CN104876275A - Low temperature preparation method of layered perovskite - Google Patents

Low temperature preparation method of layered perovskite Download PDF

Info

Publication number
CN104876275A
CN104876275A CN201410069052.4A CN201410069052A CN104876275A CN 104876275 A CN104876275 A CN 104876275A CN 201410069052 A CN201410069052 A CN 201410069052A CN 104876275 A CN104876275 A CN 104876275A
Authority
CN
China
Prior art keywords
solution
precursor
mmol
water
laminated perovskite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201410069052.4A
Other languages
Chinese (zh)
Inventor
邹国军
杜晓蕊
王晓来
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanzhou Institute of Chemical Physics LICP of CAS
Original Assignee
Lanzhou Institute of Chemical Physics LICP of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lanzhou Institute of Chemical Physics LICP of CAS filed Critical Lanzhou Institute of Chemical Physics LICP of CAS
Priority to CN201410069052.4A priority Critical patent/CN104876275A/en
Publication of CN104876275A publication Critical patent/CN104876275A/en
Pending legal-status Critical Current

Links

Landscapes

  • Inorganic Compounds Of Heavy Metals (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a low temperature preparation method of Ruddlesden-Popper type layered perovskite. By using ''chloride ion induction effect'', a uniform layered precursor containing the chloride ions is formed, then the chloride ions in the precursor are dissociated and removed, and thus the layered structure is obtained. Compared with a traditional R-P type layered perovskite preparation method, the method has the advantage that the preparation temperature in the method is greatly reduced, so that the application scope of the type of the materials is expanded. The obtained materials possess high performance in the aspects of specific surface, thermal stability, electromagnetic performance, catalytic activity and the like.

