CN101320814B - Electrolyte material of low temperature oxide fuel battery and preparation method thereof - Google Patents
Electrolyte material of low temperature oxide fuel battery and preparation method thereof Download PDFInfo
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- CN101320814B CN101320814B CN200810022144A CN200810022144A CN101320814B CN 101320814 B CN101320814 B CN 101320814B CN 200810022144 A CN200810022144 A CN 200810022144A CN 200810022144 A CN200810022144 A CN 200810022144A CN 101320814 B CN101320814 B CN 101320814B
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Abstract
The invention discloses an electrolyte material of low-temperature oxide fuel battery and a production method thereof, the method comprises the steps of: preparing the mixed solution of the electrolyte material by combining two or more than two elements selected from the group consisting of alkali, alkaline earth metals and Zn, Mg, Bi, Al, Zr, Ti, Nb, In, Sn, Ga, Sb, Sc, Si or Sn; adding or not adding citric acid or urea in accordance with 1 to 4 times of total molar weight of the selected elements; or adding rare earth compounds in the product in accordance with 1% to 95% of the total molar weight of the selected elements; or using the prepared mixed iron solution to soak the rare earth oxides; drying the obtained product by burning and sintering for 1 to 20 hours at 700 to 850 DEG C to acquire composite oxides of two or more than two elements, or composite material of the metal composite oxide-rare earth oxide, or covering material of the metal composite oxide to the rare earth oxide; using the materials to assembly the flat 6*6 square centimeter fuel battery which can output 7.5-18 watts of power at 300-550 DEG C.
Description
Technical field
The invention belongs to the SOFC technical field; Be specifically related to electrolyte of low temperature (300-600 ℃) SOFC and preparation method thereof; Be particularly related to by being selected from the compound oxidate ceramic material that element constitutes among Li, Na, K, Ca, Ba, Sr, Mg, Zn, Bi, Al, Zr, Ti, Nb, In, Sn, Ga, Sb, Sc, Si or the Sn, and the composite material that forms by these composite oxides and rare earth oxide.。
Background technology
The research and development main flow of fuel cell is middle temperature (600-800 ℃), low temperature (300-600 ℃) SOFC (SOFC) at present.Because receive the restriction of electrolyte, most of development activities only limit to reduce with the stable micron-sized film of zirconium dioxide (YSZ) material preparation of conventional high-temperature (1000 ℃) yttrium the resistance of electrolyte, to reach the purpose that reduces the fuel battery operation temperature.But micron order film electrolyte can't guarantee fuel cell performance and repeatability, and because the restriction of YSZ conductivity still needs the operation of temperature more than 700 ℃.Therefore, the new oxide electrolysis material of research and development is the basic guarantee that realizes low temperature (300-600 ℃) SOFC.
The material of a kind of low form SOFC that Chinese patent number 00112228.2 proposes, its electrolyte be by doped cerium oxide, for example, and SDC (samarium doped cerium oxide Ce
0.9Sm
0.1O
X)+LN (Li-Na) CO
3Constitute.Owing to mix Li-Na carbonate lower softening or solution temperature is arranged; Make the working temperature of SOFC be reduced to effectively about 500 ℃; In this temperature range, superior performance is arranged, for SOFC has been explored new material to the low temperature commercialized development.But this to add salt material power attenuation below 500 ℃ the time very fast, and because the corrosivity of salt causes the stable not good enough of material and fuel cell.
One Chinese patent application numbers 200410065680.1 proposed employing cerium oxide and raw material of industry level mixed rare earth carbonate and inorganic salts or hydroxide or other oxide composite and in, low temperature ceramic oxide fuel cell and preparation technology's method, but owing to use for example SDC+LN (Li-Na) CO of doped cerium oxide
3Be electrolyte, this method still exists the corrosivity of salt and the problem of long-time stability aspect.
So far also do not see about adopting two phases or poly phase composite oxide electrolyte to realize the relevant report of high performance 300-600 ℃ low-temperature solid oxide fuel cell.
Summary of the invention
The objective of the invention is electrolyte that proposes a kind of low-temperature solid oxide fuel cell and preparation method thereof, this electrolyte chemically stable also possesses high-performance under low temperature (300-600 ℃), to overcome the above-mentioned defective of prior art.The electrolyte of low-temperature solid oxide fuel cell of the present invention; It is characterized in that: be by being selected from two kinds or two or more elements among Li, Na, K, Ca, Ba, Sr, Mg, Zn, Bi, Al, Zr, Ti, Nb, In, Sn, Ga, Sb, Sc, Si or the Sn; The compound oxidate ceramic material of the above-mentioned element that each element constitutes according to its any proportioning that accounts for selected element integral molar quantity 1%-99% molar fraction, and the composite material that forms by these composite oxides and rare earth oxide.
