CN100416904C - Technique for preparing perovskite type ionic conductor material composite doped by alkaline earth and transition metal - Google Patents

Technique for preparing perovskite type ionic conductor material composite doped by alkaline earth and transition metal Download PDF

Info

Publication number
CN100416904C
CN100416904C CNB200610016003XA CN200610016003A CN100416904C CN 100416904 C CN100416904 C CN 100416904C CN B200610016003X A CNB200610016003X A CN B200610016003XA CN 200610016003 A CN200610016003 A CN 200610016003A CN 100416904 C CN100416904 C CN 100416904C
Authority
CN
China
Prior art keywords
minutes
doped
transition metal
ionic conductor
conductor material
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.)
Expired - Fee Related
Application number
CNB200610016003XA
Other languages
Chinese (zh)
Other versions
CN1960046A (en
Inventor
赵捷
马叙
包俊成
王志奇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin University of Technology
Original Assignee
Tianjin University of Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tianjin University of Technology filed Critical Tianjin University of Technology
Priority to CNB200610016003XA priority Critical patent/CN100416904C/en
Publication of CN1960046A publication Critical patent/CN1960046A/en
Application granted granted Critical
Publication of CN100416904C publication Critical patent/CN100416904C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • Y02E60/50—Fuel cells

Landscapes

  • Fuel Cell (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The procedure for preparing material of ion conductor includes following steps: using oxides of Mg, Fe, Co, SrCO3 and analytical pure La2O3 and Ga2O3 as raw materials; through washing, filtering, drying and grinding to obtain original powder body with Mg, Sr, Fe, Co being doped in advance; isostatic pressing the powder body at room temperature; placing block material between die and porcelain plate to carry out sintering after ZrO2 powder with Ga2O3 being doped is put into furnace; finally, cooling in furnace. The prepared new type electrolyte material SOFC possesses advantages of low cost, favorable ionic conductivity, and low energy consumption. Composite-doped ionic conductor of lanthanum of gallic acid synthesized by the procedure restrains volatilization of Ga component and distortion of sample in sintering procedure effectively. Controlling heating up rate and heat preservation is in favor of forming single phase of perovskite, and raising density of sample.

