CN103151533A - Solid oxide fuel cell composite cathode Ln2CuO4-Ce0.9Gd0.1O1.95 and preparation method thereof - Google Patents
Solid oxide fuel cell composite cathode Ln2CuO4-Ce0.9Gd0.1O1.95 and preparation method thereof Download PDFInfo
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The invention relates to a solid oxide fuel cell composite cathode Ln2CuO4-Ce0.9Gd0.1O1.95 and a preparation method thereof. The invention relates to a cell composite cathode material and a preparation method thereof, aiming at solving the problem that the catalytic activity and electro-chemical property of the cathode material are pool. The solid oxide fuel cell composite cathode Ln2CuO4-Ce0.9Gd0.1O1.95 is made of Ln2CuO4 and solid electrolyte Ce0.9Gd0.1O1.95; the method comprises the steps of: I. weighing; II. preparing mixed stock; III. preparing a prefabricated body; and IV. preparing the solid oxide fuel cell composite cathode Ln2CuO4-Ce0.9Gd0.1O1.95. According to the solid oxide fuel cell composite cathode Ln2CuO4-Ce0.9Gd0.1O1.95 and the preparation method thereof, the reaction active site of the cathode is extended into the overall cathode material, the active region of the oxygen reduction reaction can be enlarged, and the electrochemical property of the cathode can be improved. The preparation method is used for preparing solid oxide fuel cell composite cathode.
Description
Technical field
The present invention relates to battery composite cathode material and preparation method thereof.
Background technology
Intermediate temperature solid oxide fuel cell is a kind of novel energy conversion equipment, and the advantage of the aspects such as, environmental friendliness efficient because of it just day by day is subject to various countries and payes attention to widely.Yet the reduction of battery operational temperatures can cause the rapid decline of electrode activity, and the performance impact of cathode material the performance quality of whole battery system.Therefore, be a key issue for the electrode performance that improves existing cathode material.Constructing good composite cathode material can increase the three phase boundary reactivity zone of electrode reaction, improves the mixed conductivity of material, and then improves the chemical property of cathode material.
Summary of the invention
The present invention will solve the catalytic activity of cathode material and the poor problem of chemical property, and compound cathode of solid oxide fuel battery Ln is provided
2CuO
4-Ce
0.9Gd
0.1O
1.95And preparation method thereof.
Compound cathode of solid oxide fuel battery Ln
2CuO
4-Ce
0.9Gd
0.1O
1.95By weight percentage by 50%～90% Ln
2CuO
4With 10%～50% solid electrolyte Ce
0.9Gd
0.1O
1.95Make, wherein Ln is Pr, Nd, Sm or Eu element.
Preparation power compound cathode of solid oxide fuel battery Ln
2CuO
4-Ce
0.9Gd
0.1O
1.95Method, complete according to the following steps:
One, take by weight percentage 50%～90% Ln
2CuO
4With 10%～50% solid electrolyte Ce
0.9Gd
0.1O
1.95
Two, the Ln that step 1 is taken
2CuO
4With solid electrolyte Ce
0.9Gd
0.1O
1.95Mix, then add terpinol, mix, obtain mixed slurry;
Three, the mixed slurry that step 2 is obtained is coated in Ce
0.9Gd
0.1O
1.95Then the surface of electrolyte ceramics sheet is placed in baking oven, is to keep 12h～15h under 200 ℃ of conditions in temperature, obtains the precast body on the solid electrolyte sheet surface;
The precast body on the electrolyte ceramics sheet surface that four, again step 3 is obtained is placed in Muffle furnace, be sintering 6h～10h under the air atmosphere condition of 400 ℃～600 ℃ in temperature, then be sintering 4h in the air atmosphere environment of 900 ℃～1100 ℃ in temperature, obtain compound cathode of solid oxide fuel battery Ln on electrolyte ceramics sheet surface
2CuO
4-Ce
0.9Gd
0.1O
1.95
The invention has the beneficial effects as follows: it is inner that composite cathode of the present invention expands to whole cathode material to the avtive spot of cathode reaction, increased the active region of oxygen reduction reaction, thereby improved the chemical property of negative electrode.The advantage of composite cathode is to utilize to mix CeO in the mixed conductor negative electrode
2Base electrolyte material, the thermal matching of raising electrode and solid electrolyte increases the mixed conductivity of whole electrode material, thereby improves catalytic activity and the chemical property of cathode material.Because doping electrolyte powder powder material is identical with electrolyte structure, this can improve electrode and electrolytical combination degree, improves the stability of electrode structure when high temperature.Negative electrode of the present invention is in the temperature range of 500～700 ℃, and electro catalytic activity is high, and polarization resistance is low, thereby obtains a kind of general high activity and the compound cathode of solid oxide fuel battery of high long-time stability.The inventive method is simple, convenient operation.
