CN1747212A - Structure of fuel battery electrode/sandwich/electrolyte from solid oxide - Google Patents

Structure of fuel battery electrode/sandwich/electrolyte from solid oxide Download PDF

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CN1747212A
CN1747212A CNA2005101126012A CN200510112601A CN1747212A CN 1747212 A CN1747212 A CN 1747212A CN A2005101126012 A CNA2005101126012 A CN A2005101126012A CN 200510112601 A CN200510112601 A CN 200510112601A CN 1747212 A CN1747212 A CN 1747212A
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electrolyte
electrode
interlayer
sandwich
solid oxide
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王世忠
钟昊
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Xiamen University
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Xiamen University
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Abstract

The invention is all-purpose, high activity and high stability, and can improve performance of electrode. It comprises electrode, interlayer and electrolyte. The interlayer is located between electrode and electrolyte. The composition of interlayer is identical with electrode. The electrolyte is doped LaGaO3 with identical Lax1Re1-x1Gax2Mgx3M1-x2-x3Ox4, and Re is Sr, Ca and Ba alkali earth metal, and M is Fe, Co and Ni transition metal. The x1, x2, x3, and x4 are stoichiometric numbers.

Description

A kind of fuel battery electrode/sandwich/electrolyte from solid oxide structure
Technical field
The present invention relates to a kind of Solid Oxide Fuel Cell, especially relate to a kind of general high activity, high stability intermediate temperature solid oxide fuel cell electrode/sandwich/electrolyte structure.
Background technology
Fuel cell is a kind of chemical energy-device for converting electric energy, can continuously chemical energy be converted to electric energy efficiently.Actual service efficiency is 2-3 a times of ordinary hot machine.Intermediate temperature solid oxide fuel cell (ITSOFC) is a kind of efficient, eco-friendly electrical energy production mode.Yet the reduction of battery operational temperatures causes the rapid decline of electrode activity, therefore develop high performance in warm electrode material be an emphasis of present people's research.(United States Patent (USP) No.6586127B1) is warm electrolyte in the extraordinary class of performance to the lanthanum gallate series material of Ishihara invention, because this electrolytical invention time is shorter, lacks the development of corresponding electrode material.
Reported in the document that the lanthanum gallate of utilizing interlayer to improve to mix is the method (Wang Shizhong etc. of electrolytical Solid Oxide Fuel Cell nickel anode performance, Acta PhySico-Chimica Sinica, 2003,19 (9): 849), used sandwich material is the contour oxygen-ion conduction material of cerium oxide (SDC) of strontium doping, and its principle is for improving the performance of electrode by the oxygen transmission activity that changes electrode/electrolyte interface.This method is because the SDC sandwich material that adds and the electrolytical physics of the lanthanum gallate of doping, chemical property are different, reaction between interlayer and the electrolyte can take place in cell preparation process and long-time running process, and there is difference in the thermal coefficient of expansion between interlayer and the electrolyte, interlayer can take place in the preparation process of interlayer and battery heating-cooling process and electrolytically peels off or ruptures.
Summary of the invention
The objective of the invention is at the not good shortcoming of existing solid oxide fuel cell electrode performance, a kind of general, high activity, high stability are provided, can significantly improve the intermediate temperature solid oxide fuel cell electrode/sandwich/electrolyte structure of electrode performance.
The present invention is provided with electrode, interlayer and electrolyte, and interlayer is between electrode and electrolyte, and the composition of interlayer is identical with electrolyte.The lanthanum gallate of said electrolyte for mixing has identical or close La X1Re 1-x1Ga X2Mg X3M 1-x2-x3O X4(Re is alkaline-earth metal such as Sr, Ca, Ba to simplest formula, M is transition metal such as Fe, Co, Ni, x1, x2, x3, x4 are stoichiometric number), and have high oxygen ionic conductivity, the said close only stoichiometric number change that is meant, said high oxygen ionic conductivity is meant that the conductivity under the battery operation temperature is higher than 0.01S.cm -1
Said electrode is the mixed conductor negative electrode, or metal anode, or mixed conductor negative electrode and oxygen ion conductor, or mixed conductor negative electrode and oxonium ion-electron mixed conductor, or metal anode and oxygen ion conductor, or the combination electrode of metal anode and oxonium ion-electron mixed conductor formation.Said mixed conductor negative electrode is Ln xSr 1-xCoO 3(Ln is a rare earth element, x=0.9-0.5) or Ln xSr 1-xCo yFe 1-yO 3(Ln is a rare earth element, x=0.9-0.5, y=0-1) mixed conductor oxide; Said metal anode is the nickel metal anode; Said combination electrode is Ln xSr 1-xCoO 3(Ln is a rare earth element, x=0.9-0.5) or Ln xSr 1-xCo yFe 1-yO 3(Ln is a rare earth element, x=0.9-0.5, and y=0-1) mixed conductor oxide material or nickel metal anode have consistent or close La with the lanthanum gallate electrolyte of doping X1Re 1-x1Ga X2Mg X3M 1-x2-x3O X4Simplest formula (Re is alkaline-earth metal such as Sr, Ca, Ba, and M is transition metal such as Fe, Co, Ni, x1, and x2, x3, x4 are stoichiometric number), and have the combination electrode that high oxygen ionic conductivity material mixing forms.
