CN106750190B - The porous aromatic skeleton compound preparation method of the high conductivity of thermostable and its application in Proton Exchange Membrane Fuel Cells - Google Patents
The porous aromatic skeleton compound preparation method of the high conductivity of thermostable and its application in Proton Exchange Membrane Fuel Cells Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
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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
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
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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
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present invention relates to the porous aromatic skeleton compound preparation method of the high conductivity of thermostable and its in the application of Proton Exchange Membrane Fuel Cells, belong to technical field of function materials；Use high specific surface area porous organic material as manufactured high stability after skeleton absorption higher boiling acid, the novel conductive material of high conductivity；Above-mentioned high specific surface area porous organic material is poly- Tetrabenzene methane (PAF-1), and higher boiling acid includes: 98%H2SO4, 89%H3PO4, 85%H3PO4；Specific preparation method includes: that suitable higher boiling acid is added in the poly- Tetrabenzene methane of porous organic material (PAF-1) of high-specific surface area to be stirred overnight, it is filtered under conditions of anhydrous and oxygen-free, final product is made in the lower 100 DEG C of dryings of vacuum condition in obtained solid.Preparation method simple process of the present invention, yield is high, without using auxiliary agent.New material made from this method has thermostable, and high conductivity can be applied in Proton Exchange Membrane Fuel Cells, provides new approaches for the relevant field of fuel cell.
Description
Technical field
The present invention relates to field of functional materials, and in particular to the porous aromatic skeleton of the high conductivity with thermostable
Compound preparation method and its application in Proton Exchange Membrane Fuel Cells use high specific surface area porous organic backbone material
Material is used as skeleton, is made after absorption higher boiling acid with thermostable, the porous aromatic skeleton compound of high conductivity.It can answer
For providing new approaches for fuel cell related fields in Proton Exchange Membrane Fuel Cells.
Background technique
Proton Exchange Membrane Fuel Cells has small in size, light weight, and power density is high, and starting is fast, noiseless, no pollution etc.
Advantage has broad application prospects.Proton Exchange Membrane Fuel Cells is by anode, cathode, the portions such as catalyst and proton exchange membrane
It is grouped as.Proton exchange membrane is the heart of Proton Exchange Membrane Fuel Cells, its effect in a fuel cell is dual: first is that
Hydrogen ion channel is provided as electrolyte, second is that preventing them from directly having an effect as diaphragm isolation polarization response gas.Its
Working principle is: H2Fuel enters anode, due to having catalyst, H on electrode2It is catalytically oxidized to H+And e-。H+Pass through proton
Exchange membrane enters anode, the O with cathode2It reacts, generates H2O, and electronics is flowed through from anode to cathode, generates electric current.Cause
This, as follows in the chemical equation that anode occurs:
It is as follows in the chemical reaction that cathode occurs:
Proton exchange membrane is the key problem in technology of fuel cell, and the superiority and inferiority of performance directly affects the workability of fuel cell
Can, cost and application prospect.Therefore, the heat in battery research work is had become for the research of Proton Exchange Membrane Fuel Cells
One of point.
Currently, either fuel is H2/O2PEMFC or the proton exchange that uses of direct methanol fuel cell (DMFC)
Film is all almost the Nafion series membranes of Dupont company, U.S. production, although Nafion perfluoro sulfonic acid membrane has mechanical strength
The advantages that height, chemical stability is good, proton conductivity height (when larger water content), but at high cost, the disadvantages pole such as operating temperature is low
The earth limits the application of PEMFC, and optimum working temperature is 80 DEG C, its water content can be made to drastically reduce more than this temperature, led
Electric rate declines rapidly, and proton conduction relies heavily on moisture content.Once temperature is increased to 100 DEG C or more, moisture content can be with
The form of vapor evaporates, and proton conductivity is thus also greatly reduced.It is confined to such status and is unsuitable for medium temperature fuel
Battery (operating temperature is at 120 DEG C -200 DEG C), therefore exploitation electric conductivity is excellent, can work under conditions of high-temperature anhydrous new
Type proton exchange membrane is the hot topic studied now.Defect of the present invention than being directed to perfluorosulfonic acid proton exchange film in more detail, is situated between
It has continued with H2SO4@PAF-1,H3PO4@PAF-1 is the no-water high-temperature conduction research of material.
Summary of the invention
Its thermal stability and the high porous aromatic skeleton compound of conductivity are prepared the object of the present invention is to provide a kind of
Method.