Description

A kind of low temperature preparation method of laminated perovskite
Technical field
The present invention relates to a kind of preparation method of laminated perovskite, particularly relate to a kind of Ruddlesden-Popper type laminated perovskite A 3b 2o 7low temperature preparation method.
Background technology
Ruddlesden-Popper(R-P) type laminated perovskite is a kind of perovskite-like type composite oxides with laminate structure, and its molecular formula can be abbreviated as A n+1b no 3n+1or AO (ABO 3) n, its basic structure can think that halite layer AO inserts original uhligite and the two-dimentional intercalation configuration formed.Sequential 2 D makes it have superior thermostability; Meanwhile, the halite layer AO comprising macrocation defines loose specular layer, is conducive to the interlayer transmission of oxygenate kind or ion, makes it have superior transmission performance.From nineteen fifty-seven, S. N. Ruddlesden and P. Popper has synthesized Sr first 3ti 2o 7(S. N. Ruddlesden and P. Popper, Acta Cryst., 1958,11,54.) since, superior oxygen transmission performance, thermodynamic stability and thermochemistry consistency make such material earn widespread respect, and have good Research Prospects in fields such as electricity, magnetic, light, catalysis, oxygen permeable film, intermediate temperature fuel cells.Y. Maeno etc. (Y. Maeno et al., Nature, 1994,372,532-534.) report R-P type laminated perovskite Sr 2ruO 4supraconductivity, even if find that laminated perovskite still has superior conductivity not containing Cu element.K.-N. Jung etc. (K.-N. Jung et al., Chem. Commun., 2012,48,9406-9408.) find at Li-O 2in battery, laminated perovskite La 1.7ca 0.3ni 0.75cu 0.25o 4significantly can promote Li 2o 2oxidation.Be widely studied in magnetic fields as ferromagnetic laminated perovskite.Y. Moritomo etc. (Y. Moritomo et al., Nature, 1996,380,141-144.) report laminated perovskite (La, Sr) n+1mn no 3n+1giant magnetoresistance effect.H. Asano etc. (H. Asano et al., Appl. Phys. Lett., 1997,70,2303-2305.) have studied laminated perovskite La afterwards 2-2xca 1+2xmn 2o 7in epitaxial film and polycrystalline bulk time magnetic transport performance.D. Neiner etc. (D. Neiner et al., Chem. Mater., 2006, 18, 518-524.) and synthesize laminated perovskite Li 0.3ni 0.85la 2ti 3o 10, this compound presents ferromegnetism rarely found in nickel-based oxide.In addition, the ionic channel that laminated perovskite is loose makes it come into one's own gradually in photocatalysis field.Reported have Pb 2ga 2nb 2o 10and RbPb 2nb 2o 7(K.G. Kanade et al., Int. J. Hydrogen Energ., 2008,33,6904-6912.), ABi 2ta 2o 9(A=Ca, Sr, Ba) (Y. Li et al., J. Solid State Chem., 2008,181,2653-2659.) etc.But, laminated perovskite high-performance further expand and study the restriction being but subject to its preparation condition.Traditional technology of preparing condition is harsh, generally needs high temperature (>=1300 ° of C), high pressure and longer calcination time (15 ~ 36 h) (N.H. Hur et al., Solid State Commun., 1999,112,61-65; T. Murata et al., J. Magn. Magn. Mater., 2006,303,138-141; Y. Tsujimoto et al., Chem. Commun., 2011,47,3263-3265.).This causes such material generally to have lower specific surface area, and preparation condition harshness causes implementing difficulty, is unfavorable for its widespread use.
Summary of the invention
The object of the invention is to obtain a kind of simple to operate, suitability wide and prepare Ruddlesden-Popper(R-P at a lower temperature) method of type laminated perovskite.
The object of the invention is to be achieved through the following technical solutions:
The present invention is the method for a kind of low-temperature growth R-P type laminated perovskite proposed on the basis of sol-gel method, we utilize " chlorion inductive effect " to form the stratiform presoma containing chlorion, detach the chlorion in removing precursor again, thus obtain laminate structure.
A low temperature preparation method for laminated perovskite, it is characterized in that the method successively step be:
1) by La 3+, Ce 3+, Sr 2+, Ca 2+, Ba 2+one or more salt and Mn 2+, Co 2+, Ni 2+, Zr 4+, Ti 4+one or more salt mix water-soluble formation solution A, by the chlorine source containing chlorion and the common water-soluble formation solution B of coordination agent, described coordination agent is one or more of PVA after citric acid, EDTA, glycine, degraded and citric acid glycol ester; Mixing A and B solution, stir, dehydration, dry, the precursor powder of calcining acquisition containing chlorion;
