CN1635658A - Middle and low temperature ceramic oxide fuel cell and preparation process - Google Patents
Middle and low temperature ceramic oxide fuel cell and preparation process Download PDFInfo
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- CN1635658A CN1635658A CNA2004100656801A CN200410065680A CN1635658A CN 1635658 A CN1635658 A CN 1635658A CN A2004100656801 A CNA2004100656801 A CN A2004100656801A CN 200410065680 A CN200410065680 A CN 200410065680A CN 1635658 A CN1635658 A CN 1635658A
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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
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Abstract
This invention refers to low ceramic oxide fuel cell and preparation method, which is characteristic of that the industrial raw material grade mixed carbonic acid rareearth (or ion doped cerium oxide), inorganic salt or oxyhydroxide, or other oxide powder are used as the raw material, uniformly mixed according to definite proportion and abraded, then used as electrolyte for fuel cell. Said invention can be used in industrial large scale production of fuel cell.
Description
Technical field
The present invention relates to, low temperature (below 650 ℃) ceramic oxide fuel cell and preparation technology's method.
Background technology
The high cost of conventional high-temperature (more than 800 ℃) oxide fuel cell becomes it and enters business-like bottleneck.Chinese patent ZL 00 1 12228.2 (patent application day: on April 21st, 2000, Granted publication day: on May 19th, 2004) disclosed cerium oxide base composite material as in, the electrolyte of low temperature (below 600 ℃) pottery/oxide fuel cell shown that high performance and huge commercialization are worth.On this material foundation, will develop new fuel cell, have the market competitiveness.The development of this new fuel cell also provides strong support and new way for developing rich rare earth resources of China and its high-tech industry.
The moulding of pottery/oxide fuel cell and amplification technique are that it enters a practical key problem in technology.Though traditional ceramics and oxide fuel cell moulding and amplification technique are numerous, and extremely successful example is also arranged, based on the forming materials of oxide composite electrolyte and the amplification technique of fuel cell many differences are arranged, can't indiscriminately imitate.We must develop moulding and the fuel cell amplification technique that is fit to rare earth base composite material, realize its industrial applications.
Summary of the invention
The present invention is intended to: provide on a kind of basis of cerium oxide (mainly the being doped cerium oxide) based composite electrolyte of invention in early days, develop the electrolyte of new rare earth material, further reduce cost, during development a new generation can the marketization, the low temperature ceramic oxide fuel cell material.
Another object of the present invention is: provide a kind of manufacturing process simple, easy to operate, in being suitable for producing in enormous quantities, preparation technology's method of low temperature ceramic oxide fuel cell.
The technical solution that realizes the foregoing invention purpose is as follows:
1, in, the low temperature ceramic oxide fuel cell material, it is characterized in that: it is the composite material that is formed by raw material of industry level mixed rare earth carbonate and other inorganic compound or oxide; They are to form by the simple and mechanical ground and mixed of the raw material of following component, or obtain through the uniform temperature sintering processes:
Raw material of industry level mixed rare earth carbonate 50-99,
More than one inorganic salts or oxyhydroxide 0-70,
Perhaps more than one other oxide or doping oxide 0-90;
Wherein said inorganic salts are: lithium chloride, sodium chloride, strontium chloride, lithium fluoride, calcirm-fluoride, barium fluoride, lithium carbonate, sodium carbonate, potash, calcium carbonate, magnesium carbonate, brium carbonate, strontium carbonate, cesium nitrate, rubidium nitrate, lithium sulfate, magnesium sulfate, calcium sulfate, wherein any two or more the mixture in lithium phosphate, calcium phosphate, potassium phosphate or they;
Wherein said oxyhydroxide is: wherein any two or more the mixture in lithium hydroxide, NaOH, potassium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide or they;
Wherein said other oxide is: wherein any two or more the mixture in bismuth oxide, aluminium oxide, zirconia, silica, calcium oxide, strontium oxide strontia, barium monoxide, magnesium oxide, samarium oxide, gadolinium oxide, yittrium oxide, scandium oxide, gallium oxide, lanthana or they;
Wherein said doping oxide is the oxide that above-mentioned oxide forms through ion doping; These oxides also comprise the oxide of various oxonium ions and proton conductor, as ion doping lanthanum gallate, ion doping cerium acid barium (strontium) or the barium zirconate (strontium) of perovskite structure; Described doping oxide also comprises the ion doping cerium oxide.
