CN103881123A - Preparation method of PBI/H3PO4 doped film for high temperature fuel cells - Google Patents
Preparation method of PBI/H3PO4 doped film for high temperature fuel cells Download PDFInfo
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- CN103881123A CN103881123A CN201210563270.4A CN201210563270A CN103881123A CN 103881123 A CN103881123 A CN 103881123A CN 201210563270 A CN201210563270 A CN 201210563270A CN 103881123 A CN103881123 A CN 103881123A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
A preparation method of a PBI/H3PO4 doped film for high temperature fuel cells comprises pretreatment of a PBI film, phosphoric acid soaking of the PBI film, and drying, wherein the phosphoric acid soaking and drying steps are repeated to ensure that the phosphoric acid content in the PBI film reaches 500% of the film mass, and that films treated at different batches are consistent. The method has the advantages of simple and controllable process, suitability for batch production, high consistency in phosphoric acid content in the film, strong uniformity, difficulty to loss of phosphoric acid after long-term storage, stable content, and the like, and the phosphoric acid doped PBI film prepared by the method has the advantages of high conductivity and good cell discharge performance when used as an electrolyte film of a high temperature fuel cell.
Description
Technical field
The present invention relates to a kind of PBI/H used for high-temperature fuel cell
3pO
4the preparation method of doping.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) is a kind of electro-chemical conversion device that the chemical energy of fuel is directly changed into electric energy, and it has, and the advantages such as effciency of energy transfer is high, pollution-free, noiselessness, long service life have broad application prospects in fields such as space flight, traffic, portable power sources.
Proton exchange membrane is the core component of PEMFC, and people use the perfluor type sulfonate film taking Nafion film as representative to carry out the development research of fuel cell mostly at present.But the high proton electric conductivity of this class film depends on the existence of water, therefore its use temperature is conventionally low 100 DEG C.The problems such as it is poisoning that lower temperature operation condition faces such as Catalyst for CO fuel cell in the time of practical application, and the hydro-thermal difficult management of system and the recovery utilization rate of heat energy are low.This will make PEMFC be applied in electrical source of power aspect, face fuel requirement reformation purification, heat radiation difficulty, complex structure and total energy and imitate low inferior practical problems.For PEMFC operating temperature is brought up to more than 100 DEG C, development high temperature PEMFC technology, is an important developing direction.
At present, while using phosphate-doped polymeric film as polybenzimidazole (PBI), even caused people's great attention because phosphoric acid still has certain proton conductive ability under anhydrous state.PBI is a class heteroaromatic compound, has good chemistry and thermostability; Adulterating after mineral acid, can make temperature of fuel cell operation up to 200 DEG C as solid proton conductor, and can under the condition of humidification, operate at normal pressure with not.
PBI can react synthetic by condensation polymerization.In all PBI polymkeric substance, on each benzoglyoxaline repeating unit-N group can be combined in the mode of hydrogen bond with acid, thereby be expected to present good proton conductivity.PBI film for high-temperature fuel cell is processed and is improved its specific conductivity by impregnation of phosphoric acid, because phosphorus acid content in PBI film after impregnation of phosphoric acid will be up to more than 500wt.%.Therefore, in steeping process, phosphoric acid concentration changes greatly, certainly will affect homogeneity and the consistence of phosphoric acid in PBI film, finally affects PBI/H
3pO
4the homogeneity of phosphoric acid and different batches PBI/H in doping
3pO
4the consistence of doping.
Patent 200710190632.9 discloses a kind of method of utilizing polybenzimidazole-phosphoric acid-water ternary system to prepare phosphate-doped polybenzimidazole membrane, in the method, first by preparation PBI-phosphoric acid mixed solution and be placed on sheet glass to obtain the phosphate-doped film of PBI-, then the phosphoric acid that gained film immerses 20-60wt.% is obtained to the phosphate-doped film of PBI-of high phosphorus acid content.In present method preparation process, mixed solution is placed on sheet glass to process and may arrives and cause non-uniform film thickness even and then cause film
The consistence of the film of the inhomogeneous and different batches of middle phosphorus acid content is not high, is unwell to batch production and commercial applications.
