CN106750190A - The porous aromatic skeleton compound its preparation method of the high conductivity of thermostable and its application in Proton Exchange Membrane Fuel Cells - Google Patents

The porous aromatic skeleton compound its preparation method of the high conductivity of thermostable and its application in Proton Exchange Membrane Fuel Cells Download PDF

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CN106750190A
CN106750190A CN201611045846.2A CN201611045846A CN106750190A CN 106750190 A CN106750190 A CN 106750190A CN 201611045846 A CN201611045846 A CN 201611045846A CN 106750190 A CN106750190 A CN 106750190A
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paf
aromatic skeleton
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exchange membrane
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CN106750190B (en
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贲腾
裘式纶
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ZHUHAI STATE KEY LABORATORY OF INORGANIC SYNTHESIS & PREPARATIVE CHEMISTRY JILIN UNIVERSITY
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Abstract

Porous aromatic skeleton compound its preparation method the present invention relates to the high conductivity of thermostable and its application in Proton Exchange Membrane Fuel Cells, belong to technical field of function materials；The high stability being made after adsorbing higher boiling acid as skeleton using high specific surface area porous organic material, 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：Add appropriate higher boiling acid to be stirred overnight in the poly- Tetrabenzene methane of the porous organic material of high-specific surface area (PAF 1), filtered under conditions of anhydrous and oxygen-free, the solid for obtaining is obtained final product in the lower 100 DEG C of dryings of vacuum condition.Preparation method process is simple of the present invention, yield is high, without using auxiliary agent.New material obtained in the method has a thermostable, high conductivity, in can be applied to Proton Exchange Membrane Fuel Cells, for the related field of fuel cell provides new approaches.

Description

The porous aromatic skeleton compound its preparation method of the high conductivity of thermostable and It is in the application of Proton Exchange Membrane Fuel Cells
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 its preparation method and its application in Proton Exchange Membrane Fuel Cells, it uses high specific surface area porous organic backbone material Material is made with thermostable, the porous aromatic skeleton compound of high conductivity as skeleton after absorption higher boiling acid.Can answer In for Proton Exchange Membrane Fuel Cells, for fuel cell association area provides new approaches.
Background technology
Proton Exchange Membrane Fuel Cells has small volume, and light weight, power density is high, starts fast, noiselessness, no pollution etc. Advantage, has broad application prospects.Proton Exchange Membrane Fuel Cells is by anode, negative electrode, the portion such as catalyst and PEM It is grouped into.PEM is the heart of Proton Exchange Membrane Fuel Cells, and its effect in a fuel cell is dual：One is Hydrogen ion passage is provided as electrolyte, two is to prevent them from directly having an effect as barrier film isolation polarization response gas.Its Operation principle is：H2Fuel enters anode, due to carrying catalyst, H on electrode2It is catalytically oxidized to H+And e-。H+By proton Exchange membrane enters into anode, the O with negative electrode2React, generate H2O, and electronics flows through from anode to negative electrode, produces electric current.Cause This, the chemical equation occurred in anode is as follows：
The chemical reaction occurred in negative electrode is as follows：
PEM is the key problem in technology of fuel cell, and the quality of its performance directly affects the workability of fuel cell Energy, 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.
At present, either fuel is H2/O2PEMFC, or the proton exchange that DMFC (DMFC) is used Film is all almost the Nafion series membranes of Dupont companies of U.S. production, although Nafion perfluoro sulfonic acid membranes have mechanical strength Height, chemical stability is good, the advantages of proton conductivity (during larger water content) high, but high cost, the low shortcoming pole of operating temperature The earth limits the application of PEMFC, and its optimum working temperature is 80 DEG C, can drastically reduce its water content more than this temperature, is led Electric rate declines rapidly, and the conduction of its proton relies heavily on moisture content.Once temperature be increased to 100 DEG C and more than, moisture content can be with The form of vapor is evaporated, and proton conductivity is thus also greatly reduced.It is confined to such present situation and is unsuitable for middle temperature fuel Battery (operating temperature is at 120 DEG C -200 DEG C), therefore exploitation electric conductivity is excellent, what can be worked under conditions of high-temperature anhydrous is new Type PEM is the hot topic of present research.The present invention than for the defect of perfluorosulfonic acid proton exchange film, being situated between in more detail Continue with H2SO4@PAF-1,H3PO4@PAF-1 are the conductive research of the no-water high-temperature of material.