For the purpose for realizing foregoing invention, the technical solution adopted by the present invention is as follows: preparation thermostabilization is good and conductivity
High porous aromatic skeleton compound, comprising the following steps:
(1) higher boiling acid, stirring at normal temperature mistake are added in the poly- Tetrabenzene methane PAF-1 of high specific surface area porous organic material
Night, the higher boiling acid are 98%H2SO4, 89%H3PO4, 85%H3PO4One of；
(2) mixture that filtering stirs evenly is filtered in the glove box of anhydrous and oxygen-free with glass membrane filter, in 100 DEG C
It is 10 hours dry under vacuum state, obtain final product: the porous aromatic skeleton chemical combination of the high conductivity with thermostable
Object.
The high specific surface area porous organic framework material (PAF-1) is porous material, with thermostable.Dry
Dry N2Under, thermal stability reaches 450 DEG C, and under dry air, thermal stability reaches 400 DEG C, " Angew.Chem.Int.Ed,
2009,48,9457-9460".It can guarantee its good thermal stability in this, as compound made of skeleton, can be used for high temperature
Under the conditions of the material that works, to adapt to its work requirements.
Higher boiling acid is the H that concentration is 98%2SO4, concentration be 89% H3PO4, concentration be 85% H3PO4Deng acid in its
One of.The feature of these higher boiling inorganic acid maximums is that volatility is low, and boiling point is high.The H that concentration is 98%2SO4Boiling point reaches
338 DEG C, the H that concentration is 89%3PO4Boiling point be 261 DEG C, concentration be 85% H3PO4Boiling point be 158 DEG C.These characteristics are
Manufacture heat-resisting material is laid a good foundation.
It is another object of the present invention to provide the high porous aromatic skeletons of a kind of good thermal stability and conductivity
Application of the compound in Proton Exchange Membrane Fuel Cells field.
The conductivity of technical solution provided by the invention to achieve the above object, test material includes the following steps:
(1) higher boiling acid, stirring at normal temperature mistake are added in the poly- Tetrabenzene methane PAF-1 of high specific surface area porous organic material
Night, the higher boiling acid are 98%H2SO4, 89%H3PO4, 85%H3PO4One of；
(2) mixture that filtering stirs evenly is filtered in the glove box of anhydrous and oxygen-free with glass membrane filter, in 100 DEG C
It is 10 hours dry under vacuum state, obtain final product: the porous aromatic skeleton chemical combination of the high conductivity with thermostable
Object；
(3) dry final product is ground into uniform powder, tabletting in mortar；
(4) tabletting is clipped in the middle with two panels gold plaque of the same size respectively, is in close contact, and extraction wire composition is distinguished at the two poles of the earth
Simple electric installation is placed in closed 50mL two mouth flask, and N is full of in bottle2And connect N2Balloon to ensure stable gas pressure,
Conducting wire is connected with electrochemical workstation；
(5) conductivity test is carried out to above-mentioned material under 25 DEG C -250 DEG C, normal pressure.
The finished product size dimension of the uniform powder tabletting is diameter 5mm, thickness 1mm.
The gold plaque size is diameter 5mm, and gold used is the gold of 99.99% purity.Purpose is to be resistant to the corrosion of concentrated acid
And high temperature resistant.
In the closed two mouth flask of 50mL, flask internal thermometer, flask is placed in electric heating cover described device, realizes temperature
Control operation, bottle is interior to be full of nitrogen, to guarantee the stabilization of gas, external N2Balloon is to ensure stable gas pressure.
The porous aromatic skeleton compound of the present invention has good heat resistance and electric conductivity, under high temperature operating condition
Superior performance, apply has good development prospect in fuel cell related fields.
The beneficial effects of the present invention are:
Preparation method simple process of the present invention, yield is high, without using auxiliary agent.New material made from this method has super
Heat-resisting quantity, high conductivity can be applied in Proton Exchange Membrane Fuel Cells, provide new think of for the relevant field of fuel cell
Road.
