CN109437320A - It is a kind of to utilize cyclohexanol-water two-phase interface reaction preparation α-Fe2O3The method and purposes of nano particle - Google Patents
It is a kind of to utilize cyclohexanol-water two-phase interface reaction preparation α-Fe2O3The method and purposes of nano particle Download PDFInfo
- Publication number
- CN109437320A CN109437320A CN201811316350.3A CN201811316350A CN109437320A CN 109437320 A CN109437320 A CN 109437320A CN 201811316350 A CN201811316350 A CN 201811316350A CN 109437320 A CN109437320 A CN 109437320A
- Authority
- CN
- China
- Prior art keywords
- nano particle
- cyclohexanol
- water
- solution
- utilize
- 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
Links
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 46
- LYJAIAHSQKJJAL-UHFFFAOYSA-N cyclohexanol;hydrate Chemical compound O.OC1CCCCC1 LYJAIAHSQKJJAL-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 20
- 229910003145 α-Fe2O3 Inorganic materials 0.000 claims abstract description 43
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002245 particle Substances 0.000 claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 15
- 230000001376 precipitating effect Effects 0.000 claims abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 12
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 239000007773 negative electrode material Substances 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 38
- 229910000859 α-Fe Inorganic materials 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 239000011889 copper foil Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 230000001276 controlling effect Effects 0.000 claims description 3
- 238000007796 conventional method Methods 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- -1 hexamethylene alcohol Chemical compound 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004153 renaturation Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000006467 substitution 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
- C01G49/06—Ferric oxide [Fe2O3]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
-
- 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
-
- 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
-
- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- 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
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
It is a kind of to utilize cyclohexanol-water two-phase interface reaction preparation α-Fe2O3The method and purposes of nano particle are suitable for the fields such as lithium ion battery, supercapacitor.This method is uniformly mixed the source of iron for being dissolved in cyclohexanol with the aqueous solution of precipitating reagent；Mixed liquor is placed in closed reaction vessel and carries out hydro-thermal reaction；Natural cooling after reaction, then separated, purified up to target product.Gained α-Fe2O3Lithium battery is made as negative electrode material in nano particle, and method and process is simple, reproducible, and it is raw materials used be easy to get, the purity is high of products obtained therefrom, good dispersion, uniform particle diameter and controllable are easily enlarged production.In addition, the cyclohexanol in this method is reusable, the energy is effectively saved and has reduced environmental pollution.By α-Fe2O3Nano particle is used as lithium ion battery negative material, electrochemical performance, therefore with good economic efficiency and vast market prospect.
Description
Technical field
The present invention relates to a kind of preparation methods of transition metal oxide, especially a kind of to be suitable for lithium ion battery, surpass
The fields such as grade capacitor utilize cyclohexanol-water two-phase interface reaction preparation α-Fe2O3The method of nano particle.
Background technique
As a kind of environmentally friendly energy storage device, lithium ion battery (LIBs) be widely used in portable electronic product,
The daily life fields such as electric vehicle.It is well known that realizing commercialization till now from lithium ion battery, negative electrode material used is basic
On be all graphite.However, the specific capacity due to graphite material is low, reversible capacity is only 372mA/g, thus greatly limit lithium from
The development of sub- battery.As people are to the rapid growth of high capacity energy storage device demand, a new generation's low cost, height are researched and developed
Capacity and the excellent lithium ion battery negative material of high rate performance and cycle performance have become urgently to be resolved at present one and ask
Topic.
Iron oxide (α-Fe2O3) material have good chemical stability, make frequently as high-temperature resistant coating and inorganic pigment
With.In recent years, application of the material in fields such as lithium ion battery, supercapacitors also results in the extensive of material scholars
Concern.α-Fe2O3As the substitution negative electrode material of commercial graphite, each lattice element can be with 6 moles of deintercalation of Li ion, therefore
The advantages that showing high theoretical capacity (1007mA/g), low cost and environment friendly.Moreover, α-Fe2O3As lithium-ion electric
The property of pond negative electrode material can be effectively controlled by changing the size and shape of ferric oxide particles.Due to nanometer ruler
Very little α-Fe2O3The transmission of lithium ion can be enhanced in material, and mitigates the strain of conversion reaction in nanoparticle, therefore α-Fe2O3
Nanosizing just becomes a kind of simple and easy method for manufacturing novel high-capacity lithium battery.
