CN104328456B - 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
- Publication number
- CN104328456B CN104328456B CN201410452896.7A CN201410452896A CN104328456B CN 104328456 B CN104328456 B CN 104328456B CN 201410452896 A CN201410452896 A CN 201410452896A CN 104328456 B CN104328456 B CN 104328456B
- Authority
- CN
- China
- Prior art keywords
- electrode material
- fevo
- vanadate electrode
- application
- vanadate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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
Landscapes
- Inert Electrodes (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Catalysts (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 is and in particular to a kind of can occur reversible phase in version
Electrolytic tank of solid oxide vanadate cathode material.
Background technology
High-temperature solid oxide electrolyzer is a kind of efficient energy conversion device, and electrolysis of water steam can be made at high temperature
Standby hydrogen, electrolysis carbon dioxide prepares carbon monoxide, has good kinetics and thermodynamic property.For cationic solid
The Main Function of oxide electrolysis pool cathode (fuel electrodes) be provide water vapour or carbon dioxide decomposition reaction place and electronics
The passage of conduction.Therefore, fuel electrode except need and adjacent component capabilities match, having under long-term operation state
It is necessary to possess good electronic conduction ability and electro catalytic activity beyond the compatibility and stability, and in hot conditionss
The lower holding structure performance stable with composition.
Water vapour is carried out with the cathode material that catalytic decomposition adopted at first is some noble metals and transition metal, such as Ni,
Pt, Co, Ti etc., this kind of material has higher activity, and can keep stable under reducing atmosphere.But, pure metal is made
Fuel electrode for electrolytic tank of solid oxide has a lot of defects.As thermal coefficient of expansion between metal electrode and electrolyte
Mismatch, overpotential that electrolyzer thermal shock resistance is poor, electrode reaction active sites are few, easy generation is high etc..In addition, solid oxygen
The fuel electrode room of compound electrolyzer is high temperature, high wet atmosphere, and simple metal electrode is susceptible to sinter, and leads to electrolyzer
Performance degradation.Simple metal is greatly limited separately as electrolytic tank of solid oxide fuel electrode material, now little
Using.Use composite cathode material, such as Ni-YSZ at present more.In Ni-YSZ ceramic metal, Ni and YSZ is in very wide temperature model
All without reacting in enclosing, YSZ can effectively suppress Ni particle agglomeration, roughening as support frame, improves solid oxidation
The stability of thing electrolyzer.Meanwhile, thermal coefficient of expansion and the YSZ electrolyte phase of composite cathode can be made by adjusting doping ratio
Closely, enhance chemical stability, and in Ni-YSZ fuel electrode, electrode reaction region extends to inside fuel electrode
Certain depth, thus increased electrode reaction active sites, improves the performance of electrolyzer.But under higher operating temperatures, gold
Belong to Ni base composite cathode and be easily oxidized into NiO thus losing electric conductivity and catalytic performance, here it is Ni base composite cathode
The main cause of exhaustion.Further, since the higher catalysis activity of W metal there is also the phenomenon of carbon distribution, impact catalysis is lived
Property.Ceramic base perofskite type oxide La0.8Sr0.2TiO3And La0.75Sr0.25Cr0.5Mn0.5O3Etc. developing rapidly, show
Replace the trend of nickel base electrode.Ceramic base La0.2Sr0.8TiO3+δMaterial has high mixed conductivity, catalysis activity and good
Oxidation-reduction stability the advantages of caused extensive concern, but La0.2Sr0.8TiO3+δExist during high-temperature electrolysis easily by oxygen
Change and catalysis activity is less than the defects such as traditional metal electrodes and constrains its development.Compared with Ni-based combination electrode, LaxSr1- xCryMn1-yO3-δ(LSCM) it is that a kind of catalysis activity is high and the material of redox-stable, there is very little polarization resistance,
High-temperature solid oxide electrolyzer field causes huge concern, is p-type electric-conducting mechanism yet with LSCM, in recovery voltage
Under, LSCM produces larger polarization resistance so that current efficiency reduces, and therefore also needs to improve and optimizate further.