2) in a kettle., under alkaline condition, hydro-thermal or solvent heat treatment are carried out to precursor powder, after filtration, washing, drying, calcining, obtain target product and Ruddlesden-Popper type laminated perovskite.
In the present invention, the chlorine-containing compound as chlorine source is one or more of the hydrochloride of metal, p-Chlorobenzoic acid amide and ammonium chloride.
In the present invention, the calcining temperature of precursor is 600 ° of C ~ 1100 ° C.
In the present invention, basic solution precursor being carried out to hydro-thermal or solvent heat treatment is NH 4hCO 3, (NH 4) 2cO 3, NH 3h 2o, K 2cO 3, methane amide, trolamine, pyridine, aniline, quadrol, one or more water formed of anionite-exchange resin, ethanol or ethylene glycol solutions.
In the present invention, the temperature of precursor being carried out to hydrothermal treatment consists or solvent heat treatment is 80 ° of C ~ 220 ° C.
In the present invention, the calcining temperature of final product is 600 ° of C ~ 1100 ° C.
Outstanding feature of the present invention is:
Compared with traditional R-P type laminated perovskite preparation method, preparation temperature reduces greatly, and the range of application of such material is expanded; Simple to operate, expense is cheap, can adapt to the needs of large-scale commercial production; Resulting materials shows high-performance in specific surface, thermostability, electromagnetic performance, catalytic activity etc.; " chlorion inductive effect " thought in the method extends in the synthesis of nanometer complex oxide material.
Accompanying drawing explanation
Fig. 1 is product La 3mn 2o 7+ δpowder x-ray diffraction spectrogram.
Fig. 2 is product LaCa 2mn 2o 7powder x-ray diffraction spectrogram.
Embodiment
There is provided following examples for setting forth spy of the present invention further, but embodiments of the present invention are not limited to following examples.
Embodiment 1:
By 6.50 g La (NO 3) 36H 2o (15 mmol), 2.68 g Mn (NO 3) 2solution (50 wt%, 7.5 mmol), and 0.50 g MnCl 2(2.5 mmol) is water-soluble, forms solution A; By 6.33 g citric acids (30 mmol) and 2.25 g NH 4hCO 3(28.5 mmol) is water-soluble, forms solution B.Mixed with B solution by A, stir, underpressure distillation, dehydration forms denseer jelly, and drying afterwards, roasting 5 h under 700 ° of C, obtain blue-black precursor powder.Take 1.00 g precursor powder, contain 0.10 mol L -1nH 4hCO 3in the autoclave of solution, react 12 h under 80 ° of C, suction filtration is separated, deionized water, washing with alcohol, and dry, roasting 2 h under 800 ° of C, obtains blue-black laminated perovskite La thereupon 3mn 2o 7+ δpowder.
Embodiment 2:
By 2.17 g La (NO 3) 36H 2o (5 mmol), 2.39 g Ca (NO 3) 24H 2o (10 mmol), 2.68 g Mn (NO 3) 2solution (50 wt%, 7.5 mmol), and 0.50 g MnCl 2(2.5 mmol) is water-soluble, forms solution A; By 6.33 g citric acids (30 mmol) and 2.25 g NH 4hCO 3(28.5 mmol) is water-soluble, forms solution B.Mixed with B solution by A, stir, underpressure distillation, dehydration forms denseer jelly, and dry, roasting 5 h under 800 ° of C, obtains precursor powder thereupon.Take 1.00 g precursor powder, contain 0.10 mol L -1nH 4hCO 3in the autoclave of solution, react 12 h under 120 ° of C, suction filtration is separated, deionized water, washing with alcohol, and dry, roasting 2 h under 800 ° of C, obtains laminated perovskite LaCa thereupon 2mn 2o 7powder.
Embodiment 3:
By 1.73 g La (NO 3) 36H 2o (4 mmol), 0.53 g Ba (NO 3) 2and 1.17 g Co (NO 3) 26H 2o (4 mmol) is water-soluble, forms solution A; By water-soluble to 2.53 g citric acids (12 mmol) and 0.26 g p-Chlorobenzoic acid amide (2 mmol), form solution B.Mixed with B solution by A, stir, underpressure distillation, dehydration forms denseer jelly, and dry, roasting 2 h under 1000 ° of C, obtains precursor powder thereupon.Take 1.00 g precursor powder, contain 0.10 mol L -1nH 4hCO 3in the autoclave of solution, react 8 h under 120 ° of C, rear suction filtration is separated, deionized water, washing with alcohol, and dry, roasting 2 h under 700 ° of C, obtains blue-black laminated perovskite La thereupon 2baCo 2o 7powder.
Embodiment 4:
By 1.30 g La (NO 3) 36H 2o (3 mmol), 1.27 g Sr (NO 3) 24H 2o (6 mmol), and 2.15 g Mn (NO 3) 2solution (50 wt%, 6 mmol) is water-soluble, forms solution A; By water-soluble to 3.80 g citric acids (18 mmol) and 0.38 g p-Chlorobenzoic acid amide (3 mmol), form solution B.Mixed with B solution by A, stir, underpressure distillation, dehydration forms denseer jelly, and dry, roasting 5 h under 700 ° of C, obtains precursor powder thereupon.Take 1.00 g precursor powder, in the autoclave containing the methane amide aqueous solution, react 6 h under 150 ° of C, suction filtration is separated, deionized water, washing with alcohol, and dry, roasting 2 h under 700 ° of C, obtains laminated perovskite LaSr thereupon 2mn 2o 7powder.
Embodiment 5:
By 1.43 g Ca (NO 3) 24H 2o (6 mmol), 1.29 g Zr (NO 3) 45H 2o (3 mmol), and 0.33 g ZrOCl 28H 2o (1 mmol) is water-soluble, forms solution A; By 2.53 g citric acids (12 mmol) and 0.79 g NH 4hCO 3(10 mmol) is water-soluble, forms solution B.Mixed with B solution by A, stir, underpressure distillation, dehydration forms denseer jelly, and dry, roasting 5 h under 800 ° of C, obtains precursor powder thereupon.Take 1.00 g precursor powder, containing in the autoclave of formamide soln, react 8 h under 160 ° of C, suction filtration is separated, deionized water, washing with alcohol, and dry, roasting 2 h under 800 ° of C, obtains laminated perovskite Ca thereupon 3zr 2o 7powder.
Embodiment 6:
By 0.87 g La (NO 3) 36H 2o (2 mmol), 0.95 g Ca (NO 3) 24H 2o (4 mmol), 1.29 g Zr (NO 3) 45H 2o (3 mmol), and 0.33 g ZrOCl 28H 2o (1 mmol) is water-soluble, forms solution A; 2.53 g citric acids are mixed with 1.12 g ethylene glycol, after esterification, obtains citric acid glycol ester, be dissolved in distilled water, obtain solution B.Mixing A and B solution, stir, underpressure distillation, and dehydration forms denseer jelly, and dry, roasting 5 h under 700 ° of C, obtains precursor powder thereupon.Taking 1.00 g precursor powder, is reaction medium with ethylene glycol, adds 3.00 g 717 type anionite-exchange resin, in autoclave, react 6 h under 200 ° of C, suction filtration is separated, deionized water, washing with alcohol, drying, roasting 2 h under 800 ° of C, obtains laminated perovskite LaCa thereupon 2zr 2o 7powder.
Embodiment 7:
By 0.87 g Ce (NO 3) 36H 2o (2 mmol), 1.05 g Ba (NO 3) 2(4 mmol), 1.07 g Mn (NO 3) 2solution (50 wt%, 3 mmol), and 0.20 g MnCl 2(1 mmol) is water-soluble, forms solution A; 2.53 g citric acids are mixed with 1.12 g ethylene glycol, after esterification, obtains citric acid glycol ester, be dissolved in distilled water, obtain solution B.Mixing A and B solution, underpressure distillation, dehydration forms denseer jelly, and dry, roasting 5 h under 800 ° of C, obtains precursor powder thereupon.Take 1.00 g precursor powder, with the mixing solutions (1: 2) of water and ethylene glycol for medium, add 1.06 g aniline, in autoclave, react 5 h under 180 ° of C, suction filtration is separated, deionized water, washing with alcohol, drying, roasting 2 h under 700 ° of C, obtains laminated perovskite CeBa thereupon 2mn 2o 7powder.
Embodiment 8:
By 2.60 g La (NO 3) 36H 2o (6 mmol), 1.07 g Mn (NO 3) 2solution (50 wt%, 3 mmol), and 0.20 g MnCl 2(1 mmol) is water-soluble, forms solution A; 4.40 g polyvinyl alcohol (PVA) are dissolved in distilled water, are made into the aqueous solution of 7%, after degraded, are solution B.Mixed with B solution by A, stir, underpressure distillation, dehydration forms denseer jelly, and dry, roasting 2 h under 750 ° of C, obtains precursor powder thereupon.Take 1.00 g precursor powder, in the autoclave containing the trolamine aqueous solution, react 5 h under 180 ° of C, suction filtration is separated, deionized water, washing with alcohol, and dry, roasting 2 h under 700 ° of C, obtains blue-black laminated perovskite La thereupon 3mn 2o 7+ δpowder.
Embodiment 9:
1.36 g tetrabutyl titanates (4 mmol) are dissolved in ethanol, add 1.43 g Ca (NO 3) 24H 2o (6 mmol), slowly hydrolysis forms Sol A.2.53 g citric acids are mixed with 1.12 g ethylene glycol, adds a small amount of dissolve with ethanol, after esterification, obtain citric acid glycol ester; Be dissolved in distilled water, then added 0.26 g p-Chlorobenzoic acid amide, obtained solution B.Mixing A and B solution, underpressure distillation, dehydration forms denseer jelly, and dry, roasting 5 h under 800 ° of C, obtains precursor powder thereupon.Take 1.00 g precursor powder, containing in the autoclave of formamide soln, react 8 h under 150 ° of C, suction filtration is separated, deionized water, washing with alcohol, and dry, roasting 2 h under 700 ° of C, obtains laminated perovskite Ca thereupon 3ti 2o 7powder.

