CN102942364A - Zinc oxide-carbonate co-doped cerium barium zirconate proton conductor material and preparation method thereof - Google Patents
Zinc oxide-carbonate co-doped cerium barium zirconate proton conductor material and preparation method thereof Download PDFInfo
- Publication number
- CN102942364A CN102942364A CN2012104332524A CN201210433252A CN102942364A CN 102942364 A CN102942364 A CN 102942364A CN 2012104332524 A CN2012104332524 A CN 2012104332524A CN 201210433252 A CN201210433252 A CN 201210433252A CN 102942364 A CN102942364 A CN 102942364A
- Authority
- CN
- China
- Prior art keywords
- carbonate
- proton conductor
- mole
- conductor material
- barium zirconate
- 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.)
- Pending
Links
Images
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
- Y02E60/50—Fuel cells
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Fuel Cell (AREA)
Abstract
The invention relates to a zinc oxide-carbonate co-doped cerium barium zirconate proton conductor material and a preparation method thereof, belonging to the field of solid oxide fuel cells. The method disclosed herein comprises the following steps: firstly synthesizing yttrium oxide-doped cerium barium zirconate proton conductor powder by solid phase method, then mixing with zinc oxide and carbonate or composite carbonate, conducting dry pressing and isostatic compaction, then conducting high temperature burying sintering to obtain the zinc oxide-carbonate co-doped cerium barium zirconate proton conductor material. An anode-supported electrolyte part is prepared by lamination co-press technology, then a Ba0.5Sr0.5Co0.8Fe0.2O2.9 cathode slurry is coated on one side of the electrolyte, and an anode-supported unit cell is assembled to test. According to the invention, the invention provides a preparation method of a medium and low temperature solid oxide fuel cell electrolyte material, has the characteristics of low cost of raw materials and preparation and simple process, on the premise that the conductivity of the material is guaranteed at medium and low temperature, the material has good chemical stability, the unit cell has good output performance, and the method lays a foundation for developing solid oxide fuel cells.
Description
Technical field
The invention belongs to the Solid Oxide Fuel Cell technical field, relate to zinc oxide-carbonate codoped cerium barium zirconate proton conductor material and preparation method thereof.
Background technology
Solid Oxide Fuel Cell (SOFC) is as a kind of novel power generation device, with its high-level efficiency, pollution-free, structure of whole solid state with to the characteristics such as extensive adaptability of pluralities of fuel gas, obtained in recent years common concern.Ionogen is one of parts of most critical in the SOFC system, and electrolytical performance quality is directly determining performance and the life-span of SOFC.The ionogen of traditional SOFC is take oxonium ion as main transmission mechanism, and Typical Representative is Y
2O
3Stablize ZrO
2(YSZ).But its too high working temperature (above 800 ℃) has been brought the problems such as the matching, job stability, cost of manufacture of sealing, material.The eighties in 20th century Japan scientist Iwahara(Iwahara H, Esaka T, Uchida H, Maeda N (1981) Solid State Ionics 3-4:359～363) find that some perovskite-type compounds have high proton conductive 450 to 600 ℃ of conditions, the researchist has done many research to it both at home and abroad.Compare with the SOFC of traditional oxygen ion conduction, the SOFC of protonically conducting electrolyte has many advantages: the conductivity temperature influence of (1) proton conductor is little, has potential higher specific conductivity under middle temperature or low temperature.(2) fuel is difficult for being diluted.In battery operated process, water is to produce in the negative electrode interval, and produces at the fuel end unlike oxygen ion conductor.(3) proton itself is less than positively charged ion, so its migration activation energy is relatively less, uses more favourable under middle low temperature.This is wherein especially with the BaCeO of Yttrium oxide doping
3And BaZrO
3, caused people's concern with its good performance.BaZrO
3Stable chemical nature, mechanical property is superior, but its preparation difficulty, 1700 ℃ of sintering temperatures high (〉), soaking time long (〉 6 hours) and (Fumitada Iguchi, et al (2009) Solid State Ionics 180:563～568; F.Iguchi, et al (2009) The Electrochemical Society 25:1759～1766), and the crystal boundary specific conductivity is lower; BaCeO
3Have good specific conductivity, but BaCeO
3Electronic conductance and ionic conductance are also large, and the proton shifting number is low, and chemical stability is relatively poor, at CO
2Easily react in the atmosphere and generate CeO
2With corresponding carbonic acid thing, thereby cause the decline of specific conductivity, reduce the work-ing life of fuel cell, perhaps the atmosphere in combustion gas purity and the reaction process is had relatively high expectations, thereby cause higher use cost and maintenance cost.Relatively poor chemical stability is restriction BaCeO
3As the electrolytical principal element of proton.For independent BaCeO
3And BaZrO
3, as if high proton electroconductibility and high stability are difficult to satisfactory to both parties.The unlimited solid solution BaCe that the two combines
1-xZr
xO
3-δJust become the object of people's broad research, but still existed sintering temperature too high, the high proton electricity is led with high stability and is difficult to the problems such as compatible.