Description

The preparation technology that alkaline earth and transition metal are perovskite type ionic conductor material composite doped
[technical field]
The present invention relates to solid electrolyte material, particularly a kind of alkaline earth and perovskite type ionic conductor material composite doped preparation technology of transition metal who is used for intermediate temperature solid oxide fuel cell.
[background technology]
Solid electrolyte is mainly used in Solid Oxide Fuel Cell (SOFC), transducer, electro-catalysis, film separation and membrane reactor etc., has broad application prospects in fields such as the energy, metallurgy, chemical industry and environmental protection.Wherein, SOFC is with its generating efficiency height, and is wide to fuel tolerance, do not have corrosion, full curing, and extremely low NOx and SOx, noise and dust emission etc. are called as green energy resource.
Traditional Solid Oxide Fuel Cell adopts the stable zirconia (YSZ) of the yttrium of fluorite structure as solid electrolyte, its working temperature must just can reach sufficiently high ionic conductivity about 1000 ℃, so high temperature will be down because electrolyte, electrode and the difference of the thermal coefficient of expansion that is connected storeroom and the chemical reaction between the interface will make the SOFC life-span reduce sharply.If can reduce to the SOFC working temperature below 800 ℃, its life-span is expected to prolong three times; Simultaneously, increase the fail safe of SOFC operation.At present, have higher ionic conductivity, stable solid electrolyte under the preparation of solid electrolyte and the research medium and low temperature, reduction SOFC working temperature etc. is the main field of present research-and-development activity.With LaGaO 3Be matrix, research doping composition and preparation technology are the focuses that people study concern.Current subject matter has the following aspects:
One, control dephasign.At first, element doping is the ABO of base with the lanthanum gallate 3Perovskite structure in preparation process, SrLaGa can occur 3O 7, SrLaGaO 4Deng dephasign, all can produce certain influence to structure, chemical stability and the conductivity of material.Secondly, because Ga 2O 3Volatilization, make doped lanthanum gallate A position and B position cation mol ratio nonstoichiometry ratio, impelled SrLaGaO 4The formation of dephasign.
Two, in the high-temperature sintering process, Ga 2O 3Decompose, Ga occurs 2O and O 2Volatilization or vaporization phenomenon.Because the effusion of gas makes sample expand, density reduces.
Three, the synthetic powder of sol-gel process is to use superfine powder, and purity requirement is very high, and the superfine powder of preparing is because surface energy is higher and easily form hard aggregation, and sintering character is relatively poor.
Four, some solid phase reactions fever circle temperature height, energy consumption is big, needs to grind repeatedly, and uniformity is relatively poor and be prone to dephasign.
[summary of the invention]
Purpose of the present invention is intended to for overcoming the deficiencies in the prior art, and a kind of alkaline earth and the perovskite type ionic conductor material composite doped preparation technology of transition metal are provided, and its raw material and preparation cost are cheap, and synthesis technique is simple, ionic conductivity is good, has also reduced energy consumption simultaneously.
The invention discloses the perovskite type ionic conductor material composite doped preparation technology of a kind of alkaline earth and transition metal, it is characterized in that obtaining by following steps:
(1) with the oxide of Mg, Fe, Co, SrCO 3, and analyze pure La 2O 3And Ga 2O 3Be raw material, be made into the metal ion mixture that meets stoichiometric proportion;
(2) add hydrogenperoxide steam generator, the final pH value of solution is adjusted to 7～8, and washing and filtering 80 ℃～100 ℃ dryings 120～240 minutes, grinds and evenly obtains the pre-original powder that mixes of Mg, Sr, Fe or Co;
(3) with above-mentioned alkaline-earth metal and the pre-original powder that mixes of transition metal, isostatic compaction under room temperature 180～220MPa kept 5～15 minutes, made the block materials of required form;
(4) above-mentioned block materials is placed between mould and the porcelain plate, in stove, puts into simultaneously and be mixed with Ga 2O 3ZrO 2Behind the powder, the beginning sintering; When sintering, programming rate is controlled at per minute and rises 2 ℃～8 ℃, wherein: when being warming up to 300 ℃～400 ℃, be incubated 30～60 minutes; When continuing to be warming up to 850 ℃～950 ℃ again, be incubated 30～60 minutes; Be warming up to 1350 ℃～1400 ℃ at last, be incubated 120～240 minutes, cool to room temperature then with the furnace, make the alkaline-earth metal that is used for intermediate temperature solid oxide fuel cell and transient metal doped perovskite structure ionic conductor material.
