CN102867967B - A kind of all-vanadium liquid flow energy storage battery electrode material and application thereof - Google Patents
A kind of all-vanadium liquid flow energy storage battery electrode material and application thereof Download PDFInfo
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- CN102867967B CN102867967B CN201110187033.8A CN201110187033A CN102867967B CN 102867967 B CN102867967 B CN 102867967B CN 201110187033 A CN201110187033 A CN 201110187033A CN 102867967 B CN102867967 B CN 102867967B
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- Y02E60/30—Hydrogen technology
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Abstract
The invention discloses a kind of all-vanadium liquid flow energy storage battery electrode material and application thereof.Described electrode using carbon element class material as matrix, surface impregnation or be coated with eelctro-catalyst.This eelctro-catalyst has resistance to highly acid, and can retention stablize in the strong acid strong oxidizing property environment of all-vanadium flow system, the electrode material of preparation, to VO
2+/ VO
2 +and V
2+/ V
3+two oxidation-reduction pairs all have higher catalytic activity, effectively improve the invertibity of two oxidation-reduction pairs, effectively improve the energy conversion efficiency of VRB, achieve the controllability to all-vanadium liquid flow energy storage battery efficiency.
Description
Technical field
The present invention relates to a kind of electrode material and application thereof, particularly all-vanadium liquid flow energy storage battery electrode material and application thereof.
Background technology
Liquid flow energy storage battery is a kind of novel secondary battery.Different from the common batteries that active material to be stored in inside battery by other, electrolyte is stored in the storage tank of outside batteries by it, realizes electrolysis circulating in battery compartment, and complete the charge and discharge process of battery by fluid pump and transfer pipeline.Such battery has system flexibly (power/capacity can independent design), the advantage such as capacitance of storage is large, addressing is free, is applicable to extensive energy storage field.Compare other energy storage technology, it also have energy conversion efficiency high, can the feature such as deep discharge, safety and environmental protection, maintenance cost be low.Can be widely used in the energy storage of the renewable energy power generation such as wind energy, solar energy, the electric power enabling it produce exports continuously and stably; Can be used to carry out " peak load shifting " electrical network, balancing electric power supply and demand; Emergency power system, stand-by station etc. can be done in addition.All-vanadium liquid flow energy storage battery (Vanadium redox battery, VRB) has prospect and representational a kind of liquid flow energy storage battery most in liquid flow energy storage battery.It adopts the different valence state ion of same metal element respectively as positive and negative electrode active material, largely avoid the cross pollution of electrolyte solution.In addition, its security and stability is good, energy conversion efficiency is high, long service life (life-span > 15 years), low cost of manufacture, evokes the research and development interest that people are strong, and starts to enter the commercialization popularization stage.
Electrode material is one of critical material in liquid flow energy storage battery, it self not containing active material, do not react, but provide the place of reaction for the active material dissolved in the liquid phase, battery completes the conversion between electric energy-chemical energy in electrode material surface.For all-vanadium flow system, the reaction that battery both sides occur has:
Positive pole: VO
2 ++ 2H
++ e
-=VO
2++ H
2o
Negative pole: V
3++ e
-=V
2+
All-vanadium flow system requires that electrode material has following performance: 1. high catalytic activity, has good activity and invertibity to both sides oxidation-reduction pair, reduces the electrochemical polarization of battery; 2. high-specific surface area, for reaction provides more active sites; 3. good electron conduction, is conducive to the ohmic internal resistance reducing battery; Suitable pore passage structure and surface has hydrophily, is convenient to the diffusion transport of electrolyte, reduces the concentration polarization of battery.4. good mechanical performance and corrosion resistance, washing away of fluid-resistant, can keep stable in the environment of strong acid Strong oxdiative.5. with low cost.
