CN102201589A - Nano electrolyte material for mesothermal solid oxide fuel cell and preparation method of nano electrolyte material - Google Patents
Nano electrolyte material for mesothermal solid oxide fuel cell and preparation method of nano electrolyte material Download PDFInfo
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Abstract
The invention provides a nano electrolyte material for a mesothermal solid oxide fuel cell and a preparation method of the nano electrolyte material, and relates to a nano electrolyte material for a solid oxide fuel cell and the preparation method of the nano electrolyte material. By the invention, the problems that the ionic conductivity of a mesothermal region of the conventional electrolyte material for the mesothermal solid oxide fuel cell is low and the preparation temperature of the conventional oxyen ion conductor electrolyte material is higher can be solved. The electrolyte material is cerium oxide base oxygen ion conductive electrolyte nano powder doped with rare-earth element ions and cobalt ions and prepared by weighing CeO2, rare-earth element nitrate and cobalt nitrate, grinding and mixing uniformly, adding mixed inorganic alkali, heating, washing and drying. Within the temperature of 500 to 700 DEG C, the ionic conductivity is high and reaches 0.047Scm<-1> at most; due to doping of Co3<+>, the conduction performance of the electrolyte material is enhanced and the ionic conductivity is increased, and the electrochemical performance of the CeO2 electrolyte doped with the single rare-earth Nd3<+> ion is improved.
Description
Technical field
The present invention relates to nanometer electrolyte that a kind of Solid Oxide Fuel Cell uses and preparation method thereof.
Background technology
Solid Oxide Fuel Cell is a kind of energy source device of working under hot conditions, and energy utilization efficiency is the first-selected alternative energy source of thermo-power station, gas turbine and automobile up to about 80%.Traditional Solid Oxide Fuel Cell serviceability temperature reaches 1000 ℃ usually, and this can bring a series of problems to fuel cell technology: for example material is aging, the phase counterdiffusion between the constituent element etc.The exploitation intermediate temperature solid oxide fuel cell has become one of focus direction of its research.Traditional solid-oxide fuel battery electrolyte material (ZrO
2)
1-x(Y
2O
3)
xNo longer be applicable to intermediate temperature solid oxide fuel cell at oxygen ionic conductivity lower below 1000 ℃.Warm area has the vital task that high performance electrolyte becomes the development fuel cell technology in the exploitation.
Summary of the invention
The objective of the invention is in order to solve the warm area ionic conductivity that has the nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell now lower, be not suitable for working under mesophilic condition, and the existing high problem of oxygen ion conductor electrolyte preparation temperature, the invention provides a kind of nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell and preparation method thereof.
The cerium oxide base oxide ion conduction electrolyte nano powder that the nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell of the present invention is rare earth element ion and cobalt ions codope, chemical formula is Ce
(1-x-y)Re
xCo
yO
2-δ, x: y=4～20: 1 wherein, x+y=0.21～0.25, δ=0.10～0.12, Re is a rare earth element.
Described rare earth element ion is Nd
3+, Sm
3+, Gd
3+, Eu
3+Perhaps Pr
3+
The preparation method who is used for the nanometer electrolyte of intermediate temperature solid oxide fuel cell of the present invention realizes by following steps: one, take by weighing 75%～79% CeO by mole percentage
2And 21%～25% rare earth element nitrate and cobalt nitrate mixture, control wherein that the mol ratio of neodymium nitrate and cobalt nitrate is 4～20: 1 in neodymium nitrate and the cobalt nitrate mixture, then with CeO
2, rare earth element nitrate and cobalt nitrate ground and mixed get mixed material; Two, in the mixed material that step 1 obtains, add alkali metal inorganic base mixture, stir mixed material, then mixed material is incubated 48～96h under 200～280 ℃ of conditions, naturally cool to room temperature again, get white powder, wherein the mass ratio of alkali metal inorganic base mixture of Jia Ruing and mixed material is 3.7～4: 1; Three, the washing of the white powder that step 2 obtained and filter wet powder, then wet powder is incubated 8～15h under 50～80 ℃ of conditions, must be used for the nanometer electrolyte Ce of intermediate temperature solid oxide fuel cell
(1-x-y)Nd
xCo
yO
2-δ, x: y=4～20: 1 wherein, x+y=0.21～0.25, the preparation method of the nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell is finished in δ=0.10～0.12.
The mixture of alkali metal inorganic base described in the step 2 of the present invention is two kinds a mixture among LiOH, NaOH, KOH, RbOH and the CsOH, and the mixed proportion between two kinds of alkali metal inorganic bases is mixed with low being as the criterion of eutectic point.
The preparation method who is used for the nanometer electrolyte of intermediate temperature solid oxide fuel cell of the present invention has used alkali metal inorganic base (having strong basicity, as highly basic NaOH and KOH), can with glass in SiO
2Reaction generates sodium metasilicate, introduces impurity to product, therefore, should not adopt glass container among the preparation method of the present invention, and should adopt the container of ability highly basic, as polytetrafluoroethylcontainer container (its strong alkali-acid resistance, and the highest can being heated to about 280 ℃).
The present invention is the nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell, is Ce
(1-x-y)Nd
xCo
yO
2-δSystem, wherein the Ce ion is+4 valencys, and rare earth ion is+3 valencys, and rare earth ion replaces the Ce ion, owing to for the maintenance system electric neutrality, can produce the oxygen room of some, improves the oxygen ionic conductivity of material.Be+3 valencys under the Co ion usual conditions, its introducing is except can introducing the oxygen room, and is lower with the binding energy of oxonium ion, causes that the conducting power of oxonium ion increases, and then improves the oxygen ion conduction rate.
The nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell of the present invention is single fluorite structure compound, has higher degree of crystallinity.Nanometer electrolyte of the present invention is to be assembled by wheat head shape nano particle to be assembled into the coralliform particle.
Nanometer electrolyte of the present invention is in 500～700 ℃ temperature range, and ionic conductivity is higher, can reach 0.047Scm
-1Thereby, obtain a kind of general high activity and the nanometer electrolyte that is used for Solid Oxide Fuel Cell of high long-time stability.
With the nanometer electrolyte compression moulding under 200 MPas that is used for intermediate temperature solid oxide fuel cell of the present invention, sintering obtained fine and close electrolyte ceramics sheet in 12 hours in 1300～1400 ℃, air atmosphere then; Be coated with the platinum slurry then in the both sides of electrolyte ceramics sheet, sintering makes porous platinum to electrode again.Adopt the complex impedance spectra measuring technology then, utilize two electrode systems under air conditions the resistance of nanometer electrolyte of the present invention to be tested, the result shows that the conductivity that is used for the nanometer electrolyte of intermediate temperature solid oxide fuel cell of the present invention is issued to 0.043～0.11Scm at 800 ℃
-1, 700 ℃ are issued to 0.022～0.047Scm
-1, 600 ℃ are issued to 0.0089～0.015Scm
-1, 500 ℃ are issued to 0.0032～0.0042Scm
-1Be respectively 2.52～6.47 times (800 ℃) of the cerium oxide base oxide ion conduction electrolyte nano material mixed of the rare earth ion list of containing transition metal cobalt ions not under the relevant temperature,～6.71 times 3.10 (700 ℃), 3.18～12 times (600 ℃), 5.82～24.29 times (500 ℃).Co is described
3+The doping of ion improves the conductive performance of electrolyte, has increased ionic conductivity, has improved single rare earth Nd
3+Ion doping CeO
2The electrolyte electrochemical performance.
Preparation method of the present invention is simple to operate, mild condition (200～280 ℃); The advantage of synthetic nanometer electrolyte is that degree of crystallinity is higher, is nano particle, is easy to sinter into dense ceramic material, the oxygen ionic conductivity of low-temperature space in the increase, thereby the chemical property of raising electrolyte.Because dopant ion has lower chemical valence state, this can improve intracrystalline oxygen vacancy concentration, improves the stability of electrolyte under the different partial condition.
The nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell of the present invention, utilize dopant ion to have the chemical valence state lower than cerium ion, and certain difference is arranged with the binding ability of oxonium ion, concentration and migration that this has improved the crystals oxygen ion vacancy make it have higher oxygen ionic conductivity and present stronger electrochemical stability under the different partial conditions.Reduce simultaneously particle size to a certain extent, increase particle surface activity and reactivity worth, make it be easier to sinter into dense ceramic material at a lower temperature, thereby improve the electrolyte performance.
Description of drawings
Fig. 1 is the X-ray diffraction spectrogram of the nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell of embodiment 12; Fig. 2 is the Ce of embodiment 12
0.78Nd
0.2Co
0.02O
1.89The field emission scanning electron microscope photo of nanometer electrolyte; Fig. 3 is the conductivity curve chart of the nanometer electrolyte of embodiment 12 and 13, and wherein " ■-" is concrete 12 the Ce that implements
0.78Nd
0.2Co
0.02O
1.89The conductivity curve of nanometer electrolyte, " ●-" be concrete 13 the Ce that implements
0.8Nd
0.2O
1.9Electrolytical conductivity curve; Fig. 4 is the conductivity curve chart of the nanometer electrolyte of embodiment 15 and 16, wherein " ●-" be concrete 15 the Ce that implements
0.75Nd
0.2Co
0.05O
1.88The conductivity curve of nanometer electrolyte, " ■-" are concrete 16 the Ce that implements
0.79Nd
0.2Co
0.01O
1.9The conductivity curve of nanometer electrolyte; Fig. 5 is the conductivity curve chart of the nanometer electrolyte of embodiment 17 and 18, wherein " ●-" be the Ce of embodiment 17
0.78Sm
0.2Co
0.02O
1.89The conductivity curve of nanometer electrolyte, " ■-" are concrete 18 the Ce that implements
0.8Sm
0.2O
1.9The conductivity curve of electrolyte; Fig. 6 is the conductivity curve chart of the nanometer electrolyte of embodiment 19 and 20, wherein " ●-" be the Ce of embodiment 19
0.78Gd
0.2Co
0.02O
1.89The conductivity curve of nanometer electrolyte, " ■-" are concrete 20 the Ce that implements
0.8Gd
0.2O
1.9The electrolytical conductivity curve of nanometer.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the combination in any between each embodiment.
Embodiment one: present embodiment is the nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell, and it is the cerium oxide base oxide ion conduction electrolyte nano powder of rare earth element ion and cobalt ions codope, and chemical formula is Ce
(1-x-y)Re
xCo
yO
2-δ, x: y=4～20: 1 wherein, x+y=0.21～0.25, δ=0.10～0.12, Re is a rare earth element.
The nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell of present embodiment is single fluorite structure compound, has higher degree of crystallinity.
The nanometer electrolyte of present embodiment is to assemble the coralliform particle that is assembled into by wheat head shape nano particle.
The nanometer electrolyte of present embodiment is in 500～700 ℃ temperature range, and ionic conductivity is higher, can reach 0.11Scm
-1Thereby, obtain a kind of general high activity and the nanometer electrolyte that is used for Solid Oxide Fuel Cell of high long-time stability.