The lanthanum gallate of said electrolyte for mixing has La X1Re 1-x1Ga X2Mg X3M 1-x2-x3O X4Simplest formula (Re is alkaline-earth metal such as Sr, Ca, Ba, and M is transition metal such as Fe, Co, Ni, x1, and x2, x3, x4 are stoichiometric number), and have high oxygen ionic conductivity.The composition of interlayer is consistent or close with the lanthanum gallate electrolyte of doping.
The present invention has identical or close La by adopting to add with electrolyte between electrode/electrolyte interface X1Re 1-x1Ga X2Mg X3M 1-x2-x3O X4(Re is alkaline-earth metal such as Sr, Ca, Ba to simplest formula, M is transition metal such as Fe, Co, Ni, x1, x2, x3, x4 is a stoichiometric number), and has an activity that high oxygen ionic conductivity interlayer has significantly improved electrode, its principle has changed electrolytical surface texture for the adding by interlayer, replacing electrode/electrolyte interface with the electrode/sandwich interface with good three phase boundary (gas phase/electrode/electrolyte) and two-phase interface (electrode/electrolyte) structure becomes the key reaction zone, thereby has improved the activity of electrode.Because interlayer has identical or close composition with the lanthanum gallate electrolyte of doping, therefore the chemistry and the thermal compatibility that have height, and interlayer and electrode have very high interface combination degree, thereby make the electrode/sandwich/electrolyte structure have high stability.When electrode is that mixed conductor negative electrode or metal anode electrode material have consistent or close La with the lanthanum gallate electrolyte with doping X1Re 1-x1Ga X2Mg X3M 1-x2-x3O X4(Re is alkaline-earth metal such as Sr, Ca, Ba to simplest formula, M is transition metal such as Fe, Co, Ni, x1, x2, x3, x4 is a stoichiometric number), and have the combination electrode that high oxygen ionic conductivity material mixing forms, the network configuration that can further form the lanthanum gallate material of the doping that has high oxygen ionic conductivity among electrolyte-interlayer-combination electrode three makes electrode have the electro-chemical activity and stability of height.
Principle of the present invention is to utilize that lanthanum gallate electrolyte with doping of preparation has identical La between the lanthanum gallate electrolyte that mixes and electrode X1Re 1-x1Ga X2Mg X3M 1-x2-x3O X4(Re is alkaline-earth metal such as Sr, Ca, Ba to simplest formula, M is transition metal such as Fe, Co, Ni, x1, x2, x3, x4 are stoichiometric number), and has an interlayer of high oxygen ionic conductivity material powder, changed the bath surface pattern and with the sintering character of electrode, its result has increased the area of gas phase/electrode/electrolyte three phase boundary length and electrode/electrolyte two-phase interface for interlayer has changed the microstructure of electrode and electrolyte interface as the transition zone between an electrolyte and the electrode.Its final result is for replacing the crucial active region that electrode/electrolyte interface becomes reaction with the electrode/sandwich interface.The increase of three phase boundary length can directly provide new active reaction position, improves electrode performance.The increase of two-phase interface area can improve the transport capability of oxonium ion, can significantly improve the speed that is subjected to oxonium ion transmission control reaction.Because sandwich material has identical or close composition and structure with the lanthanum gallate electrolyte of doping, thereby have the chemistry and the thermal compatibility of height, can guarantee the stability of electrolyte/interlayer.Because electrode/sandwich has interfacial structure well, can improve the stability of electrode.Behind the combination electrode that electrode employing electrode material itself prepares with the sandwich material powder, can further form the network configuration of the lanthanum gallate hyperoxia ionic conductivity material that mixes among electrolyte-interlayer-combination electrode three, make electrode have the electro-chemical activity and stability of height.
