CN117127260A - Method for growing perovskite nickel oxide compound monocrystal under normal pressure - Google Patents
Method for growing perovskite nickel oxide compound monocrystal under normal pressure Download PDFInfo
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- 229910000480 nickel oxide Inorganic materials 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 29
- -1 nickel oxide compound Chemical class 0.000 title claims abstract description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 107
- 239000013078 crystal Substances 0.000 claims abstract description 88
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000011780 sodium chloride Substances 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 5
- 230000007246 mechanism Effects 0.000 claims abstract description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 31
- 230000004907 flux Effects 0.000 claims description 25
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 8
- SDCJMBBHNJPYGW-UHFFFAOYSA-L disodium;hydrogen carbonate;chloride Chemical compound [Na+].[Na+].Cl.[O-]C([O-])=O SDCJMBBHNJPYGW-UHFFFAOYSA-L 0.000 claims description 7
- 230000007704 transition Effects 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 3
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 3
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 3
- 230000003993 interaction Effects 0.000 claims description 3
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 3
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 3
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 claims description 3
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 12
- 239000001301 oxygen Substances 0.000 abstract description 12
- 229910021193 La 2 O 3 Inorganic materials 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 14
- 238000002156 mixing Methods 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 7
- 238000000634 powder X-ray diffraction Methods 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000007716 flux method Methods 0.000 description 5
- 238000001144 powder X-ray diffraction data Methods 0.000 description 5
- 238000012876 topography Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical class [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000877463 Lanio Species 0.000 description 1
- 229910013618 LiCl—KCl Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
- C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
- C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
- C30B9/12—Salt solvents, e.g. flux growth
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
- H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention relates to a method for growing perovskite nickel oxide compound monocrystal under normal pressure, which uses Ni source and La 2 O 3 As raw material, anhydrous K is adopted 2 CO 3 Or Na (or) 2 CO 3 And taking the mixture of NaCl and the fluxing agent as the fluxing agent, heating to melt the raw materials, cooling to the growth temperature, growing crystals under normal pressure, and removing the fluxing agent after the growth is finished to obtain La n+1 Ni n O 3n+1 (n=2, 3) crystals. The invention utilizes the fluxing agent method, does not need high pressure, breaks away from the high oxygen pressure condition for the first time, and realizes the growth of perovskite nickel oxide compound R under normal pressure n+1 Ni n O 3n+1 (n=2-7) monocrystal, greatly lowering crystal growth threshold, reducing danger in growth process and solving the problem of material for nickel-base high-temperature superconductive mechanism researchThe key problems of the platform have important basic research value and potential application prospect.
Description
Technical Field
The invention relates to a method for growing perovskite nickel oxide compound monocrystal under normal pressure, belonging to the technical field of crystal materials.
Background
Understanding the interactions of lattice, charge, spin and orbital degrees of freedom and their controlling physical properties, such as superconductivity, pang Ci resistance, metal-insulator phase transition, and multiferroics, is a central challenge for strongly correlated material research. Nickel oxide has attracted considerable attention due to its fundamental research and technically important physical properties, including the inclusion of the infinite layer square coordination oxide R 1-x A x NiO 2 (r=la, pr, nd, a=sr; r=la, a=ca) and five layers Nd 6 Ni 5 O 12 Superconductivity at normal pressure and La 3 Ni 2 O 7 High temperature superconductivity, RNiO, with critical transition temperature up to 80K at 14.0-43.5GPa 3 Metal-insulator phase transition and multiferroics in (r=pr-Lu), R 2-x Sr x NiO 4 (r=la—nd) and La 4 Ni 3 O 8 Charge/spin fringe phase, pr in (a) 4 Ni 3 O 8 Large orbital polarization and metal behavior similar to that of medium and high temperature superconducting copper oxides, and three layers of nickel oxide R 4 Ni 3 O 10 (r=la, pr, nd) the charge and spin density waves interleave to produce a metal-metal phase transition. However, some key fundamental scientific issues surrounding nickel oxide physics remain unsolved, including but not limited to square planar nickel oxide at normal pressure and La at high pressure 3 Ni 2 O 7 Origin of superconductivity, role of hydrogen in superconductivity, RNiO 2 Crystalline structure and magnetic ground state of (2), RNiO 3 Single crystals with anisotropy are ideal material platforms to solve the above key basic scientific problems.