VRB electrode material is divided into two classes substantially: metal species electrode and carbon element class electrode.People attempt with gold, lead, titanium, titanium base platinum and titanium base yttrium oxide etc. as VRB electrode material.VO
2+/ VO
2 +electricity is to showing electrochemical reaction irreversibility on gold electrode.Lead electrode and Ti electrode are then easy at Surface Creation passivating film, cause resistance to increase and are unfavorable for carrying out further of reaction.Titanium base platinum electrode avoids the problem of Ti electrode Surface Creation passivating film, all shows good electro-chemical activity at both positive and negative polarity.Titanium base yttrium oxide (DSA) electrode has higher invertibity.But high cost limits the large-scale application of these two kinds of electrodes.Carbon element class electrode material is of a great variety, comprises carbon paper, carbon cloth, carbon felt, carbon nano-tube etc.This kind of electrode material conductivity is higher, and chemistry, electrochemical stability are good, abundant raw material source, moderate, is current comparatively ideal VRB electrode material.But the raisings further such as the electro catalytic activity of such material has.In order to improve the electro catalytic activity of carbon element class electrode material, researchers have attempted multiple method of modifying to it, and these methods are classified as physics, chemistry two large classes.Physical method comprises air atmosphere heat treatment, plasma treatment, Microwave Treatment etc.Chemical method comprises ion-exchange, soda acid process, electrochemical oxidation, introducing active group, element doping etc.The raising of electro catalytic activity is for the polarization of reduction battery electrochemical, and improve energy conversion efficiency, raising charge and discharge current density and battery system energy density tool are of great significance.
Summary of the invention
The object of the invention is to overcome the problem existing for existing all-vanadium liquid flow energy storage battery electrode material, provides a kind of all-vanadium liquid flow energy storage battery electrode material.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of all-vanadium liquid flow energy storage battery electrode material, described electrode using carbon element class material as matrix, surface impregnation or be coated with eelctro-catalyst.
Described carbon element class material is carbon fiber, and carbon fiber is carbon paper, carbon cloth or carbon felt.
Eelctro-catalyst is carbon oxygen carrier compound, and mass loading amount is 20 ~ 80%.
Described oxide is tungsten oxide, molybdenum oxide, ruthenium-oxide.
Described carbon carrier is carbon nano-tube, carbon nano-fiber or carbon spheric granules.
Carbon element class material be carbon paper in carbon fiber or carbon cloth time, eelctro-catalyst load amount is 0.5-3mg/cm
2.
Described eelctro-catalyst is mixed using Nafion or PTFE binder-impregnated or coating carbon fiber surface as VRB positive pole and negative material.
A kind of all-vanadium liquid flow energy storage battery eelctro-catalyst, is taken carbon as carrier, with tungsten salt for presoma, is prepared from by different preparation methods.Be coated in the electrode material that carbon paper fiber can be used as liquid flow energy storage battery.
Described carbon carrier comprise in activated carbon powder, graphite powder, carbon nano-tube, carbon fiber etc. one or more.
Described tungsten salt precursor body comprises ammonium tungstate, ammonium metatungstate, wolframic acid are received, tungsten chloride, tungsten carbonyl etc.
It is 20% ~ 80% that described carbon carries tungstic acid eelctro-catalyst containing tungstic acid mass fraction.
It is mixed using Nafion or PTFE binder-impregnated or coating carbon fiber surface or as VRB positive pole and negative material that described carbon carries tungstic acid eelctro-catalyst.
Above-mentioned carbon carries tungstic acid eelctro-catalyst preparation method and adopts following steps to prepare:
1 infusion process (clock and the Dalian Chemistry and Physics Institute of fragrant Chinese Academy of Sciences Ph.D. Dissertation, the research of the non-platinum of high-performance proton exchange membrane fuel cell and low platinum eelctro-catalyst)
1) at room temperature, by in tungsten salt precursor body one or both be dissolved in water, mixed alkoxide solution, wherein, alcohol can adopt in ethanol, propyl alcohol, isopropyl alcohol one or more, the volume ratio of water and alcohol controls 1: 1 ~ 1: 5, and every 100mg tungsten presoma 1 ~ 3g water, mixed alkoxide solution dissolve.Under ultrasonication, presoma is dissolved and obtains clarified solution;
2) in above-mentioned system, carbon carrier is added, ultrasonication 12 ~ 24h.Carbon carrier used comprise carbon dust, graphite powder, carbon nano-tube, carbon fiber one or more.Control the mass ratio of tungsten presoma and carbon carrier 1: 4 ~ 4: 1.
3) by step 2) the suspension system prepared inserts in thermostat water bath, and control water temperature at 80 DEG C ~ 90 DEG C, mechanical agitation, by solvent evaporate to dryness.Afterwards, put into vacuum drying chamber and carry out vacuumize 8 ~ 16h, control vacuum drying chamber temperature at 80 DEG C ~ 120 DEG C.
4) by step 3) carbon prepared carries tungsten presoma and carries out the heat treatment of inert gas atmosphere, adopt nitrogen or argon gas to be protection gas, heat-treat according to following program in high temperature process furnances:
5) until step 4) be cooled to room temperature after, sample is taken out from tube furnace, adopt ball mill carry out ball milling or grind with agate mortar, feasible finished product.
