CN108400361A - A kind of the mesoporous silicon fuel battery proton exchange film and preparation method of loaded by heteropoly acid - Google Patents
A kind of the mesoporous silicon fuel battery proton exchange film and preparation method of loaded by heteropoly acid Download PDFInfo
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The present invention relates to the mesoporous silicon fuel battery proton exchange films and preparation method of a kind of loaded by heteropoly acid, belong to fuel cell barrier film technical field.The technical problem to be solved by the present invention is to provide the mesoporous silicon fuel battery proton exchange films and preparation method of a kind of loaded by heteropoly acid.Heteropoly acid is filled in the rodlike skeletal internal of one-dimensional hollow Nano and provides proton conducting channel by the method for the present invention, while silica-base material equally has certain proton conductivity under low temperature and high relative humidity or high temperature low humidity, to improve its proton conduction property.And the tolerance and thermal stability of the soda acid of silica-base material are good, can reduce loss and decomposition that membrane material uses under the conditions of extensive, to extend its service life.The film that the method for the present invention is prepared solves the problems, such as that heteropllyacids proton exchange membrane stability is poor, while by silica-base material auxiliary proton conduction, having further promotion for the proton conduction efficiency of membrane material.
Description
Technical field
The present invention relates to the mesoporous silicon fuel battery proton exchange films and preparation method of a kind of loaded by heteropoly acid, belong to fuel
Battery diaphragm technical field.
Background technology
Fuel cell is a kind of hair that the chemical energy of fuel and oxidant is directly changed into electric energy by electrochemical reaction
Electric installation.Mainly it is made of anode, cathode, electrolyte and ancillary equipment.Since fuel cell has, efficient, startup is fast, dirty
Contaminate the advantages that small, it is considered to be it is hopeful largely to provide the 4th kind of generation technology of electric energy after wind-force, waterpower and solar energy,
It is a kind of green energy resource technology, " energy shortage " and " environmental pollution " this two hang-up that the current world faces can be effectively relieved,
Realize the diversification of the energy.Proton Exchange Membrane Fuel Cells（PEMFC）Other than the general characteristic for having fuel cell, also have
Have and starts that fast, electroless liquid stream is lost, corrosion-free, energy transformation ratio is high, long lifespan, light-weight, small, pollution-free and infrared spoke
The features such as penetrating is with a wide range of applications in traffic power source, portable power supplies and stationary electric power plant field of power supplies.
In fuel battery inside, proton exchange membrane（PEMFC）Channel is provided for the migration and conveying of proton so that proton passes through
It crosses film and reaches cathode from anode, circuit is constituted with the electronics transfer of external circuit, electric current is outwardly provided, therefore proton exchange membrane
Performance plays very important effect to the performance of fuel cell, its quality directly affects the service life of battery.Proton is handed over
It changes film to be applied not only to proton conducting and obstruct the supporter of fuel, oxidant or catalyst, to ensure that fuel cell is normally transported
Row, proton exchange membrane should have excellent chemical stability, thermal stability and good proton-conducting, meanwhile, film surface with
Catalyst surface should contact well, can effectively prevent gas diffusion, obstruct oxidant and fuel contact etc..By far the most commonly used matter
Proton exchange remains as perfluoro sulfonic acid membrane, such as the Nafion membrane etc. of DuPont Corporation, the high-quality transport factor of perfluoro sulfonic acid membrane,
The advantage of low operating temperature, strong acid-base tolerance level is obvious, but disadvantage is also very prominent, and the control of temperature and humidity is wanted
Ask more accurate, with the raising of temperature or the reduction of humidity, water content reduces rapidly in traditional Nafion membrane, leads to conductivity
Decline, Nafion membrane is shunk, and then results in the appearance for the shortcomings of film reduces with both sides Catalytic Layer contact area, affects proton
The performance of exchange film fuel battery, thus under high temperature, low moisture environments membrane material easily quick aging to reduce its service life,
And its process prepared is complex and difficult.Therefore, it is necessary to be improved to existing proton exchange membrane.It is passed to overcome
The performance shortcomings that system Nafion membrane is shown in high temperature, low humidity, in recent years to the improved method of traditional Nafion series membranes
It is more and more, wherein heteropllyacids substance is due to its excellent proton conductivity, by the extensive concern of researcher.