The preparation method of the electrolyte of low-temperature solid oxide fuel cell of the present invention is characterized in that operating procedure is following:
Step 1, will be selected from the nitrate of any two kinds or two or more elements among Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Mg, Bi, Al, Zr, Ti, Nb, In, Ga, Sb, Si or the Sn or dissolve in the compound of nitric acid, be mixed with the hybrid ionic solution of total ion concentration at 0.01-1.0M with deionized water; Wherein the molar fraction of each selected ion (for example: 40Li is selected between 1%-99%
+/ 60Zn
2+, 30K
+/ 70Zn
2+, 20Ca
2+/ 60Zn
2+/ 20Al
3+);
Step 2, select for use one of following mode to handle:
1., in the hybrid ionic solution of above-mentioned steps 1 chosen elements, extraordinarily go into citric acid or urea, after stirring, dryout, obtain fine powder to sending out the raw meal body burning by the 1-4 of chosen elements integral molar quantity; Again with the fine powder of gained at 700-850 ℃ of sintering 1-20 hour, promptly obtain a kind of oxide fuel battery electrolyte material of the present invention;
Or 2.; In the hybrid ionic solution of said step 1 chosen elements; Add rare earth compound by the 1%-95% of chosen elements integral molar quantity, this rare earth compound comprises nitrate compound cerous nitrate, samaric nitrate or the yttrium nitrate of rare earth, or various ion doping cerium oxide, lanthana, yttrium oxide, samarium oxide, gadolinium oxide, neodymia, protactinium oxide; Or mixed rare earth carbonate, or mixed rare earth carbonate is through 1-10 hour resulting mixed rare-earth oxide of 800 ℃ of calcinings; In the solution of above-mentioned compounds containing rare earth, the 1-4 of 1 chosen elements integral molar quantity extraordinarily goes into citric acid or urea set by step again, or not adding citric acid or urea; After stirring, dryout and obtain fine powder; The fine powder of gained at 700-850 ℃ of sintering 1-20 hour, is promptly obtained the hybrid ceramic electrolyte of another kind of the present invention by chosen elements oxide and rare earth oxide;
Or 3.; In the hybrid ionic solution of said step 1 chosen elements, by the 1%-95% adding rare earth compound of chosen elements integral molar quantity, this rare earth compound comprises nitrate compound cerous nitrate, samaric nitrate or the yttrium nitrate of rare earth; Or cerium oxide; Or various ion doping cerium oxide, lanthana, yttrium oxide, samarium oxide, gadolinium oxide, neodymia or protactinium oxide, or mixed rare earth carbonate, or by mixed rare earth carbonate through 1-10 hour resulting mixed rare-earth oxide of 800 ℃ of calcinings; In the described hybrid ionic solution of step 1, soak more than 1 minute these rare earth oxides; Remove surplus liquid then; With the rare earth oxide after soaking through 700-850 ℃ of sintering 1-20 hour; Obtain of the present invention another by the lapping of chosen elements oxide to rare earth oxide---promptly be kernel with the rare earth oxide, coated outside the fuel battery electrolyte material of metal or semiconductor and their composite oxides.
In the method for the present invention; The technology path of a material preparation is to adopt colloidal sol, gel method to combine firing method; That is: with the nitrate of two kinds in the said available scope or multiple element or dissolve in the compound of nitric acid, between 1%-95%, select (like above-mentioned mol ratio of giving an example: 40Li according to amount shared molar fraction in the amount of total chosen elements of every kind of chosen elements
+/ 60Zn
2+, 30K
+/ 70Zn
2+, 20Ca
2+/ 60Zn
2+/ 20Al
3+), water is deployed into the liquid of 0.01-1.0M (mol), and the 1-4 by the chosen elements integral molar quantity extraordinarily goes into citric acid then; Heat and stir the gel that changes thickness up to liquid at 200 ℃, continue to stir heating; Drying obtains fluffy fine powder until rapid burning; Perhaps the gel of thickness is placed in the baking oven and kept 12-24 hour, obtain fluffy dried glue at 120 ℃; At last at 700-850 ℃ of sintering 1-20 hour, obtain bi-component or multi-component oxide and with the compound of rare earth oxide, be the electrolyte that can be used for 300-600 ℃ of low temperature SOFC.
Said combustion process also can be carried out step by step, that is, the gel of thickness is placed on is heated to 300-500 ℃ in groom's stove, and combustible is removed in the burning of material body, obtains fluffy fine powder; Continue to be heated to 700-850 ℃, sintering 1-20 hour, obtain at last fluffy bi-component of quality or multi-component oxide and with the compound of rare earth, be the electrolyte that can be used for 300-600 ℃ of low temperature SOFC.
Also can directly dryout the selected ion mixed solution of above-mentioned preparation without colloidal sol, gel, through 700-850 ℃ of sintering 1-20 hour, promptly obtain bi-component or multi-component oxide and with the composite oxides electrolyte of rare earth oxide.
According to the method for the invention; From alternative ion Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Mg, Bi, Al, Zr, Ti, Nb, In, Ga, Sb, Si or Sn, select any 2 kinds, 3 kinds or multiple element, can construct thousand, the prescription of ten thousand kind of material.These prescriptions do not depend on and use what chemicals do not depend on how to prepare yet, and key is to comprise above-mentioned said element, and the multiple component oxide material of being made up of 2,3 or a plurality of these elements.Change two components that are used for low temperature (300-600 ℃) oxide fuel cell (LTSOFC) and the multi-component oxide electrolysis material that obtains with this thinking and method, all belong to protection category of the present invention.