Detailed description of the invention
In order to be more easily understood the contents of the present invention, according to specific embodiments of the present invention and with reference to the accompanying drawings,
The present invention is described in further detail, in which:
Fig. 1 is the porous aromatic skeleton compound 98%H of the high conductivity with heat-resisting quantity of embodiment 12SO4@PAF-
The infrared spectrum of 1 and porous organic framework compound PAF-1；
Fig. 2 is the porous aromatic skeleton compound 98%H of the high conductivity with heat-resisting quantity of embodiment 12SO4@PAF-
1 and porous organic framework compound PAF-1 is in N2Thermogravimetric spectrogram under atmosphere；
Fig. 3 is the porous aromatic skeleton compound 98%H of the high conductivity with heat-resisting quantity of embodiment 12SO4@PAF-
The AC impedance figure of 1 25 DEG C and 250 DEG C of heating for the first time；
Fig. 4 is the porous aromatic skeleton compound 98%H of the high conductivity with heat-resisting quantity of embodiment 12SO4@PAF-
The AC impedance figure of 1 second of 25 DEG C and 250 DEG C of heating；
Fig. 5 is the porous aromatic skeleton compound 98%H of the high conductivity with heat-resisting quantity of embodiment 12SO4@PAF-
The AC impedance figure of 1 25 DEG C and 75 DEG C of third time heating；
Fig. 6 is the porous aromatic skeleton compound 89%H of the high conductivity with heat-resisting quantity of embodiment 23PO4@PAF-
The infrared spectrum of 1 and porous organic framework compound PAF-1；
Fig. 7 is the porous aromatic skeleton compound 89%H of the high conductivity with heat-resisting quantity of embodiment 23PO4@PAF-
1 and porous organic framework compound PAF-1 is in N2Thermogravimetric spectrogram under atmosphere；
Fig. 8 is the porous aromatic skeleton compound 89%H of the high conductivity with heat-resisting quantity of embodiment 23PO4@PAF-
The AC impedance figure of 1 25 DEG C and 250 DEG C of heating for the first time；
Fig. 9 is the porous aromatic skeleton compound 85%H of the high conductivity with heat-resisting quantity of embodiment 33PO4@PAF-
The infrared spectrum of 1 and porous organic framework compound PAF-1；
Figure 10 is the porous aromatic skeleton compound 85%H of the high conductivity with heat-resisting quantity of embodiment 33PO4@
PAF-1 and porous organic framework compound PAF-1 are in N2Thermogravimetric spectrogram under atmosphere；
Figure 11 is the porous aromatic skeleton compound 85%H of the high conductivity with heat-resisting quantity of embodiment 33PO4@
The AC impedance figure of PAF-1 25 DEG C and 250 DEG C of heating for the first time；
Figure 12 is the porous aromatic skeleton compound 85%H of the high conductivity with heat-resisting quantity of embodiment 33PO4@
The AC impedance figure of second of 25 DEG C and 250 DEG C of heating of PAF-1；
Figure 13 is the porous aromatic skeleton compound 85%H of the high conductivity with heat-resisting quantity of embodiment 33PO4@
The AC impedance figure that 25 DEG C and 250 DEG C of heating of PAF-1 third time；
Figure 14 is PAF-1 structure chart.
Specific embodiment
The present invention is described in further details below by example, these examples are only used to illustrate the present invention, and unlimited
The scope of the present invention processed.
Embodiment 1
The H for being 98% with concentration2SO4Porous aromatic skeleton compound 98% is prepared as higher boiling acid dip material
H2SO4@PAF-1 and as high conducting material application the following steps are included:
Step 1: taking the poly- Tetrabenzene methane of 27mg, the H that 15mL concentration is 98% is added2SO4, it is stirred overnight at normal temperatures and pressures.
Step 2: by the mixture of step 1 in the glove box of anhydrous and oxygen-free, blue-black is obtained by filtration with glass membrane filter
Color solid.Black-and-blue filter cake is 10 hours dry under 100 DEG C of vacuum conditions, obtains final product 98%H2SO4@PAF-1 solid
74mg。
The final product H that step 2 is obtained2SO4@PAF-1 carry out IR spectrum scanning, and with former porous material PAF-1 into
Row compares, and spectrogram is shown in Fig. 1.
It can be seen from the figure that higher boiling acid H2SO4It has entered in porous material PAF-1, and has been stabilized.
Wave number is 774cm-1It is the S-O stretching vibration in sulfuric acid.
Wave number is 1039,1099,1124.5cm-1It is S=O symmetrical stretching vibration in sulfuric acid.
The final product H that step 2 is obtained2SO4@PAF-1 carries out thermogravimetric analysis, and is compared with former porous material PAF-1
Compared with thermogravimetric analysis figure is shown in Fig. 2.
The thermal stability situation of material as we can see from the figure, substance is all present in skeleton at 450 DEG C, until
450 DEG C, this is the collapsing temperature of skeleton.
Step 3: the product after taking drying is ground into uniform powder in mortar, and about 20mg powder is taken to press in tablet press machine
Piece, sheet of diameter 5mm, thick 1mm.
