CN103199287B - Method for promoting densification of silicon-based apatite through doping Cu - Google Patents
Method for promoting densification of silicon-based apatite through doping Cu Download PDFInfo
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- CN103199287B CN103199287B CN201310128005.8A CN201310128005A CN103199287B CN 103199287 B CN103199287 B CN 103199287B CN 201310128005 A CN201310128005 A CN 201310128005A CN 103199287 B CN103199287 B CN 103199287B
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- doping
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- 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
Abstract
The invention relates to a method for promoting the densification of silicon-based apatite through doping Cu, belonging to the field of solid oxide fuel cells. According to the method, the silicon-based apatite (the molecular formula is La9.33+xSi6O26+1.5x, wherein x is equal to 0-0.67) is prepared by adopting a citric acid-nitrate method, the sintering activity of powder can be effectively improved through doping Cu at Si site, the densification of the material is promoted, the relative density can be improved by more than 6% under the condition of sintering at equal temperature, and the problem that the silicon-based apatite electrolyte material is difficult to sinter and densify can be solved.
Description
Technical field
The present invention relates to a kind of method that Cu doping promotes the densification of silica-based apatite electrolyte, belong to field of solid oxide fuel.
Background technology
Along with earth environment pollution is increasingly serious with energy scarcity, seek the important directions that energy conversion efficiency height and eco-friendly new energy technology have become current scientific and technical research.The advantages such as Solid Oxide Fuel Cell (SOFC) has that energy utilization rate is high, cleanliness without any pollution, fuel tolerance are strong, structure of whole solid state, are acknowledged as one of most potential energy technology of 21 century.
Solid Oxide Fuel Cell is mainly comprised of anode, negative electrode, electrolyte and four parts of connecting material.Based on traditional electrolyte---the required higher (800-1000 of operating temperature of SOFC of the zirconia (YSZ) of stabilized with yttrium oxide
oc).So high working temperature has been brought series of problems, as the sealing difficulty of the reaction between battery component, electrode sintering and battery pile etc.Therefore, in order to reduce costs, improve stability and the reliability of battery system, development intermediate temperature SOFC (500-750
oc) be inexorable trend.Electrolyte is the key that reduces SOFC operating temperature.Due to YSZ, conductivity is lower under mesophilic condition, and battery efficiency is reduced greatly, so develop satisfactory electrolyte under mesophilic condition, is one of emphasis of research at present.Silica-based apatite electrolyte relies on it, and high conductivity and oxide-ionic transport number, gentle thermal coefficient of expansion and good doping characteristic and chemical stability etc. become one of important replacer of YSZ under mesophilic condition.
First the electrolyte of SOFC needs to have higher density, to prevent mutually shuttling back and forth of fuel gas and oxygen, guarantees the higher open circuit voltage of battery.The densification temperature of the silica-based apatite electrolyte of preparing with traditional solid reaction process often needs 1650
oabove (the Yoshioka H of C; Nojiri Y, Tanase S. Ionic conductivity and fuel cell properties of apatite-type lanthanum silicates doped with Mg and containing excess oxide ions. Solid State Ionics. 2008; 179:2165-2169. Nojiri Y, Tanase S, Iwasa M, et al. Ionic conductivity of apatite-type solid electrolyte material, La
10 xba
xsi
6o
27 x/2(x=0 – 1), and its fuel cell performance. Journal of Power Sources. 2010; 195:4059-4064).So high preparation temperature has not only increased the waste of the energy and the requirement high to equipment, and has brought difficulty to the battery preparation of electrode supporting structure.Adopt more advanced sintering technology, can effectively reduce silica-based apatite material densification temperature.For example, the solid phase method that the use such as Panteix are traditional has been prepared silica-based apatite powder material, utilizes hot pressed sintering, at 35 MPa, 1400
ounder the condition of C, prepared density at more than 95% potsherd (Panteix P J; Julien I; Assollant D B; et al. Synthesis and characterization of oxide ions conductors with the apatite structure for intermediate temperature SOFC [J]. Materials Chemistry and Physics, 2006; 95:313-320), but advanced sintering technology is to the having relatively high expectations of equipment, and has increased preparation cost.It by Liquid preparation methods nano-powder material, is the another kind of approach that reduces silica-based apatite electrolyte densification temperature, sol-gel process (Celerier S for example, Laberty C, Ansart F, et al. New chemical route based on sol – gel process for the synthesis of oxyapatite La
9.33si
6o
26[J]. Ceramics International, 2006,32 (3): 271-276), citric acid-nitrate method (Zhou J, Ye X F, Li J L, et al. Synthesis and characterization of apatite-type La
9.67si
6-xal
xo
26.5-x/2electrolytematerials and compatible cathode materials[J]. Solid State Ionics, 2011; 201:81 – 86. Jothinathan E; Vanmeensel K; Vleugels J, et al. Synthesis of nano-crystalline apatite type electrolyte powders for solid oxide fuel cells. Journal of the European Ceramic Society. 2010; 30:1699-1706.) etc.But these methods promote that the degree of densification is still limited, thereby affected the practical application of silica-based apatite electrolyte.Therefore be necessary to continue to explore the new method that effectively reduces silica-based apatite electrolyte densification temperature.