Traditional α-Fe2O3Technology of preparing there are at high cost, reaction temperature is high, the time is long, particle size is big and pattern not
The problems such as regular, therefore be badly in need of developing simple, efficient, the low-cost method of one kind to prepare α-Fe2O3Nano particle.So
And up to the present only have minority, mono-dispersed nano α-Fe uniform about scale2O3Material preparation report.The present invention is in hydro-thermal
In system, purity is high, regular shape, uniform particle sizes and good dispersion are prepared using cyclohexanol-water two-phase interface reaction for the first time
α-Fe2O3Nano particle.It is raw materials used it is cheap, be easy to get, synthetic method is simple, and solvent for use can reuse, operating procedure
Controllability is high, convenient for large-scale production.Obtained α-Fe2O3Nano particle is expected to be applied to lithium in single or compound form
In ion battery, supercapacitor and its related fields.
Summary of the invention
Technical problem: the invention aims to overcome shortcoming in the prior art, a kind of solution reaction temperature is provided
The problems such as degree is high, the time is long, particle size is big, pattern is irregular utilizes cyclohexanol-water two-phase interface reaction preparation nano oxygen
Change the method and purposes of iron particle.
Technical solution: of the invention utilizes cyclohexanol-water two-phase interface reaction preparation α-Fe2O3The method of nano particle, will
The source of iron for being dissolved in cyclohexanol is uniformly mixed with the aqueous solution of precipitating reagent, then makes the two in cyclohexanol-water using hydro-thermal method
Reaction preparation α-Fe at two-phase interface2O3Nano particle；It is real by regulating and controlling the parameters such as concentration, temperature, time in reaction process
Now to α-Fe2O3The convenience of nano particle, controlledly synthesis, and it is more uniform finally to obtain purity is high, good dispersion, particle diameter distribution
α-Fe2O3Nano particle；Specific step is as follows:
(1) source of iron being added in cyclohexanol, obtains clear solution 1 after stirring, the molar concentration of solution 1 is 0.01~
0.5mol/L；
(2) precipitating reagent is dissolved in deionized water, obtains solution 2, the molar concentration of solution 2 is 0.05~5mol/L；
(3) solution 1 and solution 2 are mixed and stirred for uniformly；
(4) material after mixing is transferred in closed, pressure-resistant reaction vessel and carries out hydro-thermal reaction；
(5) after the reaction was completed, product taking-up is separated, washed and is dried, obtain α-Fe russet2O3Particle.
Source of iron in the step (1) is one of ferric acetyl acetonade, Iron(III) chloride hexahydrate, ferric nitrate or a variety of.
Precipitating reagent in the step (2) is one of sodium hydroxide, ammonium hydroxide, potassium hydroxide, ammonium chloride or a variety of.
The molar ratio of step (3) solution 1 and the precipitating reagent in solution 2 and source of iron is 0.05~10:1.
The temperature that hydro-thermal reaction is carried out in the step (4) is 150~250 DEG C；Reaction time is 1~30h；Mixing speed
For 0~200rpm.
Gained α-Fe in the step (5)2O3The particle size range of nano particle is between 20~100nm, the dispersibility of particle
Height, particle diameter distribution are uniform.
