CN102731090A - Anode material of direct-hydrocarbon solid oxide fuel cell and preparation method thereof - Google Patents
Anode material of direct-hydrocarbon solid oxide fuel cell and preparation method thereof Download PDFInfo
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- CN102731090A CN102731090A CN2012102207498A CN201210220749A CN102731090A CN 102731090 A CN102731090 A CN 102731090A CN 2012102207498 A CN2012102207498 A CN 2012102207498A CN 201210220749 A CN201210220749 A CN 201210220749A CN 102731090 A CN102731090 A CN 102731090A
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- 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
Abstract
The invention discloses an anode material of a direct-hydrocarbon solid oxide fuel cell and a preparation method thereof. According to the invention, codoping of La at site A and Cr at site B is carried out on perovskite type SrTiO3, defects of site A are controlled, and a molecular formula obtained after doping is La0.3Sr0.55Ti1-xCrxO3, wherein x is 0.05 to 0.2. The La-Cr codoped strontium titanate anode material prepared in the invention has high ionic conductivity and good chemical compatibility with the electrolyte YSZ, can be used for a direct-hydrocarbon solid oxide fuel cell and has stable performance. As the doping amount of Cr increases, the ionic conductivity of the La-Cr codoped strontium titanate anode material becomes greater at first and smaller later and is increased to 1.2 * 10<-2> S/cm at a temperature of 800 DEG C, thereby improving the work performance of the direct-hydrocarbon solid oxide fuel cell and promoting practical progress of the direct-hydrocarbon solid oxide fuel cell.
Description
Technical field
The present invention relates to a kind of anode material and preparation method thereof, be specifically related to a kind of direct hydrocarbon polymer anode of solid oxide fuel cell material and preparation method thereof.
Background technology
SOFC (Solid oxide fuel cell; Abbreviation SOFC) belongs to third generation fuel battery energy origin system; It is compared with other fuel cell; Except possess the general efficient of fuel cell high, pollute the advantage such as little, also have the total solids encapsulating structure and to unique advantages such as suit property of pluralities of fuel, be considered to the tool fuel cell of development prospect.SOFC is mainly by the porous cathode and anode, fine and close dielectric substrate and bipolar plates or be connected formation such as material.Wherein anode not only will provide the place for the electrochemical reaction of fuel gas; Also to play katalysis to the oxidizing reaction of fuel gas; Also will play a part electronics and gas that shift reaction produces simultaneously, therefore, the performance of anode material plays crucial effects to the performance of entire cell.
At present, obstruction SOFC commercialization process mainly is battery cost and life-span.Directly,, therefore, be considered to reduce the key of SOFC system cost owing to can adopt the modular design of simplifying more cheaply with the fuel of hydrocarbon polymer as SOFC.Existing Ni/YSZ (yttria stabilized zirconia is called for short YSZ) is though composite ceramics is with H
2With the reformation hydrocarbon gas be the desirable anode material of the SOFC of fuel, still, according to document (R.J. Gorte, H. Kim; J.M. Vohs, Novel SOFC anodes for the direct electrochemical oxidation of hydrocarbon, Journal of Power Sources; 2002,106:10-15) with (Y. X. Lu, S. Laura; A solid oxide fuel cell system fed with hydrogen sulfide and nature gas, Journal of Power Sources, 2004; 135:184-191) report, when directly being fuel with the hydrocarbon polymer, the formation of Ni/YSZ anode meeting catalysis C-C key produces carbon laydown; And because some impurity, particularly sulphur in the Sweet natural gas, meeting and Ni reaction form NiS; Make Ni that sulfur poisoning take place and lose katalysis, simultaneously, the change and the problems such as Ni particle sintering, reunion of Ni/YSZ long-time running meeting at high temperature generating electrodes size.These problems all will cause the decay of battery operated performance.Therefore; Searching can directly be carried out catalytic oxidation but the SOFC anode material that do not produce carbon laydown and sulfur poisoning is urgent and necessary to hydrocarbon fuel; It will make the hydrocarbon gas that are comparatively cheap, wide material sources that comprise gasoline, propane, Sweet natural gas etc. become possibility as SOFC fuel, and this will promote the commercialization process of SOFC.
