CN104328456A - Reversible phase transition vanadate electrode material, and preparation method and application thereof - Google Patents
Reversible phase transition vanadate electrode material, and preparation method and application thereof Download PDFInfo
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- CN104328456A CN104328456A CN201410452896.7A CN201410452896A CN104328456A CN 104328456 A CN104328456 A CN 104328456A CN 201410452896 A CN201410452896 A CN 201410452896A CN 104328456 A CN104328456 A CN 104328456A
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- 239000007772 electrode material Substances 0.000 title claims abstract description 32
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 230000002441 reversible effect Effects 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 230000007704 transition Effects 0.000 title abstract 3
- 239000007787 solid Substances 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 13
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000004567 concrete Substances 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 239000002689 soil Substances 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052751 metal Inorganic materials 0.000 abstract description 18
- 239000002184 metal Substances 0.000 abstract description 18
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 239000010406 cathode material Substances 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 229910002590 FeV2O4 Inorganic materials 0.000 abstract 1
- 230000010287 polarization Effects 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000000446 fuel Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 7
- 230000009467 reduction Effects 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000001218 confocal laser scanning microscopy Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003411 electrode reaction Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910002119 nickel–yttria stabilized zirconia Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910002437 Ce0.8Sm0.2O2−δ Inorganic materials 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 102100034013 Gamma-glutamyl phosphate reductase Human genes 0.000 description 1
- 101001133924 Homo sapiens Gamma-glutamyl phosphate reductase Proteins 0.000 description 1
- 229910002155 La0.75Sr0.25Cr0.5Mn0.5O3 Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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- 239000011435 rock Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Inert Electrodes (AREA)
- Catalysts (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention discloses a reversible phase transition vanadate electrode material, and a preparation method and an application thereof. The chemical formula of the vanadate electrode material is FeVO4, the vanadate electrode material has a reversible phase transition property, that is, FeVO4 is reduced to form reducing products formed by FeV2O4 and Fe, and the reducing products are oxidized to generate the FeVO4. The above cathode material has high conductivity in reducing atmosphere, allows a metal iron catalyst to be precipitated, has a high catalytic activity, and has good performances as a high temperature solid oxide electrolytic cell cathode material.
Description
Technical field
The present invention relates to a kind of cathode of electrolytic tank design of material field, be specifically related to a kind of electrolytic tank of solid oxide vanadate cathode material that reversible phase in version can occur.
Background technology
High-temperature solid oxide electrolyzer is a kind of energy conversion device efficiently, and at high temperature electrolysis of water steam can prepare hydrogen, and electrolysis carbonic acid gas prepares carbon monoxide, has good kinetics and thermomechanical property.Main Function for cationic cathode of electrolytic tank of solid oxide (fuel electrodes) is to provide the place of water vapor or carbon dioxide decomposition reaction and the passage of electronic conduction.Therefore, fuel electrode except need and adjacent component capabilities match, have beyond chemical compatibility and stability under long-term operation state, also must possess good electronic conduction ability and electro catalytic activity, and the performance that holding structure is stable with composition under the high temperature conditions.
