CN102867967A - Electrode material for all vanadium redox energy storage battery and application thereof - Google Patents
Electrode material for all vanadium redox energy storage battery and application thereof Download PDFInfo
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Abstract
The invention discloses an electrode material for an all vanadium redox energy storage battery and an application thereof. The electrode comprises carbon materials as matrix, and the electrode surface is dipped or coated with an electro-catalyst. The electro-catalyst has strong acid resistance and can keep stable in the strong-acidic strong-oxidizing environment of the all vanadium flow system. The prepared electrode material has high catalytic activity to two redox couples which are VO<2+>/VO2<+> and V<2+>/V<3+>, effectively improves the reversibility of the redox couples, effectively raises the energy conversion efficiency of the Vanadium Redox Battery (VRB), and realizes the controllability of the efficiency of the all vanadium redox energy storage battery.
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.From other that common batteries that active material is stored in inside battery is different, it is stored in electrolyte the storage tank of outside batteries, realizes electrolysis circulating in the battery cavity by fluid pump and transfer pipeline, and finishes the charge and discharge process of battery.The advantages such as such battery has system flexible (but power/capacity independent design), capacitance of storage is large, addressing is free are applicable to extensive energy storage field.Compare other energy storage technology, but it also have the characteristics such as the high deep discharge of energy conversion efficiency, safety and environmental protection, maintenance cost be low.Can be widely used in the renewable energy power generation energy storage such as wind energy, solar energy, the electric power of its generation can be exported continuously and stably; Can be used to electrical network is carried out " peak load shifting " the balancing electric power supply and demand; Can do emergency power system, stand-by station etc. 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 the liquid flow energy storage battery.It adopts the different valence state ion of metallic element of the same race respectively as the positive and negative electrode active material, has avoided to a great extent 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 year), low cost of manufacture, evokes the strong research and development interest of people, and begins to enter commercialization and promote the stage.
Electrode material is one of critical material in the liquid flow energy storage battery, and it self does not contain active material, does not react, but the place of reaction is provided for being dissolved in active material in the liquid phase, and battery is finished conversion between electric energy-chemical energy in electrode material surface.For the all-vanadium flow system, the reaction that the battery both sides occur has:
Anodal: VO
2 ++ 2H
++ e
-=VO
2++ H
2O
Negative pole: V
3++ e
-=V
2+
The all-vanadium flow system requires electrode material to have following performance: 1. high catalytic activity, the both sides oxidation-reduction pair is had good activity and invertibity, and reduce the electrochemical polarization of battery; 2. high-specific surface area is for reaction provides more active sites; 3. good electron conduction is conducive to reduce the ohmic internal resistance of battery; Suitable pore passage structure and surface have hydrophily, are convenient to the diffusion transport of electrolyte, reduce the concentration polarization of battery.4. good mechanical performance and corrosion resistance, washing away of fluid-resistant can keep stable in the environment of the strong oxidation of strong acid.5. with low cost.
The 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 the VRB electrode material.VO
2+/ VO
2 +Electricity is to showing the electrochemical reaction irreversibility at gold electrode.Lead electrode and titanium electrode be then easily at the Surface Creation passivating film, and what cause resistance to increase being unfavorable for reacting further carries out.Titanium base platinum electrode has avoided the titanium electrode surface to generate the problem of passivating film, all shows preferably electro-chemical activity at both positive and negative polarity.Titanium base yttrium oxide (DSA) electrode has higher invertibity.But the expensive large-scale application that limits 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 class electrode material conductivity is higher, and chemistry, electrochemical stability is good, and raw material sources are abundant, and moderate cost is present comparatively ideal VRB electrode material.But the further raisings 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 processing, electrochemical oxidation, introducing active group, element doping etc.The raising of electro catalytic activity improves energy conversion efficiency for reducing the battery electrochemical polarization, improves charge and discharge current density and battery system energy density tool and is of great significance.
Summary of the invention
The object of the invention is to overcome existing all-vanadium liquid flow energy storage battery with the existing problem of electrode material, and a kind of all-vanadium liquid flow energy storage battery electrode material is provided.
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 with 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 the 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.
When carbon element class material was carbon paper in the carbon fiber or carbon cloth, eelctro-catalyst load amount was 0.5-3mg/cm
2
Described eelctro-catalyst mixed with 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 take carbon as carrier, take tungsten salt as presoma, is prepared from by different preparation methods.It is coated in the electrode material that can be used as liquid flow energy storage battery on the carbon paper fiber.