Step 4: it is respectively in flakes 5mm with diameter, the gold plaque of thick 0.2mm is in close contact as electrode, it is clipped among it,
Gold plaque is the gold that purity is 99.99%.Being with the purpose of high-purity gold can effectively resistance to concentrated acid corrosion and high temperature resistant.It draws respectively at the two poles of the earth
Conducting wire composition electric installation is simultaneously connected with electrochemical workstation.
Step 5: the electric installation that step 4 is made is placed in the closed two mouth flask of 50mL, flask internal thermometer, in electric heating
Temperature actuated is realized in heating in set.Full of nitrogen to guarantee that material work environmental gas is stablized in bottle, the external N of two mouth flask2Gas
Ball is to guarantee stable gas pressure.Between 25 DEG C -250 DEG C under normal pressure, every 25 DEG C of heatings once carry out with temperature above-mentioned material
The conductivity test of variation.AC impedance figure is shown in Fig. 3.And it is recorded as the ac impedance measurement to heat up for the first time.(table 1)
Table 1:98%H2SO4@PAF-1 first time heating ac impedance measurement result
| Material | Conductivity(S cm-1) | conditions |
| H2SO4@PAF-1 | 1.5×10-2 | 25 DEG C, 0%RH |
| H2SO4@PAF-1 | 3.1×10-2 | 50 DEG C, 0%RH |
| H2SO4@PAF-1 | 5.2×10-2 | 75 DEG C, 0%RH |
| H2SO4@PAF-1 | 6.7×10-2 | 100 DEG C, 0%RH |
| H2SO4@PAF-1 | 6.4×10-2 | 125 DEG C, 0%RH |
| H2SO4@PAF-1 | 6.5×10-2 | 150 DEG C, 0%RH |
| H2SO4@PAF-1 | 6.8×10-2 | 175 DEG C, 0%RH |
| H2SO4@PAF-1 | 7.7×10-2 | 200 DEG C, 0%RH |
| H2SO4@PAF-1 | 8.6×10-2 | 225 DEG C, 0%RH |
| H2SO4@PAF-1 | 9.1×10-2 | 250 DEG C, 0%RH |
From table 1 we can see that material of the invention in high temperature up to 250 DEG C, conductivity is still relatively very high, Er Qiesui
The raising of temperature, conductivity be gradually increasing this illustrate temperature increase, be conducive to the conductance of this material.
Step 6: in order to test its cycle performance, after first round heating test, temperature is restored to room temperature, and other conditions are not
Become, heats up again, test its conductivity changed with temperature change.AC impedance figure is shown in Fig. 4.And it is recorded as second liter
The ac impedance measurement of temperature.(table 2)
Table 2:98%H2SO4Second of the@PAF-1 ac impedance measurement result that heats up
| Material | Conductivity(S cm-1) | conditions |
| H2SO4@PAF-1 | 2.4×10-2 | 25 DEG C, 0%RH |
| H2SO4@PAF-1 | 4.5×10-2 | 50 DEG C, 0%RH |
| H2SO4@PAF-1 | 6.5×10-2 | 75 DEG C, 0%RH |
| H2SO4@PAF-1 | 6.6×10-2 | 100 DEG C, 0%RH |
| H2SO4@PAF-1 | 6.7×10-2 | 125 DEG C, 0%RH |
| H2SO4@PAF-1 | 7.3×10-2 | 150 DEG C, 0%RH |
| H2SO4@PAF-1 | 7.7×10-2 | 175 DEG C, 0%RH |
| H2SO4@PAF-1 | 8.2×10-2 | 200 DEG C, 0%RH |
| H2SO4@PAF-1 | 8.4×10-2 | 225 DEG C, 0%RH |
| H2SO4@PAF-1 | 8.8×10-2 | 250 DEG C, 0%RH |
From table 2 we can see that material of the invention in high temperature up at 250 DEG C, conductivity is still very high, and with
The raising of temperature, conductivity are gradually increasing this and illustrate that temperature increases, and are conducive to the conductance of this material.
Step 7: after the second wheel heating, temperature is again restored to room temperature, and other conditions are constant, heats up again, tests
Its rising with temperature and the conductivity changed.AC impedance figure is shown in Fig. 5.And it is recorded as the AC impedance that third time heats up and surveys
Examination.(table 3)
Table 3:98%H2SO4@PAF-1 third time heating ac impedance measurement result
| material | Conductivity(S cm-1) | conditions |
| H2SO4@PAF-1 | 1.2×10-2 | 25 DEG C, 0%RH |
| H2SO4@PAF-1 | 1.9×10-2 | 50 DEG C, 0%RH |
| H2SO4@PAF-1 | 3.6×10-2 | 75 DEG C, 0%RH |
From table 3 we can see that material of the invention still remains visible its of conductivity after third time heats up uses the longevity
It orders functional.