ZnO is as a kind of effective sintering aid, in preparation cerium barium zirconate material, be widely used (Peter Babilo, etal (2005) J.Am.Ceram.Soc., 88[9]: 2362～2368; Cuijuan Zhang, et al (2009) Int.J.HydrogenEnergy, 34:2739～2746).In order further to improve the conductivity of zirconium cerium acid barium material, this seminar had proposed development zirconium cerium acid barium-inorganic salt compound electrolyte material, and had applied for Patents (CN 101037331A, CN102180667A, CN 102515750A).In this class matrix material, except using ZnO as the sintering aid, a large amount of all kinds of inorganic salt with proton conductive have also been added, by microstructure design and control, make inorganic salt be uniformly distributed in crystal boundary, improve the crystal boundary specific conductivity, solved the restriction of crystal to material electric conductivity, improved the total conductivity of material.But materials causes the problems such as material density reduction owing to can occur the inorganic salt volatilization during high temperature sintering, causes its application of putting into production certain difficulty can occur.
Summary of the invention
Content of the present invention is to prepare Yttrium oxide doping cerium barium zirconate proton conductor powder by solid-phase synthesis, the common a small amount of zinc oxide and a small amount of carbonate or compound carbonate of adding is as sintering aid, utilize carbonate more than certain temperature, to change liquid phase into, by liquid phase sintering mechanism to reduce sintering temperature, take dry-pressing and isostatic pressing, prepare zinc oxide-carbonate codoped cerium barium zirconate proton conductor material through sintering again, purpose be to provide a kind of preparation technology simple, with low cost, to CO
2Or H
2The novel proton conductor material of the SOFC of good output performance is stablized and had to O atmosphere.
Zinc oxide among the present invention-carbonate codoped cerium barium zirconate proton conductor material and preparation method thereof, concrete technical scheme is as follows:
Zinc oxide-carbonate codoped cerium barium zirconate proton conductor material and preparation method thereof, its feature is as follows:
Cerium barium zirconate (BaCe with 10% mole of Yttrium oxide doping
0.8-xZr
xY
0.2O
3-δ1:1≤Ce/Zr≤7:1, i.e. 0.1≤x≤0.4) is matrix (hereinafter to be referred as matrix), then adds 1～6% mole of ZnO and 0.5～3% mole of carbonate or compound carbonate, obtain zinc oxide-carbonate codoped cerium barium zirconate proton conductor material (hereinafter to be referred as proton conductor material).Wherein ZnO and carbonate or compound carbonate play the effect that reduces sintering temperature jointly as sintering aid; The existence of trace carbonate residue in the situation that substantially do not change material electroconductibility, can also improve the anti-CO of material simultaneously
2Or H
2O stability.
Described carbonate or compound carbonate are yellow soda ash or Quilonum Retard or salt of wormwood or its combination; The Ce:Zr mol ratio is 1:1～7:1 in the described cerium barium zirconate.
Add a small amount of ZnO and a small amount of carbonate or compound carbonate among the present invention jointly as sintering aid, particularly utilize carbonate more than certain temperature, to change liquid phase into, by liquid phase sintering mechanism, play the effect that reduces sintering temperature.A small amount of carbonate or compound carbonate are after acceleration of sintering, because of its at high temperature partly volatilization, only remaining a small amount of carbonate.The existence of these a small amount of carbonate residues in the situation that substantially do not change the material proton conductive, can also improve the anti-CO of material
2Or H
2The stability of O.The anode-supported elementary cell of assembling has good output characteristic take proton conductor material as ionogen.
Zinc oxide of the present invention-carbonate codoped cerium barium zirconate proton conductor material is prepared by two-step approach.
The first step is with BaCO
3, CeO
2, ZrO
2And Y
2O
3Be raw material, according to BaCO
3: (CeO
2+ ZrO
2): Y
2O
3Be 1:0.8:0.1 molar ratio batching (1:1≤CeO wherein
2: ZrO
2≤ 7:1), and then mixed 8 hours take dehydrated alcohol as the medium ball milling, drying, obtained the cerium barium zirconate matrix powder (hereinafter to be referred as matrix powder) of 10% mole of Yttrium oxide doping in 7～15 hours 1200～1320 ℃ of calcinings after grinding, sieving;
Second step take 1 mole of matrix powder as benchmark, adds 0.01～0.06 mole of ZnO powder and 0.005～0.03 mole of carbonate or compound carbonate powder, above-mentioned raw materials is carried out ball milling mix, and drying, obtains the proton conductor powder after grinding, sieving.The proton conductor powder is put into mould, dry-pressing formed under 50～150MPa pressure, again through static pressure such as 150～300MPa; Subsequently with the green compact sample of gained in 1250～1350 ℃ of sintering 2～6 hours in air atmosphere, make zinc oxide-carbonate codoped cerium barium zirconate proton conductor material (hereinafter to be referred as proton conductor material).Heat-up rate is 2～5 ℃/minute during sintering, adopts the burning mode of burying, and soon base substrate carries out sintering among being embedded in the zinc oxide consistent with the base substrate composition-carbonate codoped cerium barium zirconate proton conductor powder.