It is a kind of to utilize cyclohexanol-water two-phase interface reaction preparation α-Fe2O3The application of nano particle, by gained α-Fe2O3It receives
Lithium battery is made as negative electrode material in rice grain, the specific steps are as follows:
(1) by α-Fe2O3The ratio that nano particle and acetylene black, sodium carboxymethylcellulose are 70:20:10 according to weight ratio
Mixing is fully ground or stirs 5~10h after deionized water is added thereto；The mixture of paste is uniformly coated to copper foil
On, and place it in dry at 100 ± 20 DEG C；Tabletting is carried out to the copper foil for being coated with said mixture, then cuts into electrode slice；
(2) using electrode slice as cathode, fastening lithium ionic cell is assembled into using conventional method in an argon atmosphere, then
Take out the test for carrying out constant current charge-discharge capacity and cycle performance.
The utility model has the advantages that the present invention in hydrothermal system, utilizes cyclohexanol-water two-phase interface reaction preparation α-Fe2O3Nanometer
Grain；Firstly, the source of iron for being dissolved in cyclohexanol is uniformly mixed with the aqueous solution of precipitating reagent；Mixed liquor is placed in closed reaction
In container, source of iron and precipitating reagent is made to carry out hydro-thermal reaction at cyclohexanol-water two-phase interface；Natural cooling after reaction, then
It separated, purified, the final α-Fe for obtaining purity is high, regular shape, uniform particle sizes and good dispersion2O3Nano particle.Original used
Material is cheap, is easy to get, and synthetic method is simple, and solvent for use can reuse, and operating procedure controllability is high, convenient for extensive raw
It produces.By α-Fe2O3Nano particle is used as the negative electrode material of lithium ion battery, can get excellent chemical property.With the prior art
It compares, the invention has the following advantages that
(1) α-Fe is prepared using cyclohexanol-water two-phase interface reaction for the first time2O3Nano particle, preparation method is simply, again
Renaturation is good, easily operated；Products obtained therefrom be regular appearance, particle size range between 20~100nm, it is of uniform size, with high purity
Monocrystalline α-Fe2O3Nano particle；It is relatively easy to large-scale industrial production.
(2) since reaction is carried out in the interface of hexamethylene alcohol and water two-phase, cyclohexanol is reusable, effectively
It has saved the energy and has reduced environmental pollution in ground.
(3) due to its structural advantage, the α-Fe2O3It is shown when nano particle is used as lithium ion battery negative material
Excellent chemical property: under the current condition of 100mA/g, for the first time and second of discharge capacity is respectively 1510 Hes
1290mAh/g, capacity tends towards stability thereafter；When successively elevated currents are to 200,500,1000,2000,5000mA/g,
Capacity is respectively 1280,1210,1100,900mAh/g；When electric current restores again to 100mA/g, capacity still is able to extensive
It answers to 1200mAh/g, and 100 circle of circulation is unattenuated, shows excellent specific capacity, high rate performance and cyclical stability.
(4) α-Fe prepared by the present invention2O3Nano particle had not only overcome the low disadvantage of traditional carbon negative pole material specific capacity, but also
It solves the problems, such as that stable circulation present in conventional transition metal oxide negative electrode material is poor, therefore there is good economic effect
Benefit and vast market prospect.
Detailed description of the invention:
Fig. 1 is α-Fe of the invention2O3The X-ray powder diffraction figure of nano particle.
Fig. 2 is α-Fe of the invention2O3The transmission electron microscope photo of nano particle.
Fig. 3 is α-Fe of the invention2O3The electron scanning micrograph of nano particle.
Fig. 4 is α-Fe of the invention2O3The charging and discharging curve that nano particle institute's assembled battery is enclosed at first three.
Fig. 5 is α-Fe of the invention2O3The charge and discharge cycles figure of nano particle.