Adopt the electrolyte of the prepared above-mentioned low temperature oxide fuel battery that obtains of method of the present invention that a common characteristic is arranged; The compound of two or more elements that will select exactly (being typically nitrate) prepares and 700-850 ℃ of sintering through wet-chemical by certain set of dispense ratio; Form multiple component oxide and with the composite material of rare earth oxide, be the electrolyte that can be used for low temperature SOFC.The working temperature of this material is between 300-600 ℃.Owing to be all solid state oxide composite, solved the problem of salt corrosion with stability.Particularly realized the high performance SOFCs of low temperature (300-600 ℃).
It is 200410065680.1 " in, low temperature ceramic oxide fuel cell and preparation technology's method " that the present invention is based on success that Chinese patent number is 00112228.2 early oxidation cerium based composite electrolyte and the follow-up patent No., further improves and develops the particularly electrolyte of low temperature (300-600 ℃) oxide fuel cell (LTSOFC) of high-performance oxide fuel cell.Adopt the act as a fuel electrolyte of battery of the above-mentioned material of the present invention's preparation, the 6 * 6cm that further constructs according to one Chinese patent application number be 200410065680.1 " in, low temperature ceramic oxide fuel cell and preparation technology's method " and fuel cell auxiliary electrode material
2The fuel cell of area can be at 300-550 ℃ of power output 7.5-18 watt.Obtained excellent fuel battery performance through the test proof, particularly improved the performance of fuel cell significantly, reached 300-700mW/cm at low temperature (300-600 ℃)
2, and can keep good stable property.
Compare with existing oxide fuel cell material, the present invention has following outstanding advantage:
1. all solid state oxide electrolysis material that is used for fuel cell of the present invention has been realized 300-600 ℃ SOFC, is the breakthrough of SOFC material/technology.
2. the present invention has avoided and has solved the salt corrosion property and the low-temperature stability problem of cerium oxide-salt composite material.
3. the present invention has also improved the power output of fuel cell low temperature (300-600 ℃) simultaneously, has improved the cryogenic property and the stability of fuel cell.
4. because the present invention can reach low temperature, the high-performance of SOFCs, reduced manufacturing cost, opened up a new way for further developing product with market competitiveness SOFC.
5. the present invention makes the realization of low temperature, high-performance SOFC technology more expand its application at traffic and portable power source, power, and is not limited only to the scope of application of traditional SOFC at stationary electric power plant.
6. the new material of the present invention's proposition designs and development method; Break traditional SOFC structure electrolyte and must use the restriction of oxygen ion conductor; And use various pairs, many/as to answer the oxide of component, the wide new function material development space and the degree of freedom is provided.
It is the functional material of base that the present invention has further developed with two components or the full oxide material of multicomponent, has realized high performance 300-600 ℃ low-temperature solid oxide fuel cell, does not also see similar relevant report so far.Low temperature (300-600 ℃) SOFC of all these all solid state oxide electrolysis material structures does collector electrode and catalyst without noble metal, and all material is with low cost.The invention of these materials is SOFC has been made real broken property to low temperatureization, commercialization contribution.The thousands of routine experimental result of having done confirms that the present invention has generality and superiority, and its great potential and using value are still among exploitation.The exploitation of the electrolyte of low temperature of the present invention, all solid state oxide fuel cell of high-performance and develop into the fuel cell high-tech industry strong support and new approach are provided.
Description of drawings
Fig. 1 is the stereoscan photograph of a kind of exemplary complex oxide LiZn oxide parcel samarium doped cerium oxide (SDC) composite material of the present invention;
Fig. 2 is the transmission electron microscope photo of LiZn oxide to the composite material of SDC parcel.
The typical conductivity of material-temperature relation curve that Fig. 3 obtains respectively for 3 kinds of different modes in the step 2 of the inventive method and with the comparison curves of traditional single phase material SDC.
The material that Fig. 4 obtains respectively for 3 kinds of different modes in the step 2 of the inventive method is that the fuel cell of electrolyte structure obtains representational current-voltages (I-V) and electric current-power (I-P) curve from 6 * 6 square centimeters of flat plate cells actual measurements under different temperatures.
Embodiment
Below in conjunction with accompanying drawing, the present invention is specifically described in detail through more embodiment.
Embodiment 1:
The present invention relates to further specify as follows with embodiment below with different formulations and three types of high-performance SOFC electrolytes that different preparation methods obtain:
1) selected metal ion compound.Available typical ion or element are Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Mg, Bi, Al, Zr, Ti, Nb, In, Ga, Sb, Si or Sn among the present invention;
2) from above-mentioned preferred ion or element, select any 2 kinds, 3 kinds or multiple, shared molar fraction is in the 1%-99% scope in the total amount of chosen elements or ion according to selected each element or ion, and preparation concentration is the hybrid ionic solution of 0.01-1.0M;
3) preparation method adopts sol-gel process to combine firing method.