For structure and the performance of estimating and characterize proton conductor material, the present invention has measured phase, microtexture, compactness, specific conductivity and the chemical stability etc. of electrolyte, and take proton conductor material as ionogen, take with nickel oxide-starch-proton conductor powder as anode, with Ba
0.5Sr
0.5Co
0.8Fe
0.2O
3-δ(BSCF) be negative electrode, its elementary cell that is assembled into anode-supported is tested.
Anode is 2 layers of composite structure, one deck is base layer, one deck is functional layer, the preparation method of anode-supported electrolyte part is: anode substrate layer adopts nickel oxide-starch-above-mentioned second step proton conductor powder (mass ratio 4:1:6), and anode functional layer adopts nickel oxide-above-mentioned second step proton conductor powder (mass ratio 4:6).Adopt lamination to press altogether technology, it is that the 15mm mould carries out dry-pressing formed that the matrix powder of anode substrate layer powder, anode functional layer powder and a small amount of above-mentioned second step preparation steadily, slowly, is evenly put into diameter successively, pressure is 50～150MPa, again through static pressure such as 150～250MPa; Subsequently with the green compact sample of gained in 1250～1350 ℃ of sintering 2～6 hours (burying burning) in air atmosphere, namely get the anode-supported electrolyte part.Heat-up rate is 2～5 ℃/minute during sintering, adopts the burning mode of burying, and soon base substrate carries out sintering among being embedded in the zinc oxide consistent with electrolyte ingredient-carbonate codoped cerium barium zirconate proton conductor powder.
Cathode powder BSCF adopts the preparation of EDTA-combined citric acid complexometry: with Ba (NO
3)
2, Sr (NO
3)
2, Co (NO
3)
36H
2O, Fe (NO
3)
39H
2O is raw material, and according to stoichiometric, raw material heated while stirring is dissolved in EDTA-NH
3H
2In the O aqueous solution, the mol ratio of EDTA, citric acid and all metal ions is 1:1.5:1, between regulator solution pH value to 7～8.To obtain precursor powder behind the water evaporate to dryness, this precursor powder is heated to certain temperature and just can spontaneous combustion occurs and become the black powder, then 250 ℃ of pre-burnings 5 hours in air, and 1000 ℃ of calcinings made the BSCF cathode powder in 10 hours in air again.Cathode slurry is carried out mixed grinding by BSCF powder, Terpineol 350, ethyl cellulose according to mass ratio 50:50:5 and is made.
In the manual BSCF cathode slurry that evenly applies of anode-supported electrolyte part ionogen one side, insulation is 2 hours in 1000 ℃ of air, and making anode-supported zinc oxide-carbonate codoped cerium barium zirconate proton conductor is electrolytical elementary cell (hereinafter to be referred as elementary cell).
It is matrix that the present invention adopts Yttrium oxide doping cerium barium zirconate, the common a small amount of ZnO and a small amount of carbonate or compound carbonate of introducing is as sintering aid, more than certain temperature, carbonate forms liquid phase, and the present invention utilizes liquid phase sintering mechanism to promote the sintering of electrolyte.A small amount of carbonate or compound carbonate after acceleration of sintering, because of its at high temperature part volatilization, can residual a small amount of carbonate, the existence of a small amount of residual carbon hydrochlorate in the situation that substantially do not change material electroconductibility, can also effectively improve the anti-CO of proton conductor material
2Or H
2The chemical stability of O makes material have good proton conductive and good chemical stability concurrently.
The present invention be easy to get from the market, cheap raw material sets out, the preparation method is simple, and is with low cost.The present invention has prepared zinc oxide with good chemical stability and proton conductive-carbonate codoped cerium barium zirconate proton conductor material, and the specific conductivity expection under medium and low temperature of this material can reach 10
-2Siemens/cm is for the exploitation Solid Oxide Fuel Cell is laid a good foundation.Has wide market application foreground.
Description of drawings
Pass into CO among Fig. 1: the embodiment 1
2The independent X that adds zinc oxide (a) and add zinc oxide+carbonate (b) sample-ray diffraction collection of illustrative plates after the atmosphere.
The scanning electronic microscope of proton conductor material section (SEM) photo behind the sintering among Fig. 2: the embodiment 2.
The SEM photo that an independent interpolation zinc oxide proton conductor material (a) and interpolation zinc oxide+carbonate proton conductor material (b) were processed in 100 ℃ of boiling water after 10 hours among Fig. 3: the embodiment 2 compares.
Do not add and add Na among Fig. 4: the embodiment 2
2CO
3After the specific conductivity curve of proton conductor material.