The lanthanum gallate that The present invention be directed to mix is the method that electrolytical Solid Oxide Fuel Cell has provided a general raising electrode performance, by having identical La at electrode/electrolyte interface intermediate preparation one deck with the lanthanum gallate electrolyte of doping X1Re 1-x1Ga X2Mg X3M 1-x2-x3O X4Simplest formula (Re is alkaline-earth metal such as Sr, Ca, Ba, and M is transition metal such as Fe, Co, Ni, x1, and x2, x3, x4 are stoichiometric number), and have electro-chemical activity and the stability that high oxygen ionic conductivity material clip layer has significantly improved electrode.Electrode can be Ln xSr 1-xCoO 3(Ln is a rare earth element, x=0.9-0.5) or Ln xSr 1-xCo yFe 1-yO 3(Ln is a rare earth element, x=0.9-0.5, and y=0-1) mixed conductor oxide, perhaps nickel metal anode, and above-mentioned electrode material is with having identical La with the lanthanum gallate electrolyte that mixes X1Re 1-x1Ga X2Mg X3M 1-x2-x3O X4Simplest formula (Re is alkaline-earth metal such as Sr, Ca, Ba, and M is transition metal such as Fe, Co, Ni, x1, and x2, x3, x4 are stoichiometric number), and have the combination electrode that high oxygen ionic conductivity material powder is mixed and made into.
Description of drawings
Fig. 1 has SSC-LSGMC5 (15wt%) the electrode sections SEM figure on the LSGMC5 electrolyte of different temperatures roasting LSGMC5 interlayer for load: (a) no interlayer, (b) 1573K interlayer, (c) 1673K interlayer, (d) 1748K interlayer.
Fig. 2 is that load has SSC-LSGMC5 (15wt%) polarization of electrode curve on the LSGMC5 electrolyte of different temperatures roasting LSGMC5 interlayer in 973K, the oxygen: 1a 1673K, 1b 1748K, 1c 1573K, 2 no interlayer samples.
Fig. 3 has before and after SSC-LSGMC5 (15wt%) electrode polarization on the LSGMC5 electrolyte of 1673K roasting LSGMC5 interlayer for load, in the oxygen, the electrode polarization resistance under the different temperatures.
Fig. 4 is the ac impedance spectroscopy that load has SSC-LSGMC5 (15wt%) electrode on the LSGMC5 electrolyte of LSGMC5 or LSGMC9 interlayer in 973K, the oxygen: a LSGMC5, and b LSGMC9, c does not have interlayer.
Fig. 5 is the polarization curve that load has LSCF8282-LSGMC5 (15wt%) negative electrode on the LSGM9182 electrolyte of LSGMC5 interlayer in 1053K, the air.
Fig. 6 is the polarization curve that load has Ni-LSGMC9 (10wt%) anode on the LSGM9182 electrolyte of LSGMC5 interlayer in 873K, the hydrogen.
Embodiment
Following examples will further specify in conjunction with the accompanying drawings sandwich of the present invention and to electrode activity with stability raising.
Embodiment 1
Embodiment 1 has prepared and has been carried on La 0.8Sr 0.2Ga 0.8Mg 0.15Co 0.05O 3(LSGMC5) the LSGMC5 interlayer of the different temperatures sintering on the electrolyte, and on interlayer sintering Sm 0.5Sr 0.5CoO 3-La 0.8Sr 0.2Ga 0.8Mg 0.15Co 0.05O 3(SSC-LSGMC5 (15wt%)) combination electrode material has been investigated the influence of LSGMC5 interlayer sintering temperature for electrode, interlayer and electrode/sandwich/electrolyte interface.