Patent of invention CN105406091A discloses a kind of Kynoar-heteropoly acid-chitosan compound proton exchange membrane
Preparation method.This method obtains polyvinylidene fluoride film by electrostatic spinning first, then passes through superpower poly- more of adhesiveness
Heteropoly acid is coated on fiber surface by bar amine, then the natural polymer chitosan of lotus positive electricity is filled into the hole of tunica fibrosa,
It can effectively prevent heteropoly acid during battery use using electrostatic interactions strong between chitosan and heteropoly acid
Losing issue, while can also greatly increase the mechanical performance of tunica fibrosa, obtained composite membrane has at a room temperature and a high temperature
There are high proton conductivity and mechanical performance.
Patent of invention CN103351576A discloses imidazole micro-capsule hybrid membrane carried heteropoly acid-sulfonated polyether-ether-ketone composite membrane and preparation
And application.The film is made of with sulfonated polyether-ether-ketone the imidazole micro-capsule hybrid membrane of phosphotungstic acid load；Preparation method includes：By gathering
Ether ether ketone prepares sulfonated polyether-ether-ketone；Pass through sol-gel method synthetic silica microballoon with ethyl orthosilicate；With 1- vinyl
Imidazoles is the hybrid microspheres that monomer synthesizes the shell containing imidazoles through precipitating condistillation method；Imidazole micro-capsule hybrid membrane is obtained with HF solution etches；It will
Imidazole micro-capsule hybrid membrane is soaked in the imidazole micro-capsule hybrid membrane that load phosphotungstic acid is obtained in phosphotungstic acid aqueous solution；The imidazole micro-capsule hybrid membrane of load phosphotungstic acid is added
Enter into the casting solution formed by sulfonated polyether-ether-ketone, casting solution is cast to obtain imidazole micro-capsule hybrid membrane carried heteropoly acid-sulfonated polyether ether
Ketone composite membrane.
The above patent is the proton exchange membrane being improved using heteropoly acid, still, unstable due to heteropoly acid
Property, cause heteropllyacids proton exchange membrane stability poor, can not be used in commercialization.Therefore for heteropolyacid-based conjunction
At proton exchange membrane stability improve have highly important practical significance.
Invention content
For disadvantages described above, the object of the present invention is to provide a kind of mesoporous silicon fuel cell proton exchanges of loaded by heteropoly acid
Film and preparation method.
First technical problem that the present invention solves is to provide a kind of mesoporous silicon fuel cell proton friendship of loaded by heteropoly acid
Change the preparation method of film.
The preparation method of the mesoporous silicon fuel battery proton exchange film of loaded by heteropoly acid of the present invention, includes the following steps：
1）The preparation of monodimension nano stick：By exchange of solvent method by organic synthesis be monodimension nano stick；
2）Silica-base material coats the preparation of nanometer rods：After silica-base material is ground, washing, with monodimension nano stick and additive
Mixing, and water is added, in the reactor of sealing, 10~72h is reacted at 100~350 DEG C, silicon atom is made to be coated on a wiener
On the outside of rice stick, silica-base material cladding nanometer rods are obtained；Wherein, the addition of water is that every gram of silica-base material is added 0.5~5mL's
Water；
3）The preparation of one-dimensional hollow Nano silicon rod powder body material：Under an inert atmosphere, silica-base material cladding nanometer rods are forged
It burns, removes organic phase, obtain one-dimensional hollow Nano silicon rod powder body material；
4）Heteropoly acid fills the preparation of mesoporous nano silicon rod：By weight in heteropoly acid by one-dimensional hollow Nano silicon rod powder body material
2~5:1 mixing, makes heteropoly acid fill to hollow silicon rod using high pressure and capillary effect, obtains heteropoly acid filling nanometer and is situated between
Hole silicon rod；
5）Film forming：Heteropoly acid filling mesoporous nano silicon rod is prepared as membrane material, obtains the mesoporous silicon fuel cell of loaded by heteropoly acid
Proton exchange membrane.
Heteropoly acid is filled in the rodlike skeletal internal of one-dimensional hollow Nano and provides proton conducting channel, together by the method for the present invention
When silica-base material under low temperature and high relative humidity or high temperature low humidity equally have certain proton conductivity, to improve its proton pass
Lead performance.And the tolerance and thermal stability of the soda acid of silica-base material are good, can reduce what membrane material used under the conditions of extensive
Loss and decomposition, to extend its service life.
Wherein, step 1）To prepare 1-dimention nano bar material, prepared using existing exchange of solvent method.
Exchange of solvent method is that the variation of the solubility in different solvents using organic compound is brilliant to prepare organic sodium.First
Compound is dissolved in selected good solvent, then uses micro syringe, inject the solvent into the chemical combination of violent stirring
In the poor solvent of object, pass through aggregation of the organic molecule in poor solvent, you can obtain organic nanocrystal.In this process
In, it is desirable that good solvent and poor solvent can dissolve each other without split-phase each other, meanwhile, dissolving of the organic compound in two kinds of solvents
Degree should there are marked differences.The advantages of this method is easy to operate, and reaction condition is mild.