Specific embodiments
Embodiment 1
According to BaCe
0.4Zr
0.4Y
0.2O
2.9Stoichiometric ratio, get 1 mole of BaCO
3, 0.4 mole of CeO
2, 0.4 mole of ZrO
2, 0.1 mole of Y
2O
3, mixed 8 hours take dehydrated alcohol as the medium ball milling, drying, grind, sieve, obtained the cerium barium zirconate matrix powder of 10% mole of Yttrium oxide doping in 10 hours 1320 ℃ of calcinings.Then in 1 mole of matrix powder, add 0.06 mole of ZnO and 0.02 mole of K
2CO
3, ball milling mixed 6 hours, drying, grind, sieve after, carry out the mixed powder mould of packing into dry-pressing formed, pressure is 50MPa, passes through the static pressure such as 200MPa again; Base substrate adopts and buries burning mode sintering in 1350 ℃ of air, and 5 ℃/minute of temperature rise rates are incubated 5 hours, then naturally cool to room temperature, make BaCe
0.4Zr
0.4Y
0.2O
2.9-ZnO-K
2CO
3Proton conductor material.This proton conductor material is put into 100 ℃ of boiling water processed 10 hours, it is stable that its structure still keeps.This proton conductor material is put into carbon dioxide atmosphere be warming up to 1000 ℃ and be incubated 2 hours, X-ray diffraction analysis (Fig. 1) shows, only adds separately the proton conductor material of zinc oxide at CO
2After processing in the atmosphere, occurred impurity peaks in the structure, CO has been described
2With electrolyte reaction has occured, this material less stable; And the proton conductor material that adds zinc oxide+carbonate is passing through CO
2After the atmosphere, the crystalline structure of material does not change, and does not have impurity peaks to occur, and illustrates CO
2Stability better.Therefore, BaCe
0.4Zr
0.4Y
0.2O
2.9-ZnO-K
2CO
3The proton conductor aggregate performance goes out good anti-CO
2Or H
2The O chemical stability.
According to BaCe
0.5Zr
0.3Y
0.2O
2.9Stoichiometric ratio, take by weighing 1 mole of BaCO
3, 0.5 mole of CeO
2, 0.3 mole of ZrO
2, 0.1 mole of Y
2O
3, mixed 8 hours take dehydrated alcohol as the medium ball milling, then through super-dry, grind and sieve, obtained 10% mole of yttrium oxide doped with cerium barium zirconate matrix powder in 10 hours 1300 ℃ of lower calcinings.In 1 mole of matrix powder, add subsequently 0.04 mole of ZnO and 0.005 mole of Na
2CO
3, ball milling mixed 6 o'clock, again drying, grind, sieve, the mould of then mixed powder being packed into carries out dry-pressing formed, pressure is 100MPa, passes through the static pressure such as 200MPa again; Base substrate adopts and buries burning mode sintering in 1320 ℃ of air, and 2 ℃/minute of temperature rise rates are incubated 2 hours, then naturally cool to room temperature, make BaCe
0.5Zr
0.3Y
0.2O
2.9-ZnO-Na
2CO
3Proton conductor material.Fig. 2 is the SEM photo of this proton conductor material section behind the sintering.This proton conductor material is put into carbon dioxide atmosphere be warming up to 1000 ℃ and be incubated 2 hours, X-x ray diffraction analysis x shows that its structure does not change.This proton conductor material is put into 100 ℃ of boiling water processed 10 hours, also still keep stable.Fig. 3 (a) is that the proton conductor material of only independent interpolation zinc oxide is processed the SEM photo after 10 hours in 100 ℃ of boiling water, and Fig. 3 (b) is that the proton conductor material of interpolation zinc oxide+carbonate is processed the SEM photo after 10 hours in 100 ℃ of boiling water.Compare as seen with undressed proton conductor material SEM photo (Fig. 2), the microstructure characteristic that only adds separately the proton conductor material of zinc oxide has occured comparatively significantly to change.And the proton conductor material that adds zinc oxide+carbonate remains unchanged substantially, and this material aggregate performance goes out good anti-CO
2Or H
2The O chemical stability.Fig. 4 is not for adding and add Na
2CO
3After the specific conductivity curve of proton conductor material, can find out and add a small amount of Na
2CO
3After, how many impacts are the specific conductivity of material be not subject to, and specific conductivity still reaches 7.68 * 10 in the time of 700 ℃
-3S/cm adds Na
2CO
3Rear proton conductor material still shows good chemical property.
According to BaCe
0.6Zr
0.2Y
0.2O
2.9Stoichiometric ratio, take by weighing 1 mole of BaCO
3, 0.6 mole of CeO
2, 0.2 mole of ZrO
2, 0.1 mole of Y
2O
3, mixed 8 hours take dehydrated alcohol as the medium ball milling, through super-dry, grind and sieve, obtained the cerium barium zirconate matrix powder of 10% mole of Yttrium oxide doping in 15 hours 1250 ℃ of calcinings.Then in 1 mole of matrix powder, add 0.01 mole of ZnO and 0.03 mole of Li
2CO
3, ball milling mixed 5 hours, again drying, grind, sieve, carry out the mixed powder mould of packing into dry-pressing formed, pressure is 50MPa, passes through the static pressure such as 250MPa again; Base substrate adopts and buries burning mode sintering in 1300 ℃ of air, and 1 ℃/minute of temperature rise rate is incubated 6 hours, then naturally cools to room temperature, makes BaCe
0.6Zr
0.2Y
0.2O
2.9-ZnO-Li
2CO
3Proton conductor material.This proton conductor material is put into carbon dioxide atmosphere be warming up to 1000 ℃ and be incubated 2 hours, X-ray diffraction the analysis showed that its structure does not change.This proton conductor material is put into 100 ℃ of boiling water processed 10 hours, also still keep stable.This proton conductor material aggregate performance goes out good anti-CO
2Or H
2The O chemical stability, specific conductivity can reach 9.24 * 10 in the time of 700 ℃
-3S/cm, chemical property is good.