The hybrid ionic solution formula of first's embodiment of the invention:
Get 0.025 mole of M (NO
3)
y(y=1-2; M=Li, Na, K, Rb, Cs, Ca, Sr or Ba) and 0.025 mole of other 2,3 or 4 valence metal ion: be typically Zn
2+, Mg
2+, Al3
2+, Bi
3+Or Zr
4+Water-soluble compound such as Zn (NO
3)
26H
2O, Mg (NO
3)
26H
2O, Al (NO
3)
39H
2O, Bi (NO
3)
39H
2O or ZrOCl
28H
2O uses deionized water or distilled water to be deployed into according to the liquid of total concentration of metal ions as 0.5M, as:
1), to Zn (NO
3)
26H
2O gets 0.025 mole, and gets 0.025 mole of M (NO in addition respectively
3)
y(M=Li, Na, K, Rb, Cs, Ca, Sr or Ba, y=1 or 2), wherein any M are deployed into different M ions of 1-8 kind and Zn
2+The hybrid metal ion concentration of ion is the solution of 0.25M; In fact; Because above-mentioned chosen elements Zn, Li, Na, K, Rb, Cs, Ca, Sr or Ba; The shared molar fraction of its each component can be selected at 1-99%, so just can have thousand, ten thousand kind of prescription, just 50: 50 a kind of equal component formula of enumerating here (down with) wherein;
2), to Mg (NO
3)
26H
2O gets 0.025 mole, and gets 0.025 mole of M (NO in addition respectively
3)
y(M=Li, Na, K, Rb, Cs, Ca, Sr or Ba, y=1 or 2), wherein any M are deployed into 9-16 number different M ion and Mg
2+The hybrid metal ion concentration of ion is the solution of 0.5M;
3), equally, to Al (NO
3)
39H
2O is with M (NO
3)
y(M=Li, Na, K, Rb, Cs, Ca, Sr or Ba, y=1 or 2), wherein any M are deployed into 17-24 number different M ion and Al
3+The solution of the mixing 0.5M of ion;
4), similarly, get 0.025 mole of M (NO
3)
y(M=Li, Na, K, Rb, Cs, Ca, Sr or Ba; Y=1 or 2), wherein any M is with 0.015 mole of Al (NO
3)
39H
2O and 0.01 mole of Bi (NO
3)
39H
2O mixes, and is deployed into 25-32 number different M ion and Al
3+/ Bi
3+Ion mixes the solution that total ion concentration is 1.0M;
5), get 0.025 mole of M (NO
3)
y(M=Li, Na, K, Rb, Cs, Ca, Sr or Ba, y=1 or 2), wherein any M and 0.015 mole of Al (NO
3)
39H
2O and 0.01 mole of ZrOCl
28H
2O mixes, and is deployed into 33-40 number different M ion and Al
3+/ Zr
4+Ion mixes the solution that total ion concentration is 0.5M;
6), get 0.025 mole of M (NO
3)
y(M=Li, Na, K, Rb, Cs, Ca, Sr or Ba, y=1 or 2), wherein any M and 0.015 mole of Zn (NO
3)
2.6H
2O and 0.01 mole of ZrOCl
28H
2O mixes, and is deployed into 40-48 number different M ion and Zn
2+/ Zr
4+The total ion concentration that ion mixes is the solution of 0.25M.
2: the 49-59# of embodiment fill a prescription as follows:
49, with the 0.02mol potassium silicate to the 0.02mol zinc nitrate, be deployed into K
+/ Si
4+/ Zn
2+The total ion concentration that ion mixes is the solution of 0.05M.
50, with the 0.02mol alumina silicate to the 0.02mol zinc nitrate, be deployed into Al
3+/ Si
4+/ Zn
2+The total ion concentration that ion mixes is the solution of 0.1M.
51, with the 0.02mol sodium metasilicate to 0.01mol zinc nitrate and 0.01mol stannic chloride, be deployed into Na
+/ Si
4+/ Zn
2+/ Sn
2+Ion mixes the solution that total ion concentration is 0.25M.
52, with the 0.02mol alumina silicate to 0.01mol zinc nitrate and 0.01mol stannic chloride, be deployed into Al
3+/ Si
4+/ Zn
2+/ Sn
2+Ion mixes the solution that total ion concentration is 0.3M.
53, with the 0.02mol silmag to 0.02mol potassium nitrate, be deployed into Si
4+/ Mg
2+/ K
+Ion mixes the solution that total ion concentration is 0.5M.
54, with 0.01mol zinc nitrate and 0.01mol silmag to 0.02mol potassium nitrate, be deployed into Si
4+/ Mg
2+/ Zn
2+/ K
+The solution of the mixing 0.5M of ion.
55, with 0.01mol zinc nitrate and 0.01mol silmag, be deployed into Si
4+/ Mg
2+/ Zn
2+Ion mixes the solution that total ion concentration is 1.0M.
56,0.01 potassium silicate: 0.01 magnesium nitrate is deployed into Si
4+/ Mg
2+/ K
+Ion mixes the solution that total ion concentration is 1.0M.
57,0.01 alumina silicate: 0.01 oxygen chlorine zirconium is deployed into Si
4+/ Al
3+/ Zr
4+The total ion concentration that ion mixes is the solution of 0.5M.
58,0.01 potassium silicate: 0.01 magnesium nitrate is deployed into Si
4+/ K
+/ Mg
2+The total ion concentration that ion mixes is the solution of 0.5M.
