CN108306035A - A kind of composite organic siloxane phosphate electrolyte film in fuel cell and preparation method - Google Patents
A kind of composite organic siloxane phosphate electrolyte film in fuel cell and preparation method Download PDFInfo
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Abstract
A kind of composite organic siloxane phosphate electrolyte film in fuel cell of present invention offer and preparation method, after evenly mixing by organosilan and phosphate, concentrated nitric acid is added and carries out condensation reaction, fully filtering drying obtains gel-like material after reaction, gel rubber material is coated uniformly on porous ceramics film surface, being put into vacuum drying oven after compacting and carrying out repeatedly positive pressuring drying under the conditions of 120 DEG C keeps film fine and close, obtains Ceramic Composite silica alkane phosphate dielectric film.The present invention overcomes traditional Proton Exchange Membrane Fuel Cells due to the limitation of organic polymer membrane material, and operation temperature area is relatively narrow, and to influence the catalytic performance of proton conductivity and catalyst and the defect in service life, the dielectric film proton transfer rate of preparation reaches 10‑2S/cm grades, alcohols rejection rate is good, and operating temperature is higher, can be improved to about 240 DEG C, solves the problems, such as that traditional proton exchange membrane operation temperature area is relatively narrow, can be widely used in fuel cell field as membrane material.
Description
Technical field
The present invention relates to fuel cell material fields, and in particular to a kind of composite organic siloxane phosphate fuel cell electricity
Solve plasma membrane and preparation method.
Background technology
Due to non-renewable for traditional fossil fuel, and environmental pollution caused by during use is serious, seeks ring
The renewable sources of energy of guarantor's type are the severe tasks of 21 century facing mankind.Fuel cell (Fuel cell) is a kind of novel energy
Source technology directly converts the chemical energy of fuel to electric energy by electrochemical reaction, and fuel used is hydrogen, methanol and hydrocarbon
The hydrogen-rich materials such as class, there are no pollution to the environment and with high energy efficiency and high power density, therefore, fuel cell has
Have broad application prospects.
Proton Exchange Membrane Fuel Cells (Proton Exchange Membrane Fuel Cell, PEMFC)) it is after alkali
Property fuel cell (AFC), phosphoric acid fuel cell (PAFC), molten carbonate fuel cell (MCFC) and solid oxide fuel electricity
Pond (SOFC) and the 5th Replacing fuel battery to grow up have energy conversion rate using polymeric membrane as solid electrolyte
The features such as high and low temperature starts, electroless matter is revealed, is widely used in light-duty vehicle, portable power and small drive device.
PEMFC is mainly made of components such as end plate, bipolar plates and membrane electrodes.Membrane electrode is the core component of PEMFC, mainly by gas
Diffusion layer, Catalytic Layer and proton exchange membrane are constituted.Proton exchange membrane (PEM) is the key that Proton Exchange Membrane Fuel Cells portion
Part directly affects battery performance and service life.
Proton Exchange Membrane Fuel Cells proton exchange membrane mainly has fluosulfonic acid type proton exchange membrane, non-fluorinated polymer proton to hand over
Change the types such as film.Fluosulfonic acid type proton exchange membrane is the Nafion of DuPont Corporation@Film, in 150 DEG C of strong acid and oxidation ring
It remains to keep good stability, high mechanical strength and conductivity high at high humidity, but Nafion in border@Class film is still deposited
The water content in proton conductivity depends critically upon film, the conductivity of film declines apparent when low humidity；Operating temperature is more than water
Boiling point is easy to be dehydrated and it is made to lose proton conductivity of phosphoric acid, is not used to medium temperature (100~200 DEG C) fuel cell；High temperature
When film easily occur chemical degradation, generate toxicity；Monomer synthesis is difficult, and of high cost, waste product is difficult；For methanol fuel electricity
The shortcomings of methanol leakage easily occurs when pond.It is expensive for perfluorosulfonic acid type proton exchange membrane, due to organic polymer membrane material
Limitation, the shortcomings of operation temperature area is relatively narrow, catalytic performance and service life to influence proton conductivity and catalyst, people's exploitation
Go out nonfluorinated proton exchange membrane, polyphenylene oxide, aromatic polyester, polybenzimidazoles, polyimides, polysulfones, polyketone etc. are passed through into matter
Sonization processing is used for PEMFC, such as the proton exchange polymer network-type film of ionomer, but when being mismatched there is also acid-base pair
Interionic binding force is weaker, leads to the failure of ionomer under high temperature, and the film dimensions stability of the System forming is made to decline.