Claims (6)

1. a low temperature preparation method for laminated perovskite, it is characterized in that the method successively step be:
1) by La 3+, Ce 3+, Sr 2+, Ca 2+, Ba 2+one or more salt and Mn 2+, Co 2+, Ni 2+, Zr 4+, Ti 4+one or more salt mix water-soluble formation solution A, by the chlorine source containing chlorion and the common water-soluble formation solution B of coordination agent, described coordination agent is one or more of PVA after citric acid, EDTA, glycine, degraded and citric acid glycol ester; Mixing A and B solution, stir, dehydration, dry, the precursor powder of calcining acquisition containing chlorion;
2) in a kettle., under alkaline condition, hydro-thermal or solvent heat treatment are carried out to precursor powder, after filtration, washing, drying, calcining, obtain target product and Ruddlesden-Popper type laminated perovskite.
2. the method for claim 1, the chlorine-containing compound that it is characterized in that as chlorine source is one or more of the hydrochloride of metal, p-Chlorobenzoic acid amide and ammonium chloride.
3. the method for claim 1, is characterized in that the calcining temperature of precursor is 600 ° of C ~ 1100 ° C.
4. the method for claim 1, is characterized in that basic solution precursor being carried out to hydro-thermal or solvent heat treatment is NH 4hCO 3, (NH 4) 2cO 3, NH 3h 2o, K 2cO 3, methane amide, trolamine, pyridine, aniline, quadrol, one or more water formed of anionite-exchange resin, ethanol or ethylene glycol solutions.
5. the method for claim 1, is characterized in that the temperature of precursor being carried out to hydrothermal treatment consists or solvent heat treatment is 80 ° of C ~ 220 ° C.
6. the method for claim 1, is characterized in that the calcining temperature of final product is 600 ° of C ~ 1100 ° C.
CN201410069052.4A 2014-02-28 2014-02-28 Low temperature preparation method of layered perovskite Pending CN104876275A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410069052.4A CN104876275A (en) 2014-02-28 2014-02-28 Low temperature preparation method of layered perovskite

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410069052.4A CN104876275A (en) 2014-02-28 2014-02-28 Low temperature preparation method of layered perovskite

Publications (1)

Publication Number Publication Date
CN104876275A true CN104876275A (en) 2015-09-02

Family

ID=53944002

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410069052.4A Pending CN104876275A (en) 2014-02-28 2014-02-28 Low temperature preparation method of layered perovskite

Country Status (1)

Country Link
CN (1) CN104876275A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105601272A (en) * 2016-01-28 2016-05-25 桂林电子科技大学 Ultralow loss limit type Mgn+1TinO3n+1 microwave ceramic and making method thereof
CN106953012A (en) * 2017-02-24 2017-07-14 哈尔滨工业大学深圳研究生院 Perovskite thin film, method and its solar cell device prepared by a kind of aniline solvent
CN107362795A (en) * 2017-08-04 2017-11-21 内蒙古大学 A kind of preparation method of three layers of Ca-Ti ore type wind resource assessment gas combustion catalyst of high temperature resistant support type
CN108671926A (en) * 2018-04-02 2018-10-19 河北科技大学 The preparation method of one type Ruddlesden-Popper type Ca-Ti ore type catalysis materials
CN110002851A (en) * 2019-04-04 2019-07-12 安阳师范学院 A kind of laminated perovskite Ca3Mn2O7The preparation method of ceramic material
CN111740015A (en) * 2020-06-27 2020-10-02 苏州大学 Perovskite precursor solution for improving stability of perovskite solar cell
CN113136621A (en) * 2021-04-21 2021-07-20 南京大学 Layered nickel oxide with high-efficiency catalytic activity and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101041472A (en) * 2007-03-16 2007-09-26 北京化工大学 Method for preparing perovskite-like composite metallic oxide by lamina
CN101475209A (en) * 2009-01-09 2009-07-08 北京工业大学 Preparation of layered perovskite YBa2Cu3O7 hollow spherical and porous micron particle
CN102875145A (en) * 2012-09-29 2013-01-16 中国科学技术大学 Layered perovskite structural ceramic and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101041472A (en) * 2007-03-16 2007-09-26 北京化工大学 Method for preparing perovskite-like composite metallic oxide by lamina
CN101475209A (en) * 2009-01-09 2009-07-08 北京工业大学 Preparation of layered perovskite YBa2Cu3O7 hollow spherical and porous micron particle
CN102875145A (en) * 2012-09-29 2013-01-16 中国科学技术大学 Layered perovskite structural ceramic and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DU XIAORUI ET AL.: "A novel strategy for low-temperature synthesis of Ruddlesden–Popper type layered perovskite La3Mn2O7+δ for methane combustion", 《JOURNAL OF MATERIALS CHEMISTRY A》 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105601272A (en) * 2016-01-28 2016-05-25 桂林电子科技大学 Ultralow loss limit type Mgn+1TinO3n+1 microwave ceramic and making method thereof
CN106953012A (en) * 2017-02-24 2017-07-14 哈尔滨工业大学深圳研究生院 Perovskite thin film, method and its solar cell device prepared by a kind of aniline solvent
CN107362795A (en) * 2017-08-04 2017-11-21 内蒙古大学 A kind of preparation method of three layers of Ca-Ti ore type wind resource assessment gas combustion catalyst of high temperature resistant support type
CN107362795B (en) * 2017-08-04 2021-06-15 内蒙古大学 Preparation method of high-temperature-resistant load type three-layer perovskite type air exhaust gas combustion catalyst
CN108671926A (en) * 2018-04-02 2018-10-19 河北科技大学 The preparation method of one type Ruddlesden-Popper type Ca-Ti ore type catalysis materials
CN108671926B (en) * 2018-04-02 2021-06-15 河北科技大学 Preparation method of Ruddlesden-Popper-like perovskite type catalytic material
CN110002851A (en) * 2019-04-04 2019-07-12 安阳师范学院 A kind of laminated perovskite Ca3Mn2O7The preparation method of ceramic material
CN111740015A (en) * 2020-06-27 2020-10-02 苏州大学 Perovskite precursor solution for improving stability of perovskite solar cell
WO2021258630A1 (en) * 2020-06-27 2021-12-30 苏州大学 Perovskite precursor solution for improving stability of perovskite solar cell
CN111740015B (en) * 2020-06-27 2022-08-12 苏州大学 Perovskite precursor solution for improving stability of perovskite solar cell
CN113136621A (en) * 2021-04-21 2021-07-20 南京大学 Layered nickel oxide with high-efficiency catalytic activity and preparation method thereof