The content of the invention
Its heat endurance and the high porous aromatic skeleton compound of conductance are prepared it is an object of the invention to provide a kind of Method.
To realize the purpose of foregoing invention, the technical scheme that the present invention takes is as follows：Prepare thermally-stabilised good and conductance High porous aromatic skeleton compound, comprises 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 At night, described higher boiling acid is 98%H2SO4, 89%H3PO4, 85%H3PO4In one kind；
(2) mixture that filtering stirs uses glass film filter suction filtration in the glove box of anhydrous and oxygen-free, in 100 DEG C Dried 10 hours under vacuum state, obtain final product：The porous aromatic skeleton chemical combination of the high conductivity with thermostable Thing.
The high specific surface area porous organic framework material (PAF-1) is porous material, and it has thermostable.Dry Dry N2Under, heat endurance reaches 450 DEG C, and under dry air, heat endurance reaches 400 DEG C,《Angew.Chem.Int.Ed, 2009,48,9457-9460》.Its good heat endurance is can guarantee that in this, as the new compound that skeleton is made, be can be used for The material worked under hot conditions, to adapt to its work requirements.
Higher boiling acid is the H that concentration is 98%2SO4, concentration is 89% H3PO4, concentration is 85% H3PO4Deng acid in its In one kind.The characteristics of these higher boiling inorganic acids are maximum is low volatility, and boiling point is high.Concentration is 98% H2SO4Boiling point reaches 338 DEG C, concentration is 89% H3PO4Boiling point be 261 DEG C, concentration is 85% H3PO4Boiling point be 158 DEG C.These characteristics are Manufacture exotic material is laid a good foundation.
It is another object of the present invention to provide the high porous aromatic skeleton of a kind of good thermal stability and conductance Application of the compound in Proton Exchange Membrane Fuel Cells field.
The technical scheme that the present invention is provided to achieve the above object, the conductance of test material comprises 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 At night, described higher boiling acid is 98%H2SO4, 89%H3PO4, 85%H3PO4In one kind；
(2) mixture that filtering stirs uses glass film filter suction filtration in the glove box of anhydrous and oxygen-free, in 100 DEG C Dried 10 hours under vacuum state, obtain final product：The porous aromatic skeleton chemical combination of the high conductivity with thermostable Thing；
(3) dry final product is ground to form into uniform powder, compressing tablet in mortar；
(4) compressing tablet is clipped in the middle with two panels gold plaque of the same size respectively, is in close contact, the two poles of the earth difference extraction wire composition Simple electric installation, is placed in two mouthfuls of flasks of closed 50mL, and N is full of in bottle2And connect N2Balloon to ensure stable gas pressure, Wire is connected with electrochemical workstation；
(5) at 25 DEG C -250 DEG C, conductivity test is carried out to above-mentioned material under normal pressure.
The finished product size dimension of the uniform powder compressing tablet is diameter 5mm, thickness 1mm.
The gold electrode size is diameter 5mm, and thickness 1mm, 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 mouthfuls of flasks of 50mL, flask internal thermometer, flask is placed in electric heating cover described device, realizes temperature Control operation, is full of nitrogen, to ensure the stabilization of gas, external N in bottle2Balloon is ensuring stable gas pressure.
The porous aromatic skeleton compound of the present invention has good heat resistance and electric conductivity, under high temperature condition of work Superior performance, apply has good development prospect in fuel cell association area.