The conductivity of the nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell of present embodiment is issued to 0.043～0.11Scm at 800 ℃
-1, 700 ℃ are issued to 0.022～0.047Scm
-1, 600 ℃ are issued to 0.0089～0.015Scm
-1, 500 ℃ are issued to 0.0032～0.0042Scm
-1Be respectively 2.52～6.47 times (800 ℃) of the cerium oxide base oxide ion conduction electrolyte nano material mixed of the rare earth ion list of containing transition metal cobalt ions not under the relevant temperature,～6.71 times 3.10 (700 ℃), 3.18～12 times (600 ℃), 5.82～24.29 times (500 ℃).Co is described
3+The doping of ion improves the conductive performance of electrolyte, has increased ionic conductivity, has improved single rare earth Nd
3+Ion doping CeO
2The electrolyte electrochemical performance.
Embodiment two: what present embodiment and embodiment one were different is that described rare earth element ion is Nd
3+, Sm
3+, Gd
3+, Eu
3+Perhaps Pr
3+Other parameter is identical with embodiment one.
Embodiment three: what present embodiment was different with embodiment one or two is the nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell, it is the cerium oxide base oxide ion conduction electrolyte nano powder of neodymium rare earth element ion and cobalt ions codope, and chemical formula is Ce
(1-x-y)Nd
xCo
yO
2-δ, x: y=4～10: 1 wherein, x+y=0.22～0.25, δ=0.10～0.12.Other parameter is identical with embodiment one or two.
Embodiment four: present embodiment is the preparation method who is used for the nanometer electrolyte of intermediate temperature solid oxide fuel cell, and it is realized by following steps: one, take by weighing 75%～79% CeO by mole percentage
2And 21%～25% rare earth element nitrate and cobalt nitrate mixture, control wherein that the mol ratio of neodymium nitrate and cobalt nitrate is 4～20: 1 in neodymium nitrate and the cobalt nitrate mixture, then with CeO
2, rare earth element nitrate and cobalt nitrate ground and mixed get mixed material; Two, in the mixed material that step 1 obtains, add alkali metal inorganic base mixture, stir mixed material, then mixed material is incubated 48～96h under 200～280 ℃ of conditions, naturally cool to room temperature again, get white powder, wherein the mass ratio of alkali metal inorganic base mixture of Jia Ruing and mixed material is 3.7～4: 1; Three, the washing of the white powder that step 2 obtained and filter wet powder, then wet powder is incubated 8～15h under 50～80 ℃ of conditions, must be used for the nanometer electrolyte Ce of intermediate temperature solid oxide fuel cell
(1-x-y)Nd
xCo
yO
2-δ, x: y=4～20: 1 wherein, x+y=0.21～0.25, the preparation method of the nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell is finished in δ=0.10～0.12.
Present embodiment prepares as the embodiment one described nanometer electrolyte Ce that is used for intermediate temperature solid oxide fuel cell
(1-x-y)Nd
xCo
yO
2-δ, x: y=4～20: 1 wherein, x+y=0.21～0.25, δ=0.10～0.12, the fluorite structure compound for single has higher degree of crystallinity, is assembled the coralliform particle that is assembled into by wheat head shape nano particle.
The CeO that the present embodiment step 1 takes by weighing
2All reach 99.99% with the quality purity of rare earth element nitrate, the quality purity of cobalt nitrate is 99.0%.
The preparation method of present embodiment has prepared the higher novel solid oxide fuel battery nano electrolyte of degree of crystallinity under the condition of comparatively gentle (200～280 ℃), thereby simplify the electrolytical technology of preparation, improve the chemical property of fuel cell.
The preparation method of present embodiment is simple to operate, mild condition (200～280 ℃); The advantage of synthetic nanometer electrolyte is that degree of crystallinity is higher, is nano particle, is easy to sinter into dense ceramic material, the oxygen ionic conductivity of low-temperature space in the increase, thereby the chemical property of raising electrolyte.Because dopant ion has lower chemical valence state, this can improve intracrystalline oxygen vacancy concentration, improves the stability of electrolyte under the different partial condition.
Embodiment five: present embodiment and embodiment four are different is that alkali metal inorganic base mixture is two kinds a mixture among LiOH, NaOH, KOH, RbOH and the CsOH in the step 2.Other step and parameter are identical with embodiment four.
Mixed proportion in the present embodiment between two kinds of alkali metal inorganic bases is as the criterion when low with eutectic point, mixes.
Embodiment six: what present embodiment and embodiment four were different is that alkali metal inorganic base mixture is the mixture of NaOH and KOH in the step 2, and the mass ratio of NaOH and KOH is 0.9～1.1: 1.Other step and parameter are identical with embodiment four.
With other NaOH and KOH mass ratio mix alkali metal inorganic base mixture, the eutectic point of the alkali metal inorganic base mixture of present embodiment is minimum.
Embodiment seven: what present embodiment and embodiment four, five or six were different is in the step 2 mixed material to be incubated 60～84h under 220～260 ℃ of conditions.Other step and parameter are identical with embodiment four or five.
Embodiment eight: what present embodiment and embodiment four, five or six were different is in the step 2 mixed material to be incubated 72h under 240 ℃ of conditions.Other step and parameter are identical with embodiment four or five.
Embodiment nine: present embodiment is different with one of embodiment four to eight is that white powder washing that in the step 3 step 2 is obtained and the concrete operations of filtering are: the white powder distilled water immersion that step 2 is obtained, filter with the normal pressure funnel then, in the process of filtration the white powder on the filter paper in the funnel is washed for several times with distilled water.Other step and parameter are identical with one of embodiment four to eight.