2, according to above-mentioned 1 described in, the low temperature ceramic oxide fuel cell material, it is characterized in that: described raw material of industry level mixed rare earth carbonate material composition is: TREO 40-50, lanthana (La
2O
3) 30-40, cerium oxide (CeO
2) 50-60, protactinium oxide (Pr
6O
11) 5-6, neodymia (Nd
2O
3) 0.05-0.3, samarium oxide (Sm
2O
3)＜0.01, yittrium oxide (Y
2O
3)＜0.04; Its treatment process condition is:
With mixed rare earth carbonate sintering processes more than 10 minutes or under more than or equal to 300 ℃ of temperature conditions without sintering processes.
3, according to above-mentioned 1 described in, the low temperature ceramic oxide fuel cell material, it is characterized in that: in described, the low temperature ceramic oxide fuel cell material handled 0.5-2 hour at 100-700 ℃ of sintering temperature.
4, according to above-mentioned 1 described in, the preparation technology of low temperature ceramic oxide fuel cell: it is characterized in that:
Comprise following operation:
A, inferior combination electrode bisque and metal collector bisque or nickel foam (or various wire netting) with nickel foam or various wire netting, anode and electrolytical combination electrode bisque, negative electrode tentatively are pressed into the five in one composite bed;
B, under 1-100 ton pressure with the compression moulding of five in one composite bed, or hot-forming under 300 ℃ of-800 ℃ of temperature;
Described anode and negative electrode are metal oxide electrode, the metal oxide of described anode is nickel oxide (NiO), the metal oxide of described negative electrode is the ion doping lanthana (LaSrMnO3) of Ca-Ti ore type, lanthanum (or barium) strontium cobalt iron oxide (La (Ba) SrCoFeO), strontium cobalt iron oxide (SrFeCoO) or bronze base oxide, i.e. M
xTO3 (M is, Li, and Na, K, Ca, Sr, Ba, T are transition metal);
The metal oxide of described anode and negative electrode is the composite material of nickel oxide, cupric oxide and iron oxide, and (three's ratio can be between any proportioning! ) three's mixture scope of accounting for the male or female total amount is 0-99%, residual components also contains one or more other materials except above-mentioned three kinds of materials, and described material is: lithium, sodium, potassium, calcium, strontium, barium, magnesium, zinc, cobalt, tin, manganese, chromium, platinum, silver, carbon, palladium;
Described metal collector bisque anode is pure anode electrode powder, and negative electrode is for being silver, carbon mixing bisque, and silver, carbon mixed proportion are: 1-90;
Described electrolyte bisque be described in above-mentioned 1 in, the low temperature ceramic oxide fuel cell material;
Described nickel foam is the commercial material of common nickel/hydrogen battery bought of market (comprising Ni, Ni-Co, the model in component such as Ni-Cu and different apertures);
Described wire netting is nickel, copper, iron, stainless steel, silver and relevant alloy.
5, according to above-mentioned 4 described in, the preparation technology of low temperature ceramic oxide fuel cell: it is characterized in that:
Comprise following operation:
A, make the combination electrode bisque of three-in-one and negative electrode and the metal collector bisque or nickel foam (or various wire netting) the two unification composite beds of nickel foam or various wire netting, anode and electrolytical combination electrode bisque and dielectric substrate respectively;
B, under 1-100 ton pressure with three-in-one and two unification composite bed compression mouldings, or hot-forming under 300 ℃ of-800 ℃ of temperature;
C, under 1-100 ton pressure with above-mentioned three-in-one composite bed compression moulding, or under 300 ℃ of-800 ℃ of temperature hot-forming after, make cathode layer and cathodic metal collector electrode with silk screen printing or injection or brushing method.