Summary of the invention
The present invention is directed to prior art and prepare PBI/H
3pO
4h in doping process
3pO
4lack of homogeneity in PBI film, H in film prepared by different batches
3pO
4the shortcomings such as content consistence is poor, adopt repeatedly the method for dipping to carry out PBI film phosphate-doped, are improving PBI/H
3pO
4doping H
3pO
4conforming between homogeneity and each batch of film improved the phosphorus acid content in doping simultaneously and then improved the ionic conductivity of this film, and concrete scheme of the present invention is as follows:
A kind of PBI/H used for high-temperature fuel cell
3pO
4the preparation method of doping, comprises the following steps,
1) pre-treatment of PBI film: the PBI film of cutting out is placed in to the container that fills deionized water, and described container is placed in to 50-100 DEG C of water-bath processes after 1-12 hour, take out PBI film drying treatment 0.5-2 hour in 80-180 DEG C of baking oven;
2) weighing of PBI film: by step 1) gained PBI film mark piecewise, weigh, record;
3) the pickling processing of PBI film: will be through the step 2 of weighing) the PBI film of gained inserts in container, and inject phosphoric acid solution in described container, and ensure all PBI films of phosphoric acid solution submergence, described container is placed in to oil bath pan thermal treatment 1-96 hour at 80-160 DEG C, obtain PBI/H
3pO
4a doping;
4) PBI/H
3pO
4the drying treatment of a doping: by step 3) gained PBI/H
3pO
4a doping is inserted in vacuum drying oven and under 80-180 DEG C of condition, is dried 0.5-5 hour, obtains dried PBI/H
3pO
4a doping;
5) PBI/H
3pO
4weighing of a doping: by dried step 4) gained PBI/H
3pO
4one time doping is weighed under room temperature, record;
6) calculating of phosphorus acid content: adopt following formula to calculate the phosphorus acid content in PBI film, PBI film quality before phosphorus acid content per-cent=(the front PBI film quality of PBI film quality-pickling after pickling)/pickling;
7) PBI/H
3pO
4the preparation of doping: if phosphorus acid content is more than or equal to preset value X, PBI/H in the PBI film that described in employing step 6), method of calculation calculate
3pO
4prepared by doping;
If phosphorus acid content is less than preset value X in PBI film, repeat successively above-mentioned steps 3)-6), till being more than or equal to preset value X to phosphorus acid content in PBI film, obtain PBI/H
3pO
4doping.
The concentration of described phosphoric acid solution is 65wt.%-98wt.%.
The area of the PBI film flooding in every liter of phosphoric acid solution in described step 3) is 100-2000cm
2.
Described immersion condition is that oil bath temperature is 80 ~ 160 DEG C, and the treatment time is 1 ~ 48 hour;
Described good immersion condition is that oil bath temperature is 100 ~ 150 DEG C, and 12 ~ 72 hours treatment times are better;
Described best immersion condition is that oil bath temperature is 110 ~ 130 DEG C, and 24 ~ 48 hours treatment times are best.
PBI film must be dried after soaking phosphoric acid in vacuum drying oven, and preferably 100 ~ 150 DEG C of described bake out temperatures, are preferably 110 ~ 130 DEG C.
PBI film quality before phosphorus acid content per-cent=(after pickling PBI film quality-pickling before PBI film quality)/pickling, in gained film, phosphorus acid content preset value X is 100 ~ 650%, 300 ~ 600% better, 450 ~ 550% is best.
High-temperature fuel cell film for impregnation of phosphoric acid is various types of PBI films, comprises one or two or more kinds in AB-PBI, mPBI, F6-PBI, OO-PBI, OSO2-PBI, Py-PBI, Py-O-PBI, SO2-PBI or SPBI.
Brief description of the drawings
Fig. 1 is by comparative example 1 and embodiment 4 the data obtaineds draw single treatment and repeated drying is processed phosphorus acid content homogeneity curve in PBI film; Respectively same batch of single impregnation and the PBI film of impregnation drying processing are repeatedly got to 10 samples, weigh and calculate phosphorus acid content in dipping caudacoria, curve plotting.In figure, can find out, the film phosphorus acid content fluctuation of word dip treating is larger, and repeatedly in the film of impregnation drying processing, phosphorus acid content fluctuation is less, and same batch of homogeneity is better.