The beneficial effects of the invention are as follows：
Preparation method process is simple of the present invention, yield is high, without using auxiliary agent.New material obtained in the method has super Heat-resisting quantity, high conductivity can be applied in Proton Exchange Membrane Fuel Cells, newly think for the related field of fuel cell provides Road.
Brief description of the drawings
In order that present disclosure is more easily understood, below according to specific embodiment of the invention and with reference to accompanying drawing, The present invention is further detailed explanation, wherein：
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 intensification 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 25 DEG C and 250 DEG C of intensification；
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 intensification；
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 intensification 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 is 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 intensifications 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@ Second AC impedance figure of 25 DEG C and 250 DEG C of intensification 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 of 25 DEG C and 250 DEG C of PAF-1 third times intensification；
Figure 14 is PAF-1 structure charts.
Specific embodiment
The present invention is described in further details below by example, these examples are only used for illustrating the present invention, do not limit The scope of the present invention processed.
Embodiment 1
With the H that concentration is 98%2SO4Porous aromatic skeleton compound 98% is prepared as higher boiling acid dip material H2SO4The@PAF-1 and application as conducting material high is comprised the following steps：
Step 1：The poly- Tetrabenzene methanes of 27mg are taken, 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 filtrated to get with glass film filter Color solid.Black-and-blue filter cake obtains final product 98%H in being dried 10 hours under 100 DEG C of vacuum conditions2SO4@PAF-1 solids 74mg。
The final product H obtained to step 22SO4@PAF-1 carry out IR spectrum scanning, and enter with former porous material PAF-1 Row compares, and spectrogram is shown in Fig. 1.
It can be seen that higher boiling acid H2SO4In having enter into porous material PAF-1, and stable existence.
Wave number is 774cm-1It is the S-O stretching vibrations in sulfuric acid.
Wave number is 1039,1099,1124.5cm-1It is S=O symmetrical stretching vibrations in sulfuric acid.
The final product H obtained to step 22SO4@PAF-1 carry out thermogravimetric analysis, and are compared with former porous material PAF-1 Compared with thermogravimetric analysis figure is shown in Fig. 2.
The heat endurance situation of material as we can see from the figure, during material is all present in skeleton at 450 DEG C, until 450 DEG C, this is the temperature of caving in of skeleton.
Step 3：Take dried product and uniform powder is ground to form in mortar, take about 20mg powder and pressed in tablet press machine Piece, sheet of diameter 5mm, thick 1mm.
Step 4：Use the gold plaque of a diameter of 5mm, thick 0.2mm to be in close contact as electrode respectively in flakes, press from both sides therebetween, Gold plaque is the gold that purity is 99.99%.Being with high-purity gold purpose can effectively resistance to concentrated acid corrosion and high temperature resistant.Draw respectively at the two poles of the earth Wire constitutes electric installation and is connected with electrochemical workstation.
Step 5：The electric installation of step 4 system is placed in the closed two mouthfuls of flasks of 50mL, flask internal thermometer, in electrical heating Temperature actuated is realized in heating in set.Nitrogen is full of in bottle to ensure material work environmental gas stabilization, two mouthfuls of external N of flask2Gas Ball is ensureing stable gas pressure.Under normal pressure between 25 DEG C -250 DEG C, every 25 DEG C of intensifications are once carried out with temperature to above-mentioned material The conductivity test of change.AC impedance figure is shown in Fig. 3.And it is recorded as the ac impedance measurement for heating up for the first time.(table 1)
Table 1：98%H2SO4@PAF-1 first time intensification ac impedance measurement results
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 is in high temperature up to 250 DEG C, conductance is still relatively very high, Er Qiesui The rising of temperature, conductance is gradually increasing this explanation temperature and raises, and is conducive to the conductance of this material.
Step 6：In order to test its cycle performance, after the first round heats up test, temperature returns to room temperature, and other conditions are not Become, heat up again, test its conductance 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 intensification ac impedance measurement result of@PAF-1
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, conductance is still very high, and with The rising of temperature, conductance is gradually increasing this explanation temperature and raises, and is conducive to the conductance of this material.