Various mixed rare earth carbonates (LCP)-salt or compound electrolyte and the electrode of oxide/proton conductor with the inventive method preparation have prepared monocell, 13 mm dias (0.64 active area) under the dry powder sheeting moulding process.The battery performance that records is shown in Fig. 2.Preferably fuel battery performance is near 1 watt (600 ℃).Illustrate that these composite electrolytes reach good performance, in can being applied to fully, low-temp ceramics/oxide fuel cell.The most important thing is the use of industrialization raw material mixed rare earth carbonate (LCP), solved the cheap difficult problem of producing of fuel cell material heavy industrialization.
With dry powder sheeting moulding process system mixed rare earth carbonate (LCP) composite electrolyte monocell and the heap that comprises two batteries, 20 mm dias (2.27 square centimeters of active areas).Punching block with 20 mm dias inserts anode successively, the wire netting of electrolyte and negative electrode powder and colleeting comb such as nickel, copper, iron, silver; Fuel cell is in 5-50MP and 580 ℃ of following hot pressing moulding.The fuel battery performance measurement result is shown in Fig. 1.As seen from the figure, reach near 1 watt at 580 ℃ of following monocells, the heap of two batteries reaches 2 watts.And with doped cerium oxide-carbonate composite electrolyte fuel cell performance better (its result also is shown in Fig. 1, reaches more than 2 watts).
With mixed rare earth carbonate (LCP)-carbonate and doped cerium oxide-carbonate compound electrolyte material, different technology: ceramic spraying, making/assembling fuel cell, 2.27 square centimeters of active areas, reach better monocell performance under 580 ℃ respectively, 1.1 and 1.3 watts.This battery with the further compression moulding of hot-pressing technique, is improved fuel battery performance and reaches more than 1.5 watts.
Use same material, different technology, dry powder spraying is made each parts of fuel cell, fuel battery assembled, 14 square centimeters of active areas, its performance reaches more than 4 watts.This battery with the further compression moulding of hot-pressing technique, is improved fuel battery performance and reaches more than 5 watts, see Fig. 2 (a) and (b).
Use same material, different technology: the band casting, making/fuel battery assembled, 14 square centimeters of active areas, 550 ℃ and 600 ℃ of battery performances that place an order reach more than 3 watts and 4 watts.This battery with the further compression moulding of hot-pressing technique, is improved fuel battery performance and reaches more than 4 watts and 5 watts.
Use same material, different technology supports with nickel screen or nickel foam respectively, and is equipped with anode support (about 0.8-1.0 millimeters thick) with the dry powder sheeting legal system, slurry The tape casting moulding electrolyte (about 0.1-0.2 millimeters thick), and negative electrode is made in silk screen printing.Electrolyte slurry is made solvent with alcohol or acetone, the electrolyte powder is dispersed in the slurry of furnishing suitable concn in this solvent.According to the degree of flow casting molding, in above-mentioned slurry, can add a little organic binder and dispersant.Fuel battery assembled, 14 square centimeters of active areas, the monocell performance reaches more than 5 watts.With this battery hot-pressing technique, with the further compression moulding of ceramic spraying parts, improve fuel battery performance and reach more than 6 watts, see Fig. 3.
Use same material, different technology respectively with nickel screen or nickel foam support, and is equipped with cathode support body (about 0.8-1.0 millimeters thick) with the dry powder sheeting legal system, slurry The tape casting moulding electrolyte (about 0.1-0.2 millimeters thick), and anode is made in silk screen printing.Fuel battery assembled, 14 square centimeters of active areas, the monocell performance reaches nearly 4 watts.This battery with the further compression moulding of hot-pressing technique, is improved fuel battery performance and reaches more than 4 watts.