Embodiment 4
According to BaCe
0.55Zr
0.25Y
0.2O
2.9Stoichiometric ratio, get 1 mole of BaCO
3, 0.55 mole of CeO
2, 0.25 mole of ZrO
2, 0.1 mole of Y
2O
3, mixed 8 hours take dehydrated alcohol as the medium ball milling, drying, grind, sieve, obtained the cerium barium zirconate matrix powder of 10% mole of Yttrium oxide doping in 10 hours 1270 ℃ of calcinings.Then in 1 mole of matrix powder, add 0.06 mole of ZnO and 0.02 mole of K
2CO
3, ball milling mixed 6 hours, again drying, grind, sieve.Carry out the mixed powder mould of packing into dry-pressing formed, pressure is 150MPa, passes through the static pressure such as 300MPa again; Base substrate adopts and buries burning mode sintering in 1270 ℃ of air, and 3 ℃/minute of temperature rise rates are incubated 3 hours, then naturally cool to room temperature, obtain having the BaCe of superperformance
0.55Zr
0.25Y
0.2O
2.9-ZnO-K
2CO
3Proton conductor material.This proton conductor material is put into carbon dioxide atmosphere be warming up to 1000 ℃ and be incubated 2 hours, X-x ray diffraction analysis x shows that its structure does not change.This proton conductor material is put into 100 ℃ of boiling water processed 10 hours, also still keep stable.This proton conductor material aggregate performance goes out good anti-CO
2Or H
2The O chemical stability, specific conductivity is 8.56 * 10 in the time of 700 ℃
-3S/cm.
According to BaCe
0.7Zr
0.1Y
0.2O
2.9Stoichiometric ratio, get 1 mole of BaCO
3, 0.7 mole of CeO
2, 0.1 mole of ZrO
2, 0.1 mole of Y
2O
3, mixed 8 hours take dehydrated alcohol as the medium ball milling, drying, grind, sieve, obtained the cerium barium zirconate matrix powder of 10% mole of Yttrium oxide doping in 10 hours 1200 ℃ of calcinings.Then in 1 mole of matrix powder, add 0.04 mole of ZnO and 0.005 mole of Li
2CO
3, ball milling mixed 6 hours, again drying, grind, sieve after, carry out the mixed powder mould of packing into dry-pressing formed, pressure is 50MPa, passes through the static pressure such as 150MPa again; Base substrate adopts and buries burning mode sintering in 1250 ℃ of air, and 2 ℃/minute of temperature rise rates are incubated 4 hours, then naturally cool to room temperature, make the BaCe with superperformance
0.7Zr
0.1Y
0.2O
2.9-ZnO-Li
2CO
3Proton conductor material.This proton conductor material is put into carbon dioxide atmosphere be warming up to 1000 ℃ and be incubated 2 hours, X-x ray diffraction analysis x shows that its structure does not change.This proton conductor material is put into 100 ℃ of boiling water processed 10 hours, also still keep stable.This proton conductor material aggregate performance goes out good anti-CO
2Or H
2The O chemical stability, specific conductivity reaches 10.13 * 10 in the time of 700 ℃
-3S/cm shows and adds Li
2CO
3After, the chemical property of proton conductor material obtains larger improvement.
Embodiment 6
According to BaCe
0.65Zr
0.15Y
0.2O
2.9Stoichiometric ratio, get 1 mole of BaCO
3, 0.65 mole of CeO
2, 0.15 mole of ZrO
2, 0.1 mole of Y
2O
3, mixed 8 hours take dehydrated alcohol as the medium ball milling, drying, grind, sieve, obtained the cerium barium zirconate matrix powder of 10% mole of Yttrium oxide doping in 7 hours 1250 ℃ of calcinings.Then in 1 mole of matrix powder, add 0.01 mole of ZnO and 0.03 mole of compound carbonate (0.015 mole of Li
2CO
3+ 0.015 mole of K
2CO
3), ball milling mixed 6 hours, again drying, grind, sieve, carry out the mixed powder mould of packing into dry-pressing formed, pressure is 100MPa, passes through the static pressure such as 200MPa again; Base substrate adopts and buries burning mode sintering in 1300 ℃ of air, and 2 ℃/minute of temperature rise rates are incubated 3 hours, then naturally cool to room temperature, make the BaCe with superperformance
0.65Zr
0.15Y
0.2O
2.9-ZnO-(Li
2CO
3-K
2CO
3) proton conductor material.This proton conductor material is put into carbon dioxide atmosphere be warming up to 1000 ℃ and be incubated 2 hours, X-x ray diffraction analysis x shows that its structure does not change.This proton conductor material is put into 100 ℃ of boiling water processed 10 hours, also still keep stable.This proton conductor material aggregate performance goes out good anti-CO
2Or H
2The O chemical stability, specific conductivity reaches 9.45 * 10 in the time of 700 ℃
-3S/cm shows that adding compound carbonate also can realize good chemical property.
