CN104617290A - Homogenous precipitation method for preparing Fe2O3 nanobelt and Fe2O3 nanobelt-carbon composite material - Google Patents
Homogenous precipitation method for preparing Fe2O3 nanobelt and Fe2O3 nanobelt-carbon composite material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 78
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 72
- 239000002127 nanobelt Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000001556 precipitation Methods 0.000 title claims abstract description 37
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title abstract 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000000463 material Substances 0.000 claims abstract description 35
- 238000002360 preparation method Methods 0.000 claims abstract description 24
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- 239000008139 complexing agent Substances 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 8
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 123
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002041 carbon nanotube Substances 0.000 claims description 17
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- 235000006408 oxalic acid Nutrition 0.000 claims description 11
- -1 iron ion Chemical class 0.000 claims description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 9
- 239000004966 Carbon aerogel Substances 0.000 claims description 8
- 229960005070 ascorbic acid Drugs 0.000 claims description 8
- 235000010323 ascorbic acid Nutrition 0.000 claims description 8
- 239000011668 ascorbic acid Substances 0.000 claims description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 229940062993 ferrous oxalate Drugs 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 5
- 229940039790 sodium oxalate Drugs 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-L Oxalate Chemical compound [O-]C(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-L 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- 238000012983 electrochemical energy storage Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 9
- 229910000904 FeC2O4 Inorganic materials 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000002244 precipitate Substances 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 27
- 238000010438 heat treatment Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 10
- 238000005119 centrifugation Methods 0.000 description 8
- 239000012467 final product Substances 0.000 description 8
- 238000000643 oven drying Methods 0.000 description 8
- 229910052573 porcelain Inorganic materials 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000004087 circulation Effects 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000593 microemulsion method Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- AJGPQPPJQDDCDA-UHFFFAOYSA-N azanium;hydron;oxalate Chemical compound N.OC(=O)C(O)=O AJGPQPPJQDDCDA-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011366 tin-based material Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- 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
- H01M4/362—Composites
-
- 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
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Nanotechnology (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
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- Microelectronics & Electronic Packaging (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A homogenous precipitation method for preparing a Fe2O3 nanobelt and a Fe2O3 nanobelt-carbon composite material comprises the following steps: reacting a complexing agent C2O4<2-> with Fe<3+> in a solution to generate a soluble [Fe(C2O4)3]<3+> complex, reducing Fe (III) to Fe (II) by using a reducing agent, and reacting Fe (II) with C2O4<2-> in the above solution to generate a FeC2O4 precipitate or to generate the FeC2O4 precipitate homogenously precipitated on a carbon material in order to obtain FeC2O4 or a FeC2O4/carbon composite material precursor; and carrying out calcining treatment at a certain temperature to prepare the Fe2O3 nanobelt or the Fe2O3 nanobelt/carbon composite material. The Fe2O3 nanobelt/carbon has excellent electrochemical performances as a lithium ion battery negative material. The carbon material can effectively buffer the volume change of Fe2O3 in the charge and discharge process to improve the cycle stability of the composite material, and also can form an effective conductive network in order to facilitate rapid transfer of electrons and improve the rate performance of the composite material. The above preparation method has the advantages of low device requirements, mild preparation conditions, simple process, short period, low cost, and suitableness for large scale production.
Description
Technical field
The invention belongs to new energy materials and electrochemical field, be specifically related to one and prepare Fe
2o
3the homogeneous precipitation method of nanobelt and the composite material with carbon thereof.
Background technology
Lithium ion battery has that operating voltage is high, specific energy is large, memory-less effect, pollution-free, self-discharge rate is low and the advantage such as long service life, is the best secondary cell system of current combination property.Be widely used in the portable consumer electronics fields such as mobile phone, notebook computer, digital camera, and expanded to the field such as electric automobile and energy-storage battery gradually.