Content of the invention
The present invention is oxidized easily for metal current electrode and catalysis activity deficiency of reunion and ceramic electrode etc. occurs,
It is possible to carry out the FeVO of reversible phase in version4As cathode of electrolytic tank of solid oxide material, using FeVO4Reversible phase in version,
Can be analyzed to metal Fe catalyst and FeV under reducing atmosphere2O4It is ensured that material has enough catalysis activities, and the material generating
Material holding structure in reducing atmosphere is stable, and then obtains chemical property preferable cathode of electrolytic tank of solid oxide material.
The concrete technical scheme of the present invention is：
The vanadate electrode material of the reversible phase in version of the present invention, its feature is：Its constitutional chemistry formula is FeVO4.
The vanadate electrode material of the reversible phase in version of the present invention, its feature lies also in：Described vanadate electrode material is permissible
Carry out reversible phase in version, will described vanadate electrode material FeVO4Under 700-750 DEG C of reducing atmosphere reduce, generate by
FeV2O4The reduzate constituting with Fe, after described reduzate is aoxidized under 700-800 DEG C of oxidation environment, generates institute again
State vanadate electrode material FeVO4；H in described reducing atmosphere2Percentage by volume is 5%, balance of Ar (5%H2/Ar)；Described
Oxidation environment is in air atmosphere.
The vanadate electrode material of the present invention is with iron sesquioxide and vanadic anhydride as raw material, by solid reaction process
Prepare.
What the material solid reaction process of the present invention synthesized concretely comprises the following steps：
A, weigh iron sesquioxide and vanadic anhydride according to stoichiometric proportion as reaction raw materials；
B, will described reaction raw materials load ball mill ball grinder in, in ball grinder add agate ball as grinding medium
Matter, is subsequently adding acetone as ball milling dispersant, and acetone adds to and covers 2/3rds of ball milling tank volume；
C, with 1000 revs/min of ball milling speed ball milling 15 minutes, make iron sesquioxide and vanadic anhydride mix homogeneously,
Obtain compound；
D, by compound be dried then tabletting, then at 750 DEG C calcine 10 hours, obtain calcining piece；
F, by described calcining piece pulverize in mortar, obtain final product vanadate electrode material FeVO4.
Described in step d, drying is in air atmosphere, and 0.5～1.5h is dried at 150 DEG C.
Tabletting described in step d be under 4MP pressure by drying after compound be pressed into a diameter of 12～18mm, thickness be 1～
The piece of 3mm.
Invention further provides described vanadate electrode material FeVO4As high-temperature solid oxide cathode of electrolytic tank
The application of material, its operationally electrode be in reducing atmosphere, the FeV now generating2O4Phase structure is stable, and Fe has higher
Metal catalytic activity, can promote electrode activation, reduce polarization resistance, improve electrode performance.And work as electrode and be in oxidation ring
In border, electrode material will not be reunited due to oxidation as the metal electrodes such as Ni, thus leading to electrode to lose activity.
Fe and FeV2O4Again reaction generates FeVO4.Therefore, FeVO4Redox reversible be used on cathode of electrolytic tank material,
There is greater advantage.
FeVO with the present invention4The method preparing the Symmetrical cells of high-temperature solid oxide electrolyzer as cathode material
It is：By the cathode powder of synthesis and Ce0.8Sm0.2O2-δ(SDC) with mass ratio 65:35 mixing, add ethyl cellulose terpineol to make
Hole, prepares combination electrode material.It is fully ground, it is equably coated in stable zirconium oxide (YSZ) electrolyte of fine and close yttrium
Surface, through 3 hours of 1000 DEG C of calcinings.Coat silver paste as current collection fluid layer in electrode surface, with filamentary silver as wire, make symmetrical
Battery.
Compared with the prior art, the beneficial effects of the present invention is：
1 the invention provides a kind of vanadate electrode material FeVO of reversible phase in version4And preparation method thereof, preparation side
Method is simple, prepared FeVO4Reversible phase in version can be carried out so as to as electrode active can be effectively facilitated during cathode material
Changing, reducing polarization resistance, thus improving electrode performance.