Described carbon carrier comprises one or more in activated carbon powder, graphite powder, carbon nano-tube, the carbon fiber etc.
Described tungsten salt precursor body comprises that ammonium tungstate, ammonium metatungstate, wolframic acid are received, tungsten chloride, tungsten carbonyl etc.
Described carbon carries the tungstic acid eelctro-catalyst, and to contain the tungstic acid mass fraction be 20%～80%.
It is mixed with Nafion or PTFE binder-impregnated or coating carbon fiber surface or as VRB positive pole and negative material that described carbon carries the tungstic acid eelctro-catalyst.
Above-mentioned carbon carries tungstic acid eelctro-catalyst preparation method and adopts the following steps preparation:
1 infusion process (clock and the Dalian Chemistry and Physics Institute of fragrant Chinese Academy of Sciences doctorate paper, the research of the non-platinum of high-performance Proton Exchange Membrane Fuel Cells and low platinum eelctro-catalyst)
1) at room temperature, with in the tungsten salt precursor body one or both be dissolved in water, the mixed alkoxide solution, wherein, alcohol can adopt one or more in ethanol, propyl alcohol, the isopropyl alcohol, water is controlled at 1: 1 with the volume ratio of alcohol～and 1: 5, every 100mg tungsten presoma dissolves with 1～3g water, mixed alkoxide solution.Under the ultrasonication, make the presoma dissolving obtain clarified solution;
2) in above-mentioned system, add carbon carrier, ultrasonication 12～24h.Used carbon carrier comprises one or more of carbon dust, graphite powder, carbon nano-tube, carbon fiber.The mass ratio of control tungsten presoma and carbon carrier was at 1: 4～4: 1.
3) with step 2) preparation the suspension system insert in the thermostat water bath, control water temperature at 80 ℃～90 ℃, mechanical agitation is with the solvent evaporate to dryness.Afterwards, put into vacuum drying chamber and carry out vacuumize 8～16h, control vacuum drying chamber temperature is at 80 ℃～120 ℃.
4) with step 3) carbon of preparation carries the tungsten presoma and carries out the heat treatment of inert gas atmosphere, adopts nitrogen or argon gas to be protection gas, heat-treat in high temperature process furnances according to following program:
5) until step 4) be cooled to room temperature after, sample is taken out from tube furnace, adopt ball mill to carry out ball milling or grind feasible finished product with agate mortar.
2 template (Nilofar Asim, American Journal of Applied Sciences 6 (7): 1424-1428,2009)
1) cationicsurfactants is dissolved in the deionized water, the CTAB micellar aqueous solution that ultrasonic dissolution obtains clarifying, the concentration of CTAB is controlled at 0.015～0.05mol/L;
2) measure a certain amount of solution, drip proper ammonia solution in the solution, after add again a certain amount of alcohol, water is controlled at 1: 1 with the volume ratio of alcohol～1: 2, adds an amount of carbon dust, ultrasonic 30～60min;
3) add the pure level of analysis WCl under the high degree of agitation effect
6, the mass ratio of control tungsten presoma and carbon carrier is 1: 4～4: 0 ℃ of water bath with thermostatic control reaction of Isosorbide-5-Nitrae, 3～5h;
4) by centrifugal, washing, vacuumize, and according to:
The electrode material preparation method, adopt the following steps preparation:
(1) carbon that takes by weighing an amount of preparation carries the tungstic acid eelctro-catalyst, be added in one or more the solvent of ethanol, propyl alcohol or isopropyl alcohol, electricity urge the mass ratio of agent and solvent be controlled at 1: 5～1: 15, ultrasonic dispersion 30～60min, the an amount of Nafion solution of rear adding or PTFE solution are made binding agent, the mass ratio of control 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 behind each dipping and processes, until reach required load amount.Perhaps above-mentioned system is coated in the surface of carbon fiber with the method for blade coating, spraying, reaches required load amount.
This carbon carries the electrode material that the tungstic acid eelctro-catalyst is coated in the preparation of carbon fiber-based surface, can be used as simultaneously positive pole and the negative material of all-vanadium liquid flow energy storage battery.