La 0.8Sr 0.2Ga 0.8Mg 0.15Co 0.05O 3(LSGMC5) electrolyte is synthetic with solid-phase synthesis, and used initial feed is La 2O 3(99.99% mass fraction, down together), SrCO 3(99.5%), MgO (99.5%), Ga 2O 3(99.99%) and CoO (99.99%).Above-mentioned raw materials grinds 0.5h than mixing the back with mortar by metering, and dry back is at 1273K pre-burning 6h.Sample after the pre-burning depresses to the disk that diameter is 2.0cm at 274.6MPa, and in air 1748K roasting 6h.Sample after the roasting grinds to form the thick thin slice of uniform 0.3mm with the grinding and polishing machine.
The SSC powder adopts solid phase method synthetic, and raw material is Sm 2O 3(99.99%), SrCO 3(99.99%), Co (CH 3COO) 2.4H 2O (99.99%).After raw material adds alcohol and grinds 0.5h with mortar, at 923-1023K pre-burning 2h.After sample after the pre-burning adds alcohol grinding 0.5h, at 1273-1373K roasting 6-12h.Sample after the pre-burning adds alcohol and grinds behind the 0.5h standby.
The LSGMC5 powder adopts solid-phase synthesis synthetic.La with high-purity (99.99%) 2O 3, Ga 2O 3, SrCO 3, MgO, CoO mix and to be incorporated in ball milling 12-24h in the alcohol medium, dry back is at 1473-1673K roasting 2-24h.After the roasting, ball milling 6-12h in the alcohol medium, the particles of powder degree is less than 10 μ m.Being prepared as directly of combination electrode mixes above-mentioned LSGMC5 powder with electrode powder, then ball milling 2-12h in the alcohol medium.Combination electrode material is made into slurry.
At first utilize method for printing screen LSGMC5 interlayer and at different temperatures (1573K to 1748K) roasting 6h in the printing of the both sides of blank electrolysis matter, the thickness of interlayer is 2-5 μ m, and then have SSC-LSGMC5 of the same area (15wt%) composite cathode, roasting 2h under the 1223K air conditions printing on the interlayer.
The microstructure that 1223K is sintered in SSC-LSGMC5 (15wt%) combination electrode cross section on the LSGMC5 interlayer of load on LSGMC5 bath surface and the LSGMC5 electrolyte is shown in Fig. 1.As seen from Figure 1, the microstructure of SSC combination electrode is comparatively typical porous electrode, and the introducing of interlayer does not bring influence to the electrode microstructure.Structure among Fig. 1 (a) shows, under the situation that does not have interlayer to exist, the SSC electrode combines relatively poorly with electrolytical, has a large amount of holes between electrode and the electrolyte interface.Fig. 1 (b) is the microstructure of the electrode/electrolyte interlayer behind the adding 1573K roasting interlayer.Interlayer has loose structure.Fig. 1 (c) is for containing the sample of 1673K roasting interlayer, therefrom can observe the thin film sandwich that one deck compact structure is arranged between electrolyte and the electrode, thickness is about 2-5 μ m, good sintering takes place in interlayer and electrolyte body, fuse into one, but still can observe interface of existence between interlayer and the electrolyte.Electrode and combining of LSGMC5 interlayer are much better than the combination degree of electrode/electrolyte interface among Fig. 1 (a).Fig. 1 (d) is for containing the sample of 1748K roasting interlayer, the interlayer that increases fully and electrolyte fuse into one, significantly do not distinguish between interlayer and the electrolyte, but comparison diagram 1 (a) with (d) can obviously find, add that the roughness of bath surface significantly increases behind the interlayer.The combination degree of electrode and interlayer is very good among Fig. 1 (d), and similar to the situation of Fig. 1 (c), the contact area at electrode/sandwich interface and intensity all obviously are better than electrode/electrolyte interface.The result of Fig. 1 shows, have high temperature (＞1673K) electrode of sintering interlayer sample and the interface of interlayer have tangible sintering phenomenon, and form and extend to the skeleton structure of electrode interior, and do not have in the sample of interlayer electrode with electrolytical combine very loose.The introducing of interlayer has increased electrode/electrolyte/gas phase three phase boundary and electrode/electrolyte two-phase interface significantly.
Tested electro-chemical activity, investigated the facilitation of interlayer electrode activity with the SSC-LSGMC5 that contains interlayer (15wt%) combination electrode of method for preparing.Known three-electrode system in the document is adopted in the test of electrode polarization curve, utilizes potentiostatic method to carry out.Test condition is in the 973K oxygen, the results are shown in Fig. 2.Fig. 2 shows, the high temperature interlayer mix the activity that has significantly improved electrode, under identical overpotential, the electrode that contains interlayer has far above no interlayer polarization of electrode electric current.