In recent years, for the anode material of direct hydrocarbon polymer SOFC, what study morely is to have ABO
3The SrTiO of structure
3The perovskite type ceramic oxide compound of base.SrTiO
3Material can keep the stable of structure and character in very wide temperature and oxygen partial pressure scope.The SrTiO of stoichiometric ratio
3Catalytic activity and specific conductivity are all very low; Can not directly be used for anode material; But it has very strong doping ability at A and B position; Metals ion with lower valency mixes to the A position, because electroneutral requirement can cause the valence state of B position metals ion to raise or produce the oxygen room, wherein the generation in oxygen room is the key that material has the oxygen-ion conduction performance; And the catalytic activity of material and electron conduction are mainly determined by the B position transition metal ion of uhligite, thereby can mix through A, B position and carry out modification to it.According to document (D.P. Fagg, V.V. Kharton, J.R. Frade, A.A.L. Ferreira, Stability and mixed ionic – electronic conductivity of (Sr, La) (Ti, Fe) O
3-δPerovskites, Solid State Ionics, 2003,156:45-57) report, the SrTiO after the doping
3Show good mixing ion-electron conductive capability, thereby can convert traditional electrode/gas/ionogen three phase boundary into simple gas/electrode two-phase interface, increased the electrochemical reaction area; Significantly reduced the polarization of electrode loss, simultaneously, according to document (O. A.Marina; N. L.Canfield, J.W. Stevenson, Thermal; Electrical, and electrocatalytical properties of lanthanum-doped strontium titanate, Solid State Ionics; 2002,149:21-28) with (J. Canales-Vazquez, S.W. Tao; J.T.S. Irvine, Electrical properties in La
2Sr
4Ti
6O
19-δ: a potential anode for high temperature fuel cells, Solid State Ionics, 2003,159:159-165) report, adulterated SrTiO
3Material also has certain electrochemical catalysis performance to the oxidizing reaction of hydrocarbon fuel.And, according to document (J.C. Ruiz-Morales, J. Canales-Vazquez, C. Savaniu; Et al., Disruption of extended defects in solid oxide fuel cell anodes for methane oxidation, Nature; 2006,439:568-571) with (R. Mukundan, E.L. Brosha; F.H. Garzon, Sulfur tolerant anodes for SOFCs, Electrochemical and Solid-State Letters; 2004,7:A5-A7) report is because doping SrTiO
3Be full ceramic oxide material, thereby when using hydrocarbon fuel, can not produce phenomenons such as carbon laydown, sulfur poisoning, and at high temperature have the structural stability higher than Ni/YSZ.Adulterated SrTiO
3Can be compatible with multiple electrolyte, physics and chemical reaction can not take place, through the codoped of A, B position, can also regulate the thermal expansivity with control material, therefore be considered to one of good candidate material of direct hydrocarbon polymer SOFC anode.
At present about doping SrTiO
3The research of class anode material mainly concentrates on its electric conductivity aspect.The adulterated SrTiO of La
3Under higher temperature, bigger doping and lower oxygen partial pressure, can obtain bigger specific conductivity.Document (Sun Xiufu, Guo Ruisong, Li Juan. La doping SrTiO
3The anode material performance study. power technology, 2006,30 (10): 842-844,848) with La the Sr of A position is mixed, find the adulterated Sr of La
1-1.5xLa
xTiO
3Conductivity of electrolyte materials and La
2O
3Doping is relevant, works as La
2O
3The sample Sr of doping when being 0.15mol
0.55La
0.3TiO
3Total conductivity the highest, but the ionic conductivity of material is not tested.And the Cr element has crucial meaning to the stability that improves material, catalytic performance and to the tolerance of sulphur.Therefore, the present invention with Cr to Sr
0.55La
0.3TiO
3In B position Ti mix, prepared a kind of novel strontium titanate doping anode material, inquired into the doping scope of Cr in material, and total conductivity, the ionic conductivity of material measured.
Summary of the invention
The present invention is directed to Ni/YSZ composite ceramics anode and in direct hydrocarbon polymer SOFC, be prone to produce carbon laydown, sulfur poisoning and Ni particle sintering, reunion during operation, and existing SrTiO
3Problems such as base anode material specific conductivity is low propose a kind of stable performance, New type of S OFC anode material La that electric conductivity is high
0.3Sr
0.55Ti
1-xCr
xO
3, promptly at perovskite typed SrTiO
3The A position carry out the doping of La, the doping of Cr is carried out in the B position, and control A position defective, improves the specific conductivity of anode material, and then improves the serviceability of direct hydrocarbon polymer SOFC.This material and ionogen YSZ have good chemical compatibility.