59,0.01 potassium silicate: 0.01 oxygen chlorine zirconium is deployed into Si
4+/ K
+/ Zr
4+The total ion concentration that ion mixes is the solution of 0.25M.
Above-mentioned cited silicate is potassium silicate, sodium metasilicate, alumina silicate and silicon magnesium compound, and they all are the carriers of good preparation oxide containing silicon; If meet insufficient hydrolysis, can add an amount of acid dissolving in addition.
Embodiment 3: more prescription
Can be from following ion: Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Mg, Bi, Al, Zr, Ti, Nb, In, Ga, Sb, Si or Sn any 2 kinds, 3 kinds or multiple element construct more polygamy side, slightly lift as follows again:
Get x mole MNO respectively
3(M=Li, Na, K, Rb or Cs) gets wherein any or two kinds of M elements, for example: and Li, Na or K, get y mole N (II) (NO again
3)
2(y=1-x); N (II) is the divalent metal ion, is typically Ca
2+, Sr
2+, Ba
2+, Zn
2+Or Mg
2+, according to M: N=1: 1 mol ratio obtains Li-N; Na-N; The 60-75 kind of K-N embodiment solution (being generally 0.1-1.0M concentration).
Embodiment 4: further use (III/IV) (NO of M '
3)
39H
2O (M ' (III/IV) be 3 valencys or 4 valence metal ions, be typically Al
3+, Bi
3+, Zr
4+, Ti
4+, Nb
3+Or In
3+Attention: carbonate compound or other compound that can also use these elements are with nitric acid or other acid dissolving), and use deionized water or distilled water to be deployed into to mix with above-mentioned 1 valency or divalent metal ion solution as the liquid of 1M according to total concentration of metal ions and obtain.According to 1: 1 mol ratio, obtain Li-M '; Na-M '; The 76-123 kind of K-M ' (adding up to 18 kinds) and N-M ' (adding up to 30 kinds) embodiment solution (being generally 0.1-1.0M concentration).
In brief; Through any 2 kinds, 3 kinds or multiple element and different component marks among above-mentioned ion: Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Mg, Bi, Al, Zr, Ti, Nb, In, Ga, Sb, Si or the Sn; Can construct thousand, ten thousand kind of prescription, can't all describe one by one.
The top example of lifting is just used any chemicals in order material preparation prescription of the present invention to be described, not to be depended on, does not also depend on how to prepare, and key is to comprise above-mentioned element, and the composite oxide material that is generated by 2,3 or a plurality of these elements; So above-mentioned giving an example should be as limitation of the present invention.As long as because according to method of the present invention, just nature can be prepared and develop out multifarious kind of prescription for preparing material of the present invention.
The preparation of the electrolyte of second portion low-temperature solid oxide fuel cell of the present invention
Embodiment 5:
One, the preparation of metal (or semiconductor) two components or multicomponent composite oxides:
To in above-mentioned metal ion (or semiconductor) formulations prepared from solutions, extraordinarily go into citric acid by the 1-4 according to the molal quantity of selecting metal or semiconductor element total concentration; Heat and stir the gel that changes thickness up to liquid at 200 ℃; Continue to stir; Heating, drying obtains fluffy fine powder until rapid burning.Said process also can carry out under the higher temperature in groom's stove as under 400 ℃; Perhaps the gel with thickness is placed in the baking oven, keeps 12-24 hour at 120 ℃, obtains very fluffy dried glue usually.At 700-850 ℃ of sintering 1-20 hour, obtain bi-component, three components or multicomponent metal (or semiconductor element) composite oxide powder at last, be the electrolyte of the SOFC that can be used for low temperature 300-600 ℃.
Two, the preparation of metal (or semiconductor) oxide-rare earth oxide composite material:
As previously mentioned, the 1-95% scope according to the integral molar quantity of chosen elements or ion adds rare earth compound in above-mentioned hybrid ionic formulations prepared from solutions.These comprise nitrate compound: like cerous nitrate, samarium, yttrium perhaps dissolves in the compound of nitric acid; Comprise rare earth oxide, this rare earth oxide can be various ion doping cerium oxide, or cerium oxide (CeO
2), lanthana (La
2O
3), yttrium oxide (Y
2O
3), samarium oxide (Sm
2O
3), gadolinium oxide (Gd
2O
3), neodymia (Nd
2O
3), protactinium oxide (Pr
2O
3) or mixed rare earth carbonate, and mixed rare earth carbonate is through 1-10 hour resulting mixed rare-earth oxide (LCP) of 800 ℃ of calcinings.1-4 according to chosen elements or ion total mole number extraordinarily goes into citric acid then, heats and stir the gel that changes thickness up to liquid at 200 ℃, continue to stir, and heating, drying obtains fluffy fine powder until rapid burning; Said process also can carry out under the higher temperature in groom's stove (as 400 ℃); Perhaps the gel of thickness is placed in the baking oven in 120 ℃ and kept 12-24 hour, obtain very fluffy dried glue usually.At 700-850 ℃ of sintering 1-20 hour, obtain the compound of bi-component or multicomponent element oxide and rare earth oxide at last.Cited these materials that come out of top embodiment all can be used for the electrolyte of low temperature 300-600 ℃ SOFC.