The invention has the beneficial effects as follows:
1, the novel electrolytes material of SOFC of the present invention has raw material and preparation cost is cheap, and synthesis technique is simple, and ionic conductivity is good, has also reduced energy consumption simultaneously.Adopt the fuel cell output performance of the composite mixed ionic conductor material of alkaline earth and transition metal good, reached the YSZ level at the electrical property of 800 ℃ of ion conductors, promptly output current density reaches 1.1.
2, preparation technology of the present invention is by adopting directly synthetic alkaline earth and the composite mixed lanthanum gallate ion conductor of transition metal.Can effectively suppress the volatilization of Ga component in the sintering process and the flexural deformation of sample, stop by the control heating rate and at low temperature (300 ℃～400 ℃) and high temperature (850 ℃～950 ℃) insulation simultaneously, help the formation of single perovskite phase and the density of raising sample.
[embodiment]
The present invention be directed to molecular structural formula is A mB 1-mC nD 1-nO kAlkaline-earth metal and the composite mixed perovskite oxide material of transition metal, wherein: A mBe selected from La and lanthanide series or their combination; A and B also represent to occupy perovskite oxide the A lattice-site element and be selected from Sr, Ca and Ba; C and D represent to occupy perovskite oxide the B lattice-site different elements and be selected from Mn, Mg, Co and Fe; The value of m is 0.7～1.0, and the value of n is 0.3～1.0, and the value of k is 2.5～3.2.Its preparation technology is characterized as:
The first step is raw material and analyzes pure La2O3 and Ga2O3 is a raw material with the oxide of analytically pure Mg, Fe, Co and SrCO3, is made into the metal ion mixture that meets stoichiometric proportion;
Second step added hydrogenperoxide steam generator, and the final pH value of solution is adjusted to 7～8, and washing and filtering 80 ℃～100 ℃ dryings 120～240 minutes, grinds and evenly obtains Mg, Sr, the pre-original powder that mixes of Fe (Co);
The 3rd step, above-mentioned alkaline-earth metal and the pre-original powder that mixes of transition metal are at room temperature made 180～220MPa isostatic compaction, kept 30～60 minutes, make the block materials of required form, wait to be sintered;
The 4th goes on foot, and above-mentioned block materials is placed between mould and the porcelain plate begin sintering, puts in stove simultaneously and is mixed with Ga 2O 3ZrO 2Powder, strict control heating rate (keeping 4 ℃～8 ℃/minute) when sintering.Rise to 300 ℃～400 ℃ insulations and stopped 30～60 minutes, continue to heat up, be incubated 30～60 minutes again at 850 ℃～950 ℃, be warming up to 1350 ℃～1400 ℃ at last, the size insulation is defined as 120～240 minutes per sample, after cool to room temperature with the furnace.
The phase transformation and the electrical conduction mechanism of lanthanum gallate structure after the present invention mixes: pure LaGaO 3Be rhombic system under the room temperature, GaO in the lattice 6Octahedron demonstrates tangible inclination, undergoes phase transition in the time of 150 ℃, changes rhombohedral system into by rhombic system.Sr and Mg mix to LaGaO 3The LaGaO that consists of LSGM of structure 3Be monoclinic system under the room temperature, twice phase transformation takes place between 250～1000 ℃, change monocline (false water chestnut face) crystallographic system into by monocline (false quadrature) crystallographic system between 250～500 ℃, change water chestnut face crystallographic system into by monocline (false water chestnut face) crystallographic system between 500～750 ℃.Because GaO in the lattice 6Octahedra inclination causes that the two structure all departs from desirable cubic perovskite structure.Doping makes GaO 6Octahedra gradient reduces, simultaneously, and along with the rising of temperature, GaO 6Octahedral gradient reduces.Trend towards desirable cubic perovskite structure.Sr at a low price, Mg is respectively to La 3+, Ga 3+After part replaces,, produce the oxygen room in order to keep the electric neutrality of system, according to Kroger-Vink defective representation, Sr=Sr ' La+1P2Vo.., Mg=Mg ' Ga+1P2Vo.., oxonium ion moves by the oxygen room, and therefore, suitable doping can improve the oxygen ionic conductivity of LaGaO3.