Common organic phase is suitable for the present invention.
Preferably, monodimension nano stick is prepared as organic phase in the present invention 1,12- benzos.
1,12- benzos（1,12-Benzoperylene）, it is pistac crystal.1,12- benzos used in the present invention
It is all made of commercially available.
Preferably, described to be by the concrete operations that organic synthesis is monodimension nano stick by exchange of solvent method：It prepares dense
Degree is the toluene solution of 1, the 12- benzos of 0.2~0.8mmol/L, then takes the 1,12- of 200~600 μ L with micro syringe
The toluene solution of benzo injects in 5mL methanol solvates, quiet after 2~5min of stirring under the stir speed (S.S.) of 1500~3000rpm
It sets, obtains monodimension nano stick.Since the solubility of 1,12- benzos in methyl alcohol is less than the solubility in toluene, molecule will
Assemble in methanol solvate, and gradually appear the particle of suspension, finally there is the precipitation of yellow green to occur, i.e. monodimension nano stick.
It is observed under SEM, these nano bar-shape materials are linear, and length is up to more than ten microns, and pattern is single, has no other patterns
Nano particle exists.
Preferably, the toluene solution for 1, the 12- benzos that preferably compound concentration is 0.5mmol/L, then with micro-
Amount syringe takes the toluene solution of 1, the 12- benzos of 400 μ L, injects in 5mL methanol solvates, in the stir speed (S.S.) of 2500rpm
It is stood after lower stirring 3min, obtains monodimension nano stick.
Step 2）The preparation of nanometer rods is coated for silica-base material, specific step is：Silica-base material is ground, water
It after washing, is mixed with monodimension nano stick and additive, and water is added, in the reactor of sealing, react 10 at 100~350 DEG C
~72h makes silica-base material be coated on the outside of monodimension nano stick, obtains silica-base material cladding nanometer rods；Wherein, the addition of water is
The water of 0.5~5mL is added in every gram of silica-base material.
Preferably, step 2）In, the silica-base material is SiO2Or silicate.Silica-base material needs are ground, wash
Deng pretreatment.Preferably, silica-base material is mechanically ground or is pulverized into uniform powder with such as hammer-mill, ball mill etc., so
Afterwards with water in mass ratio 1:1~100, more preferably 1:4~50 mixing soaking and washing enough time such as 0.5~4h.Most pass through afterwards
Drying is washed, pretreated silica-base material is obtained.
In the method for the invention, the additive is at least one of hydrochloric acid, sodium hydroxide, sodium carbonate, ammonium chloride.
The principle that additive adjusts reaction is that hydrochloric acid adjusting is added can to increase activity with system pH；Be added sodium hydroxide or
Sodium carbonate can soften silica, improve the activity of silica.
The weight ratio of silica-base material, monodimension nano stick and additive has a certain impact to hydro-thermal reaction.Preferably, step
2）In, the weight ratio of silica-base material, monodimension nano stick and additive is：1~10:0.3~4:0.1~0.5；Preferred steps 2）
In, the weight ratio of silica-base material, monodimension nano stick and additive is：5:3:0.4.
Preferably, step 2）In, 12h is reacted at 300 DEG C, the addition of water is that 3mL is added in every gram of silica-base material
Water.
Step 3）In, mainly by calcining, internal organic phase is removed using inert gas shielding high-temperature calcination, obtains one
Tie up hollow Nano silicon rod powder body material.The temperature and time of calcining, which is subject to, removes organic phase.Preferably, step 3）In, calcining
Temperature be 600~1000 DEG C, calcination time be 2~6h；It is preferred that the temperature calcined is 800 DEG C, calcination time 4h.
In order to avoid oxidation reaction occurs in calcining, need to be calcined in an inert atmosphere.Common inert atmosphere
It is suitable for the present invention, such as helium, neon, argon gas or nitrogen etc..
Step 4）Primarily to nano-pore Jie's silicon rod of heteropoly acid filling is prepared, the method used is Low Temperature Thermal
Platen press.
Hot pressing is powder metallurgy development and application a kind of hot forming techniques earlier.The present invention uses Low Temperature Thermal platen press, leads to
Crossing capillary effect makes heteropoly acid fill to one-dimensional hollow Nano silicon rod, obtains heteropoly acid and fills mesoporous nano silicon rod.