Lift the examples of implementation of some representative formulations below.
Embodiment 6:
In 123 solution formulas of the above-mentioned representativeness of selecting, get any solution and add cerous nitrate/or cerium oxide according to the 1%-95% of its total metal (or semiconductor) element mole; Can produce very many prescriptions again; Select prescription (20 metallic elements in molar ratio: 80 rare earth ceriums of 3 typical components; 50 metallic elements: 50 rare earth ceriums; 80 metallic elements: be example 20 rare earth ceriums), fully stir and remain on 100 ℃.Repeat the sol-gel process and the firing method process of above-mentioned material preparation then; At 700-850 ℃ of sintering 1-5 hour, can obtain hundreds of kind bi-component or multi-component oxide-rare earth oxide (cerium oxide) compound at last, can be used as the electrolyte of low temperature (300-600 ℃) SOFC.
Embodiment 7:
Better with the above-mentioned plain cerium oxide effect of doped cerium oxide (typical case is like yttrium, samarium, gadolinium or lanthanum doping of cerium oxide) replacement.For example use 10-20mol% yttrium, lanthanum, samarium, gadolinium doped cerium oxide; Prepare mixed solution to nitrate compound of their elements or their oxide with nitric acid dissolve according to doping content 10-20mol% and cerous nitrate; Repeat the composite material of above-prepared metal (or semiconductor) oxide-cerium oxide then fully; Can obtain the composite material of various element oxide-rare earth oxides (doped cerium oxide) equally, can be used for the electrolyte of low temperature (300-600 ℃) SOFC.
Other rare earth element comprises that scandium, yttrium, lanthanum, praseodymium, neodymium, samarium, europium or gadolinium replace cerium; Can use top same procedure preparation; Further preference is that the nitrate compound of yttrium, lanthanum, samarium or gadolinium element or their oxide are used nitric acid dissolve; Repeat top step equally, can obtain the composite material of various metal oxide-rare earth oxides, can be used as the electrolyte of low temperature (300-600 ℃) SOFC.
Preferred in addition rare earth oxide is raw material of industry level mixed rare earth carbonate and 800 ℃ of calcinings of raw material of industry level mixed rare earth carbonate warp 1-10 hour resulting mixed rare-earth oxide (LCP) above-mentioned cerous nitrate of replacement or cerium oxide, and other preparation method is with metal (or semiconductor) oxide-the cerium oxide composite material is identical.So, can obtain the more composite material of poly-metal deoxide-mixed rare-earth oxide, can be used as the electrolyte of low temperature (300-600 ℃) SOFC.
What should point out emphatically is, give an example son just for explain of the present invention ingenious with enrich part, embodiment is too numerous to mention, can not be limited to this.
Three, metal (or semiconductor) composite oxides are to the preparation of the lapping of rare earth oxide:
Embodiment 8:
In preparation above-mentioned element oxide-rare earth oxide composite material, can also prepare the lapping of this element oxide to rare earth oxide.Implementation method is following: with getting any solution in 123 solution formulas of the above-mentioned representativeness of enumerating.Get the 50-100 milliliter, this solution of 0.5-1M concentration soaks an amount of (0.1-100 gram) rare earth oxide (various rare earth oxides are as stated) in room temperature to 150 ℃, and soak time is any, be preferably from 1 minute to 1 week, follow stirring simultaneously or do not stir.Remove unnecessary supernatant liquid then, with the rare earth oxide after soaking through 700-850 ℃ sintering 1-10 hour, promptly obtain the lapping of various metals or semiconductor (like silicon or tin) oxide to rare earth oxide.
Enumerate the result that some typical fuel cells are implemented measurement with form below, prove the practicality and the high-performance of these materials of the present invention.The cited actual measured results that all is based on large tracts of land fuel cell (6 * 6 square centimeters).
Table 1. representative fuel cell is measured data under different temperatures
(6 * 6 square centimeters of battery measured datas are calculated)
231
#K-Mg-Zn oxide electrolyte 357
#The Li-Mg-Zn oxide
701
#K-Mg-Ba-oxide composite S DC 759
#Li-Zn oxide parcel SDC
521
#K-Zn-Ba-GDC (gadolinium doped Ce O
2) 659
#K-Mg-Zn wraps up LCP
Fig. 1 has provided the stereoscan photograph of a kind of exemplary complex oxide LiZn oxide parcel Sm doped cerium oxide (SDC) composite material of the present invention; Can see that from this stereoscan photograph prepared material is the nanoscale electrolyte below 100 nanometers.
Fig. 2 is the transmission electron microscope photo of LiZn oxide of the present invention to the composite material of Sm doped cerium oxide (SDC) parcel; From this transmission electron microscope photo, can see, evenly cover/wrapped up one deck LiZn oxide at the SDC particle surface.Its integument thickness is about 10 nanometers.