In order to overcome traditional Proton Exchange Membrane Fuel Cells due to the limitation of organic polymer membrane material as possible, operation temperature area compared with
It is narrow, it is new by preparing to influence catalytic performance and the service life and the shortcomings of poor alcohol-rejecting ability of proton conductivity and catalyst
Type composite membrane also has correlative study.
Chinese invention patent application number 201310129877.6 discloses a kind of proton exchange membrane and preparation method thereof, with poly-
Being made in such as 150-200 DEG C of high temperature with the compacting of polyphosphoric acids blend film PBO/PPA mixed serums to penylene Benzo-dioxazole has
Excellent high proton conductivity, film forming and mechanical property, polyparaphenylene's Benzo-dioxazole matter suitable for high-temperature fuel cell
Proton exchange.But program raw material film forming is poor, since component swelling coefficient is different, leads to the reduction of proton exchange film quality,
And preparation process is cumbersome, and the time is long.
It is therefore proposed that a kind of fuel battery proton exchange film stablized in high temperature operating conditions lower structure, overcomes traditional fluorine
Sulfonic acid proton exchange film operation temperature area is relatively narrow, to influence the catalytic performance of proton conductivity and catalyst and lacking for service life
It falls into, there is highly important practical significance for the patulous research of proton exchange membrane warm area.
Invention content
For traditional Proton Exchange Membrane Fuel Cells due to the limitation of organic polymer membrane material, operation temperature area is relatively narrow, to
Proton conductivity and the catalytic performance of catalyst and the defect in service life are influenced, the present invention proposes a kind of composite organic siloxane phosphoric acid
Ester electrolyte film in fuel cell and preparation method thereof, dielectric film proton transfer rate is high, and alcohols rejection rate is good, operating temperature compared with
Height solves the problems, such as that traditional proton exchange membrane operation temperature area is relatively narrow.
To solve the above problems, one aspect of the present invention provides a kind of composite organic siloxane phosphate fuel-cell electrolyte
Film, the dielectric film are：With porous metal oxide ceramics for basic three-dimensional framework, siloxanes phosphate catalytic activity material
Material infiltrates the porous ceramics film surface and the internal structure of composite membrane formed, and when work, the siloxanes phosphate electrolyte was lived
Property material provide channel for proton propagation, while ensureing the stability of material structure.
Preferably, the porous metal oxide ceramics are one in magnesia ceramics, aluminium oxide ceramics, titanium oxide ceramics
Kind or two or more combinations, porous metal oxide ceramics aperture are 10-300 microns.
On the other hand a kind of preparation method of composite organic siloxane phosphate electrolyte film in fuel cell is provided, using more
Raw material of the mesoporous metal oxide ceramic powder as three-dimensional framework, organosilan, dimethyl short chain phosphate are as active material
Raw material, specific preparation method is as follows：
（1）70-93.8 mass parts organosilan is uniformly mixed with the dimethyl short chain phosphate of 6.2-30 mass parts, control strip
Part is that mixing speed is more than 100 revs/min, and temperature is 100-170 DEG C, is stirred under nitrogen protection atmosphere, nitrogen flow 3-
It 50mL/ minutes, after the completion of stirring, is cooled to room temperature, is evacuated to 300-800Pa, remove the bubble in cementitious compositions, obtain
Cementitious compositions；
（2）Concentrated nitric acid is added into the cementitious compositions, carries out condensation reaction, fully filtering drying obtains gel after reaction
Material；
（3）The gel-like material is coated uniformly on porous metal oxide ceramic surface, vacuum drying oven is put into after compacting
Positive pressuring drying is carried out repeatedly under the conditions of 120 DEG C keeps film fine and close, obtains Ceramic Composite silica alkane phosphate dielectric film.