2nd, the present invention is with FeVO4As high-temperature solid oxide cathode of electrolytic tank material, this material can in reducing atmosphere
Generate the FeV of Fe metal simple-substance and spinel structure2O4, and there is redox reversible；High-temperature solid oxide electrolyzer
During negative electrode work, electrode is in reducing atmosphere, the FeV now generating2O4Phase structure keeps stable, and Fe has higher metal
Catalysis activity, can promote electrode activation, reduce polarization resistance, thus improving electrode performance；When electrode is in oxidation environment,
Fe and FeV2O4Again reaction generates FeVO4, the agglomeration of catalyst will not occur, it is to avoid oxidizing condition bottom electrode loses
Activity.
3rd, the FeVO of the present invention4When being in reducing atmosphere, due to there is the metal simple-substance Fe separating out, using this material as electricity
Pole, excellent using the Symmetrical cells electrode performance that YSZ assembles as electrolyte.
Brief description
Fig. 1 is the XRD spectrum of embodiment 1 products therefrom；
Fig. 2 is embodiment 1 products therefrom FeVO4In 5%H2XRD spectrum after reducing 5 hours through 750 DEG C in/Ar environment；
Fig. 3 is embodiment 1 gained FeVO4After reduction, product calcines the XRD spectrum of 5 hours in air atmosphere；
Fig. 4 is FeVO4In the Symmetrical cells with YSZ as electrolyte, the polarization electricity of lower 800 DEG C of different hydrogen dividing potential drop atmosphere
Resistance.
Specific embodiment
Embodiment 1：0.04mol FeVO4The synthesis of material, the electrochemistry of the sign of phase and Symmetrical cells after oxidoreduction
The test of AC impedance.
According to the chemical formula ratio of material, weigh 3.1938g Fe respectively2O3(analysis is pure) and 3.64g V2O5As reaction
Raw material；Reaction raw materials are put in the ball grinder that volume is 100ml, the use of agate ball is abrasive media, plus acetone (adds to covering
In ball grinder 2/3rds) as dispersant, with 1000 revs/min of speed ball milling 15 minutes in ball mill, it is allowed to mixed
Close uniformly, obtain compound；By compound in air atmosphere, 1h is dried at 150 DEG C, then takes appropriate powder to press in 4MP
Power depresses to diameter and is about the piece that 15mm thickness is about 2mm, finally at 750 DEG C, institute's tabletting is calcined 10 hours, will calcine
Piece afterwards is pulverized in mortar, obtains final product target product vanadate electrode material FeVO4.
Measure the collection of illustrative plates of made powder through XRD powder diffraction method, (refine is repairing by correlated variabless with GSAS refine
Just so that the process that meets of theoretical construct model and experimental data, and from refine result can be reliable draw crystal
Constant.), result is as shown in Figure 1.In Fig. 1, the XRD spectrum of actual sample and theoretical model essentially coincide, and crystal Cheng Xiangdu is described
Preferably, the crystal constant of oxidation state sample obtains also by refine.
Take partly made powder, be placed in 5%H2In/Ar environment, 750 DEG C reduce 5 hours, carry out XRD test after reduction, card
Bright FeVO4Decompose and generate FeV2O4With simple substance Fe, the XRD refine of gained, as shown in Fig. 2 generate FeV2O4For spinel structure,
Preferably, when 2 Θ are about 44.6 °, the peak of ferrum simple substance, generates FeV after reduction is described in degree of crystallinity2O4With simple substance Fe this two
Phase.
The catabolite of reduction gained is placed in the air calcine 5 hours at 750 DEG C, the powder obtaining carries out XRD test,
Prove the reversibility of phase in version, as shown in figure 3, explanation FeVO4FeV is generated after reduction2O4With simple substance Fe, by product oxygen again
After change, and can react and obtain FeVO4, no other dephasigns generation.Using the reversibility of phase in version, this material can be under the reducing conditions
Generate the stable phase of spinel structure and the Fe with metal catalytic activity, and be again transformed into FeVO after aoxidizing4Stable knot
Structure.
