CN1694282A - Cathode for whole vanadium oxide reduction flow battery and preparation method thereof - Google Patents
Cathode for whole vanadium oxide reduction flow battery and preparation method thereof Download PDFInfo
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- CN1694282A CN1694282A CN 200510020779 CN200510020779A CN1694282A CN 1694282 A CN1694282 A CN 1694282A CN 200510020779 CN200510020779 CN 200510020779 CN 200510020779 A CN200510020779 A CN 200510020779A CN 1694282 A CN1694282 A CN 1694282A
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Abstract
This invention relates to an electrode used in V oxide liquid flow battery, which takes a metal foil/net as the collector deposited with Ir, Ta, Mg, Co, Ag, Ru, Mn and Fe on the surface. The electrode has high mechanical strength, high non-corrodibility against strong acid and keeps high electrochemical activation. When it has the same thickness with that of carbon conduction plastics, or even thinner, it has even better tensile strength and bending strength, suitable for increasing the volume ratio energy of the battery. Charge, discharge experiment in 2M V electrolyte is carried out taking this invented electrode as the positive, graphite electrode as the negative, N-115 Nafion as the membranes when the current density is set, the voltage efficiency is increased by 10% to that of carbon electrodes.
Description
Technical field
The present invention relates to a kind of accumulation energy type fluid flow pattern battery-all-vanadium ionic liquid flow battery, belong to the vanadium cell field.
Background technology
Vanadium cell is one of powerful environmental protection storage battery of present growth momentum, its manufacturing, uses and discarded process does not all produce harmful substance.All-vanadium ionic liquid flow battery is because different valence state ion comparative electrode current potential is higher, but degree of depth high current density discharge, charging is rapid, and the energy transformation ratio height can prepare the MW class battery pack, and the large power long time provides electric energy, and application is very wide.
It is electrolyte as the positive and negative electrode active material that all-vanadium ionic liquid flow battery (hereinafter to be referred as vanadium cell) employing contains vanadium solution, by peristaltic pump positive and negative electrode electrolyte is pumped into positive and negative half-cell respectively, on positive and negative electrode, finish electron exchange and realize its charge and discharge.Particularly mechanical performance and chemical property such as charge and discharge performance have bigger influence to the character of electrode and associated materials to the physics of vanadium cell, chemical property.At present, the vanadium cell of bibliographical information mainly adopts carbon element class material with electrode.This class material has anti-preferably strong acid corrosivity, and through after the modification, higher electro-chemical activity is arranged.But its surface is etched easily during used as positive electrode, and the mechanical strength of carbon element class material is lower.Therefore, overcome the defective of carbon element class material, seek a kind of good vanadium cell, become the important directions that vanadium cell is studied with electrode and material thereof.Studies show that, plating electro-chemical activity and the invertibity that DSA (Dimension Stable Anode) that yttrium oxide makes shows on the Ti electrode in the application of chlor-alkali, chlorate and electroplating industry, SkyllasKazacosm in 1987 etc. are applied to the vanadium cell positive pole, but because the oxygen evolution potential of such electrode is low, therefore its current efficiency is not high, and about 80%.(1.Rychcik?M，Skyllas?Kazacosm.Evalution?of?electrode?materials?for?allvanadium?redox-flow?cell[J].J?Power?Sources，1987，19：45-54.2.Skyllas?Kazacosm.Material?selection?and?performance?characteristics?of?new?vanadium?redox?flow?cell[A].Proc?International?Energy’88，Gold?Coast：1988-09.)。Metal forming/net can improve mechanical strength as vanadium redox battery with positive electrode, is a difficult problem but how to make its anti-strong acid corrosion and keep higher electro-chemical activity, needs number of research projects.
Summary of the invention
The object of the present invention is to provide a kind of all-vanadium ionic liquid flow battery electrode, particularly relate to the electrode of vanadium redox battery, another object of the present invention is to provide the preparation method of this electrode.
Vanadium redox battery provided by the invention is that the surface deposition composite metal oxide obtains with the metal forming/net of the sulfuric acid corrosion resistant collector as electrode with positive pole.