Concrete technical scheme of the present invention is: perovskite typed SrTiO
3The A position be the doping of 30mol%La, the B position is that Cr mixes, and control A position defective, the molecular formula behind the codoped is: La
0.3Sr
0.55Ti
1-xCr
xO
3, x=0.05～0.2 wherein.Material of the present invention can use Hydrocerol A-nitrate process synthetic, also can be synthetic with solid reaction process.Be the compound method that example is introduced material of the present invention with Hydrocerol A-nitrate process below, concrete steps are:
A, press La
0.3Sr
0.55Ti
1-xCr
xO
3The stoichiometric ratio of (x=0.05～0.2) takes by weighing raw material tetrabutyl titanate, La (NO
3)
36H
2O, Sr (NO
3)
2And Cr (NO
3)
39H
2O;
B, tetrabutyl titanate is dissolved in an amount of dilute nitric acid solution, heating in water bath stirs until the solution clarification, and this solution is designated as A liquid;
C, with La (NO
3)
36H
2O, Sr (NO
3)
2And Cr (NO
3)
39H
2O dissolves in the appropriate amount of deionized water, gets settled solution B liquid;
D, pour B liquid into A liquid and mix, the mol ratio in Hydrocerol A and total metals ion be (1.3～2) then: 1 ratio adding Hydrocerol A, again with ammoniacal liquor regulator solution pH value to 7～8, through heated and stirred dewater the purple clear gel;
E, with gel place heat under 190～250 ℃ in the baking oven porous spumescence presoma;
F, with spumescence presoma grind into powder in mortar, in 800～1300 ℃ of scopes, calcine then, obtain synthetic La, Cr codoped SrTiO
3Powder;
G, with above-mentioned synthetic La, Cr codoped SrTiO
3Powder is labeled as LSTC, and wherein the Cr doping is 10mol%, and calcine the powder that obtains down for 800 ℃ and be labeled as LSTC10-800, all the other and the like.
The invention has the advantages that, for perovskite typed SrTiO
3Material carries out A, B position codoped, and control A position defective, thereby causes the increase of oxygen vacancy concentration, with respect to the do not mix material of Cr of B position, La
0.3Sr
0.55Ti
1-xCr
xO
3The ionic conductivity of material is significantly improved.La
0.3Sr
0.55Ti
1-xCr
xO
3Ionic conductivity increases afterwards earlier with the increase of Cr doping and slightly reduces, preferably molecular formula is La
0.3Sr
0.55Ti
0.9Cr
0.1O
3, the total conductivity during 800 ℃ of this materials is 54.6S/cm, ionic conductivity is 1.2 * 10
-2S/cm, the total conductivity in the time of 900 ℃ is 52.5S/cm, ionic conductivity is 1.4 * 10
-2S/cm is the do not mix La of Cr of B position
0.3Sr
0.55TiO
33 times of material ionic conductivity.Control Cr ionic incorporation, can obtain the perovskite structural material of pure phase.Like Fig. 1 a is that B position doping Cr amount is the XRD figure of 0.10 material; The peak position of each characteristic peak is consistent with the peak position of each characteristic peak in the XRD standard diagram of strontium titanate doping (Fig. 1 b) not among the figure; Any other dephasign peak do not occur, material shows as the calcium titanium ore structure of pure phase.
Description of drawings
Fig. 1 is the XRD figure and the not XRD standard diagram contrast of strontium titanate doping of the powder of embodiment 1 preparation.
Fig. 2 is the SEM figure of the powder of embodiment 8 preparations.
Embodiment
Embodiment 1
Press La
0.3Sr
0.55Ti
0.9Cr
0.1O
3Stoichiometric ratio take by weighing raw material tetrabutyl titanate, La (NO
3)
36H
2O, Sr (NO
3)
2And Cr (NO
3)
39H
2O.Earlier tetrabutyl titanate is dissolved in an amount of rare nitric acid, heated and stirred is clarified until solution in 70 ℃ of water-baths, and this solution is designated as A liquid.Again with La (NO
3)
36H
2O, Sr (NO
3)
2And Cr (NO
3)
39H
2O dissolves in the appropriate amount of deionized water, gets settled solution B liquid.Pouring B liquid into A liquid and mix, is that the ratio of 1.3:1 adds Hydrocerol A in the mol ratio of Hydrocerol A and total metals ion then, regulates pH value to 7～8 with ammoniacal liquor, in 90 ℃ of water-baths heated and stirred dewater purple gel.Then with gel place heat under 190 ℃ in the baking oven porous spumescence presoma.With spumescence presoma grind into powder,, obtain the SrTiO of La, Cr codoped then 800 ℃ of calcinings down
3Powder.
