CN106745319A - A kind of ferroso-ferric oxide micro Nano material, preparation method and applications - Google Patents
A kind of ferroso-ferric oxide micro Nano material, preparation method and applications Download PDFInfo
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- CN106745319A CN106745319A CN201611228828.8A CN201611228828A CN106745319A CN 106745319 A CN106745319 A CN 106745319A CN 201611228828 A CN201611228828 A CN 201611228828A CN 106745319 A CN106745319 A CN 106745319A
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- ferroso
- ferric oxide
- nano material
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- oxide micro
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 229940056319 ferrosoferric oxide Drugs 0.000 title claims abstract description 74
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000012046 mixed solvent Substances 0.000 claims abstract description 22
- 238000001338 self-assembly Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 potassium ferricyanide Chemical compound 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 235000011187 glycerol Nutrition 0.000 claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 6
- 238000004146 energy storage Methods 0.000 claims abstract description 5
- 239000002105 nanoparticle Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 150000005846 sugar alcohols Polymers 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 claims 11
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- 230000005291 magnetic effect Effects 0.000 description 21
- 239000000047 product Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 238000013019 agitation Methods 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 235000013339 cereals Nutrition 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 238000002601 radiography Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- 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
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
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- Manufacturing & Machinery (AREA)
- Compounds Of Iron (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a kind of ferroso-ferric oxide micro Nano material, preparation method and applications, the potassium ferricyanide is dissolved in the mixed solvent of water and glycerine, it is three-dimensional self assembly chondritic to use the step of solvent-thermal method one to prepare ferroso-ferric oxide, the kernel of its chondritic is constituted for nano particle, the superficies of ball are to be inlayed to be interwoven by polyhedron nanometer sheet, and the diameter of its ball is at 1~3 micron.Compared with prior art, the synthetic method of ferroso-ferric oxide micro Nano material prepared by the present invention is extremely simple, with low cost, a step is completed, easy to operate, favorable reproducibility, and three-dimensional self assembly chondritic can be obtained in the presence of glycerine.And product is the features such as have size uniform, purity high, low cost, be easy to industrialized production.Obtained product shows excellent performance in terms of lithium ion battery energy storage, with potential actual application value.
Description
Technical field
The invention belongs to magnetic technical field of micro nano material preparation, and in particular to a kind of micro-nano material of ferroso-ferric oxide
Material, preparation method and applications.
Background technology
Ferroso-ferric oxide micro Nano material as a kind of important magnetic material, because it has excellent magnetic performance, its
It is widely used in many fields, for example：Magnetohydrodynamic(MHD) generator, biological medicine, microwave absorption, the storage of magnetics radiography, magnetic recording
Equipment, catalyst and carrier etc..
At present, preparing the method for ferroso-ferric oxide has the methods such as collosol and gel, thermal decomposition, co-precipitation.Solvent-thermal method is most
The nearly simple preparation method with good controllable operating for growing up, recent years, its preparation technology obtained greatly sending out
Exhibition.Such as, Li etc. (Angew.Chem.Int.Ed.2005,44,2782-2785) with ferric trichloride as source of iron, ethylene glycol as solvent,
Polyethylene glycol is controlling agent, sodium acetate is accelerator, and monodispersed ferroso-ferric oxide sub-micro is prepared using the method for solvent heat
Rice ball.The method is although workable, but there is the shortcomings of preparation technology is complicated, additive is more, or even is not added with sodium acetate
Cannot just obtain magnetic-particle at all.Singapore building profound and powerful writing seminar (Angew.Chem.Int.Ed.2013,52,4165-
4168) it is source of iron to report one kind and use ferric trichloride, with ethylene glycol and ethylenediamine as solvent, before being prepared using solvent-thermal method
Drive body, then calcine 2 hours in 450 degree under nitrogen protection, obtain the three-dimensional self-assembled hollow spherical structure of ferroso-ferric oxide, it is clear that
Do same step and its complexity and also to use to the disagreeableness ethylenediamine of environment.Chinese patent (CN102153150A) publication date
2011-08-17 discloses one kind with frerrous chloride, ascorbic acid, urea, oleic acid as raw material, and the mixture of water and ethanol is molten
Agent, obtains micro nano structure ferroso-ferric oxide hollow ball, but, there is raw material and add many, condition requirement again in the preparation method
Miscellaneous the shortcomings of.Equally, Chinese patent (CN102190332A) publication date 2011-09-21, discloses a kind of with ferric iron source, hair
Infusion, stabilizer have prepared nano ferriferrous oxide hollow ball in being dissolved in polyalcohol according to a certain percentage, are not difficult to find out the party
Method also requires that harsh and complicated.In addition, Chinese patent (CN103480323A) publication date 2014-01-01 discloses a kind of by height
Molysite, sodium acetate, ethylene glycol, lauryl mercaptan etc. prepare the method with hierarchy ferroso-ferric oxide microballoon for raw material.