Specific embodiment
Of the invention utilizes cyclohexanol-water two-phase interface reaction preparation α-Fe2O3The method of nano particle: hexamethylene will be dissolved in
The source of iron of alcohol is uniformly mixed with the aqueous solution of precipitating reagent, then makes the two in cyclohexanol-water two-phase interface using hydro-thermal method
Place's reaction preparation α-Fe2O3Nano particle；By regulating and controlling the parameters such as concentration, temperature, time in reaction process, realize to α-
Fe2O3The convenience of nano particle, controlledly synthesis, and finally obtain purity is high, good dispersion, the more uniform α-Fe of particle diameter distribution2O3
Nano particle；Specific step is as follows:
(1) source of iron being added in cyclohexanol, obtains clear solution 1 after stirring, the molar concentration of solution 1 is 0.01~
0.5mol/L；The source of iron is one of ferric acetyl acetonade, Iron(III) chloride hexahydrate, ferric nitrate or a variety of.
(2) precipitating reagent is dissolved in deionized water, obtains solution 2, the molar concentration of solution 2 is 0.05~5mol/L；
The precipitating reagent is one of sodium hydroxide, ammonium hydroxide, potassium hydroxide, ammonium chloride or a variety of.
(3) solution 1 and solution 2 are mixed and stirred for uniformly；The solution 1 and precipitating reagent in solution 2 and source of iron are rubbed
You are than being 0.05~10:1.
(4) material after mixing is transferred in closed, pressure-resistant reaction vessel and carries out hydro-thermal reaction；The carry out hydro-thermal
The temperature of reaction is 150~250 DEG C；Reaction time is 1~30h；Mixing speed is 0~200rpm.
(5) after the reaction was completed, product taking-up is separated, washed and is dried, obtain α-Fe russet2O3Particle.Institute
State gained α-Fe2O3The particle size range of nano particle is between 20~100nm, and the dispersibility of particle is high, particle diameter distribution is uniform.
Of the invention utilizes cyclohexanol-water two-phase interface reaction preparation α-Fe2O3The application of nano particle: by gained α-
Fe2O3Lithium battery is made as negative electrode material in nano particle, the specific steps are as follows:
(1) by α-Fe2O3The ratio that nano particle and acetylene black, sodium carboxymethylcellulose are 70:20:10 according to weight ratio
Mixing is fully ground or stirs 5~10h after deionized water is added thereto；The mixture of paste is uniformly coated to copper foil
On, and place it in dry at 100 ± 20 DEG C；Tabletting is carried out to the copper foil for being coated with said mixture, then cuts into electrode slice；
(2) using electrode slice as cathode, fastening lithium ionic cell is assembled into using conventional method in an argon atmosphere, then
Take out the test for carrying out constant current charge-discharge capacity and cycle performance.
Below in conjunction with the embodiment in attached drawing, the present invention is further illustrated:
Embodiment 1: 1.059g ferric acetyl acetonade (Fe (acac) is accurately weighed3) be put into container, 15mL is added thereto
Cyclohexanol, obtained solution 1 after stirring and dissolving；The 2.5mL ammonium hydroxide that mass percentage concentration is 25~28% is measured in another container,
Then 17.5mL deionized water is added to be diluted, obtained solution 2；Solution 1 and solution 2 are mixed evenly, and will be mixed
Material afterwards is transferred in closed, pressure-resistant reaction vessel and is heated, and reacts 30h under the conditions of 150 DEG C, mixing speed is
100rpm；After product cooled to room temperature, closed reaction vessel is opened, and filter with Buchner funnel, deionized water and nothing
Water-ethanol washs repeatedly, then is obtained α-Fe russet after natural drying2O3Grain products.
Embodiment 2: 0.1g ferric acetyl acetonade (Fe (acac) is accurately weighed3) be put into container, 20mL ring is added thereto
Hexanol, obtained solution 1 after stirring and dissolving；It weighs 0.1g sodium hydroxide (NaOH) to be added in another container, 10mL is added thereto
Deionized water, obtained solution 2 after stirring, dissolution；Solution 1 and solution 2 are mixed evenly, and the material after mixing is shifted
To in closed, pressure-resistant reaction vessel, 5h, mixing speed 150rpm are reacted under the conditions of 250 DEG C；Product is naturally cooled to
After room temperature, open closed reaction vessel, and be centrifuged, deionized water and acetone wash repeatedly, be dried in vacuo after obtain it is reddish brown
α-the Fe of color2O3Grain products.