The growth of bulk nickel oxide single crystals is still a significant challenge: (1) At present contain Ni + The low-valence nickel oxide compound of (2) cannot be directly synthesized but is prepared by the method of valence>Performing topology reduction preparation on the 2+ nickel oxide; (2) Nickel valence>All 2+ perovskite nickel oxide compounds need to be subjected to crystal growth under high oxygen pressure, for example, laNiO with edge dimension larger than 1mm is grown by using the floating zone method crystal growth technology under the conditions of oxygen pressure of 30-150, 20, 15, 290 and 140bar 3 、La 4 Ni 3 O 10 、La 3 Ni 2 O 7 、PrNiO 3 And Pr (Pr) 4 Ni 3 O 10 Bulk single crystals. However, the high-pressure floating zone furnace is expensive, high-pressure oxygen atmosphere exists, and the safety requirement is high, so that the development of basic research and application research is limited to a great extent.
Another method is a combination of flux method and high oxygen pressure technique, but adopts high pO 2 The flux method is more difficult to grow crystals and RNiO with edge dimensions of about 100 microns have been reported 3 The growth technology of monocrystal has growth condition of 900-1500 deg.c, pressure of 4-4.5 GPa and very strict condition. Recently, klein et al utilized LiCl-KCl as a flux at oxygen partial pressure pO 2 Successful growth of RNiO at t=850 ℃ with =2000 bar 3 (R=Nd, sm, gd, dy, Y, ho, er, lu) microcrystals with a size of 75 microns at maximum, for example, chinese patent document CN115787060A filed earlier by the applicant discloses the growth and application of rare earth perovskite nickel oxide high-pressure flux method crystals, wherein NiO and R are used as the materials 2 O 3 The method comprises the steps of taking a raw material R as a rare earth element, carrying out crystal growth under the condition of filling oxygen into an alkali flux system, heating to 400-500 ℃ to fully melt the raw material, cooling to a growth temperature to enable the crystal to grow, and obtaining a rare earth perovskite nickel oxide compound RNiO after the growth is finished 3 The crystal size can reach 45-60 mu m. The technology greatly reduces the growth temperature and the oxygen pressure.
In general, high oxygen pressure conditions are required for the growth of high valence state nickel oxide single crystals, either by a high pressure float zone method or a high pressure flux method, which is a pending problem, and the growth of high valence state nickel base oxide single crystals at normal pressure is not yet reported successfully, because of the severe requirements on equipment, high cost and high threshold.
Disclosure of Invention
In order to address the deficiencies of the prior art,in particular to a method for growing perovskite nickel oxide single crystal under normal pressure, which adopts a novel fluxing agent system, wherein the fluxing agent system is potassium carbonate (K) 2 CO 3 ) Or a sodium carbonate-sodium chloride mixture (Na 2 CO 3 -NaCl) is separated from the high oxygen pressure condition for the first time, thereby realizing the growth of perovskite nickel oxide compound R under normal pressure n+1 Ni n O 3n+1 (n=2 to 7) single crystals.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
a method for growing perovskite nickel oxide single crystal under normal pressure, wherein the perovskite nickel oxide single crystal has a general formula of R n+1 Ni n O 3n+1 N=2 to 7, r is a rare earth element, and the method comprises the following steps:
taking Ni source and rare earth oxide as raw materials according to stoichiometric ratio, adopting anhydrous potassium carbonate (K) 2 CO 3 ) Or a sodium carbonate-sodium chloride mixture (Na 2 CO 3 -NaCl) is used as a fluxing agent, the temperature is firstly increased to melt the raw materials, then the temperature is reduced to the growth temperature, the crystal growth is carried out under the normal pressure condition, and the perovskite nickel oxide single crystal is obtained after the growth is finished.
According to a preferred embodiment of the invention, the perovskite nickel oxide compound has the formula R n+1 Ni n O 3n+1 Wherein R is selected from lanthanum (La), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) or lutetium (Lu).
Further preferably, R is selected from lanthanum (La) alone, or a blend of lanthanum (La) with other rare earth ions.