In sum, method made above has the following disadvantages：1st, the reagent chemicals toxicity for being used during preparation method
Greatly, it is unfriendly to environment；2nd, synthesis self-assembled structures are usually prepared using stepwise reaction or template, and step is complicated and requires severe
Carve；3rd, product it is impure, it is easy reunion and oxidation, magnetic performance it is poor；4th, preparation flow complexity, raw material addition are more, cause high cost, no
Easily promote and industrialize.
The content of the invention
In order to solve the above technical problems, it is of the invention there is provided a kind of preparation method of ferroso-ferric oxide micro Nano material,
The step solvent-thermal method for using, the simple low cost of raw material.
It is three-dimensional self assembly chondritic present invention also offers a kind of ferroso-ferric oxide micro Nano material.
It is also an object of the present invention to provide a kind of application of ferroso-ferric oxide micro Nano material on energy storage device.
A kind of preparation method of ferroso-ferric oxide micro Nano material that the present invention is provided, comprises the following steps：
A, water and polyalcohol are mixed, obtain mixed solvent；
B, the mixed solvent that soluble ferric iron salt is dissolved in step A preparations, after stirring and evenly mixing, heating response obtains product；
C, product are washed, dried, and obtain ferroso-ferric oxide micro Nano material.
Further, step A reclaimed waters and the volume ratio of polyalcohol are 3~20：1.The polyalcohol is selected from glycerine.
Soluble ferric iron salt is selected from the potassium ferricyanide in step B；
Further, soluble ferric iron salt is 0.001~0.2mol/L in the concentration of mixed solvent.
Further, heating response described in step B refers to be reacted 3~50 hours at 140~210 DEG C.
Step C is specially：Product naturally cools to room temperature, by product Magnetic Isolation, with deionized water, ethanol washed product
3~5 times, in being dried under vacuum to constant weight at 40~80 DEG C, you can obtain ferroso-ferric oxide micro Nano material.
A kind of ferroso-ferric oxide micro Nano material that the present invention is provided, is prepared using the above method, four oxidation
Three-iron micro Nano material is three-dimensional self assembly chondritic, and the kernel of ball is made up of nano particle, and the superficies of ball are by many
Face body nanometer sheet is inlayed and is interwoven, and the diameter of ball is at 1~3 micron.
A kind of application of the ferroso-ferric oxide micro Nano material that the present invention is provided on energy storage device；
Further, the ferroso-ferric oxide micro Nano material is made the application of lithium ion battery negative material.
Further, have particular application as：
The ferroso-ferric oxide micro Nano material that will be prepared：Acetylene black：PVDF is according to 6：2：2 mass ratio, enters in mortar
Row is sized mixing after grinding 40 minutes, the slurry that will be mixed up, and uniform application is on Copper Foil.100~120 DEG C of common drying box is then placed in do
Dry 6 hours, place into 120 DEG C 10 hours in vacuum drying chamber.Taking-up tabletting machine, pressure is 5~10Mpa.Carry out again
Cut-parts, the electrode slice of system.The assembled battery in glove box, with lithium piece as positive pole, barrier film is made with polyethylene, with 1mol/L's
LiPF6(volume ratio is 1:1 ethylene carbonate and dimethyl carbonate mixed liquor), it is assembled into simulated battery.Using the new prestige in Shenzhen
The battery test system (BST8-MA) of your Co., Ltd's production measures the data of simulated battery, and voltage range is 0.01~3V, with
Current density 500mA/g carries out charge-discharge test.Cyclic voltammetry curve is that (electricity is determined on electrochemical workstation CHI660E
Pressure scope is 0~3V, sweeps speed for 0.1mV/s).