Summary of the invention
The object of the present invention is to provide a kind of simple, with low cost while can effectively promote the method for silica-based apatite electrolyte densification.The present invention has prepared the silica-based apatite electrolyte of Cu doping by citric acid-nitrate method.By the doping of Cu, can effectively improve the sintering activity of material, promote the densification of material.Technical scheme is as follows:
A) according to molecular formula La
9.33+xsi
6-ycu
yo
26+1.5x-yin (0≤x≤0.67), the stoichiometric proportion of each element takes required La
2o
3, tetraethoxysilane (TEOS) and Cu (NO
3)
23H
2o.By La
2o
3and Cu (NO
3)
23H
2o is dissolved in deionized water and a certain amount of nitric acid, and deionized water and metal ion (comprise Si
4+) amount of substance ratio be 10 ~ 50:1, the amount of substance ratio of nitric acid and metal ion is 5 ~ 20:1; Add amount of substance than for the citric acid of 1:1 and ethylene glycol are as complexing agent, complexing agent is 1 ~ 3:1 with the amount of substance ratio of metal ion; Adding concentration is that 28% ammoniacal liquor regulates pH value to 2 ~ 7; After TEOS is dissolved in to a certain amount of absolute ethyl alcohol, add above-mentioned solution, the amount of substance ratio of absolute ethyl alcohol and TEOS is 30 ~ 80:1; Constantly stir and make solution fully mix rear immigration 70 ~ 90
oevaporation in the water-bath of C, until wet gel forms, then moves into baking oven 70 ~ 120
othe dry xerogel that forms of C, is then heated to xerogel its burning, forms fluffy precursor powder after burning.
B) above-mentioned precursor powder is moved into grind after Muffle furnace calcining 5 ~ 10 h sieve in (160 order), dry-pressing formed, then in air, high temperature sintering 4-10 h obtains fine and close material.
The doping y of described Cu is between 0 to 0.7; The calcining heat of presoma is 800-1000
oc; The sintering temperature of powder body material is 1400-1600
oc.
The present invention utilizes citric acid-nitrate method to prepare the silica-based apatite electrolyte La of Cu doping
9.33+xsi
6-ycu
yo
26+1.5x-y(0≤x≤0.67,0<y≤0.7), gained powder body material has good sintering activity, has effectively promoted the densification of material.
Accompanying drawing explanation
Fig. 1 is the profile scanning Electronic Speculum figure that example 1 of the present invention obtains sample.
Fig. 2 is the profile scanning Electronic Speculum figure that example 2 of the present invention obtains sample.
Fig. 3 is the profile scanning Electronic Speculum figure that example 3 of the present invention obtains sample.
Fig. 4 is the X ray electronic diffraction collection of illustrative plates that example 1,2 and 3 of the present invention obtains sample.
Embodiment
below in conjunction with example, the present invention is described further, but be not limited to protection scope of the present invention.
example 1:
For the facilitation of contrast Cu doping to material densification, spy does plain sample, i.e. this example.Preparation La
9.67si
6o
26.5:
A) by 3.937 g La
2o
3be dissolved in 20 ml deionized waters and 30 ml concentration are the mixed liquor of 65wt% nitric acid, to be dissolvedly add 13.922 g citric acids and 4.112 g ethylene glycol after completely, magnetic agitation solution is to clarification.
B) with the ammoniacal liquor of 28 wt%, regulate pH to 2-3.