The factor that influences lanthanum gallate conductivity have following some: the first, the influence that alkaline-earth metal ions mixes to the lanthanum gallate conductivity mainly is reflected in the ionic radius aspect.Ga 3+Ionic radius less (62pm) does not produce dephasign in order to make the back compound that mixes, and the Ga case is selected the Mg with its ionic radius coupling 2+(72pm) comparatively suitable, La 3+(106pm) doping of case low price ion is the effective means that improves oxygen ionic conductivity.Oxonium ion must overcome certain activation energy in lattice, could pass through 2A+B " bottleneck " district, arrives the oxygen room.The second, GaO 6Octahedral gradient plays restrictive function to oxygen ions migrate, and octahedral gradient is high more, and oxygen ions migrate passage " bottle footpath " is more little, and migration is obstructed.According to the said structure analysis, make GaO owing to mix 6Octahedral gradient reduces, and crystal symmetry increases, and the oxygen ions migrate passage is unimpeded, thereby oxygen ions migrate activation energy is reduced, and conductivity increases.Along with the increase of doping, oxygen vacancy concentration increases, and conductivity increases, but doping surpasses to a certain degree, because reunite in the oxygen room, bunch close, simultaneously because the appearance of dephasign descends conductivity.Mix for the A case, because Sr 2+Radius is than La 3+Big slightly, so the doping effect is than Ca 2+Good, but radius is too big (as Ba 2+) dephasign appears easily when mixing, and the doping effect is followed successively by Sr＞Ba＞Ca.In very wide partial pressure of oxygen scope, has very high chemical stability.The 3rd, transition metal ions (T) is to the influence of the lanthanum gallate character of alkaline earth metal doping.By research the doping of Fe, Co, Ni, Cu, Mn is discovered, Fe, Co, Ni mix and effectively raise the ionic conductivity of LaGaO3, find that simultaneously electron conduction increases to some extent when replacing Ga with Fe or Cr, but ionic conduction occupying an leading position still, is mixed conductor at this moment.We studies show that sample still can keep good ionic conductivity under high keto sectional pressure after 15%Co mixes, when continuing to improve the content hybrid conductive rate height that Co mixes; After 20%Fe mixed, sample hybrid conductive rate height also can occur under low oxygen partial pressure, and the two is expected to become the novel SOFC of a class.The electrolyte that Fe and Co are mixed has highly stable and under very wide partial pressure of oxygen, ion guide Fe 3+(64pm), Co 3+(61pm), Ni 3+(60pm) ionic radius and Ga 3+Closely, make them at LaGaO 3Can stable existence in the lattice.Doping decreases battery open circuit voltage, and order is: not doping＞Fe＞＞Ni＞Co because, Fe 3+Than Co 3+And Ni 3+Stable, still, the back power density of mixing is significantly improved, and order is: Ni＞Co＞＞Fe＞do not mix.The doping of transition metal ions has improved the ionic conductivity of the lanthanum gallate solid electrolyte of alkaline earth metal doping effectively, and is simultaneously, also influential to the thermal coefficient of expansion of solid electrolyte; Increase along with Co content; The thermal coefficient of expansion of LSGMC increases fast, and Fe mixes to the almost not influence of the coefficient of expansion of LSGMF.
Embodiment 1: to La 0.2Sr 0.8Ga 0.2Mg 0.8Fe 0.5O 2.8Electrolyte, adopt above-mentioned prepared:
The first step: proportioning meets La: Sr: Ga: Mg: Fe=2: 8: 2: 8: 5;
Second step added hydrogenperoxide steam generator, and the final pH value of solution is adjusted to 7～8, and washing and filtering 80 ℃ of dryings 120 minutes, grinds the evenly pre-original powder that mixes;
The 3rd step, the second original powder that goes on foot the pre-doping that obtains is at room temperature made the 200MPa isostatic compaction, kept 60 minutes, make the block materials of required form, wait to be sintered;
The 4th goes on foot, and the 3rd step block materials is placed between mould and the porcelain plate begin sintering, puts in stove simultaneously and is mixed with Ga 2O 3ZrO 2Powder, heating rate keeps 4 ℃.Rise to 300 ℃ of insulations and stopped 60 minutes, continue to heat up, be incubated 60 minutes again, be warming up to 1400 ℃ at last, be defined as 120 minutes, cool to room temperature with the furnace at 950 ℃.
Embodiment 2: to La 0.2Sr 0.8Ga 0.18Mg 0.8Co 0.3O 2.8Electrolyte, adopt above-mentioned prepared:
The first step: proportioning meets La: Sr: Ga: Mg: Fe=2: 8: 18: 8: 3;
Second step added hydrogenperoxide steam generator, and the final pH value of solution is adjusted to 7～8, and washing and filtering 100 ℃ of dryings 150 minutes, grinds the evenly pre-original powder that mixes;
The 3rd step, the second original powder that goes on foot the pre-doping that obtains is at room temperature made the 180MPa isostatic compaction, kept 30 minutes, make the block materials of required form, wait to be sintered;
The 4th goes on foot, and the 3rd step block materials is placed between mould and the porcelain plate begin sintering, puts in stove simultaneously and is mixed with Ga 2O 3ZrO 2Powder, heating rate keeps 4 ℃.Rise to 300 ℃ of insulations and stopped 60 minutes, continue to heat up, be incubated 30 minutes again, be warming up to 1400 ℃ at last, be defined as 120 minutes, cool to room temperature with the furnace at 900 ℃.