2 template (Nilofar Asim, American Journal of Applied Sciences 6 (7): 1424-1428,2009)
1) be dissolved in deionized water by cationicsurfactants, ultrasonic dissolution obtains the CTAB micellar aqueous solution clarified, and the concentration of CTAB controls at 0.015 ~ 0.05mol/L;
2) measured amounts solution, drips proper ammonia solution in solution, after add a certain amount of alcohol again, the volume ratio of water and alcohol controls 1: 1 ~ 1: 2, adds appropriate carbon dust, ultrasonic 30 ~ 60min;
3) the pure level WCl of analysis is added under high degree of agitation effect
6, control the mass ratio of tungsten presoma and carbon carrier 1: 4 ~ 4: 3 ~ 5h is reacted in Isosorbide-5-Nitrae 0 DEG C of water bath with thermostatic control;
4) by centrifugal, washing, vacuumize, and according to:
heating schedule is heat-treated, after being cooled to room temperature, and mortar grinder.
Electrode material preparation method, adopts following steps preparation:
(1) carbon taking appropriate preparation carries tungstic acid eelctro-catalyst, be added in one or more solvent of ethanol, propyl alcohol or isopropyl alcohol, electricity urges the mass ratio of agent and solvent to control 1: 5 ~ 1: 15, ultrasonic disperse 30 ~ 60min, after add appropriate Nafion solution or PTFE solution makes binding agent, the mass ratio controlling eelctro-catalyst and binding agent is 1: 1 ~ 4: 1, more ultrasonic 30 ~ 60min;
(2) carbon paper or carbon felt are cut into required size, put into above-mentioned system and flood, dipping carries out several times, and each dip time is 5 ~ 15min, carries out drying process, until reach required load amount after each dipping.Or the method for above-mentioned system blade coating, spraying is coated in the surface of carbon fiber, reaches required load amount.
This carbon carries tungstic acid eelctro-catalyst and is coated in the electrode material prepared carbon fiber-based surface, can be used as positive pole and the negative material of all-vanadium liquid flow energy storage battery simultaneously.
Thing beneficial outcomes of the present invention is:
(1) electrode is using carbon element class material as matrix, surface impregnation or coating eelctro-catalyst, carbon oxygen carrier compound can provide higher specific area, improve the conductivity of oxide, great raising carbon element class material is to the activity of electrode reaction and invertibity, reduce electrode reaction charge transfer impedance, reduce the internal resistance of cell;
(2) synthesized a kind of novel carbon carrier composite electrocatalyst strengthened by metal oxide, synthetic method of the present invention is simple, is easy to realize producing in enormous quantities;
(3) this eelctro-catalyst has resistance to highly acid, can retention stablize in the strong acid strong oxidizing property environment of all-vanadium flow system;
(4) the carbon oxygen carrier compound composite catalyst prepared is used as positive pole and the negative electrode material of all-vanadium flow battery simultaneously, to VO
2+/ VO
2 +and V
2+/ V
3+two oxidation-reduction pairs all have higher catalytic activity.Be coated on carbon paper fiber and greatly can be strengthened its activity of kinetic reaction in battery two redox half-reactions, and effectively can be improved the invertibity of two oxidation-reduction pairs; Electrode material means the raising of the energy conversion efficiency of battery to the raising of activity and reversible improvement to cell oxidation reduction electricity, achieve the controllability to all-vanadium liquid flow energy storage battery efficiency.
Accompanying drawing explanation
Fig. 1: to carry before and after tungstic acid catalyst as VRB electrode material at 0.05M VO for carbon paper supports carbon
2++ 0.05M VO
2 ++ 3M H
2sO
4in cyclic voltammogram, sweep speed is: 10mV/s;
Fig. 2: to carry before and after tungstic acid catalyst as VRB electrode material at 0.05M V for carbon paper supports carbon
2++ 0.05M V
3++ 3M H
2sO
4in cyclic voltammogram, sweep speed is: 10mV/s;
Fig. 3: for embodiment 1 and comparative example 1 Toray060 type carbon paper support before and after eelctro-catalyst, the charging and discharging curve in VRB under 40mA/cm2;
Fig. 4: for embodiment 1 and comparative example 1SGL carbon paper support before and after eelctro-catalyst, 40mA/cm in VRB
2under charging and discharging curve.
Embodiment
The following examples further illustrate of the present invention, instead of limit the scope of the invention.