According to a preferred embodiment of the invention, the perovskite nickel oxide compound has the formula R n+1 Ni n O 3n+1 In n=2 or 3.
According to a preferred embodiment of the present invention, the Ni source is Ni or NiO. The present invention includes, but is not limited to, ni, niO, so long as a Ni source can be provided.
According to the invention, preferably, anhydrous potassium carbonate (K 2 CO 3 ) To aid in smeltingIn the preparation process, the mole ratio of the Ni source to the fluxing agent is 1: (10-100).
Further preferably, the molar ratio of Ni source to flux is 1: (30-70).
According to the invention, preference is given to using sodium carbonate-sodium chloride mixtures (Na 2 CO 3 -NaCl) is flux, the total mass of raw materials: mass of fluxing agent = 1: (5-40), na 2 CO 3 : molar ratio of nacl= (3-20): (5-15).
According to the invention, the raw materials are melted by heating, then the temperature is reduced to the growth temperature, the growth temperature is 890-1200 ℃, and the temperature reduction rate is less than 20 ℃/h in the process of reducing the temperature to the growth temperature.
Further preferably, the cooling rate is less than or equal to 1.0 ℃/h.
According to the invention, the growth cycle of the crystals is preferably not less than 2 days.
A perovskite nickel oxide single crystal, the general formula of the perovskite nickel oxide single crystal is R n+1 Ni n O 3n+1 N=2 to 7, R is a rare earth element, and the rare earth alloy is prepared by adopting the method.
The perovskite nickel oxide single crystal is applied to researching high-temperature superconducting mechanism, metal-metal phase change, charge order, spin order and the like, and is used as a parent phase to prepare three-layer and two-layer isoplane coordinated T' -structure crystals through topological reduction, so as to research the interaction between charge-spin-lattice-orbit;
in the field of fuel cells, for solid state fuel cells,
in the electrochemical field, as electrochemical catalysts.
Taking R as lanthanum (La) as an example, the invention adopts anhydrous potassium carbonate (K) 2 CO 3 ) Or a sodium carbonate-sodium chloride mixture (Na 2 CO 3 -NaCl) is used as fluxing agent, and two layers of perovskite nickel oxide compound La are obtained by successful growth 3 Ni 2 O 7 Crystalline or trilayered perovskite nickel oxide La 4 Ni 3 O 10 。
The growing condition of the invention is optimized, and the titanium ore nickel oxide with the size more than 100 mu m can be obtainedLa of things 3 Ni 2 O 7 And (5) a crystal. The obtained two-layer perovskite nickel oxide compound La 3 Ni 2 O 7 The crystals are black, have a layered structure, are stacked to form a cuboid shape, are stable at room temperature and have no decomposition deliquescence phenomenon, and the test data of the powder X-ray diffractometer are consistent with the test data of a powder diffraction standard PDF card, so that the grown crystals are La 3 Ni 2 O 7 Single crystal analysis to obtain monoclinic P2 1 Space group/m, unit cell parameters areβ＝104.817(1)°。
The growing condition of the invention is optimized, and the titanium ore nickel oxide La with the size more than 180 mu m can be obtained 4 Ni 3 O 10 Crystals, the three-layer perovskite nickel oxide La 4 Ni 3 O 10 The powder X-ray diffraction instrument has a black and layered structure, the stack is in a cuboid shape, the stack is stable at room temperature, no decomposition deliquescence phenomenon exists, the metal-metal phase transition temperature is about 140K, the test data of the powder X-ray diffraction instrument is consistent with the test data of a powder diffraction standard PDF card, and the grown crystal is La 4 Ni 3 O 10 The crystal and single crystal analysis also confirmed the structure.
The method of the present invention is not limited thereto, and is also applicable to praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu).