The present invention discharges potassium ion, iron ion, cyanogen using the potassium ferricyanide slow solution of water under uniform temperature hydrothermal condition
Radical ion, and the cyanide ion for ionizing out separates out the hydrogen ion for coming with water power and combines to form hydrogen cyanide, on the one hand, it is unnecessary to cause
Hydroxide ion presence；On the other hand, the hydrogen cyanide with reference to after is decomposed reaction under hydrothermal, generates ammonia,
The further hydroxide ion number in increase system.Under double effect effect, the pH value that result in reaction system increases, molten
Liquid is in alkaline environment.So simultaneously, the iron ion for discharging is complexed to form complex by glycerol molecule, and then causes iron ion
It is not precipitated under alkaline environment in the early stage, with the carrying out of reaction, pH reaches the iron ion to a certain degree, being complexed in alkali
Property environment under by glycerol molecule partial reduction generate ferrous ion, start group in the presence of assembling agent glycerol molecule in this way
Dress, through precipitating, being cured into magnetic ferroferric oxide three-dimensional self assembly hyperstructure.During total, the presence of cyanide ion
Laid the foundation to provide alkaline environment, and complexing agent had both been played a part of in the presence of glycerine, it is therefore prevented that iron ion and hydroxyl
The precipitation of ion, plays a part of reducing agent again, by ferric iron back into ferrous iron, has finally promoted magnetic ferroferric oxide three
Tie up the acquisition of self assembly hyperstructure.
Compared with prior art, raw material of the present invention is used less, only the potassium ferricyanide, three kinds of raw materials of water and glycerine, reacts bar
Part is gentle, method is simple, one-step synthesis；And the product purity of generation is high, uniform particle sizes, magnetic performance are good；It is prepared by the present invention
Ferroso-ferric oxide micro Nano material pattern it is special, with three-dimensional self assembly chondritic, the kernel of ball is nano particle composition,
The superficies of ball are to be inlayed to be interwoven by polyhedron nanometer sheet；The diameter of ball is at 1~3 micron.And used in this method
, used as reducing agent and the forming agent of material morphology, to environment and its close friend, and toxicity is low for glycerine；All raw materials are easy to get, and cost is very
Low, production procedure is short, it is easy to amplification test, not high to equipment requirement, it is easy to promotes and industrializes.
Brief description of the drawings
Fig. 1 is X-ray powder diffraction (XRD) figure of the gained ferroso-ferric oxide micro Nano material of embodiment 1；
Fig. 2 is SEM (SEM) photo of the gained ferroso-ferric oxide micro Nano material of embodiment 1；
Fig. 3 is hysteresis curve (M-H) figure of the gained ferroso-ferric oxide micro Nano material of embodiment 1；
Fig. 4 is that the continuous cyclic voltammetry curve that the gained ferroso-ferric oxide micro Nano material of embodiment 1 is 3 times circulated (sweeps speed
It it is 0.1 volt/second)；
Fig. 5 is charge and discharge cycles figure of the gained ferroso-ferric oxide micro Nano material of embodiment 1 under different current densities；
Fig. 6 is charge and discharge cycles of the gained ferroso-ferric oxide micro Nano material of embodiment 1 in the case where current density is 0.5A/g
Figure；
Fig. 7 is SEM (SEM) photo of the gained ferroso-ferric oxide micro Nano material of embodiment 2；
Fig. 8 is SEM (SEM) photo of the gained ferroso-ferric oxide micro Nano material of embodiment 3；
Fig. 9 is SEM (SEM) photo of the gained ferroso-ferric oxide micro Nano material of embodiment 4；
Figure 10 is SEM (SEM) photo of the gained ferroso-ferric oxide micro Nano material of embodiment 5.
Specific embodiment
With reference to embodiment, the present invention is described in detail.
Embodiment 1
A kind of preparation method of ferroso-ferric oxide micro Nano material, step includes：
The preparation of A, mixed solvent：
The water of 37 volumes is mixed with the glycerine of 3 volumes, magnetic agitation 30 minutes is configured to uniform mixed solvent.
B, prepare ferroso-ferric oxide micro Nano material：
A certain amount of potassium ferricyanide is dissolved in the mixed solvent of above-mentioned 40 volume, magnetic agitation forms concentration and is
The orange solution of 0.02mol/L, the solution of above-mentioned acquisition is transferred in ptfe autoclave, sealing, in 180 DEG C
Reacted 5 hours in baking oven；
C, washing and drying：
Room temperature is naturally cooled to after above-mentioned end, by product centrifugation, with deionized water and ethanol washed product 3-5
It is secondary, in being dried under vacuum to constant weight at 60 DEG C, you can obtain ferroso-ferric oxide micro Nano material.
Prepared ferroso-ferric oxide micro Nano material, with three-dimensional self assembly chondritic, the kernel of ball is nanometer
Grain composition, the superficies of ball are to be inlayed to be interwoven by polyhedron nanometer sheet, the three-dimensional spherical knot of self assembly ferroso-ferric oxide
1.0~2.5 microns of the diameter of structure.