Embodiment 1
The ammonium metatungstate that 200mg analyzes pure level is dissolved in 10g alcohol, water mixed solution, and alcohol, water volume ratio are 1: 2, and ultrasonic dissolution adds 50mg activated carbon powder after obtaining clarified solution, ultrasonication 12h, and rear 80 DEG C of water-baths are by solvent evaporate to dryness.Put into 100 DEG C of vacuum drying chamber vacuumize 12h, according to: heating schedule is heat-treated, and after being cooled to room temperature, mortar grinder gets product.Make binding agent with the Nafion solution of appropriate 5wt%, with spray gun spraying on Toray060 type carbon paper, controlling eelctro-catalyst load amount is 2.5mg/cm
2.
What utilize preparation scribbles the Toray060 type carbon paper assembling all-vanadium liquid flow energy storage battery that carbon carries tungstic acid eelctro-catalyst, and collector plate is graphite cake, graphite cake is carved with the flowing that flow field is electrolyte and provides passage.Adopt Nafion115 type cation-exchange membrane to be battery diaphragm, film effective area be 9cm
-2.In electrolyte, vanadium ion concentration is 1.50mol L
-1, H
2sO
4concentration is 3mol L
-1.At 40mA cm
-2current density carry out charge-discharge test.The all-vanadium liquid flow energy storage battery current efficiency of assembling is 87.9%, and voltage efficiency is 82.6%, and energy efficiency is 72.6%.
Comparative example 1
Compared with embodiment 1, electrode material is changed to the Toray060 type carbon paper supporting eelctro-catalyst process, other conditions are constant.Battery current efficiency is 88.1%, and voltage efficiency is 73.4%, and energy efficiency is 64.7%.Compared with the Toray060 type carbon paper supporting eelctro-catalyst process, to scribble the battery of carbon paper for electrode that carbon carries tungstic acid eelctro-catalyst, its voltage efficiency phase and energy efficiency all increase significantly.Illustrate that carbon carries tungstic acid eelctro-catalyst and is coated in the electrochemical polarization that carbon paper surface effectively can reduce electrode reaction, reduce electrode reaction resistance, thus the internal resistance of cell is reduced, and then improve the voltage efficiency of battery, and finally improve the energy efficiency of all-vanadium liquid flow energy storage battery.
Embodiment 2
Cationicsurfactants is dissolved in deionized water, ultrasonic dissolution obtains the CTAB aqueous solution of 0.02mol/L, measure solution 20ml, proper ammonia solution is dripped in solution, after add 20ml ethanol again, add 15g graphite powder, ultrasonic 30min, add 54mg under high degree of agitation effect and analyze pure level WCl
6, 40 DEG C of water bath with thermostatic control reaction 4h, by centrifugal, washing, vacuumize, and according to: heating schedule is heat-treated, after being cooled to room temperature, and mortar grinder.Make binding agent with the Nafion solution of appropriate 5wt%, with spray gun spraying on SL type carbon paper, controlling eelctro-catalyst load amount is 2.5mg/cm2.
What utilize preparation scribbles the SGL carbon paper assembling all-vanadium liquid flow energy storage battery that carbon carries tungstic acid eelctro-catalyst, and collector plate is graphite cake, graphite cake is carved with the flowing that flow field is electrolyte and provides passage.Adopt Nafion115 type cation-exchange membrane to be battery diaphragm, film effective area be 9cm
-2.In electrolyte, vanadium ion concentration is 1.50mol L
-1, H
2sO
4concentration is 3mol L
-1.At 40mA cm
-2current density carry out charge-discharge test.The all-vanadium liquid flow energy storage battery current efficiency of assembling is 90.7%, and voltage efficiency is 91.7%, and energy efficiency is 83.5%.
Comparative example 2
Compared with embodiment 2, electrode material is changed to the SGL type carbon paper supporting eelctro-catalyst process, other conditions are constant.Battery current efficiency is 88.3%, and voltage efficiency is 81.4%, and energy efficiency is 71.9%.Compared with the SL type carbon paper supporting eelctro-catalyst process, to scribble the battery of carbon paper for electrode that carbon carries tungstic acid eelctro-catalyst, its voltage efficiency phase and energy efficiency all increase significantly.Illustrate that carbon carries tungstic acid eelctro-catalyst and is coated in the electrochemical polarization that carbon paper surface effectively can reduce electrode reaction, reduce electrode reaction resistance, thus the internal resistance of cell is reduced, and then improve the voltage efficiency of battery, and finally improve the energy efficiency of all-vanadium liquid flow energy storage battery.