Fig. 2 changes for processing 6 days phosphorus acid contents of placement by comparative example 2 and embodiment 5 the data obtained lists drafting time processing with repeated drying; By single impregnation and after repeatedly the PBI film of impregnation drying processing is handled well, place phosphorus acid content in 24 hours test membranes 6 days respectively.In figure, curve shows, after long-time placement, in the PBI film of single impregnation treatment, phosphorus acid content is obvious with prolongation reduction storage period, and after repeatedly the PBI film of impregnation drying processing is placed for a long time, in film, phosphorus acid content reduces slower.
Fig. 3 is by the performance curve of comparative example 1 and embodiment 4 gained PBI film assembled batteries; Wherein in PBI film, phosphorus acid content is 550%, and battery testing temperature is 180 DEG C, normal pressure hydrogen, flow velocity 50SCCM; Atmospheric oxygen, flow velocity 100SCCM.Test set is Arbin electronic load.
Embodiment
The present invention is described in detail by the following examples, but the present invention is not limited only to embodiment.
Embodiment 1:
Cut out ab-PBI film 10 × 10cm
24, the PBI film of cutting out is placed in to large beaker, by washed with de-ionized water, then PBI film is put into the beaker that fills high purity water, put into 50-100 degree Celsius of water-bath and process 12 hours.By the finely dispersed PBI film air oven of putting into, carry out drying and processing.120 degrees Celsius, 2 hours.Weigh, record.85% phosphoric acid is slowly injected to 4 beakers that fill respectively PBI film, the whole submergence PBI of phosphoric acid film.Put into respectively 4 oil cauldron heat treated, oil temperature is respectively 90,100,110,120 degrees Celsius.In the time of 2,6,12,24 hours, take out vacuum drying and weigh, when calculating phosphorus acid content and being respectively 2 hours, temperature is that in 90,100,110,120 degrees Celsius of PBI films, phosphorus acid content is respectively: 108%, 116%, 121%, 317%; 6 hours time, temperature is that in 90,100,110,120 degrees Celsius of PBI films, phosphorus acid content is respectively: 128%, 134%, 149%, temperature is that in 90,100,110,120 degrees Celsius of PBI films, phosphorus acid content is respectively 398%, 12 hour time: 120%, 196%, 253%, 445%; 24 hours time, temperature is that in 90,100,110,120 degrees Celsius of PBI films, phosphorus acid content is respectively: 140%, 299%, 342%, 536%.
Embodiment 2:
Cut out ab-PBI film 10 × 10cm
23, the PBI film of cutting out is placed in to large beaker, by washed with de-ionized water, then PBI film is put into the beaker that fills high purity water, put into 50-100 degree Celsius of water-bath and process 12 hours.By the finely dispersed PBI film air oven of putting into, carry out drying and processing.120 degrees Celsius, 2 hours.Weigh, record.Respectively 65%, 85%, 98% phosphoric acid is slowly injected to 3 beakers that fill PBI film, the whole submergence PBI of phosphoric acid film.Put into respectively 3 oil cauldron heat treated, oil temperature is 120 degrees Celsius.65%, 85% phosphoric acid is processed 30 hours, and 98% phosphoric acid is processed half hour, is disposed and takes out vacuum drying and weigh.Calculating phosphorus acid content in 30 hours PBI films of 65% phosphoric acid processing is 376%; Calculating phosphorus acid content in 30 hours PBI films of 85% phosphoric acid processing is 542%; Calculating phosphorus acid content in 30 hours PBI films of 98% phosphoric acid processing is 556%.
Embodiment 3:
Cut out ab-PBI film 6 × 10cm
215, the PBI film of cutting out is placed in to large beaker, by washed with de-ionized water, then PBI film is put into the beaker that fills high purity water, put into 50-100 degree Celsius of water-bath and process 12 hours.By the finely dispersed PBI film air oven of putting into, carry out drying and processing.120 degrees Celsius, 2 hours.Weigh, record.85% phosphoric acid is slowly injected to the beaker that fills PBI film, the whole PBI films of submergence.Put into oil cauldron heat treated, 120 degrees Celsius of oil temperatures.In the time of 5,7.5,12.5,17,36 hours, take out 6 testing samples carrying out mark, vacuum drying is weighed, and calculates phosphorus acid content.5 hours dry rear phosphoric acid average contents of 6 samples are 383%; Within 7.5 hours, dry rear phosphoric acid average content is 401%; Within 12.5 hours, dry rear phosphoric acid average content is 424%; Within 17 hours, dry rear phosphoric acid average content is 504%; Within 36 hours, dry rear phosphoric acid average content is 576%.
