CN104201408B - A kind of Cu silica-based apatite electrolyte of doping and preparation method thereof - Google Patents
A kind of Cu silica-based apatite electrolyte of doping and preparation method thereof Download PDFInfo
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- CN104201408B CN104201408B CN201410373711.3A CN201410373711A CN104201408B CN 104201408 B CN104201408 B CN 104201408B CN 201410373711 A CN201410373711 A CN 201410373711A CN 104201408 B CN104201408 B CN 104201408B
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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
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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
- H01M2008/1293—Fuel cells with solid oxide electrolytes
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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
- 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 discloses the purpose of the present invention, to aim to provide a kind of preparation technology easy, with low cost, can be effectively improved the Cu of silica-based apatite electrolyte electrical conductivity simultaneously and adulterate silica-based apatite electrolyte and preparation method thereof.The present invention uses sol-gal process to be prepared for the silica-based apatite electrolyte La of Si position doping Cu10‑xSi6‑yCuyO26+1.5x‑y, wherein 0≤x≤0.67,0.7 < y≤2；The doping of Cu can be effectively improved the ionic conductivity of material.The present invention is at the Si position of silica-based apatite system doping Cu, due to Cu2+Ionic radius more than Si4+, Cu doping can increase cell parameter and the size of oxygen migration passage, promote the mobility of carrier, so Cu doping can reach to improve the purpose of electrical conductivity.Under identical Cu doping, reduce the cation vacancy quantity of La position, the oxonium ion quantity of system can be increased, thus improve the quantity of the carrier in oxonium ion transition process, improve the electrical conductivity of material further.
Description
Technical field
The invention belongs to SOFC technical field, be specifically related to a kind of Cu doping silica-based apatite electricity
Solve material and preparation method thereof.
Background technology
Constantly increase at demand for energy, under background that traditional fossil energy is day by day exhausted, find environmental friendliness, energy turns
Change efficiency height, simple process, new forms of energy with low cost become the focus that researcher pays close attention to.SOFC
(SOFC) can not limited by Carnot cycle directly the chemical energy in fuel and oxidant is converted to electric energy under constant temperature, so
Having a highest energy conversion efficiency, meanwhile, fuel cell also has low noise, discharges oxysulfide, nitrogen oxygen hardly
The advantages such as the pollutants such as compound, structure of whole solid state scale can be adjusted flexibly, thus become the most concerned a kind of new energy technology.
Electrolyte is the core component of SOFC, and the performance of electrolyte directly determines
The operating temperature of SOFC, serviceability etc..The electrolyte of SOFC should possess ionic conductivity height, electronic conductivity
Low, in the good chemical matching the best with electrode material of fuel and oxidizing atmosphere stability inferior and matched coefficients of thermal expansion
Etc. character.The ionic conductivity that silica-based apatite electrolyte is the highest, this point work effect to reducing SOFC
Rate, reduces battery system operation cost, improves battery system stability and all has and have very important significance, in addition, and silica-based phosphorus
Lime stone electrolyte can accommodate multiple doped chemical and doping content widely, has good heat endurance and chemically stable
Property, therefore become the electrolyte of a kind of great potential.
Electrolyte should possess the high ionic conductivity of comparison (higher than 1mS cm-1) use of SOFC could be met
Requirement.The general structure of silica-based apatite electrolyte can write La10(SiO4)6O2, due to the particularity of structure, can hold simultaneously
Receive cation vacancy and beyond stoichiometric proportion interstitial oxygen concentration exist, with the Lacking oxygen migration mechanism of other oxygen ion conductor materials
Different, it is considered that the conduction pattern of silica-based apatite be gap mechanism (Roushown Ali, Masatomo Yashima,
Yoshitaka Matsushita.Diffusion Path of Oxide Ions in an Apatite-Type Ionic
Conductor La967Si5.7Mg0.3O26.24[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 La9.67(SiO4)6O2.5[J].