Wherein, described metal forming/net is titanium, tin, lead metal paper tinsel/net, described composite metal oxide is for having the mixing of the metal oxide of catalytic action, can be two or more hopcalite of Ir, Ta, Mg, Co, Ag, Ru, Mn, Fe V (V)/right electrochemical redox reaction of V (IV) electricity.The mass percent that these oxides account for entire electrode is 0.01～10%, is preferably between 0.1～1.0%.
The thickness of the collector of electrode provided by the invention is 0.01～5.0mm, and deposit thickness is 0.01-100 μ m.
The preparation method of electrode provided by the invention is: the metal forming/net with sulfuric acid corrosion resistant is removed the collector of greasy dirt oxide as electrode through surface treatment, by thermal decomposition method, sol-gel method, electro-deposition and electrostatic spraying, sputtering method, method such as plasma-deposited surface deposition metal oxide, obtain the vanadium cell positive electrode of mechanical performance and chemical property excellence at collector.
Wherein, described colloidal sol---gel method: prepare the gel of the salting liquid of required oxide with conventional method, gel is sprayed on collector metal forming/online dry, and carries out pyrolysis and acid treatment, clean and obtain electrode of the present invention.
Wherein, spraying can be used air gun, chemical vapour deposition (CVD) or physical vaporous deposition, also can spray repeatedly for several times by thickness as required.
Electro-deposition method is meant that slaine, additive and solvent are even, and to transfer pH to 0-6.5 be electrolyte, is anodal with the platinum guaze, and tinsel such as Titanium, tin, lead or net sheet are negative pole, at 1-100mA/cm
2Current density under carry out Constant Electric Current deposition, clean, dryly also carry out pyrolysis and acid treatment, clean and obtain electrode of the present invention.Acid treatment and last purpose of cleaning are with part solubility in acid oxide removal, to increase the specific area of electrode, improve the electrode reaction activity.
Wherein decomposition temperature is 300-600 ℃ in the above-mentioned steps, and the time is 1-70 minute; The concentration of acid is 0.1～6M during acid treatment, acid treatment time 1～120min.The control of described heat decomposition temperature and time is bigger to the performance impact of electrode.Temperature is too high, the reaction time is when long, may be with the metallic matrix oxidation, thus increase the resistance of electrode; Temperature is crossed low or reaction time when too short, and the area load substance decomposition is incomplete, and it is active or reduce active material utilization to influence electrode reaction.
The present invention selects for use the paper tinsel/net of the metal of sulfuric acid corrosion resistant such as titanium, tin, lead etc. as collector, at the surface deposition of collector V (V)/right electrochemical redox of V (IV) electricity had the composite metal oxide of catalytic action by thermal decomposition method, sol-gel method, electro-deposition and electrostatic spraying, sputtering method, method such as plasma-deposited, improved its overpotential for oxygen evolution, obtain acidproof, the vanadium cell positive electrode of mechanical performance and chemical property excellence.
Electrode with method preparation of the present invention is a positive pole, graphite electrode is a negative pole, and N-115 Nafion film is a barrier film, carries out the charge and discharge experiment in the V electrolyte of 2M, when one timing of charge and discharge current density, voltage efficiency improves nearly 10% when making positive pole than carbon element class electrode.Collector of the present invention is tinsel or wire netting, at thickness identical or than carbon element class electric conducting material thinner (as be carbon element class conductive plastics thickness 10%) time, still have better tensile strength and flexural strength, help improving the volume of battery specific energy.
The invention will be further described below by the mode of specific embodiment, but should not be construed as is limitation of the invention further, according to foregoing of the present invention, the technology that modification, replacement or change realized of making other various ways all belongs to scope of the present invention.
Embodiment
The preparation of embodiment 1 electrode of the present invention (DSA-1)
Prepare gel according to conventional sol-gel process: by mass ratio is to take by weighing chloro-iridic acid, TaCl at 3: 2: 1
5, MgCl
2Slaine is dissolved in respectively in n-butanol or the distilled water, the solution of various slaines is mixed, with NaHCO
3The pH value of regulator solution obtains colloidal sol to 1-3.Colloidal sol was placed 2 hours, obtained gel.