Step 7：After second wheel intensification terminates, temperature is again restored to room temperature, and other conditions are constant, heat up again, test Its rising with temperature and the conductance that changes.AC impedance figure is shown in Fig. 5.And it is recorded as the AC impedance survey that third time heats up Examination.(table 3)
Table 3：98%H2SO4@PAF-1 third time intensification ac impedance measurement results
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 has visible its of conductance after third time heats up uses the longevity Life is functional.
Embodiment 2
With the H that concentration is 89%3PO4Porous aromatic skeleton compound 89% is prepared as higher boiling acid dip material H3PO4@PAF-1 and as the application of conducting material.The method of the present embodiment is substantially the same manner as Example 1, difference be with Concentration is 98% H3PO4The H that concentration is 98% is instead of as higher boiling acid dip material2SO4.Preparation is comprised the following steps：
Step 1：The poly- Tetrabenzene methanes of 26mg are taken, 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 filtrated to get with glass film filter Solid.Purple filter cake obtains final product 89%H in being dried 10 hours under 100 DEG C of vacuum conditions3PO4@PAF-1,227mg.
The final product 89%H obtained to step 23PO4@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 H3PO4In having enter into porous material PAF-1, and stable existence.Wave number is 980cm-1It is P-O stretching vibrations.Wave number is 1161cm-1It is P=O stretching vibrations.Wave number is 2555-1960cm-1It is that P-H stretches Vibration.Wave number is 2555-1960cm-1It is O-H stretching vibrations (phosphate radical and the extraneous O- for forming hydrogen bond in phosphate group of hydrogen bond H keys).
The final product 89%H obtained to step 23PO4@PAF-1 carry out thermogravimetric analysis, and enter with former porous material PAF-1 Row compares, and thermogravimetric analysis figure is shown in Fig. 7.
The heat endurance situation of material, dramatic decrease is started at 135 DEG C as we can see from the figure, the sour material below 450 DEG C Material is all present in skeleton, and until 450 DEG C, this is the temperature of caving in of skeleton.
Step 3：Take dried product and uniform powder is ground to form in mortar, take about 20mg powder and pressed in tablet press machine Piece, sheet of diameter 5mm, thick 1mm.
Step 4：Use the gold plaque of a diameter of 5mm, thick 0.2mm to be in close contact as electrode respectively in flakes, press from both sides therebetween, Gold plaque is the gold that purity is 99.99%.Being with high-purity gold purpose can effectively resistance to concentrated acid corrosion and high temperature resistant.Draw respectively at the two poles of the earth Wire constitutes electric installation and is connected with electrochemical workstation.
Step 5：The electric installation of step 4 system is placed in the closed two mouthfuls of flasks of 50mL, flask internal thermometer, in electrical heating Temperature actuated is realized in heating in set.Nitrogen is full of in bottle to ensure material work environmental gas stabilization, two mouthfuls of external N of flask2Gas Ball is ensureing stable gas pressure.Under normal pressure between 25 DEG C -250 DEG C, every 25 DEG C of intensifications are once carried out with temperature to above-mentioned material The conductivity test of change.AC impedance figure is shown in Fig. 8.And it is recorded as the ac impedance measurement for heating up for the first time.(table 4)
Table 4：89%H3PO4@PAF-1 first time intensification ac impedance measurement results
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, electrical conductivity is still very high, and with The rising proton conductivity of temperature is gradually increasing, and this explanation temperature raises the Proton conducting for being conducive to this material.This material is also special Shi He not work at high temperature.But heat endurance is especially desirable not enough, temperature is up to 250 DEG C, beyond this temperature material Material can not circulate the second task.