Embodiment 2
The H for being 89% with concentration3PO4Porous aromatic skeleton compound 89% is prepared as higher boiling acid dip material
H3PO4@PAF-1 and application as conducting material.The method of the present embodiment is substantially the same manner as Example 1, the difference is that with
The H that concentration is 98%3PO4The H for being 98% instead of concentration as higher boiling acid dip material2SO4.Preparation the following steps are included:
Step 1: taking the poly- Tetrabenzene methane of 26mg, the H that 15mL concentration is 98% is added2SO4, it is stirred overnight at normal temperatures and pressures.
Step 2: by the mixture of step 1 in the glove box of anhydrous and oxygen-free, purple is obtained by filtration with glass membrane filter
Solid.Purple filter cake is 10 hours dry under 100 DEG C of vacuum conditions, obtains final product 89%H3PO4@PAF-1,227mg.
The final product 89%H that step 2 is obtained3PO4@PAF-1 carry out IR spectrum scanning, and with former porous material
PAF-1 is compared, and spectrogram is shown in Fig. 6.
From fig. 6 it can be seen that higher boiling acid H3PO4It has entered in porous material PAF-1, and has been stabilized.Wave number is
980cm-1It is P-O stretching vibration.Wave number is 1161cm-1It is P=O stretching vibration.Wave number is 2555-1960cm-1It is P-H flexible
Vibration.Wave number is 2555-1960cm-1For O-H stretching vibration (phosphate radical and the extraneous O- for forming hydrogen bond in phosphate group of hydrogen bond
H key).
The final product 89%H that step 2 is obtained3PO4@PAF-1 carry out thermogravimetric analysis, and with former porous material PAF-1 into
Row compares, and thermogravimetric analysis figure is shown in Fig. 7.
The thermal stability situation of material as we can see from the figure, in 135 DEG C of beginning dramatic decreases, in 450 DEG C or less sour materials
Material is all present in skeleton, and until 450 DEG C, this is the collapsing temperature of skeleton.
Step 3: the product after taking drying is ground into uniform powder in mortar, and about 20mg powder is taken to press in tablet press machine
Piece, sheet of diameter 5mm, thick 1mm.
Step 4: it is respectively in flakes 5mm with diameter, the gold plaque of thick 0.2mm is in close contact as electrode, it is clipped among it,
Gold plaque is the gold that purity is 99.99%.Being with the purpose of high-purity gold can effectively resistance to concentrated acid corrosion and high temperature resistant.It draws respectively at the two poles of the earth
Conducting wire composition electric installation is simultaneously connected with electrochemical workstation.
Step 5: the electric installation that step 4 is made is placed in the closed two mouth flask of 50mL, flask internal thermometer, in electric heating
Temperature actuated is realized in heating in set.Full of nitrogen to guarantee that material work environmental gas is stablized in bottle, the external N of two mouth flask2Gas
Ball is to guarantee stable gas pressure.Between 25 DEG C -250 DEG C under normal pressure, every 25 DEG C of heatings once carry out with temperature above-mentioned material
The conductivity test of variation.AC impedance figure is shown in Fig. 8.And it is recorded as the ac impedance measurement to heat up for the first time.(table 4)
Table 4:89%H3PO4@PAF-1 first time heating ac impedance measurement result
| Material | Proton conductivity (S cm-1) | Test condition |
| H3PO4@PAF-1 | 7.1×10-3 | 25 DEG C, 0%RH |
| H3PO4@PAF-1 | 2.4×10-2 | 50 DEG C, 0%RH |
| H3PO4@PAF-1 | 9.6×10-2 | 75 DEG C, 0%RH |
| H3PO4@PAF-1 | 1.6×10-1 | 100 DEG C, 0%RH |
| H3PO4@PAF-1 | 2.1×10-1 | 125 DEG C, 0%RH |
| H3PO4@PAF-1 | 2.235×10-1 | 150 DEG C, 0%RH |
| H3PO4@PAF-1 | 2.232×10-1 | 175 DEG C, 0%RH |
| H3PO4@PAF-1 | 2.212×10-1 | 200 DEG C, 0%RH |
| H3PO4@PAF-1 | 2.5×10-1 | 225 DEG C, 0%RH |
| H3PO4@PAF-1 | 2.7×10-1 | 250 DEG C, 0%RH |
From table 4 we can see that material of the invention reaches 250 DEG C in high temperature, conductivity is still very high, and with
The raising proton conductivity of temperature is gradually increasing, this illustrates that temperature increases the Proton conducting for being conducive to this material.This material is also special
It is not suitble to work at high temperature.But thermal stability is especially desirable not enough, temperature is up to 250 DEG C, exceeds this temperature material
Material cannot recycle the second task.
