon after dilution
Acid sodium solution is squeezed into alkali tank, and alkali tank temperature control is 32 DEG C, mixing speed 250r/min.The concentrated sulfuric acid is diluted to matter with softened water
Measuring percent concentration is 33%, and the sulfuric acid solution after dilution is squeezed into sour tank, and sour tank temperature control is 32 DEG C, mixing speed 150r/
min.Chemical additives sodium tripolyphosphate (mass ratio: addition is added according to required aperture value in sulfuric acid solution after dilution
Amount is 0.6:100), the sulfuric acid in sour tank is squeezed into reaction kettle with sodium tripolyphosphate mixed liquor later, until being beaten after proper height
Infrared heating reaction kettle is opened, is kept for 42 DEG C of temperature of reaction kettle, sodium silicate solution in alkali tank is passed through by fog-spray nozzle using centrifugal pump
It squeezes into reaction kettle, stirs, sulfuric acid starts to react with sodium tripolyphosphate mixed liquor and sodium silicate solution, controls reaction time 1-
1.3 hours, due to using chemical additives, the additive amount by controlling chemical additives controlled nucleus shape and the speed of growth.
Two, the reaction time arrive after open reaction kettle discharge gate, synthesize resulting gel particles by constent temperature heater inner cavity
It is drop in receiver after heating, constent temperature heater is using infrared heating as heat source, the constent temperature heater inner cavity temperature of control
Degree is 50 DEG C, and constent temperature heater cavity length is adjusted according to required partial size.By infrared heating in constent temperature heater
Micro- heat effect of chamber, gel particles nucleus nucleation rate in dropping process is accelerated, while the liquid water in nucleus is heated light
Microdilatancy overcomes the deformation for causing nucleus to generate due to gravity, ensure that the uniformity of gel particles pore-size distribution.
Three, falling into the gel particles of receiver, (adjustable as needed, concentration is by a certain concentration consolidation agent solution
0.3%, temperature be 6 DEG C of hydroxylamine hydrochloride solutions) immersion, soaking time be 3-3.5 hour, completion gel particles solid state.Later,
It bleeds off and consolidates agent solution in receiver, be passed through receiver using 90 DEG C of saturated vapors, heat is dried 5-6 hours, and solid state is completed
Gel particles carry out expanding treatment by being heat-treated, after steam expanding treatment；Ultrasonic oscillator is opened, ultrasonic frequency is
35KHz, power 0.6w/cm2, through-hole and reaming are carried out to gel particles by ultrasonic wave again, get through the micropore of gel particles,
And it is connected with each other；
Four, gel particles are squeezed into water washing tank later, addition concentration is 0.5:100(mass ratio) acid infusion formic acid solution progress acid
Bubble processing, acid bubble temperature is 35-45 DEG C, and the acid bubble processing time is 3-3.5 hours, and acid bubble bleeds off sour infusion solution after having handled,
Addition concentration is 0.5:100(mass ratio) the progress alkali bubble processing of alkali infusion triethanolamine solution, it is 35-50 DEG C that alkali, which steeps temperature, alkali
The bubble processing time is 3.5-4 hour, and alkali bubble solution is bled off after the processing of alkali bubble, squeezes into 70-80 DEG C of pure water by going here and there water in the way of four
Wash 5 times, washing water bled off after washing, squeeze into concentration be 0.2:100(mass ratio) surface modifier sodium hexametaphosphate solution, table
Face modification temperature is 30-45 DEG C, and the surface modification treatment time is 2.5-3 hours, and after surface modification treatment is complete, gel particles are placed in
Drying roller is dried, and is dried 2.5 hours using 120 DEG C of heat.
Five, the material dried is put into water washing tank, squeezes into N-Methyl pyrrolidone, adjacent benzene two respectively in water washing tank
Formic acid dioctyl ester, gamma-aminopropyl-triethoxy-silane, ethyl orthosilicate.Material and N-Methyl pyrrolidone, phthalic acid two
Monooctyl ester, gamma-aminopropyl-triethoxy-silane, ethyl orthosilicate are mixed in a certain ratio；Specific mixed proportion is as follows:
N-Methyl pyrrolidone: dioctyl phthalate: gamma-aminopropyl-triethoxy-silane: ethyl orthosilicate: material
Mixed volume ratio are as follows: 750:700:600:500:600；
It uses compressed air for power, material in water washing tank is mixed, incorporation time is 6.5-7.5 hours, will be mixed
Material reached in drying roller using conveyer belt, control 450 DEG C of drying roller temperature, reaction time 4.5-5 hour.It will drying
Good material obtains even aperture distribution using pulverizer crushing and classification, and aperture is adjustable (5-120nm), high mechanical strength,
The good direct alcohol fuel cell profiled porous cathode support body material of heat resistance.