Preferably, the viscosity of the organosilan is 45-400mPas, and the organosilan is tetramethylsilane, diformazan
One kind in base diethylsilane, hexamethyldisiloxane, cyclomethicone.
Preferably, the viscosity of dimethyl short chain phosphate is 22-101mPas, and the dimethyl short chain phosphate is two
Methyl chloroethylphosphate, dimethyl ethyl phosphate, dimethyl hydroxy ethyl phosphate, dimethyl trichloroethyl phosphate, two
One kind in methylphosphorothioate, dimethyl ethenyl phosphate, dimethyl propyl phosphate.
Preferably, the molar ratio of the concentrated nitric acid and organosilan is 1:The mass concentration of 100-150, concentrated nitric acid are 90%-
98%。
Preferably, it is 70-100 DEG C that the temperature of porous metal oxide is kept in the coating procedure, is convenient for organic silica
Alkane phosphate penetrates into porous metal oxide pores gap.
Preferably, the pressing process is to prevent from destroying porous metals using press device, control pressure 1-30kPa
Oxide ceramics skeleton.
Preferably, the positive pressuring drying is using hot wind medium, and control hot blast temperature is 120 DEG C, wind speed 10-30m/s,
Artificial acceleration dry film.
For traditional Proton Exchange Membrane Fuel Cells due to the limitation of organic polymer membrane material, operation temperature area is relatively narrow, to
It influences proton conductivity and the catalytic performance of catalyst and the defect in service life, the present invention uniformly mixes organosilan with phosphate
Afterwards, concentrated nitric acid is added and carries out condensation reaction, fully filtering drying obtains gel-like material after reaction, and gel rubber material is uniformly coated
Being put into vacuum drying oven after porous ceramics film surface, compacting and carrying out repeatedly positive pressuring drying under the conditions of 120 DEG C keeps film fine and close,
Obtain Ceramic Composite silica alkane phosphate dielectric film.The present invention by prepare Ceramic Composite silica alkane phosphate dielectric film,
The modified siloxane phosphate of formation has comb-type structure, that is, there are a large amount of Si-O-P keys, provides channel for proton propagation, simultaneously
Ensure stability of the material structure under medium temperature.Methyl oxidation on the outside of phosphate can be made outside carbon atom grafting by concentrated nitric acid
Great amount of hydroxy group active group, strong hydrogen bonding can improve the migration rate of proton.Ceramic membrane is as substrate three-dimensional framework, siloxanes
Phosphate filling is used as proton transmitting channel wherein, and nitrate anion is free in organic phase passes through electronegativity as proton adsorption agent
Attract proton and lure that it is migrated to cathode into, and then solves the problems, such as that traditional proton exchange membrane operation temperature area is relatively narrow.
A kind of composite organic siloxane phosphate electrolyte film in fuel cell prepared by the present invention and existing fluosulfonic acid type
Proton exchange membrane has a clear superiority, such as in terms of the operating temperature range of proton exchange membrane, proton-conducting and mechanical strength
Shown in table 1.
Table 1：
A kind of composite organic siloxane phosphate electrolyte film in fuel cell of present invention offer and preparation method thereof, with the prior art
It compares, the feature and excellent effect protruded is：
1, a kind of composite organic siloxane phosphate electrolyte film in fuel cell of present invention proposition and preparation method thereof, by organosilicon
Alkane after evenly mixing, is added concentrated nitric acid and carries out condensation reaction with phosphate, and fully filtering drying obtains gel-like material after reaction,
Gel rubber material is coated uniformly on porous ceramics film surface, vacuum drying oven is put into after compacting and is carried out repeatedly under the conditions of 120 DEG C
Positive pressuring drying keeps film fine and close, and Ceramic Composite silica alkane phosphate dielectric film is prepared.Dielectric film proposed by the present invention
Proton transfer rate is high（10-2S/cm grades）, alcohols rejection rate is good, and operating temperature is higher（It can be improved to about 240 DEG C）, solve tradition
The relatively narrow problem in proton exchange membrane operation temperature area.