Carrying out catalytic decomposition cathode material adopted at first to water vapor is some precious metals and transition metal, and as Ni, Pt, Co, Ti etc., this kind of material has higher activity, and can keep stable under reducing atmosphere.But pure metal has a lot of defect as the fuel electrode of electrolytic tank of solid oxide.As the overpotential etc. that thermal expansivity between metal electrode with electrolyte does not mate, electrolyzer thermal shock resistance is poor, few, the easy generation of electrode reaction active sites is high.In addition, the fuel electrode room of electrolytic tank of solid oxide is high temperature, high humidity atmosphere, and simple metal electrode easily sinters, and causes the performance degradation of electrolyzer.Pure metal is greatly limited as electrolytic tank of solid oxide fuel electrode material separately, seldom adopts now.Use composite cathode material at present, such as Ni-YSZ more.In Ni-YSZ sintering metal, Ni and YSZ can not react in very wide temperature range, and YSZ can effectively suppress Ni particle agglomeration, alligatoring as support frame, improves the stability of electrolytic tank of solid oxide.Simultaneously, the thermal expansivity of composite cathode can be made close with YSZ ionogen by adjustment doping ratio, enhance chemical stability, and in Ni-YSZ fuel electrode, electrode reaction region can extend to the inner certain depth of fuel electrode, thus add electrode reaction active sites, improve the performance of electrolyzer.But under higher operating temperatures, W metal base composite cathode is easy to be oxidized to NiO thus loses conductivity and catalytic performance, the major cause of Ni base composite cathode exhaustion that Here it is.In addition, the higher catalytic activity due to W metal also there will be the phenomenon of carbon distribution, affects catalytic activity.Ceramic base perofskite type oxide La
0.8sr
0.2tiO
3and La
0.75sr
0.25cr
0.5mn
0.5o
3etc. developing rapidly, show the trend replacing nickel base electrode.Ceramic base La
0.2sr
0.8tiO
3+ δmaterial has the advantages such as high mixed conductivity, catalytic activity and good oxidation-reduction stability and has caused extensive concern, but La
0.2sr
0.8tiO
3+ δeasily oxidized and catalytic activity constrains its development lower than defects such as traditional metal electrodes when there is high-temperature electrolysis.Compared with Ni-based combined electrode, La
xsr
1-xcr
ymn
1-yo
3-δ(LSCM) be the high and material of redox-stable of a kind of catalytic activity, there is very little polarization resistance, huge concern is caused in high-temperature solid oxide electrolyzer field, but due to LSCM be p-type electric-conducting mechanism, under recovery voltage, LSCM produces larger polarization resistance thus current efficiency is reduced, and therefore also needs to improve and optimizate further.
Summary of the invention
The present invention is directed to metal current electrode easily oxidized and occur to reunite and the catalytic activity of ceramic electrode not enough etc., the FeVO of reversible phase in version can be carried out
4as cathode of electrolytic tank of solid oxide material, utilize FeVO
4reversible phase in version, can be analyzed to metal Fe catalyzer and FeV under reducing atmosphere
2o
4, ensure that material has enough catalytic activitys, and the material generated holding structure in reducing atmosphere is stablized, and then obtains the good cathode of electrolytic tank of solid oxide material of chemical property.
Concrete technical scheme of the present invention is:
The vanadate electrode materials of the reversible phase in version of the present invention, its feature is: its constitutional chemistry formula is FeVO
4.
The vanadate electrode materials of the reversible phase in version of the present invention, its feature is also: described vanadate electrode materials can carry out reversible phase in version, by described vanadate electrode materials FeVO
4reduce under 700-750 DEG C of reducing atmosphere, generate by FeV
2o
4reduzate with Fe is formed, after being oxidized by described reduzate, generates described vanadate electrode materials FeVO under 700-800 DEG C of well-oxygenated environment again
4; H in described reducing atmosphere
2percent by volume is 5%, and surplus is Ar (5%H
2/ Ar); Described well-oxygenated environment is in air atmosphere.
Vanadate electrode materials of the present invention be with ferric oxide and Vanadium Pentoxide in FLAKES for raw material, prepared by solid reaction process.
The concrete steps of material solid reaction process synthesis of the present invention are:
A, to take ferric oxide and Vanadium Pentoxide in FLAKES according to stoichiometric ratio as reaction raw materials;
B, described reaction raw materials loaded in the ball grinder of ball mill, in ball grinder, add agate ball as grinding medium, then add acetone as Ball milling agent, acetone adds to 2/3rds of ball covering on soil grinding jar volume;
C, with the ball milling speed ball milling 15 minutes of 1000 revs/min, ferric oxide and Vanadium Pentoxide in FLAKES are mixed, obtain compound;
D, by compound drying then compressing tablet, then at 750 DEG C calcine 10 hours, obtain calcining sheet;
F, described calcining sheet to be pulverized in mortar, obtain vanadate electrode materials FeVO
4.
