CN103296296B - A kind of hydrogen-chlorine fuel cell perforated membrane and Synthesis and applications thereof - Google Patents
A kind of hydrogen-chlorine fuel cell perforated membrane and Synthesis and applications thereof Download PDFInfo
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- CN103296296B CN103296296B CN201210052189.XA CN201210052189A CN103296296B CN 103296296 B CN103296296 B CN 103296296B CN 201210052189 A CN201210052189 A CN 201210052189A CN 103296296 B CN103296296 B CN 103296296B
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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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Abstract
A kind of hydrogen-chlorine fuel cell perforated membrane and Synthesis and applications thereof, high molecular polymer and nano-oxide particles ultrasonic dissolution is comprised the steps: to be made into preparation liquid in organic solvent, phase inversion preparation is adopted to have the polymer-inorganic perforated membrane of asymmetric configuration structure, obtained thickness is 25-150 μm, and porosity is 60-80%.The thickness of perforated membrane prepared by the present invention, porosity, pore size and oxide-doped amount are easy to control, and the film made protects that acid amount is high, and intensity is good, and cost is low, and preparation method is simple, can perform well in hydrogen-chlorine fuel cell.
Description
Technical field
The present invention relates to a kind of to be dissolved in hydrogen-chlorine fuel cell perforated membrane that the chlorine in hydrochloric acid is raw material and preparation method thereof, be specifically related to a kind of method adopting phase inversion directly to prepare hydrogen-chlorine fuel cell Hydrophilized porous membrane.
Background technology
Hydrogen-chlorine fuel cell using hydrogen as fuel, chlorine as oxidant, there is electrochemical reaction in both, the chemical energy be stored in wherein is directly changed into electric energy in the battery respectively, can produce the hydrochloric acid of desired concn simultaneously.Therefore a kind of electrolyte membrance is needed cathode and anode to be isolated.Proton exchange membrane (PEM) is one of core component of Proton Exchange Membrane Fuel Cells (PEMFC), desirable PEM should have that proton conductivity is high, gas and low, the high ion selectivity of Test Liquid Permeability of Core, sufficiently high mechanical strength, thermal stability and chemical stability, and there is suitable cost performance.
At present, the research of hydrogen-chlorine fuel cell is also in the exploratory stage, according to literature search, only there are several sections of documents and 4 patent (USP 4128701 both at home and abroad, CN 86104831, CN 1805196, JP3150803-U), but these patents are all the selection optimization about the electrode material such as battery system or catalyst, wherein electrolyte membrance all adopts business Nafion film or directly uses the solution such as hydrochloric acid as electrolyte, not about the research of newtype dielectric film, and find that the cell cathode side raw material of report mostly is liquid (chlorine is dissolved in hydrochloric acid), anode-side is then hydrogen, this feeding manner is similar to direct methanol fuel cell (DMFC), therefore DMFC proton-conductive films can be used for reference.The people such as Peled have prepared a kind of nanoporous proton-conductive films, and it is with the PVDF of doping silicon dioxide particle for raw material, and casting film in an oven, adsorbs different acid solution afterwards, has very high proton-conducting, and is successfully applied in DMFC.But this membrane porosity and adsorber acid amount lower.
Can perforated membrane (as milipore filter or NF membrane) in water draw separation industries based on this thinking, this film is mostly dissymmetrical structure, namely very thin there is optionally cortex (general thickness is 0.1-1 μm) and being made up of (porosity is very high) the porous subgrade of equivalent material by one, and it is different according to institute's environment for use, can be adulterated different acid solutions wherein, makes film have very high conductivity.
Summary of the invention
Object of the present invention, except providing a kind of hydrogen-chlorine fuel cell perforated membrane, is also to provide a kind of phase inversion that adopts directly to prepare the preparation method of hydrogen-chlorine fuel cell with silica-doped polyethersulfone porous membrane.
For achieving the above object, the technical solution used in the present invention can realize as follows:
A kind of hydrogen-chlorine fuel cell perforated membrane, it is the polymer-inorganic perforated membrane prepared by high molecular polymer and nano-oxide particles; Nano-oxide mass fraction in polymeric base layer is 0.5-30wt.%.
