CN104201408A - Cu-doped silicon-based apatite electrolyte material and preparation method of Cu-doped silicon-based apatite electrolyte material - Google Patents
Cu-doped silicon-based apatite electrolyte material and preparation method of Cu-doped silicon-based apatite electrolyte material Download PDFInfo
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- CN104201408A CN104201408A CN201410373711.3A CN201410373711A CN104201408A CN 104201408 A CN104201408 A CN 104201408A CN 201410373711 A CN201410373711 A CN 201410373711A CN 104201408 A CN104201408 A CN 104201408A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
- H01M2300/0074—Ion conductive at high temperature
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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 aims at providing a Cu-doped silicon-based apatite electrolyte material which has simple preparation technology, is low in cost and meanwhile can effectively improve the conductivity of the silicon-based apatite electrolyte material, and a preparation method of the Cu-doped silicon-based apatite electrolyte material. According to the invention, the Si-position Cu-doped silicon-based apatite electrolyte material, namely La(10-x)Si(6-y)Cu(y)O(26+1.5x-y), is prepared by utilizing a sol-gel method, wherein x is larger than or equal to 0 and smaller than or equal to 0.67, and y is larger than 0.7 and smaller than or equal to 2; doping of Cu can effectively improve the ion conductivity of the material. According to the invention, Si position of a silicon-based apatite system is doped with Cu, the doped Cu can increase cell parameters and the size of an oxygen migration channel because the ion radius of Cu<2+> is larger than that of Si<4+>, and the migration rate of a current carrier is increased, so that the purpose of improving the conductivity is achieved by the doped Cu. Under the condition of same doping mount of Cu, the oxygen ion amount of the system can be increased by lowering the positive ion vacancy amount of La position, so that the amount of the current carrier in the oxygen ion migration process is increased, and the conductivity of the material is further improved.
Description
Technical field
The invention belongs to Solid Oxide Fuel Cell technical field, specifically relate to doped silicon based apatite electrolyte of a kind of Cu and preparation method thereof.
Background technology
Constantly increase at demand for energy, traditional fossil energy is day by day under exhausted background, finds that environmental friendliness, energy conversion efficiency are high, simple process, new forms of energy with low cost become the focus that researcher pays close attention to.Solid Oxide Fuel Cell (SOFC) can directly be converted to electric energy by the chemical energy in fuel and oxidant under constant temperature, not limited by Carnot cycle, so there is very high energy conversion efficiency, meanwhile, fuel cell also has low noise, discharge the pollutant such as oxysulfide, nitrogen oxide, structure of whole solid state scale hardly the advantage such as can adjust flexibly, thereby becomes a kind of wide concerned new energy technology.
Electrolyte is the core component of Solid Oxide Fuel Cell, and the performance of electrolyte is directly determining working temperature, the serviceability etc. of SOFC.The electrolyte of SOFC should possess that ionic conductivity is high, electronic conductivity is low, in good, good with the electrode material character such as chemical matching and matched coefficients of thermal expansion of fuel and oxidizing atmosphere stability inferior.Silica-based apatite electrolyte higher ionic conductivity under mesophilic condition, this point is to reducing the operating efficiency of SOFC, reduce battery system operation cost, raising battery system stability all tool has very important significance, in addition, silica-based apatite electrolyte can hold multiple doped chemical and doping content widely, has good thermal stability and chemical stability, therefore becomes a kind of electrolyte that has potentiality.