Embodiment 4:
Cut out ab-PBI film 6 × 10cm
215, and to wherein 10 mark, the PBI film of cutting out is placed in to large beaker, by washed with de-ionized water, then PBI film is put into the beaker that fills high purity water, put into 50-100 degree Celsius of water-bath and process 12 hours.By the finely dispersed PBI film air oven of putting into, carry out drying and processing.120 degrees Celsius, 2 hours.Weigh, record.85% phosphoric acid is slowly injected to the beaker that fills PBI film, the whole PBI films of submergence.Put into oil cauldron heat treated, 120 degrees Celsius of oil temperatures.Dried and flood again every 7 hours, process continuously 5 total immersions and steep 35 hours.After final drying, take out 10 testing samples carrying out mark, calculate phosphorus acid content and be respectively 587%, 601%, 576%, 590%, 568%, 559%, 573%, 585%, 564%, 571%.
Embodiment 5:
In order to prove after PBI film immersion phosphoric acid, the stability of phosphorus acid content in film, to distinguish 5 impregnation drying impregnation drying processing again, the total immersion stain PBI film of 36 hours, after placing for some time, test its phosphorus acid content variation, every test in 24 hours once, continuously tested 144 hours, along with phosphorus acid content in the prolongation film of placing is respectively: 576%, 556%, 556%, 555%, 544%, 545%.
Embodiment 6:
Cut out ab-PBI film 6 × 10cm
215, and to wherein 5 mark, the PBI film of cutting out is placed in to large beaker, by washed with de-ionized water, then PBI film is put into the beaker that fills high purity water, put into 50-100 degree Celsius of water-bath and process 12 hours.By the finely dispersed PBI film air oven of putting into, carry out drying and processing.120 degrees Celsius, 2 hours.Weigh, record.85% phosphoric acid is slowly injected to the beaker that fills PBI film, the whole PBI films of submergence.Put into oil cauldron heat treated, 120 degrees Celsius of oil temperatures.Dried and flood again every 8 hours, process continuously 6 total immersions and steep 48 hours, do altogether 5 batches.After final drying, take out 5 testing samples carrying out mark, calculate phosphorus acid content.Five batches of phosphorus acid content mean values are respectively 580%, 573%, 563%, 565%, 572%.
Embodiment 7:
Cut out m-PBI film 10 × 10cm
21, the PBI film of cutting out is placed in to large beaker, by washed with de-ionized water, then PBI film is put into the beaker that fills high purity water, put into 50-100 degree Celsius of water-bath and process 12 hours.By the finely dispersed PBI film air oven of putting into, carry out drying and processing.120 degrees Celsius, 2 hours.Weigh, record.85% phosphoric acid is slowly injected to the beaker that fills PBI film, the whole PBI films of submergence.Put into oil cauldron heat treated, 120 degrees Celsius of oil temperatures.Process 30 hours, weighed in 120 DEG C of vacuum dryings every 5 hours, calculating phosphorus acid content is 600%.
Comparative example 1:
Cut out 15 ab-PBI film 10 × 10cm
2and to wherein 10 mark, the PBI film of cutting out is placed in to large beaker, by washed with de-ionized water, then PBI film is put into the beaker that fills high purity water, put into 50-100 degree Celsius of water-bath and process 12 hours.By the finely dispersed PBI film air oven of putting into, carry out drying and processing.120 degrees Celsius, 2 hours.Weigh, record.85% phosphoric acid is slowly injected to the beaker that fills PBI film, the whole PBI films of submergence.Put into oil cauldron heat treated.120 degrees Celsius of oil temperatures, process 36 hours.By the PBI film of handling well, blot surperficial phosphoric acid with filter paper, good 10 of mark are weighed and calculate phosphorus acid content and be respectively: 522%, 578%, 582%, 513%, 571%, 553%, 546%, 553%, 569%, 531%.
Comparative example 2:
In order to prove after PBI film immersion phosphoric acid, the stability of phosphorus acid content in film, by the continuous 36 hours good PBI films of impregnation of phosphoric acid aftertreatment, after placing for some time, test its phosphorus acid content variation, every test in 24 hours once, continuously tested 144 hours, along with phosphorus acid content in the prolongation film of placing is respectively: 556%, 494%, 504%, 508%, 512%, 504%.