2, electrolyte film in fuel cell proposed by the present invention can be widely used in as membrane material in fuel cell field.
3, the method for the present invention is simple, and the fuel battery proton exchange film performance prepared is stablized, and processing performance is good, be easy into
Row industrialized development.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）It is 25mPas's by the viscosity that 70 mass parts viscosity are 45mPas organosilans tetramethylsilane and 30 mass parts
Dimethyl chloroethylphosphate uniformly mixes, and control condition is that mixing speed is more than 100 revs/min, and temperature is 160 DEG C, in nitrogen
It is stirred under gas shielded atmosphere, nitrogen flow is 3mL/ minutes, after the completion of stirring, is cooled to room temperature, is evacuated to 800Pa, is removed
Bubble in cementitious compositions obtains cementitious compositions；
（2）It is added concentrated nitric acid into the cementitious compositions, the molar ratio of the concentrated nitric acid and organosilan is 1:112, dense nitre
The mass concentration of acid is 90%, carries out condensation reaction, fully filtering drying obtains gel-like material after reaction；
（3）By the gel-like material be coated uniformly on aperture be 300 micron porous metal oxides magnesium ceramics on, it is described
It is 70 DEG C that the temperature of porous magnesia ceramics is kept in coating procedure, penetrates into porous metals oxidation convenient for organosiloxane phosphate
Object hole is put into vacuum drying oven and uses press device, control pressure 3kPa, not destroy under the conditions of 120 DEG C after compacting
Porous magnesia Ceramics Ceramic skeleton, carrying out repeatedly positive pressuring drying keeps film fine and close, and positive pressuring drying is using hot wind medium, control
Hot blast temperature is 120 DEG C, wind speed 10m/s, and artificial acceleration dry film obtains Ceramic Composite silica alkane phosphate dielectric film
With porous magnesia ceramics be basic three-dimensional framework, siloxanes phosphate catalytic activity material infiltrate magnesia ceramics surface and
The structure of composite membrane that pore interior is formed, when working under mesophilic condition, the siloxanes phosphate catalytic activity material is
Proton, which is propagated, provides channel, while ensureing the stability of material structure.
The composite organic siloxane phosphate intermediate temperature fuel cell dielectric film prepared in the present embodiment is subjected to proton friendship
Alcohols rejection rate, proton-conducting and the mechanical strength etc. for changing film are tested, and test result is as shown in table 2.It will be compound
Organosiloxane phosphate intermediate temperature fuel cell dielectric film prepares the membrane module of monocell, uses carbon as proton exchange membrane
Paper is as diffusion layer, and the mass fraction of Pt is 60% in Pt/C catalyst.The membrane module prepared is assembled into 5cm × 5cm
Monocell carries out monocell test.Test condition is hydrogen flowing quantity 120mLmin-1, oxygen flow 70mLmin-1。
Open-circuit voltage is respectively 753mV at 240 DEG C, and maximum power generation density is respectively 45.8mWcm -2 。
Embodiment 2
（1）It is 101mPas's by the viscosity that 78 mass parts viscosity are 400mPas dimethyl diethylsilane and 22 mass parts
Dimethyl ethyl phosphate uniformly mixes, and control condition is that mixing speed is more than 100 revs/min, and temperature is 130 DEG C, in nitrogen
It is stirred under protective atmosphere, nitrogen flow is 25mL/ minutes, after the completion of stirring, is cooled to room temperature, and 500Pa is evacuated to, and is removed glutinous
Property mixture in bubble, obtain cementitious compositions；
（2）It is added concentrated nitric acid into the cementitious compositions, the molar ratio of the concentrated nitric acid and organosilan is 1:150, dense nitre
The mass concentration of acid is 95%, carries out condensation reaction, fully filtering drying obtains gel-like material after reaction；