Single fuel cell can drive 8 to 12 electric fans (0.4-0.5 watt of electric fan average power) respectively, and this apparatus for demonstrating resembles a wind power station.
On above-mentioned enforcement basis, further optimize and integrated process: respectively with nickel screen or nickel foam and band casting, The tape casting or dry powder sheeting prepare anode support (about 0.8-1.0 millimeters thick), prepare fuel-cell electrolyte (using mixed rare earth carbonate (LCP)-carbonate and doped cerium oxide-carbonate composite material respectively is electrolyte) with dry powder spraying or The tape casting, (about 0.1-0.2 millimeters thick), dry powder spraying or silk screen printing prepare fuel battery negative pole, successfully made the area battery of 11 * 11 square centimeters (100 square centimeters of active areas), battery is through hot-pressing processing.All can reach more than 30 watts with above-mentioned prepared at 600 ℃ of battery performances that place an order, see Fig. 4.
On the basis of the above, increase the metal currect collecting net of negative electrode again, silver particularly, the copper or the iron net of nickel or silver-plated, nickel, chromium, fuel cell performance can further be improved.
On the basis of the above, further optimize and integrated process: prepare cathode support body (about 0.8-1.0 millimeters thick) with nickel screen or nickel foam and band casting or dry powder sheeting respectively, The tape casting or dry powder spraying are made electrolyte, dry powder spraying or silk screen printing prepare anode of fuel cell, successfully made the area battery of 11 * 11 square centimeters (100 square centimeters of active areas), battery is through hot-pressing processing.Can both reach about more than 25 watts at 600 ℃ of battery performances that place an order with above-mentioned prepared.
New fuel cell of the present invention develop into the rich rare earth resources of exploitation China and its high-tech industry provides strong support and new way.
Description of drawings
Fig. 1 is I-V (current-voltage) curve and I-P (electric current-power) curve of typical SDC (samarium doped cerium oxide)-carbonate (a) and LCP-carbonate (b) composite electrolyte fuel-cell single-cell and two fuel cell packs, 600 ℃.
Fig. 2 is I-V (current-voltage) curve and I-P (electric current-power) curve of monocell, 14 square centimeters of active areas.(a) 600 ℃ of following performances of LCP-carbonate composite electrolyte monocell; (b) 600 ℃ of following performances of monocell after the further hot pressing of this battery.
Fig. 3 is (current-voltage) curve of the I-V under the monocell all temps and I-P (electric current-power) curve, 14 square centimeters of active areas, 580 ℃.(a): LCP-carbonate and (b): SDC (samarium doped cerium oxide)-carbonate composite electrolyte fuel cell.
Fig. 4 is I-V (current-voltage) curve and I-P (electric current-power) curve of monocell, 100 square centimeters of active areas, 600 ℃. (a): LCP-carbonate and (b): SDC (samarium doped cerium oxide)-carbonate composite electrolyte fuel cell.
Fig. 5 is one-shot forming technique figure.
Fig. 6 is three-in-one and two unification composite molding technique flow charts.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in detail by more embodiment.
The present invention is with raw material of industry level mixed rare earth carbonate (or ion doping cerium oxide) and inorganic salts or oxyhydroxide or the evenly mixing by a certain percentage of other oxide powder, just can be used as electrolyte after the grinding and be used for fuel cell, compound also can use through grinding after calcining.As described in following embodiment 1-23.
Embodiment 1
Get raw material of industry level mixed rare earth carbonate 100 grams
Raw material is handled: be divided into for two steps
The first step, raw material of industry level mixed rare earth carbonate material can be carried out low-temperature sintering, low-temperature sintering time, apparent temperature and deciding.As: at 500 ℃ below the temperature, sintering 3 hours; 800 ℃ of left and right sides temperature, sintering 2 hours; About 900 ℃ of temperature, sintering 0.5-1 hour.The raw material that does not carry out sintering processes also can directly use.