With air gun gel is sprayed on the metal forming of 0.5mm/online, in drying box, after 60-100 ℃ of drying, is sprayed into 10～100 μ m repeatedly.After the drying, in Muffle furnace 300-600 ℃ heat treatment 10-70 minute.
Electrode after heat treatment places 1-2M sulfuric acid to soak 1-4 hour, after the taking-up, cleans with distilled water, gets target electrode.
With this electrode is positive pole, and graphite electrode is a negative pole, and N-115 Nafion film is a barrier film, carries out the charge and discharge experiment in the V electrolyte of 2M, when the charge and discharge current density is 30mA/cm
2The time, the voltage efficiency on the prepared metal/oxide electrode is 88.3%, and is that the cell voltage efficient of positive pole is 80.1% with carbon element class electrode.
With the tensile strength that 4507 type universal tensile testing machines are tested the thick carbon element class electrode of the thick DSA-1 electrode of 0.54mm and 5.0mm respectively, result such as table 1.The ICP emission spectrum detects the DSA-1 electrode, and composite oxides account for 8% of entire electrode.
The preparation of embodiment 2 electrodes of the present invention (DSA-2)
By mass ratio is to take by weighing chloro-iridic acid, TaCl at 3: 2
5Be dissolved in the n-butanol, with NaHCO
3The pH value of regulator solution.With the platinum guaze is anodal, and the paillon foil or the net sheet of Titanium, tin, lead etc. are negative pole, and it is electrolyte that solution is joined by above-mentioned institute.At 1-100mA/cm
2Current density under carry out Constant Electric Current deposition.Sedimentation time is 3-30 minute, determines according to the thickness of required sedimentary deposit.
After the paillon foil of the Titanium after the electro-deposition, tin, lead etc. or net sheet clean in distilled water, 60-100 ℃ of drying in drying box.After the drying, in Muffle furnace 300-600 ℃ heat treatment 10-70 minute.
Electrode after heat treatment places 1-2M sulfuric acid to soak 1-4 hour, after the taking-up, cleans with distilled water, gets target electrode.
By electrochemistry and the mechanical property that the method for embodiment 1 is tested 0.52 thick DSA-2 electrode, relevantly the results are shown in Table 1.The ICP emission spectrum detects the DSA-2 electrode, and the content of composite oxides is 1%.
The preparation of embodiment 3 electrodes of the present invention (DSA-3)
By mass ratio is 1: 2: 2: 3 take by weighing chloro-iridic acid, AgNO
3, TaCl
5, MgCl
2Be dissolved in the n-butanol, with NaHCO
3The pH value of regulator solution is made the required colloidal solution of conventional electrostatic spraying method, sprays to the electrostatic spraying instrument on the paillon foil or net sheet of Titanium, tin, lead etc.Determine the time of spraying according to the thickness of required sedimentary deposit.
Paillon foil or net sheet 60-100 ℃ of drying in drying box after spraying.After the drying, in Muffle furnace 300-600 ℃ heat treatment 10-70 minute.
Electrode after heat treatment places 1-2M sulfuric acid to soak 1-4 hour, after the taking-up, cleans with distilled water, gets target electrode.
Press the electrochemistry and the mechanical property of the thick DSA-3 electrode of the method test 0.51mm of embodiment 1, relevantly the results are shown in Table 1.The ICP emission spectrum detects the DSA-3 electrode, and the content of composite oxides is 0.01%.
Electrode of the present invention and carbon pole performance comparison result are as follows:
Table 1 electrode performance relatively
Electrode thickness of electrode mm coating layer thickness μ m voltage efficiency/% tensile strength/MPa
DSA-1 0.54 40 88.3 408
DSA-2 0.52 20 89.2 487
DSA-3 0.51 10 88.7 493
Carbon element 5.0 0 80.1 7.8
The above results shows, thickness of electrode of the present invention is under 10% the situation of carbon element class electric conducting material, still has better tensile strength, and its tensile strength is more than 60 times of carbon pole; Simultaneously, the voltage efficiency of positive electrode of the present invention is done to improve when anodal nearly 10% than carbon element class electrode, be a kind of new, high mechanical properties, and anti-strong acid corrosion also keeps the vanadium cell positive electrode of higher electro-chemical activity.