Embodiment 3: 2.7g ferric chloride hexahydrate (FeCl is accurately weighed3·6H2O it) is put into container, 15mL is added thereto
Cyclohexanol prepares solution 1 after stirring and dissolving；The 3mL ammonium hydroxide that mass percentage concentration is 25~28% is measured to be added in another container,
Then 17mL deionized water is added to stir evenly, solution 2 is made；Solution 1 and solution 2 are mixed evenly, and will be after mixing
Material be transferred in closed, pressure-resistant reaction vessel, under the conditions of 200 DEG C stand reaction 3 hours；Product is naturally cooled to
After room temperature, closed reaction vessel is opened, and filter with Buchner funnel, deionized water and dehydrated alcohol wash repeatedly, then through nature
α-Fe russet is obtained after drying2O3Grain products.
Gained α-Fe of the invention2O3Through Bruker D8 ADVANCE x-ray powder diffraction instrument, (Cu K α is penetrated nano particle
Line, wavelengthScanning leg speed is 0.08 °/sec) it is accredited as pure α-Fe2O3, as shown in Figure 1, being marked with JCPDS card
Quasi- value (No.33-0664) matches, and no other impurity peaks occur.
Using 1011 transmission electron microscope of JEM and SU-8200 scanning electron microscopic observation α-Fe2O3The pattern of nano particle,
As a result as shown in Figures 2 and 3 respectively.Gained α-Fe2O3The main particle group by size range at 40-60nm nanometers of nano particle
At, and particle dispersion is high, shape is relatively regular, particle size distribution range is narrow.
By gained α-Fe2O3Nano particle is applied to the manufacturing process of lithium ion battery: firstly, pressing certain weight score
Also known as take α-Fe2O3Three kinds of nano particle, acetylene black and sodium carboxymethylcellulose substances, deionized water is then added thereto, fills
Divide grinding or stirring；The mixture of paste is uniformly coated on copper foil, and places it in baking oven and is dried；To being coated with
The copper foil of said mixture is rolled, and electrode slice is cut into；Electrode slice, diaphragm and lithium piece are being full of argon gas in conventional manner
Environment in be assembled into button cell, further take out carry out constant current charge-discharge capacity and cycle performance test.
Gained α-Fe2O3Lithium battery is made as negative electrode material in nano particle, electrochemical property test result such as Fig. 4 and
Shown in Fig. 5.Under the current condition of 100mA/g, battery is for the first time and second of discharge capacity is respectively 1510 and 1290mAh/
G, capacity tends towards stability thereafter；When successively elevated currents are to 200,500,1000,2000,5000mA/g, capacity is respectively
1280,1210,1100,900mA·h/g；When electric current restores to 100mA/g, capacity still is able to restore to 1200mAh/
G, and 100 circle of circulation is unattenuated, shows excellent specific capacity, high rate performance and cyclical stability.
Claims (7)
1. a kind of utilize cyclohexanol-water two-phase interface reaction preparation α-Fe2O3The method of nano particle, it is characterized in that: ring will be dissolved in
The source of iron of hexanol is uniformly mixed with the aqueous solution of precipitating reagent, then makes the two in two phase boundary of cyclohexanol-water using hydro-thermal method
Reaction preparation α-Fe at face2O3Nano particle；By regulating and controlling the parameters such as concentration, temperature, time in reaction process, realize to α-
Fe2O3The convenience of nano particle, controlledly synthesis, and finally obtain purity is high, good dispersion, the more uniform α-Fe of particle diameter distribution2O3
Nano particle；Specific step is as follows:
(1) source of iron being added in cyclohexanol, obtains clear solution 1 after stirring, the molar concentration of solution 1 is 0.01~
0.5mol/L；
(2) precipitating reagent is dissolved in deionized water, obtains solution 2, the molar concentration of solution 2 is 0.05~5mol/L；
(3) solution 1 and solution 2 are mixed and stirred for uniformly；
(4) material after mixing is transferred in closed, pressure-resistant reaction vessel and carries out hydro-thermal reaction；
(5) after the reaction was completed, product taking-up is separated, washed and is dried, obtain α-Fe russet2O3Particle.