Journal of Materials Chemistry, 2008,20:5055-5060).Silica-based Apatite materials structure is present in c
The oxygen passage that axle is parallel, interstitial oxygen concentration is generally present in oxygen passage, and moves to the direction being parallel and perpendicular to c-axis by oxygen passage
Moving, constitute gap mechanism, be thus not difficult to find out, the size of oxygen passage, mobility and activation energy for oxonium ion rise
To vital effect, it is considered that oxygen passage is the biggest, oxonium ion is the easiest to be migrated wherein.A large amount of about at material
The research of La position and the doping of Si position shows, the different element that adulterates in La with Si position has different shadows to the electrical conductivity of material
Ring, such as, as the element such as Mg less at La position Doped ions radius, reducing but as a small amount of Mg of electrical conductivity can be caused
When being entrained in Si position, but considerably increase 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.) it addition, the quantity of La position cation vacancy often with system interstitial oxygen concentration
Quantity is relevant, thus also has a certain impact electrical conductivity, such as the La at B and Ga codope9.33+x(SiO4)6O2+1.5xIn system,
As B Yu Ga doping content one timing, La9.67(SiO4)5(GeO4) O2500oThe electrical conductivity of C is 1.0 mS cm-1, and La10
(SiO4)5(GeO4) O2.5500oThe electrical conductivity of C is then 2.4 mS cm-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 is to oxonium ion
Conduction serves significant contribution.
The present invention is at the Si position of silica-based apatite system doping Cu, due to Cu2+Ionic radius more than Si4+, Cu doping can
To increase cell parameter and the size of oxygen migration passage, promote the mobility of carrier, so Cu mixes when less amount of doping
The miscellaneous purpose that can reach to improve electrical conductivity.Under identical Cu doping, reduce the cation vacancy quantity of La position, Ke Yizeng
Add the oxonium ion quantity of system, thus improve the quantity of the carrier in oxonium ion transition process, improve the electricity of material further
Conductance.
Summary of the invention
In order to solve above-mentioned technical problem present in prior art, the purpose of the present invention aims to provide a kind of preparation technology
Easy, with low cost, the Cu doping silica-based apatite electricity of silica-based apatite electrolyte electrical conductivity can be effectively improved simultaneously
Solve material and preparation method thereof.The present invention uses sol-gal process to be prepared for the silica-based apatite electrolyte material of Si position doping Cu
Material, the doping of Cu can be effectively improved the ionic conductivity of material.
Technical scheme is as follows:
A kind of Cu silica-based apatite electrolyte of doping, it is characterised in that: described Cu doping silica-based apatite electrolysis
The molecular formula of material is: La10-xSi6-yCuyO26+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 above-mentioned Cu silica-based apatite electrolyte of doping, it is characterised in that specifically comprise the following steps that
A, by molecular formula La10-xSi6-yCuyO26+1.5x-yIn each element chemistry metering score another name take respective quality
La2O3, tetraethyl orthosilicate (TEOS) and Cu (NO3)2·3H2O；
B, tetraethyl orthosilicate (TEOS) dissolving in appropriate absolute ethyl alcohol, absolute ethyl alcohol is 20 ~ 80:1 with the volume ratio of TEOS,
Add appropriate complexing agent, complexing agent and Si4+The ratio of ion is 1 ~ 3:1, forms homogeneous solution A；
C, by La2O3With Cu (NO3)2·3H2O is dissolved in the mixed liquor of a certain amount of nitric acid and deionized water, and nitric acid is with whole
The mol ratio of metal ion is 5 ~ 20:1, 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 the mol ratio of whole metal ions, adds shape after the ammoniacal liquor regulation pH to 1 ~ 5 that concentration is 28wt%
Uniformly solution B；
D, solution A is slowly added dropwise into solution B, obtains solution C；
E, solution C is sufficiently stirred for, is placed in water-bath, 60 ~ 90oUnder C, evaporation becomes transparent gel, is put by gel
In baking oven, 100 ~ 300oIt is heated to gel combustion under C, obtains the precursor powder of fluffy grey；
F, the precursor powder obtained uniformly is ground it is placed in Muffle furnace, 900oC calcines 6 ~ 10h, the material that will obtain
Material powder is placed in agate mortar, grinds 1 ~ 3h, after shaping in air atmosphere 1550 ~ 1650oC sinters 1 ~ 5h, obtains densification
Cu adulterate silica-based apatite electrolyte.
Preferably, the described sintering temperature in step f is 1600oC, sintering time is 3h.