Preferably, the heteropoly acid is phosphotungstic acid, phosphomolybdic acid, containing sulfonic organic acid or contains the organic of carboxyl
Acid.
Preferably, step 4）In, by one-dimensional hollow Nano silicon rod powder body material in heteropoly acid by weight 3:1 is mixed
It closes.
It is furthermore preferred that step 4）In, the high pressure is 25~35MPa, and preferably pressure is 30MPa.
Step 5）For the process of film forming, existing physical means may be used or powder body material is prepared as by Low Temperature Heat Treatment
Membrane material, technique used by the step is the prior art, is not elaborated herein.
Second technical problem that the present invention solves is to provide a kind of mesoporous silicon fuel cell proton friendship of loaded by heteropoly acid
Change film.
The mesoporous silicon fuel battery proton exchange film of loaded by heteropoly acid of the present invention, is prepared by the above method.The film is
The rodlike skeletal internal of one-dimensional hollow Nano is filled in by heteropoly acid, proton conducting channel is provided, while silica-base material is in low temperature and high relative humidity
Equally there is down certain proton conductivity, to improve its proton conduction property.And the tolerance of the soda acid of silica-base material
Property and thermal stability are good, loss and decomposition that membrane material uses under the conditions of extensive can be reduced, to extend its service life.
Compared with prior art, the present invention has the advantages that：
Heteropoly acid is filled in the rodlike skeletal internal of one-dimensional hollow Nano and provides proton conducting channel, while silicon by the method for the present invention
Sill equally has certain proton conductivity under low temperature and high relative humidity, to improve its proton conduction property.And silicon substrate
The tolerance and thermal stability of the soda acid of material are good, can reduce loss and decomposition that membrane material uses under the conditions of extensive, to
Extend its service life.
The film that the method for the present invention is prepared solves the problems, such as that heteropllyacids proton exchange membrane stability is poor, while by
Silica-base material assists proton conduction, has further promotion for the proton conduction efficiency of membrane material.
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
The mesoporous silicon fuel battery proton exchange film of loaded by heteropoly acid is prepared using following steps：
1）The preparation of monodimension nano stick：By exchange of solvent method by organic synthesis be monodimension nano stick；Wherein, the organic phase
For 1,12- benzos, concrete operations are：Compound concentration is the toluene solution of 1, the 12- benzos of 0.8mmol/L, then with micro-
Amount syringe takes the toluene solution of 1, the 12- benzos of 200 μ L, injects in 5mL methanol solvates, in the stir speed (S.S.) of 1500rpm
It is stood after lower stirring 5min, obtains monodimension nano stick.
2）Silica-base material coats the preparation of nanometer rods：After silica-base material is ground, washing, and monodimension nano stick and add
Add agent to mix, and water is added, in the reactor of sealing, react 72h at 100 DEG C, obtains silica-base material cladding nanometer rods；Its
In, the addition of water is the water that 0.5mL is added in every gram of silica-base material；The silica-base material is SiO2；The additive is hydrochloric acid,
And the weight ratio of silica-base material, monodimension nano stick and additive is：1:4:0.1.
3）The preparation of one-dimensional hollow Nano silicon rod powder body material：Under an inert atmosphere, by silica-base material coat nanometer rods into
Row calcining removes organic phase, and the temperature of calcining is 600 DEG C, calcination time 6h, obtains one-dimensional hollow Nano silicon rod powder body material.
4）Heteropoly acid fills the preparation of mesoporous nano silicon rod：By one-dimensional hollow Nano silicon rod powder body material in heteropoly acid by weight
Measure ratio 2:1 mixing, makes heteropoly acid fill to one-dimensional hollow Nano silicon rod using high pressure and capillary effect, obtains heteropoly acid and fills out
Fill mesoporous nano silicon rod；The heteropoly acid is phosphotungstic acid；Pressure is 35MPa.
5）Film forming：Heteropoly acid filling mesoporous nano silicon rod is prepared as membrane material, obtains the mesoporous silicon fuel of loaded by heteropoly acid
Battery proton exchange membrane.
Temperature be 80 DEG C, humidity be 40% under conditions of, survey proton conductivity, see conductivity change with time to
The stability of film is measured, the results are shown in Table 1.
Embodiment 2
The mesoporous silicon fuel battery proton exchange film of loaded by heteropoly acid is prepared using following steps：
1）The preparation of monodimension nano stick：By exchange of solvent method by organic synthesis be monodimension nano stick；Wherein, the organic phase
For 1,12- benzos, concrete operations are：Compound concentration is the toluene solution of 1, the 12- benzos of 0.2mmol/L, then with micro-
Amount syringe takes the toluene solution of 1, the 12- benzos of 600 μ L, injects in 5mL methanol solvates, in the stir speed (S.S.) of 3000rpm
It is stood after lower stirring 2min, obtains monodimension nano stick.