2. according to claim 1 utilize cyclohexanol-water two-phase interface reaction preparation α-Fe2O3The method of nano particle,
Be characterized in that: the source of iron in the step (1) is one of ferric acetyl acetonade, Iron(III) chloride hexahydrate, ferric nitrate or a variety of.
3. according to claim 1 utilize cyclohexanol-water two-phase interface reaction preparation α-Fe2O3The method of nano particle,
Be characterized in that: the precipitating reagent in the step (2) is one of sodium hydroxide, ammonium hydroxide, potassium hydroxide, ammonium chloride or a variety of.
4. according to claim 1 utilize cyclohexanol-water two-phase interface reaction preparation α-Fe2O3The method of nano particle,
Be characterized in that: the molar ratio of step (3) solution 1 and the precipitating reagent in solution 2 and source of iron is 0.05~10:1.
5. according to claim 1 utilize cyclohexanol-water two-phase interface reaction preparation α-Fe2O3The method of nano particle,
Be characterized in that: the temperature that hydro-thermal reaction is carried out in the step (4) is 150~250 DEG C；Reaction time is 1~30h；Stirring speed
Degree is 0~200rpm.
6. according to claim 1 utilize cyclohexanol-water two-phase interface reaction preparation α-Fe2O3The method of nano particle,
It is characterized in that: gained α-Fe in the step (5)2O3The particle size range of nano particle is between 20~100nm, the dispersion of particle
Property it is high, particle diameter distribution is uniform.
7. according to claim 1-6 utilize cyclohexanol-water two-phase interface reaction preparation α-Fe2O3Nano particle
Application, it is characterised in that: by gained α-Fe2O3Lithium battery is made as negative electrode material in nano particle, the specific steps are as follows:
(1) by α-Fe2O3Nano particle and acetylene black, sodium carboxymethylcellulose are mixed according to the ratio that weight ratio is 70:20:10,
After deionized water is added thereto, 5~10h is fully ground or stirred；The mixture of paste is uniformly coated on copper foil, and
It places it in dry at 100 ± 20 DEG C；Tabletting is carried out to the copper foil for being coated with said mixture, then cuts into electrode slice；
(2) using electrode slice as cathode, fastening lithium ionic cell is assembled into using conventional method in an argon atmosphere, is then taken out
Carry out the test of constant current charge-discharge capacity and cycle performance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811316350.3A CN109437320A (en) | 2018-11-07 | 2018-11-07 | It is a kind of to utilize cyclohexanol-water two-phase interface reaction preparation α-Fe2O3The method and purposes of nano particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811316350.3A CN109437320A (en) | 2018-11-07 | 2018-11-07 | It is a kind of to utilize cyclohexanol-water two-phase interface reaction preparation α-Fe2O3The method and purposes of nano particle |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109437320A true CN109437320A (en) | 2019-03-08 |
Family
ID=65551717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811316350.3A Pending CN109437320A (en) | 2018-11-07 | 2018-11-07 | It is a kind of to utilize cyclohexanol-water two-phase interface reaction preparation α-Fe2O3The method and purposes of nano particle |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109437320A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113149081A (en) * | 2021-04-30 | 2021-07-23 | 湘潭大学 | Amorphous film coated alpha-Fe2O3Preparation method and application of nano spherical material |
| CN113201766A (en) * | 2021-05-06 | 2021-08-03 | 云南大学 | Preparation method of hematite photoanode |
-
2018
- 2018-11-07 CN CN201811316350.3A patent/CN109437320A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| XUN-LIANG CHENG ET AL.: ""Cauliflower-likeα-Fe2O3 microstructures: Toluene–water interfaceassisted synthesis, characterization, and applications in wastewater treatment and visible-light photocatalysis"", 《CHEMICAL ENGINEERING JOURNAL》 * |