Can be, to hydrochloric acid or chlorine, there is the poly-inclined tetrafluoroethene (PVDF) of well tolerable property, Kynoar-hexafluoropropylene copolymer (PVDF-HFP), Phthalazinone polyether-ketone (PPEK), polysulfones (PSF) or polyether sulfone (PES) with high molecular polymer;
Nano-oxide is silicon dioxide (particle diameter 2-200nm), titanium dioxide (particle diameter 2-200nm) or meso-porous molecular sieve material (MCM-41 (particle diameter 2-10nm) or SBA-15 (particle diameter 5-50nm)).
High boiling solvent used is the good solvent of high molecular polymer, is DMSO, DMF, DMAC or NMP;
Additive is glycerine, dimethyl carbonate, diethyl carbonate, carbonate propanediol fat or PVP.
Described polymer-inorganic perforated membrane is the perforated membrane of asymmetric configuration structure, it is made up of dense layer surface and loose porous basic unit, refer to that the perforated membrane of the asymmetric configuration structure be made up of same material is porosity and the aperture that the porosity of side and aperture are all less than opposite side, form the perforated membrane of the asymmetric configuration structure be made up of dense layer surface and loose porous basic unit; Maybe can be described as: described polymer-inorganic perforated membrane is the perforated membrane of asymmetric configuration structure, refer to the top layer with the densification arranging orderly micropore and based on the perforated membrane of the asymmetric configuration structure of the bottom of finger-like pore structure.
The preparation method of described perforated membrane: by high molecular polymer and nano-oxide particles ultrasonic dissolution in high boiling organic solvent and additive mixed solution, adopts phase inversion preparation to have the polymer-inorganic perforated membrane of asymmetric configuration structure.
Be specially;
A. casting solution is prepared, comprise and account for the polymeric substrates that casting solution mass fraction is 5-25wt.%, with the nano-oxide accounting for polymer 0.5-30wt.%, wherein nano-oxide is silicon dioxide (particle diameter 2-200nm), titanium dioxide (particle diameter 2-200nm) or meso-porous molecular sieve material (MCM-41 (particle diameter 2-10nm) or SBA-15 (particle diameter 5-50nm)) etc.Solvents is the mixed solution of the high boiling solvents such as DMSO, DMF, DMAC and NMP of 60-95wt.% (45-95wt%) and 0-35wt.% (0-30wt%) additive, and wherein additive can be glycerine, dimethyl carbonate, diethyl carbonate, carbonate propanediol fat, PVP etc.;
B. above-mentioned casting solution stirs 0.5-20h at temperature 20-100 DEG C, ultrasonic 0.5-3h, and the homogeneous polymer solution obtained static or vacuum defoamation 0.5-10h at temperature 20-90 DEG C makes final casting solution;
C. adopt scraper by above-mentioned casting solution blade coating on a glass, by the thickness regulating scraper height to carry out controlling diaphragm, obtained film thickness is 25-150 μm;
D. glass plate flatly being put into temperature is in the coagulating bath of 20-80 DEG C, takes out after static 0.5-24h, dries after film is soaked 0.5-24h in absolute ethyl alcohol or n-hexane in air;
E., after the film dried being processed 0.5-10h at temperature 20-90 DEG C in concentration 1-6M hydrochloric acid solution, can use in hydrogen-chlorine fuel cell.
The present invention can be have the poly-inclined tetrafluoroethene (PVDF) of well tolerable property, Kynoar-hexafluoropropylene copolymer (PVDF-HFP), the polyether-ether-ketone of sulfonation, Phthalazinone polyether-ketone (PPEK), polysulfones (PSF) or polyether sulfone (PES) etc. to hydrochloric acid or chlorine for the preparation of the polymer that hydrogen-chlorine fuel cell perforated membrane adopts, consider the liquid hydrochloric acid in hydrogen-chlorine fuel cell running and chlorine gas environment, optimum should be have fine chemical stability and hydrophilic polyether sulfone.Perforated membrane average pore size prepared by the present invention is about 5-20nm, and porosity is 60-80%, and water absorption rate is 150-250%, and minimum bubbling pressure is 0.075-0.5MPa.
Tool of the present invention has the following advantages:
1. method of operation is simple, easy, and the perforated membrane thickness made, membrane porosity, membrane aperture size and oxide-doped amount are easy to control, protect acid amount high, intensity is good, and cost is low, environmental friendliness, safe and reliable, be easy to large-scale production, can be advantageously applied in hydrogen-chlorine fuel cell.