Electrolyte should possess higher ionic conductivity (higher than 1mScm
-1) could meet the instructions for use of SOFC.The electrolytical general structure of silica-based apatite can be write La
10(SiO
4)
6o
2due to the particularity of structure, the interstitial oxygen concentration existence that can hold cation vacancy simultaneously and exceed stoichiometric proportion, different from the oxygen Void diffusing mechanism of other oxygen ion conductor materials, conduction pattern that it is generally acknowledged silica-based apatite is gap mechanism (Roushown Ali, Masatomo Yashima, Yoshitaka Matsushita.Diffusion Path of Oxide Ions in an Apatite-Type Ionic Conductor La
967si
5.7mg
0.3o
26.24[J] .Journal of Materials Chemistry.2008,20:5203-5208.Alisonn Jones, Peter R.Slater, M. Saiful Islam.Local Defect Structures and Ion Transport Mechanisms in the Oxygen-Excess Apatite La
9.67(SiO
4)
6o
2.5[J] .Journal of Materials Chemistry, 2008,20:5055-5060).In silica-based apatite material structure, be present in the parallel oxygen passage of c-axis, interstitial oxygen concentration is generally present in oxygen passage, and move to the direction that is parallel and perpendicular to c-axis by oxygen passage, form gap mechanism, be not difficult to find out that thus the size of oxygen passage plays vital effect for mobility and the activation energy of oxonium ion, it is generally acknowledged that oxygen passage is larger, oxonium ion is migration more therein just.Studies show that about the La position at material and the doping of Si position in a large number, the different element that adulterates in La and Si position has different impacts to the conductivity of material, for example, when at the less element of La position doping ionic radius during as Mg, can cause conductivity reduction however in the time that a small amount of Mg is entrained in Si position, but greatly increased ionic conductivity (Kinoshita T, Iwata T, Bechade E.Effect of Mg substitution on crystal structure and oxide-ion conductivity of apatite-type lanthanum silicates[J]. Solid State Ionics, 2010, 181:1024-1032.Yoshioka H, Tanase S. Magnesium doped lanthanum silicate with apatite-type structure as an electrolyte for intermediate temperature solid oxide fuel cells[J]. Solid State Ionics, 2005, 176:2395-2398.) in addition, the quantity of La position cation vacancy is often relevant with the quantity of system interstitial oxygen concentration, thereby also conductivity is had a certain impact, as the La at B and Ga codope
9.33+x(SiO
4)
6o
2+1.5xin system, as B and one timing of Ga doping content, La
9.67(SiO
4)
5(GeO
4) O
2500
othe conductivity of C is 1.0 mScm
-1, and La
10(SiO
4)
5(GeO
4) O
2.5500
othe conductivity of C is 2.4 mScm
-1(Najib A, Sansom J E H, Tolchard J R. Doping strategies to optimize the oxide ion conductivity in apatite-type ionic conductors[J] .Dalton Transactions, 2004,19:3106-3109) illustrate that interstitial oxygen concentration has played significant contribution to oxygen ion conduction.
The present invention is in the Si position of silica-based apatite system doped with Cu, due to Cu
2+ionic radius be greater than Si
4+, Cu doping can increase the size of cell parameter and oxygen migrating channels, promotes the mobility of charge carrier, so Cu doping can reach the object of raising conductivity in the time of the doping of small amount.Under identical Cu doping, reduce the cation vacancy quantity of La position, can increase the oxonium ion quantity of system, thereby improve the quantity of the charge carrier in oxygen ions migrate process, further improve the conductivity of material.
Summary of the invention
In order to solve the above-mentioned technical problem existing in prior art, it is easy, with low cost that object of the present invention aims to provide a kind of preparation technology, can effectively improve doped silicon based apatite electrolyte of Cu of silica-based apatite electrolyte conductivity and preparation method thereof simultaneously.The present invention uses sol-gal process to prepare the silica-based apatite electrolyte of Si position doped with Cu, and the doping of Cu can effectively improve the ionic conductivity of material.
Technical scheme of the present invention is as follows:
The doped silicon based apatite electrolyte of a kind of Cu, is characterized in that: the molecular formula of the doped silicon based apatite electrolyte of described Cu is: La
10-xsi
6-ycu
yo
26+1.5x-y, wherein 0≤x≤0.67,0.7<y≤2.
Preferably, described x=0.33, y=0.8,1.4 or 2.