（3）By the gel-like material be coated uniformly on aperture be 240 micron porous metal oxides magnesium ceramics on, it is described
It is 80 DEG C that the temperature of porous magnesia ceramics is kept in coating procedure, penetrates into porous metals oxidation convenient for organosiloxane phosphate
Object hole is put into vacuum drying oven and uses press device, control pressure 30kPa, not destroy under the conditions of 120 DEG C after compacting
Porous magnesia Ceramics Ceramic skeleton, carrying out repeatedly positive pressuring drying keeps film fine and close, and positive pressuring drying is using hot wind medium, control
Hot blast temperature is 120 DEG C, wind speed 25m/s, and artificial acceleration dry film obtains Ceramic Composite silica alkane phosphate dielectric film
With porous magnesia ceramics be basic three-dimensional framework, siloxanes phosphate catalytic activity material infiltrate magnesia ceramics surface and
The structure of composite membrane that pore interior is formed, when working under mesophilic condition, the siloxanes phosphate catalytic activity material is
Proton, which is propagated, provides channel, while ensureing the stability of material structure.
The composite organic siloxane phosphate intermediate temperature fuel cell dielectric film prepared in the present embodiment is subjected to proton friendship
Alcohols rejection rate, proton-conducting and the mechanical strength etc. for changing film are tested, and test result is as shown in table 2.It will be compound
Organosiloxane phosphate intermediate temperature fuel cell dielectric film prepares the membrane module of monocell, uses carbon as proton exchange membrane
Paper is as diffusion layer, and the mass fraction of Pt is 60% in Pt/C catalyst.The membrane module prepared is assembled into 5cm × 5cm
Monocell carries out monocell test.Test condition is hydrogen flowing quantity 120mLmin-1, oxygen flow 70mLmin-1。
Open-circuit voltage is respectively 764mV at 240 DEG C, and maximum power generation density is respectively 47.4mWcm -2 。
Embodiment 3
（1）By 93.8 mass parts viscosity be in 340mPas cyclomethicones with the viscosity of 6.2 mass parts it is 22mPas's
Dimethyl hydroxy ethyl phosphate uniformly mixes, and control condition is that mixing speed is more than 100 revs/min, and temperature is 120 DEG C, in nitrogen
It is stirred under gas shielded atmosphere, nitrogen flow is 34mL/ minutes, after the completion of stirring, is cooled to room temperature, is evacuated to 750Pa, is removed
Bubble in cementitious compositions obtains cementitious compositions；
（2）It is added concentrated nitric acid into the cementitious compositions, the molar ratio of the concentrated nitric acid and organosilan is 1:144, dense nitre
The mass concentration of acid is 95%, carries out condensation reaction, fully filtering drying obtains gel-like material after reaction；
（3）It is 145 um porous magnesia ceramics and porous alumina ceramic that the gel-like material, which is coated uniformly on aperture,
Surface, it is 85 DEG C that the temperature of porous metal oxide is kept in the coating procedure, is penetrated into convenient for organosiloxane phosphate more
Mesoporous metal oxide hole, vacuum drying oven is put into after compacting is using press device, control pressure under the conditions of 120 DEG C
14kPa, not destroy porous metal oxide ceramic skeleton, carrying out repeatedly positive pressuring drying keeps film fine and close, and positive pressuring drying is to adopt
With hot wind medium, control hot blast temperature is 120 DEG C, wind speed 15m/s, and artificial acceleration dry film obtains Ceramic Composite silica
Alkane phosphate dielectric film with porous metal oxide ceramics be basic three-dimensional framework, siloxanes phosphate catalytic activity material
The porous ceramics film surface and the internal structure of composite membrane formed are infiltrated, it is described when working under 100-240 DEG C of medium temperature condition
Siloxanes phosphate catalytic activity material provides channel for proton propagation, while ensureing the stability of material structure.