Claims (1)

1. alkaline earth and the perovskite type ionic conductor material composite doped preparation technology of transition metal is characterized in that obtaining by following steps:
(1) with the oxide of Fe or Co, the oxide of Mg, SrCO 3And analyze pure La 2O 3And Ga 2O 3Be raw material, be made into the metal ion mixture that meets stoichiometric proportion;
(2) add hydrogenperoxide steam generator, the final pH value of solution is adjusted to 7～8, and washing and filtering 80 ℃～100 ℃ dryings 120～240 minutes, grinds and evenly obtains the pre-original powder that mixes of Fe or Co and Mg, Sr;
(3) with above-mentioned alkaline-earth metal and the pre-original powder that mixes of transition metal, isostatic compaction under room temperature 180～220MPa kept 30～60 minutes, made the block materials of required form;
(4) above-mentioned block materials is placed between mould and the porcelain plate, in stove, puts into simultaneously and be mixed with Ga 2O 3ZrO 2Behind the powder, the beginning sintering; When sintering, programming rate is controlled at per minute and rises 2 ℃～8 ℃, wherein: when being warming up to 300 ℃～400 ℃, be incubated 30～60 minutes; When continuing to be warming up to 850 ℃～950 ℃ again, be incubated 30～60 minutes; Be warming up to 1350 ℃～1400 ℃ at last, be incubated 120～240 minutes, cool to room temperature then with the furnace, make the alkaline-earth metal that is used for intermediate temperature solid oxide fuel cell and transient metal doped perovskite structure ionic conductor material.
CNB200610016003XA 2006-09-28 2006-09-28 Technique for preparing perovskite type ionic conductor material composite doped by alkaline earth and transition metal Expired - Fee Related CN100416904C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB200610016003XA CN100416904C (en) 2006-09-28 2006-09-28 Technique for preparing perovskite type ionic conductor material composite doped by alkaline earth and transition metal

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB200610016003XA CN100416904C (en) 2006-09-28 2006-09-28 Technique for preparing perovskite type ionic conductor material composite doped by alkaline earth and transition metal

Publications (2)

Publication Number Publication Date
CN1960046A CN1960046A (en) 2007-05-09
CN100416904C true CN100416904C (en) 2008-09-03

Family

ID=38071602

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB200610016003XA Expired - Fee Related CN100416904C (en) 2006-09-28 2006-09-28 Technique for preparing perovskite type ionic conductor material composite doped by alkaline earth and transition metal

Country Status (1)

Country Link
CN (1) CN100416904C (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101792928B (en) * 2010-03-30 2012-06-27 山东大学 High temperature piezocrystal of melilite structure and preparation method and application thereof
CN102151526A (en) * 2010-07-23 2011-08-17 兰州理工大学 Method for regulating iron magnetic transition temperature of perovskite magnanite
CN106927793A (en) * 2017-04-07 2017-07-07 桂林理工大学 A kind of cobaltatess fast-ionic conductor and preparation method thereof
KR20200027631A (en) * 2018-09-05 2020-03-13 현대자동차주식회사 A membrane-electrode assembly for a fuel cell having improved durability and manufacturing method thereof
CN110743592B (en) * 2019-10-25 2022-09-13 天津理工大学 Perovskite photocatalyst and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6004688A (en) * 1997-07-16 1999-12-21 The Board Of Regents Of The University Of Texas System Solid oxide fuel cell and doped perovskite lanthanum gallate electrolyte therefor
CN1383224A (en) * 2001-04-23 2002-12-04 中国科学技术大学 Composite coagualted electrolyte of doped lanthanum gallate-inorganic salt used for medium-temp fuel battery
CN1560951A (en) * 2004-03-05 2005-01-05 厦门大学 Intermediat-temp solid oxide fuel cell electrolytic of high-efficient preventing carbon deposit and its preparation method
US20050106447A1 (en) * 2003-11-18 2005-05-19 The University Of Chicago Iron-based perovskite cathodes for solid oxide fuel cells