Present embodiment can be washed alkali metal inorganic base residual on the white powder off.
Embodiment ten: what present embodiment was different with one of embodiment four to nine is in the step 3 wet powder to be incubated 12h under 60 ℃ of conditions.Other step and parameter are identical with one of embodiment four to nine.
Embodiment 11: what present embodiment was different with one of embodiment four to ten is that step 1 middle rare earth element nitrate is neodymium nitrate, samaric nitrate, gadolinium nitrate, europium nitrate or praseodymium nitrate.Other step and parameter are identical with one of embodiment four to ten.
Embodiment 12: present embodiment is the nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell, and it is the cerium oxide base oxide ion conduction electrolyte nano powder of rare earth element neodymium ion and cobalt ions codope, and chemical formula is Ce
0.78Nd
0.2Co
0.02O
1.89
The X-ray diffraction spectrogram of the nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell of present embodiment is single fluorite structure compound as shown in Figure 1, and diffraction peak intensity is bigger, has higher degree of crystallinity, and does not have other thing and generate mutually.
Adopt field emission scanning electron microscope (FE-SEM) that the nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell of present embodiment is carried out the microstructure morphology observation, the field emission scanning electron microscope photo that obtains as shown in Figure 2, as shown in Figure 2, the electrolyte of present embodiment is a wheat head shape nano particle, length is about 500 nanometers, and a plurality of wheat head particle accumulations are assembled into the coralliform particle.
The nanometer electrolyte sintering that is used for intermediate temperature solid oxide fuel cell of present embodiment is prepared into the electrolyte ceramics sheet, concrete operations are: it is 15 millimeters circular die that the nanometer electrolyte that will be used for intermediate temperature solid oxide fuel cell is poured diameter into, being pressed into diameter then under 200 MPas is 15 millimeters, thickness is 5 millimeters disk, again the disk of compression moulding sintering in 1300～1400 ℃, air atmosphere is formed fine and close electrolyte ceramics sheet in 12 hours; The diameter of the electrolyte ceramics sheet that sintering obtains is 10 millimeters, and thickness is 1～2 millimeter.Be coated with platinum slurry (the expensive platinum that grinds in Kunming is already produced) then in the both sides of electrolyte ceramics sheet, area is 78.5mm
2, the electrolyte ceramics sheet that will be coated with the platinum slurry again forms porous platinum to electrode after heating under 800 ℃ of conditions was removed organic solvent in 1 hour.
Present embodiment adopts the complex impedance spectra measuring technology: utilize porous platinum to electrode (preparing previously), in two electrode systems, 300～800 ℃ air atmosphere, the nanometer electrolyte of present embodiment is tested, the analytical test result gets resistance value, size according to porous electrode is transformed into conductivity value with resistance value again, shown in " ■-" curve among Fig. 3.The result shows Ce
0.78Nd
0.2Co
0.02O
1.89The electrolytical conductivity of nanometer is up to 0.11Scm in the time of 800 ℃
-1, in the time of 700 ℃, conductivity is 0.047Scm
-1In the time of 600 ℃, conductivity is 0.015Scm
-1In the time of 500 ℃, conductivity is 0.0038Scm
-1As seen, the nanometer electrolyte of present embodiment has good conductivity 0.0038～0.047Scm at middle warm area (500～700 ℃)
-1
Embodiment 13: present embodiment is contrast experiment 1, pure Ce
0.8Nd
0.2O
1.9The nanometer electrolyte is rare earth element ion Nd
3+The cerium oxide base oxide ion conduction electrolyte nano powder of singly mixing.
According to the pure Ce of the method described in the embodiment 12 with present embodiment
0.8Nd
0.2O
1.9Nanometer electrolyte sintering is prepared into the electrolyte ceramics sheet, prepares porous platinum again to electrode.And, obtain the conductivity value of the nanometer electrolyte of present embodiment according to embodiment 12 described complex impedance spectra measuring technologies, shown in " ●-" curve among Fig. 3.The result shows Ce
0.8Nd
0.2O
1.9Electrolytical conductivity is the highest 0.017Scm that just reaches in the time of 800 ℃
-1, in the time of 700 ℃, conductivity is 0.007Scm
-1In the time of 600 ℃, conductivity is 0.002Scm
-1In the time of 500 ℃, conductivity is 4.3 * 10
-4Scm
-1
As seen from Figure 3, under 800 ℃, the Ce of embodiment 12
0.78Nd
0.2Co
0.02O
1.89The conductivity of nanometer electrolyte is embodiment 13 pure Ce
0.8Nd
0.2O
1.96.47 times of nanometer electrolyte; Under 700 ℃, it is 6.71 times; Under 600 ℃, it is 7.5 times; Under 500 ℃, 8.84 times.
Embodiment 14: present embodiment is the embodiment 12 described Ce that are used for intermediate temperature solid oxide fuel cell
0.78Nd
0.2Co
0.02O
1.89The preparation method of nanometer electrolyte, it is realized by following steps: one, take by weighing 3.0000 gram CeO
2, 1.9586 gram Nd (NO
3)
36H
2O and 0.1300 gram Co (NO
3)
26H
2O (is and takes by weighing 78% CeO by metal ion molar percentage
2, 20% neodymium nitrate and 2% cobalt nitrate), then with CeO
2, neodymium nitrate and cobalt nitrate ground and mixed get mixed material; Two, in the mixed material that step 1 obtains, add 20 gram alkali metal inorganic base mixtures, stir mixed material, then mixed material is incubated 72h under 240 ℃ of conditions, naturally cool to room temperature again, white powder; Three, the washing of the white powder that step 2 obtained and filter wet powder, then wet powder is incubated 12h under 60 ℃ of conditions, must be used for the nanometer electrolyte Ce of intermediate temperature solid oxide fuel cell
0.78Nd
0.2Co
0.02O
1.89, finish the preparation method of the nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell.