The Advantageous Effects of the present invention is: the invention provides a kind of Cu silica-based apatite electrolyte of doping, logical
Cross the Cu that adulterates in the Si position of silica-based apatite system, due to Cu2+Ionic radius more than Si4+, Cu doping can increase structure cell ginseng
Number and the size of oxygen migration passage, promote the mobility of carrier, so Cu doping can reach to carry when less amount of doping
The purpose of high conductivity.Under identical Cu doping, reduce the cation vacancy quantity of La position, can increase the oxygen of system from
Quantum count, thus improve the quantity of the carrier in oxonium ion transition process, improve the electrical conductivity of material further.Meanwhile, originally
The preparation technology of invention is easy, with low cost, and the product of preparation is single apatite phase, and free from admixture produces mutually, dense electrolyte
Material has 1mS cm-1Above electrical conductivity, the doping of Cu significantly improves the electrical conductivity of material.
Accompanying drawing explanation
Fig. 1 is that the present invention obtains sample La10-xSi6-yCuyO26+1.5x-yThe X ray diffracting spectrum of (x=0.33, y=0.8).
Detailed description of the invention
Below in conjunction with the accompanying drawings and the present invention is described in further details by embodiment.
Embodiment 1
This example is La10-xSi6-yCuyO26+1.5x-yThe sample of (x=0.33, y=0.8), prepares La9.67Si5.2Cu0.8O25.7Sample
Product:
1. 6.556g citric acid and 1.937g ethylene glycol being dissolved in 20ml deionized water, it is anhydrous that 3.250gTEOS is dissolved in 60ml
Ethanol, then two kinds of solution are uniformly mixed to form solution A.
2. by 4.724 g La2O3It is dissolved in 25 ml deionized waters and mixed liquor that 40 ml concentration are 65wt% nitric acid, treats
0.580gCu (NO is added after dissolving completely3)2·3H2O, adds 13.197g citric acid and 3.898g ethylene glycol, adds dense
Degree is the ammoniacal liquor regulation pH to 1 ~ 3 of 28%, and magnetic agitation solution, to clarification, forms solution B.
3. solution A is slowly added into solution B, obtains uniform clear solution C.
4. will move into 80 after solution C magnetic agitation 6 hoC water-bath is until gel occurs；Gel is moved in baking oven and dry
In 250 after GanoC lights and obtains precursor powder.
5. 900 after precursor powder being groundoC calcines 8h, and it is quiet that powder calcining obtained grinds, 150MPa is cold etc.
Electric furnace is put into, 1600 after moldedoSinter 3h under C, air atmosphere and obtain electrolyte.
The consistency being recorded material by Archimedes's drainage is 94.4%.The thing of XRD detection material is single phosphorus mutually
Lime stone phase, free from admixture produces mutually.By measuring the electrical conductivity of the AC impedance conversion material under different temperatures, material is at 600 DEG C
Under electrical conductivity be 3.6mS cm-1。
Embodiment 2
The present embodiment is La10-xSi6-yCuyO26+1.5x-yThe sample of (x=0.33, y=1.4).Preparation
La9.67Si4.6Cu1.4O25.1Sample:
1. 5.800g citric acid and 1.713g ethylene glycol being dissolved in 20ml deionized water, it is anhydrous that 2.875gTEOS is dissolved in 60ml
Ethanol, then two kinds of solution are uniformly mixed to form solution A.
2. by 4.724 g La2O3With 1.015g Cu (NO3)2·3H2O is dissolved in 25 ml deionized waters and 40 ml concentration
For the mixed liquor of 65wt% nitric acid, 13.953g citric acid and the 4.121g ethylene glycol of adding the most afterwards to be dissolved, addition concentration
Being the ammoniacal liquor regulation pH to 1 ~ 3 of 28%, magnetic agitation solution, to clarification, forms solution B.
3. solution A is slowly added into solution B, obtains uniform clear solution C.
4. will move into 80 after solution C magnetic agitation 6 hoC water-bath is until gel occurs；Gel is moved in baking oven and dry
In 250 after GanoC lights and obtains precursor powder.
5. 900 after precursor powder being groundoC calcines 9 h, and it is quiet that the powder that calcining obtained grinds, 150MPa is cold etc.
Electric furnace is put into, 1600 after moldedoSinter 3h under C, air atmosphere and obtain electrolyte.