By the cathode powder of synthesis and Ce0.8Sm0.2O2-δ(SDC) with mass ratio 65:35 mixing, add ethyl cellulose pine
Oleyl alcohol pore-creating, prepares combination electrode material.After being fully ground, gained combination electrode slurry is equably coated in the YSZ electricity of densification
The surface of solution matter, through 3 hours of 1000 DEG C of temperature lower calcinations.Coat silver paste as current collection fluid layer in electrode surface, with filamentary silver be
Wire, makes Symmetrical cells.Carry out ac impedance measurement with Symmetrical cells, obtain the pole under different hydrogen dividing potential drops under the conditions of 800 DEG C
Change resistance, as shown in Figure 4.Increase with hydrogen dividing potential drop, polarization resistance reduces continuous, in 80%H2/ 20%N2Under atmosphere, polarization
Resistance is 2.55 Ω cm2.With the increase of hydrogen dividing potential drop, FeVO4It is reduced generation FeV2O4Also 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 (5)
1. a kind of application of vanadate electrode material it is characterised in that：Described vanadate electrode material is used for as high-temp solid
Oxidate electrolytic cell cathode material；
The chemical formula of described vanadate electrode material is FeVO4；
Described vanadate electrode material can carry out reversible phase in version, and described reversible phase in version refers to：By described vanadic acid salt electrode
Material FeVO4Reduce under 700-750 DEG C of reducing atmosphere, generate by FeV2O4The reduzate constituting with Fe, will be described also original
After thing aoxidizes under 700-800 DEG C of oxidation environment, generate described vanadate electrode material FeVO again4；H in described reducing atmosphere2
Percentage by volume is 5%, balance of Ar；Described oxidation environment is in air atmosphere.
2. according to claim 1 application it is characterised in that：Described vanadate electrode material is with iron sesquioxide and five
V 2 O is raw material, is prepared by solid reaction process.
3. according to claim 1 and 2 application it is characterised in that：Described vanadate electrode material adopts solid state reaction
Method synthesizes, and concretely comprises the following steps：
A, weigh iron sesquioxide and vanadic anhydride according to stoichiometric proportion as reaction raw materials；
B, described reaction raw materials are loaded in the ball grinder of ball mill, ball grinder adds agate ball as abrasive media, so
Add acetone as ball milling dispersant afterwards, acetone adds to and covers 2/3rds of ball milling tank volume；
C, with 1000 revs/min of ball milling speed ball milling 15 minutes, make iron sesquioxide and vanadic anhydride mix homogeneously, obtain
Compound；
D, by compound be dried, tabletting, then at 750 DEG C calcine 10 hours, obtain calcining piece；
E, by described calcining piece pulverize in mortar, obtain final product vanadate electrode material FeVO4.
4. according to claim 3 application it is characterised in that：
Described in step d, drying is in air atmosphere, and 0.5～1.5h is dried at 150 DEG C.
5. according to claim 3 application it is characterised in that：
Tabletting described in step d be under 4MPa pressure by drying after compound be pressed into a diameter of 12～18mm, thickness be 1～3mm
Piece.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410452896.7A CN104328456B (en) | 2014-09-05 | 2014-09-05 | Reversible phase transition vanadate electrode material, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410452896.7A CN104328456B (en) | 2014-09-05 | 2014-09-05 | Reversible phase transition vanadate electrode material, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104328456A CN104328456A (en) | 2015-02-04 |
| CN104328456B true CN104328456B (en) | 2017-02-08 |
Family
ID=52403260
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410452896.7A Active CN104328456B (en) | 2014-09-05 | 2014-09-05 | Reversible phase transition vanadate electrode material, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104328456B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106011456B (en) * | 2016-08-02 | 2017-12-08 | 北京科技大学 | A kind of method that vanadium by Rock coal containing alum is enriched with and vanadium enrichment mutually regulates and controls |
| 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 |
| CN114481175B (en) * | 2022-01-25 | 2023-09-26 | 电子科技大学 | Repairable solid symmetrical electrolytic cell device based on strontium ferrite electrode catalytic layer |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4115110A (en) * | 1977-04-08 | 1978-09-19 | Earth Sciences, Inc. | Vanadium recovery process |