The composite organic siloxane phosphate intermediate temperature fuel cell dielectric film prepared in the present embodiment is subjected to proton friendship
Alcohols rejection rate, proton-conducting and the mechanical strength etc. for changing film are tested, and test result is as shown in table 2.It will be compound
Organosiloxane phosphate intermediate temperature fuel cell dielectric film prepares the membrane module of monocell, uses carbon as proton exchange membrane
Paper is as diffusion layer, and the mass fraction of Pt is 60% in Pt/C catalyst.The membrane module prepared is assembled into 5cm × 5cm
Monocell carries out monocell test.Test condition is hydrogen flowing quantity 120mLmin-1, oxygen flow 70mLmin-1。
Open-circuit voltage is respectively 732mV at 240 DEG C, and maximum power generation density is respectively 45.1mWcm -2 。
Embodiment 4
（1）By 88.5 mass parts viscosity be 210mPas hexamethyldisiloxane and the viscosity of 11.5 mass parts is 35mPas
Dimethyl trichloroethyl phosphate uniformly mix, control condition be mixing speed be more than 100 revs/min, temperature be 160 DEG C,
It being stirred under nitrogen protection atmosphere, nitrogen flow is 45mL/ minutes, after the completion of stirring, is cooled to room temperature, is evacuated to 450Pa,
The bubble in cementitious compositions is removed, cementitious compositions are obtained；
（2）It is added concentrated nitric acid into the cementitious compositions, the molar ratio of the concentrated nitric acid and organosilan is 1:130, dense nitre
The mass concentration of acid is 96%, carries out condensation reaction, fully filtering drying obtains gel-like material after reaction；
（3）The gel-like material is coated uniformly on the aggregate surface that aperture is 10 um porous titanium oxide ceramics, the painting
It is 85 DEG C that the temperature of porous metal oxide is kept during covering, and penetrates into porous titanium oxide ceramics convenient for organosiloxane phosphate
Hole is put into vacuum drying oven and uses press device, control pressure 1kPa more not destroy under the conditions of 120 DEG C after compacting
Pore titanium oxide ceramic skeleton, carrying out repeatedly positive pressuring drying keeps film fine and close, and positive pressuring drying is to control hot wind temperature using hot wind medium
Degree is 120 DEG C, wind speed 10m/s, artificial acceleration dry film, obtains Ceramic Composite silica alkane phosphate dielectric film with porous
Titanium oxide ceramics is basic three-dimensional framework, and siloxanes phosphate catalytic activity material infiltrates the porous titanium oxide ceramic surface
The structure of composite membrane formed with inside, when working under 100-240 DEG C of medium temperature condition, the siloxanes phosphate catalytic activity
Material provides channel for proton propagation, while ensureing the stability of material structure.
The composite organic siloxane phosphate intermediate temperature fuel cell dielectric film prepared in the present embodiment is subjected to proton friendship
Alcohols rejection rate, proton-conducting and the mechanical strength etc. for changing film are tested, and test result is as shown in table 2.It will be compound
Organosiloxane phosphate intermediate temperature fuel cell dielectric film prepares the membrane module of monocell, uses carbon as proton exchange membrane
Paper is as diffusion layer, and the mass fraction of Pt is 60% in Pt/C catalyst.The membrane module prepared is assembled into 5cm × 5cm
Monocell carries out monocell test.Test condition is hydrogen flowing quantity 120mLmin-1, oxygen flow 70mLmin-1。
Open-circuit voltage is respectively 758mV at 240 DEG C, and maximum power generation density is respectively 46.8mWcm -2 。
Embodiment 5
（1）It is 101mPa by the viscosity that 93.8 mass parts viscosity are 320mPas dimethyl diethylsilane and 6.2 mass parts
The dimethyl ethenyl phosphate of s uniformly mixes, and control condition is that mixing speed is more than 100 revs/min, and temperature is 170 DEG C,
It is stirred under nitrogen protection atmosphere, nitrogen flow is 50mL/ minutes, after the completion of stirring, is cooled to room temperature, is evacuated to 300Pa, removes