Second step, the mixed rare earth carbonate material after the sintering processes is mixed with other composition, fully grinding is carried out sintering afterwards, sintering time, apparent temperature and deciding.200 ℃ of temperature, sintering 5 hours; 700 ℃ of temperature, sintering 0.5-1 hour.
Embodiment 2
Get raw material of industry level mixed rare earth carbonate amount 100 grams
Concrete operations are the same
Embodiment 3
Get raw material of industry level mixed rare earth carbonate amount 100 grams
Lithium carbonate amount 150 grams
Potash amount 10 grams
Concrete operations are the same
Embodiment 4
Get raw material of industry level mixed rare earth carbonate amount 100 grams
Concrete operations are the same
Embodiment 5
Get raw material of industry level mixed rare earth carbonate amount 100 grams
Amount of sodium hydroxide 15 grams
Concrete operations are the same
Embodiment 6
Get raw material of industry level mixed rare earth carbonate amount 100 grams
Lithium hydroxide amount 12 grams
Concrete operations are the same
Embodiment 7
Get raw material of industry level mixed rare earth carbonate amount 100 grams
Lithium carbonate amount 12 grams
Brium carbonate amount 2.5 grams
Calcium carbonate quantity 2.5 grams
Concrete operations are the same
Embodiment 8
Get raw material of industry level mixed rare earth carbonate amount 100 grams
Lithium carbonate amount 12 grams
Brium carbonate amount 2.5 grams
Strontium carbonate amount 2.5 grams
Embodiment 9
Get raw material of industry level mixed rare earth carbonate amount 100 grams
Lithium carbonate amount 12 grams
Calcium carbonate quantity 2.5 grams
Strontium carbonate amount 2.5 grams
Get raw material of industry level mixed rare earth carbonate amount 100 grams
Aluminium oxide or aluminium hydroxide amount 10 grams
Concrete operations are the same
Embodiment 11
Get raw material of industry level mixed rare earth carbonate amount 100 grams
Calcium carbonate quantity 5 grams
Zirconia amount 5 grams
Calcium oxide content 5 grams
Concrete operations are the same
Embodiment 12
Get raw material of industry level mixed rare earth carbonate amount 100 grams
Lithium carbonate amount 12 grams
Magnesium carbonate amount 10 grams
Silica amount 2.5 grams
Magnesium oxide 2.5 grams
Concrete operations are the same
Embodiment 13
Get raw material of industry level mixed rare earth carbonate amount 100 grams
Bismuth oxide amount 5 grams
Calcium oxide content 5 grams
Concrete operations are the same
Embodiment 14
Get raw material of industry level mixed rare earth carbonate amount 100 grams
Magnesium sulfate amount 5 grams
Amount of sodium hydroxide 10 grams
Alundum (Al amount 5 grams
Silica amount 5 grams
Concrete operations are the same
Get raw material of industry level mixed rare earth carbonate amount 100 grams
Calcium sulfate amount 5 grams
Zirconia amount 2.5 grams
Magnesium oxide amount 2.5 grams
Concrete operations are the same
Embodiment 16
Get raw material of industry level mixed rare earth carbonate amount 100 grams
Zirconia amount 5 grams
Alundum (Al or aluminium hydroxide amount 5 grams
Magnesium oxide amount 5 grams
Concrete operations are the same
Embodiment 17
Get raw material of industry level mixed rare earth carbonate amount 100 grams
Amount of sodium hydroxide 10 grams
Calcium hydroxide amount 5 grams
Magnesium hydroxide amount 5 grams
Alundum (Al or aluminium hydroxide amount 5 grams
Magnesium oxide amount 5 grams
Concrete operations are the same
Embodiment 18
Get raw material of industry level mixed rare earth carbonate amount 100 grams
Calcium phosphate amount 5 grams
Zirconia amount 5 grams
Magnesium oxide amount 5 grams
Concrete operations are the same
Embodiment 19
Get raw material of industry level mixed rare earth carbonate amount 100 grams
Zirconia amount 5 grams
Magnesium oxide amount 5 grams
Concrete operations are the same
Get raw material of industry level mixed rare earth carbonate amount 100 grams
Fluorine China lithium amount 10 grams
Fluorine China calcium amount 5 grams
Alundum (Al or aluminium hydroxide amount 5 grams
Calcium oxide content 5 grams
Concrete operations are the same
Embodiment 21
