CN102299353A - Application of organic-inorganic composite membrane in acid electrolyte redox energy storage battery - Google Patents
Application of organic-inorganic composite membrane in acid electrolyte redox energy storage battery Download PDFInfo
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Abstract
The invention relates to an organic-inorganic composite ion exchange membrane applied to an acid electrolyte redox energy storage battery and a preparation method thereof. The invention further relates to the acid electrolyte redox energy storage battery including the polymer ion exchange membrane in the invention. The preparation method of the composite ion exchange membrane is simple. The large batch production is easy to realize. The prepared composite ion exchange membrane has good mechanical strength and has good proton conduction performance and excellent penetration insulation performance of positive and negative ions in the acid electrolyte redox energy storage battery.
Description
Technical field
The present invention relates to a kind of polybenzimidazoles class cluster ion exchange membrane and preparation method thereof, the particularly application of such amberplex in liquid-flow energy storage battery with acidic electrolyte.
Background technology
The energy is the important foundation of national economy sustainable development and national security.Secondary energy sources utilize form to electric power as cleaning easily, and along with expanding economy, demand increases day by day.The ambient pressure that a large amount of consumption caused of fossil energy becomes increasingly conspicuous.Therefore, save fossil energy, research and development and utilize regenerative resource to become the grand strategy of countries in the world energy security and sustainable development on a large scale.Renewable energy system such as solar energy, wind energy has unstable and discontinuous unstable state feature, and extensive high-efficiency energy-storage system that need be supporting with it guarantees the continuity and the stability of generating electricity and powering.Compare with other energy storage technology, the liquid flow energy storage battery that contains acidic electrolysis bath is a kind of electrochemical energy storage new technology, having the energy conversion efficiency height, an advantage such as system design is flexible, capacitance of storage is big, but the free deep discharge of addressing, safety and environmental protection, maintenance cost are low, is one of one preferred technique of extensive high-efficiency energy-storage technology.All-vanadium liquid flow energy storage battery is (charge and discharge cycles＞16000 time), efficient height (charge-discharge energy efficient＞75%), life-span long (life-span＞15 year), low cost and other advantages because safe, good stability, is considered to have most in the liquid flow energy storage battery prospect and representational a kind of energy-storage battery.
Amberplex had both played and had isolated positive and negative electrode electrolyte as one of critical component of liquid flow energy storage battery, played the effect that the ionic conduction passage is provided for positive and negative electrode electrolyte again.Therefore require amberplex to have good ionic conductivity, ion selectivity and chemical stability.Skyllas-kazacos etc. think after some commercialization films are estimated, except some perfluoro sulfonic acid membranes (as Flemion, Nation etc.) have the sufficiently stable combination property, other film (as Selemion CMV, CMS, AMV, DMV, ASS, DSV etc.) is all stable inadequately (J.ApplElectrochem in acid vanadium solution, 2004,34 (2): 137).But discover that though business-like perfluoro sulfonic acid membrane has stronger mechanical strength and chemical stability, in vanadium redox battery, use the permeability height that has vanadium ion, both positive and negative polarity has tangible water transport phenomena in the charge and discharge process.In addition perfluoro sulfonic acid membrane complex manufacturing, preparation condition harshness, cost an arm and a leg, seriously restricted the practicability and the industrialization of all-vanadium liquid flow energy storage battery.
Polybenzimidazoles is the special engineering plastics of a class excellent combination property, after last century, be developed the sixties, has been used as the matrix resin of fiber, adhesive, foamed plastics and laminated product or fiber coiling product usefulness.Because polybenzimidazoles has excellent thermal stability, chemical stability and dimensional stability, the polybenzimidazoles that acid or alkali mix has good ionic conductivity, thereby from the latter stage nineties, is widely used in the research field of fuel cell.At present, on the market unique business-like polybenzimidazole resin [2,2 '-(-phenylene)-5,5 '-bisbenzimidazole 1, this resin exists infusibility to melt, indissoluble is separated, unmanageable defective for poly-.And, the film of poly-[2,2 '-(-phenylene)-5,5 '-bisbenzimidazole] preparation of full aromatic structure, nitrogen that can be protonated is less, and resistance is bigger.Therefore, from the flow battery angle of practical application, develop targetedly and have excellent dissolution and processing characteristics polybenzimidazoles base polymer, can under relatively mild condition, prepare amberplex, obtain amberplex with low cost, as in liquid-flow energy storage battery with acidic electrolyte, to have higher stability and electrical property.