Embodiment 2 ~ 6
Be that with preparing method's difference of embodiment 1 doping of its Cr and calcining temperature are different, as shown in table 1.
Table 1
6 kinds of powder body materials of above-mentioned preparation are carried out the XRD test, and wherein the X diffraction peak of the powder LSTC10-800 of embodiment 1 preparation is shown in Fig. 1 a.Can find out that by Fig. 1 a each characteristic diffraction peak peak position (seeing Fig. 1 b) is consistent in the XRD standard diagram of each diffraction peak peak position and strontium titanate doping not of powder LSTC10-800 of embodiment 1 preparation; Any other dephasign peak do not occur, this shows that material has monophasic calcium titanium ore structure.And the XRD figure of the powder LSTC20 of embodiment 2 preparations shows that SrCrO is arranged in the material
4Dephasign exists, but along with calcining temperature is elevated to 1000 ℃, SrCrO from 800 ℃
4Dephasign thereupon disappear (embodiment 3).For the LSTC30 powder, its XRD figure shows, SrCrO not only behind 1000 ℃ of calcining 5h
4Dephasign still exists, but also new dephasign Cr occurred
2O
3(embodiment 5), when calcining temperature further is elevated to 1300 ℃, SrCrO
4The dephasign peak disappears, and Cr
2O
3Dephasign peak become more obviously (embodiment 6).Therefore, the doping of Cr in the LSTC powder is 0.3 to be unsuitable.
Embodiment 7
Press La
0.3Sr
0.55Ti
0.95Cr
0.05O
3Stoichiometric ratio take by weighing raw material tetrabutyl titanate, La (NO
3)
36H
2O, Sr (NO
3)
2And Cr (NO
3)
39H
2O.Earlier tetrabutyl titanate is dissolved in an amount of rare nitric acid, heated and stirred is clarified until solution in 70 ℃ of water-baths, and this solution is designated as A liquid.Again with La (NO
3)
36H
2O, Sr (NO
3)
2And Cr (NO
3)
39H
2O dissolves in the appropriate amount of deionized water, gets settled solution B liquid.Pouring B liquid into A liquid and mix, is that the ratio of 1.5:1 adds Hydrocerol A in the mol ratio of Hydrocerol A and total metals ion then, regulates pH value to 7～8 with ammoniacal liquor, in 90 ℃ of water-baths heated and stirred dewater purple gel.Then with gel place heat under 210 ℃ in the baking oven porous spumescence presoma.With spumescence presoma grind into powder,, obtain the SrTiO of La, Cr codoped then 1000 ℃ of calcinings down
3Powder LSTC5-1000.
The LSTC5-1000 powder is mixed by the weight ratio of 1:1 with the YSZ powder, then mixed powder is ground compressing tablet behind the 30min in agate mortar, again with the green sheet of compacting at 1400 ℃ of sintering 5h; Take out after cooling, the last XRD of the being test of in agate mortar, pulverizing, the result shows; In the XRD figure of LSTC5-1000/YSZ except the characteristic peak of YSZ and LSTC; Do not have the peak of third phase to occur, this shows that LSTC and YSZ can also keep phase stability separately down at 1400 ℃, and chemical reaction does not take place; That is, LSTC and YSZ ionogen have good chemical compatibility.
Embodiment 8
Press La
0.3Sr
0.55Ti
0.9Cr
0.1O
3Stoichiometric ratio take by weighing raw material tetrabutyl titanate, La (NO
3)
36H
2O, Sr (NO
3)
2And Cr (NO
3)
39H
2O.Earlier tetrabutyl titanate is dissolved in an amount of rare nitric acid, heated and stirred is clarified until solution in 70 ℃ of water-baths, and this solution is designated as A liquid.Again with La (NO
3)
36H
2O, Sr (NO
3)
2And Cr (NO
3)
39H
2O dissolves in the appropriate amount of deionized water, gets settled solution B liquid.Pouring B liquid into A liquid and mix, is that the ratio of 2:1 adds Hydrocerol A in the mol ratio of Hydrocerol A and total metals ion then, regulates pH value to 7～8 with ammoniacal liquor, in 90 ℃ of water-baths heated and stirred dewater purple gel.Then with gel place heat under 250 ℃ in the baking oven porous spumescence presoma.With spumescence presoma grind into powder,, obtain the SrTiO of La, Cr codoped then 800 ℃ of calcinings down
3Powder LSTC10-800, the SEM test of this powder is as shown in Figure 2.Can be found out that by Fig. 2 powder granule is evenly tiny, particle diameter is about 50nm.