Utilize the AC impedance method to investigate to contain the stability of 1673K roasting interlayer electrode.Known three-electrode system in the document is adopted in the test of AC impedance experiment, utilizes the constant potential mode to carry out.Test condition is in the 973K oxygen.Between polarized area be-600mV to 600mV every 100mV polarization 10min.The polarization experiment temperature range is 1073K to 873K, and every interval 50K is a measurement temperature, circulates 3 times.The results are shown in Fig. 3.After having carried out strong polarization and process heating-cooling circulation, the electrode polarization resistance that contains the interlayer sample is preceding close with polarization, shows that the interlayer sample has high activity and stability.
Embodiment 1 shows that adding the LSGMC5 interlayer identical with electrolyte between LSGMC5 electrolyte and SSC-LSGMC5 (15wt%) electrode has significantly improved the activity of SSC-LSGMC5 (15wt%) electrode with stable.
Embodiment 2
Embodiment 2 is being to add the La that has close composition with electrolyte between SSC-LSGMC5 (15wt%) negative electrode of electrolytic cell and the LSGMC5 electrolyte with LSGMC5 0.8Sr 0.2Ga 0.8Mg 0.11Co 0.09O 3(LSGMC9) sandwich material has been tested the change of electrode performance.
The preparation process of LSGMC9 interlayer powder is with LSGMC5 among the embodiment 1, and the interlayer sintering temperature is 1573-1723K.The SSC-LSGMC5 cathode preparation method is with embodiment 1.
Known three-electrode system in the document is adopted in the test of AC impedance experiment, utilizes the constant potential mode to carry out, and test condition is that test result is shown in Fig. 4 in the 973K oxygen.The result of Fig. 4 shows, is the performance that interlayer can significantly improve electrode equally with the LSGMC9 that has a close composition with the LSGMC5 electrolyte, and the activity that adopts LSGMC9 interlayer electrode a little more than corresponding be the electrode of interlayer with LSGMC5.
Embodiment 3
Embodiment 3 is with La 0.9Sr 0.1Ga 0.8Mg 0.2O 3(LSGM9182) be the La of electrolytic cell 0.8Sr 0.2Co 0.8Fe 0.2O 3-La 0.8Sr 0.2Ga 0.8Mg 0.15Co 0.05O 3Add the La that has close composition with electrolyte between (LSCF8282-LSGMC5 (15wt%)) negative electrode and the LSGM9182 electrolyte 0.8Sr 0.2Ga 0.8Mg 0.15Co 0.05O 3(LSGMC5) interlayer of material has been tested the change of LSCF8282-LSGMC5 (15wt%) electrode performance.
La 0.9Sr 0.1Ga 0.8Mg 0.2O 3(LSGM) electrolyte is synthetic with solid-phase synthesis, and used initial feed is La 2O 3(99.99% mass fraction, down together), SrCO 3(99.5%), MgO (99.5%) and Ga 2O 3(99.99%).Above-mentioned raw materials grinds 0.5h than mixing the back with mortar by metering, and dry back is at 1273K pre-burning 6h.Sample after the pre-burning depresses to the disk that diameter is 2.0cm at 274.6MPa, and in air 1773K roasting 6h.Sample after the roasting grinds to form the thick thin slice of uniform 0.3mm with the grinding and polishing machine.The LSCF8282 powder adopts solid phase method synthetic, and raw material is La 2O 3(99.99% mass fraction, down together), SrCO 3(99.99%), Co (CH 3COO) 2.4H 2O (99.99%), Fe 2O 3(99.99%).After raw material adds alcohol and grinds 0.5h with mortar, at 923-1023K pre-burning 2h.After sample after the pre-burning adds alcohol grinding 0.5h, at 1273-1373K roasting 6-12h.Sample after the pre-burning adds alcohol and grinds behind the 0.5h standby.The preparation method of LSGMC5 powder who is used to prepare interlayer and LSCF8282-LSGMC5 (15wt%) composite cathode is with embodiment 1.The preparation process of LSGMC5 interlayer is with embodiment 1, and the interlayer sintering temperature is 1573-1723K.