Negative material is one of key composition of lithium ion battery, is the key factor determining lithium ion battery whole synthesis performance.Negative material mainly graphitic carbon material in current business-like lithium ion battery, its theoretical specific capacity is 372mAhg
-1, can not meet the demand of height ratio capacity lithium ion battery of new generation, for this reason, one of Novel anode material focus becoming Study on Li-ion batteries of research and development height ratio capacity.In the research of height ratio capacity Novel anode material, silica-base material, tin-based material, transition metal oxide are (as Fe
2o
3, Fe
3o
4, NiO, Co
3o
4) etc. all receive the very big concern of people.Wherein, Fe
2o
3because having height ratio capacity, (theoretical capacity is 1007mAhg
-1), the advantage such as low cost, environmental friendliness and abundant raw materials and be seen as the very potential lithium ion battery negative material of one.But, Fe
2o
3in embedding/de-lithium process, be attended by larger change in volume, the incidental reunion of material and efflorescence, cause the rapid decaying cycle poor stability of capacity; Fe simultaneously
2o
3be semiconductor, conductivity is poor, causes its high rate performance also not ideal.Therefore, how Fe is improved
2o
3cyclical stability and the raising high rate performance of negative material just become the prerequisite and key that realize its practical application.For solving the problem, researcher is to Fe
2o
3carry out a large amount of modification work.Modified measures numerous at present can be divided into design preparation to have the Fe of nanostructure
2o
3with structure Fe
2o
3the large class of composite material two.Design preparation has the Fe of nanostructure
2o
3can reduce the transfer distance of electronics or ion, improve electrochemical reaction active, nanostructure effectively can alleviate its bulk effect in charge and discharge process simultaneously, and then improves its chemical property.Build Fe
2o
3composite material is that another kind is commonly used and effective method of modifying, by Fe
2o
3the activity little with good conductivity, bulk effect or inert matter compound, these materials effectively can cushion Fe on the one hand
2o
3change in volume in charge and discharge process, can provide effective electronics to spread out of passage on the other hand, thus effectively improve the chemical property of material.Build Fe
2o
3-carbon composite is Fe
2o
3the Typical Representative of based composites.
Fe representative in document and patent
2o
3base negative material comprises:
The micro emulsion that Wang etc. are formed in water with glycerine steeps for template, adopts hydro thermal method to prepare the Fe that diameter is about 1 μm
2o
3hollow ball, used as showing good cyclical stability during negative material, with 200mAg
-1current density discharge and recharge, 100 times circulation after its reversible capacity still can remain on 710mAhg
-1, be obviously better than solid Fe
2o
3particle (J.Am.Chem.Soc., 2011,133 (43), 17146-17148).The employing such as Liu hydro thermal method has been prepared diameter and has been about 60-80nm Fe
2o
3nanometer rods, under the multiplying power of 0.1C during discharge and recharge, its first discharge capacity be 1332mAhg
-1, after 30 circulations, capacity is 763mAhg
-1, far above commercialization micro-meter scale Fe
2o
3112mAhg
-1.（Electrochimica Acta,2009,54(6),1733-1736）。The employing such as Gao micro emulsion method has synthesized the Fe that width is about 20-40nm
2o
3nanobelt, used as showing during lithium ion battery negative material, higher embedding, de-lithium is active, and it is put first, charging capacity is respectively 1068 and 701mAhg
-1, but cyclical stability is poor.（CrystEngComm,2011,13(20),6045-6049）。Yu etc. adopt the method for chemical vapour deposition (CVD) to adopt AAO to be the CNTs that Template preparation internal diameter is about 55nm, then adopt the method for dipping-calcining by Fe
2o
3be filled in CNTs, after removing AAO template, prepared Fe
2o
3-CNTs composite material.This composite material is with 35mAg
-1current density charge and discharge cycles 40 times circulation after its reversible capacity be 768mAhg
-1(Chem.Commun, 2010,46 (45), 8576-8578).In patent CN102427129A, Pan Hongge etc. are with business-like Fe
2o
3powder and material with carbon element carry out ball-milling treatment and have prepared ferrous oxide/carbon composite in conjunction with Technology for Heating Processing, have good cyclical stability, but specific capacity are relatively low when this material is used for lithium ion battery negative.In patent CN103227324A, Zhao Hailei etc. adopt sol-gal process to prepare the iron oxide presoma with aerogel structure, prepare iron oxide/carbon composite material after further heat treatment, when this material is used as negative pole, there is higher initial reversible capacity, but cyclical stability has been undesirable.