Claims (9)
1, a kind of cathode for whole vanadium oxide reduction flow battery, it is characterized in that: with the collector of metal forming/net as electrode, the surface deposition composite metal oxide obtains, described composite metal oxide is the mixing of the multiple oxide among Ir, Ta, Mg, Co, Ag, Ru, Mn, the Fe, and its thickness is 0.01-100 μ m.
2, cathode for whole vanadium oxide reduction flow battery according to claim 1 is characterized in that: described metal forming/net is titanium, tin or lead metal paper tinsel/net.
3, cathode for whole vanadium oxide reduction flow battery according to claim 2 is characterized in that: described composite metal oxide accounts for the 0.01-10wt% of electrode.
4, cathode for whole vanadium oxide reduction flow battery according to claim 3 is characterized in that: described composite metal oxide accounts for the 0.1-1.0wt% of electrode.
5, cathode for whole vanadium oxide reduction flow battery according to claim 1 is characterized in that: the thickness of described collector is 0.01～5.0mm, and the thickness of composite metal oxide is 0.01-100 μ m.
6, a kind of method for preparing the described cathode for whole vanadium oxide reduction flow battery of claim 1 comprises:
A, metal forming/net are through the collector of surface treatment as electrode;
B, at the surface deposition composite metal oxide of collector, obtain cathode for whole vanadium oxide reduction flow battery.
7, preparation method according to claim 6 is characterized in that: the described surface deposition composite metal oxide of b step is by thermal decomposition method, sol-gel method, electro-deposition, sputtering method, plasma-deposited or method of electrostatic spraying realization.
8, preparation method according to claim 7, it is characterized in that: described sol-gel method is: the gel for preparing the salting liquid of required oxide with conventional method, gel is sprayed on collector metal forming/online, dry, and in 300-600 ℃ of decomposition, with concentration is that acid treatment is carried out in the acid of 0.1～6M, cleans and obtains cathode for whole vanadium oxide reduction flow battery.
9, preparation method according to claim 8 is characterized in that: described gel being sprayed on collector metal forming/online, is to adopt air gun, chemical vapour deposition (CVD) or physical vaporous deposition spraying to realize.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100347898C (en) * | 2005-11-18 | 2007-11-07 | 清华大学 | Galvanic pile structure of energy-storing unit of oxidation-reduction fluid flow battery |
| CN100545321C (en) * | 2007-11-05 | 2009-09-30 | 攀钢集团攀枝花钢铁研究院 | Graphite felt surface modifying method and modified graphite felt |
| CN101465417B (en) * | 2007-12-19 | 2010-07-28 | 中国科学院金属研究所 | Electrochemical treatment method for improving vanadium cell electrode material activity |
| WO2010088847A1 (en) * | 2009-02-06 | 2010-08-12 | 北京金能燃料电池有限公司 | Electrode for a flow battery |
| CN101619465B (en) * | 2008-07-02 | 2010-12-22 | 中国科学院大连化学物理研究所 | Method for preparing vanadium battery solution or adjusting capacity and special device thereof |
| CN102315462A (en) * | 2010-06-29 | 2012-01-11 | 中国科学院青岛生物能源与过程研究所 | Electrode used for vanadium redox flow battery and preparation method for electrode |
| CN102625960A (en) * | 2009-06-30 | 2012-08-01 | 雷沃尔特科技有限公司 | Metal-air flow battery |
| CN101997129B (en) * | 2009-08-27 | 2013-09-18 | 中国科学院金属研究所 | Liquid flow battery |
| CN107026272A (en) * | 2016-02-01 | 2017-08-08 | 台湾奈米碳素股份有限公司 | Method for manufacturing nitrogen-containing carbon electrode and flow battery thereof |