Drying described in steps d is in air atmosphere, dry 0.5 ~ 1.5h at 150 DEG C.
Compressing tablet described in steps d be under 4MP pressure by drying after compound be pressed into that diameter is 12 ~ 18mm, thickness is the sheet of 1 ~ 3mm.
Invention further provides described vanadate electrode materials FeVO
4as the application of high-temperature solid oxide cathode of electrolytic tank material, its operationally electrode be in reducing atmosphere, the FeV now generated
2o
4phase structure is stablized, and Fe has higher metal catalytic activity, can promote electrode activation, reduces polarization resistance, improves electrode performance.And when electrode is in well-oxygenated environment, electrode materials as the metal electrodes such as Ni, can not be reunited due to oxidation, thus causes electrode to lose activity.Fe and FeV
2o
4again reaction generates FeVO
4.Therefore, FeVO
4redox reversible be used on cathode of electrolytic tank material, there is greater advantage.
With FeVO of the present invention
4the method preparing the Symmetrical cells of high-temperature solid oxide electrolyzer as cathode material is: by the cathode powder of synthesis and Ce
0.8sm
0.2o
2-δ(SDC) mix with mass ratio 65:35, add the pore-creating of ethyl cellulose Terpineol 350, prepare combination electrode material.Abundant grinding, was coated in zirconium white (YSZ) the electrolytical surface that fine and close yttrium is stable equably by it, through 1000 DEG C of calcinings 3 hours.Coat silver slurry as current collection fluid layer at electrode surface, be wire with filamentary silver, make Symmetrical cells.
Compared with the prior art, beneficial effect of the present invention is:
1, the invention provides a kind of vanadate electrode materials FeVO of reversible phase in version
4and preparation method thereof, preparation method is simple, prepared FeVO
4can reversible phase in version be carried out, enable it effectively promote electrode activation as during cathode material, reduce polarization resistance, thus improve electrode performance.
2, the present invention is with FeVO
4as high-temperature solid oxide cathode of electrolytic tank material, this material can generate the FeV of Fe metal simple-substance and spinel structure in reducing atmosphere
2o
4, and there is redox reversible; During the work of high-temperature solid oxide cathode of electrolytic tank, electrode is in reducing atmosphere, the FeV now generated
2o
4phase structure keeps stable, and Fe has higher metal catalytic activity, can promote electrode activation, reduces polarization resistance, thus improves electrode performance; When electrode is in well-oxygenated environment, Fe and FeV
2o
4again reaction generates FeVO
4, the agglomeration of catalyzer can not be there is, avoid oxidizing condition lower electrode and lose activity.
3, FeVO of the present invention
4when being in reducing atmosphere, owing to there is the metal simple-substance Fe separated out, using this material as electrode, the Symmetrical cells electrode performance assembled using YSZ as ionogen is excellent.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of embodiment 1 products therefrom;
Fig. 2 is embodiment 1 products therefrom FeVO
4at 5%H
2through the XRD figure spectrum of 750 DEG C of reduction after 5 hours in/Ar environment;
Fig. 3 is embodiment 1 gained FeVO
4reduction after product calcines the XRD figure spectrum of 5 hours in air atmosphere;
Fig. 4 is FeVO
4be in electrolytical Symmetrical cells with YSZ, the polarization resistance that different hydro dividing potential drop atmosphere is lower 800 DEG C.
Embodiment
Embodiment 1:0.04mol FeVO
4the synthesis of material, the test of the sign of phase and the electrochemical AC impedance of Symmetrical cells after redox.