Table 1 is by phosphorus acid content in different dipping time PBI films under embodiment 1 gained differing temps; PBI film immersion, in 85% phosphoric acid solution, is set to respectively to 90,100,110,120 DEG C by oil bath pan temperature, when dipping time is 2,6,12,24 hours under each temperature condition, takes out to dry and weigh, calculate phosphorus acid content in film.In table, data show along with the rising of dipping temperature and the prolongation of time, and the phosphorus acid content in PBI film increases, and when 120 DEG C of dippings, phosphorus acid content increase is comparatively obvious.
Table 1
Table 2 is the impact on phosphorus acid content in PBI film by embodiment 2 gained phosphoric acid concentrations; Respectively by PBI film immersion in 98,85, in 65% phosphoric acid solution, oil bath pan temperature is 120 DEG C, dipping time takes out while being 0.5,30,30 hour to dry and weighs, and calculates phosphorus acid content in film.Data show that phosphoric acid concentration improves, and the phosphoric acid required time that floods same concentration in PBI film reduces, and the PBI film phosphorus acid content of same dipping time low phosphorus acid dipping is lower.
Table 2
| Film numbering | Phosphoric acid concentration | Heating temperature | Heat-up time | Phosphoric acid percentage composition |
| A | 98% | 120℃ | 0.5h | 556 |
| B | 85% | 120℃ | 30h | 542 |
| C | 65% | 120℃ | 30h | 376 |
Table 3 is with drying treatment PBI film phosphorus acid content batch repeatedly by embodiment 3 gained; The PBI film of same batch processed is got to 5 samples, in the time of dry weighing each time, counter phosphorus acid content and batch mean value.In table, data show, same batch of repeatedly impregnation drying processing, and along with the increase of dipping time, in PBI film, phosphorus acid content increases gradually, and in 36 hours caudacorias, phosphorus acid content all exceedes 550%.
Table 3
Table 4 is for repeatedly to process PBI film phosphorus acid content by embodiment 6 gained different batches; By under 5 batches of 120 degrees celsius, the 85% phosphoric acid repeatedly PBI film of drying treatment is got respectively 5 samples, weigh to calculate repeatedly to flood phosphorus acid content in caudacoria, and calculating mean value.In table, data show, the PBI film that different batches is repeatedly processed, and every a collection of film phosphorus acid content mean value homogeneity is better.
Table 4
| Film numbering | 1 | 2 | 3 | 4 | 5 |
| A | 581 | 572 | 553 | 563 | 578 |
| B | 606 | 578 | 583 | 571 | 582 |
| C | 556 | 582 | 554 | 553 | 563 |
| D | 593 | 563 | 569 | 583 | 571 |
| E | 565 | 571 | 558 | 553 | 564 |
| Mean value | 580 | 573 | 563 | 565 | 572 |
Claims (7)
1. a PBI/H used for high-temperature fuel cell
3pO
4the preparation method of doping, is characterized in that: comprises the following steps,
1) pre-treatment of PBI film: the PBI film of cutting out is placed in to the container that fills deionized water, and described container is placed in to 50-100 DEG C of water-bath processes after 1-12 hour, take out PBI film drying treatment 0.5-2 hour in 80-180 DEG C of baking oven;
2) weighing of PBI film: by step 1) gained PBI film mark piecewise, weigh, record;
3) the pickling processing of PBI film: will be through the step 2 of weighing) the PBI film of gained inserts in container, and inject phosphoric acid solution in described container, and ensure all PBI films of phosphoric acid solution submergence, described container is placed in to oil bath pan thermal treatment 1-96 hour at 80-160 DEG C, obtain PBI/H
3pO
4a doping;
4) PBI/H
3pO
4the drying treatment of a doping: by step 3) gained PBI/H
3pO
4a doping is inserted in vacuum drying oven and under 80-180 DEG C of condition, is dried 0.5-5 hour, obtains dried PBI/H
3pO
4a doping;
5) PBI/H
3pO
4weighing of a doping: by dried step 4) gained PBI/H
3pO
4one time doping is weighed under room temperature, record;
6) calculating of phosphorus acid content: adopt following formula to calculate the phosphorus acid content in PBI film, PBI film quality before phosphorus acid content per-cent=(the front PBI film quality of PBI film quality-pickling after pickling)/pickling;
7) PBI/H
3pO
4the preparation of doping: if phosphorus acid content is more than or equal to preset value X, PBI/H in the PBI film that described in employing step 6), method of calculation calculate
3pO
4prepared by doping;
If phosphorus acid content is less than preset value X in PBI film, repeat successively above-mentioned steps 3)-6), till being more than or equal to preset value X to phosphorus acid content in PBI film, obtain PBI/H
3pO
4doping.