Similar Documents

Publication Publication Date Title
CN104876275A (en) Low temperature preparation method of layered perovskite
Narendar et al. Synthesis, decomposition and crystallization characteristics of peroxo− citrato− niobium: an aqueous niobium precursor
CN105562122B (en) A kind of metal oxide and its preparation method and application of Ca-Ti ore type core-shell structure
CN101565210B (en) Method for preparing cobaltosic oxide powders with high tapping density by combining nanostructure
CN102173775A (en) Method for preparing neodymium-doped yttrium aluminum garnet micro/nano powder by spray freeze-drying
CN104528799A (en) Preparation method of ultrafine magnesium-based rare earth hexaaluminate powder
CN103771529A (en) Bismuth ferrite nano cylinder and preparation method thereof
CN102602988B (en) Method for preparing lithium titanate (Li4Ti5O12) with large specific area
Bhat et al. Mn and Ce doping in hydrothermally derived CaSnO3 perovskite nanostructure. A facile way to enhance optical, magnetic and electrochemical properties
CN103803664B (en) A kind of preparation method of tricobalt tetroxide band core nano-hollow ball
CN109659602A (en) A kind of hydrotalcite-modified lithium lanthanum zirconium oxygen solid electrolyte and preparation method thereof
CN103898607A (en) Preparation method of perovskite type lead titanate monocrystal nanosheet
CN102674442A (en) Method for preparing strontium titanate nano powder through microwave hydrothermal method
CN105722790B (en) The manufacture method of barium carbonate powder
Chen et al. Mild hydrothermal synthesis and magnetic properties of the manganates Pr1− xCaxMnO3
CN104085925A (en) Preparation method of LATON perovskite-type oxynitride powder
CN101693520B (en) Industrialized process for preparing cerium oxide nano-rods doped with rare earth elements
CN108428904B (en) Cerium-silver-containing hydrotalcite oxygen reduction catalyst and preparation method and application thereof
CN109179478B (en) Method for preparing porous perovskite type metal oxide
Lv et al. Gamma-Bi 4 V 2 O 11–a layered oxide material for ion exchange in aqueous media
CN100391855C (en) Method for preparing manganiferous oxide
Makovec et al. Hydrothermal synthesis of La1− XSrXMnO3 dendrites
CN108336384A (en) A kind of the niobium modification doping barium cerate electrolyte and preparation method of fuel cell
CN112615045A (en) Electrolyte material for solid lithium ion battery and preparation method thereof
Du et al. Low-Temperature Synthesis of Ruddlesden–Popper Type Layered Perovskite La x Ca 3− x Mn 2 O 7 for Methane Combustion

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
EXSB Decision made by sipo to initiate substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20150902