The CeO that takes by weighing in the present embodiment step 1
2And Nd (NO
3)
36H
2The quality purity of O all reaches 99.99%, Co (NO
3)
26H
2The quality purity of O reaches 99.0%; And in the step 1 with CeO
2, neodymium nitrate and cobalt nitrate be placed on ground and mixed 10min in the agate mortar.
The alkali metal inorganic base mixture that adds in the present embodiment step 2 and the mass ratio of mixed material are 3.93: 1, alkali metal inorganic base mixture is the mixture of NaOH and KOH, NaOH 10.3g wherein, KOH 9.7g, the mass ratio of promptly controlling NaOH and KOH is 1.06: 1.
Present embodiment prepares the embodiment 12 described Ce that are used for intermediate temperature solid oxide fuel cell
0.78Nd
0.2Co
0.02O
1.89The nanometer electrolyte has good conductivity 0.0038～0.047Scm at middle warm area (500～700 ℃)
-1
Embodiment 15: present embodiment is the nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell, and it is the cerium oxide base oxide ion conduction electrolyte nano powder of rare earth element neodymium ion and cobalt ions codope, and chemical formula is Ce
0.75Nd
0.2Co
0.05O
1.88
The X-ray diffraction spectrogram of the nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell of present embodiment is same as in figure 1, is single fluorite structure compound, and diffraction peak intensity is bigger, has higher degree of crystallinity, and does not have other thing and generate mutually.The electrolyte of present embodiment is a wheat head shape nano particle, and length is about 500 nanometers, and a plurality of wheat head particle accumulations are assembled into the coralliform particle.
According to the Ce of the method described in the embodiment 12 with present embodiment
0.75Nd
0.2Co
0.05O
1.88Nanometer electrolyte sintering is prepared into the electrolyte ceramics sheet, prepares porous platinum again to electrode.And, obtain the Ce of present embodiment according to embodiment 12 described complex impedance spectra measuring technologies
0.75Nd
0.2Co
0.05O
1.88The conductivity value of nanometer electrolyte is shown in " ●-" curve among Fig. 4.The result shows Ce
0.75Nd
0.2Co
0.05O
1.88Electrolytical conductivity is the highest 0.084Scm that just reaches in the time of 800 ℃
-1, in the time of 700 ℃, conductivity is 0.033Scm
-1In the time of 600 ℃, conductivity is 0.014Scm
-1In the time of 500 ℃, conductivity is 0.0042Scm
-1。Has good conductivity 0.0042～0.033Scm at middle warm area (500～700 ℃)
-1
Under 800 ℃, the Ce of present embodiment
0.78Nd
0.2Co
0.02O
1.89The conductivity of nanometer electrolyte is embodiment 13 pure Ce
0.8Nd
0.2O
1.94.94 times of nanometer electrolyte; Under 700 ℃, it is 4.71 times; Under 600 ℃, it is 7.0 times; Under 500 ℃, 9.77 times.
The Ce of present embodiment
0.75Nd
0.2Co
0.05O
1.88The preparation method of nanometer electrolyte compares with embodiment 14, takes by weighing in step 1 the quality difference of raw material, and other step and parameter are identical with embodiment 14.The Ce of present embodiment
0.75Nd
0.2Co
0.05O
1.88Take by weighing 3.0000 gram CeO in the preparation method's of nanometer electrolyte the step 1
2, 2.0368 gram Nd (NO
3)
36H
2O and 0.3381 gram Co (NO
3)
26H
2O (is and takes by weighing 75% CeO by metal ion molar percentage
2, 20% neodymium nitrate and 5% cobalt nitrate).The alkali metal inorganic base mixture that wherein adds in the step 2 and the mass ratio of mixed material are 3.72: 1.
Embodiment 16: present embodiment is the nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell, and it is the cerium oxide base oxide ion conduction electrolyte nano powder of rare earth element neodymium ion and cobalt ions codope, and chemical formula is Ce
0.79Nd
0.2Co
0.01O
1.9
The X-ray diffraction spectrogram of the nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell of present embodiment is same as in figure 1, is single fluorite structure compound, and diffraction peak intensity is bigger, has higher degree of crystallinity, and does not have other thing and generate mutually.The electrolyte of present embodiment is a wheat head shape nano particle, and length is about 500 nanometers, and a plurality of wheat head particle accumulations are assembled into the coralliform particle.
According to the Ce of the method described in the embodiment 12 with present embodiment
0.79Nd
0.2Co
0.01O
1.9Nanometer electrolyte sintering is prepared into the electrolyte ceramics sheet, prepares porous platinum again to electrode.And, obtain the Ce of present embodiment according to embodiment 12 described complex impedance spectra measuring technologies
0.79Nd
0.2Co
0.01O
1.9The conductivity values of nanometer electrolyte is shown in " ■-" curve among Fig. 4.The result shows Ce
0.79Nd
0.2Co
0.01O
1.9Electrolytical conductivity is the highest 0.073Scm that just reaches in the time of 800 ℃
-1, in the time of 700 ℃, conductivity is 0.034Scm
-1In the time of 600 ℃, conductivity is 0.0135Scm
-1In the time of 500 ℃, conductivity is 0.0035Scm
-1。Has good conductivity 0.0035～0.034Scm at middle warm area (500～700 ℃)
-1
Under 800 ℃, the Ce of present embodiment
0.78Nd
0.2Co
0.02O
1.89The conductivity of nanometer electrolyte is embodiment 13 pure Ce
0.8Nd
0.2O
1.94.29 times of nanometer electrolyte; Under 700 ℃, it is 4.86 times; Under 600 ℃, it is 6.75 times; Under 500 ℃, 8.14 times.