Embodiment 3
The H for being 85% with concentration3PO4Porous aromatic skeleton compound 85% is prepared as higher boiling acid dip material
H3PO4@PAF-1 and application as conducting material.The method of the present embodiment is substantially the same manner as Example 1, the difference is that with
The H that concentration is 85%3PO4The H for being 98% instead of concentration as higher boiling acid dip material2SO4.Preparation the following steps are included:
Step 1: taking the poly- Tetrabenzene methane of 28mg, the H that 15mL concentration is 85% is added3PO4, it is stirred overnight at normal temperatures and pressures.
Step 2: by the mixture of step 1 in the glove box of anhydrous and oxygen-free, being obtained by filtration with glass membrane filter dark purple
Color solid.Darkviolet filter cake is 10 hours dry under 100 DEG C of vacuum conditions, obtains final product 85%H3PO4@PAF-1 solid
258mg。
The final product 85%H that step 2 is obtained3PO4@PAF-1 carry out IR spectrum scanning, and with former porous material
PAF-1 is compared, and spectrogram is shown in Fig. 9.
It can be seen from the figure that higher boiling acid H3PO4It has entered in porous material PAF-1, and has been stabilized.
Wave number is 989cm-1It is P-O stretching vibration.
Wave number is 1115,1284cm-1It is P=O stretching vibration.
Wave number is 2331cm-1It is P-H stretching vibration.
Wave number is 2859cm-1For O-H stretching vibration (there are O-H keys for phosphate radical and extraneous formation hydrogen bond).
The final product 85%H that step 2 is obtained3PO4@PAF-1 carry out thermogravimetric analysis, and with former porous material PAF-1 into
Row compares, and thermogravimetric analysis figure is shown in Figure 10.
The thermal stability situation of material as we can see from the figure is begun to decline at about 225 DEG C, until be about 450 DEG C again
Degree is weightless, this is the collapsing temperature of skeleton.Thermal stability is obviously better than the material that embodiment 2 is made.
Step 3: the product after taking drying is ground into uniform powder in mortar, and about 20mg powder is taken to press in tablet press machine
Piece, sheet of diameter 5mm, thick 1mm.
Step 4: it is respectively in flakes 5mm with diameter, the gold plaque of thick 0.2mm is in close contact as electrode, it is clipped among it,
Gold plaque is the gold that purity is 99.99%.Being with the purpose of high-purity gold can effectively resistance to concentrated acid corrosion and high temperature resistant.It draws respectively at the two poles of the earth
Conducting wire composition electric installation is simultaneously connected with electrochemical workstation.
Step 5: the electric installation that step 4 is made is placed in the closed two mouth flask of 50mL, flask internal thermometer, in electric heating
Temperature actuated is realized in heating in set.Full of nitrogen to guarantee that material work environmental gas is stablized in bottle, the external N of two mouth flask2Gas
Ball is to guarantee stable gas pressure.Between 25 DEG C -250 DEG C under normal pressure, every 25 DEG C of heatings once carry out with temperature above-mentioned material
The conductivity test of variation.AC impedance figure is shown in Figure 11.And it is recorded as the ac impedance measurement to heat up for the first time.(table 5)
Table 5:85%H3PO4@PAF-1 first time heating ac impedance measurement result
| Material | Proton conductivity (S cm-1) | Test condition |
| H3PO4@PAF-1 | 5.2×10-2 | 25 DEG C, 0%RH |
| H3PO4@PAF-1 | 9.7×10-2 | 50 DEG C, 0%RH |
| H3PO4@PAF-1 | 1.4×10-1 | 75 DEG C, 0%RH |
| H3PO4@PAF-1 | 1.7×10-1 | 100 DEG C, 0%RH |
| H3PO4@PAF-1 | 2.0×10-1 | 125 DEG C, 0%RH |
| H3PO4@PAF-1 | 2.2×10-1 | 150 DEG C, 0%RH |
| H3PO4@PAF-1 | 2.4×10-1 | 175 DEG C, 0%RH |
| H3PO4@PAF-1 | 2.5×10-1 | 200 DEG C, 0%RH |
| H3PO4@PAF-1 | 2.8×10-1 | 225 DEG C, 0%RH |
| H3PO4@PAF-1 | 3.1×10-1 | 250 DEG C, 0%RH |
From table 5 it may be seen that material of the invention is still very high up to 250 DEG C of conductivities in high temperature, and with temperature
Raising conductivity be gradually increasing this and illustrate that temperature increases and be conducive to the conduction of this material.