| CN111477893A (en) * | 2020-05-11 | 2020-07-31 | 辽宁大学 | Electrospun carbon nanofiber composite material with functional components distributed in longitudinal gradient manner, preparation method of electrospun carbon nanofiber composite material and application of electrospun carbon nanofiber composite material in vanadium battery |
| CN111540914A (en) * | 2020-05-11 | 2020-08-14 | 辽宁大学 | Preparation method of functional porous graphene integrated electrode material and application of functional porous graphene integrated electrode material in vanadium battery |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5336572A (en) * | 1993-06-14 | 1994-08-09 | Valence Technology, Inc. | Vanadium oxide cathode active material and method of making same |
| DE10108695A1 (en) * | 2001-02-23 | 2002-09-05 | Varta Geraetebatterie Gmbh | Galvanic element with at least one lithium intercalating electrode |
| CN2502443Y (en) * | 2001-08-26 | 2002-07-24 | 孙虹杰 | Polar liquid flow all-vanadium ion oxidation and reduction energy storage device |
| CN1307733C (en) * | 2003-07-04 | 2007-03-28 | 中南大学 | Method for preparing electrode for full-vanadium ion liquid flow battery |
| CN1304640C (en) * | 2003-09-18 | 2007-03-14 | 攀枝花钢铁有限责任公司钢铁研究院 | Process for electrolyzing preparing electrolyte of full vanadium ion flow battery |
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- 2005-04-22 CN CN2005100207794A patent/CN100407477C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100347898C (en) * | 2005-11-18 | 2007-11-07 | 清华大学 | Galvanic pile structure of energy-storing unit of oxidation-reduction fluid flow battery |
| CN100545321C (en) * | 2007-11-05 | 2009-09-30 | 攀钢集团攀枝花钢铁研究院 | Graphite felt surface modifying method and modified graphite felt |
| CN101465417B (en) * | 2007-12-19 | 2010-07-28 | 中国科学院金属研究所 | Electrochemical treatment method for improving vanadium cell electrode material activity |
| CN101619465B (en) * | 2008-07-02 | 2010-12-22 | 中国科学院大连化学物理研究所 | Method for preparing vanadium battery solution or adjusting capacity and special device thereof |
| WO2010088847A1 (en) * | 2009-02-06 | 2010-08-12 | 北京金能燃料电池有限公司 | Electrode for a flow battery |
| CN102625960A (en) * | 2009-06-30 | 2012-08-01 | 雷沃尔特科技有限公司 | Metal-air flow battery |
| CN101997129B (en) * | 2009-08-27 | 2013-09-18 | 中国科学院金属研究所 | Liquid flow battery |
| CN102315462A (en) * | 2010-06-29 | 2012-01-11 | 中国科学院青岛生物能源与过程研究所 | Electrode used for vanadium redox flow battery and preparation method for electrode |
| CN102315462B (en) * | 2010-06-29 | 2014-04-16 | 中国科学院青岛生物能源与过程研究所 | Electrode used for vanadium redox flow battery and preparation method for electrode |
| CN107026272A (en) * | 2016-02-01 | 2017-08-08 | 台湾奈米碳素股份有限公司 | Method for manufacturing nitrogen-containing carbon electrode and flow battery thereof |
| CN107026272B (en) * | 2016-02-01 | 2020-04-21 | 台湾奈米碳素股份有限公司 | Method for manufacturing nitrogen-containing carbon electrode and flow battery thereof |
| CN111477893A (en) * | 2020-05-11 | 2020-07-31 | 辽宁大学 | Electrospun carbon nanofiber composite material with functional components distributed in longitudinal gradient manner, preparation method of electrospun carbon nanofiber composite material and application of electrospun carbon nanofiber composite material in vanadium battery |
| CN111540914A (en) * | 2020-05-11 | 2020-08-14 | 辽宁大学 | Preparation method of functional porous graphene integrated electrode material and application of functional porous graphene integrated electrode material in vanadium battery |
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| CN100407477C (en) | 2008-07-30 |
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