The Ce of present embodiment
0.79Nd
0.2Co
0.01O
1.9The preparation method of nanometer electrolyte compares with embodiment 14, and the alkali metal inorganic base mixture quality that adds in the quality that takes by weighing raw material in step 1 and the step 2 was different, other step and parameter were identical with embodiment 14.The Ce of present embodiment
0.79Nd
0.2Co
0.01O
1.9Take by weighing 3.0000 gram CeO in the preparation method's of nanometer electrolyte the step 1
2, 1.9336 gram Nd (NO
3)
36H
2O and 0.0642 gram Co (NO
3)
26H
2O (is and takes by weighing 79% CeO by metal ion molar percentage
2, 20% neodymium nitrate and 1% cobalt nitrate), add 19.99 gram alkali metal inorganic base mixtures in the step 2.The alkali metal inorganic base mixture that wherein adds in the step 2 and the mass ratio of mixed material are 4: 1.
Embodiment 17: present embodiment is the nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell, and it is the cerium oxide base oxide ion conduction electrolyte nano powder of rare earth element samarium ion and cobalt ions codope, and chemical formula is Ce
0.78Sm
0.2Co
0.02O
1.89
The X-ray diffraction spectrogram of the nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell of present embodiment is same as in figure 1, is single fluorite structure compound, and diffraction peak intensity is bigger, has higher degree of crystallinity, and does not have other thing and generate mutually.The electrolyte of present embodiment is a wheat head shape nano particle, and length is about 500 nanometers, and a plurality of wheat head particle accumulations are assembled into the coralliform particle.
According to the Ce of the method described in the embodiment 12 with present embodiment
0.78Sm
0.2Co
0.02O
1.89Nanometer electrolyte sintering is prepared into the electrolyte ceramics sheet, prepares porous platinum again to electrode.And, obtain the Ce of present embodiment according to embodiment 12 described complex impedance spectra measuring technologies
0.78Sm
0.2Co
0.02O
1.89The conductivity value of nanometer electrolyte is shown in " ●-" curve among Fig. 5.The result shows Ce
0.78Sm
0.2Co
0.02O
1.89Electrolytical conductivity is the highest 0.062Scm that just reaches in the time of 800 ℃
-1, in the time of 700 ℃, conductivity is 0.029Scm
-1In the time of 600 ℃, conductivity is 0.012Scm
-1In the time of 500 ℃, conductivity is 0.0034Scm
-1Has good conductivity 0.0034～0.029Scm at middle warm area (500～700 ℃)
-1
The Ce that is used for intermediate temperature solid oxide fuel cell of present embodiment
0.78Sm
0.2Co
0.02O
1.89The preparation method of nanometer electrolyte is: one, take by weighing 3.0000 gram CeO
2, 1.9861 gram Sm (NO
3)
36H
2O and 0.1300 gram Co (NO
3)
26H
2O (is and takes by weighing 78% CeO by metal ion molar percentage
2, 20% samaric nitrate and 2% cobalt nitrate?), then with CeO
2, samaric nitrate and cobalt nitrate ground and mixed get mixed material; Two, in the mixed material that step 1 obtains, add 20 gram alkali metal inorganic base mixtures, stir mixed material, then mixed material is incubated 72h under 240 ℃ of conditions, naturally cool to room temperature again, white powder; Three, the washing of the white powder that step 2 obtained and filter wet powder, then wet powder is incubated 12h under 60 ℃ of conditions, must be used for the nanometer electrolyte Ce of intermediate temperature solid oxide fuel cell
0.78Sm
0.2Co
0.02O
1.89, finish the preparation method of the nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell.Wherein, the CeO that takes by weighing in the step 1
2And Sm (NO
3)
36H
2The quality purity of O all reaches 99.99%, Co (NO
3)
26H
2The quality purity of O reaches 99.0%; And in the step 1 with CeO
2, samaric nitrate and cobalt nitrate be placed on ground and mixed 10min in the agate mortar.The alkali metal inorganic base mixture that adds in the step 2 and the mass ratio of mixed material are 3.91: 1, and alkali metal inorganic base mixture is the mixture of NaOH and KOH, and the mass ratio of wherein controlling NaOH and KOH is 1.06: 1.
Embodiment 18: present embodiment is contrast experiment 2, pure Ce
0.8Sm
0.2O
1.9The nanometer electrolyte is rare earth element ion Sm
3+The cerium oxide base oxide ion conduction electrolyte nano powder of singly mixing.
According to the pure Ce of the method described in the embodiment 12 with present embodiment
0.8Sm
0.2O
1.9Nanometer electrolyte sintering is prepared into the electrolyte ceramics sheet, prepares porous platinum again to electrode.And, obtain the conductivity values of the nanometer electrolyte of present embodiment, shown in " ■-" curve among Fig. 5 according to embodiment 12 described complex impedance spectra measuring technologies.The result shows Ce
0.8Sm
0.2O
1.9Electrolytical conductivity is the highest 0.019Scm that just reaches in the time of 800 ℃
-1, in the time of 700 ℃, conductivity is 0.0061Scm
-1In the time of 600 ℃, conductivity is 0.0010Scm
-1In the time of 500 ℃, conductivity is 1.4 * 10
-4Scm
-1
As seen from Figure 5, under 800 ℃, the Ce of embodiment 17
0.78Sm
0.2Co
0.02O
1.89The conductivity of nanometer electrolyte is the pure Ce of embodiment 18
0.8Sm
0.2O
1.93.26 times of the conductivity of nanometer electrolyte; Under 700 ℃, it is 4.75 times; Under 600 ℃, it is 12 times; Under 500 ℃, it is 24.29 times.