The useful result of thing of the present invention is:
(1) electrode with 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, improve greatly carbon element class material to activity and the invertibity of electrode reaction, reduce the electrode reaction charge transfer impedance, reduce the internal resistance of cell;
(2) synthesized a kind of novel carbon carrier composite electrocatalyst that passes through the metal oxide enhancing, synthetic method of the present invention is simple, is easy to realize producing in enormous quantities;
(3) this eelctro-catalyst has anti-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 of preparation 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.It is coated in strengthens greatly on the carbon paper fiber that it is active at kinetic reactions of two redox half-reactions of battery, and can effectively improve the invertibity of two oxidation-reduction pairs; Electrode material has been realized the controllability to all-vanadium liquid flow energy storage battery efficient to the raising that raising and reversible improvement of battery oxidation-reduction pair activity means the energy conversion efficiency of battery.
Description of drawings
Fig. 1: carry before and after the tungstic acid catalyst as the 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: carry before and after the tungstic acid catalyst as the 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 supports eelctro-catalyst front and back, the charging and discharging curve in VRB under the 40mA/cm2 with Comparative Examples 1 Toray060 type carbon paper;
Fig. 4: for embodiment 1 supports eelctro-catalyst front and back, 40mA/cm in VRB with Comparative Examples 1SGL carbon paper
2Under charging and discharging curve.
Embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1
The ammonium metatungstate that 200mg analyzes pure level is dissolved in 10g alcohol, the water mixed solution, and alcohol, water volume ratio are 1: 2, and ultrasonic dissolution obtains adding the 50mg activated carbon powder after the clarified solution, ultrasonication 12h, and rear 80 ℃ of water-baths are with the solvent evaporate to dryness.Put into 100 ℃ of vacuum drying chamber vacuumize 12h, according to: heating schedule is heat-treated, be cooled to room temperature after, mortar grinds and to get product.Nafion solution with an amount of 5wt% is made binding agent, and on Toray060 type carbon paper, control eelctro-catalyst load amount is 2.5mg/cm with spray gun spraying
2
Utilize the Toray060 type carbon paper assembling all-vanadium liquid flow energy storage battery that carbon carries the tungstic acid eelctro-catalyst that scribbles of preparation, collector plate is graphite cake, is carved with the flow field at graphite cake the mobile passage that provides of electrolyte is provided.Adopting Nafion115 type cation-exchange membrane is battery diaphragm, film effective area be 9cm
-2Vanadium ion concentration is 1.50mol L in the electrolyte
-1, H
2SO
4Concentration is 3mol L
-1At 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 Examples 1
Compare with embodiment 1, electrode material is changed to does not do the Toray060 type carbon paper that supports the eelctro-catalyst processing, other conditions are constant.Battery current efficient is 88.1%, and voltage efficiency is 73.4%, and energy efficiency is 64.7%.Do not compare with doing the Toray060 type carbon paper that supports the eelctro-catalyst processing, carry the carbon paper of tungstic acid eelctro-catalyst as the battery of electrode to scribble carbon, its voltage efficiency phase and energy efficiency all increase significantly.Illustrate that carbon carries the tungstic acid eelctro-catalyst and is coated in the electrochemical polarization that the carbon paper surface energy effectively reduces electrode reaction, reduce electrode reaction resistance, thereby the internal resistance of cell is reduced, and then improved the voltage efficiency of battery, and finally improved the energy efficiency of all-vanadium liquid flow energy storage battery.
Embodiment 2
Cationicsurfactants is dissolved in the deionized water, ultrasonic dissolution obtains the CTAB aqueous solution of 0.02mol/L, measure solution 20ml, in solution, drip proper ammonia solution, after add again 20ml ethanol, add the 15g graphite powder, ultrasonic 30min adds 54mg and analyzes pure level WCl under the high degree of agitation effect
6, 40 ℃ of waters bath with thermostatic control reaction 4h, by centrifugal, washing, vacuumize, and according to: heating schedule is heat-treated, be cooled to room temperature after, mortar grinds.Nafion solution with an amount of 5wt% is made binding agent, and on SL type carbon paper, control eelctro-catalyst load amount is 2.5mg/cm2 with spray gun spraying.