Step 6: in order to test its cycle performance, after first round heating test, temperature is restored to room temperature, and other conditions are not
Become, heats up again, test its conductivity changed with temperature change.AC impedance figure is shown in Figure 12.And it is recorded as second
The ac impedance measurement of heating.(table 6)
Table 6:85%H3PO4Second of the@PAF-1 ac impedance measurement result that heats up
| Material | Proton conductivity (S cm-1) | Test condition |
| H3PO4@PAF-1 | 5.0×10-2 | 25 DEG C, 0%RH |
| H3PO4@PAF-1 | 1.1×10-1 | 50 DEG C, 0%RH |
| H3PO4@PAF-1 | 1.4×10-1 | 75 DEG C, 0%RH |
| H3PO4@PAF-1 | 1.7×10-1 | 100 DEG C, 0%RH |
| H3PO4@PAF-1 | 1.9×10-1 | 125 DEG C, 0%RH |
| H3PO4@PAF-1 | 1.9×10-1 | 150 DEG C, 0%RH |
| H3PO4@PAF-1 | 2.0×10-1 | 175 DEG C, 0%RH |
| H3PO4@PAF-1 | 2.1×10-1 | 200 DEG C, 0%RH |
| H3PO4@PAF-1 | 2.2×10-1 | 225 DEG C, 0%RH |
| H3PO4@PAF-1 | 2.3×10-1 | 250 DEG C, 0%RH |
From table 6 it may be seen that material of the invention in high temperature up to 250 DEG C, conductivity is still very high, and with temperature
The raising of degree, conductivity are gradually increasing this and illustrate that temperature increases the conduction for being conducive to this material.
Step 7: after the second wheel heating, temperature is again restored to room temperature, and other conditions are constant, heats up again, tests
Its rising with temperature and the conductivity changed.AC impedance figure is shown in Figure 13.And it is recorded as the AC impedance that third time heats up
Test.(table 7)
Table 7:85%H3PO4@PAF-1 third time heating ac impedance measurement result
| Material | Proton conductivity (S cm-1) | Test condition |
| H3PO4@PAF-1 | 4.52×10-2 | 25 DEG C, 0%RH |
| H3PO4@PAF-1 | 9.01×10-2 | 50 DEG C, 0%RH |
| H3PO4@PAF-1 | 1.33×10-1 | 75 DEG C, 0%RH |
| H3PO4@PAF-1 | 1.69×10-1 | 100 DEG C, 0%RH |
| H3PO4@PAF-1 | 1.78×10-1 | 125 DEG C, 0%RH |
| H3PO4@PAF-1 | 1.81×10-1 | 150 DEG C, 0%RH |
| H3PO4@PAF-1 | 1.80×10-1 | 175 DEG C, 0%RH |
| H3PO4@PAF-1 | 1.83×10-1 | 200 DEG C, 0%RH |
| H3PO4@PAF-1 | 1.80×10-1 | 225 DEG C, 0%RH |
| H3PO4@PAF-1 | 1.80×10-1 | 250 DEG C, 0%RH |
From table 7 it may be seen that material of the invention in high temperature up to 250 DEG C, conductivity is still very high, and with temperature
The raising of degree, conductivity are gradually increasing this and illustrate that temperature increases, and are conducive to the conduction of this material.This material is also particularly suitable in height
The lower work of temperature.And being still able to maintain good performance after third time heats up, then it is splendid that performance is recycled in it.
The above, the present invention are made with high temperature resistant using acid dip method and have the porous aromatic skeleton of high conductivity
Object is closed, used raw material chemical property is stablized, and preparation cost is low, and condition is easy to control, and it is reproducible, and there is splendid stabilization
Property, superior electric conductivity can be in the energy, the fields such as electric appliance such as automobile, has a wide range of applications in portable device, especially
As the exchange membrane material in Proton Exchange Membrane Fuel Cells, have thermostable can high efficiency be recycled for multiple times.Relatively
Existing material, material can be such that the research field of Proton Exchange Membrane Fuel Cells has to use meaning.The dipping that the present invention uses
Acid includes the H that concentration is 98%2SO4, concentration be 89% H3PO4, concentration be 85% H3PO4, wherein concentration is 85%
H3PO4Effect be optimal.