2）Silica-base material coats the preparation of nanometer rods：After silica-base material is ground, washing, and monodimension nano stick and add
Add agent to mix, and water is added, in the reactor of sealing, react 10h at 350 DEG C, obtains silica-base material cladding nanometer rods；Its
In, the addition of water is the water that 5mL is added in every gram of silica-base material；The silica-base material is silicate；The additive is chlorination
Ammonium, and the weight ratio of silica-base material, monodimension nano stick and additive is：10:0.3:0.5.
3）The preparation of one-dimensional hollow Nano silicon rod powder body material：Under an inert atmosphere, by silica-base material coat nanometer rods into
Row calcining removes organic phase, and the temperature of calcining is 1000 DEG C, calcination time 2h, obtains one-dimensional hollow Nano silicon rod powder material
Material.
4）Heteropoly acid fills the preparation of mesoporous nano silicon rod：By one-dimensional hollow Nano silicon rod powder body material in heteropoly acid by weight
Measure ratio 5:1 mixing, makes heteropoly acid fill to one-dimensional hollow Nano silicon rod using using high pressure and capillary effect, obtains miscellaneous more
Acid filling mesoporous nano silicon rod；The heteropoly acid is phosphomolybdic acid；Pressure is 25MPa.
5）Film forming：Heteropoly acid filling mesoporous nano silicon rod is prepared as membrane material, obtains the mesoporous silicon fuel of loaded by heteropoly acid
Battery proton exchange membrane.
Temperature be 80 DEG C, humidity be 40% under conditions of, survey proton conductivity, see conductivity change with time to
The stability of film is measured, the results are shown in Table 1.
Embodiment 3
The mesoporous silicon fuel battery proton exchange film of loaded by heteropoly acid is prepared using following steps：
1）The preparation of monodimension nano stick：By exchange of solvent method by organic synthesis be monodimension nano stick；Wherein, the organic phase
For 1,12- benzos, concrete operations are：Compound concentration is the toluene solution of 1, the 12- benzos of 0.4mmol/L, then with micro-
Amount syringe takes the toluene solution of 1, the 12- benzos of 300 μ L, injects in 5mL methanol solvates, in the stir speed (S.S.) of 2000rpm
It is stood after lower stirring 4min, obtains monodimension nano stick.
2）Silica-base material coats the preparation of nanometer rods：After silica-base material is ground, washing, and monodimension nano stick and add
Add agent to mix, and water is added, in the reactor of sealing, react 15h at 250 DEG C, obtains silica-base material cladding nanometer rods；Its
In, the addition of water is the water that 4mL is added in every gram of silica-base material；The silica-base material is SiO2；The additive is hydroxide
Sodium, and the weight ratio of silica-base material, monodimension nano stick and additive is：4:3:0.3.
3）The preparation of one-dimensional hollow Nano silicon rod powder body material：Under an inert atmosphere, by silica-base material coat nanometer rods into
Row calcining removes organic phase, and the temperature of calcining is 700 DEG C, calcination time 3h, obtains one-dimensional hollow Nano silicon rod powder body material.
4）Heteropoly acid fills the preparation of mesoporous nano silicon rod：By one-dimensional hollow Nano silicon rod powder body material in heteropoly acid by weight
Measure ratio 3:1 mixing, makes heteropoly acid fill to one-dimensional hollow Nano silicon rod using high pressure and capillary effect, obtains heteropoly acid and fills out
Fill mesoporous nano silicon rod；The heteropoly acid is to contain sulfonic organic acid；Pressure is 35MPa.
5）Film forming：Heteropoly acid filling mesoporous nano silicon rod is prepared as membrane material, obtains the mesoporous silicon fuel of loaded by heteropoly acid
Battery proton exchange membrane.
Temperature be 80 DEG C, humidity be 40% under conditions of, survey proton conductivity, see conductivity change with time to
The stability of film is measured, the results are shown in Table 1.
Embodiment 4
The mesoporous silicon fuel battery proton exchange film of loaded by heteropoly acid is prepared using following steps：
1）The preparation of monodimension nano stick：By exchange of solvent method by organic synthesis be monodimension nano stick；Wherein, the organic phase
For 1,12- benzos, concrete operations are：Compound concentration is the toluene solution of 1, the 12- benzos of 0.5mmol/L, then with micro-
Amount syringe takes the toluene solution of 1, the 12- benzos of 400 μ L, injects in 5mL methanol solvates, in the stir speed (S.S.) of 2500rpm
It is stood after lower stirring 3min, obtains monodimension nano stick.