Get raw material of industry level mixed rare earth carbonate amount 100 grams
Fluorine China lithium amount 10 grams
Fluorine China barium amount 10 grams
Alundum (Al or aluminium hydroxide amount 5 grams
Magnesium oxide amount 5 grams
Concrete operations are the same
Embodiment 22
Get raw material of industry level mixed rare earth carbonate amount 100 grams
Alundum (Al or aluminium hydroxide amount 5 grams
Germanium oxide amount 5 grams
Concrete operations are the same
Embodiment 23
Get raw material of industry level mixed rare earth carbonate amount 100 grams
Alundum (Al or aluminium hydroxide amount 10 grams
Cerium oxide amount 10 grams
Concrete operations are the same
Embodiment 24
Get raw material of industry level mixed rare earth carbonate amount 10 grams
Lithium metaaluminate (LiAlO2) amount 3 grams
Concrete operations are the same
Embodiment 25
Get raw material of industry level mixed rare earth carbonate amount 10 grams
Lithium metaaluminate (LiAlO2) amount 3 grams
Lithium carbonate amount 1.5 grams
Lithium carbonate amount 1 gram
Concrete operations are the same
Embodiment 26
Get raw material of industry level mixed rare earth carbonate amount 10 grams
Ion doping lanthanum gallate amount 4 grams
Concrete operations are the same
Embodiment 27
Get raw material of industry level mixed rare earth carbonate amount 10 grams
Ion doping lanthanum gallate amount 3 grams
Lithium carbonate amount 1.5 grams
Lithium carbonate amount 1.0 grams
Concrete operations are the same
Embodiment 28
Get raw material of industry level mixed rare earth carbonate amount 10 grams
Ion doping cerium acid barium (strontium) or barium zirconate (strontium) amount 3 grams
Concrete operations are the same
Embodiment 29
Get raw material of industry level mixed rare earth carbonate amount 10 grams
Ion doping cerium acid barium (strontium) or barium zirconate (strontium) amount 2 grams
Lithium carbonate amount 1.5 grams
Lithium carbonate amount 1.0 grams
Concrete operations are the same
Get the ion doping cerium oxide, general chemical formula is M
xCe
1-xO
2(x=0.1-0.4), M=Ca
2+, Sr
2+, Ba
2+, Zn
2+, Mg
2+), Gd
3+, Sm
3+, Y
3+, Pr
3+), replace raw material of industry level mixed rare earth carbonate, M
xCe
1-xO
2Component repeats above-mentioned all embodiment from 10-95%, all sets up, and concrete operations are the same.Can obtain quite or better compound electrolyte material of performance.
On the basis of this material invention,, can enumerate the thousands of kind prescriptions of preparation material according to the method for foregoing description.These embodiment only are that wherein very limited being used for for example illustrates, are not limited.
Technology of the present invention can be divided into two big operations, and the one, raw material is handled, and the 2nd, processing and forming.Below the contour machining procedure process is described in detail.
Processing and forming:
Embodiment 31:
One-shot forming technique, see Fig. 5, use the pressure straight forming, both successively with nickel foam or various wire netting, nickel oxide, cupric oxide, iron oxide and lithium, magnesium, cobalt, tin, manganese, zinc, platinum, silver, carbon, the composite material anode of one of palladium (nickel oxide wherein, cupric oxide, iron oxide is respectively 30%, lithium, magnesium, cobalt, tin, manganese, zinc, platinum, palladium, silver, carbon, one of palladium is 10%)/electrolytical compound (mixing) electrode powder (electrode and electrolyte mixed weight proportioning are by 1-100%) of embodiment 1, compound (mixing) powder of electrolyte powder and lanthana (LaSrMnO3) negative electrode/electrolyte and silver/carbon dust (being the metal collector powder) insert a mould successively, or fill out successively on the supporter of nickel foam or various wire nettings, in suitable pressure (the 0.1-100 ton is looked the battery size size and decided) compression moulding next time.Also be hot-forming between the 300-800C at a certain temperature simultaneously.The fuel cell size of last moulding is fixed by the size of the supporter of mould or nickel foam or various wire nettings.