2. hydrogen-chlorine fuel cell all adopts business Nafion film or PBI-H at present
3pO
4high temperature membrane, perforated membrane is applied in hydrogen-chlorine fuel cell by the present invention, has novelty.
3. adopt the present invention to prepare the polyether sulfone-SiO that thickness is 115 μm
2perforated membrane hydrogen-chlorine fuel cell performance is better than the battery performance that the close E.I.Du Pont Company of thickness business-like Nafion 115 film (125 μm) is assembled.
Accompanying drawing explanation
Fig. 1 is the film lower surface containing the polyethersulfone porous membrane of 0.5wt.% silicon dioxide, film upper surface and film section photo under a scanning electron microscope prepared by embodiment 1; PES perforated membrane scanning electron microscope (SEM) photograph a) lower surface; B) upper surface; C) section;
Fig. 2 is the polyethersulfone porous membrane film lower surface containing 10wt.% silicon dioxide, film upper surface and film section photo under a scanning electron microscope prepared by embodiment 2; SiO
2for PES perforated membrane scanning electron microscope (SEM) photograph a) lower surface during 10wt.%; B) upper surface; C) section;
Fig. 3 is the cell performance curve figure of embodiment 2; SiO
2for the H that the PES perforated membrane of 10wt.% is assembled
2/ Cl
2fuel battery performance;
Fig. 4 is the polyethersulfone porous membrane film lower surface containing 15wt.% silicon dioxide, film upper surface and film section photo under a scanning electron microscope prepared by embodiment 3; SiO
2for PES perforated membrane scanning electron microscope (SEM) photograph a) lower surface during 15wt.%; B) upper surface; C) section;
Fig. 5 is the Performance comparision figure of the Nafion115 film assembled battery of embodiment 3 and E.I.Du Pont Company; SiO
2for the H that PES perforated membrane during 15wt.% and Nafion115 film are assembled
2/ Cl
2fuel battery performance contrasts.
Embodiment
Embodiment 1: by highly purified for 1g polyether sulfone (PES, molecular weight M
w=58000), 0.005g SiO
2(particle diameter 20-30nm), 4.6g analytically pure DMAC and 0.3g carbonate propanediol fat mix, 60 DEG C of lower magnetic forces stir 5h, ultrasonic mixing 1h, standing at room temperature 3h deaeration, striking film forming under room temperature, to occur in the water under room temperature by liquid phase to the inversion of phases of solid phase and film forming (thickness is 85 μm), after during 2h, film to be soaked in absolute ethyl alcohol 4h, in 1M hydrochloric acid, 40 DEG C are boiled 3h, put in watery hydrochloric acid stand-by.Gained film has dissymmetrical structure (film lower surface, upper surface and section electromicroscopic photograph are shown in accompanying drawing 1), the contact angle of gained film surface water droplet is 76.3 °, porosity is 70.86%, water absorption rate is 178.4%, average pore size is 13.9nm, smallest bubbles point pressure is 0.075MPa, and by the film surface liquid wiped clean of boiling in acid, testing its room temperature ionic conductivity is 0.05S cm
-1.
Embodiment 2: by 0.9g PES (M
w=58000), 0.1g SiO
2(particle diameter 20-30nm), 4.2gDMF and 0.26g PVP mix, stirred at ambient temperature 1h, ultrasonic mixing 0.5h, 60 DEG C of vacuum defoamation 1h, knifing on a glass under room temperature, inversion of phases film forming (film thickness 70 μm) in 30 DEG C of water, soaks 1 day in n-hexane, dry in air, in 3M hydrochloric acid, 80 DEG C are boiled 1h.Gained film has dissymmetrical structure (film lower surface, upper surface and section electromicroscopic photograph are shown in accompanying drawing 2), the contact angle of gained film surface water droplet is 65.8 °, porosity is 71.1%, water absorption rate is 201.6%, average pore size is 12.3nm, smallest bubbles point pressure is 0.1MPa, and by the film surface liquid wiped clean of boiling in acid, testing its room temperature ionic conductivity is 0.106S cm
-1.
Adopt method described in patent CN02127802.4 to prepare hydrophilic cathode (catalyst is 70%Pt/C), in electrode, catalyst Pt carrying capacity is 1mg cm
-2.Anode adopts commercialization gas-diffusion electrode (new driving source company), and in electrode, catalyst Pt carrying capacity is 0.4mg cm
-2.For guaranteeing that electrode contacts with the effective of film, reduce the contact resistance between electrode and film, negative electrode and anode are placed in respectively prepared film both sides (film compacted zone is towards anode), 1min is suppressed under 100 DEG C and 0.1MP in hydraulic press, rapid taking-up cooling, obtains membrane electrode three-in-one (MEA).