The invention has the technical characteristics and advantages that:
1. there have been prior literature reports (Zhang, j.et al Phys. Rev. Mater.4,83402 (2020);
liu, z., sun et al sci.child Phys.mech.Astron.66,217411 (2023) grown La at 20bar and 15bar oxygen pressures, respectively, using high pressure float zone technology 4 Ni 3 O 10 With La 3 Ni 2 O 7 And (5) a crystal. In contrast, the invention utilizes the flux method to explore a flux system, and obtains the perovskite nickel oxide compound R of sub-millimeter level at normal pressure for the first time n+ 1 Ni n O 3n+1 (n=2-7), the limit that the bulk single crystal of the nickel oxide in the high oxidation state can only grow under high oxygen pressure is broken through, and the preparation difficulty of the crystal is greatly reduced. The growth condition is easy to realize, the operation is simple, the growth period is short, and the perovskite nickel oxide compound R with larger size can be easily obtained n+1 Ni n O 3n+1 (n=2 to 7), the rate can be further reduced to improve the crystal quality, and the raw material amount can be further increased to obtain a larger-sized single crystal.
2. Taking R as lanthanum (La) as an example, the invention adopts anhydrous potassium carbonate (K) 2 CO 3 ) Or a sodium carbonate-sodium chloride mixture (Na 2 CO 3 -NaCl) is used as fluxing agent, and two layers of perovskite nickel oxide La with larger size are successfully grown 3 Ni 2 O 7 Crystalline or trilayered perovskite nickel oxide La 4 Ni 3 O 10 Stable at room temperature and no decomposition deliquescence.
Drawings
FIG. 1 is La prepared in example 1 4 Ni 3 O 10 A microscopic topography of the crystal;
FIG. 2 is La prepared in example 1 4 Ni 3 O 10 Powder XRD pattern of the crystals;
FIG. 3 is La prepared in example 2 4 Ni 3 O 10 A microscopic topography of the crystal;
FIG. 4 is La prepared in example 2 4 Ni 3 O 10 Powder XRD pattern of the crystals;
FIG. 5 is La prepared in example 3 4 Ni 3 O 10 A microscopic topography of the crystal;
FIG. 6 is La prepared in example 3 4 Ni 3 O 10 Powder XRD pattern of the crystals;
FIG. 7 is La prepared in example 4 4 Ni 3 O 10 A microscopic topography of the crystal;
FIG. 8 is La prepared in example 4 4 Ni 3 O 10 Powder XRD pattern of the crystals;
FIG. 9 is La prepared in example 5 3 Ni 2 O 7 (Single Crystal)Is a microscopic topography of (2);
FIG. 10 is La prepared in example 5 3 Ni 2 O 7 Powder XRD pattern of single crystals.
Detailed Description
The invention will be further illustrated with reference to specific examples, but is not limited thereto. The Ni source to flux ratios mentioned below are all molar ratios, and the Ni sources mentioned below are all Ni (including but not limited to Ni, niO, etc.).
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
For La 4 Ni 3 O 10 The crystal is mainly carried out by two fluxing agent systems, namely K 2 CO 3 Flux system and Na 2 CO 3 NaCl flux system. For K 2 CO 3 Flux system, growth temperature is 1200-890 ℃, ni source: k (K) 2 CO 3 (molar ratio) =1: (10-100), the cooling rate is<10 ℃/h, the growth period is more than or equal to 2 days. While for Na 2 CO 3 The growth temperature of the NaCl fluxing agent system is between 1100 and 500 ℃, and the raw materials are: flux = 1: (5-40) (mass ratio), wherein Na 2 CO 3 NaCl= (3-20): (5-15) (molar ratio), and the growth period is more than or equal to 2 days.
For La 3 Ni 2 O 7 Crystals, mainly of K 2 CO 3 Flux systems.
Example 1
K 2 CO 3 Flux system for preparing La under normal pressure 4 Ni 3 O 10 Single crystal:
(1) Ni, la 2 O 3 Mixing according to stoichiometric ratio, adding flux anhydrous K 2 CO 3 Ni and anhydrous K 2 CO 3 The molar ratio of (2) is 1:65, uniformly mixing to obtain a crystal growth material;
(2) Putting the crystal growth material into an alumina crucible with the volume phi of 30mm multiplied by 30mm, putting the crucible into a muffle furnace, heating to 1050 ℃, preserving heat for 24 hours, reducing the temperature to 890 ℃ at the speed of 3.3 ℃/h, and enabling the crystal growth material to spontaneously crystallize, wherein the growth period is 3 days, thus obtaining La 4 Ni 3 O 10 And (5) a crystal.