Embodiment 32:
Composite molding technique, see Fig. 6, prepare i respectively) metal collector net (or nickel foam)/nickel oxide, the three-in-one composite ceramic slab (0.8-1mm is thick) of the anode combination electrode substrate of the composite material of cupric oxide and iron oxide/form as the electrolyte of embodiment 2, through or all can (in the foregoing invention content, describe preparation process in detail without heat treated, as supporter at nickel foam or the elder generation's compacting of various wire netting or injection or brushing combination electrode, use dry powder spraying then, the band casting, various wet chemistry methods are made and are gone up dielectric substrate, pass through the preliminary compression moulding of certain pressure again); The ii) spraying or the combination electrode of silk screen printing negative electrode (or anode) on metal collector net or nickel foam form on the metal collector net (or nickel foam)/parts (negative electrode directly can be sprayed/be sprinkled upon metal collector net (or nickel foam) preliminary compression moulding under certain pressure) of barium strontium cobalt iron oxide (BaSrFeCoO) negative electrode two unifications.At last these two parts are passed through with hot-forming (temperature is between 300-800 ℃, and pressure is decided on battery size between 2 to 100 tons).Last one technology also can be directly with above-mentioned two parts compression moulding sintering moulding in-1.0 hours in 5 minutes between 500-700 ℃ again.
Embodiment 33:
Composite molding technique 2, in the three-in-one composite ceramic slab (0.8-1mm is thick) of the anode combination electrode substrate of the composite material of metal collector net (or nickel foam)/nickel oxide, cupric oxide and the iron oxide of above-mentioned preparation/form as the electrolyte of embodiment 2, fully after the moulding with screen printing technique or injection or negative electrode is made in brushing and collector electrode obtains complete fuel cell.
Claims (5)
1, in, the low temperature ceramic oxide fuel cell material, it is characterized in that: it is the composite material that is formed by raw material of industry level mixed rare earth carbonate and other inorganic compound or oxide; They are to form by the simple and mechanical ground and mixed of the raw material of following component, or obtain through the uniform temperature sintering processes:
Raw material of industry level mixed rare earth carbonate 10-99,
More than one inorganic salts or oxyhydroxide 0-70,
Perhaps more than one other oxide or doping oxide 0-90;
Wherein said inorganic salts are: lithium chloride, sodium chloride, strontium chloride, lithium fluoride, calcirm-fluoride, barium fluoride, lithium carbonate, sodium carbonate, potash, calcium carbonate, magnesium carbonate, brium carbonate, strontium carbonate, cesium nitrate, rubidium nitrate, lithium sulfate, magnesium sulfate, calcium sulfate, cesium hydrogen sulfate, lithium phosphate, calcium phosphate, calcium monohydrogen phosphate (sodium, potassium), wherein any two or more the mixture in potassium phosphate (sodium) or they;
Wherein said oxyhydroxide is: wherein any two or more the mixture in lithium hydroxide, NaOH, potassium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide or they;
Wherein said other oxide is: bismuth oxide, aluminium oxide, zirconia, silica, calcium oxide, strontium oxide strontia, barium monoxide, magnesium oxide, samarium oxide, gadolinium oxide, yittrium oxide, scandium oxide, gallium oxide, lanthana, wherein any two or more the mixture in lithium metaaluminate (LiAlO2) or they;
Wherein said doping oxide is the oxide that above-mentioned oxide forms through ion doping; These oxides also comprise the oxide of various oxonium ions and proton conductor, as ion doping lanthanum gallate, ion doping cerium acid barium (strontium) or the barium zirconate (strontium) of perovskite structure; Described doping oxide also comprises the ion doping cerium oxide.