Gained MEA is assembled into fuel cell, test battery performance on monocell evaluating apparatus.Test performance curve is shown in accompanying drawing 3.Cell operating conditions is as follows: battery temperature is 40 DEG C, hydrogen flow rate 110mlmin
-1, without humidification, normal pressure, chlorine is first dissolved in 3M HCl, enters cell cathode afterwards by peristaltic pump, and flow velocity is 850ml min
-1.
Embodiment 3: by 0.85g PES (M
w=58000), 0.15g SiO
2(particle diameter 10-20nm), 4gDMAC and 0.25g glycerine ultrasonic mixing 3h, stirred at ambient temperature 5h, deaeration in 60 DEG C of vacuum drying ovens, knifing in room temperature lower glass plate, put into inversion of phases film forming (115 μm) in 50 DEG C of water afterwards, after 4h, film is soaked 12h in absolute ethyl alcohol, in 3M hydrochloric acid, 60 DEG C are boiled 3h, put in watery hydrochloric acid stand-by.Gained film has dissymmetrical structure (film lower surface, upper surface and section electromicroscopic photograph are shown in accompanying drawing 4), the contact angle of gained film surface water droplet is 64.1 °, porosity is 75.31%, water absorption rate is 213.4%, average pore size is 9.46nm, smallest bubbles point pressure is 0.31MPa, and by the film surface liquid wiped clean of boiling in acid, testing its room temperature ionic conductivity is 0.15S cm
-1.
Adopt this film preparation MEA, the Nafion115 of business, with embodiment 2, is prepared MEA according to the method in enforcement 2 by the electrode of employing and preparation method, the battery performance of more than test two MEA on monocell evaluating apparatus.The operating condition of battery is with embodiment 2.Test battery performance curve is shown in accompanying drawing 5.200mA cm
-2time, PES-SiO
2(15wt.%) cell voltage of film assembling is the cell voltage of 0.610V, Nafion115 film assembling is 0.863V, and battery maximum power density is respectively 195.3mWcm
-2with 126.0mW cm
-2.
Claims (7)
1. a hydrogen-chlorine fuel cell perforated membrane, is characterized in that:
It is the polymer-inorganic perforated membrane prepared by high molecular polymer and nano-oxide particles; Nano-oxide mass fraction in polymeric base layer is 0.5-30wt.%;
Described polymer-inorganic perforated membrane is the perforated membrane of asymmetric configuration structure, it is made up of dense layer surface and loose porous basic unit, refer to that the perforated membrane of the asymmetric configuration structure be made up of same material is porosity and the aperture that the porosity of side and aperture are all less than opposite side, form the perforated membrane of the asymmetric configuration structure be made up of dense layer surface and loose porous basic unit.
2., according to perforated membrane according to claim 1, it is characterized in that:
, to hydrochloric acid or chlorine, there is the poly-inclined tetrafluoroethene (PVDF) of well tolerable property, Kynoar-hexafluoropropylene copolymer (PVDF-HFP), Phthalazinone polyether-ketone (PPEK), polysulfones (PSF) or polyether sulfone (PES) with high molecular polymer;
The MCM-41 that the silicon dioxide of nano-oxide to be particle diameter be 2-200nm, particle diameter are the titanium dioxide of 2-200nm, particle diameter is 2-10nm or particle diameter are the SBA-15 of 5-50nm.
3., according to perforated membrane according to claim 1, it is characterized in that:
High boiling solvent used is the good solvent of high molecular polymer, is DMSO, DMF, DMAC or NMP;
Additive is glycerine, dimethyl carbonate, diethyl carbonate, carbonate propanediol fat or PVP.
4. a preparation method for perforated membrane described in claim 1,2 or 3, is characterized in that:
By high molecular polymer and nano-oxide particles ultrasonic dissolution in high boiling organic solvent and additive mixed solution, phase inversion preparation is adopted to have the polymer-inorganic perforated membrane of asymmetric configuration structure.