Utilize three electrode polarization technical testings among the embodiment 1 and added the polarization curve that is carried on LSCF8282-LSGMC5 (15wt%) negative electrode on the LSGM9182 electrolyte before and after the LSGMC5 interlayer.Test condition is that test result is shown in Fig. 5 in the 1053K air.The result of Fig. 5 shows, is the performance that interlayer has significantly improved electrode with the LSGMC5 that has a close composition with the LSGM9182 electrolyte, contains interlayer polarization of electrode electric current under the equipolarization overpotential apparently higher than the electrode that does not contain interlayer.
Embodiment 4
Embodiment 4 has tested the change of Ni-LSGMC5 electrode performance being to add the interlayer that has the LSGMC5 material of close composition with electrolyte between Ni-LSGMC9 (10wt%) anode of electrolytic cell and the LSGM9182 electrolyte with La0.9Sr0.1Ga0.8Mg0.2O3 (LSGM9182).
La0.9Sr0.1Ga0.8Mg0.2O3 (LSGM) electrolyte preparation method is identical with embodiment 3.The preparation method of LSGMC5 powder who is used to prepare interlayer and Ni-LSGMC5 composite anode is with embodiment 1.The preparation process of LSGMC5 interlayer is with embodiment 1, and the interlayer sintering temperature is 1573-1723K.
Ni-LSGMC9 (10wt%) composite anode adopts immersion process for preparing: can be with the LSGMC5 powder for preparing and an amount of Ni (NO3) 26H2O solution coevaporation, residue is at 973k pre-burning 2h, add alcohol and grind 0.5h, at 1000-1273K roasting 6h with the aluminium oxide mortar.
Utilize three electrode polarization technical testings among the embodiment 1 and added the polarization curve that is carried on Ni-LSGMC9 (10wt%) composite anode on the LSGM9182 electrolyte before and after the LSGMC5 interlayer.Test condition is that test result is shown in Fig. 6 in the 873K hydrogen.The result of Fig. 6 shows, with the LSGMC5 that has close structure and a composition with the LSGM9182 electrolyte is the performance that interlayer has significantly improved Ni-LSGMC9 (10wt%) composite anode, contains interlayer polarization of electrode electric current under the equipolarization overpotential apparently higher than the electrode that does not contain interlayer.
Embodiment 5
Below provide the concrete preparation process of interlayer, at first prepare with the lanthanum gallate electrolyte that mixes and have identical La by solid phase method or solwution method X1Re 1-x1Ga X2Mg X3M 1-x2-x3O X4Simplest formula (Re is alkaline-earth metal such as Sr, Ca, Ba, and M is transition metal such as Fe, Co, Ni, x1, and x2, x3, x4 are stoichiometric number), and have high oxygen ionic conductivity material powder, with the lanthanum gallate electrolyte La of typical strontium, magnesium doping 0.9Sr 0.1Ga 0.8Mg 0.2O 3Or the lanthanum gallate electrolyte La of strontium, magnesium, three kinds of element dopings of cobalt 0.8Sr 0.2Ga 0.8Mg 0.2-xCo xO 3Be example, the concrete composition of sandwich material can be used La xSr 1-xGa yMg zCo 1-y-zO 3(x=0.95-0.75, y=0.9-0.7, z=0.1-0.3 (z≤＜1-y)) expression.Wherein fairly simple, effective a kind of preparation method is a solid-phase synthesis.La with high-purity (＞99.95%) 2O 3, Ga 2O 3, SrCO 3, MgO, CoO raw material mix and be incorporated in ball milling 12-24h in the alcohol medium, dry back is at 1273-1773K roasting 2-24h.After the roasting, ball milling 6-24h in the alcohol medium, the granularity of electrolyte powder is less than 10 μ m.
The concrete preparation method of interlayer is: the sandwich material powder that will synthesize is made into slurry; Utilize method for printing screen to be printed in the electrolytical surface of lanthanum gallate of doping, the thickness of interlayer is at 1-10 μ m; According to the difference of sandwich material powder preparation temperature with interlayer at 1273-1773K roasting 0.5-10h.