The consistency being recorded material by Archimedes's drainage is 97.8%.The thing of XRD detection material is single phosphorus mutually
Lime stone phase, free from admixture produces mutually.By measuring the electrical conductivity of the AC impedance conversion material under different temperatures, material is at 600 DEG C
Under electrical conductivity be 6.5mS cm-1。
Embodiment 3
The present embodiment is La10-xSi6-yCuyO26+1.5x-yThe sample of (x=0.33, y=2).Preparation La9.83Si4Cu2O24.5Sample
Product:
1. 5.043g citric acid and 1.490g ethylene glycol being dissolved in 20ml deionized water, it is anhydrous that 2.500gTEOS is dissolved in 60ml
Ethanol, then two kinds of solution are uniformly mixed to form solution A.
2. by 4.724 g La2O3With 1.450g Cu (NO3)2·3H2O is dissolved in 25 ml deionized waters and 40 ml concentration
For the mixed liquor of 65wt% nitric acid, 14.710g citric acid and the 4.345g ethylene glycol of adding the most afterwards to be dissolved, addition concentration
Being the ammoniacal liquor regulation pH to 1 ~ 3 of 28%, magnetic agitation solution, to clarification, forms solution B.
3. solution A is slowly added into solution B, obtains uniform clear solution C.
4. will move into 80 after solution C magnetic agitation 6 hoC water-bath is until gel occurs；Gel is moved in baking oven and dry
In 250 after GanoC lights and obtains precursor powder.
5. 900 after precursor powder being groundoC calcines 9 h, the powder that calcining obtained grinds, dry-pressing formed after
Put into electric furnace, 1600oSinter 3h under C, air atmosphere and obtain electrolyte.
The consistency being recorded material by Archimedes's drainage is 98.3%.The thing of XRD detection material is single phosphorus mutually
Lime stone phase, free from admixture produces mutually.By measuring the electrical conductivity of the AC impedance conversion material under different temperatures, material is at 600 DEG C
Under electrical conductivity be 7.6mS cm-1。
Claims (4)
1. the Cu silica-based apatite electrolyte of doping, it is characterised in that: the described Cu silica-based apatite electrolyte of doping
The molecular formula of material is: La10-xSi6-yCuyO26+1.5x-y, wherein 0≤x≤0.67,0.7 < y≤2.
Cu the most according to claim 1 adulterates silica-based apatite electrolyte, it is characterised in that: described x=0.33, y
=0.8,1.4 or 2.
3. the preparation method of the Cu silica-based apatite electrolyte of doping described in a claim 1 or 2, it is characterised in that
Specifically comprise the following steps that
A, by molecular formula La10-xSi6-yCuyO26+1.5x-yIn each element chemistry metering score another name take the La of respective quality2O3, positive silicon
Acetoacetic ester (TEOS) and Cu (NO3)2·3H2O；
B, tetraethyl orthosilicate (TEOS) dissolving in appropriate absolute ethyl alcohol, absolute ethyl alcohol is 20 ~ 80:1 with the volume ratio of TEOS, then adds
Enter appropriate complexing agent, complexing agent and Si4+The ratio of ion is 1 ~ 3:1, forms homogeneous solution A；
C, by La2O3With Cu (NO3)2·3H2O is dissolved in the mixed liquor of a certain amount of nitric acid and deionized water, nitric acid and whole metals
The mol ratio of ion is 5 ~ 20:1, 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 the mol ratio of whole metal ions, is formed after adding the ammoniacal liquor regulation pH to 1 ~ 5 that concentration is 28wt%
Homogeneous solution B；
D, solution A is slowly added dropwise into solution B, obtains solution C；
E, solution C is sufficiently stirred for, is placed in water-bath, 60 ~ 90oUnder C, evaporation becomes transparent gel, and gel is placed in baking
In case, 100 ~ 300oIt is heated to gel combustion under C, obtains the precursor powder of fluffy grey；
F, the precursor powder obtained uniformly is ground it is placed in Muffle furnace, 900oC calcines 6 ~ 10h, the material powder that will obtain
It is placed in agate mortar, grinds 1 ~ 3h, after shaping in air atmosphere 1550 ~ 1650oC sinters 1 ~ 5h, and the Cu obtaining densification mixes
Miscellaneous silica-based apatite electrolyte.
The preparation method of the Cu the most according to claim 3 silica-based apatite electrolyte of doping, it is characterised in that: described
Step f in sintering temperature be 1600oC, sintering time is 3h.
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