The above, the concrete form based on main feature of the present invention are not limited in above-described embodiment, in reference
When the preferred embodiment description present invention, those skilled in the art be can be appreciated that:, can under without departing from spirit of that invention principle
A variety of different modification variations can be made, omits and replaces.There are many combination or it can also change as changed stephanoporate framework or leaching
Stain acid, such etc., it is identical that these, which change acquired effect with above-described embodiment,.Which point therefore no matter come from
See, above embodiment of the invention can only all be considered the description of the invention and cannot limit the present invention, with the present invention
Any variation in the comparable meaning and scope of claims is all considered as including within the scope of the claims.
Claims (5)
1. the preparation method of the porous aromatic skeleton compound of the high conductivity of thermostable, it is characterised in that: including as follows
Step:
(1) higher boiling acid is added in the poly- Tetrabenzene methane PAF-1 of high specific surface area porous organic material, stirring at normal temperature is overnight, institute
The higher boiling acid stated is 98% H2SO4、89% H3PO4、85% H3PO4One of；
(2) mixture that filtering stirs evenly is filtered in the glove box of anhydrous and oxygen-free with glass membrane filter, in 100 DEG C of vacuum
It is 10 hours dry under state, obtain final product: the porous aromatic skeleton compound of the high conductivity with thermostable.
2. application of the porous aromatic skeleton compound in terms of Proton Exchange Membrane Fuel Cells, it is characterised in that: the porous virtue
Fragrant framework compound is using poly- Tetrabenzene methane as skeleton, and the compound formed after absorption higher boiling acid has very high conductivity；
Especially under 150-250 DEG C of hot conditions, superior working performance is shown, operating temperature range meets high temperature fuel electricity
The operating temperature in pond, can be applied in Proton Exchange Membrane Fuel Cells, and porous aromatic skeleton compound is applied to proton exchange
The testing procedure of conductivity in terms of membrane cell is as follows:
(1) higher boiling acid is added in the poly- Tetrabenzene methane PAF-1 of high specific surface area porous organic material, stirring at normal temperature is overnight, institute
The higher boiling acid stated is 98% H2SO4、89% H3PO4、85% H3PO4One of；
(2) mixture that filtering stirs evenly is filtered in the glove box of anhydrous and oxygen-free with glass membrane filter, in 100 DEG C of vacuum
It is 10 hours dry under state, obtain final product: the porous aromatic skeleton compound of the high conductivity with thermostable；
(3) dry final product is ground into uniform powder, tabletting in mortar；
(4) tabletting is clipped in the middle with two panels gold plaque of the same size respectively, is in close contact, and it is simple that extraction wire composition is distinguished at the two poles of the earth
Electric installation is placed in closed 50mL two mouth flask, and N is full of in bottle2And connect N2Balloon is drawn with ensuring stable gas pressure
Conducting wire be connected with electrochemical workstation；
(5) conductivity test is carried out to above-mentioned material under 25 DEG C -250 DEG C, normal pressure.
3. application of the porous aromatic skeleton compound according to claim 2 in terms of Proton Exchange Membrane Fuel Cells,
Be characterized in that: the finished product size dimension of the tabletting is diameter 5mm, thickness 1mm.
4. application of the porous aromatic skeleton compound according to claim 2 in terms of Proton Exchange Membrane Fuel Cells,
Be characterized in that: the gold plaque size is diameter 5mm, and thickness 0.2mm, gold used is the gold of 99.99% purity.
5. application of the porous aromatic skeleton compound according to claim 2 in terms of Proton Exchange Membrane Fuel Cells,
Be characterized in that: in the closed two mouth flask of 50mL, flask internal thermometer, flask is placed in electric heating cover described device, is realized
Temperature actuated, bottle is interior to be full of nitrogen, to guarantee the stabilization of gas, external N2Balloon is to ensure stable gas pressure.
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| PCT/CN2017/096575 WO2018095074A1 (en) | 2016-11-24 | 2017-08-09 | Ultra-high-temperature resistant, high-conductivity porous aromatic framework compound and method for preparation thereof, and application thereof in proton-exchange membrane fuel cell |
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| CN109728345B (en) * | 2018-12-29 | 2020-09-22 | 吉林大学 | Porous aromatic polymer with strong lithium storage capacity and high proton transmission efficiency as well as preparation method and application thereof |
| CN111154074B (en) * | 2020-01-13 | 2022-08-02 | 东北师范大学 | Sulfonate porous aromatic skeleton material and application thereof |
| WO2023108215A1 (en) * | 2021-12-14 | 2023-06-22 | Monash University | Porous interlayer |
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