Testing La 4 Ni 3 O 10 The microscopic morphology of the crystallites is shown in fig. 1. As can be seen from FIG. 1, la is obtained 4 Ni 3 O 10 The crystallite size is 10-50 μm.
Testing La 4 Ni 3 O 10 The X-ray powder diffraction pattern of the crystallites is shown in figure 2. As can be seen from FIG. 2, the La was obtained in accordance with the standard card (PDF#04-009-1774) 4 Ni 3 O 10 And (5) a crystal.
Example 2
K 2 CO 3 Flux system for preparing La under normal pressure 4 Ni 3 O 10 Single crystal:
(1) Ni, la 2 O 3 Mixing according to stoichiometric ratio, adding flux anhydrous K 2 CO 3 ，Ni：K 2 CO 3 =1: 33, mixing uniformly to obtain crystal growth material,
(2) Putting the crystal growth material into an alumina crucible with the volume phi of 50mm multiplied by 50mm, putting the crucible into a muffle furnace, heating to 1050 ℃, preserving heat for 48 hours, and then cooling to 920 ℃ at the speed of 0.83 ℃/h to enable the crystal growth material to spontaneously crystallize, and obtaining La after the growth period of 7 days 4 Ni 3 O 10 And (5) a crystal.
Testing La 4 Ni 3 O 10 The microscopic morphology of the crystallites is shown in fig. 3. As can be seen from FIG. 3, la is obtained 4 Ni 3 O 10 The crystallite size is 40-100 μm.
Testing La 4 Ni 3 O 10 The X-ray powder diffraction pattern of the crystallites is shown in fig. 4. As can be seen from FIG. 4, the La was obtained in accordance with the standard card (PDF#04-009-1774) 4 Ni 3 O 10 And (5) a crystal.
Example 3
K 2 CO 3 Flux system for preparing La under normal pressure 4 Ni 3 O 10 Single crystal:
(1) Ni, la 2 O 3 Mixing according to stoichiometric ratio, adding flux anhydrous K 2 CO 3 ，Ni：K 2 CO 3 =1: 38, uniformly mixing to obtain a crystal growth material,
(2) The crystal growth was charged into an alumina crucible having a volume of Φ50mm×50mm. Heating to 1050 ℃, preserving heat for 48 hours, cooling to 960 ℃ at the speed of 0.55 ℃/h, and enabling the La to be spontaneously crystallized and grow for 3 days 4 Ni 3 O 10 And (5) a crystal.
Testing La 4 Ni 3 O 10 The microscopic morphology of the crystallites is shown in fig. 5. As can be seen from FIG. 5, la is obtained 4 Ni 3 O 10 The crystallite size is 40-180 μm.
Testing La 4 Ni 3 O 10 The X-ray powder diffraction pattern of the crystallites is shown in fig. 6. As can be seen from FIG. 6, the La was obtained in accordance with the standard card (PDF#04-009-1774) 4 Ni 3 O 10 And (5) a crystal.
Example 4
Na 2 CO 3 La is prepared under normal pressure by NaCl flux system 4 Ni 3 O 10 Single crystal:
(1) Ni, la 2 O 3 Mixing according to stoichiometric ratio, adding flux Na 2 CO 3 、NaCl，Ni、La 2 O 3 Total mass: mass ratio of fluxing agent = 1:22, na 2 CO 3 : molar ratio of NaCl = 11:9, obtaining a crystal growth material,
(2) Putting the crystal growth material into an alumina crucible with the volume of phi 40mm multiplied by 38mm, heating to 950 ℃, preserving heat for 24 hours, cooling to 500 ℃ at the speed of 75 ℃/h, and enabling the crystal growth material to spontaneously crystallize, wherein the growth period is 2 days, thus obtaining La 4 Ni 3 O 10 And (5) a crystal.
Testing La 4 Ni 3 O 10 The microscopic morphology of the crystallites is shown in fig. 7. As can be seen from FIG. 7, la is obtained 4 Ni 3 O 10 The crystallite size is 1-20 μm.