In sum, for the research of iron oxide material as lithium ion battery negative material in document and patent report, adopt template, hydro thermal method, micro emulsion method and sol-gel process to prepare iron oxide based negative material more.The most technical process of these methods is comparatively complicated, and cost is high, and homogeneity of product is poor.
The present invention is reduced to ferrous ion with ferric ion in simple reduction reaction modulation solution first, impel homogeneous precipitation to react to occur, oxalic ferrous precipitation or make ferrous oxalate precipitate uniform deposition on carbonaceous material, prepare ferrous oxalate or ferrous oxalate/carbon composite; Fe has been obtained again after uniform temperature calcination processing
2o
3nanobelt or Fe
2o
3nanobelt/carbon composite.The method technical process is simple, and preparation condition is gentle, and cost is low, reproducible and be convenient to large-scale production.The material of synthesis has good microcosmic composite construction, shows excellent chemical property when using it for lithium ion battery negative material.
Summary of the invention
The object of the invention is for current Fe
2o
3the shortcoming of negative material cycle performance difference and high rate performance difference, provides one and prepares Fe
2o
3the homogeneous precipitation method of nanobelt and the composite material with carbon thereof.
The invention provides one and prepare Fe
2o
3the homogeneous precipitation method of nanobelt and the composite material with carbon thereof, utilizes complexing agent C
2o
4 2-with the Fe in solution
3+reaction generates solvable [Fe (C
2o
4)
3]
3+complex compound, recycling reducing agent reduction Fe(III) be Fe(II), Fe(II) with solution in C
2o
4 2-reaction generates FeC
2o
4precipitation or uniform deposition FeC on the carbonaceous material
2o
4precipitation, obtains FeC
2o
4or FeC
2o
4/ carbon composite presoma; Fe has been obtained again after uniform temperature calcination processing
2o
3nanobelt or Fe
2o
3nanobelt/carbon composite; Concrete steps are as follows:
1) dispersed carbon material: take required quality carbonaceous material and be dispersed in solvent and form suspension-turbid liquid;
Wherein, the dispersing mode of carbonaceous material is one or both in ultrasonic disperse, dispersed with stirring;
2) reaction solution is prepared: trivalent inorganic molysite and complexing agent are dissolved in solvent, or are dissolved in the suspension-turbid liquid containing material with carbon element; Again reducing agent is added wherein, and continuous stirring reaction, be precipitated product;
3) by step 2) the centrifugal or isolated by filtration of the precipitated product that obtains, washing, and in 40 ~ 85 DEG C of vacuumizes, obtain FeC
2o
4or FeC
2o
4/ carbon composite;
4) FeC step 3) obtained
2o
4or FeC
2o
4/ carbon composite calcines 0.5 ~ 24h in protective atmosphere at 250 ~ 900 DEG C, obtained Fe
2o
3nanobelt or Fe
2o
3nanobelt/carbon composite.
Preparation Fe provided by the invention
2o
3the homogeneous precipitation method of nanobelt and the composite material with carbon thereof, the carbonaceous material described in step 1) is one or more in carbon nano-tube, carbon aerogels, mesoporous carbon, expanded graphite, Graphene, conductive carbon black, Cabot Super-conductive carbon BP2000, active carbon; The conductivity of carbonaceous material is more than or equal to 0.1Scm
-1, specific area is more than or equal to 50m
2g
-1, pore volume is more than or equal to 0.2cm
3g
-1.