Above-mentioned LSTC10-800 powder is fully ground the back cross 100 mesh sieves in agate mortar, take by weighing the pressure pressed moulding at 180MPa in stainless steel mould of a certain amount of powder then, place High Temperature Furnaces Heating Apparatus at 1400 ℃ of following sintering 5h on the green compact that are pressed into again.The color of sheet is by the faint yellow grey black that becomes behind the sintering.Adopt four end leads method to measure the total conductivity of material then, the blocking electrode method is measured the ionic conductivity of material, and the total conductivity during 800 ℃ of this materials is 54.6S/cm, and ionic conductivity is 1.2 * 10
-2S/cm, the total conductivity in the time of 900 ℃ is 52.5S/cm, ionic conductivity is 1.4 * 10
-2S/cm, the La of Cr and do not mix in the B position
0.3Sr
0.55TiO
3The ionic conductivity of material is merely 4.7 * 10
-3S/cm.
Embodiment 9
According to La
0.3Sr
0.55Ti
0.8Cr
0.2O
3Stoichiometric ratio take by weighing La
2O
3, SrCO
3, Cr
2O
3And TiO
2, be medium with the deionized water, ball milling 10h in agate jar after mixing, is dried in baking oven.The powder grinding of oven dry is sieved in (100 order), and the powder after sieving is contained in the alumina crucible, and is synthetic in 1000 ℃ of insulation 8h.Powder XRD test after synthetic shows the calcium titanium ore structure with pure phase.
The synthetic powder is sieved (100 order), dry-pressing formed under 180MPa, 5%H
2In/Ar the atmosphere, 1400 ℃ of insulation 10h densification sinterings adopt four end leads method to measure the total conductivity of material, and the blocking electrode method is measured the ionic conductivity of material, and the total conductivity during 800 ℃ of this materials is 50.3S/cm, and ionic conductivity is 1.1 * 10
-2S/cm.
The LSTC20-1000 powder that obtains with Hydrocerol A-nitrate process among the embodiment 3 is pressed method compressing tablet, sintering, the testing conductivity described in the embodiment 8.The result shows, Hydrocerol A-nitrate process synthetic LSTC20-1000 material, and total conductivity is 51.8S/cm in the time of 800 ℃, ionic conductivity is 1.16 * 10
-2S/cm is more or less the same with solid phase method synthetic conductivity of electrolyte materials.
Claims (3)
1. a direct hydrocarbon polymer anode of solid oxide fuel cell material is characterized in that, to perovskite typed SrTiO
3Carry out the codoped of A position La, B position Cr, and control A position defective, the molecular formula behind the codoped is:
La
0.3Sr
0.55Ti
1-xCr
xO
3, x=0.05～0.2 wherein.
2. La as claimed in claim 1, Cr codoped strontium titanate anode of solid oxide fuel cell material is characterized in that the molecular formula behind the codoped is: La
0.3Sr
0.55Ti
0.9Cr
0.1O
3
3. direct hydrocarbon polymer anode of solid oxide fuel cell preparation methods is characterized in that concrete steps are following:
A, press La
0.3Sr
0.55Ti
1-xCr
xO
3Stoichiometric ratio take by weighing raw material tetrabutyl titanate, La (NO
3)
36H
2O, Sr (NO
3)
2And Cr (NO
3)
39H
2O, x=0.05～0.2;
B, tetrabutyl titanate is dissolved in the dilute nitric acid solution, heating in water bath stirs until the solution clarification, and this solution is designated as A liquid;
C, with La (NO
3)
36H
2O, Sr (NO
3)
2And Cr (NO
3)
39H
2O dissolves in the deionized water, gets settled solution B liquid;
D, pour B liquid into A liquid and mix, the mol ratio in Hydrocerol A and total metals ion be (1.3～2) then: 1 ratio adding Hydrocerol A, again with ammoniacal liquor regulator solution pH value to 7～8, through heated and stirred dewater purple gel;
E, with gel place heat under 190～250 ℃ in the baking oven porous spumescence presoma;
F, with spumescence presoma grind into powder in mortar, in 800～1300 ℃ of scopes, calcine then, obtain synthetic La, Cr codoped SrTiO
3Powder.