Fig. 3 reaches the comparison curves with traditional samarium doped cerium oxide (SDC) for the typical conductivity-temperature relation curve of the different materials of employing different preparation methods acquisitions of the present invention.Be followed successively by from top to bottom among Fig. 3: the curve a of Li-Zn-oxide parcel SDC; The curve b of K-Mg-Al-GDC; The curve c of Li-Mg-oxide; The curve d of K-Si-Mg-LCP; K-Mg-Zn-Al-YDC curve e; The curve f of Li-Zn-Zr oxide; The curve g of pure SDC.Visible by Fig. 3, LiZn-oxide parcel SDC reaches high conductivity, and the conductivity that reaches 1000 ℃ of 0.15S/cm and traditional single phase YSZ (yttrium-stabile zirconium dioxide) more than 400 ℃ is suitable; And SDC is 10 at 400 ℃
-5S/cm, low 4 magnitudes; The prepared material electric conductivity of the present invention is suitable as the electrolyte of low temperature oxide fuel battery all far above the conductivity of SDC.
Fig. 4 is that the fuel cell of electrolyte structure obtains representational current-voltage (I-V) and electric current-power (I-P) curve at 500 ℃ from 6 * 6 square centimeters of (having 25 square centimeters of active areas) flat plate cell actual measurements for the different materials that adopts different preparation method of the present invention to obtain.Be followed successively by from top to bottom among Fig. 4: the I-V curve h of K-Mg-Ba-SDC electrolyte fuel battery; The electrolytical I-V curve of LiZn oxide parcel SDC i; The I-V curve j of K-Mg-Zn-oxide electrolyte; The I-P curve k of K-Mg-Ba-SDC electrolyte fuel battery; The electrolytical I-P curve of LiZn oxide parcel SDC l; The I-P curve m of K-Mg-Zn-oxide electrolyte.Visible by Fig. 4, with curve h, the K-Mg-Ba-SDC electrolyte shown in the k has obtained best fuel battery performance in these batteries, and its maximum output current reaches 21 amperes, and peak power output reaches 17.5 watts.
Adopting material of the present invention is the fuel cell of electrolyte structure, can be at 300-550 ℃ of power output 7.5-18 watt.
In a word, cited these materials of the above embodiment of the present invention have been expanded thinking, have been set up platform for exploitation is applicable to the electrolyte functional material of 300-600 ℃ SOFC, and the development space and the degree of freedom of wide advanced material are provided.
The preferred technology path of the chemical preparation of top indication is a wet chemistry method, mainly obtains nano level metal or semiconductor element (like silicon or tin) oxide and is used for the electrolyte of low temperature, high-performance SOFC with the rare earth material compound with sol-gel process and firing method.
Can select from following ion: Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Mg, Bi, Al, Zr, Ti, Nb, In, Ga, Sb, Si or Sn according to the present invention that any 2 kinds, 3 kinds or multiple element construct thousand, ten thousand kind of material prescription.These prescriptions do not depend on and use what chemicals do not depend on how to prepare yet, and key is to comprise above-mentioned element, and the electrolyte of being made up of 2,3 or a plurality of these elements that is used for low temperature oxide fuel battery (LTSOFC).As long as according to method of the present invention, just can match, develop out multifarious kind of prescription for preparing electrolyte of the present invention naturally.
With this thinking and method change two kinds of obtaining or multi-component composite oxides and with the composite material of rare earth oxide formation; The electrolyte that all can be used as low temperature (300-600 ℃) oxide fuel cell (LTSOFC) all belongs to protection category of the present invention.
Claims (4)
1. the preparation method of the electrolyte of a low-temperature solid oxide fuel cell is characterized in that operating procedure is following:
Step 1, will be selected from the nitrate of any two kinds or two or more elements among Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Mg, Bi, Al, Zr, Ti, Nb, In, Ga, Sb, Si or the Sn or dissolve in the compound of nitric acid, be mixed with the hybrid ionic solution of total ion concentration at 0.01-2.0M;
Step 2, in the hybrid ionic solution of above-mentioned steps 1 chosen elements, extraordinarily go into citric acid or urea by the 1-4 of chosen elements integral molar quantity, after stirring, dryout to sending out the raw meal body burning, obtain fine powder; The fine powder of gained at 700-850 ℃ of sintering 1-20 hour, is promptly obtained oxide fuel battery electrolyte material.
2. the preparation method of the electrolyte of a low-temperature solid oxide fuel cell is characterized in that operating procedure is following:
Step 1, will be selected from the nitrate of any two kinds or two or more elements among Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Mg, Bi, Al, Zr, Ti, Nb, In, Ga, Sb, Si or the Sn or dissolve in the compound of nitric acid; Be mixed with the hybrid ionic solution of total ion concentration at 0.01-2.0M; And extraordinarily go into citric acid or urea by the 1-4 of chosen elements integral molar quantity, stir;
Step 2, the 1%-95% by the chosen elements integral molar quantity in step 1 product add rare earth compound; This rare earth compound comprises nitrate compound cerous nitrate, samaric nitrate or the yttrium nitrate of rare earth; Or cerium oxide; Or ion doping cerium oxide, lanthana, yttrium oxide, samarium oxide, gadolinium oxide, neodymia or protactinium oxide; Or mixed rare earth carbonate, or by this mixed rare earth carbonate through 800 ℃ the calcining 1-10 hour resulting mixed rare-earth oxide;
After the product of step 3, abundant whipping step 2 is extremely even, dryout, obtain fine powder to sending out the raw meal body burning; The fine powder of gained at 700-850 ℃ of sintering 1-20 hour, is promptly obtained to be used for the compound electrolyte material of oxide-rare earth oxide of 300-600 ℃ SOFC.