Embodiment 4, the present invention mention a kind of direct alcohol fuel cell profiled porous cathode support body that the present invention mentions
The preparation method of material,
One, with modulus for 3.3 ± 0.02, the high-quality sodium metasilicate and purity of iron content≤0.02 are 98.5%, and impurity content is lower than
The concentrated sulfuric acid of 50ppm is raw material, is diluted after sodium metasilicate is carried out material, and dilution mass percent concentration is 27%, the silicon after dilution
Acid sodium solution is squeezed into alkali tank, and alkali tank temperature control is 38 DEG C, mixing speed 250r/min.The concentrated sulfuric acid is diluted to matter with softened water
Measuring percent concentration is 37%, and the sulfuric acid solution after dilution is squeezed into sour tank, and sour tank temperature control is 38 DEG C, mixing speed 150r/
min.Chemical additives sodium tripolyphosphate (mass ratio: addition is added according to required aperture value in sulfuric acid solution after dilution
Amount is 4.0:100), the sulfuric acid in sour tank is squeezed into reaction kettle with sodium tripolyphosphate mixed liquor later, until leading to after proper height
Infrared heating reaction kettle is crossed, is kept for 48 DEG C of temperature of reaction kettle, sodium silicate solution in alkali tank is passed through by fog-spray nozzle using centrifugal pump
It squeezes into reaction kettle, stirs, sulfuric acid starts to react with sodium tripolyphosphate mixed liquor and sodium silicate solution, and the control reaction time 1 is small
When, due to using chemical additives, the additive amount by controlling chemical additives controls nucleus shape and the speed of growth.
Two, the reaction time arrive after open reaction kettle discharge gate, synthesize resulting gel particles by constent temperature heater inner cavity
It is drop in receiver after heating, constent temperature heater is using infrared heating as heat source, the constent temperature heater inner cavity temperature of control
Degree is 60 DEG C, and constent temperature heater cavity length is adjusted according to required partial size.By infrared heating in constent temperature heater
Micro- heat effect of chamber, gel particles nucleus nucleation rate in dropping process is accelerated, while the liquid water in nucleus is heated light
Microdilatancy overcomes the deformation for causing nucleus to generate due to gravity, ensure that the uniformity of gel particles pore-size distribution.
Three, falling into the gel particles of receiver, (adjustable as needed, concentration is by a certain concentration consolidation agent solution
2.2%, temperature be 70 DEG C of hydroxylamine hydrochloride solutions) immersion, soaking time be 3 hours, complete gel particles solid state.Later, it bleeds off
Agent solution is consolidated in receiver, is passed through receiver using 95 DEG C of saturated vapors, heat is dried 5 hours, the gel particles that solid state is completed
Expanding treatment is carried out by being heat-treated, after steam expanding treatment；Open ultrasonic oscillator, ultrasonic frequency 35KHz, power
0.6w/cm2, through-hole and reaming are carried out to gel particles by ultrasonic wave again, get through the micropore of gel particles, and be connected with each other；
Four, gel particles are squeezed into water washing tank later, addition concentration is 1:100(mass ratio) the sour bubble of acid infusion formic acid solution progress
Processing, acid bubble temperature is 45 DEG C, and the acid bubble processing time is 3-3.5 hours, and acid bubble bleeds off sour infusion solution after having handled, and is added dense
Degree is 1.0:100(mass ratio) the progress alkali bubble processing of alkali infusion triethanolamine solution, it is 50 DEG C that alkali, which steeps temperature, the alkali bubble processing time
It is 3.5-4 hours, alkali bubble solution is bled off after the processing of alkali bubble, squeezes into 80 DEG C of pure water and washed 5 times in the way of string four, put after washing
Fall washing water, squeeze into concentration be 0.8:100(mass ratio) surface modifier sodium hexametaphosphate solution, surface modification temperature be 45
DEG C, the surface modification treatment time is 2.5-3 hours, after surface modification treatment is complete, gel particles merging drying roller dried,
It is dried 2.5 hours using 120 DEG C of heat.