Embodiment 7
According to BaCe
0.45Zr
0.35Y
0.2O
2.9Stoichiometric ratio, with 1 mole of BaCO
3, 0.45 mole of CeO
2, 0.35 mole of ZrO
2, 0.1 mole of Y
2O
3, mixed 8 hours take dehydrated alcohol as the medium ball milling, drying, grind, sieve, obtained the cerium barium zirconate matrix powder of 10% mole of Yttrium oxide doping in 12 hours 1300 ℃ of calcinings.Then in 1 mole of matrix powder, add 0.05 mole of ZnO and 0.01 mole of compound carbonate (0.005 mole of Li
2CO
3+ 0.005 mole of Na
2CO
3), ball milling mixed 6 hours, again drying, grind, sieve after, carry out the mixed powder mould of packing into dry-pressing formed, pressure is 50MPa, passes through the static pressure such as 250MPa again; Base substrate adopts and buries burning mode sintering in 1300 ℃ of air, and 3 ℃/minute of temperature rise rates are incubated 3 hours, then naturally cool to room temperature, make the BaCe with superperformance
0.45Zr
0.35Y
0.2O
2.9-ZnO-(Li
2CO
3-Na
2CO
3) proton conductor material.This proton conductor material is put into carbon dioxide atmosphere be warming up to 1000 ℃ and be incubated 2 hours, X-x ray diffraction analysis x shows that its structure does not change.This proton conductor material is put into 100 ℃ of boiling water processed 10 hours, also still keep stable.This proton conductor material aggregate performance goes out good anti-CO
2Or H
2The O chemical stability, specific conductivity is 7.41 * 10 in the time of 700 ℃
-3S/cm.
Application Example 1
With BaCe
0.5Zr
0.3Y
0.2O
2.9-ZnO-Na
2CO
3Proton conductor material is ionogen, prepares the electrolyte part green compact of anode-supported by preceding method, adopts and buries the burning mode at 1320 ℃ of sintering in air, 2 ℃/minute of temperature rise rates, be incubated 2 hours, then naturally cool to room temperature, obtain the electrolyte part of anode-supported.The electrolyte part of this anode-supported is evenly applied the BSCF cathode slurry by hand in ionogen one side, calcine in 1000 ℃ of air, 2 ℃/minute of temperature rise rates are incubated 2 hours, naturally cool to room temperature, obtain elementary cell.Resulting elementary cell is sealed on the self-control battery testing test tube with the silver slurry, filamentary silver is drawn as collector in two ends, is warming up to 400～700 ℃, and anode passes into hydrogen, negative pole blasts air, and (CHI660C) tests battery performance with electrochemical workstation.In the time of 500,600,700 ℃, the open circuit voltage of battery is respectively 1.094V, 1.072V, 1.014V, and peak power output density is respectively 102mWcm
-2, 189mWcm
-2, 302mWcm
-2
Application Example 2
With BaCe
0.65Zr
015Y
0.2O
2.9-ZnO-Na
2CO
3Proton conductor material is ionogen, adopts and Application Example 1 identical method and process, obtains elementary cell and carries out electrochemical property test.In the time of 500,600,700 ℃, the open circuit voltage of battery is respectively 1.087V, 1.066V, 1.011V, and peak power output density is respectively 161mWcm
-2, 261mWcm
-2, 405mWcm
-2
Application Example 3
With BaCe
0.7Zr
0.1Y
0.2O
2.9-ZnO-Li
2CO
3Proton conductor material is ionogen, adopts and Application Example 1 identical method and process, obtains elementary cell and carries out electrochemical property test.In the time of 500,600,700 ℃, the open circuit voltage of battery is respectively 1.087V, 1.066V, 1.01V, and peak power output density is respectively 201mWcm
-2, 309mWcm
-2, 509mWcm
-2
The zinc oxide that the present invention proposes-carbonate codoped cerium barium zirconate proton conductor material and preparation method, be described by embodiment, person skilled obviously can be changed or suitably change and combination content as herein described within not breaking away from content of the present invention, spirit and scope, realizes the present invention.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are deemed to be included in spirit of the present invention, scope and the content.
Claims (3)
1. zinc oxide-carbonate codoped cerium barium zirconate proton conductor material is characterized in that: with the cerium barium zirconate (BaCe of 10% mole of Yttrium oxide doping
0.8-xZr
xY
0.2O
3-δ, 1≤Ce/Zr≤7, i.e. 0.1≤x≤0.4) and be matrix, then add 1～6% mole of ZnO and 0.5～3% mole of carbonate or compound carbonate, obtain zinc oxide-carbonate codoped cerium barium zirconate proton conductor material.