Embodiment 19: present embodiment is the nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell, and it is the cerium oxide base oxide ion conduction electrolyte nano powder of rare earth element gadolinium ion and cobalt ions codope, and chemical formula is Ce
0.78Gd
0.2Co
0.02O
1.89Is it right for the following footnote numerical value of oxygen?
The X-ray diffraction spectrogram of the nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell of present embodiment is same as in figure 1, is single fluorite structure compound, and diffraction peak intensity is bigger, has higher degree of crystallinity, and does not have other thing and generate mutually.The electrolyte of present embodiment is a wheat head shape nano particle, and length is about 500 nanometers, and a plurality of wheat head particle accumulations are assembled into the coralliform particle.
According to the Ce of the method described in the embodiment 12 with present embodiment
0.78Gd
0.2Co
0.02O
1.89Nanometer electrolyte sintering is prepared into the electrolyte ceramics sheet, prepares porous platinum again to electrode.And, obtain the Ce of present embodiment according to embodiment 12 described complex impedance spectra measuring technologies
0.78Gd
0.2Co
0.02O
1.89The conductivity values of nanometer electrolyte is shown in " ●-" curve among Fig. 6.The result shows Ce
0.78Gd
0.2Co
0.02O
1.89Electrolytical conductivity is the highest 0.043Scm that just reaches in the time of 800 ℃
-1, in the time of 700 ℃, conductivity is 0.022Scm
-1In the time of 600 ℃, conductivity is 0.0089Scm
-1In the time of 500 ℃, conductivity is 0.0032Scm
-1。Has good conductivity 0.0032～0.022Scm at middle warm area (500～700 ℃)
-1
The Ce that is used for intermediate temperature solid oxide fuel cell of present embodiment
0.78Gd
0.2Co
0.02O
1.89The preparation method of nanometer electrolyte is: one, take by weighing 3.0000 gram CeO
2, 2.0167 gram Gd (NO
3)
36H
2O and 0.1300 gram Co (NO
3)
26H
2O (is and takes by weighing 78% CeO by metal ion molar percentage
2, 20% gadolinium nitrate and 2% cobalt nitrate), then with CeO
2, gadolinium nitrate and cobalt nitrate ground and mixed get mixed material; Two, in the mixed material that step 1 obtains, add 20 gram alkali metal inorganic base mixtures, stir mixed material, then mixed material is incubated 72h under 240 ℃ of conditions, naturally cool to room temperature again, white powder; Three, the washing of the white powder that step 2 obtained and filter wet powder, then wet powder is incubated 12h under 60 ℃ of conditions, must be used for the nanometer electrolyte Ce of intermediate temperature solid oxide fuel cell
0.78Gd
0.2Co
0.02O
1.89, finish the preparation method of the nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell.Wherein, the CeO that takes by weighing in the step 1
2And Gd (NO
3)
36H
2The quality purity of O all reaches 99.99%, Co (NO
3)
26H
2The quality purity of O reaches 99.0%; And in the step 1 with CeO
2, gadolinium nitrate and cobalt nitrate be placed on ground and mixed 10min in the agate mortar.The alkali metal inorganic base mixture that adds in the step 2 and the mass ratio of mixed material are 3.89: 1, and alkali metal inorganic base mixture is the mixture of NaOH and KOH, and the mass ratio of wherein controlling NaOH and KOH is 1.06: 1.
Embodiment 20: present embodiment is contrast experiment 3, pure Ce
0.8Gd
0.2O
1.9The nanometer electrolyte is rare earth element ion Gd
3+The cerium oxide base oxide ion conduction electrolyte nano powder of singly mixing.
According to the pure Ce of the method described in the embodiment 12 with present embodiment
0.8Gd
0.2O
1.9Nanometer electrolyte sintering is prepared into the electrolyte ceramics sheet, prepares porous platinum again to electrode.And, obtain the conductivity values of the nanometer electrolyte of present embodiment, shown in " ■-" curve among Fig. 6 according to embodiment 12 described complex impedance spectra measuring technologies.The result shows Ce
0.8Gd
0.2O
1.9Electrolytical conductivity is the highest 0.017Scm that just reaches in the time of 800 ℃
-1, in the time of 700 ℃, conductivity is 0.0071Scm
-1In the time of 600 ℃, conductivity is 0.0028Scm
-1In the time of 500 ℃, conductivity is 5.5 * 10
-4Scm
-1
As seen from Figure 6, under 800 ℃, the Ce of embodiment 19
0.78Gd
0.2Co
0.02O
1.89The conductivity of nanometer electrolyte is the pure Ce of embodiment 18
0.8Gd
0.2O
1.92.52 times of the conductivity of nanometer electrolyte; Under 700 ℃, it is 3.10 times; Under 600 ℃, it is 3.18 times; Under 500 ℃, it is 5.82 times.
Abscissa among Fig. 3 to Fig. 6 is 1000/T, and wherein T is a kelvin degree, and unit is K
-1, for the ease of understanding, with the mark of its corresponding Celsius temperature correspondence in upper side frame.
Claims (10)
1. the nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell, the nanometer electrolyte that it is characterized in that being used for intermediate temperature solid oxide fuel cell is the cerium oxide base oxide ion conduction electrolyte nano powder of rare earth element ion and cobalt ions codope, and chemical formula is Ce
(1-x-y)Re
xCo
yO
2-δ, x: y=4～20: 1 wherein, x+y=0.21～0.25, δ=0.10～0.12, Re is a rare earth element.
2. the nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell according to claim 1 is characterized in that described rare earth element ion is Nd
3+, Sm
3+, Gd
3+, Eu
3+Perhaps Pr
3+。
3. the nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell according to claim 1, it is characterized in that being used for the nanometer electrolyte of intermediate temperature solid oxide fuel cell, it is the cerium oxide base oxide ion conduction electrolyte nano powder of neodymium rare earth element ion and cobalt ions codope, and chemical formula is Ce
(1-x-y)Nd
xCo
yO
2-δ, x: y=4～10: 1 wherein, x+y=0.22～0.25, δ=0.10～0.12.
4. the preparation method who is used for the nanometer electrolyte of intermediate temperature solid oxide fuel cell as claimed in claim 1, the preparation method who it is characterized in that being used for the nanometer electrolyte of intermediate temperature solid oxide fuel cell realizes by following steps: one, take by weighing 75%～79% CeO by mole percentage
2And 21%～25% rare earth element nitrate and cobalt nitrate mixture, control wherein that the mol ratio of neodymium nitrate and cobalt nitrate is 4～20: 1 in neodymium nitrate and the cobalt nitrate mixture, then with CeO
2, rare earth element nitrate and cobalt nitrate ground and mixed get mixed material; Two, in the mixed material that step 1 obtains, add alkali metal inorganic base mixture, stir mixed material, then mixed material is incubated 48～96h under 200～280 ℃ of conditions, naturally cool to room temperature again, get white powder, wherein the mass ratio of alkali metal inorganic base mixture of Jia Ruing and mixed material is 4: 1; Three, the washing of the white powder that step 2 obtained and filter wet powder, then wet powder is incubated 8～15h under 50～80 ℃ of conditions, must be used for the nanometer electrolyte Ce of intermediate temperature solid oxide fuel cell
(1-x-y)Nd
xCo
yO
2-δ, x: y=4～20: 1 wherein, x+y=0.21～0.25, the preparation method of the nanometer electrolyte that is used for intermediate temperature solid oxide fuel cell is finished in δ=0.10～0.12.
5. the preparation method who is used for the nanometer electrolyte of intermediate temperature solid oxide fuel cell according to claim 4 is characterized in that alkali metal inorganic base mixture in the step 2 is two kinds a mixture among LiOH, NaOH, KOH, RbOH and the CsOH.
6. the preparation method who is used for the nanometer electrolyte of intermediate temperature solid oxide fuel cell according to claim 4, it is characterized in that alkali metal inorganic base mixture is the mixture of NaOH and KOH in the step 2, the mass ratio of NaOH and KOH is 0.9～1.1: 1.
7. according to claim 4, the 5 or 6 described preparation methods that are used for the nanometer electrolyte of intermediate temperature solid oxide fuel cell, it is characterized in that in the step 2 mixed material being incubated 60～84h under 220～260 ℃ of conditions.
8. according to claim 4, the 5 or 6 described preparation methods that are used for the nanometer electrolyte of intermediate temperature solid oxide fuel cell, it is characterized in that in the step 2 mixed material being incubated 72h under 240 ℃ of conditions.
9. according to claim 4, the 5 or 6 described preparation methods that are used for the nanometer electrolyte of intermediate temperature solid oxide fuel cell, it is characterized in that in the step 3 wet powder being incubated 12h under 60 ℃ of conditions.
10. according to claim 4, the 5 or 6 described preparation methods that are used for the nanometer electrolyte of intermediate temperature solid oxide fuel cell, it is characterized in that step 1 middle rare earth element nitrate is neodymium nitrate, samaric nitrate, gadolinium nitrate, europium nitrate or praseodymium nitrate.
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Cited By (2)
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|---|---|---|---|---|
| CN110444796A (en) * | 2019-09-10 | 2019-11-12 | 东北大学 | A method of improving solid-oxide fuel battery electrolyte conductivity |
| CN112779555A (en) * | 2020-12-25 | 2021-05-11 | 山东科技大学 | High-performance solid oxide electrolytic cell and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5001021A (en) * | 1989-12-14 | 1991-03-19 | International Fuel Cells Corporation | Ceria electrolyte composition |
| US20010007381A1 (en) * | 1998-11-13 | 2001-07-12 | Christoph Kleinlogel | Process for the production of sintered ceramic oxide |
-
2011
- 2011-04-14 CN CN2011100939482A patent/CN102201589B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5001021A (en) * | 1989-12-14 | 1991-03-19 | International Fuel Cells Corporation | Ceria electrolyte composition |
| US20010007381A1 (en) * | 1998-11-13 | 2001-07-12 | Christoph Kleinlogel | Process for the production of sintered ceramic oxide |
Non-Patent Citations (1)
| Title |
|---|
| 孙明涛等: "CeO2基固体电解质材料研究进展", 《稀土》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110444796A (en) * | 2019-09-10 | 2019-11-12 | 东北大学 | A method of improving solid-oxide fuel battery electrolyte conductivity |
| CN110444796B (en) * | 2019-09-10 | 2022-05-17 | 东北大学 | Method for improving electrolyte conductivity of solid oxide fuel cell |
| CN112779555A (en) * | 2020-12-25 | 2021-05-11 | 山东科技大学 | High-performance solid oxide electrolytic cell and preparation method thereof |
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