C) after 3.125 g TEOS are dissolved in 60 ml absolute ethyl alcohols, add above-mentioned solution; After magnetic agitation 3 h, move into 80
oc water-bath is until gel appearance; Gel is moved into 80
oin C baking oven, dry afterwards in 250
oc lights and obtains precursor powder.
D) by precursor powder 900
oc calcines 9 h, and powder that calcining is obtained grinds and sieve in (160 order), put into electric furnace after dry-pressing formed, 1550
ounder C, air atmosphere, sintering 6 h obtain final material, and the density that records material by Archimedes's drainage is 87.6%.The thing of XRD test material is single apatite phase mutually.
example 2:
This example is the sample of Cu doping y=0.1.Preparation La
9.67si
5.9cu
0.1o
26.4:
A) by 3.937 g La
2o
3be dissolved in 20 ml deionized waters and 30 ml concentration are the mixed liquor of 65wt% nitric acid, add 0.060 g Cu (NO
3)
23H
2o, 13.922 g citric acids and the 4.112 g ethylene glycol of adding afterwards completely to be dissolved, magnetic agitation solution is to clarification.
B) with the ammoniacal liquor of 28 wt%, regulate pH to 2-3.
C) after 3.073 g TEOS are dissolved in 60 ml absolute ethyl alcohols, add above-mentioned solution; After magnetic agitation 3 h, move into 80
oc water-bath is until gel appearance; Gel is moved into 80
oin C baking oven, dry afterwards in 250
oc lights and obtains precursor powder.
D) by precursor powder 900
oc calcines 9 h, and powder that calcining is obtained grinds and sieve in (160 order), put into electric furnace after dry-pressing formed, 1550
ounder C, air atmosphere, sintering 6 h obtain final material, and the density that records material by Archimedes's drainage is 93.8%.The thing of XRD test material is single apatite phase mutually, without second-phase impurity, occurs.
example 3:
This example is the sample of Cu doping y=0.5.Preparation La
9.67si
5.5cu
0.5o
26:
A) by 3.937 g La
2o
3be dissolved in 20 ml deionized waters and 30 ml concentration are the mixed liquor of 65wt% nitric acid, add 0.302 g Cu (NO
3)
23H
2o, 13.922 g citric acids and the 4.112 g ethylene glycol of adding afterwards completely to be dissolved, magnetic agitation solution is to clarification.
B) with the ammoniacal liquor of 28 wt%, regulate pH to 2-3.
C) after 2.865 g TEOS are dissolved in 60 ml absolute ethyl alcohols, add above-mentioned solution; After magnetic agitation 3 h, move into 80
oc water-bath is until gel appearance; Gel is moved into 80
oin C baking oven, dry afterwards in 250
oc lights and obtains precursor powder.
D) by precursor powder 900
oc calcines 9 h, and powder that calcining is obtained grinds and sieve in (160 order), put into electric furnace after dry-pressing formed, 1550
ounder C, air atmosphere, sintering 6 h obtain final material, and the density that records material by Archimedes's drainage is 95.0%.The thing of XRD test material is single apatite phase mutually, without second-phase impurity, occurs.
Claims (1)
1. Cu doping promotes a method for silica-based apatite electrolyte densification, it is characterized in that, in Si position doped with Cu, the doping of Cu is 0<y≤0.7, by molecular formula, is expressed as La
9.33+xsi
6-ycu
yo
26+1.5x-yx=0 ~ 0.67 wherein; Electrolytical dense material preparation method is as follows:
A) according to molecular formula La
9.33+xsi
6-ycu
yo
26+1.5x-yin the stoichiometric proportion of each element take required La
2o
3, tetraethoxysilane is TEOS and Cu (NO
3)
23H
2o; By La
2o
3and Cu (NO
3)
23H
2o is dissolved in the mixed solution of deionized water and a certain amount of nitric acid, and the amount of substance ratio of deionized water and metal ion is 10 ~ 50:1, and the amount of substance ratio of nitric acid and metal ion is 5 ~ 20:1; In mixed solution, add complexing agent, then to add concentration be that 28% ammoniacal liquor regulates pH value to 2 ~ 3, finally add the ethanol solution that is dissolved with TEOS; Constantly stir and make solution fully mix rear immigration 70 ~ 90
oevaporation in the water-bath of C, until wet gel forms, then moves into baking oven 70 ~ 120
othe dry xerogel that forms of C; Xerogel is heated to its burning, after burning, forms fluffy precursor powder; Wherein the ratio of absolute ethyl alcohol and TEOS is 30 ~ 80:1; Complexing agent is 1 ~ 3:1 with the amount of substance ratio of metal ion; The composition of complexing agent is citric acid and ethylene glycol, and ratio is 1:1;
B) above-mentioned precursor powder is moved into Muffle furnace calcining 5 ~ 10 h and ground 160 mesh sieves, dry-pressing formed afterwards, then in air, high temperature sintering 4-10 h obtains fine and close material; The calcining heat of described presoma is 800-1000
oc; The dense sintering temperature of material is 1400-1600
oc.