According to the chemical formula ratio of material, take 3.1938g Fe respectively
2o
3(analytical pure) and 3.64g V
2o
5as reaction raw materials; Reaction raw materials is put into the ball grinder that volume is 100ml, use agate ball is grinding medium, adds acetone (adding to 2/3rds in ball covering on soil grinding jar) as dispersion agent, with the speed ball milling 15 minutes of 1000 revs/min in ball mill, make it to mix, obtain compound; By compound in air atmosphere, dry 1h at 150 DEG C, then the sheet that appropriate powder becomes diameter to be about 15mm thickness to be about 2mm at 4MP pressure is got, finally institute's compressing tablet is calcined 10 hours at 750 DEG C, sheet after calcining is pulverized in mortar, obtains target product vanadate electrode materials FeVO
4.
Measure the collection of illustrative plates of made powder through XRD powder diffraction method, with GSAS refine (refine is the correction by correlated variables, makes the process of theoretical construct Model and experiment data fit, and from refine result can be reliable draw lattice constant.), result is as shown in Figure 1.In Fig. 1, the XRD figure spectrum of actual sample overlaps substantially with theoretical model, and illustrate that crystal Cheng Xiangdu is better, the lattice constant of oxidation state sample is also obtained by refine.
Get the made powder of part, be placed in 5%H
2in/Ar environment, 750 DEG C are reduced 5 hours, carry out XRD test, prove FeVO after reduction
4decompose and generate FeV
2o
4with simple substance Fe, the XRD refine of gained, as shown in Figure 2, the FeV of generation
2o
4for spinel structure, degree of crystallinity is better, when 2 Θ are about 44.6 °, occurs the peak of iron simple substance, generates FeV after reduction is described
2o
4with this two-phase of simple substance Fe.
The degradation production of reduction gained is placed in air 750 DEG C of calcinings 5 hours, the powder obtained carries out XRD test, proves the reversibility of phase in version, as shown in Figure 3, FeVO is described
4feV is generated after reduction
2o
4with simple substance Fe, after being again oxidized by product, FeVO can be obtained by reacting again
4, generate without other dephasigns.Utilize the reversibility of phase in version, this material can generate the stable phase of spinel structure under the reducing conditions and have the Fe of metal catalytic activity, and again changes FeVO into after oxidation
4rock steady structure.
By the cathode powder of synthesis and Ce
0.8sm
0.2o
2-δ(SDC) mix with mass ratio 65:35, add the pore-creating of ethyl cellulose Terpineol 350, prepare combination electrode material.After abundant grinding, gained combined electrode slurry is coated in equably the fine and close electrolytical surface of YSZ, through 1000 DEG C of temperature lower calcinations 3 hours.Coat silver slurry as current collection fluid layer at electrode surface, be wire with filamentary silver, make Symmetrical cells.Carry out ac impedance measurement with Symmetrical cells, obtain the polarization resistance that different hydro under 800 DEG C of conditions divides pressure, as shown in Figure 4.Along with hydrogen dividing potential drop increase, polarization resistance in continuous reduction, at 80%H
2/ 20%N
2under atmosphere, polarization resistance is 2.55 Ω cm
2.Along with the increase of hydrogen dividing potential drop, FeVO
4be reduced and generate FeV
2o
4also can increase with the amount of simple substance Fe, due to the increase of metal Fe catalyst content, the activation of electrode can be promoted, and then reduce polarization resistance, improve electrode performance.
Claims (7)
1. a vanadate electrode materials for reversible phase in version, is characterized in that: the chemical formula of described vanadate electrode materials is FeVO
4.
2. the vanadate electrode materials of reversible phase in version according to claim 1, is characterized in that: described vanadate electrode materials can carry out reversible phase in version, and described reversible phase in version refers to: by described vanadate electrode materials FeVO
4reduce under 700-750 DEG C of reducing atmosphere, generate by FeV
2o
4reduzate with Fe is formed, after being oxidized by described reduzate, generates described vanadate electrode materials FeVO under 700-800 DEG C of well-oxygenated environment again
4;
H in described reducing atmosphere
2percent by volume is 5%, and surplus is Ar;
Described well-oxygenated environment is in air atmosphere.