Testing La 4 Ni 3 O 10 The X-ray powder diffraction pattern of the crystallites is shown in fig. 8. As can be seen from FIG. 8, the La was obtained in accordance with the standard card (PDF#04-009-1774) 4 Ni 3 O 10 And (5) a crystal.
Example 5
K 2 CO 3 Flux system for preparing La under normal pressure 3 Ni 2 O 7 Single crystal:
(1) Ni, la 2 O 3 Mixing according to stoichiometric ratio, adding flux anhydrous K 2 CO 3 ，Ni：K 2 CO 3 Molar ratio = 1:37, to obtain a crystal growth material,
(2) Putting the crystal growth material into an alumina crucible with the volume of phi 35mm multiplied by 50mm, heating to 1050 ℃, preserving heat for 72 hours, cooling to 1000 ℃ at the speed of 1 ℃/h, and enabling the crystal growth material to spontaneously crystallize, wherein the growth period is 6 days, thus obtaining La 3 Ni 2 O 7 And (5) a crystal.
Testing the prepared La 3 Ni 2 O 7 As shown in FIG. 9, the microstructure of the crystallites and La obtained from FIG. 9 3 Ni 2 O 7 The crystallite size is 40-105 μm.
Testing La 3 Ni 2 O 7 The X-ray powder diffraction pattern of the crystallites is shown in fig. 10. From FIG. 10As can be seen, the La was obtained in accordance with the standard card (PDF # 04-009-1772) 3 Ni 2 O 7 And (5) a crystal.
Claims (10)
1. A method for growing perovskite nickel oxide single crystal under normal pressure, wherein the perovskite nickel oxide single crystal has a general formula of R n+ 1 Ni n O 3n+1 N=2 to 7, r is a rare earth element, and the method comprises the following steps:
taking Ni source and rare earth oxide as raw materials according to stoichiometric ratio, adopting anhydrous potassium carbonate (K) 2 CO 3 ) Or a sodium carbonate-sodium chloride mixture (Na 2 CO 3 -NaCl) is used as a fluxing agent, the temperature is firstly increased to melt the raw materials, then the temperature is reduced to the growth temperature, the crystal growth is carried out under the normal pressure condition, and the perovskite nickel oxide single crystal is obtained after the growth is finished.
2. The process according to claim 1, wherein the perovskite nickel oxide compound of formula R n+1 Ni n O 3n+1 Wherein R is selected from lanthanum (La), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) or lutetium (Lu).
3. The method according to claim 1, wherein R is selected from lanthanum (La) alone, or a blend of lanthanum (La) with other rare earth ions.
4. The process according to claim 1, wherein the perovskite nickel oxide compound of formula R n+1 Ni n O 3n+1 In n=2 or 3.
5. The method of claim 1, wherein the Ni source is Ni or NiO.
6. The method according to claim 1, wherein anhydrous potassium carbonate (K 2 CO 3 ) In the case of flux, the molar ratio of Ni source to flux is 1: (10-100), preferablyThe molar ratio of Ni source to flux is 1: (30-70).
7. The method according to claim 1, characterized in that a sodium carbonate-sodium chloride mixture (Na 2 CO 3 -NaCl) is flux, the total mass of raw materials: mass of fluxing agent = 1: (5-40), na 2 CO 3 : molar ratio of nacl= (3-20): (5-15).
8. The method according to claim 1, wherein the raw materials are melted by heating and then cooled to a growth temperature of 890-1200 ℃, the cooling rate is less than 20 ℃/h, preferably the cooling rate is less than or equal to 1.0 ℃/h, and the growth period of the crystal is more than or equal to 2 days in the process of cooling to the growth temperature.
9. A perovskite nickel oxide single crystal, the general formula of the perovskite nickel oxide single crystal is R n+1 Ni n O 3n+1 N=2 to 7, r is a rare earth element, and is prepared by the method according to any one of claims 1 to 8.
10. The use of the perovskite nickel oxide compound single crystal according to claim 9 for studying high temperature superconducting mechanism, metal-metal phase transition, charge order, spin order, etc., and as a parent phase, preparing three-layer and two-layer planar coordinated T' structure crystals by topology reduction, studying charge-spin-lattice-orbital interactions;
in the field of fuel cells, for solid state fuel cells,
in the electrochemical field, as electrochemical catalysts.
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