Summary of the invention
The object of the present invention is to provide cluster ion exchange membrane of a kind of polybenzimidazoles/inorganic nano-particle and preparation method thereof, with and application in liquid-flow energy storage battery with acidic electrolyte.The present invention is based on the good hydrophilicity of inorganic nano-particle and inhale acidity, in polybenzimidazole resin, introduce inorganic nano-particle, improve the proton-conducting of amberplex.The present invention is dispersed in the polybenzimidazoles amberplex inorganic nano-particle by to inorganic nano particle modified, has solved the agglomeration traits of the inorganic particulate that direct doping causes.
The compound amberplex of organic-inorganic is used in liquid-flow energy storage battery with acidic electrolyte, and described amberplex is made up of inorganic phase and organic facies, and inorganic phase and organic facies mass ratio are 2-30: 100;
Organic facies is a polybenzimidazoles family macromolecule material, is polybenzimidazole resin, and its general structure is as follows,
Its general structure is as follows:
R represents one of following structure:
Used inorganic phase nano particle is: one or more in silicon dioxide, zirconium dioxide, ceria, the titanium dioxide.
The preparation process of this kind composite membrane is as follows:
(1) a certain amount of inorganic oxide nanoparticles is scattered in a kind of in DMSO, DMAC, NMP, the DMF solvent, and add with respect to the surfactant of inorganic oxide nanoparticles weight 1-5wt% as: a kind of particles that make wherein such as dodecyl sodium sulfate, polysorbate60, Tween 80, TBAB, triethylamine fully disperse, and fully stir about 0.5-5 hour at 20-100 ℃;
(2) polybenzimidazole resin of adding certain percentage in the solution of step (1).Wherein the quality percentage composition of polybenzimidazole resin in solution is 2-10%.Being stirred to resin at 50-100 ℃ of constant temperature dissolves fully;
(3) with the solution direct pouring of step (2) on glass plate or corrosion resistant plate, in 60～100 ℃ of following drying 〉=5h, 80～150 ℃ of vacuumize 〉=1h film forming then.
With the film immersion concentration of preparation is 1～16mol L
-1Sulfuric acid or phosphoric acid solution in 1h at least, obtain polybenzimidazoles class cluster ion exchange membrane, the thickness of film is between 10～200 μ m.
Direct blending is adopted in above-mentioned preparation, in order to improve the dispersiveness of nano particle in solution, added surfactant as dispersant, the preparation method is simple to operation, but also be not limited in this kind preparation method, common also can prepare this type of composite membrane as sol-gel process.
The present invention also provides the liquid-flow energy storage battery with acidic electrolyte of the polybenzimidazoles class cluster ion exchange membrane that comprises this method preparation, particularly contains the all-vanadium liquid flow energy storage battery of such composite membrane.
Useful result of the present invention is:
(1) the composite membrane preparation method of the present invention's preparation is simple, and inorganic nano-particle can effectively improve the acid energy of suction in the composite membrane, helps improving the proton-conducting of film.
(2) polybenzimidazoles of selecting in this system has fine solubility, easily processing.
(3) inorganic nano-particle easily disperses by after surfactant modified in the composite membrane of this method preparation, the problem of having avoided inorganic nano-particle to reunite effectively.
(4) such cluster ion exchange membrane is applied to the obstruct both positive and negative polarity iontophoretic injection performance that liquid-flow energy storage battery with acidic electrolyte has good proton conduction performance and excellence.
Description of drawings
Fig. 1 is the infrared figure of the composite membrane of embodiment 1 preparation.
Fig. 2 is the stress-strain diagram of the composite membrane of embodiment 1 preparation.
Fig. 3 is the charging and discharging curve of whole vanadium oxide reduction battery when 80mA cm-2 of the ion exchange polymer film of embodiment 1 preparation.
Embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
0.2 gram nano silicon is dissolved in 20ml DMSO and joins in the conical flask of 250ml, add the 1ml triethylamine then, stirs 1 hour formation settled solution.2 gram polybenzimidazoles are joined in the above-mentioned solution, be warming up to 50 ℃-100 ℃, be stirred to the solution clarification.To glass plate, push away flat solution-cast with the casting film cutter.After under 80 ℃ dry 20 hours, film is taken off from glass plate.Dry polymer film soaking at room temperature is handled 5h in 4M sulfuric acid, obtain the cluster ion exchange membrane that thickness is about 35 μ m.Fig. 1 is the infrared figure of preparation composite membrane, has confirmed the structure of prepared composite membrane.It is 105MPa that the stress-strain diagram of film such as Fig. 2, film get hot strength, and modulus of elasticity is 3.6GPa, has shown the favorable mechanical performance.
0.4 gram nano silicon is dissolved in 20ml DMSO and joins in the conical flask of 250ml, add the 2ml triethylamine then, stirs 1 hour formation settled solution.2 gram polybenzimidazoles are joined in the above-mentioned solution, be warming up to 50 ℃-100 ℃, be stirred to the solution clarification.To glass plate, push away flat solution-cast with the casting film cutter.After under 80 ℃ dry 20 hours, film is taken off from glass plate.Dry polymer film soaking at room temperature is handled 5h in 4M sulfuric acid, obtain the cluster ion exchange membrane that thickness is about 35 μ m.
0.2 gram nano titanium oxide is dissolved in 20ml DMSO, joins in the conical flask of 250ml, add the 1ml triethylamine then, stir and formed settled solution in 1 hour, then 2 gram polybenzimidazoles are joined in the above-mentioned solution, be warming up to 50 ℃-100 ℃, be stirred to the solution clarification.To glass plate, push away flat solution-cast with the casting film cutter.After under 80 ℃ dry 20 hours, film is taken off from glass plate.Dry polymer film soaking at room temperature is handled 5h in 4M sulfuric acid, obtain the cluster ion exchange membrane that thickness is about 35 μ m.
0.2 gram nano zirconium dioxide is dissolved in 20ml DMSO, joins in the conical flask of 250ml, add the 1ml triethylamine then, stir and formed settled solution in 1 hour, then 2 gram polybenzimidazoles are joined in the above-mentioned solution, be warming up to 50 ℃-100 ℃, be stirred to the solution clarification.To glass plate, push away flat solution-cast with the casting film cutter.After under 80 ℃ dry 20 hours, film is taken off from glass plate.Dry polymer film soaking at room temperature is handled 5h in 4M sulfuric acid, obtain the cluster ion exchange membrane that thickness is about 35 μ m.
With silica containing composite polyphenylene among the embodiment 1 and imidazol ion exchange membrane assembling vanadium redox battery, activated carbon-fiber felt is a Catalytic Layer, and graphite cake is a bipolar plates, and the film effective area is 9cm
-2, current density is 80mA cm
-2, vanadium ion concentration is 1.50mol L in the electrolyte
-1, H
2SO
4Concentration is 3mol L
-1The flow battery current efficiency of assembling is 99.3%, and voltage efficiency is 83.6%, and energy efficiency is 84.2%.The battery charging and discharging curve is seen Fig. 3, among the figure charging interval and discharge time suitable substantially, it is quite mild to discharge, and shows that the vanadium permeability of film is quite low.
Compare 1: change above-mentioned film into pure polybenzimidazoles amberplex, other conditions are constant.Battery current efficient is 97.7%, and voltage efficiency is 81.8%, and energy efficiency is 80.0%.Compare with pure polybenzimidazoles amberplex, preparation contain 10% silicon dioxide polybenzimidazoles cluster ion exchange membrane energy efficiency mutually and voltage efficiency all increase significantly.Embodiment 1 prepared composite membrane and polybenzimidazoles amberplex is soaked in the 3M sulfuric acid solution, and its swelling ratio is respectively 29.85% and 40.19%, has increased by 10 percentage points.The introducing of silicon dioxide is described, has improved the acid energy of suction of film effectively, reduced the interior resistance of film in the all-vanadium liquid flow energy storage battery system simultaneously, improved its voltage efficiency.