Utilize the SGL carbon paper assembling all-vanadium liquid flow energy storage battery that carbon carries the tungstic acid eelctro-catalyst that scribbles of preparation, collector plate is graphite cake, is carved with the flow field at graphite cake the mobile passage that provides of electrolyte is provided.Adopting Nafion115 type cation-exchange membrane is battery diaphragm, film effective area be 9cm
-2Vanadium ion concentration is 1.50mol L in the electrolyte
-1, H
2SO
4Concentration is 3mol L
-1At 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 Examples 2
Compare with embodiment 2, electrode material is changed to does not do the SGL type carbon paper that supports the eelctro-catalyst processing, other conditions are constant.Battery current efficient is 88.3%, and voltage efficiency is 81.4%, and energy efficiency is 71.9%.Do not compare with doing the SL type carbon paper that supports the eelctro-catalyst processing, carry the carbon paper of tungstic acid eelctro-catalyst as the battery of electrode to scribble carbon, its voltage efficiency phase and energy efficiency all increase significantly.Illustrate that carbon carries the tungstic acid eelctro-catalyst and is coated in the electrochemical polarization that the carbon paper surface energy effectively reduces electrode reaction, reduce electrode reaction resistance, thereby the internal resistance of cell is reduced, and then improved the voltage efficiency of battery, and finally improved the energy efficiency of all-vanadium liquid flow energy storage battery.
Carbon of the present invention carries the 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 the electrode material for preparing on the carbon fiber, can improve greatly carbon fiber to activity and the invertibity of electrode reaction, reduces the electrode reaction charge transfer impedance, reduces the internal resistance of cell, and VRB energy content of battery conversion efficiency is improved by a relatively large margin.Realized the controllability to all-vanadium liquid flow energy storage battery efficient.
Claims (9)
1. all-vanadium liquid flow energy storage battery electrode material, described electrode with carbon element class material as matrix, surface impregnation or be coated with eelctro-catalyst.
2. electrode material according to claim 1, it is characterized in that: described carbon element class material is carbon fiber.
3. electrode material according to claim 2, it is characterized in that: described carbon fiber is carbon paper, carbon cloth or carbon felt.
4. electrode material according to claim 1, it is characterized in that: eelctro-catalyst is carbon oxygen carrier compound, and the mass loading amount is 20～80%.
5. electrode material according to claim 4, it is characterized in that: described oxide is one or more in tungsten oxide, molybdenum oxide, the ruthenium-oxide.
6. electrode material according to claim 4, it is characterized in that: described carbon carrier is carbon nano-tube, carbon nano-fiber or carbon spheric granules.
7. electrode material according to claim 1 is characterized in that:
When described carbon element class material was carbon paper in the carbon fiber or carbon cloth, eelctro-catalyst load amount was 0.5-3mg/cm
2
8. electrode material according to claim 1 is characterized in that:
Described eelctro-catalyst mixed with Nafion or PTFE binder-impregnated or coating carbon fiber surface as VRB positive pole and negative material.
9. application such as electrode material as described in one of claim 1-6 is characterized in that: the electrode of the described electrode material preparation of one of claim 1-6 can be used in the all-vanadium liquid flow energy storage battery.
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Cited By (16)
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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 |
| CN103531827A (en) * | 2013-10-31 | 2014-01-22 | 大连交通大学 | Method for improving electrochemical activity of graphite felt of positive electrode of flow battery |
| CN104319406A (en) * | 2014-11-03 | 2015-01-28 | 刘奇 | Preparation method of high-performance composite carbon felt |
| 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 |
| CN104716335A (en) * | 2013-12-15 | 2015-06-17 | 中国科学院大连化学物理研究所 | Electrode for liquid flow batteries, 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 |
| 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 |
| 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 |
| 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 |
| ES2646938A1 (en) * | 2016-06-15 | 2017-12-18 | Innotecno Development S.L. | Procedure for modifying carbon electrodes for use in vanadium redox flow batteries (Machine-translation by Google Translate, not legally binding) |
| 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 |
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| 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 |
| CN103531827A (en) * | 2013-10-31 | 2014-01-22 | 大连交通大学 | Method for improving electrochemical activity of graphite felt of positive electrode of flow battery |
| 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 |
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| CN104319406A (en) * | 2014-11-03 | 2015-01-28 | 刘奇 | Preparation method of high-performance composite 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 |
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| 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 |
| 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 |
| 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 |
| CN110867587A (en) * | 2019-11-29 | 2020-03-06 | 常州大学 | Neutral water system mixed liquid flow battery with high power and long service life based on pyridylphenoxazine |
| 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 |
| CN111715209A (en) * | 2020-05-18 | 2020-09-29 | 浙江工业大学 | Gas phase preparation method of tungsten trioxide/graphite felt composite material |
| 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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