2）Silica-base material coats the preparation of nanometer rods：After silica-base material is ground, washing, and monodimension nano stick and add
Add agent to mix, and water is added, in the reactor of sealing, react 28h at 200 DEG C, obtains silica-base material cladding nanometer rods；Its
In, the addition of water is the water that 1mL is added in every gram of silica-base material；The silica-base material is silicate；The additive is hydrochloric acid
And ammonium chloride, and the weight ratio of silica-base material, monodimension nano stick and additive is：7:2:0.4.
3）The preparation of one-dimensional hollow Nano silicon rod powder body material：Under an inert atmosphere, by silica-base material coat nanometer rods into
Row calcining removes organic phase, and the temperature of calcining is 900 DEG C, calcination time 3h, obtains one-dimensional hollow Nano silicon rod powder body material.
4）Heteropoly acid fills the preparation of mesoporous nano silicon rod：By one-dimensional hollow Nano silicon rod powder body material in heteropoly acid by weight
Measure ratio 3.5:1 mixing, makes heteropoly acid fill to one-dimensional hollow Nano silicon rod using high pressure and capillary effect, obtains heteropoly acid
Fill mesoporous nano silicon rod；The heteropoly acid is the organic acid containing carboxyl；Pressure is 28MPa.
5）Film forming：Heteropoly acid filling mesoporous nano silicon rod is prepared as membrane material, obtains the mesoporous silicon fuel of loaded by heteropoly acid
Battery proton exchange membrane.
Temperature be 80 DEG C, humidity be 40% under conditions of, survey proton conductivity, see conductivity change with time to
The stability of film is measured, the results are shown in Table 1.
Embodiment 5
The mesoporous silicon fuel battery proton exchange film of loaded by heteropoly acid is prepared using following steps：
1）The preparation of monodimension nano stick：By exchange of solvent method by organic synthesis be monodimension nano stick；Wherein, the organic phase
For 1,12- benzos, concrete operations are：Compound concentration is the toluene solution of 1, the 12- benzos of 0.5mmol/L, then with micro-
Amount syringe takes the toluene solution of 1, the 12- benzos of 400 μ L, injects in 5mL methanol solvates, in the stir speed (S.S.) of 2500rpm
It is stood after lower stirring 3min, obtains monodimension nano stick.
2）Silica-base material coats the preparation of nanometer rods：After silica-base material is ground, washing, and monodimension nano stick and add
Add agent to mix, and water is added, in the reactor of sealing, react 48h at 300 DEG C, obtains silica-base material cladding nanometer rods；Its
In, the addition of water is the water that 2mL is added in every gram of silica-base material；The silica-base material is sodium metasilicate；The additive is hydrochloric acid
And ammonium chloride, and the weight ratio of silica-base material, monodimension nano stick and additive is：5:3:0.4.
3）The preparation of one-dimensional hollow Nano silicon rod powder body material：Under an inert atmosphere, by silica-base material coat nanometer rods into
Row calcining removes organic phase, and the temperature of calcining is 700 DEG C, calcination time 5h, obtains one-dimensional hollow Nano silicon rod powder body material.
4）Heteropoly acid fills the preparation of mesoporous nano silicon rod：By one-dimensional hollow Nano silicon rod powder body material in heteropoly acid by weight
Measure ratio 4:1 mixing, makes heteropoly acid fill to one-dimensional hollow Nano silicon rod using high pressure and capillary effect, obtains heteropoly acid and fills out
Fill mesoporous nano silicon rod；The heteropoly acid is phosphomolybdic acid；Pressure is 32MPa.
5）Film forming：Heteropoly acid filling mesoporous nano silicon rod is prepared as membrane material, obtains the mesoporous silicon fuel of loaded by heteropoly acid
Battery proton exchange membrane.
Temperature be 80 DEG C, humidity be 40% under conditions of, survey proton conductivity, see conductivity change with time to
The stability of film is measured, the results are shown in Table 1.
Embodiment 6
The mesoporous silicon fuel battery proton exchange film of loaded by heteropoly acid is prepared using following steps：
1）The preparation of monodimension nano stick：By exchange of solvent method by organic synthesis be monodimension nano stick；Wherein, the organic phase
For 1,12- benzos, concrete operations are：Compound concentration is the toluene solution of 1, the 12- benzos of 0.5mmol/L, then with micro-
Amount syringe takes the toluene solution of 1, the 12- benzos of 400 μ L, injects in 5mL methanol solvates, in the stir speed (S.S.) of 2500rpm
It is stood after lower stirring 3min, obtains monodimension nano stick.