Compare 2: change above-mentioned film into Nafion 115 films that E.I.Du Pont Company produces, other conditions are constant.Battery current efficient is 94.8%, and voltage efficiency is 88.9%, and energy efficiency is 84.5%.Compare with business-like Nafion, the polybenzimidazoles amberplex that contains the pyridine group of preparation is under the suitable prerequisite of energy efficiency, and current efficiency significantly improves (improving 5 percentage points).The polybenzimidazoles base polymer is described, has reduced vanadium ion effectively and interpenetrated the cross pollution that causes, improved the current efficiency of battery.
Claims (5)
1. the compound amberplex of organic-inorganic is used in liquid-flow energy storage battery with acidic electrolyte, it is characterized in that: described amberplex is made up of inorganic phase and organic facies, and inorganic phase and organic facies mass ratio are 2-30: 100;
Organic facies is a polybenzimidazoles family macromolecule material, is polybenzimidazole resin, and its general structure is as follows,
Wherein n is a positive integer, 20≤n≤100, and R represents one of following structure:
Inorganic is the nano particle of inorganic oxide mutually.
2. application according to claim 1 is characterized in that: described inorganic oxide is one or more in nano silicon, zirconium dioxide, ceria, the titanium dioxide.
3. application according to claim 1 is characterized in that: described cluster ion exchange membrane adopts following method preparation:
(1) in the desired amount inorganic oxide nanoparticles is scattered in one or more mixed solvents of DMSO, DMAC, NMP, DMF, and add a kind of in surfactant dodecyl sodium sulfate with respect to inorganic oxide nanoparticles weight 1-5wt%, polysorbate60, Tween 80, TBAB, the triethylamine, fully stirred about 0.5-5 hour at 20-100 ℃;
(2) in the solution of step (1), add polybenzimidazole resin; Wherein the quality percentage composition of polybenzimidazole resin in solution is 2-10%; Being stirred to resin at 50-100 ℃ of constant temperature dissolves fully;
(3) with the solution direct pouring of step (2) on glass plate or corrosion resistant plate, in 60～100 ℃ of following drying 〉=5h, 80～150 ℃ of vacuumize 〉=1h film forming then, the thickness of film is between 10～200 μ m.
4. application according to claim 3 is characterized in that: the film of preparation is immersed sulfuric acid or more than the phosphatase 11 h, obtains polybenzimidazoles class cluster ion exchange membrane.
5. application according to claim 3 is characterized in that: sulfuric acid or concentration of phosphoric acid are at 1～16mol L
-1Between.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102945977A (en) * | 2012-11-09 | 2013-02-27 | 江南石墨烯研究院 | Composite proton exchange membrane for methanol fuel cell and preparation method of composite proton exchange membrane |
| CN103682210A (en) * | 2012-09-06 | 2014-03-26 | 中国科学院大连化学物理研究所 | Application of organic-inorganic porous composite diaphragm in flow energy storage battery |
| CN103887536A (en) * | 2014-03-13 | 2014-06-25 | 清华大学 | Method for preparing polybenzimidazole proton exchange membrane subjected to inorganic material hybridization |
| CN105990594A (en) * | 2015-02-12 | 2016-10-05 | 张华民 | Preparation method for electrolyte used for acidic flow battery |
| CN107674417A (en) * | 2017-09-20 | 2018-02-09 | 大连理工大学 | A kind of non-ionic hydrophilic side chain polybenzimidazole membrane and preparation method thereof |
| CN108400362A (en) * | 2018-02-05 | 2018-08-14 | 大连理工大学 | A kind of side chain type alkyl sulfonate polybenzimidazole amberplex and preparation method thereof |
