CN103199287A - 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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- CN103199287A CN103199287A CN2013101280058A CN201310128005A CN103199287A CN 103199287 A CN103199287 A CN 103199287A CN 2013101280058 A CN2013101280058 A CN 2013101280058A CN 201310128005 A CN201310128005 A CN 201310128005A CN 103199287 A CN103199287 A CN 103199287A
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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
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Technical field
The present invention relates to the method that a kind of Cu doping promotes the densification of silica-based apatite electrolyte, belong to field of solid oxide fuel.
Background technology
Along with the 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.Solid Oxide Fuel Cell (SOFC) has advantages such as energy utilization rate height, cleanliness without any pollution, fuel tolerance are strong, structure of whole solid state, is acknowledged as 21 century one of the most potential energy technology.
Solid Oxide Fuel Cell mainly is made up of anode, negative electrode, electrolyte and four parts of connection 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 a series of problems, as the sealing difficulty of the reaction between battery component, electrode sintering and battery pile etc.Therefore, in order to reduce cost, improve stability and the reliability of battery system, warm SOFC (500-750 in the development
oC) be inexorable trend.Electrolyte is the key that reduces the SOFC operating temperature.Conductivity is lower under mesophilic condition owing to YSZ, makes battery efficiency reduce greatly, and satisfactory electrolyte is one of emphasis of research at present so develop under mesophilic condition.Silica-based apatite electrolyte relies on it, and high conductivity and oxygen ions migrate number, gentle thermal coefficient of expansion and good doping characteristic and chemical stability etc. make it become one of important replacer of YSZ under mesophilic condition.
The electrolyte of SOFC at first needs to have higher density, to prevent shuttling back and forth mutually of fuel gas and oxygen, guarantees the higher open circuit voltage of battery.Densification temperature with the silica-based apatite electrolyte of traditional solid reaction process preparation 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 cell preparation of electrode supporting structure.Adopt advanced sintering technology, can effectively reduce silica-based apatite material densification temperature.For example, the solid phase method that usefulness such as Panteix are traditional has prepared silica-based apatite powder material, utilizes hot pressed sintering, at 35 MPa, 1400
oPrepared density under the condition of C at (the Panteix P J of the potsherd more than 95%, 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 has increased preparation cost to the having relatively high expectations of equipment.Preparing nano-powder material by liquid phase method 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 process (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 have influenced the practical application of silica-based apatite electrolyte.Therefore be necessary to continue to explore the new method of the silica-based apatite electrolyte of effective reduction 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 that Cu mixes by citric acid-nitrate process.Can effectively improve the sintering activity of material by the doping of Cu, 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-yThe stoichiometric proportion of each element takes by weighing required La in (0≤x≤0.67)
2O
3, tetraethoxysilane (TEOS) and Cu (NO
3)
23H
2O.With 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+) the 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 as complexing agent, complexing agent is 1 ~ 3:1 with the amount of substance ratio of metal ion; Adding concentration is ammoniacal liquor adjusting pH value to 2 ~ 7 of 28%; TEOS is dissolved in a certain amount of absolute ethyl alcohol adds above-mentioned solution afterwards, the amount of substance ratio of absolute ethyl alcohol and TEOS is 30 ~ 80:1; Constantly stir and make solution fully mix back immigration 70 ~ 90
oEvaporation forms until wet gel in the water-bath of C, moves into baking oven then 70 ~ 120
oThe dry xerogel that forms of C is heated to xerogel its burning then, forms fluffy precursor powder after the burning.
B) above-mentioned precursor powder is moved into grind after Muffle furnace calcining 5 ~ 10 h sieve in (160 order), dry-pressing formed, high temperature sintering 4-10 h obtains fine and close material in air then.
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 process to prepare the silica-based apatite electrolyte La that Cu mixes
9.33+xSi
6-yCu
yO
26+1.5x-y(0≤x≤0.67,0＜y≤0.7), the gained powder body material has good sintering activity, has effectively promoted the densification of material.
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Description of drawings
Fig. 1 obtains the profile scanning Electronic Speculum figure of sample for example 1 of the present invention.
Fig. 2 obtains the profile scanning Electronic Speculum figure of sample for example 2 of the present invention.
Fig. 3 obtains the profile scanning Electronic Speculum figure of sample for example 3 of the present invention.
Fig. 4 obtains the X ray electronic diffraction collection of illustrative plates of sample for example 1 of the present invention, 2 and 3.
Embodiment
The present invention is described further below in conjunction with example, but be not limited to protection scope of the present invention.
Example 1:
Cu mixes to the facilitation of material densification for contrast, and the spy does plain sample, i.e. this example.Preparation La
9.67Si
6O
26.5:
A) with 3.937 g La
2O
3Be dissolved in 20 ml deionized waters and 30 ml concentration are the mixed liquor of 65wt% nitric acid, treat to add 13.922 g citric acids and 4.112 g ethylene glycol after the dissolving fully, magnetic agitation solution is to clarification.
B) regulate pH to 2-3 with the ammoniacal liquor of 28 wt%.
C) after being dissolved in 3.125 g TEOS in the 60 ml absolute ethyl alcohols, add above-mentioned solution; Move into 80 after magnetic agitation 3 h
oThe C water-bath occurs until gel; Gel is moved into 80
oOven dry is afterwards in 250 in the C baking oven
oC lights and obtains precursor powder.