2）Silica-base material coats the preparation of nanometer rods：After silica-base material is ground, washing, and monodimension nano stick and add
Add agent to mix, and water is added, in the reactor of sealing, react 12h at 300 DEG C, obtains silica-base material cladding nanometer rods；Its
In, the addition of water is the water that 3mL is added in every gram of silica-base material；The silica-base material is sodium metasilicate；The additive is hydrochloric acid
And ammonium chloride, and the weight ratio of silica-base material, monodimension nano stick and additive is：5:3:0.4.
3）The preparation of one-dimensional hollow Nano silicon rod powder body material：Under an inert atmosphere, by silica-base material coat nanometer rods into
Row calcining removes organic phase, and the temperature of calcining is 800 DEG C, calcination time 4h, obtains one-dimensional hollow Nano silicon rod powder body material.
4）Heteropoly acid fills the preparation of mesoporous nano silicon rod：By one-dimensional hollow Nano silicon rod powder body material in heteropoly acid by weight
Measure ratio 3:1 mixing, makes heteropoly acid fill to one-dimensional hollow Nano silicon rod using high pressure and capillary effect, obtains heteropoly acid and fills out
Fill mesoporous nano silicon rod；The heteropoly acid is phosphotungstic acid；Pressure is 30MPa.
5）Film forming：Heteropoly acid filling mesoporous nano silicon rod is prepared as membrane material, obtains the mesoporous silicon fuel of loaded by heteropoly acid
Battery proton exchange membrane.
Temperature be 80 DEG C, humidity be 40% under conditions of, survey proton conductivity, see conductivity change with time to
The stability of film is measured, the results are shown in Table 1.
Comparative example 1
It measures perfluoro sulfonic acid membrane, that is, Nafion membrane and obtains proton conductivity.It is 80 DEG C in temperature, under conditions of humidity is 40%, surveys matter
Electron conductivity sees that conductivity changes with time, and the results are shown in Table 1.
Test environment is：In the hydrogen flowing quantity 80mLmin-1 of identical conditions, oxygen flow 50mLmin-1, work temperature
After spending at 90 DEG C a period of time that works, the performance change of proton conductivity.As shown in table 1.
Table 1
| Number | Proton conductivity after work 2h（S/cm） | Proton conductivity after work 12h（S/cm） | Proton conductivity after working 5 days（S/cm） | Proton conductivity after working 30 days（S/cm） |
| Embodiment 1 | 0.196 | 0.194 | 0.192 | 0.189 |
| Embodiment 2 | 0.194 | 0.192 | 0.191 | 0.189 |
| Embodiment 3 | 0.198 | 0.16 | 0.195 | 0.192 |
| Embodiment 4 | 0.197 | 0.196 | 0.194 | 0.193 |
| Embodiment 5 | 0.196 | 0.194 | 0.193 | 0.191 |
| Embodiment 6 | 0.199 | 0.197 | 0.196 | 0.194 |
| Comparative example 1 | 0.194 | 0.188 | 0.079 | 0.031 |
Claims (10)
1. a kind of preparation method of the mesoporous silicon fuel battery proton exchange film of loaded by heteropoly acid, which is characterized in that including as follows
Step：
1）The preparation of monodimension nano stick：By exchange of solvent method by organic synthesis be monodimension nano stick；
2）Silica-base material coats the preparation of nanometer rods：After silica-base material is ground, washing, with monodimension nano stick and additive
Mixing, and water is added, in the reactor of sealing, 10~72h is reacted at 100~350 DEG C, so that silica-base material is coated on one-dimensional
On the outside of nanometer rods, silica-base material cladding nanometer rods are obtained；Wherein, the addition of water is that every gram of silica-base material is added 0.5~5mL's
Water；
3）The preparation of one-dimensional hollow Nano silicon rod powder body material：Under an inert atmosphere, silica-base material cladding nanometer rods are forged
It burns, removes organic phase, obtain one-dimensional hollow Nano silicon rod powder body material；
4）Heteropoly acid fills the preparation of mesoporous nano silicon rod：By weight in heteropoly acid by one-dimensional hollow Nano silicon rod powder body material
2~5:1 mixing, makes heteropoly acid fill to one-dimensional hollow Nano silicon rod using high pressure and capillary effect, obtains heteropoly acid and fills out
Fill mesoporous nano silicon rod；
5）Film forming：Heteropoly acid filling mesoporous nano silicon rod is prepared as membrane material, obtains the mesoporous silicon fuel cell of loaded by heteropoly acid
Proton exchange membrane.