The preparation method of the doped silicon based apatite electrolyte of above-mentioned Cu, is characterized in that, concrete steps are as follows:
A, by molecular formula La
10-xsi
6-ycu
yo
26+1.5x-yin each element chemistry metering score another name get the La of respective quality
2o
3, tetraethoxysilane (TEOS) and Cu (NO
3)
23H
2o;
B, tetraethoxysilane (TEOS) is dissolved in to appropriate absolute ethyl alcohol, the volume ratio of absolute ethyl alcohol and TEOS is 20 ~ 80:1, then adds appropriate complexing agent, complexing agent and Si
4+the ratio of ion is 1 ~ 3:1, forms homogeneous solution A;
C, by La
2o
3and Cu (NO
3)
23H
2o is dissolved in the mixed liquor of a certain amount of nitric acid and deionized water, and nitric acid is 5 ~ 20:1 with the mol ratio of whole metal ions, and deionized water is 10 ~ 40:1 with the ratio of whole metal ion mol ratios; Add complexing agent, complexing agent is 1 ~ 4:1 with whole mol ratios of metal ions again, then to add concentration be that the ammoniacal liquor of 28wt% regulates pH to 1 ~ 5 rear formation homogeneous solution B;
D, solution A is slowly added dropwise to solution B, obtains solution C;
E, solution C is fully stirred, be placed in water-bath, 60 ~ 90
ounder C, evaporation becomes transparent gel, gel is placed in to baking oven, 100 ~ 300
ounder C, be heated to gel combustion, obtain the precursor powder of fluffy grey;
F, the precursor powder obtaining is evenly ground and is placed in Muffle furnace, 900
oc calcines 6 ~ 10h, and the material powder obtaining is placed in to agate mortar, grinds 1 ~ 3h, after moulding in air atmosphere 1550 ~ 1650
oc sintering 1 ~ 5h, obtains the doped silicon based apatite electrolyte of fine and close Cu.
Preferably, the sintering temperature in described step f is 1600
oc, sintering time is 3h.
Useful technique effect of the present invention is: the invention provides the doped silicon based apatite electrolyte of a kind of Cu, by the Si position doped with Cu in silica-based apatite system, due to Cu
2+ionic radius be greater than Si
4+, Cu doping can increase the size of cell parameter and oxygen migrating channels, promotes the mobility of charge carrier, so Cu doping can reach the object of raising conductivity in the time of the doping of small amount.Under identical Cu doping, reduce the cation vacancy quantity of La position, can increase the oxonium ion quantity of system, thereby improve the quantity of the charge carrier in oxygen ions migrate process, further improve the conductivity of material.Meanwhile, preparation technology of the present invention is easy, with low cost, and the product of preparation is single apatite phase, and free from admixture produces mutually, and dense electrolyte material has 1mScm
-1above conductivity, the doping of Cu has obviously improved the conductivity of material.
Brief description of the drawings
Fig. 1 is that the present invention obtains sample La
10-xsi
6-ycu
yo
26+1.5x-ythe X ray diffracting spectrum of (x=0.33, y=0.8).
Embodiment
Below in conjunction with accompanying drawing and embodiment, the present invention is described in further details.
embodiment 1
This example is La
10-xsi
6-ycu
yo
26+1.5x-ythe sample of (x=0.33, y=0.8), preparation La
9.67si
5.2cu
0.8o
25.7sample:
1. 6.556g citric acid and 1.937g ethylene glycol are dissolved in to 20ml deionized water, 3.250gTEOS is dissolved in 60ml absolute ethyl alcohol, then two kinds of solution are uniformly mixed to form to solution A.
2. by 4.724 g La
2o
3be dissolved in 25 ml deionized waters and 40 ml concentration are the mixed liquor of 65wt% nitric acid, to be dissolvedly add 0.580gCu (NO after completely
3)
23H
2o, then add 13.197g citric acid and 3.898g ethylene glycol, adding concentration is that 28% ammoniacal liquor regulates pH to 1 ~ 3, magnetic agitation solution, to clarification, forms solution B.