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| CN104779398A (en) * | 2015-04-27 | 2015-07-15 | 上海邦民新能源科技有限公司 | Solid oxide fuel cell anode material and anode provided with same |
| CN105908211A (en) * | 2016-05-05 | 2016-08-31 | 东北林业大学 | Electrolytic cell device with high temperature steam electrolysis and stable operation functions, preparation method of electrolytic cell, and using method of electrolytic cell device |
| CN105976892A (en) * | 2016-03-22 | 2016-09-28 | 红河学院 | Lanthanum indium co-doped strontium titanate conductor material and preparation method thereof |
| CN105989908A (en) * | 2016-07-21 | 2016-10-05 | 红河学院 | A and B-site co-doped SrTiO3 mixed conductor material |
| CN106098137A (en) * | 2016-06-30 | 2016-11-09 | 红河学院 | A, B position codope strontium titanates mixed conductor material that a kind of A position is vacant |
| CN109346703A (en) * | 2018-10-30 | 2019-02-15 | 肇庆市华师大光电产业研究院 | A kind of lanthanum co-doped strontium titanates negative electrode material of lithium ion battery nickel and preparation method thereof |
| CN109637694A (en) * | 2018-12-21 | 2019-04-16 | 红河学院 | A kind of A, B codope strontium titanates conductor material and preparation method thereof |
| CN114447384A (en) * | 2022-01-26 | 2022-05-06 | 湖北大学 | A-site defective perovskite structure fuel cell electrolyte, preparation method thereof and fuel cell |
| CN115745008A (en) * | 2022-10-26 | 2023-03-07 | 浙江大学杭州国际科创中心 | Bismuth ferrite doped perovskite material and preparation method and application thereof |
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| CN104779398A (en) * | 2015-04-27 | 2015-07-15 | 上海邦民新能源科技有限公司 | Solid oxide fuel cell anode material and anode provided with same |
| CN105976892A (en) * | 2016-03-22 | 2016-09-28 | 红河学院 | Lanthanum indium co-doped strontium titanate conductor material and preparation method thereof |
| CN105908211A (en) * | 2016-05-05 | 2016-08-31 | 东北林业大学 | Electrolytic cell device with high temperature steam electrolysis and stable operation functions, preparation method of electrolytic cell, and using method of electrolytic cell device |
| CN105908211B (en) * | 2016-05-05 | 2017-12-26 | 东北林业大学 | A kind of preparation of electrolytic cell device, electrolytic cell of high-temperature electrolysis water hydrogen manufacturing stable operation and the application method of electrolytic cell device |
| CN106098137A (en) * | 2016-06-30 | 2016-11-09 | 红河学院 | A, B position codope strontium titanates mixed conductor material that a kind of A position is vacant |
| CN105989908A (en) * | 2016-07-21 | 2016-10-05 | 红河学院 | A and B-site co-doped SrTiO3 mixed conductor material |
| CN105989908B (en) * | 2016-07-21 | 2018-03-09 | 红河学院 | A kind of A, B position codope strontium titanates mixed conductor material |
| CN109346703A (en) * | 2018-10-30 | 2019-02-15 | 肇庆市华师大光电产业研究院 | A kind of lanthanum co-doped strontium titanates negative electrode material of lithium ion battery nickel and preparation method thereof |
| CN109637694A (en) * | 2018-12-21 | 2019-04-16 | 红河学院 | A kind of A, B codope strontium titanates conductor material and preparation method thereof |
| CN114447384A (en) * | 2022-01-26 | 2022-05-06 | 湖北大学 | A-site defective perovskite structure fuel cell electrolyte, preparation method thereof and fuel cell |
| CN115745008A (en) * | 2022-10-26 | 2023-03-07 | 浙江大学杭州国际科创中心 | Bismuth ferrite doped perovskite material and preparation method and application thereof |
| CN115745008B (en) * | 2022-10-26 | 2024-02-13 | 浙江大学杭州国际科创中心 | Bismuth ferrite doped perovskite material and preparation method and application thereof |
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