The bubble in cementitious compositions is removed, cementitious compositions are obtained；
（2）It is added concentrated nitric acid into the cementitious compositions, the molar ratio of the concentrated nitric acid and organosilan is 1:150, dense nitre
The mass concentration of acid is 93%, carries out condensation reaction, fully filtering drying obtains gel-like material after reaction；
（3）The gel-like material is coated uniformly on the aggregate surface that aperture is 80 um porous gold aluminium oxide ceramics, it is described
It is 85 DEG C that the temperature of porous metal oxide is kept in coating procedure, penetrates into Woelm Alumina pottery convenient for organosiloxane phosphate
Porcelain hole is put into vacuum drying oven and uses press device, control pressure 23kPa, not destroy under the conditions of 120 DEG C after compacting
Porous alumina ceramic ceramic skeleton, carrying out repeatedly positive pressuring drying keeps film fine and close, and positive pressuring drying is using hot wind medium, control
Hot blast temperature is 120 DEG C, wind speed 18m/s, and artificial acceleration dry film obtains Ceramic Composite silica alkane phosphate dielectric film
With porous alumina ceramic for basic three-dimensional framework, siloxanes phosphate catalytic activity material impregnating porous alumina ceramic membrane
Surface and the internal structure of composite membrane formed, when working under 100-240 DEG C of medium temperature condition, the siloxanes phosphate electrolyte
Active material provides channel for proton propagation, while ensureing the stability of material structure.
The composite organic siloxane phosphate intermediate temperature fuel cell dielectric film prepared in the present embodiment is subjected to proton friendship
Alcohols rejection rate, proton-conducting and the mechanical strength etc. for changing film are tested, and test result is as shown in table 2.It will be compound
Organosiloxane phosphate intermediate temperature fuel cell dielectric film prepares the membrane module of monocell, uses carbon as proton exchange membrane
Paper is as diffusion layer, and the mass fraction of Pt is 60% in Pt/C catalyst.The membrane module prepared is assembled into 5cm × 5cm
Monocell carries out monocell test.Test condition is hydrogen flowing quantity 120mLmin-1, oxygen flow 70mLmin-1。
Open-circuit voltage is respectively 782mV at 240 DEG C, and maximum power generation density is respectively 49.9mWcm -2 。
Comparative example 1
Using fluosulfonic acid type proton exchange membrane Nafion117 films purchased in market as proton exchange membrane, the performance of Nafion117 films is carried out
It measures, the results showed that：The proton conductivity of Nafion117 films is 0.087Scm -1, methanol permeability 6.10 × 10 -6cm2 s-1；The swelling coefficient of the Nafion117 is 19%.Using carbon paper as diffusion layer, the mass fraction of Pt in Pt/C catalyst
It is 60%, prepares the membrane module of monocell, the membrane module prepared is assembled into 5cm × 5cm monocells, carries out monocell survey
Examination.Test condition is hydrogen flowing quantity 120mLmin -1, oxygen flow 70mLmin -1.Open-circuit voltage is distinguished at 240 DEG C
For 237mV, maximum power generation density is respectively 14.3mWcm-2 。
Table 2
The proton exchange composite membrane of the invention prepared is can be seen that in 100-240 DEG C of medium temperature item from above-described embodiment and comparative example
When working under part, there is good proton conduction property, the methanol permeability of the proton exchange composite membrane prepared in the present invention is relatively low,
Satisfactory mechanical property.
Claims (9)
1. a kind of composite organic siloxane phosphate electrolyte film in fuel cell, which is characterized in that the dielectric film is：With more
Mesoporous metal oxide ceramics is basic three-dimensional framework, and siloxanes phosphate catalytic activity material infiltrates the porous ceramic film table
Face and the internal structure of composite membrane formed, when work the siloxanes phosphate catalytic activity material be proton propagate provide it is logical
Road.