Carbon of the present invention carries tungstic acid composite electrocatalyst, and synthetic method is simple, and product chemically-resistant, electrochemical corrosion are good, and is easy to realize producing in enormous quantities.This eelctro-catalyst is coated in electrode material prepared by carbon fiber, can improve carbon fiber greatly to the activity of electrode reaction and invertibity, reduces electrode reaction charge transfer impedance, reduces the internal resistance of cell, VRB cell power conversion efficiency is improved by a relatively large margin.Achieve the controllability to all-vanadium liquid flow energy storage battery efficiency.
Claims (6)
1. the application of electrode material in all-vanadium flow battery, is characterized in that, described electrode material using carbon element class material as matrix, surface impregnation or be coated with eelctro-catalyst; Eelctro-catalyst is carbon oxygen carrier compound, and mass loading amount is 20 ~ 80%; Described oxide is tungsten oxide.
2. application according to claim 1, is characterized in that: described carbon element class material is carbon fiber.
3. application according to claim 2, is characterized in that: described carbon fiber is carbon paper, carbon cloth or carbon felt.
4. application according to claim 1, is characterized in that: in described carbon oxygen carrier compound, carbon carrier is carbon nano-tube, carbon nano-fiber or carbon spheric granules.
5. application according to claim 1, is characterized in that:
Described carbon element class material be carbon paper in carbon fiber or carbon cloth time, eelctro-catalyst load amount is 0.5-3mg/cm
2.
6. application according to claim 1, is characterized in that:
Described eelctro-catalyst mixes using Nafion or PTFE binder-impregnated or coating carbon fiber surface as the positive pole of all-vanadium flow battery and negative material.
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| CN102683706A (en) * | 2012-01-20 | 2012-09-19 | 石家庄学院 | Preparation method of graphite felt modified electrode and preparation method of all-vanadium flow battery |
| CN103296285A (en) * | 2013-06-03 | 2013-09-11 | 大连交通大学 | Lead dioxide modified graphite felt electrode of all-vanadium redox flow battery and preparation method thereof |
| CN103531827B (en) * | 2013-10-31 | 2015-10-14 | 大连交通大学 | A kind of method improving electrochemical activity of graphite felt of positive electrode of flow battery |
| CN104716335B (en) * | 2013-12-15 | 2017-03-01 | 中国科学院大连化学物理研究所 | A kind of flow battery electrode and preparation and application |
| CN105322194A (en) * | 2014-07-30 | 2016-02-10 | 中国科学院大连化学物理研究所 | Multifunctional negative material and application thereof in all-vanadium redox flow battery |
| CN104319409A (en) * | 2014-10-15 | 2015-01-28 | 中国科学院金属研究所 | High-activity asymmetric electrode for all-vanadium redox flow battery and preparation method thereof |
| CN104319406B (en) * | 2014-11-03 | 2016-11-02 | 刘奇 | A kind of high-performance is combined the preparation method of carbon felt |
| WO2017049466A1 (en) * | 2015-09-22 | 2017-03-30 | 许昌学院 | Composite electrode material, manufacturing method thereof, and use thereof in vanadium flow battery |
| KR20180069911A (en) * | 2015-11-13 | 2018-06-25 | 아발론 배터리 (캐나다) 코포레이션 | Improved electrode for redox flow battery |
| CN105702977A (en) * | 2016-01-21 | 2016-06-22 | 邢台职业技术学院 | Bromine electrode for bromine hydride energy storage battery and preparation method of bromine electrode |
| ES2646938B1 (en) * | 2016-06-15 | 2018-09-25 | Innotecno Development S.L. | Procedure for the modification of carbon electrodes for use in vanadium redox flow batteries |
| CN106410219A (en) * | 2016-11-11 | 2017-02-15 | 攀钢集团攀枝花钢铁研究院有限公司 | All-vanadium-redox-flow-battery electrode material and preparing method thereof |
| CN106450400A (en) * | 2016-11-11 | 2017-02-22 | 攀钢集团攀枝花钢铁研究院有限公司 | All-vanadium redox flow battery |
| CN108172877A (en) * | 2018-01-09 | 2018-06-15 | 湖南德沃普新能源有限公司 | A kind of combination electrode material used for all-vanadium redox flow battery and preparation method thereof and all-vanadium flow battery |
| CN110867587B (en) * | 2019-11-29 | 2022-03-01 | 常州大学 | Neutral water system mixed liquid flow battery with high power and long service life based on pyridylphenoxazine |
| CN111715209B (en) * | 2020-05-18 | 2023-04-07 | 浙江工业大学 | Gas phase preparation method of tungsten trioxide/graphite felt composite material |
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