3. like the preparation method of claim 1 or the said low-temperature solid oxide fuel cell electrolyte of claim 2; Be characterised in that at said nitrate that adopts any two kinds or two or more elements or the compound that dissolves in nitric acid selected for use in the element; The mol ratio of the amount of the amount of every kind of chosen elements and total chosen elements is between 1%-99%; Water is deployed into the liquid of 0.01-1.0M, and the 1-4 according to the chosen elements integral molar quantity extraordinarily goes into citric acid then; Or the 1%-95% that presses the chosen elements integral molar quantity in addition adds rare earth compound; Heat and stir the gel that changes thickness up to liquid at 200 ℃, continue to stir, heating, drying obtains fluffy fine powder until rapid burning; Perhaps the gel of thickness is placed in the baking oven and kept 12-24 hour, obtain fluffy dried glue at 120 ℃; At 700-850 ℃ of sintering 1-20 hour, promptly obtain two components or multicomponent composite oxides and rare earth oxide composite material at last, be applicable to the electrolyte of 300-600 ℃ of fuel cell.
4. the preparation method of the electrolyte of a low-temperature solid oxide fuel cell is characterized in that operating procedure is following:
Step 1, will be selected from the nitrate of any two kinds or two or more elements among Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Mg, Bi, Al, Zr, Ti, Nb, In, Ga, Sb, Si or the Sn or dissolve in the compound of nitric acid; Be mixed with the hybrid ionic solution of total ion concentration at 0.01-1.0M; And extraordinarily go into citric acid or urea, or not adding citric acid or urea by the 1-4 of chosen elements integral molar quantity;
Step 2, at cerium oxide, or by Ca
2+, Sm
3+, Gd
3+, La
3+Or Pr
3+Ion doping cerium oxide, lanthana, yttrium oxide, samarium oxide, gadolinium oxide, neodymia or protactinium oxide; Or mixed rare earth carbonate; Or by mixed rare earth carbonate through 1-10 hour resulting mixed rare-earth oxide of 800 ℃ of calcinings, be dipped in the mixed solution of selected ion more than 1 minute, remove surplus liquid then; With the rare earth oxide after soaking through 700-850 ℃ of sintering 1-20 hour; Promptly to obtain with the rare earth oxide be kernel, and coated outside oxide, is applicable to the compound electrolyte material of 300-600 ℃ of fuel cell.
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| TWI388506B (en) * | 2008-12-16 | 2013-03-11 | Ind Tech Res Inst | Method for forming p type metal oxide semiconductor material |
| CN102417203A (en) * | 2011-08-31 | 2012-04-18 | 广西师范大学 | Method for preparing ultrafine ITO powder by combustion synthesis process |
| CN105140526B (en) * | 2015-07-22 | 2017-09-29 | 中国地质大学（武汉） | A kind of preparation method of fuel cell and fuel cell |
| CN105977531B (en) * | 2016-07-28 | 2018-09-14 | 上海应用技术学院 | A kind of preparation method of LiBaLaZrAlREO lithium ion solid electrolytes |
| CN108123158B (en) * | 2017-12-29 | 2020-02-21 | 成都新柯力化工科技有限公司 | Low-temperature ceramic electrolyte membrane for solid oxide fuel cell and preparation method thereof |
| CN109786795B (en) * | 2018-12-17 | 2021-10-08 | 南京晓庄学院 | Low-temperature solid oxide fuel cell based on strontium stannate/lanthanum strontium cobalt iron composite material |
| CN109830717B (en) * | 2018-12-17 | 2021-09-24 | 南京晓庄学院 | Low-temperature solid oxide fuel cell based on calcium stannate/strontium iron molybdenum composite material |
| CN109802162B (en) * | 2018-12-28 | 2021-09-24 | 南京晓庄学院 | Low-temperature solid oxide fuel cell based on zinc oxide-stannous oxide composite material |
| CN109818021B (en) * | 2018-12-28 | 2022-01-21 | 南京晓庄学院 | Low-temperature solid oxide fuel cell based on cerium oxide/ferroferric oxide composite material |
| CN110165269B (en) * | 2019-05-28 | 2022-06-24 | 盐城市新能源化学储能与动力电源研究中心 | Solid oxide fuel cell composite electrolyte and preparation method thereof |
| CN113851660B (en) * | 2021-09-22 | 2023-07-07 | 南京工业大学 | Method for improving low-temperature catalytic performance in cathode of solid oxide fuel cell |
| CN114420985A (en) * | 2021-12-16 | 2022-04-29 | 东南大学 | Rare earth oxide (M)2O3) Application in preparing low-temperature proton ceramic fuel cell |
| CN115036545A (en) * | 2022-06-15 | 2022-09-09 | 湖北大学 | Perovskite type electrolyte slurry, thin film fuel cell and preparation method |
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| CN101183716A (en) * | 2007-12-07 | 2008-05-21 | 华中科技大学 | Method of producing three-in-one electrode of solid oxide fuel battery |
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