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| CN104201408B (en) * | 2014-07-31 | 2016-08-24 | 北京科技大学 | A kind of Cu silica-based apatite electrolyte of doping and preparation method thereof |
| CN106816615A (en) * | 2016-11-28 | 2017-06-09 | 佛山市尚好门窗有限责任公司 | A kind of new middle low temperature SOFC electrolytes and preparation method thereof |
| CN110224146B (en) * | 2019-05-23 | 2021-02-26 | 湖北大学 | Low-temperature online densification method for fuel cell electrolyte |
Citations (2)
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|---|---|---|---|---|
| CN101186287A (en) * | 2007-12-07 | 2008-05-28 | 合肥学院 | Method for preparing apatite type oxide electrolyte powder |
| CN102709578A (en) * | 2012-06-05 | 2012-10-03 | 哈尔滨工业大学 | Indium or niobium epoxide apatite type lanthanum silicate mixed solid electrolyte material and preparation method thereof |
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2013
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186287A (en) * | 2007-12-07 | 2008-05-28 | 合肥学院 | Method for preparing apatite type oxide electrolyte powder |
| CN102709578A (en) * | 2012-06-05 | 2012-10-03 | 哈尔滨工业大学 | Indium or niobium epoxide apatite type lanthanum silicate mixed solid electrolyte material and preparation method thereof |
Non-Patent Citations (12)
| Title |
|---|
| E. Jothinathan等.Synthesis of nano-crystalline apatite type electrolyte powders for solid oxide fuel cells.《Journal of the European Ceramic Society》.2010,第30卷全文. * |
| E.Jothinathan等.Powdersynthesis processing and characterization of lanthanum silicates for SOFC application.《Journal of Alloys and Compounds》.2009 * |
| E.V. Tsipis等.Electrochemical behavior of mixed-conducting oxide cathodes in contact with apatite-type La10Si5AlO26.5 electrolyte.《Electrochimica Acta》.2006,第52卷全文. * |
| Electrochemical behavior of mixed-conducting oxide cathodes in contact with apatite-type La10Si5AlO26.5 electrolyte;E.V. Tsipis等;《Electrochimica Acta》;20061230;第52卷;全文 * |
| J. Zhou等.Synthesis and characterization of apatite-type La9.67Si6-xAlxO26.5-x/2 electrolyte materials and compatible cathode materials.《Solid State Ionics》.2011,第201卷(第1期),全文. * |
| Lan Zhang等.Synthesis and characterization of doped La9ASi6O26.5(A=Ca,Sr,Ba) oxyapatite electrolyte by a water-based gel-casting route.《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》.2011,第36卷全文. * |
| Powder synthesis, processing and characterization of lanthanum silicates for SOFC application;E. Jothinathan等;《Journal of Alloys and Compounds》;20091022;第495卷;全文 * |
| Synthesis and characterization of apatite-type La9.67Si6-xAlxO26.5-x/2 electrolyte materials and compatible cathode materials;J. Zhou等;《Solid State Ionics》;20110909;第201卷(第1期);全文 * |
| Synthesis and characterization of doped La9ASi6O26.5(A=Ca,Sr,Ba) oxyapatite electrolyte by a water-based gel-casting route;Lan Zhang等;《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》;20110327;第36卷;全文 * |
| Synthesis of nano-crystalline apatite type electrolyte powders for solid oxide fuel cells;E. Jothinathan等;《Journal of the European Ceramic Society》;20100125;第30卷;全文 * |
| 溶胶凝胶-自燃烧法合成La9.33Si6O26超细粉体;田长安等;《无机材料学报》;20080131;第23卷(第1期);全文 * |
| 田长安等.溶胶凝胶-自燃烧法合成La9.33Si6O26超细粉体.《无机材料学报》.2008,第23卷(第1期),全文. * |
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