The present invention is for the preparation of compound cathode of solid oxide fuel battery Ln
2CuO
4-Ce
0.9Gd
0.1O
1.95
Description of drawings
Fig. 1 is the cathode material Pr in embodiment one
2CuO
4With solid electrolyte Ce
0.9Gd
0.1O
1.95Fully mix rear at the X-ray diffraction spectrogram of 1000 ℃ of calcination after 24 hours by the 1:1 mass ratio;
Fig. 2 is the compound cathode of solid oxide fuel battery Pr in embodiment one
2CuO
4-Ce
0.9Gd
0.1O
1.95Through 900 ℃ of sintering after 4 hours with electrolyte Ce
0.9Gd
0.1O
1.95The scanning electron microscope (SEM) photograph of cross section;
Fig. 3 is the compound cathode of solid oxide fuel battery Pr of embodiment one preparation
2CuO
4-Ce
0.9Gd
0.1O
1.95And negative electrode Pr
2CuO
4AC impedance spectrogram in 700 ℃ of air, wherein the compound cathode of solid oxide fuel battery Pr of " zero " expression embodiment one preparation
2CuO
4-Ce
0.9Gd
0.1O
1.95, " " expression negative electrode Pr
2CuO
4
Fig. 4 is the compound cathode of solid oxide fuel battery Pr of embodiment one preparation
2CuO
4-Ce
0.9Gd
0.1O
1.95And negative electrode Pr
2CuO
4, cathodic polarization curve figure in 700 ℃ of lower air, wherein "●" represents compound cathode of solid oxide fuel battery Pr
2CuO
4-Ce
0.9Gd
0.1O
1.95Polarization curve, " ■ " expression negative electrode Pr
2CuO
4Cathodic polarization curve.
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 compound cathode of solid oxide fuel battery Ln
2CuO
4-Ce
0.9Gd
0.1O
1.95By weight percentage by 50%～90% Ln
2CuO
4With 10%～50% solid electrolyte Ce
0.9Gd
0.1O
1.95Make, wherein Ln is Pr, Nd, Sm or Eu element.
Embodiment two: what present embodiment was different from embodiment one is: described Ln
2CuO
4The preparation method carry out according to the following steps: press Ln
2CuO
4Stoichiometric proportion, with purity greater than 99.99% Ln
xO
yMix with CuO, wherein, x=2 or 6, y=3 or 11; Then be sintering 18h～24h under 1000 ℃～1100 ℃ conditions at grinding in ball grinder 12h～24h, then in temperature, obtain Ln
2CuO
4Other is identical with embodiment one.
Embodiment three: present embodiment and embodiment together be: described Ce
0.9Gd
0.1O
1.95The preparation method by carrying out with following step:
A, being under 50 ℃～80 ℃ conditions in temperature, is the Ce (NO of 4.4g with quality
3)
3With quality be the Gd (NO of 2.6g
3)
3Be dissolved in the 250mL deionized water, be then that 80 ℃, speed are to add thermal agitation 5h under the stirring condition of 100 rev/mins in temperature, then add the 12.0g glycine, obtain mixed solution;
B, mixed solution being stirred to homogeneous transparent, is then that under 120 ℃ of conditions, heating evaporation to the thickness jelly, is then to continue heating under 200 ℃ of conditions in temperature, until the jelly spontaneous combustion obtains buff powder in temperature;
C, the buff powder that step B is obtained are sintering 12h under 900 ℃ of air atmospheres in temperature, obtain Ce
0.9Gd
0.1O
1.95Other is identical with embodiment one.
Embodiment four: what present embodiment was different from embodiment one is: compound cathode of solid oxide fuel battery Ln
2CuO
4-Ce
0.9Gd
0.1O
1.95By weight percentage by 60%～80% Ln
2CuO
4With 20%～40% solid electrolyte Ce
0.9Gd
0.1O
1.95Make.Other is identical with embodiment one.
Embodiment five: what present embodiment was different from one of embodiment one to four is: compound cathode of solid oxide fuel battery Ln
2CuO
4-Ce
0.9Gd
0.1O
1.95By weight percentage by 70% Ln
2CuO
4With 30% solid electrolyte Ce
0.9Gd
0.1O
1.95Make.Other is identical with one of embodiment one to four.
Embodiment six: the described compound cathode of solid oxide fuel battery Ln of preparation execution mode one
2CuO
4-Ce
0.9Gd
0.1O
1.95Method, complete according to the following steps:
One, take by weight percentage 50%～90% Ln
2CuO
4With 10%～50% solid electrolyte Ce
0.9Gd
0.1O
1.95
Two, the Ln that step 1 is taken
2CuO
4With solid electrolyte Ce
0.9Gd
0.1O
1.95Mix, then add terpinol, mix, obtain mixed slurry;
Three, the mixed slurry that step 2 is obtained is coated in Ce
0.9Gd
0.1O
1.95Then the surface of electrolyte ceramics sheet is placed in baking oven, is to keep 12h～15h under 200 ℃ of conditions in temperature, obtains the precast body on the solid electrolyte sheet surface;
The precast body on the electrolyte ceramics sheet surface that four, again step 3 is obtained is placed in Muffle furnace, be sintering 6h～10h under the air atmosphere condition of 400 ℃～600 ℃ in temperature, then be sintering 4h in the air atmosphere environment of 900 ℃～1100 ℃ in temperature, obtain compound cathode of solid oxide fuel battery Ln on electrolyte ceramics sheet surface
2CuO
4-Ce
0.9Gd
0.1O
1.95
It is inner that the present embodiment composite cathode expands to whole cathode material to the avtive spot of cathode reaction, increased the active region of oxygen reduction reaction, thereby improved the chemical property of negative electrode.The advantage of composite cathode is to utilize to mix CeO in the mixed conductor negative electrode
2Base electrolyte material, the thermal matching of raising electrode and solid electrolyte increases the mixed conductivity of whole electrode material, thereby improves catalytic activity and the chemical property of cathode material.Because doping electrolyte powder powder material is identical with electrolyte structure, this can improve electrode and electrolytical combination degree, improves the stability of electrode structure when high temperature.The described negative electrode of present embodiment is in the temperature range of 500 ℃～700 ℃, and electro catalytic activity is high, and polarization resistance is low, thereby obtains a kind of general high activity and the compound cathode of solid oxide fuel battery of high long-time stability.The present embodiment method is simple, convenient operation.
Embodiment seven: what present embodiment was different from embodiment six is: take 60%～80% Ln in step 1
2CuO
4With 20%～40% solid electrolyte Ce
0.9Gd
0.1O
1.95Other is identical with embodiment six.
Embodiment eight: what present embodiment was different from embodiment six or seven is: take 70% Ln in step 1
2CuO
4With 30% solid electrolyte Ce
0.9Gd
0.1O
1.95Other is identical with embodiment six or seven.
Embodiment nine: what present embodiment was different from one of embodiment six to eight is: the described Ln of step 1
2CuO
4Middle Ln is Pr, Nd, Sm or Eu element.Other is identical with one of embodiment six to eight.
Embodiment ten: what present embodiment was different from one of embodiment six to nine is: Ln in step 2
2CuO
4With solid electrolyte Ce
0.9Gd
0.1O
1.95Gross mass and the volume ratio of terpinol be 1g:1mL.Other is identical with one of embodiment six to nine.
Adopt following examples checking beneficial effect of the present invention:
Embodiment one:
The present embodiment compound cathode of solid oxide fuel battery Pr
2CuO
4-Ce
0.9Gd
0.1O
1.95Method, complete according to the following steps:
One, take by weight percentage 60% Pr
2CuO
4With 40% solid electrolyte Ce
0.9Gd
0.1O
1.95
Two, the Pr that step 1 is taken
2CuO
4With solid electrolyte Ce
0.9Gd
0.1O
1.95Mix, then add terpinol, mix, obtain mixed slurry, wherein Pr
2CuO
4With solid electrolyte Ce
0.9Gd
0.1O
1.95Gross mass be 0.5 gram, the volume of terpinol is 0.5 milliliter;
Three, the mixed slurry that step 2 is obtained is coated in Ce
0.9Gd
0.1O
1.95Then the surface of electrolyte ceramics sheet is placed in baking oven, is to keep 12h under 200 ℃ of conditions in temperature, obtains the precast body on the solid electrolyte sheet surface;
The precast body on the electrolyte ceramics sheet surface that four, again step 3 is obtained is placed in Muffle furnace, be sintering 6h under the air atmosphere condition of 400 ℃ in temperature, then be sintering 4h in the air atmosphere environment of 900 ℃ in temperature, obtain compound cathode of solid oxide fuel battery Ln on electrolyte ceramics sheet surface
2CuO
4-Ce
0.9Gd
0.1O
1.95
The described Pr of the present embodiment
2CuO
4Adopt solid phase method to be prepared, concrete steps are as follows: with purity greater than 99.99% 5.0 gram Pr
6O
11Mix with 1.2 gram CuO raw materials, ground 24 hours in the ball mill ethanol medium; Be sintering 18 hours under 1000 ℃ of conditions in temperature again, obtain Pr
2CuO
4
The described Ce of the present embodiment
0.9Gd
0.1O
1.95The preparation of employing powders by glycine-nitrate process, concrete steps are as follows:
A, being under 80 ℃ of conditions in temperature, is the Ce (NO of 4.4g with quality
3)
3With quality be the Gd (NO of 2.6g
3)
3Be dissolved in the 250mL deionized water, be then that 80 ℃, speed are to add thermal agitation 5h under the stirring condition of 100 rev/mins in temperature, then add the 12.0g glycine, obtain mixed solution;
B, mixed solution being stirred to homogeneous transparent, is then that under 120 ℃ of conditions, heating evaporation to the thickness jelly, is then to continue heating under 200 ℃ of conditions in temperature, until the jelly spontaneous combustion obtains buff powder in temperature;
C, the buff powder that step B is obtained are sintering 12h under 900 ℃ of air atmospheres in temperature, obtain Ce
0.9Gd
0.1O
1.95
Adopt dry pressing to prepare Ce
0.9Gd
0.1O
1.95The electrolyte ceramics sheet, concrete grammar is as follows: take 1 gram Ce
0.9Gd
0.1O
1.95Powder is poured diameter into and is in the mould of 20 millimeters; Be pressed into diameter and be the disk of 20 millimeters under 220MPa pressure, disk thickness is 10 millimeters; The electrolyte ceramics sheet formed fine and close electrolyte in 10 hours at 1350 ℃ of sintering.
With Pr in the present embodiment
2CuO
4Cathode material and Ce
0.9Gd
0.1O
1.95Electrolyte powder 1:1 in mass ratio mixes, and uses zirconium oxide microballoons to be abrasive media in ball mill, and ethanol is dispersant, grinds 10 hours, forms homogeneous mixture; Continuous sintering is 24 hours under 1000 ℃ of air atmospheres, again take out grind into powder, carrying out phase with X-ray diffractometer detects as shown in Figure 1, result proves that sintering is after 24 hours under 1000 ℃ of air atmospheres, chemical reaction does not occur in cathode material and electrolyte, and illustrating both has good chemical compatibility.
The compound cathode of solid oxide fuel battery Pr of the present embodiment preparation
2CuO
4-Ce
0.9Gd
0.1O
1.95The surface sweeping Electronic Speculum figure in cross section as shown in Figure 2, result shows, the compound cathode of solid oxide fuel battery Pr that makes according to above-mentioned technological process
2CuO
4-Ce
0.9Gd
0.1O
1.95Form good contact interface, in composite cathode, distribution of particles evenly and certain loose structure arranged.
Adopt the ac impedance spectroscopy measuring technology, utilize three-electrode system come in 700 ℃ of air test material cathodic polarization resistance the AC impedance spectrogram as shown in Figure 3, wherein " " is pure Pr
2CuO
4Cathode material, " zero " is the compound cathode of solid oxide fuel battery Pr of the present embodiment preparation
2CuO
4-Ce
0.9Gd
0.1O
1.95Test result shows the compound cathode of solid oxide fuel battery Pr of the present embodiment preparation
2CuO
4-Ce
0.9Gd
0.1O
1.95Polarization resistance be 0.25ohm.cm
2, this result is pure Pr
2CuO
4/ 2nd of a cathode material (is 0.5ohm.cm under same test condition
2); This illustrates the electrolytical catalytic performance that has improved electrode that mixes, and has reduced Pr
2CuO
4The polarization resistance of negative electrode has been improved the chemical property of single negative electrode.
Electrode and reference electrode are made with platinum slurry (the expensive platinum industry of grinding in Kunming is produced).The platinum slurry is coated with invests electrolytical opposite side, the difference sintering is 4 hours under 500 ℃ and 800 ℃, forms electrode and reference electrode.
In air, probe temperature is under 700 ℃ of conditions, adopts the cathodic polarization curve of chronoamperometry test as shown in Figure 4, and wherein "●" is the compound cathode of solid oxide fuel battery Pr of the present embodiment preparation
2CuO
4-Ce
0.9Gd
0.1O
1.95Polarization curve, " ■ " represents Pr
2CuO
4Cathodic polarization curve; Result shows, at 700 ℃ of probe temperatures, 40mAcm
-2Under current density, the compound cathode of solid oxide fuel battery Pr of the present embodiment preparation
2CuO
4-Ce
0.9Gd
0.1O
1.95The cathodic polarization overpotential be 75mV, and pure Pr
2CuO
4Negative electrode under the same conditions, its cathodic polarization overpotential is 122mV.The compound cathode of solid oxide fuel battery Pr of the present embodiment preparation
2CuO
4-Ce
0.9Gd
0.1O
1.95Effectively reduce the cathode overpotential of cathode material, can improve the cathodic polarization phenomenon of fuel cell.
Claims (10)
1. compound cathode of solid oxide fuel battery Ln
2CuO
4-Ce
0.9Gd
0.1O
1.95, it is characterized in that compound cathode of solid oxide fuel battery Ln
2CuO
4-Ce
0.9Gd
0.1O
1.95By weight percentage by 50%～90% Ln
2CuO
4With 10%～50% solid electrolyte Ce
0.9Gd
0.1O
1.95Make, wherein Ln is Pr, Nd, Sm or Eu element.
2. compound cathode of solid oxide fuel battery Ln according to claim 1
2CuO
4-Ce
0.9Gd
0.1O
1.95, it is characterized in that described Ln
2CuO
4The preparation method carry out according to the following steps: press Ln
2CuO
4Stoichiometric proportion, with purity greater than 99.99% Ln
xO
yMix with CuO, wherein, x=2 or 6, y=3 or 11; Then be sintering 18h～24h under 1000 ℃～1100 ℃ conditions at grinding in ball grinder 12h～24h, then in temperature, obtain Ln
2CuO
4
3. compound cathode of solid oxide fuel battery Ln according to claim 1
2CuO
4-Ce
0.9Gd
0.1O
1.95, it is characterized in that described Ce
0.9Gd
0.1O
1.95The preparation method by carrying out with following step:
A, being under 50 ℃～80 ℃ conditions in temperature, is the Ce (NO of 4.4g with quality
3)
3With quality be the Gd (NO of 2.6g
3)
3Be dissolved in the 250mL deionized water, be then that 80 ℃, speed are to add thermal agitation 5h under the stirring condition of 100 rev/mins in temperature, then add the 12.0g glycine, obtain mixed solution;
B, mixed solution being stirred to homogeneous transparent, is then that under 120 ℃ of conditions, heating evaporation to the thickness jelly, is then to continue heating under 200 ℃ of conditions in temperature, until the jelly spontaneous combustion obtains buff powder in temperature;
C, the buff powder that step B is obtained are sintering 12h under 900 ℃ of air atmospheres in temperature, obtain Ce
0.9Gd
0.1O
1.95
4. compound cathode of solid oxide fuel battery Ln according to claim 1
2CuO
4-Ce
0.9Gd
0.1O
1.95, it is characterized in that compound cathode of solid oxide fuel battery Ln
2CuO
4-Ce
0.9Gd
0.1O
1.95By weight percentage by 60%～80% Ln
2CuO
4With 20%～40% solid electrolyte Ce
0.9Gd
0.1O
1.95Make.
5. according to claim 1 or 4 described compound cathode of solid oxide fuel battery Ln
2CuO
4-Ce
0.9Gd
0.1O
1.95, it is characterized in that compound cathode of solid oxide fuel battery Ln
2CuO
4-Ce
0.9Gd
0.1O
1.95By weight percentage by 70% Ln
2CuO
4With 30% solid electrolyte Ce
0.9Gd
0.1O
1.95Make.
6. prepare compound cathode of solid oxide fuel battery Ln claimed in claim 1
2CuO
4-Ce
0.9Gd
0.1O
1.95Method, complete according to the following steps:
One, take by weight percentage 50%～90% Ln
2CuO
4With 10%～50% solid electrolyte Ce
0.9Gd
0.1O
1.95
Two, the Ln that step 1 is taken
2CuO
4With solid electrolyte Ce
0.9Gd
0.1O
1.95Mix, then add terpinol, mix, obtain mixed slurry;
Three, the mixed slurry that step 2 is obtained is coated in Ce
0.9Gd
0.1O
1.95Then the surface of electrolyte ceramics sheet is placed in baking oven, is to keep 12h～15h under 200 ℃ of conditions in temperature, obtains the precast body on the solid electrolyte sheet surface;
The precast body on the electrolyte ceramics sheet surface that four, again step 3 is obtained is placed in Muffle furnace, be sintering 6h～10h under the air atmosphere condition of 400 ℃～600 ℃ in temperature, then be sintering 4h in the air atmosphere environment of 900 ℃～1100 ℃ in temperature, obtain compound cathode of solid oxide fuel battery Ln on electrolyte ceramics sheet surface
2CuO
4-Ce
0.9Gd
0.1O
1.95
7. preparation compound cathode of solid oxide fuel battery Ln according to claim 6
2CuO
4-Ce
0.9Gd
0.1O
1.95Method, it is characterized in that taking in step 1 60%～80% Ln
2CuO
4With 20%～40% solid electrolyte Ce
0.9Gd
0.1O
1.95
8. preparation compound cathode of solid oxide fuel battery Ln according to claim 6
2CuO
4-Ce
0.9Gd
0.1O
1.95Method, it is characterized in that taking in step 1 70% Ln
2CuO
4With 30% solid electrolyte Ce
0.9Gd
0.1O
1.95
9. preparation compound cathode of solid oxide fuel battery Ln according to claim 6
2CuO
4-Ce
0.9Gd
0.1O
1.95Method, it is characterized in that the described Ln of step 1
2CuO
4Middle Ln is Pr, Nd, Sm or Eu element.
10. preparation compound cathode of solid oxide fuel battery Ln according to claim 6
2CuO
4-Ce
0.9Gd
0.1O
1.95Method, it is characterized in that Ln in step 2
2CuO
4With solid electrolyte Ce
0.9Gd
0.1O
1.95Gross mass and the volume ratio of terpinol be 1g:1mL.
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| CN103337640A (en) * | 2013-07-04 | 2013-10-02 | 黑龙江大学 | Preparation method of solid oxide fuel cell Ln2NiO4 film cathode |
| CN104916850A (en) * | 2015-04-27 | 2015-09-16 | 上海邦民新能源科技有限公司 | Solid oxide fuel cell cathode material and solid oxide fuel cell composite cathode material and preparation method thereof and cell composite cathode preparation method |
| CN106328972A (en) * | 2016-08-29 | 2017-01-11 | 董晓 | Preparation method of mid-low temperature solid oxide fuel cell cathode material |
| CN111082111A (en) * | 2019-12-31 | 2020-04-28 | 黑龙江大学 | Intermediate-temperature solid oxide fuel cell composite cathode material and preparation method and application thereof |
| CN111092233A (en) * | 2019-12-31 | 2020-05-01 | 黑龙江大学 | Intermediate-temperature solid oxide fuel cell composite cathode material and preparation method and application thereof |
| CN111841642A (en) * | 2020-08-09 | 2020-10-30 | 北方工业大学 | Preparation method of sponge copper-based loaded composite nanorod catalytic layer material |
| CN113178586A (en) * | 2021-04-29 | 2021-07-27 | 黑龙江大学 | Solid oxide fuel cell composite cathode catalyst and preparation method and application thereof |
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| CN111082111A (en) * | 2019-12-31 | 2020-04-28 | 黑龙江大学 | Intermediate-temperature solid oxide fuel cell composite cathode material and preparation method and application thereof |
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