Embodiment 3
With the H that concentration is 85%3PO4Porous aromatic skeleton compound 85% is prepared as higher boiling acid dip material H3PO4@PAF-1 and as the application of conducting material.The method of the present embodiment is substantially the same manner as Example 1, difference be with Concentration is 85% H3PO4The H that concentration is 98% is instead of as higher boiling acid dip material2SO4.Preparation is comprised the following steps：
Step 1：The poly- Tetrabenzene methanes of 28mg are taken, 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, it is filtrated to get with glass film filter dark purple Color solid.Darkviolet filter cake obtains final product 85%H in being dried 10 hours under 100 DEG C of vacuum conditions3PO4@PAF-1 solids 258mg。
The final product 85%H obtained to step 23PO4@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 that higher boiling acid H3PO4In having enter into porous material PAF-1, and stable existence.
Wave number is 989cm-1It is P-O stretching vibrations.
Wave number is 1115,1284cm-1It is P=O stretching vibrations.
Wave number is 2331cm-1It is P-H stretching vibrations.
Wave number is 2859cm-1It is O-H stretching vibrations (phosphate radical has O-H keys with the extraneous hydrogen bond that formed).
The final product 85%H obtained to step 23PO4@PAF-1 carry out thermogravimetric analysis, and enter with former porous material PAF-1 Row compares, and thermogravimetric analysis figure is shown in Figure 10.
The heat endurance situation of material, begins to decline at about 225 DEG C as we can see from the figure, until being about 450 DEG C again Degree is weightless, and this is the temperature of caving in of skeleton.Heat endurance is substantially better than the material that embodiment 2 is made.
Step 3：Take dried product and uniform powder is ground to form in mortar, take about 20mg powder and pressed in tablet press machine Piece, sheet of diameter 5mm, thick 1mm.
Step 4：Use the gold plaque of a diameter of 5mm, thick 0.2mm to be in close contact as electrode respectively in flakes, press from both sides therebetween, Gold plaque is the gold that purity is 99.99%.Being with high-purity gold purpose can effectively resistance to concentrated acid corrosion and high temperature resistant.Draw respectively at the two poles of the earth Wire constitutes electric installation and is connected with electrochemical workstation.
Step 5：The electric installation of step 4 system is placed in the closed two mouthfuls of flasks of 50mL, flask internal thermometer, in electrical heating Temperature actuated is realized in heating in set.Nitrogen is full of in bottle to ensure material work environmental gas stabilization, two mouthfuls of external N of flask2Gas Ball is ensureing stable gas pressure.Under normal pressure between 25 DEG C -250 DEG C, every 25 DEG C of intensifications are once carried out with temperature to above-mentioned material The conductivity test of change.AC impedance figure is shown in Figure 11.And it is recorded as the ac impedance measurement for heating up for the first time.(table 5)
Table 5：85%H3PO4@PAF-1 first time intensification ac impedance measurement results
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 conductances in high temperature, and with temperature Liter high conductivity be gradually increasing this explanation temperature and raise and be conducive to the conduction of this material.
Step 6：In order to test its cycle performance, after the first round heats up test, temperature returns to room temperature, and other conditions are not Become, heat up again, test its conductance changed with temperature change.AC impedance figure is shown in Figure 12.And be recorded as second The ac impedance measurement of intensification.(table 6)
Table 6：85%H3PO4Second intensification ac impedance measurement result of@PAF-1
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 is in high temperature up to 250 DEG C, conductance is still very high, and with temperature The rising of degree, conductance is gradually increasing this explanation temperature and raises the conduction for being conducive to this material.
Step 7：After second wheel intensification terminates, temperature is again restored to room temperature, and other conditions are constant, heat up again, test Its rising with temperature and the conductance that changes.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 intensification ac impedance measurement results
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 is in high temperature up to 250 DEG C, conductance is still very high, and with temperature The rising of degree, conductance is gradually increasing this explanation temperature and raises, and is conducive to the conduction of this material.This material is also particularly suitable in height The lower work of temperature.And can still keep good performance after third time heats up, then its recycling performance is splendid.