2. the preparation method of zinc oxide as claimed in claim 1-carbonate codoped cerium barium zirconate proton conductor material is characterized in that, step is as follows:
1) with BaCO
3, CeO
2, ZrO
2And Y
2O
3Be raw material, according to BaCO
3: (CeO
2+ ZrO
2): Y
2O
3Be 1:0.8:0.1 molar ratio batching, wherein CeO
2: ZrO
2=1～7; Mixed 8 hours take dehydrated alcohol as the medium ball milling, drying, grind, sieve after, obtained the cerium barium zirconate matrix powder of 10% mole of Yttrium oxide doping in 7～15 hours 1200～1320 ℃ of calcinings;
2) take 1 mole of matrix powder as benchmark, add 0.01～0.06 mole of ZnO and 0.005～0.03 mole of carbonate or compound carbonate, after ball milling mixes, drying, grinding, sieving obtains the proton conductor powder, this powder is put into mould, dry-pressing formed under 50～150MPa pressure, again through static pressure such as 150～300MPa; Subsequently with the green compact sample of gained in 1250～1350 ℃ of sintering 2～6 hours in air atmosphere, make zinc oxide-carbonate codoped cerium barium zirconate proton conductor material.
3. conductor material as claimed in claim 2, it is characterized in that: described carbonate is yellow soda ash or Quilonum Retard or salt of wormwood or its combination.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104332524A CN102942364A (en) | 2012-11-02 | 2012-11-02 | Zinc oxide-carbonate co-doped cerium barium zirconate proton conductor material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104332524A CN102942364A (en) | 2012-11-02 | 2012-11-02 | Zinc oxide-carbonate co-doped cerium barium zirconate proton conductor material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102942364A true CN102942364A (en) | 2013-02-27 |
Family
ID=47725385
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012104332524A Pending CN102942364A (en) | 2012-11-02 | 2012-11-02 | Zinc oxide-carbonate co-doped cerium barium zirconate proton conductor material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102942364A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224394A (en) * | 2013-04-19 | 2013-07-31 | 天津大学 | Lithium carbonate modified cerium barium zirconate proton conductor material and preparation method thereof |
| CN105552415A (en) * | 2015-12-28 | 2016-05-04 | 哈尔滨工业大学 | Preparation method for rear-earth zirconate/carbonate composite electrolyte powder |
| CN106915772A (en) * | 2017-04-09 | 2017-07-04 | 桂林理工大学 | A kind of molybdate and preparation method thereof |
| CN106915775A (en) * | 2017-04-09 | 2017-07-04 | 桂林理工大学 | A kind of orthorhombic system tungstates and preparation method thereof |
| CN107230795A (en) * | 2017-05-23 | 2017-10-03 | 福州大学 | A kind of intermediate temperature solid oxide fuel cell electrolyte for possessing proton conductivity |
| CN109742430A (en) * | 2018-12-17 | 2019-05-10 | 南京晓庄学院 | It is a kind of based on barium stannate/zinc oxide composite low-temperature solid oxide fuel cell |
| CN109802162A (en) * | 2018-12-28 | 2019-05-24 | 南京晓庄学院 | Low-temperature solid oxide fuel cell based on zinc oxide-stannous oxide composite material |
| CN110707346A (en) * | 2019-08-27 | 2020-01-17 | 广东工业大学 | Double-doped BaCeO3Matrix conduction electrolyte material, preparation and application |
| CN111261916A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Thin-film proton conductor electrolyte and preparation method thereof |
| CN113773076A (en) * | 2021-09-26 | 2021-12-10 | 苏州正义新能源科技有限公司 | Fuel cell electrolyte membrane with low sintering temperature and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531587A (en) * | 2012-01-06 | 2012-07-04 | 天津大学 | Yttrium-doped barium zirconate-cerate/inorganic salt complex phase-structured proton conductor material and preparation method thereof |
-
2012
- 2012-11-02 CN CN2012104332524A patent/CN102942364A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531587A (en) * | 2012-01-06 | 2012-07-04 | 天津大学 | Yttrium-doped barium zirconate-cerate/inorganic salt complex phase-structured proton conductor material and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 20100418 Youmin Guo et al. Optimizing the modification method of zinc-enhanced sintering of BaZr0.4Ce0.4Y0.2O3-delta based electrolytes for application in an anode-supported protonic solid oxide fuel cell 第5611-5620页 1－3 第35卷, * |
| 《J Mater Sci》 20110224 Ming Zhang et al. Proton conduction in BaxCe0.8Y0.2O3-alpha + 0.04ZnO at intermediate temperatures and its application in ammonia synthesis at atmospheric pressure 第4690－4694页 1－3 第46卷, * |
| MING ZHANG ET AL.: "Proton conduction in BaxCe0.8Y0.2O3-α + 0.04ZnO at intermediate temperatures and its application in ammonia synthesis at atmospheric pressure", 《J MATER SCI》 * |
| YOUMIN GUO ET AL.: "Optimizing the modification method of zinc-enhanced sintering of BaZr0.4Ce0.4Y0.2O3-δ based electrolytes for application in an anode-supported protonic solid oxide fuel cell", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224394A (en) * | 2013-04-19 | 2013-07-31 | 天津大学 | Lithium carbonate modified cerium barium zirconate proton conductor material and preparation method thereof |