5., according to preparation method according to claim 4, it is characterized in that:
A. prepare casting solution, comprise and account for the polymeric substrates that casting solution mass fraction is 5-25wt.%, solvents is the mixed solution of 60-95wt.% high boiling solvent and 0-35wt.% additive; And their three's mass fraction sums are 100%;
The nano-oxide accounting for the 0.5-30wt.% of polymer and nano-oxide quality sum also added in casting solution;
Or a. prepares casting solution, comprise and account for the polymeric substrates that casting solution mass fraction is 5-25wt.%, solvents is the mixed solution of 45-95wt% high boiling solvent and 0-30wt% additive; And their three's mass fraction sums are 100%;
The nano-oxide accounting for the 0.5-30wt.% of polymer and nano-oxide quality sum also added in casting solution;
B. above-mentioned casting solution stirs 0.5-20h at temperature 20-100 DEG C, ultrasonic 0.5-3h, and the homogeneous polymer solution obtained static or vacuum defoamation 0.5-10h at temperature 20-90 DEG C makes final casting solution;
C. adopt scraper by above-mentioned casting solution blade coating on a glass, by the thickness regulating scraper height to carry out controlling diaphragm, obtained film thickness is 25-150 μm;
D. glass plate flatly being put into temperature is in the coagulating bath of 20-80 DEG C, takes out after static 0.5-24h, dries after film is soaked 0.5-24h in absolute ethyl alcohol or n-hexane in air;
E., after the film dried being processed 0.5-10h at temperature 20-90 DEG C in concentration 1-6M hydrochloric acid solution, can use in hydrogen-chlorine fuel cell.
6., according to the preparation method described in claim 4 or 5, it is characterized in that:
, to hydrochloric acid or chlorine, there is the poly-inclined tetrafluoroethene (PVDF) of well tolerable property, Kynoar-hexafluoropropylene copolymer (PVDF-HFP), Phthalazinone polyether-ketone (PPEK), polysulfones (PSF) or polyether sulfone (PES) with high molecular polymer;
The MCM-41 that the silicon dioxide of nano-oxide to be particle diameter be 2-200nm, particle diameter are the titanium dioxide of 2-200nm, particle diameter is 2-10nm or particle diameter are the SBA-15 of 5-50nm;
High boiling solvent used is the good solvent of high molecular polymer, is DMSO, DMF, DMAC or NMP;
Additive is glycerine, dimethyl carbonate, diethyl carbonate, carbonate propanediol fat or PVP.
7. an application for perforated membrane described in claim 1, is characterized in that:
Described perforated membrane can be used as electrolyte membrance for be dissolved in hydrogen-chlorine fuel cell that the chlorine in hydrochloric acid is raw material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104638280A (en) * | 2013-11-06 | 2015-05-20 | 中国科学院大连化学物理研究所 | Composite porous membrane used for hydrogen-chlorine fuel cells, and preparation and applications thereof |
| CN105304847B (en) * | 2014-07-30 | 2017-12-26 | 中国科学院大连化学物理研究所 | A kind of application of heat resistant type porous septum in lithium ion battery |
| US11001691B2 (en) * | 2016-07-25 | 2021-05-11 | Ube Industries, Ltd. | Porous polyether sulfone film and production method therefor |
| CN110694478A (en) * | 2019-10-09 | 2020-01-17 | 宁波泰意德过滤技术有限公司 | Ultrafiltration membrane and preparation method thereof |
| CN111023554B (en) * | 2019-11-19 | 2021-07-09 | 海信(广东)厨卫系统有限公司 | Water storage type water heater |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4128701A (en) * | 1977-12-23 | 1978-12-05 | United Technologies Corp. | Hydrogen/chlorine regenerative fuel cell |
| CN101237054A (en) * | 2008-02-03 | 2008-08-06 | 山东东岳神舟新材料有限公司 | An intercrossed enhanced full fluorin proton adulterated exchange film and its making method |
-
2012
- 2012-03-01 CN CN201210052189.XA patent/CN103296296B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4128701A (en) * | 1977-12-23 | 1978-12-05 | United Technologies Corp. | Hydrogen/chlorine regenerative fuel cell |
| CN101237054A (en) * | 2008-02-03 | 2008-08-06 | 山东东岳神舟新材料有限公司 | An intercrossed enhanced full fluorin proton adulterated exchange film and its making method |
Non-Patent Citations (1)
| Title |
|---|
| "A novel PTFE-based proton-conductive membrane";S.Reichman等;《Journal of Power Sources》;20050629;第153卷;第228-233页 * |
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