Preparation Fe provided by the invention
2o
3the homogeneous precipitation method of nanobelt and the composite material with carbon thereof, the ultrasonic disperse described in step 1) is for adopting supersonic wave cleaning machine or cell disruptor ultrasonic disperse, and ultrasonic power is 25 ~ 1000W, and ultrasonic time is 0.1 ~ 3h; Described dispersed with stirring is magnetic agitation or mechanical agitation, and the speed of stirring is 400 ~ 1000rmp, and mixing time is 0.1 ~ 3h.
Preparation Fe provided by the invention
2o
3the homogeneous precipitation method of nanobelt and the composite material with carbon thereof, step 1) and step 2) described in solvent be deionized water, methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, ethylene glycol one or more.
Preparation Fe provided by the invention
2o
3the homogeneous precipitation method of nanobelt and the composite material with carbon thereof, step 2) described in trivalent inorganic molysite be ferric nitrate, iron chloride, ferric sulfate one or more; Wherein, the mol ratio of iron ion and carbonaceous material is 1:1.5 ~ 100.
Preparation Fe provided by the invention
2o
3the homogeneous precipitation method of nanobelt and the composite material with carbon thereof, step 2) described in complexing agent be potassium oxalate, sodium oxalate, lithium oxalate, ammonium oxalate, oxalic acid one or more; Wherein, the mol ratio of the iron ion in trivalent inorganic molysite and complexing agent oxalate ion is 1:0.5 ~ 6.
Preparation Fe provided by the invention
2o
3the homogeneous precipitation method of nanobelt and the composite material with carbon thereof, step 2) described in reducing agent be one or more in sodium borohydride, potassium borohydride, hydrazine hydrate, inferior sodium phosphate, ascorbic acid; Wherein, the iron ion in trivalent inorganic molysite and the mol ratio of reducing agent are 1:0.5 ~ 3.
Preparation Fe provided by the invention
2o
3the homogeneous precipitation method of nanobelt and the composite material with carbon thereof, step 2) in add reducing agent after, mixing speed is 400 ~ 1000rmp, and reaction temperature is 0 ~ 90 DEG C, and the reaction time is 0.1 ~ 3h.
Preparation Fe provided by the invention
2o
3the homogeneous precipitation method of nanobelt and the composite material with carbon thereof, the calcining heat described in step 4) is 300 ~ 700 DEG C.
Preparation Fe provided by the invention
2o
3the homogeneous precipitation method of nanobelt and the composite material with carbon thereof, the protective atmosphere described in step 4) be air, oxygen, argon gas, nitrogen one or more.
Preparation Fe provided by the invention
2o
3the homogeneous precipitation method of nanobelt and the composite material with carbon thereof, the Fe of described preparation
2o
3nanobelt and with the Fe in the composite material of carbon
2o
3mass fraction is 5% ~ 98%, is preferably 25% ~ 90%.
Fe prepared by the method for the invention
2o
3nanobelt and be applied to the negative material in the electrochemical energy storage device of lithium ion battery or asymmetric type supercapacitor with the composite material of carbon.
The beneficial effect that the present invention has is:
First, complexing agent C
2o
4 2-with the reactant Fe in solution
3+there is complex reaction, when adding reducing agent in phase solution, Fe(III) be reduced into Fe(II), and C that is rapid and surrounding
2o
4 2-there is combination reaction, generate FeC
2o
4precipitation.Due to Fe
2+ion from the inner output of solution, the phenomenon that can effectively avoid local concentration excessive, therefore, Fe
2+c in ion and solution
2o
4 2-reaction generates FeC equably
2o
4precipitation, or FeC
2o
4precipitation uniform deposition on the carbonaceous material, has synthesized FeC
2o
4/ carbon composite.Secondly, C
2o
4 2-also play the effect of directed agents, promote the generation of nano strip material.FeC prepared by the present invention
2o
4or FeC
2o
4in/carbon composite, FeC2O4 is all in nanobelt shape structure, has obtained Fe after calcination processing
2o
3or Fe
2o
3/ carbon composite.At Fe
2o
3and Fe
2o
3fe in/carbon composite
2o
3maintain the nanobelt shape structure of its presoma ferrous oxalate, and be uniformly distributed in on material with carbon element, define good composite construction.Three, Fe
2o
3when nanobelt/carbon is used as lithium ion battery negative material, show excellent chemical property.On the one hand, with micron-sized commodity Fe
2o
3compare, Fe
2o
3nanobelt has higher electro-chemical activity and has excellent structural stability; On the other hand, in the composite, carbonaceous material effectively can cushion Fe
2o
3change in volume in charge and discharge process, improves the conductivity of material simultaneously, thus further increases cycle performance and the high rate performance of material.Finally, production equipment needed for preparation method of the present invention is simple, and preparation condition is gentle, and technique is simple, and the cycle is short, and cost is low, is applicable to large-scale production.