3. solution A is slowly added to solution B, obtain uniform clear solution C.
4. move into 80 by after solution C magnetic agitation 6 h
oc water-bath is until gel appearance; Gel is moved in baking oven and dried afterwards in 250
oc lights and obtains precursor powder.
By precursor powder grind after 900
oc calcines 8h, and the powder that calcining is obtained grinds, 150MPa cold isostatic compaction is put into electric furnace afterwards, 1600
ounder C, air atmosphere, sintering 3h obtains electrolyte.
The density that records material by Archimedes's drainage is 94.4%.The thing of XRD test material is single apatite phase mutually, and free from admixture produces mutually.By measuring the conductivity of the AC impedance conversion material under different temperatures, the conductivity of material at 600 DEG C is 3.6mScm
-1.
embodiment 2
The present embodiment is La
10-xsi
6-ycu
yo
26+1.5x-ythe sample of (x=0.33, y=1.4).Preparation La
9.67si
4.6cu
1.4o
25.1sample:
1. 5.800g citric acid and 1.713g ethylene glycol are dissolved in to 20ml deionized water, 2.875gTEOS is dissolved in 60ml absolute ethyl alcohol, then two kinds of solution are uniformly mixed to form to solution A.
2. by 4.724 g La
2o
3with 1.015g Cu (NO
3)
23H
2o is dissolved in 25 ml deionized waters and 40 ml concentration are the mixed liquor of 65wt% nitric acid, 13.953g citric acid and the 4.121g ethylene glycol of adding afterwards completely to be dissolved, adding concentration is that 28% ammoniacal liquor regulates pH to 1 ~ 3, and magnetic agitation solution, to clarification, forms solution B.
3. solution A is slowly added to solution B, obtain uniform clear solution C.
4. move into 80 by after solution C magnetic agitation 6 h
oc water-bath is until gel appearance; Gel is moved in baking oven and dried afterwards in 250
oc lights and obtains precursor powder.
By precursor powder grind after 900
oc calcines 9 h, and the powder that calcining is obtained grinds, 150MPa cold isostatic compaction is put into electric furnace afterwards, 1600
ounder C, air atmosphere, sintering 3h obtains electrolyte.
The density that records material by Archimedes's drainage is 97.8%.The thing of XRD test material is single apatite phase mutually, and free from admixture produces mutually.By measuring the conductivity of the AC impedance conversion material under different temperatures, the conductivity of material at 600 DEG C is 6.5mScm
-1.
embodiment 3
The present embodiment is La
10-xsi
6-ycu
yo
26+1.5x-ythe sample of (x=0.33, y=2).Preparation La
9.83si
4cu
2o
24.5sample:
1. 5.043g citric acid and 1.490g ethylene glycol are dissolved in to 20ml deionized water, 2.500gTEOS is dissolved in 60ml absolute ethyl alcohol, then two kinds of solution are uniformly mixed to form to solution A.
2. by 4.724 g La
2o
3with 1.450g Cu (NO
3)
23H
2o is dissolved in 25 ml deionized waters and 40 ml concentration are the mixed liquor of 65wt% nitric acid, 14.710g citric acid and the 4.345g ethylene glycol of adding afterwards completely to be dissolved, adding concentration is that 28% ammoniacal liquor regulates pH to 1 ~ 3, and magnetic agitation solution, to clarification, forms solution B.
3. solution A is slowly added to solution B, obtain uniform clear solution C.
4. move into 80 by after solution C magnetic agitation 6 h
oc water-bath is until gel appearance; Gel is moved in baking oven and dried afterwards in 250
oc lights and obtains precursor powder.
By precursor powder grind after 900
oc calcines 9 h, and powder that calcining is obtained grinds, put into electric furnace after dry-pressing formed, 1600
ounder C, air atmosphere, sintering 3h obtains electrolyte.