Embodiment 6
Below provide the preparation method of combination electrode material: the preparation of electrode material powder can adopt known solid phase synthesis or solwution method (referring to Ishihara, United States Patent (USP), No.6586127B1).Electrode powder had identical La with the lanthanum gallate electrolyte with doping X1Re 1-x1Ga X2Mg X3M 1-x2-x3O X4(Re is alkaline-earth metal such as Sr, Ca, Ba to simplest formula, M is transition metal such as Fe, Co, Ni, x1, x2, x3, x4 are stoichiometric number), and have high oxygen ionic conductivity material powder and mix and grind and make combination electrode (referring to document: Xiamen University, Chinese patent, application number 200410028515.9, the invention people is Wang Shizhong).With Sm 0.5Sr 0.5CoO 3(SSC) be example, simply introduce the preparation of electrode material.Sm 0.5Sr 0.5CoO 3(SSC) powder adopts solid phase method synthetic.Raw material is Sm 2O 3(99.99%), SrCO 3(99.99%), Co (CH 3COO) 2.4H 2O (99.99%).After raw material adds alcohol and grinds 0.5-2h with mortar, at 873-1073K pre-burning 2h.After sample after the pre-burning adds alcohol grinding 0.5h, at 1173-1573K roasting 12h.It is standby that sample after the roasting grinds the back.
Being prepared as directly of combination electrode will have identical La with the lanthanum gallate electrolyte that mixes X1Re 1-x1Ga X2Mg X3Mg 1-x2-x3O X4Simplest formula (Re is alkaline-earth metal such as Sr, Ca, Ba, and M is transition metal such as Fe, Co, Ni, x1, and x2, x3, x4 are stoichiometric number), and have high oxygen ionic conductivity material powder and the SSC powder of preparing, ball milling 2-12h in the alcohol medium then.Electrode can also be the Ln that solid-phase synthesis or solwution method are prepared xSr 1-xCoO 3(Ln is a rare earth element, x=0.9-0.5) or Ln xSr 1-xCo yFe 1-yO 3(Ln is a rare earth element, x=0.9-0.5, and y=0-1) mixed conductor oxide also can be the nickel metal anode.
The electrode material or the combination electrode that prepare are made into electrode slurry, utilize the method for printing screen lanthanum gallate bath surface of doping of interlayer that has been printed in pre-burning, the thickness of electrode is at 10-100 μ m; According to the difference of type of electrodes with electrode at 1073-1573K roasting 0.5-10h.
Has identical La from preparation with the lanthanum gallate electrolyte that mixes X1Re 1-x1Ga X2Mg X3M 1-x2-x3O X4(Re is alkaline-earth metal such as Sr, Ca, Ba to simplest formula, M is transition metal such as Fe, Co, Ni, x1, x2, x3, x4 is a stoichiometric number), and have high oxygen ionic conductivity material powder, electrode powder to electrode preparation on the lanthanum gallate electrolyte of load doping with dissection, comprise the process of preparation sandwich material powder-preparation combination electrode-silk screen printing interlayer-interlayer sintering-screen printing electrode-electrode sintering.Said preparation sandwich material powder is to utilize solid-phase synthesis or solwution method to prepare with the lanthanum gallate electrolyte that mixes to have identical La X1Re 1-x1Ga X2Mg X3M 1-x2-x3O X4Simplest formula (Re is alkaline-earth metal such as Sr, Ca, Ba, and M is transition metal such as Fe, Co, Ni, x1, and x2, x3, x4 are stoichiometric number), and have high oxygen ionic conductivity material powder; Said preparation combination electrode is to have identical La with the lanthanum gallate electrolyte that mixes X1Re 1-x1Ga X2Mg X3M 1-x2-x3O X4Simplest formula (Re is alkaline-earth metal such as Sr, Ca, Ba, and M is transition metal such as Fe, Co, Ni, x1, x2, x3, x4 are stoichiometric number), and have that high oxygen ionic conductivity material powder mixes with electrode powder and pre-burning; Said silk screen printing interlayer is for being printed in the sandwich material powder lanthanum gallate bath surface of doping with silk screen print method; Said interlayer is sintered to and will prints the lanthanum gallate electrolyte of doping with dissection at 1273-1773K roasting 0.5-10h; Said screen printing electrode is for being printed onto electrode or combination electrode slurry the sandwiching surface behind the sintering; After said electrode is sintered to the pole drying that will be printed on the interlayer, at the scope sintering 0.5-10h of 1073-1573K.

Claims (10)

1, a kind of fuel battery electrode/sandwich/electrolyte from solid oxide structure is characterized in that being provided with electrode, interlayer and electrolyte, and interlayer is between electrode and electrolyte, and the composition of interlayer is identical with electrolyte.