| CN101913651B (en) * | 2010-07-30 | 2011-12-21 | 北京工业大学 | Hydrothermal method for preparing triclinic-phase FeVO4 micro particles |
| CN102989467A (en) * | 2012-12-13 | 2013-03-27 | 中国科学院生态环境研究中心 | Titanium oxide supported ferric vanadate catalyst, as well as preparation method and use thereof |
| CN103183383A (en) * | 2011-12-28 | 2013-07-03 | 吉林师范大学 | Method for preparing LiV2O5 |
-
2014
- 2014-09-05 CN CN201410452896.7A patent/CN104328456B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4115110A (en) * | 1977-04-08 | 1978-09-19 | Earth Sciences, Inc. | Vanadium recovery process |
| CN101913651B (en) * | 2010-07-30 | 2011-12-21 | 北京工业大学 | Hydrothermal method for preparing triclinic-phase FeVO4 micro particles |
| CN103183383A (en) * | 2011-12-28 | 2013-07-03 | 吉林师范大学 | Method for preparing LiV2O5 |
| CN102989467A (en) * | 2012-12-13 | 2013-03-27 | 中国科学院生态环境研究中心 | Titanium oxide supported ferric vanadate catalyst, as well as preparation method and use thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Study on conductivity and redox stability of iron orthovanadate";Peter I. Cowin 等，;《Materials Chemistry and Physics》;20110201;第126卷(第3期);第614页摘要、第2.1节，第615页第3.1节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104328456A (en) | 2015-02-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104916850A (en) | Solid oxide fuel cell cathode material and solid oxide fuel cell composite cathode material and preparation method thereof and cell composite cathode preparation method | |
| CN104328456B (en) | Reversible phase transition vanadate electrode material, and preparation method and application thereof | |
| CN108649235A (en) | A kind of A laminated perovskite type electrode material and preparation method thereof | |
| CN108927165A (en) | A kind of perovskite structure electrode catalytic materials and its preparation method and application of lanthanum/nickel doping strontium iron molybdenum oxygen | |
| Tongyun et al. | NdFeO3 as anode material for S/O2 solid oxide fuel cells | |
| CN110451489A (en) | A kind of cobalt nitride is embedded in porous nitrogen-doped graphene material and preparation method and application | |
| CN111244470A (en) | Nano composite cathode and preparation and application thereof | |
| CN103224394A (en) | Lithium carbonate modified cerium barium zirconate proton conductor material and preparation method thereof | |
| Gao et al. | Voltage-driven reduction method to optimize in-situ exsolution of Fe nanoparticles at Sr2Fe1. 5+ xMo0. 5O6-δ interface | |
| CN101307461A (en) | Method for preparing YSZ-LSM oxygen electrode powder of solid oxidate electrolytic cell | |
| Chen et al. | A vanadium-doped La0. 5Sr0. 5FeO3-δ perovskite as a promising anode of direct carbon solid oxide fuel cells for brown coal utilization | |
| CN104051721A (en) | Preparation method and use of modified carbon black-LaMnO3 covalent composite material | |
| CN104342716B (en) | A kind of high-temperature solid oxide cathode of electrolytic tank material and preparation method thereof | |
| CN111326751B (en) | Aluminum-air battery and preparation method thereof | |
| Xi et al. | Fabrication and evaluation of Sm0. 5Sr0. 5CoO3− δ impregnated PrBaCo2O5+ δ composite cathode for proton conducting SOFCs | |
| JP6625855B2 (en) | Cell for steam electrolysis and method for producing the same | |
| CN105130426B (en) | Stable SOFC perovskite anode materials of a kind of high temeperature chemistry and preparation method thereof | |
| CN103236550B (en) | Graphene-modified nickel-base composite anode material of solid oxide fuel cell and preparation method thereof | |
| CN102867966A (en) | Porous micro-sphere post-spinel nitride calcium manganese oxygen compound, and preparation of and application thereof | |
| Ding et al. | Low-temperature protonic ceramic membrane fuel cells (PCMFCs) with SrCo0. 9Sb0. 1O3− δ cubic perovskite cathode | |
| JP6625856B2 (en) | Steam electrolysis cell | |
| Xu et al. | Compositional engineering of perovskite oxide BaCo 0.5 Fe 0.5 O 3− δ as an efficient bifunctional electrocatalyst for rechargeable zinc–air batteries | |
| KR20080003479A (en) | The processing method of co-synthesis nanosized lsm-ysz composites with enhanced electrochanmical property for solid oxide fuel cell, and the nanosized lsm-ysz composites synthesized by the above processing method | |
| Chen et al. | High-Performance La0. 9Sr0. 1Ga0. 8Mg0. 2O3-δ Electrolyte-Based Direct Raw Brown Coal Fuel Cells | |
| Yang et al. | Spatially confined catalysis-enhanced high-temperature carbon dioxide electrolysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |