CN105720277A - Three-dimensional porous perovskite catalyst La<x>Sr(1-x)Co<y>Fe<1-y>O<3> and preparation method thereof - Google Patents
Three-dimensional porous perovskite catalyst La<x>Sr(1-x)Co<y>Fe<1-y>O<3> and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
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Abstract
The invention discloses a three-dimensional porous perovskite catalyst La<x>Sr(1-x)Co<y>Fe<1-y>O<3> and a preparation method thereof. The catalyst is an anode catalyst for a lithium-air battery; the specific surface area is 20-30m<2>/g; a three-dimensional porous channel is formed in the catalyst; the porous channel provides a transmission channel for ions and gases; and a storage space is provided for a reaction product. The method comprises the following steps: weighing four nitrates at a certain ratio, dissolving the four nitrates into a mixed solution of methanol and ethylene glycol, and stirring and mixing the solution evenly to obtain a nitrate solution; soaking a PS microsphere template into the nitrate solution; and taking out and drying the PS microsphere template soaked with the nitrate solution, carrying out burning to burn off the template and obtaining the required catalyst. The catalyst can meet the requirements of an anode material for the lithium-air battery, has the advantages of being simple in preparation technology, convenient to operate, low in cost, free of pollution and the like, and can achieve large-scale production.
Description
Technical field
The invention belongs to cell catalyst preparation field, more particularly, to a kind of three-dimensional porous perovskite type catalyst LaxSr1-xCoyFe1-yO3And preparation method thereof.
Background technology
Lithium-air battery is that one lithium makees anode, and using the oxygen in air as the battery of cathode reactant, it has with gasoline combustion value theoretical energy density closely it is considered to be promise to be most the electrokinetic cell of following electric automobile.Nonaqueous lithium air cell has higher energy density and becomes study hotspot, it is mainly made up of parts such as porous air electrode, membrane for polymer (load organic electrolyte), lithium anodes, and its operation principle is: the lithium of discharge process Anodic becomes lithium cation (Li after discharging electronics+), Li+Through lithium-ion electrolyte material, be combined generation lithium oxide (Li at air cathode and oxygen and the electronics that flows through from external circuit2O) or generate lithium peroxide (Li2O2), and stay negative electrode, due to product Li2O and Li2O2All insulate non-conductive, along with exoelectrical reaction carrying out its can gradually blocking porous electrode and make reaction terminating, charging reaction also due to duct blocking and hindered.Therefore, the actual energy density of lithium-air battery is well below theoretical value, and there is the shortcomings such as higher overpotential, cycle performance be the best.
Utilizing high-performance bifunctional catalyst is the effective way solving the problems referred to above to accelerate the decomposition of product, wherein perofskite type oxide LaxSr1-xCoyFe1-yO3(LSCF) have and be well catalyzed activity, lithium-air battery can be applied to as cathod catalyst.Perofskite type oxide LaxSr1-xCoyFe1-yO3Traditional preparation method is solid reaction process, coprecipitation, sol-gal process etc., and the powder body utilizing traditional method to prepare mostly is graininess, and specific surface area is at 10m2/ below g, using low for above-mentioned specific surface area, present the perofskite type oxide cathod catalyst as lithium-air battery of nutty structure, be unfavorable for Li+With the transmission of oxygen, the overpotential of lithium-air battery is the most too high, and cycle performance is poor.Therefore, use the perofskite type oxide prepared of traditional method and be unsatisfactory for the lithium-air battery demand to cathode material.
Summary of the invention
For disadvantages described above or the Improvement requirement of prior art, the invention provides a kind of three-dimensional porous perovskite type catalyst LaxSr1-xCoyFe1-yO3And preparation method thereof, wherein utilize precursor solution to soak polystyrene microsphere template, then go removing template to prepare LSCF, can prepare specific surface area is 20～30m2/ g, structure are three-dimensional porous orderly catalyst powder, and this catalyst can meet the demand of lithium-air battery cathode material, is substantially reduced the overpotential of battery, improves its cycle performance, has the advantages such as preparation technology is simple and convenient to operate.
For achieving the above object, according to one aspect of the present invention, it is proposed that a kind of three-dimensional porous perovskite type catalyst LaxSr1-xCoyFe1-yO3, this three-dimensional porous perovskite type catalyst is as the cathod catalyst of lithium-air battery, and its specific surface area is 20～30m2/ g, has three-dimensional porous passage inside it, this porous channel provides transmission channel for ion and gas, and provides memory space for product
As it is further preferred that a diameter of 200nm-300nm of described porous channel.
It is another aspect of this invention to provide that provide a kind of three-dimensional porous perovskite type catalyst LaxSr1-xCoyFe1-yO3Preparation method, the method comprises the steps:
1) by La (NO3)2·6H2O、Sr(NO3)2、Co(NO3)2·6H2O、Fe(NO3)3·9H2Tetra-kinds of nitrate of O weigh according to the ratio of mol ratio x:1-x:y:1-y, are then dissolved in the mixed solution of a certain amount of methanol and ethylene glycol, stirring at normal temperature, until nitrate all dissolves and mix homogeneously, it is thus achieved that nitrate solution；
2) PS microsphere template is soaked in above-mentioned nitrate solution；
3) the PS microsphere template immersed with nitrate solution is taken out drying, at 500 DEG C～700 DEG C, then calcine 5h, to burn PS microsphere template, obtain inside and there is the perovskite type catalyst La of three-dimensional porous structurexSr1-xCoyFe1-yO3。
As it is further preferred that step 1) in, methanol is 1:1 with the volume ratio of ethanol, and the total concentration of nitrate solution is 1～2mol L-1；Step 2) in, PS microsphere template soak time in nitrate solution is 1h～2h.
As it is further preferred that step 3) in, the drying temperature of PS microsphere template is 50 DEG C～60 DEG C, and drying time is 4h～5h, and the heating rate of calcining is 1 DEG C/min.
As it is further preferred that step 2) in, described PS microsphere template is prepared in the following way:
A) a certain amount of dodecylbenzene sodium sulfonate and potassium peroxydisulfate are dissolved in the mixed liquor of water and ethanol, then above-mentioned mixed solution are placed in the there-necked flask of 250ml；
B) toward the styrene of addition ＜ 5ml in above-mentioned solution, it is passed through N2Atmosphere, constant temperature stirs；
C) lower the temperature after having stirred, then mixed liquor is transferred in centrifuge tube, be centrifuged washing；
D) material after above-mentioned washing is dried, it is thus achieved that PS microsphere template.
As it is further preferred that in step a) volume ratio of water and ethanol be 2:5, cumulative volume is 70ml.
As it is further preferred that in step b) whipping temp be 60 DEG C～70 DEG C, mixing time is 6h～7h.
As it is further preferred that in step c) centrifuge washing liquid be dehydrated alcohol, washing times is 3～5 times, and wherein, centrifugal speed is 2000r/min for the first time, and centrifugation time is 16h～20h, and the centrifugal speed of subsequent wash is 4000r/min, and centrifugation time is 1h.
As it is further preferred that dry in vacuum freezing drying oven in step d), drying time is 4h～6h.
In general, by the contemplated above technical scheme of the present invention compared with prior art, mainly possess following technological merit:
1. the present invention utilizes polystyrene microsphere (PS microsphere) to be soaked in LSCF nitrate precursors, and the calcining of dried reselection suitable temperature removes template to prepare LSCF, and can prepare specific surface area is 20～30m2/ g, structure are three-dimensional porous orderly catalyst powder; this catalyst can meet the demand of lithium-air battery cathode material; it is substantially reduced the overpotential in lithium-air battery charge and discharge process; it is greatly improved its capacity and cycle performance; have simultaneously preparation technology be simple and convenient to operate, low cost, the advantage such as pollution-free, can accomplish scale production.
2. the three-dimensional porous LSCF catalyst of the present invention can be as nonaqueous lithium air battery cathode catalyst, enough active place can be provided for cell reaction, realize the maximum utilization of active catalyst sites, and the quick diffusion of electronics, ion, electrolyte and oxygen in reaction；In addition, perofskite type oxide LSCF has good electric conductivity and ionic conduction ability, and the oxygen defect structure that perovskite material itself has can promote the adsorption/desorption of oxygen in course of reaction, there is provided quick transmission channel for oxonium ion, it is possible to reduce the overpotential in lithium-air battery charge and discharge process, improve capacity and the cyclical stability of battery, compared with current lithium-air battery, overpotential reduces about 5～8%, and capacity brings up to 1.5～2 times, and the circulation number of turns is up to about 200 times.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the three-dimensional porous LSCF catalyst of the embodiment of the present invention 1 preparation；
Fig. 2 is the SEM figure of the polystyrene microsphere template of the ordered arrangement of the embodiment of the present invention 1 preparation；
Fig. 3 is the XRD figure of the three-dimensional porous LSCF catalyst of the embodiment of the present invention 1 preparation；
Fig. 4 is the charge/discharge capacity figure of the lithium-air battery of the embodiment of the present invention 2 preparation；
Fig. 5 (a) and (b) are the cycle performance figures of the lithium-air battery of the embodiment of the present invention 2 preparation.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.As long as just can be mutually combined additionally, technical characteristic involved in each embodiment of invention described below does not constitutes conflict each other.
As it is shown in figure 1, the one three-dimensional porous perovskite type catalyst La that the present invention providesxSr1-xCoyFe1-yO3(LSCF), the powder body prepared unlike conventional solid reaction method and sol-gal process is in granular form, but in three-dimensional porous ordered structure, therefore has large specific surface area, specially 20～30m2/ g, inside has porous channel, and the diameter of passage is specially 200nm-300nm, and during as the cathod catalyst of lithium-air battery, this porous channel is ion and gas provides transmission channel, and provides favourable memory space for product.When this three-dimensional porous perovskite type catalyst is as lithium-air battery catalyst, three-dimensional porous passage can be the Li in course of reaction+There is provided transmission channel with oxygen, and be insulation product Li2O2Memory space is provided, in conjunction with itself have in LSCF structure oxygen defect can effectively facilitate the decomposition of product in the formation of product in discharge process and charging process, thus reduce battery overpotential, improve the cycle performance of battery.
Below the preparation method of the three-dimensional porous perovskite type catalyst of the present invention being described in detail and illustrated, this preparation method specifically includes following steps:
1) by La (NO3)2·6H2O、Sr(NO3)2、Co(NO3)2·6H2O、Fe(NO3)3·9H2Tetra-kinds of nitrate of O weigh according to the ratio of mol ratio x:1-x:y:1-y, are then dissolved in the mixed solution of a certain amount of methanol and ethylene glycol, stir at 20～30 DEG C of constant temperature, until nitrate all dissolves and mix homogeneously, it is thus achieved that nitrate solution.As preferred embodiment, methanol is 1:1 with the volume ratio of ethanol, and the total concentration of nitrate solution is 1～2mol L-1。
2) PS microsphere (polystyrene microsphere) template is soaked in above-mentioned nitrate solution, wherein, PS microsphere template uses the preparation of slightly soluble liquid method to form through centrifugal self assembly again, the granular size of microsphere is about 400nm, in sintering process, microsphere can be burned off becoming micropore, micro pore volume can shrink, and becomes the orderly duct of 200～300nm.Specifically include following steps:
A) a certain amount of dodecylbenzene sodium sulfonate (SDS) and potassium peroxydisulfate (KPS) are dissolved in the mixed liquor of water and ethanol, then above-mentioned mixed solution are placed in the there-necked flask of 250ml.Wherein, the consumption of SDS and KPS is 0.0002mol.Dispersibility due to water and ethanol can affect the pore-size distribution of microsphere, is preferably 2:5 to obtain the volume ratio of the microsphere of even aperture distribution, water and ethanol, and cumulative volume is 70ml, i.e. 20ml distilled water and 50ml ethanol；
B) toward the styrene of addition ＜ 5ml in above-mentioned solution, it is passed through N2Atmosphere, constant temperature stirs, and wherein, whipping temp is 60 DEG C～70 DEG C, and mixing time is 6h～7h；
C) it is cooled to 20～30 DEG C after having stirred, then transfers to the mixed liquor that above-mentioned reaction terminates centrifuge tube is centrifuged washing (centrifugal self assembly).As the presently preferred embodiments, centrifuge washing liquid is dehydrated alcohol, and washing times is 3～5 times, and centrifugal speed is 2000r/min for the first time, and centrifugation time is 16h～20h, and the centrifugal speed of subsequent wash is 4000r/min, and centrifugation time is 1h；
D) being dried by the material after above-mentioned washing, i.e. obtain the PS microsphere template of ordered arrangement, as in figure 2 it is shown, wherein, drying course is carried out in vacuum freezing drying oven, and drying time is 4h～6h；
3) after soaking 1h～2h, being taken out by the PS microsphere template immersed with nitrate solution and dry, then calcine 5h at 500 DEG C～700 DEG C, to burn PS microsphere template, perovskite becomes phase in calcination process, and the XRD figure obtained is as shown in Figure 3.As preferred embodiment, owing to PS microsphere is higher than 80 DEG C of easy decomposition, the drying temperature therefore selecting PS microsphere template is 50 DEG C～60 DEG C, dries the microsphere template that 4h～5h can be obtained by being dried.And calcine and can carry out in Muffle furnace, the heating rate of calcining is 1 DEG C/min.
It it is below the specific embodiment of the present invention.
Embodiment 1
Preparation PS microsphere template:
0.065g dodecylbenzene sodium sulfonate and 0.0489g potassium peroxydisulfate are dissolved in the mixed solution of 20ml distilled water and 50ml ethanol, dissolve in the there-necked flask being placed on 250ml；Add the styrene being about 3ml in the solution, be passed through N2Atmosphere stirs 6.5 hours in 70 DEG C of constant temperature；Lowering the temperature after having stirred, moved into by mixed liquor in centrifuge tube and be centrifuged washing, centrifugation rate is 2000r/min, and the time is 16h, and cleaning mixture is ethanol, and washing times is 3 times；Finally it is dried 5h with vacuum freezing drying oven, i.e. obtains the polystyrene microsphere template of ordered arrangement.
Prepare perovskite type catalyst La0.6Sr0.4Co0.2Fe0.8O3:
By La (NO3)2·6H2O、Sr(NO3)2、Co(NO3)2·6H2O、Fe(NO3)3·9H2Tetra-kinds of nitrate of O respectively weigh 0.006mol, 0.004mol, 0.002mol, 0.008mol, it is dissolved in the mixed solution of 10ml methanol and 10ml ethylene glycol, the PS microsphere template prepared by the present embodiment after stirring is soaked in wherein, take out after about 1.5h and put 60 DEG C of freeze-day with constant temperature 5h in an oven, place in Muffle furnace and calcine 5h in 650 DEG C, heating rate is 1 DEG C/min, removes PS ball template, obtains three-dimensional porous structure perovskite type catalyst La0.6Sr0.4Co0.2Fe0.8O3, as shown in Figure 1.Wherein, perofskite type oxide La0.6Sr0.4Co0.2Fe0.8O3Phase is become, as shown in Figure 3 in calcination process.
Embodiment 2
LSCF material in embodiment 1 is used as the cathod catalyst of nonaqueous lithium air cell, i.e. LSCF and material with carbon element Super P and binding agent are mixed and made into slurry, on carbon paper, make cathode electrode sheet with silk screen printing brush, then electrode slice is assembled into battery in case testing.Testing when preparing cathode slurry, the ratio of powder body and binding agent PVDF (Kynoar, polyvinylidene fluoride) is 90:10, and in powder body, the mass ratio of catalyst LSCF and carbon dust Super P is 35:55.Specifically include following steps:
First PVDF is dissolved in NMP (N-Methyl pyrrolidone, N-methyl-2-pyrrolidone) in solvent, catalyst LSCF and carbon dust Super P powder body is weighed according still further to described ratio, powder body and binding agent PVDF are placed in agate mortar grinding, period can drip appropriate NMP, the slurry being uniformly mixed after about grinding 2.5h again；Being evenly applied on carbon paper by this slurry with silk screen printing, then be placed in freeze-day with constant temperature 12 hours in 80～100 DEG C of baking ovens, obtain negative electricity pole piece, on every plate electrode sheet, the active material of coating is about about 2mg；Material needed for electrode slice and battery being prepared again is placed in argon glove box, makes button cell；Taking out battery to carry out sealing, standing, then carry out charge/discharge capacity test under pure oxygen environment, result as shown in Figure 4, can make the charge/discharge capacity of lithium-air battery from 3217mAhg according to the addition of Fig. 4,3D-LSCF catalyst-1And 1787mAhg-1It is respectively increased 6693mAhg-1And 4704mAhg-1, about bring up to 2 times of SP；The battery prepared according to same process is circulated performance test, shown in result such as Fig. 5 (a) and (b), from 58 circles, the circulation number of turns can be brought up to 198 circles according to Fig. 5,3D-LSCF, greatly improve the cycle performance of lithium-air battery.
Those skilled in the art is easy to understand; the foregoing is only presently preferred embodiments of the present invention; not in order to limit the present invention, all any amendment, equivalent and improvement etc. made within the spirit and principles in the present invention, should be included within the scope of the present invention.
Claims (10)
1. a three-dimensional porous perovskite type catalyst LaxSr1-xCoyFe1-yO3, it is characterised in that this three-dimensional porous perovskite type catalyst is as the cathod catalyst of lithium-air battery, and its specific surface area is 20～30m2/ g, has three-dimensional porous passage inside it, this porous channel provides transmission channel for ion and gas, and provides memory space for product.
Three-dimensional porous perovskite type catalyst La the most as claimed in claim 1xSr1-xCoyFe1-yO3, it is characterised in that a diameter of 200nm-300nm of described porous channel.
3. a three-dimensional porous perovskite type catalyst La as claimed in claim 1 or 2xSr1-xCoyFe1-yO3Preparation method, it is characterised in that the method comprises the steps:
1) by La (NO3)2·6H2O、Sr(NO3)2、Co(NO3)2·6H2O、Fe(NO3)3·9H2Tetra-kinds of nitrate of O weigh according to the ratio of mol ratio x:1-x:y:1-y, are then dissolved in the mixed solution of a certain amount of methanol and ethylene glycol, stirring at normal temperature, until nitrate all dissolves and mix homogeneously, it is thus achieved that nitrate solution；
2) PS microsphere template is soaked in above-mentioned nitrate solution；
3) the PS microsphere template immersed with nitrate solution is taken out drying, at 500 DEG C～700 DEG C, then calcine 5h, to burn PS microsphere template, obtain inside and there is the perovskite type catalyst La of three-dimensional porous structurexSr1-xCoyFe1-yO3。
Preparation method the most according to claim 3, it is characterised in that step 1) in, methanol is 1:1 with the volume ratio of ethanol, and the total concentration of nitrate solution is 1～2mol L-1；Step 2) in, PS microsphere template soak time in nitrate solution is 1h～2h.
Preparation method the most according to claim 3, it is characterised in that step 3) in, the drying temperature of PS microsphere template is 50 DEG C～60 DEG C, and drying time is 4h～5h, and the heating rate of calcining is 1 DEG C/min.
Preparation method the most according to claim 3, it is characterised in that step 2) in, described PS microsphere template is prepared in the following way:
A) a certain amount of dodecylbenzene sodium sulfonate and potassium peroxydisulfate are dissolved in the mixed liquor of water and ethanol, then above-mentioned mixed solution are placed in the there-necked flask of 250ml；
B) toward the styrene of addition ＜ 5ml in above-mentioned solution, it is passed through N2Atmosphere, constant temperature stirs；
C) lower the temperature after having stirred, then mixed liquor is transferred in centrifuge tube, be centrifuged washing；
D) material after above-mentioned washing is dried, it is thus achieved that PS microsphere template.
Preparation method the most according to claim 6, it is characterised in that in step a), the volume ratio of water and ethanol is 2:5, cumulative volume is 70ml.
Preparation method the most according to claim 6, it is characterised in that in step b), whipping temp is 60 DEG C～70 DEG C, and mixing time is 6h～7h.
Preparation method the most according to claim 6, it is characterized in that, in step c), centrifuge washing liquid is dehydrated alcohol, washing times is 3～5 times, wherein, centrifugal speed is 2000r/min for the first time, and centrifugation time is 16h～20h, the centrifugal speed of subsequent wash is 4000r/min, and centrifugation time is 1h.
Preparation method the most according to claim 6, it is characterised in that dry in vacuum freezing drying oven in step d), drying time is 4h～6h.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106238066A (en) * | 2016-07-29 | 2016-12-21 | 武汉理工大学 | A kind of spherical porous perovskite type catalyst La0.4sr0.6mn0.8fe0.2o3and its preparation method and application |
| CN107456973A (en) * | 2017-08-02 | 2017-12-12 | 上海纳米技术及应用国家工程研究中心有限公司 | Hierarchical self-assembly perovskite micro-sphere structure preparation method and products thereof and application |
| CN107895784A (en) * | 2017-11-14 | 2018-04-10 | 安徽工业大学 | A kind of preparation method and applications of porous Ca-Ti ore type oxide electrode material |
| CN109923715A (en) * | 2016-11-07 | 2019-06-21 | 国立研究开发法人产业技术综合研究所 | Composite particle powder, solid oxide type electrode material for battery and the solid oxide type electrode for cell using it |
| CN111646496A (en) * | 2020-04-30 | 2020-09-11 | 南京理工大学 | Highly ordered perovskite nanosheet film with high polarization characteristic and preparation method thereof |
| CN112850799A (en) * | 2021-01-26 | 2021-05-28 | 河海大学 | Preparation method of double-scale porous perovskite for chemical looping hydrogen production |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101672847A (en) * | 2009-09-30 | 2010-03-17 | 青岛科技大学 | Preparation method of protein chip glass carrier |
| US20120141906A1 (en) * | 2010-12-01 | 2012-06-07 | Samsung Electro-Mechanics Co., Ltd. | Electrode material for fuel cell, fuel cell comprising the same and method of manufacturing the fuel cell |
| CN102558410A (en) * | 2012-01-20 | 2012-07-11 | 齐齐哈尔大学 | Preparation method of self-assembled three-dimensional ordered polystyrene colloidal crystal |
| CN104399480A (en) * | 2014-11-25 | 2015-03-11 | 天津工业大学 | Preparation and application of perovskite catalyst with three-dimensional ordered macroporous structure |
-
2016
- 2016-04-12 CN CN201610225641.6A patent/CN105720277A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101672847A (en) * | 2009-09-30 | 2010-03-17 | 青岛科技大学 | Preparation method of protein chip glass carrier |
| US20120141906A1 (en) * | 2010-12-01 | 2012-06-07 | Samsung Electro-Mechanics Co., Ltd. | Electrode material for fuel cell, fuel cell comprising the same and method of manufacturing the fuel cell |
| CN102558410A (en) * | 2012-01-20 | 2012-07-11 | 齐齐哈尔大学 | Preparation method of self-assembled three-dimensional ordered polystyrene colloidal crystal |
| CN104399480A (en) * | 2014-11-25 | 2015-03-11 | 天津工业大学 | Preparation and application of perovskite catalyst with three-dimensional ordered macroporous structure |
Non-Patent Citations (2)
| Title |
|---|
| MASAHIRO SADAKANE，ET AL.: "Facile Preparation of Three-Dimensionally Ordered Macroporous Alumina, Iron Oxide, Chromium Oxide, Manganese Oxide, and Their Mixed-Metal Oxides with High Porosity", 《CHEM. MATER.》 * |
| MASAHIRO SADAKANE，ET AL.: "Facile Procedure To Prepare Three-Dimensionally Ordered Macroporous (3DOM) Perovskite-type Mixed Metal Oxides by Colloidal Crystal Templating Method", 《CHEM. MATER.》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106238066A (en) * | 2016-07-29 | 2016-12-21 | 武汉理工大学 | A kind of spherical porous perovskite type catalyst La0.4sr0.6mn0.8fe0.2o3and its preparation method and application |
| CN106238066B (en) * | 2016-07-29 | 2018-12-18 | 武汉理工大学 | A kind of spherical porous perovskite type catalyst La0.4Sr0.6Mn0.8Fe0.2O3And its preparation method and application |
| CN109923715A (en) * | 2016-11-07 | 2019-06-21 | 国立研究开发法人产业技术综合研究所 | Composite particle powder, solid oxide type electrode material for battery and the solid oxide type electrode for cell using it |
| CN109923715B (en) * | 2016-11-07 | 2020-11-10 | 国立研究开发法人产业技术综合研究所 | Composite particle powder, electrode material for solid oxide battery, and electrode for solid oxide battery using same |
| CN107456973A (en) * | 2017-08-02 | 2017-12-12 | 上海纳米技术及应用国家工程研究中心有限公司 | Hierarchical self-assembly perovskite micro-sphere structure preparation method and products thereof and application |
| CN107895784A (en) * | 2017-11-14 | 2018-04-10 | 安徽工业大学 | A kind of preparation method and applications of porous Ca-Ti ore type oxide electrode material |
| CN111646496A (en) * | 2020-04-30 | 2020-09-11 | 南京理工大学 | Highly ordered perovskite nanosheet film with high polarization characteristic and preparation method thereof |
| CN111646496B (en) * | 2020-04-30 | 2023-05-23 | 南京理工大学 | Highly ordered perovskite nano sheet film with high polarization characteristic and preparation method thereof |
| CN112850799A (en) * | 2021-01-26 | 2021-05-28 | 河海大学 | Preparation method of double-scale porous perovskite for chemical looping hydrogen production |
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