Using the gained ferroso-ferric oxide micro Nano material of case study on implementation 1 as battery electrode material, lithium ion battery is applied to,
The step of assembling and test of its simulated battery, is as follows：By ferroso-ferric oxide active material：Acetylene black：PVDF is according to 6：2：2
Mass ratio, carries out grinding of sizing mixing in mortar, after 40 minutes, the slurry that will be mixed up, and uniform application is on Copper Foil.It is then placed in common
100-120 DEG C of drying of drying box 5 hours, places into vacuum drying chamber 120 DEG C of dryings 12 hours.Taking-up tabletting machine,
Pressure is 5~10Mpa.Cut-parts, the electrode slice of system are carried out again.The assembled battery in glove box, with lithium piece as positive pole, uses polyethylene
Barrier film is made, with the LiPF of 1mol/L6(volume ratio is 1:1 ethylene carbonate and dimethyl carbonate mixed liquor), it is assembled into simulation
Battery.The battery test system (BST8-MA) produced using the new Weir Electronics Equipment Co., Ltd in Shenzhen measures simulated battery
Data, voltage range is 0.01~3V, carries out charge-discharge test with current density 500mA/g, as a result as shown in Figure 6.Circulation volt
Peace curve is to be determined on electrochemical workstation CHI660E (voltage range is 0~3V, sweeps speed for 0.1mV/s).Result is as schemed
Shown in 4.Charge and discharge cycles figure result as shown in Figure 5 under different current densities
Described ferroso-ferric oxide is carried out into Magnetic Measurement in superconducting quantum interference device (SQUID), gas saturation magnetization reaches
98emu/g (as shown in Figure 3), illustrates that ferroso-ferric oxide prepared by embodiment 1 has good magnetic performance；We will be obtained
Ferroso-ferric oxide micro Nano material is fabricated to lithium ion battery negative for negative material, and its cycle performance is tested under 0.5A/g
And capacity, though as a result show that preceding 50 circulations capacitance has decline, capacitance bottom out after 50 times, in circulation 200 times
Afterwards, tend towards stability substantially, specific discharge capacity is 1000mAh/g or so, is continued cycling through 500 times, and specific discharge capacity is always held at
More than 1000mAh/g, absolutely proves that the material has good stability and cyclicity, has in terms of lithium-ion energy storage positive
Potential using value.
Embodiment 2
A kind of preparation method of ferroso-ferric oxide micro Nano material, step includes：
The preparation of A, mixed solvent：
The water of 38 volumes is mixed with the glycerine of 2 volumes, magnetic agitation 30 minutes is configured to uniform mixed solvent.
B, prepare ferroso-ferric oxide micro Nano material：
A certain amount of potassium ferricyanide is dissolved in the mixed solvent of above-mentioned 40 volume, abundant magnetic agitation forms concentration and is
The orange solution of 0.025mol/L, the solution of above-mentioned acquisition is transferred in ptfe autoclave, sealing, in 170 DEG C
Baking oven in react 20 hours.
C, washing and drying：
Room temperature is naturally cooled to after above-mentioned end, by product centrifugation, with deionized water and ethanol washed product for several times,
In being dried under vacuum to constant weight at 65 DEG C, you can obtain ferroso-ferric oxide micro Nano material.
Prepared ferroso-ferric oxide micro Nano material, with three-dimensional self assembly chondritic, the kernel of ball is nanometer
Grain composition, the superficies of ball are to be inlayed to be interwoven by polyhedron nanometer sheet, the three-dimensional spherical knot of self assembly ferroso-ferric oxide
1.5~2.5 microns of the diameter of structure.
Embodiment 3
A kind of preparation method of ferroso-ferric oxide micro Nano material, step includes：
The preparation of A, mixed solvent：
The water of 35 volumes is mixed with the glycerine of 5 volumes, magnetic agitation 30 minutes is configured to uniform mixed solvent.
B, prepare ferroso-ferric oxide micro Nano material：
A certain amount of potassium ferricyanide is dissolved in the mixed solvent of above-mentioned 40 volume, abundant magnetic agitation forms concentration and is
The orange solution of 0.04mol/L, the solution of above-mentioned acquisition is transferred in ptfe autoclave, sealing, in 190 DEG C
Reacted 4 hours in baking oven.
C, washing and drying：
Room temperature is naturally cooled to after above-mentioned end, by product centrifugation, with deionized water and ethanol washed product for several times,
In being dried under vacuum to constant weight at 55 DEG C, you can obtain ferroso-ferric oxide micro Nano material.
Prepared ferroso-ferric oxide micro Nano material, with three-dimensional self assembly chondritic, the kernel of ball is nanometer
Grain composition, the superficies of ball are to be inlayed to be interwoven by polyhedron nanometer sheet, the three-dimensional spherical knot of self assembly ferroso-ferric oxide
1.0~2.0 microns of the diameter of structure.