2, a kind of fuel battery electrode/sandwich/electrolyte from solid oxide structure as claimed in claim 1 is characterized in that the lanthanum gallate of said electrolyte for mixing, and has identical or close La X1Re 1-x1Ga X2Mg X3M 1-x2-x3O X4Simplest formula, wherein Re is Sr, Ca, Ba alkaline-earth metal, M is Fe, Co, Ni transition metal, x1, x2, x3, x4 is a stoichiometric number, and have high oxygen ionic conductivity, and the said close only stoichiometric number change that is meant, said high oxygen ionic conductivity is meant that the conductivity under the battery operation temperature is higher than 0.01S.cm -1
3, a kind of fuel battery electrode/sandwich/electrolyte from solid oxide structure as claimed in claim 1, it is characterized in that said electrode is the mixed conductor negative electrode, or metal anode, or mixed conductor negative electrode and oxygen ion conductor, or mixed conductor negative electrode and oxonium ion-electron mixed conductor, or metal anode and oxygen ion conductor, or the combination electrode of metal anode and oxonium ion-electron mixed conductor formation.
4, a kind of fuel battery electrode/sandwich/electrolyte from solid oxide structure as claimed in claim 3 is characterized in that said mixed conductor negative electrode is LnxSr 1-xCoO 3The mixed conductor oxide, wherein Ln is a rare earth element, x=0.9-0.5; Or Ln xSr 1-xCoyFe 1-yO 3The mixed conductor oxide, wherein Ln is a rare earth element, x=0.9-0.5, y=0-1.
5, a kind of fuel battery electrode/sandwich/electrolyte from solid oxide structure as claimed in claim 3 is characterized in that said metal anode is the nickel metal anode.
6, a kind of fuel battery electrode/sandwich/electrolyte from solid oxide structure as claimed in claim 3 is characterized in that said combination electrode is Ln xSr 1-xCoO 3The mixed conductor oxide material, wherein Ln is a rare earth element, x=0.9-0.5; Or Ln xSr 1-xCo yFe 1-yO 3The mixed conductor oxide material, wherein Ln is a rare earth element, x=0.9-0.5, y=0-1.
7, a kind of fuel battery electrode/sandwich/electrolyte from solid oxide structure as claimed in claim 3 is characterized in that said combination electrode is that the nickel metal anode has consistent or close La with the lanthanum gallate electrolyte of doping X1Re 1-x1Ga X2Mg X3M 1-x2-x3O X4Simplest formula, wherein Re is Sr, Ca, Ba alkaline-earth metal, M is Fe, Co, Ni transition metal, x1, x2, x3, x4 is a stoichiometric number, and has the combination electrode that high oxygen ionic conductivity material mixing forms.
8, as claim 1 or 7 described a kind of fuel battery electrode/sandwich/electrolyte from solid oxide structures, it is characterized in that the lanthanum gallate of said electrolyte for mixing, have La X1Re 1-x1Ga X2Mg X3M 1-x2-x3O X4Simplest formula, wherein Re is Sr, Ca, Ba alkaline-earth metal, M is Fe, Co, Ni transition metal, x1, x2, x3, x4 is a stoichiometric number, and has high oxygen ionic conductivity.
9, a kind of fuel battery electrode/sandwich/electrolyte from solid oxide structure as claimed in claim 1 is characterized in that the composition of interlayer is consistent or close with the lanthanum gallate electrolyte of doping, the said close only stoichiometric number change that is meant.
10, as claim 1 or 9 described a kind of fuel battery electrode/sandwich/electrolyte from solid oxide structures, it is characterized in that the composition of interlayer has identical or close La with electrolyte X1Re 1-x1Ga X2Mg X3M 1-x2-x3O X4Simplest formula, Re is Sr, Ca, Ba alkaline-earth metal, M is Fe, Co, Ni transition metal, x1, x2, x3, x4 is a stoichiometric number, saidly closely be meant only stoichiometric number change, and have high oxygen ionic conductivity, said high oxygen ionic conductivity is meant that the conductivity under the battery operation temperature is higher than 0.01S.cm -1
CNA2005101126012A 2005-10-11 2005-10-11 Structure of fuel battery electrode/sandwich/electrolyte from solid oxide Pending CN1747212A (en)

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