| CN109888348A (en) * | 2019-04-10 | 2019-06-14 | 黑龙江大学 | Fuel cell proton membrane material solid super acids/azacyclo- graphene oxide/2,5- polybenzimidazoles preparation method |
| CN110188408A (en) * | 2019-05-08 | 2019-08-30 | 武汉理工大学 | A kind of all-vanadium flow battery energy-storage system running optimizatin method based on particle swarm algorithm |
| CN110197919A (en) * | 2018-02-27 | 2019-09-03 | 湖南省银峰新能源有限公司 | A kind of ionic conduction type porous septum used for all-vanadium redox flow battery and its preparation method and purposes |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1381107A2 (en) * | 2002-07-10 | 2004-01-14 | Honda Giken Kabushiki Kaisha | Proton conductive solid polymer electrolyte |
| CN1867614A (en) * | 2003-09-11 | 2006-11-22 | 美国丰田技术中心公司 | Phosphonic-acid grafted hybrid inorganic-organic proton electrolyte membranes (PEMs) |
| CN101035836A (en) * | 2003-12-30 | 2007-09-12 | 佩密斯股份有限公司 | Proton-conducting membrane and use thereof |
| CN101456964A (en) * | 2008-12-23 | 2009-06-17 | 东华大学 | Method for preparing aromatic polybenzimidazole resin film |
-
2010
- 2010-06-25 CN CN2010102101634A patent/CN102299353B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1381107A2 (en) * | 2002-07-10 | 2004-01-14 | Honda Giken Kabushiki Kaisha | Proton conductive solid polymer electrolyte |
| CN1867614A (en) * | 2003-09-11 | 2006-11-22 | 美国丰田技术中心公司 | Phosphonic-acid grafted hybrid inorganic-organic proton electrolyte membranes (PEMs) |
| CN101035836A (en) * | 2003-12-30 | 2007-09-12 | 佩密斯股份有限公司 | Proton-conducting membrane and use thereof |
| CN101456964A (en) * | 2008-12-23 | 2009-06-17 | 东华大学 | Method for preparing aromatic polybenzimidazole resin film |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103682210A (en) * | 2012-09-06 | 2014-03-26 | 中国科学院大连化学物理研究所 | Application of organic-inorganic porous composite diaphragm in flow energy storage battery |
| CN103682210B (en) * | 2012-09-06 | 2016-04-13 | 中国科学院大连化学物理研究所 | The application of a kind of organic-inorganic porous composite membrane in liquid flow energy storage battery |
| CN102945977A (en) * | 2012-11-09 | 2013-02-27 | 江南石墨烯研究院 | Composite proton exchange membrane for methanol fuel cell and preparation method of composite proton exchange membrane |
| CN103887536A (en) * | 2014-03-13 | 2014-06-25 | 清华大学 | Method for preparing polybenzimidazole proton exchange membrane subjected to inorganic material hybridization |
| CN105990594A (en) * | 2015-02-12 | 2016-10-05 | 张华民 | Preparation method for electrolyte used for acidic flow battery |
| CN107674417A (en) * | 2017-09-20 | 2018-02-09 | 大连理工大学 | A kind of non-ionic hydrophilic side chain polybenzimidazole membrane and preparation method thereof |
| CN108400362A (en) * | 2018-02-05 | 2018-08-14 | 大连理工大学 | A kind of side chain type alkyl sulfonate polybenzimidazole amberplex and preparation method thereof |
| CN110197919A (en) * | 2018-02-27 | 2019-09-03 | 湖南省银峰新能源有限公司 | A kind of ionic conduction type porous septum used for all-vanadium redox flow battery and its preparation method and purposes |
| CN109888348A (en) * | 2019-04-10 | 2019-06-14 | 黑龙江大学 | Fuel cell proton membrane material solid super acids/azacyclo- graphene oxide/2,5- polybenzimidazoles preparation method |
| CN109888348B (en) * | 2019-04-10 | 2021-10-08 | 黑龙江大学 | Preparation method of fuel cell proton membrane material solid super acid/aza-epoxidized graphene/2, 5-polybenzimidazole |
| CN110188408A (en) * | 2019-05-08 | 2019-08-30 | 武汉理工大学 | A kind of all-vanadium flow battery energy-storage system running optimizatin method based on particle swarm algorithm |
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