2. the preparation method of the mesoporous silicon fuel battery proton exchange film of loaded by heteropoly acid according to claim 1, special
Sign is：Step 1）In, the organic phase is 1,12- benzos.
3. the preparation method of the mesoporous silicon fuel battery proton exchange film of loaded by heteropoly acid according to claim 2, special
Sign is：It is described to be by the concrete operations that organic synthesis is monodimension nano stick by exchange of solvent method：Compound concentration be 0.2~
Then the toluene solution of 1, the 12- benzos of 0.8mmol/L takes the toluene solution of 1, the 12- benzos of 200~600 μ L, injection
In 5mL methanol solvates, is stood after stirring 2~5min under the stir speed (S.S.) of 1500~3000rpm, obtain monodimension nano stick；It is excellent
The toluene solution of 1, the 12- benzos of a concentration of 0.5mmol/L is made in apolegamy, then takes the toluene of 1, the 12- benzos of 400 μ L molten
Liquid injects in 5mL methanol solvates, is stood after stirring 3min under the stir speed (S.S.) of 2500rpm, obtains monodimension nano stick.
4. the preparation method of the mesoporous silicon fuel battery proton exchange film of loaded by heteropoly acid according to claim 1, special
Sign is：Step 2）In, the silica-base material is SiO2Or silicate；The additive be hydrochloric acid, sodium hydroxide, sodium carbonate,
At least one of ammonium chloride；The weight ratio of the silica-base material, monodimension nano stick and additive is：1~10:0.3~4:0.1
~0.5.
5. the preparation method of the mesoporous silicon fuel battery proton exchange film of loaded by heteropoly acid according to claim 1, special
Sign is：Step 2）In, 12h is reacted at 300 DEG C, the addition of water is the water that 3mL is added in every gram of silica-base material.
6. the mesoporous silicon fuel battery proton exchange film and preparation method, feature of the loaded by heteropoly acid according to right 1 exist
In：Step 3）In, the temperature of calcining is 600~1000 DEG C, and calcination time is 2~6h.
7. the preparation method of the mesoporous silicon fuel battery proton exchange film of loaded by heteropoly acid according to claim 1, special
Sign is：Step 4）In, the heteropoly acid is phosphotungstic acid, phosphomolybdic acid, containing sulfonic organic acid or contains the organic of carboxyl
Acid.
8. the preparation method of the mesoporous silicon fuel battery proton exchange film of loaded by heteropoly acid according to claim 1, special
Sign is：Step 4）In, by one-dimensional hollow Nano silicon rod powder body material and heteropoly acid by weight 3:1 mixing.
9. the preparation method of the mesoporous silicon fuel battery proton exchange film of loaded by heteropoly acid according to claim 1, special
Sign is：Step 4）In, the high pressure is 25~35MPa.
10. the preparation method of the mesoporous silicon fuel battery proton exchange film of claim 1~9 any one of them loaded by heteropoly acid
The mesoporous silicon fuel battery proton exchange film for the loaded by heteropoly acid being prepared.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109301224A (en) * | 2018-10-16 | 2019-02-01 | 中航锂电技术研究院有限公司 | A kind of preparation method and application of silicon-based composite anode material for Li-ion battery |
| CN110676496A (en) * | 2019-09-12 | 2020-01-10 | 中国石油大学(北京) | Composite proton exchange membrane and preparation method thereof |
| CN111193053A (en) * | 2020-02-28 | 2020-05-22 | 成都新柯力化工科技有限公司 | High-thermal-stability proton exchange membrane and preparation method thereof |
-
2018
- 2018-02-07 CN CN201810121724.XA patent/CN108400361A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109301224A (en) * | 2018-10-16 | 2019-02-01 | 中航锂电技术研究院有限公司 | A kind of preparation method and application of silicon-based composite anode material for Li-ion battery |
| CN110676496A (en) * | 2019-09-12 | 2020-01-10 | 中国石油大学(北京) | Composite proton exchange membrane and preparation method thereof |
| CN110676496B (en) * | 2019-09-12 | 2021-04-06 | 中国石油大学(北京) | Composite proton exchange membrane and preparation method thereof |
| CN111193053A (en) * | 2020-02-28 | 2020-05-22 | 成都新柯力化工科技有限公司 | High-thermal-stability proton exchange membrane and preparation method thereof |
| CN111193053B (en) * | 2020-02-28 | 2020-10-09 | 成都新柯力化工科技有限公司 | High-thermal-stability proton exchange membrane and preparation method thereof |
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