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6004688A (en) * 1997-07-16 1999-12-21 The Board Of Regents Of The University Of Texas System Solid oxide fuel cell and doped perovskite lanthanum gallate electrolyte therefor
CN1383224A (en) * 2001-04-23 2002-12-04 中国科学技术大学 Composite coagualted electrolyte of doped lanthanum gallate-inorganic salt used for medium-temp fuel battery
US20050106447A1 (en) * 2003-11-18 2005-05-19 The University Of Chicago Iron-based perovskite cathodes for solid oxide fuel cells
CN1560951A (en) * 2004-03-05 2005-01-05 厦门大学 Intermediat-temp solid oxide fuel cell electrolytic of high-efficient preventing carbon deposit and its preparation method

Also Published As

Publication number Publication date
CN1960046A (en) 2007-05-09

Similar Documents

Publication Publication Date Title
Zhou et al. Performances of LnBaCo2O5+ x–Ce0. 8Sm0. 2O1. 9 composite cathodes for intermediate-temperature solid oxide fuel cells
Liu et al. A new neodymium-doped BaZr0. 8Y0. 2O3− δ as potential electrolyte for proton-conducting solid oxide fuel cells
CN103390739B (en) A kind of Solid Oxide Fuel Cell ceria-based electrolyte interlayer and preparation thereof
CN104916850B (en) Cathode of solid oxide fuel cell material and have its composite cathode material and preparation method thereof and battery composite cathode preparation method
CN100481272C (en) Compound lanthanum zirconate proton conductor mixed material and preparing method thereof
Zhao et al. Performance of solid oxide fuel cells based on proton-conducting BaCe0. 7In0. 3-xYxO3-δ electrolyte
CN100462329C (en) Multi-phase structure designed high-conductive electrical zirconate barium proton conductor and preparation method thereof
CN103682373B (en) Non-cobalt intermediate temperature solid oxide fuel cell stablizes cathode material and application thereof
CN100416904C (en) Technique for preparing perovskite type ionic conductor material composite doped by alkaline earth and transition metal
CN104409742A (en) BaCoO3-delta base B-position Bi2O3-Nb2O5 co-doped cathode material of solid oxide fuel cell, preparation method and applications thereof
CN105870459A (en) High-catalytic activity composite negative electrode material of intermediate-temperature solid oxide fuel cell and preparation method of composite negative electrode material
CN103224394A (en) Lithium carbonate modified cerium barium zirconate proton conductor material 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
CN109836154A (en) A kind of method that low-temperature sintering densifies cerium oxide base separation layer in fuel cell
CN101439969A (en) Rare-earth oxide and manganese oxide co-stable zirconia ceramics and preparation thereof
CN108242554B (en) Barium cerate-based electrolyte material and preparation method and application thereof
CN102531587A (en) Yttrium-doped barium zirconate-cerate/inorganic salt complex phase-structured proton conductor material and preparation method thereof
Yang et al. Sr-substituted SmBa0. 75Ca0. 25CoFeO5+ δ as a cathode for intermediate-temperature solid oxide fuel cells
CN100517840C (en) Middle-and high-temperature solid-oxide fuel battery cathode material
CN102683720A (en) Gradient composite cathode for solid oxide fuel cell and preparation method thereof
CN108666589A (en) There is one kind low thermal coefficient of expansion solid oxide fuel cell cobalt-based cathode material to prepare and its apply
CN109687006A (en) It is a kind of based on cerium oxide/nickel oxide composite material low-temperature solid oxide fuel cell
CN101572313A (en) Cathode material for intermediate-low temperature solid oxide fuel cells and compound cathode material thereof
CN101543732B (en) Metallic oxide proton conduction material and preparation method thereof
CN108336384A (en) A kind of the niobium modification doping barium cerate electrolyte and preparation method of fuel cell

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
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20080903

Termination date: 20110928