Five, the material dried is put into water washing tank, squeezes into N-Methyl pyrrolidone, adjacent benzene two respectively in water washing tank
Formic acid dioctyl ester, gamma-aminopropyl-triethoxy-silane, ethyl orthosilicate.Material and N-Methyl pyrrolidone, phthalic acid two
Monooctyl ester, gamma-aminopropyl-triethoxy-silane, ethyl orthosilicate are mixed in a certain ratio；Specific mixed proportion is as follows:
N-Methyl pyrrolidone: dioctyl phthalate: gamma-aminopropyl-triethoxy-silane: ethyl orthosilicate: material
Mixed volume ratio are as follows: 750:700:600:500:600；
It uses compressed air for power, material in water washing tank is mixed, incorporation time is 6.5-7.5 hours, will be mixed
Material reached in drying roller using conveyer belt, control 450 DEG C of drying roller temperature, reaction time 4.5-5 hour.It will drying
Good material obtains even aperture distribution using pulverizer crushing and classification, and aperture is adjustable (5-120nm), high mechanical strength,
The good direct alcohol fuel cell profiled porous cathode support body material of heat resistance.
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 (10)
1. a kind of preparation method of direct alcohol fuel cell profiled porous cathode support body material, it is characterized in that including following mistake
Journey:
One, it using sodium metasilicate and the concentrated sulfuric acid as raw material, is diluted after sodium metasilicate is carried out material, being diluted to mass percent concentration is 25
± 2%, the sodium silicate solution after dilution is squeezed into alkali tank, and alkali tank temperature control is 35 ± 3 DEG C, stirring；The concentrated sulfuric acid is diluted with softened water
It is 35 ± 2% to percent concentration, the sulfuric acid solution after dilution is squeezed into sour tank, and sour tank temperature control is 35 ± 3 DEG C, stirring；It will dilution
Chemical additives are added according to required aperture value in sulfuric acid solution afterwards, later mix the sulfuric acid in sour tank with chemical additives
It closes liquid to squeeze into reaction kettle, until, by infrared heating reaction kettle, being kept for 45 ± 3 DEG C of temperature of reaction kettle after proper height；Using
Centrifugal pump squeezes into sodium silicate solution in alkali tank in reaction kettle by fog-spray nozzle, stirring, sulfuric acid and chemical additives mixed liquor and
Sodium silicate solution starts to react, and controls reaction time 1-1.3 hours, and the additive amount by controlling chemical additives controls nucleus shape
Shape and the speed of growth；
Two, the reaction time arrive after open reaction kettle discharge gate, synthesize resulting gel particles and heated by constent temperature heater inner cavity
After drop in receiver, constent temperature heater using infrared heating as heat source, the constent temperature heater inner cavity temperature of control is
55 ± 5 DEG C, constent temperature heater cavity length is adjusted according to required partial size；By infrared heating to constent temperature heater inner cavity
Micro- heat effect, gel particles nucleus nucleation rate in dropping process is accelerated, while liquid water in nucleus is heated slight
Expansion overcomes the deformation for causing nucleus to generate due to gravity, ensure that the uniformity of gel particles pore-size distribution；
Three, the gel particles of receiver are fallen by the immersion of consolidation agent solution, soaking time is 3-3.5 hours, completes gel particles
Solid state；Later, it bleeding off and consolidates agent solution in receiver, receiver is passed through using 90-95 DEG C of saturated vapor, heat is dried 5-6 hours,
The gel particles that solid state is completed carry out expanding treatment by being heat-treated, after steam expanding treatment；
Four, the gel particles after above-mentioned reaming are squeezed into water washing tank later, adds sour infusion and carry out sour bubble processing, acid bubble temperature is
35-45 DEG C, the acid bubble processing time is 3-3.5 hours, and acid bubble bleeds off sour infusion solution after having handled, and addition alkali infusion carries out alkali bubble
Processing, it is 35-50 DEG C that alkali, which steeps temperature, and the alkali bubble processing time is 3.5-4 hours, and alkali bubble solution is bled off after the processing of alkali bubble, squeezes into 70-
80 DEG C of pure water washing, bleeds off washing water after washing, squeezes into surface modifier, and surface modification temperature is 30-45 DEG C, and surface is modified
Handling the time is 2.5-3 hours, after surface modification treatment is complete, gel particles merging drying roller is dried, using 120 DEG C of heat
It dries 2.5 hours；
Five, the material dried is put into water washing tank, uses compressed air for power, material in water washing tank is mixed,
Incorporation time is 6.5-7.5 hours, and the material mixed is reached in drying roller using conveyer belt, controls drying roller temperature
450 DEG C, reaction time 4.5-5 hour；The crushing material dried is classified to obtain the complicated-shape porous yin of direct alcohol fuel cell
Pole support body material.