3. the vanadate electrode materials of reversible phase in version according to claim 1 and 2, is characterized in that: described vanadate electrode materials be with ferric oxide and Vanadium Pentoxide in FLAKES for raw material, prepared by solid reaction process.
4. a preparation method for the vanadate electrode materials of reversible phase in version described in claim 1 or 2, is characterized in that: described vanadate electrode materials adopts solid reaction process synthesis, and concrete steps are:
A, to take ferric oxide and Vanadium Pentoxide in FLAKES according to stoichiometric ratio as reaction raw materials;
B, described reaction raw materials loaded in the ball grinder of ball mill, in ball grinder, add agate ball as grinding medium, then add acetone as Ball milling agent, acetone adds to 2/3rds of ball covering on soil grinding jar volume;
C, with the ball milling speed ball milling 15 minutes of 1000 revs/min, ferric oxide and Vanadium Pentoxide in FLAKES are mixed, obtain compound;
D, compound is dry, compressing tablet, then calcine 10 hours at 750 DEG C, obtains calcining sheet;
F, described calcining sheet to be pulverized in mortar, obtain vanadate electrode materials FeVO
4.
5. preparation method according to claim 4, is characterized in that:
Drying described in steps d is in air atmosphere, dry 0.5 ~ 1.5h at 150 DEG C.
6. preparation method according to claim 4, is characterized in that:
Compressing tablet described in steps d be under 4MP pressure by drying after compound be pressed into that diameter is 12 ~ 18mm, thickness is the sheet of 1 ~ 3mm.
7. an application for vanadate electrode materials described in Claims 1 to 4 any one, is characterized in that: described vanadate electrode materials is used for as high-temperature solid oxide cathode of electrolytic tank material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106011456A (en) * | 2016-08-02 | 2016-10-12 | 北京科技大学 | Method for enrichment of vanadium in vanadium-containing stone coal and V-concentrating phase regulation |
| CN113332991A (en) * | 2021-05-28 | 2021-09-03 | 南华大学 | Visible light response nano polyhedral ferric vanadate thin film photoelectrode and preparation method and application thereof |
| CN114481175A (en) * | 2022-01-25 | 2022-05-13 | 电子科技大学 | Repairable solid-state symmetrical electrolytic cell device based on strontium ferrite electrode catalytic layer |
| CN114655983A (en) * | 2022-03-18 | 2022-06-24 | 合肥工业大学 | Preparation method and application of layered vanadium oxide pre-embedded with Ni/Zn double cations |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4115110A (en) * | 1977-04-08 | 1978-09-19 | Earth Sciences, Inc. | Vanadium recovery process |
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| CN106011456A (en) * | 2016-08-02 | 2016-10-12 | 北京科技大学 | Method for enrichment of vanadium in vanadium-containing stone coal and V-concentrating phase regulation |
| CN113332991A (en) * | 2021-05-28 | 2021-09-03 | 南华大学 | Visible light response nano polyhedral ferric vanadate thin film photoelectrode and preparation method and application thereof |
| CN113332991B (en) * | 2021-05-28 | 2022-06-10 | 南华大学 | Visible light response nano polyhedral ferric vanadate thin film photoelectrode and preparation method and application thereof |
| CN114481175A (en) * | 2022-01-25 | 2022-05-13 | 电子科技大学 | Repairable solid-state symmetrical electrolytic cell device based on strontium ferrite electrode catalytic layer |
| CN114481175B (en) * | 2022-01-25 | 2023-09-26 | 电子科技大学 | Repairable solid-state symmetrical electrolytic cell device based on strontium ferrite electrode catalytic layer |
| CN114655983A (en) * | 2022-03-18 | 2022-06-24 | 合肥工业大学 | Preparation method and application of layered vanadium oxide pre-embedded with Ni/Zn double cations |
| CN114655983B (en) * | 2022-03-18 | 2024-01-30 | 合肥工业大学 | Preparation method and application of pre-embedded Ni/Zn double cation layered vanadium oxide |
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