Accompanying drawing explanation
Fig. 1 is the Fe that embodiment 2 obtains
2o
3nanobelt/carbon X-ray diffractogram;
Fig. 2 is the Fe that embodiment 3 obtains
2o
3the TEM figure of nanobelt/carbon;
Fig. 3 is the Fe that embodiment 4 obtains
2o
3the charging and discharging curve of nanobelt/carbon;
Fig. 4 is the Fe that embodiment 6 obtains
2o
3the cycle performance curve of nanobelt/carbon;
Fig. 5 is the Fe that embodiment 8 obtains
2o
3the high rate performance curve of nanobelt/carbon.
Embodiment
The following examples will be further described the present invention, but not thereby limiting the invention.
Embodiment 1
First, 0.5g FeCl is got respectively
36H
2o and 0.134g sodium oxalate is dissolved in 200mL deionized water successively.Getting 0.20g ascorbic acid is dissolved in about 5mL deionized water, is then dropwise added drop-wise to by aqueous ascorbic acid in the above-mentioned solution stirred, and dropwises rear continuation stirring reaction and is about 3h.Centrifugation, utilizes deionized water that product is washed three times, is then placed in 85 DEG C of obtained yellow product of vacuum drying oven drying.Obtained yellow product is placed in porcelain boat, 700 DEG C of heat treatment 3h in air atmosphere, obtained final product Fe
2o
3nanobelt.
Embodiment 2
First, get 25.0mg carbon nano-tube (CNTs), joined in 200mL deionized water, ultrasonic agitation 3h.Then, 6.06g Fe (NO is got respectively
3)
39H
2o and 6.6g ammonium oxalate joins in the dispersion liquid of above-mentioned CNTs successively, stirs and makes it dissolve.Getting 3.52g inferior sodium phosphate is dissolved in about 10mL deionized water, then ortho phosphorous acid sodium water solution is dropwise added drop-wise to the Fe (NO stirred
3)
3, oxalic acid ammonia and CNTs mixed liquor in, dropwise rear continuation stirring reaction and be about 0.5h.Centrifugation, utilizes ethanol that product is washed three times, is then placed in 85 DEG C of obtained black product of vacuum drying oven drying.Obtained black product is placed in porcelain boat, 250 DEG C of heat treatment 3h in air atmosphere, obtained final product Fe
2o
3-CNTs composite material.
Fig. 1 is the Fe prepared
2o
3the XRD figure of/carbon, as we can see from the figure, the diffraction maximum of sample in 2 θ=26.2 ° corresponds to the diffraction maximum of CNTs in crystal face (002), and has occurred significantly corresponding to α-Fe
2o
3the diffraction maximum of phase, illustrates that the sample prepared is Fe
2o
3with CNTs composite material.