Embodiment 4
A kind of preparation method of ferroso-ferric oxide micro Nano material, step includes：
The preparation of A, mixed solvent：
The water of 74 volumes is mixed with the glycerine of 6 volumes, magnetic agitation 30 minutes is configured to uniform mixed solvent.
B, prepare ferroso-ferric oxide micro Nano material：
A certain amount of potassium ferricyanide is dissolved in the mixed solvent of above-mentioned 80 volume, abundant magnetic agitation forms concentration and is
The orange solution of 0.02mol/L, the solution of above-mentioned acquisition is transferred in ptfe autoclave, sealing, in 200 DEG C
Reacted 5 hours in baking oven.
C, washing and drying：
Room temperature is naturally cooled to after above-mentioned end, by product centrifugation, with deionized water and ethanol washed product for several times,
In being dried under vacuum to constant weight at 70 DEG C, you can obtain ferroso-ferric oxide micro Nano material.
Prepared ferroso-ferric oxide micro Nano material, with three-dimensional self assembly chondritic, the kernel of ball is nanometer
Grain composition, the superficies of ball are to be inlayed to be interwoven by polyhedron nanometer sheet, the three-dimensional spherical knot of self assembly ferroso-ferric oxide
1.2~1.8 microns of the diameter of structure.
Embodiment 5
A kind of preparation method of ferroso-ferric oxide micro Nano material, step includes：
The preparation of A, mixed solvent：
The water of 360 volumes is mixed with the glycerine of 40 volumes, magnetic agitation 30 minutes is configured to uniform mixed solvent.
B, prepare ferroso-ferric oxide micro Nano material：
A certain amount of potassium ferricyanide is dissolved in the mixed solvent of above-mentioned 40 volume, abundant magnetic agitation forms concentration and is
The orange solution of 0.08mol/L, the solution of above-mentioned acquisition is transferred in ptfe autoclave, sealing, in 180 DEG C
Reacted 50 hours in baking oven.
C, washing and drying：
Room temperature is naturally cooled to after above-mentioned end, by product centrifugation, with deionized water and ethanol washed product for several times,
In being dried under vacuum to constant weight at 50 DEG C, you can obtain ferroso-ferric oxide micro Nano material.
Prepared ferroso-ferric oxide micro Nano material, with three-dimensional self assembly chondritic, the kernel of ball is nanometer
Grain composition, the superficies of ball are to be inlayed to be interwoven by polyhedron nanometer sheet, the three-dimensional spherical knot of self assembly ferroso-ferric oxide
1.2~2.0 microns of the diameter of structure.
The foregoing is only preferable case study on implementation of the invention, all impartial changes done according to scope of the present invention patent
With modification, should all belong to covering scope of the invention.
Claims (9)
1. a kind of preparation method of ferroso-ferric oxide micro Nano material, it is characterised in that the preparation method is comprised the following steps：
A, water and polyalcohol are mixed, obtain mixed solvent；
B, soluble ferric iron salt is dissolved in step 1) mixed solvent for preparing, after stirring and evenly mixing, heating response obtains product；
C, product are washed, dried, and obtain ferroso-ferric oxide micro Nano material.
2. the preparation method of ferroso-ferric oxide micro Nano material according to claim 1, it is characterised in that step A reclaimed waters
It is 3~20 with the volume ratio of polyalcohol：1.
3. the preparation method of ferroso-ferric oxide micro Nano material according to claim 1 and 2, it is characterised in that described many
First alcohol is selected from glycerine.
4. the preparation method of ferroso-ferric oxide micro Nano material according to claim 1, it is characterised in that can in step B
Dissolubility molysite is selected from the potassium ferricyanide.
5. the preparation method of the ferroso-ferric oxide micro Nano material according to claim 1 or 4, it is characterised in that step B is molten
Property molysite mixed solvent concentration be 0.001~0.2mol/L.
6. the preparation method of ferroso-ferric oxide micro Nano material according to claim 1, it is characterised in that institute in step B
It refers to be reacted 3~50 hours at 140~210 DEG C to state heating response.
7. a kind of ferroso-ferric oxide micro Nano material, it is characterised in that prepared using the method described in claim any one of 1-6
Obtain, the ferroso-ferric oxide micro Nano material is three-dimensional self assembly chondritic, the kernel of ball is made up of nano particle, ball
Superficies are to be inlayed to be interwoven by polyhedron nanometer sheet, and the diameter of ball is at 1~3 micron.
8. application of a kind of ferroso-ferric oxide micro Nano material on energy storage device.
9. application according to claim 8, it is characterised in that the ferroso-ferric oxide micro Nano material is made lithium-ion electric
The application of pond negative material.
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