| 华丽等: ""锂电池负极α-Fe2O3纳米粒子制备及电化学性能研究"", 《湖北第二师范学院学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113149081A (en) * | 2021-04-30 | 2021-07-23 | 湘潭大学 | Amorphous film coated alpha-Fe2O3Preparation method and application of nano spherical material |
| CN113149081B (en) * | 2021-04-30 | 2022-04-29 | 湘潭大学 | Amorphous film coated alpha-Fe2O3Preparation method and application of nano spherical material |
| CN113201766A (en) * | 2021-05-06 | 2021-08-03 | 云南大学 | Preparation method of hematite photoanode |
| CN113201766B (en) * | 2021-05-06 | 2022-03-29 | 云南大学 | Preparation method of hematite photoanode |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111293300B (en) | Zinc-cobalt sulfide/carbon nano anode material and preparation method thereof | |
| CN105789584B (en) | A kind of cobaltous selenide/carbon sodium-ion battery composite negative pole material and the preparation method and application thereof | |
| CN105845889B (en) | A kind of NiCo2O4Composite material and preparation method and its application on lithium ion battery | |
| CN105552331B (en) | Iron cobalt/cobalt oxide/graphene composite material and its preparation method and application | |
| CN106252628B (en) | A kind of preparation method of manganese oxide/graphene nanocomposite material, negative electrode of lithium ion battery, lithium ion battery | |
| CN101891181B (en) | Preparation method of pure-phase high-crystallinity lithium iron phosphate | |
| CN107611365B (en) | Graphene and ferroferric oxide double-coated nano-silicon composite material, preparation method thereof and application thereof in lithium ion battery | |
| CN113206228A (en) | Zn-Mn bimetal lithium ion battery cathode material and preparation method thereof | |
| CN108281625A (en) | A kind of nanometer of compound nucleocapsid of stannic disulfide/carbosphere and preparation method thereof | |
| CN102838102B (en) | Preparation method of lithium iron phosphate monocrystalline nanorods | |
| CN111933899B (en) | Composite oxide electrode material and preparation method thereof | |
| CN109768260A (en) | A kind of two cobalts of phosphatization/carbon composite and its preparation method and application | |
| CN108232187B (en) | High-dispersion hexagonal nanosheet structure nickel-cobalt-manganese ternary cathode material and preparation method thereof | |
| CN104183827B (en) | A kind of lithium iron phosphate nano rod and preparation method thereof | |
| CN109437320A (en) | It is a kind of to utilize cyclohexanol-water two-phase interface reaction preparation α-Fe2O3The method and purposes of nano particle | |
| CN111342008A (en) | Potassium fluoride doped lithium-rich manganese-based material and preparation method and application thereof | |
| CN108467066B (en) | ZnMn with granular porous micro-nano structure2O4Lithium ion battery cathode material | |
| CN103730664A (en) | Positive electrode material of lithium sulfur battery and preparation method and application of material | |
| CN107317019B (en) | Ferrous carbonate/graphene composite material for sodium ion battery cathode and preparation method and application thereof | |
| CN107445210B (en) | High-capacity iron-based lithium ion battery anode material α -LiFeO2Preparation method of (1) | |
| CN110931780B (en) | ZnFe for lithium ion battery cathode material2O4Preparation method of nanocube | |
| CN113651359A (en) | Preparation method and application of antimony sulfide nanorod | |
| CN102556998B (en) | Preparation method of lithium iron phosphate material | |
| CN108134076B (en) | Preparation method and application of spinel lithium manganate | |
| CN105958034A (en) | Method for preparing silicon oxide coated spinel lithium-rich lithium manganate material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190308 |