2. a kind of composite organic siloxane phosphate electrolyte film in fuel cell as described in claim 1, which is characterized in that institute
State the group that porous metal oxide ceramics are one or more of magnesia ceramics, aluminium oxide ceramics, titanium oxide ceramics
It closes, porous metal oxide ceramics aperture is 10-300 microns.
3. a kind of a kind of preparation side of composite organic siloxane phosphate electrolyte film in fuel cell as described in claim 1
Method, which is characterized in that use raw material of the porous metal oxide ceramic powders as three-dimensional framework, organosilan, dimethyl are short
Raw material of the chain phosphate as active material, specific preparation method are as follows：
（1）70-93.8 mass parts organosilan is uniformly mixed with the dimethyl short chain phosphate of 6.2-30 mass parts, control strip
Part is that mixing speed is more than 100 revs/min, and temperature is 100-170 DEG C, is stirred under nitrogen protection atmosphere, nitrogen flow 3-
It 50mL/ minutes, after the completion of stirring, is cooled to room temperature, is evacuated to 300-800Pa, remove the bubble in cementitious compositions, obtain
Cementitious compositions；
（2）Concentrated nitric acid is added into the cementitious compositions, carries out condensation reaction, fully filtering drying obtains gel after reaction
Material；
（3）The gel-like material is coated uniformly on porous metal oxide ceramic surface, vacuum drying oven is put into after compacting
Positive pressuring drying is carried out repeatedly under the conditions of 120 DEG C keeps film fine and close, obtains Ceramic Composite silica alkane phosphate dielectric film.
4. a kind of preparation method of composite organic siloxane phosphate electrolyte film in fuel cell as claimed in claim 3,
It is characterized in that, the viscosity of the organosilan is 45-400mPas, and the organosilan is tetramethylsilane, dimethyl diethyl
One kind in base silane, hexamethyldisiloxane, cyclomethicone.
5. a kind of preparation method of composite organic siloxane phosphate electrolyte film in fuel cell as claimed in claim 3,
It is characterized in that, the viscosity of dimethyl short chain phosphate is 22-101mPas, and the dimethyl short chain phosphate is dimethyl chloride
Ethyl phosphonic acid ester, dimethyl ethyl phosphate, dimethyl hydroxy ethyl phosphate, dimethyl trichloroethyl phosphate, dimethyl disulfide
One kind in substituted phosphate, dimethyl ethenyl phosphate, dimethyl propyl phosphate.
6. a kind of preparation method of composite organic siloxane phosphate electrolyte film in fuel cell as claimed in claim 3,
It is characterized in that, the molar ratio of the concentrated nitric acid and organosilan is 1:The mass concentration of 100-150, concentrated nitric acid are 90%-98%.
7. a kind of preparation method of composite organic siloxane phosphate electrolyte film in fuel cell as claimed in claim 3,
It is characterized in that, it is 70-100 DEG C that the temperature of porous metal oxide is kept in the coating procedure, is convenient for organosiloxane phosphoric acid
Ester penetrates into porous metal oxide pores gap.
8. a kind of preparation method of composite organic siloxane phosphate electrolyte film in fuel cell as claimed in claim 3,
It is characterized in that, the pressing process is to prevent from destroying porous metal oxide using press device, control pressure 1-30kPa
Ceramic skeleton.
9. a kind of preparation method of composite organic siloxane phosphate electrolyte film in fuel cell as claimed in claim 3,
It is characterized in that, the positive pressuring drying is using hot wind medium, and control hot blast temperature is 120 DEG C, wind speed 10-30m/s, artificial to add
Fast dry film.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114725504A (en) * | 2022-04-29 | 2022-07-08 | 远景动力技术(江苏)有限公司 | Gel electrolyte and application thereof |
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2018
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114725504A (en) * | 2022-04-29 | 2022-07-08 | 远景动力技术(江苏)有限公司 | Gel electrolyte and application thereof |
| CN114725504B (en) * | 2022-04-29 | 2023-10-31 | 远景动力技术(江苏)有限公司 | Gel electrolyte and application thereof |
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Application publication date: 20180720 |