2. the preparation method of direct alcohol fuel cell profiled porous cathode support body material according to claim 1,
Be characterized in: the chemical additives use diallyl dimethyl ammoniumchloride, diallyl dimethyl ammoniumchloride and sulfuric acid
Mass ratio are as follows: 0.5-3.0:100.
3. the preparation method of direct alcohol fuel cell profiled porous cathode support body material according to claim 1,
Be characterized in: the consolidation agent solution uses concentration for 0.3-2.2%, and temperature is 65 ± 5 DEG C of hydroxylamine hydrochloride solutions.
4. the preparation method of direct alcohol fuel cell profiled porous cathode support body material according to claim 1,
Be characterized in: sour infusion uses formic acid solution or acetic acid solution, and addition concentration is 0.5-1:100, in mass ratio.
5. the preparation method of direct alcohol fuel cell profiled porous cathode support body material according to claim 1,
Be characterized in: alkali infusion uses triethanolamine solution, and addition concentration is 0.5-1.0:100, in mass ratio.
6. the preparation method of direct alcohol fuel cell profiled porous cathode support body material according to claim 1,
Be characterized in: surface modifier use sodium hexametaphosphate solution, concentration 0.2-0.8:100, in mass ratio.
7. the preparation method of direct alcohol fuel cell profiled porous cathode support body material according to claim 1,
It is characterized in:
In step 5, N-Methyl pyrrolidone, dioctyl phthalate, three second of γ-aminopropyl are squeezed into respectively in water washing tank
Oxysilane, ethyl orthosilicate；Material and N-Methyl pyrrolidone, dioctyl phthalate, gamma-aminopropyl-triethoxy silicon
Alkane, ethyl orthosilicate mix in proportion；
The N-Methyl pyrrolidone: dioctyl phthalate: gamma-aminopropyl-triethoxy-silane: ethyl orthosilicate: object
The mixed volume ratio of material are as follows: 750:750:500:500:500.
8. the preparation method of direct alcohol fuel cell profiled porous cathode support body material according to claim 7,
It is characterized in:
In step 5, N-Methyl pyrrolidone, dioctyl phthalate, three second of γ-aminopropyl are squeezed into respectively in water washing tank
Oxysilane, ethyl orthosilicate；Material and N-Methyl pyrrolidone, dioctyl phthalate, gamma-aminopropyl-triethoxy silicon
Alkane, ethyl orthosilicate mix in proportion；
The N-Methyl pyrrolidone: dioctyl phthalate: gamma-aminopropyl-triethoxy-silane: ethyl orthosilicate: object
The mixed volume ratio of material are as follows: 750:700:600:500:600.
9. the preparation method of direct alcohol fuel cell profiled porous cathode support body material according to claim 1,
Be characterized in: the chemical additives use sodium tripolyphosphate, the mass ratio of sodium tripolyphosphate and sulfuric acid are as follows: 0.6-4.0:100.
10. the preparation method of direct alcohol fuel cell profiled porous cathode support body material according to claim 1,
It is characterized in:
In step 3, after steam expanding treatment, then ultrasonic oscillator is opened, ultrasonic frequency 35KHz, power 0.6w/
cm2, through-hole and reaming are carried out to gel particles by ultrasonic wave again, get through the micropore of gel particles, and be connected with each other.
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| CN110295297A (en) * | 2019-06-26 | 2019-10-01 | 郭峰 | A kind of preparation method of direct alcohol fuel cell cathode support body material |
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