2. PBI/H as claimed in claim 1
3pO
4the preparation method of doping, is characterized in that: the concentration of described phosphoric acid solution is 65wt.%-98wt.%.
3. PBI/H as claimed in claim 1
3pO
4the preparation method of doping, is characterized in that: the area of the PBI film flooding in every liter of phosphoric acid solution in described step 3) is 100-2000cm
2.
4. PBI/H as claimed in claim 1
3pO
4the preparation method of doping, is characterized in that: immersion condition is that oil bath temperature is 80 ~ 160 DEG C, and the treatment time is 1 ~ 48 hour;
Immersion condition is that oil bath temperature is 100 ~ 150 DEG C preferably, and 12 ~ 72 hours treatment times are better;
Best immersion condition is that oil bath temperature is 110 ~ 130 DEG C, and 24 ~ 48 hours treatment times are best.
5. PBI/H as claimed in claim 1
3pO
4the preparation method of doping, is characterized in that: PBI film must be dried after soaking phosphoric acid in vacuum drying oven, and preferably 100～150 DEG C of described bake out temperatures, are preferably 110 ~ 130 DEG C.
6. PBI/H as claimed in claim 1
3pO
4the preparation method of doping, is characterized in that: PBI film quality before phosphorus acid content per-cent=(after pickling PBI film quality-pickling before PBI film quality)/pickling, and in gained film, phosphorus acid content preset value X is 100 ~ 650%, 300 ~ 600% better, 450 ~ 550% is best.
7. PBI/H as claimed in claim 1
3pO
4the preparation method of doping, it is characterized in that: be various types of PBI films for the high-temperature fuel cell film of impregnation of phosphoric acid, comprise one or two or more kinds in AB-PBI, mPBI, F6-PBI, OO-PBI, OSO2-PBI, Py-PBI, Py-O-PBI, SO2-PBI or SPBI.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104341607A (en) * | 2014-09-04 | 2015-02-11 | 吉林大学 | Application of polybenzimidazole polymer containing side group in proton exchange membrane |
| CN108178137A (en) * | 2016-12-08 | 2018-06-19 | 中国科学院大连化学物理研究所 | The preparation of a kind of high-purity phosphoric acid and phosphoric acid/PBI composite membranes and film and application |
| CN109575346A (en) * | 2018-12-22 | 2019-04-05 | 大连大学 | A kind of preparation method of the flexible conducting material of high temperature resistant substrate |
| CN111342097A (en) * | 2018-12-18 | 2020-06-26 | 中国科学院大连化学物理研究所 | Preparation method of electrolyte membrane with high conductivity and good mechanical property |
| CN111682248A (en) * | 2020-06-29 | 2020-09-18 | 香港科技大学 | PBI membrane activation treatment method with high proton conductivity and ion selectivity |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104341607A (en) * | 2014-09-04 | 2015-02-11 | 吉林大学 | Application of polybenzimidazole polymer containing side group in proton exchange membrane |
| CN108178137A (en) * | 2016-12-08 | 2018-06-19 | 中国科学院大连化学物理研究所 | The preparation of a kind of high-purity phosphoric acid and phosphoric acid/PBI composite membranes and film and application |
| CN111342097A (en) * | 2018-12-18 | 2020-06-26 | 中国科学院大连化学物理研究所 | Preparation method of electrolyte membrane with high conductivity and good mechanical property |
| CN109575346A (en) * | 2018-12-22 | 2019-04-05 | 大连大学 | A kind of preparation method of the flexible conducting material of high temperature resistant substrate |
| CN109575346B (en) * | 2018-12-22 | 2021-03-16 | 大连大学 | Preparation method of flexible conductive material of high-temperature-resistant substrate |
| CN111682248A (en) * | 2020-06-29 | 2020-09-18 | 香港科技大学 | PBI membrane activation treatment method with high proton conductivity and ion selectivity |
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|---|---|
| CN103881123B (en) | 2016-08-03 |
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