The density that records material by Archimedes's drainage is 98.3%.The thing of XRD test material is single apatite phase mutually, and free from admixture produces mutually.By measuring the conductivity of the AC impedance conversion material under different temperatures, the conductivity of material at 600 DEG C is 7.6mScm
-1.
Claims (4)
1. the doped silicon based apatite electrolyte of Cu, is characterized in that: the molecular formula of the doped silicon based apatite electrolyte of described Cu is: La
10-xsi
6-ycu
yo
26+1.5x-y, wherein 0≤x≤0.67,0.7<y≤2.
2. the doped silicon based apatite electrolyte of Cu according to claim 1, is characterized in that: described x=0.33, y=0.8,1.4 or 2.
3. a preparation method for the doped silicon based apatite electrolyte of the Cu described in claim 1 or 2, is characterized in that, concrete steps are as follows:
A, by molecular formula La
10-xsi
6-ycu
yo
26+1.5x-yin each element chemistry metering score another name get the La of respective quality
2o
3, tetraethoxysilane (TEOS) and Cu (NO
3)
23H
2o;
B, tetraethoxysilane (TEOS) is dissolved in to appropriate absolute ethyl alcohol, the volume ratio of absolute ethyl alcohol and TEOS is 20 ~ 80:1, then adds appropriate complexing agent, complexing agent and Si
4+the ratio of ion is 1 ~ 3:1, forms homogeneous solution A;
C, by La
2o
3and Cu (NO
3)
23H
2o is dissolved in the mixed liquor of a certain amount of nitric acid and deionized water, and nitric acid is 5 ~ 20:1 with the mol ratio of whole metal ions, and deionized water is 10 ~ 40:1 with the ratio of whole metal ion mol ratios; Add complexing agent, complexing agent is 1 ~ 4:1 with whole mol ratios of metal ions again, then to add concentration be that the ammoniacal liquor of 28wt% regulates pH to 1 ~ 5 rear formation homogeneous solution B;
D, solution A is slowly added dropwise to solution B, obtains solution C;
E, solution C is fully stirred, be placed in water-bath, 60 ~ 90
ounder C, evaporation becomes transparent gel, gel is placed in to baking oven, 100 ~ 300
ounder C, be heated to gel combustion, obtain the precursor powder of fluffy grey;
F, the precursor powder obtaining is evenly ground and is placed in Muffle furnace, 900
oc calcines 6 ~ 10h, and the material powder obtaining is placed in to agate mortar, grinds 1 ~ 3h, after moulding in air atmosphere 1550 ~ 1650
oc sintering 1 ~ 5h, obtains the doped silicon based apatite electrolyte of fine and close Cu.
4. the preparation method of the doped silicon based apatite electrolyte of Cu according to claim 3, is characterized in that: the sintering temperature in described step f is 1600
oc, sintering time is 3h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102642844A (en) * | 2012-04-18 | 2012-08-22 | 吉林大学 | Lithium chloride molten salt method for preparing lanthanum silicate electrolyte material powder with oxidapatite structure |
| CN103199287A (en) * | 2013-04-14 | 2013-07-10 | 北京科技大学 | Method for promoting densification of silicon-based apatite through doping Cu |
| WO2013118425A1 (en) * | 2012-02-07 | 2013-08-15 | 本田技研工業株式会社 | Catalyst structure for treating exhaust gas |
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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013118425A1 (en) * | 2012-02-07 | 2013-08-15 | 本田技研工業株式会社 | Catalyst structure for treating exhaust gas |
| CN102642844A (en) * | 2012-04-18 | 2012-08-22 | 吉林大学 | Lithium chloride molten salt method for preparing lanthanum silicate electrolyte material powder with oxidapatite structure |
| CN103199287A (en) * | 2013-04-14 | 2013-07-10 | 北京科技大学 | Method for promoting densification of silicon-based apatite through doping Cu |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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