| CN105552415A (en) * | 2015-12-28 | 2016-05-04 | 哈尔滨工业大学 | Preparation method for rear-earth zirconate/carbonate composite electrolyte powder |
| CN106915772A (en) * | 2017-04-09 | 2017-07-04 | 桂林理工大学 | A kind of molybdate and preparation method thereof |
| CN106915775A (en) * | 2017-04-09 | 2017-07-04 | 桂林理工大学 | A kind of orthorhombic system tungstates and preparation method thereof |
| CN107230795A (en) * | 2017-05-23 | 2017-10-03 | 福州大学 | A kind of intermediate temperature solid oxide fuel cell electrolyte for possessing proton conductivity |
| CN111261916A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Thin-film proton conductor electrolyte and preparation method thereof |
| CN111261916B (en) * | 2018-11-30 | 2021-12-07 | 中国科学院大连化学物理研究所 | Thin-film proton conductor electrolyte and preparation method thereof |
| CN109742430A (en) * | 2018-12-17 | 2019-05-10 | 南京晓庄学院 | It is a kind of based on barium stannate/zinc oxide composite low-temperature solid oxide fuel cell |
| CN109802162A (en) * | 2018-12-28 | 2019-05-24 | 南京晓庄学院 | Low-temperature solid oxide fuel cell based on zinc oxide-stannous oxide composite material |
| CN109802162B (en) * | 2018-12-28 | 2021-09-24 | 南京晓庄学院 | Low-temperature solid oxide fuel cell based on zinc oxide-stannous oxide composite material |
| CN110707346A (en) * | 2019-08-27 | 2020-01-17 | 广东工业大学 | Double-doped BaCeO3Matrix conduction electrolyte material, preparation and application |
| CN113773076A (en) * | 2021-09-26 | 2021-12-10 | 苏州正义新能源科技有限公司 | Fuel cell electrolyte membrane with low sintering temperature and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102942364A (en) | Zinc oxide-carbonate co-doped cerium barium zirconate proton conductor material and preparation method thereof | |
| Zhu et al. | Evaluation of SrSc0. 175Nb0. 025Co0. 8O3-δ perovskite as a cathode for proton-conducting solid oxide fuel cells: the possibility of in situ creating protonic conductivity and electrochemical performance | |
| Gao et al. | Infiltrated Pr2NiO4 as promising bi-electrode for symmetrical solid oxide fuel cells | |
| Huang et al. | Investigation of La2NiO4+ δ-based cathodes for SDC–carbonate composite electrolyte intermediate temperature fuel cells | |
| CN103682373B (en) | Non-cobalt intermediate temperature solid oxide fuel cell stablizes cathode material and application thereof | |
| CN104409742A (en) | BaCoO3-delta base B-position Bi2O3-Nb2O5 co-doped cathode material of solid oxide fuel cell, preparation method and applications thereof | |
| CN103208634A (en) | Composite cathode material for medium and low-temperature proton-conductive solid oxide fuel cells | |
| Guo et al. | A novel way to improve performance of proton-conducting solid-oxide fuel cells through enhanced chemical interaction of anode components | |
| CN108649235A (en) | A kind of A laminated perovskite type electrode material and preparation method thereof | |
| CN103531833A (en) | Proton conductor material in lithium/yttrium carbonate doped cerium barium zirconium complex phase structure | |
| CN112542591B (en) | Solid fuel cell and method for manufacturing the same | |
| CN100583516C (en) | A cathode material for A and B adulterated SrTiO3 solid oxide fuel battery | |
| CN103224394A (en) | Lithium carbonate modified cerium barium zirconate proton conductor material and preparation method thereof | |
| CN102842723A (en) | Intermediate temperature solid oxide fuel cell cathode material with perovskite structure and preparation method thereof | |
| Leng et al. | The effect of sintering aids on BaCe0· 7Zr0· 1Y0. 1Yb0. 1O3-δ as the electrolyte of proton-conducting solid oxide electrolysis cells | |
| Tao et al. | Pr Doped Barium Cerate as the Cathode Material for Proton‐Conducting SOFCs | |
| Devi et al. | Solid oxide fuel cell materials: a review | |
| Zhang et al. | Modification of electrocatalytic activity of BaCe0. 40Sm0. 20Fe0. 40O3− δ with Co3O4 as cathode for proton-conducting solid oxide fuel cell | |
| CN100459250C (en) | A lack phase adulated anode material for solid oxide fuel battery | |
| Yang et al. | Sr-substituted SmBa0. 75Ca0. 25CoFeO5+ δ as a cathode for intermediate-temperature solid oxide fuel cells | |
| CN102054991B (en) | Cathode material of solid oxide fuel cell and preparation method thereof | |
| CN101222059A (en) | B-position omission perovskite anode material used for solid-oxide fuel battery | |
| CN110423114A (en) | A kind of ceramic electrolyte material and preparation method thereof | |
| CN103107343A (en) | Medium and low temperature solid oxide fuel cell cathode material | |
| CN102544559B (en) | Cerium-oxide-based electrolyte for solid oxide fuel cell and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130227 |