The above, the porous aromatic skeleton with high temperature resistant and tool high conductivity is obtained using acid dip method for the present invention Compound, the raw material stable chemical nature for being used, preparation cost is low, and condition is easy to control, reproducible, and with splendid stabilization Property, its superior electric conductivity can be in the energy, the field such as electrical equipment such as automobile, is had a wide range of applications in portable set, especially As the exchange membrane material in Proton Exchange Membrane Fuel Cells, its tool thermostable can high efficiency be recycled for multiple times.Relatively Existing material, material can have the research field of Proton Exchange Membrane Fuel Cells to use meaning.The dipping that the present invention is used Acid includes H that concentration is 98%2SO4, concentration is 89% H3PO4, concentration is 85% H3PO4, wherein concentration is 85% H3PO4Effect be optimal.
The above, the concrete form based on principal character of the present invention is not limited in above-described embodiment, is referring to During the preferred embodiment description present invention, those skilled in the art can be appreciated that：Under without departing from spiritual principles of the present invention, can A variety of modification changes can be made, is omitted and is replaced.Can also there are multiple combination or change as changed stephanoporate framework or leaching Stain acid, such etc., it is identical that these change acquired effect with above-described embodiment.Which point therefore no matter come from See, above-mentioned implementation method of the invention can only all be considered the description of the invention and can not limit the present invention, with the present invention Any change in claims suitable implication and scope is all considered as being included in the range 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) in the poly- Tetrabenzene methane PAF-1 of high specific surface area porous organic material add higher boiling acid, stirring at normal temperature overnight, institute The higher boiling acid stated is 98%H2SO4, 89%H3PO4, 85%H3PO4In one kind；
(2) mixture that filtering stirs uses glass film filter suction filtration in the glove box of anhydrous and oxygen-free, in 100 DEG C of vacuum Dried 10 hours 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 the new compound formed after absorption higher boiling acid with poly- Tetrabenzene methane as skeleton, is led with very high Electric rate；Especially under 150-250 DEG C of hot conditions, superior service behaviour is shown, its operating temperature range meets high temperature The operating temperature of fuel cell, can apply in Proton Exchange Membrane Fuel Cells, and porous aromatic skeleton compound is applied to matter The testing procedure of the conductance in terms of proton exchange film fuel cell is as follows：
(1) in the poly- Tetrabenzene methane PAF-1 of high specific surface area porous organic material add higher boiling acid, stirring at normal temperature overnight, institute The higher boiling acid stated is 98%H2SO4, 89%H3PO4, 85%H3PO4In one kind；
(2) mixture that filtering stirs uses glass film filter suction filtration in the glove box of anhydrous and oxygen-free, in 100 DEG C of vacuum Dried 10 hours under state, obtain final product：The porous aromatic skeleton compound of the high conductivity with thermostable；
(3) dry final product is ground to form into uniform powder, compressing tablet in mortar；
(4) compressing tablet is clipped in the middle with two panels gold plaque of the same size respectively, is in close contact, and the two poles of the earth difference extraction wire composition is simple Electric installation, is placed in two mouthfuls of flasks of closed 50mL, and N is full of in bottle2And connect N2Balloon is drawn with ensuring stable gas pressure Wire be connected with electrochemical workstation；
(5) at 25 DEG C -250 DEG C, conductivity test is carried out to above-mentioned material under normal pressure.
3. application of the porous aromatic skeleton compound according to claim 2 in terms of Proton Exchange Membrane Fuel Cells, its It is characterised by：The finished product size dimension of the compressing tablet 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, its It is characterised by：The gold electrode size is diameter 5mm, and thickness 1mm, 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, its It is characterised by：In the closed two mouthfuls of flasks of 50mL, flask internal thermometer, flask is placed in electric heating cover described device, realizes Nitrogen is full of in temperature actuated, bottle, to ensure the stabilization of gas, external N2Balloon is ensuring stable gas pressure.
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