2, in according to claim 1, the low temperature ceramic oxide fuel cell material, it is characterized in that: described raw material of industry level mixed rare earth carbonate material composition is: TREO 40-50, lanthana (La
2O
3) 30-40, cerium oxide (CeO
2) 50-60, protactinium oxide (Pr
6O
11) 5-6, neodymia (Nd
2O
3) 0.05-0.3, samarium oxide (Sm
2O
3)＜0.01, yittrium oxide (Y
2O
3)＜0.04; Its treatment process condition is:
With mixed rare earth carbonate sintering processes more than 10 minutes or under more than or equal to 300 ℃ of temperature conditions without sintering processes.
3, in according to claim 1, the low temperature ceramic oxide fuel cell material, it is characterized in that: in described, the low temperature ceramic oxide fuel cell material handled 0.5-2 hour or without sintering processes at 100-700 ℃ of sintering temperature.
4, in according to claim 1, the preparation technology of low temperature ceramic oxide fuel cell: it is characterized in that:
Comprise following operation:
A, inferior combination electrode bisque and metal collector bisque or nickel foam (or various wire netting) with nickel foam or various wire netting, anode and electrolytical combination electrode bisque, negative electrode tentatively are pressed into the five in one composite bed;
B, under 1-100 ton pressure with the compression moulding of five in one composite bed, or hot-forming under 300 ℃ of-800 ℃ of temperature;
Described anode and negative electrode are metal oxide electrode, the metal oxide of described anode is nickel oxide (NiO), the metal oxide of described negative electrode is the ion doping lanthana (LaSrMnO3) of Ca-Ti ore type, lanthanum (or barium) strontium cobalt iron oxide (La (Ba) SrCoFeO), strontium cobalt iron oxide (SrFeCoO) or bronze base oxide, i.e. M
xTO3 (M is, Li, and Na, K, Ca, Sr, Ba, T are transition metal);
The metal oxide of described anode and negative electrode is the composite material of nickel oxide, cupric oxide and iron oxide, and (three's ratio can be between any proportioning! ) three's mixture scope of accounting for the male or female total amount is 0-99%, residual components also contains one or more other materials except above-mentioned three kinds of materials, and described material is: lithium, sodium, potassium, calcium, strontium, barium, magnesium, zinc, cobalt, tin, manganese, chromium, platinum, silver, carbon, palladium;
Described metal collector bisque anode is pure anode electrode powder, and negative electrode is silver, carbon mixing bisque, and silver, carbon mixed proportion are: 1: 90;
Described electrolyte bisque be described in above-mentioned 1 in, the low temperature ceramic oxide fuel cell material;
Described nickel foam is the commercial material of common nickel/hydrogen battery bought of market (comprising Ni, Ni-Co, the model in component such as Ni-Cu and different apertures);
Described wire netting is nickel, copper, iron, stainless steel, silver and relevant alloy.
5, in according to claim 4, the preparation technology of low temperature ceramic oxide fuel cell: it is characterized in that:
Comprise following operation:
A, make the combination electrode bisque of three-in-one and negative electrode and the metal collector bisque or nickel foam (or various wire netting) the two unification composite beds of nickel foam or various wire netting, anode and electrolytical combination electrode bisque and dielectric substrate respectively;
B, under 1-100 ton pressure with three-in-one and two unification composite bed compression mouldings, or hot-forming under 300 ℃ of-800 ℃ of temperature;
C, under 1-100 ton pressure with above-mentioned three-in-one composite bed compression moulding, or under 300 ℃ of-800 ℃ of temperature hot-forming after, make cathode layer and cathodic metal collector electrode with silk screen printing or spray/coating method.
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| CNA2004100656801A CN1635658A (en) | 2004-11-09 | 2004-11-09 | Middle and low temperature ceramic oxide fuel cell and preparation process |
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