D) with precursor powder 900
oC calcines 9 h, and the powder that calcining is obtained grinds and sieve in (160 order), put into electric furnace after dry-pressing formed, 1550
oSintering 6 h obtain final material under C, the air atmosphere, 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) with 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 treats to add 13.922 g citric acids and 4.112 g ethylene glycol after the dissolving fully, and magnetic agitation solution is to clarification.
B) regulate pH to 2-3 with the ammoniacal liquor of 28 wt%.
C) after being dissolved in 3.073 g TEOS in the 60 ml absolute ethyl alcohols, add above-mentioned solution; Move into 80 after magnetic agitation 3 h
oThe C water-bath occurs until gel; Gel is moved into 80
oOven dry is afterwards in 250 in the C baking oven
oC lights and obtains precursor powder.
D) with precursor powder 900
oC calcines 9 h, and the powder that calcining is obtained grinds and sieve in (160 order), put into electric furnace after dry-pressing formed, 1550
oSintering 6 h obtain final material under C, the air atmosphere, and the density that records material by Archimedes's drainage is 93.8%.The thing of XRD test material is single apatite phase mutually, does not have the second phase impurity and occurs.
Example 3:
This example is the sample of Cu doping y=0.5.Preparation La
9.67Si
5.5Cu
0.5O
26:
A) with 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 treats to add 13.922 g citric acids and 4.112 g ethylene glycol after the dissolving fully, and magnetic agitation solution is to clarification.
B) regulate pH to 2-3 with the ammoniacal liquor of 28 wt%.
C) after being dissolved in 2.865 g TEOS in the 60 ml absolute ethyl alcohols, add above-mentioned solution; Move into 80 after magnetic agitation 3 h
oThe C water-bath occurs until gel; Gel is moved into 80
oOven dry is afterwards in 250 in the C baking oven
oC lights and obtains precursor powder.
D) with precursor powder 900
oC calcines 9 h, and the powder that calcining is obtained grinds and sieve in (160 order), put into electric furnace after dry-pressing formed, 1550
oSintering 6 h obtain final material under C, the air atmosphere, and the density that records material by Archimedes's drainage is 95.0%.The thing of XRD test material is single apatite phase mutually, does not have the second phase impurity and occurs.
Claims (2)
1. a Cu mixes and promotes the 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, is expressed as La with molecular formula
9.33+xSi
6-yCu
yO
26+1.5x-y(x=0 ~ 0.67); 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 by weighing required La
2O
3, tetraethoxysilane is TEOS and Cu (NO
3)
23H
2O; With 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 deionized water and metal ion (comprise Si
4+) the amount of substance ratio be 10 ~ 50:1, the amount of substance ratio of nitric acid and metal ion is 5 ~ 20:1; Add complexing agent in the mixed solution, add concentration again and be 28% ammoniacal liquor and regulate pH value to 2 ~ 7, adding at last is dissolved with the ethanol solution of TEOS; Constantly stir and make solution fully mix back immigration 70 ~ 90
oEvaporation forms until wet gel in the water-bath of C, moves into baking oven then 70 ~ 120
oThe dry xerogel that forms of C; Xerogel is heated to its burning, forms fluffy precursor powder after the burning; 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, high temperature sintering 4-10 h obtains fine and close material in air then.
2. mixing according to the described Cu of claim 1 promotes the method for silica-based apatite electrolyte densification, it is characterized in that the calcining heat of described presoma is 800-1000
oC; The dense sintering temperature of material is 1400-1600
oC.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104201408A (en) * | 2014-07-31 | 2014-12-10 | 北京科技大学 | Cu-doped silicon-based apatite electrolyte material and preparation method of Cu-doped silicon-based apatite electrolyte material |
| 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 |
| CN110224146A (en) * | 2019-05-23 | 2019-09-10 | 湖北大学 | A kind of online densifying method of fuel-cell electrolyte low temperature |
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 |
-
2013
- 2013-04-14 CN CN201310128005.8A patent/CN103199287B/en not_active Expired - Fee Related
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 (6)
| Title |
|---|
| E. JOTHINATHAN等: "Powder synthesis, processing and characterization of lanthanum silicates for SOFC application", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| E. JOTHINATHAN等: "Synthesis of nano-crystalline apatite type electrolyte powders for solid oxide fuel cells", 《JOURNAL OF THE EUROPEAN CERAMIC SOCIETY》 * |
| E.V. TSIPIS等: "Electrochemical behavior of mixed-conducting oxide cathodes in contact with apatite-type La10Si5AlO26.5 electrolyte", 《ELECTROCHIMICA ACTA》 * |
| J. ZHOU等: "Synthesis and characterization of apatite-type La9.67Si6-xAlxO26.5-x/2 electrolyte materials and compatible cathode materials", 《SOLID STATE IONICS》 * |
| 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》 * |
| 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》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104201408A (en) * | 2014-07-31 | 2014-12-10 | 北京科技大学 | Cu-doped silicon-based apatite electrolyte material and preparation method of Cu-doped silicon-based apatite electrolyte material |
| 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 |
| CN110224146A (en) * | 2019-05-23 | 2019-09-10 | 湖北大学 | A kind of online densifying method of fuel-cell electrolyte low temperature |
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Granted publication date: 20141119 Termination date: 20190414 |