Embodiment 3
First, get 100mg CNTs, joined in 200mL deionized water, and utilize ultrasonic wave added dispersed with stirring 0.5h.Then, 0.5g FeCl is got respectively
36H
2o and 0.134g sodium oxalate joins in the dispersion liquid of above-mentioned CNTs successively, stirs and makes it dissolve.Get 0.20g ascorbic acid to be dissolved in about 5mL deionized water, then aqueous ascorbic acid is dropwise added drop-wise to the FeCl stirred
3, sodium oxalate and CNTs mixed liquor in, dropwise rear continuation stirring reaction and be about 3h.Centrifugation, utilizes ethanol that product is washed three times, is then placed in 85 DEG C of obtained black product of vacuum drying oven drying.Obtained black product is placed in porcelain boat, 300 DEG C of heat treatment 0.5h in air atmosphere, after under argon gas or nitrogen atmosphere in 700 DEG C of heat treatment 3h, obtained final product Fe
2o
3-CNTs composite material.
Fig. 2 is the Fe prepared
2o
3the TEM figure of nanobelt/carbon, as we can see from the figure, Fe
2o
3become nanobelt shape structure, and be laid on CNTs, define good microcosmic composite construction.
Embodiment 4
First, get 75mg Graphene (GO), joined in 200mL deionized water and ethanol mixing, and utilize ultrasonic wave added dispersed with stirring 2h.Then, 0.80g Fe is got respectively
2(SO
4)
39H
2o and 0.70g oxalic acid joins in the dispersion liquid of above-mentioned GO successively, stirs and makes it dissolve.Get 0.20g sodium borohydride to be dissolved in about 5mL deionized water, then sodium borohydride aqueous solution is dropwise added drop-wise to the Fe stirred
2(SO
4)
3, oxalic acid and GO mixed liquor in, dropwise rear continuation stirring reaction and be about 1h.Centrifugation, utilizes ethanol that product is washed three times, is then placed in 60 DEG C of obtained black product of vacuum drying oven drying.Obtained black product is placed in porcelain boat, 300 DEG C of heat treatment 1h in air atmosphere, obtained final product Fe
2o
3-GO composite material.
By the Fe of preparation
2o
3/ GO composite material is used as lithium ion battery negative material, is mixed to get slurry with acetylene black, PVDF according to the ratio of mass ratio 80:10:10.Evenly being coated on Copper Foil by slurry and obtaining work electrode, is to electrode with lithium sheet, and Celgard2325 polypropylene screen is barrier film, 1MLiPF
6/ EC+DMC (EC:DMC=1:1) is electrolyte, in the glove box being full of argon gas, be assembled into button cell.
Above-mentioned battery is carried out charge-discharge test on Land discharge and recharge instrument.Charging/discharging voltage scope 0.005 ~ 3.0V.With 100mAg
-1constant current charge-discharge, it inverse put, charge specific capacity can be respectively 1347.8 and 1033.9mAh g first
-1.Fig. 3 is prepared Fe
2o
3the charging and discharging curve figure of twice circulation before-GO composite material.
Embodiment 5
First, get 200mg mesoporous carbon, joined in 200mL deionized water and alcohol mixeding liquid, and adopt ultrasonic wave added dispersed with stirring 1h.Then, 52.5mg Fe (NO is got respectively
3)
39H
2o and 55mg oxalic acid joins in the dispersion liquid of above-mentioned mesoporous carbon successively, stirs and makes it dissolve.Get 0.30mL hydrazine hydrate solution and be dropwise added drop-wise to the Fe (NO stirred
3)
3, oxalic acid and mesoporous carbon mixed liquor in, dropwise rear continuation stirring reaction and be about 1h.Centrifugation, utilizes ethanol that product is washed three times, is then placed in 85 DEG C of obtained black product of vacuum drying oven drying.Obtained black product is placed in porcelain boat, 300 DEG C of heat treatment 1h in air atmosphere, obtained final product Fe
2o
3-mesoporous carbon composite material.
Embodiment 6
First, get 50mg carbon aerogels, joined in 200mL deionized water, and utilize ultrasonic wave added dispersed with stirring 3h.Then, 0.60g Fe (NO is got respectively
3)
39H
2o and 0.70g potassium oxalate joins in the dispersion liquid of above-mentioned carbon aerogels successively, stirs and makes it dissolve.Getting 0.40g ascorbic acid is dissolved in about 5mL deionized water, then aqueous ascorbic acid is dropwise added drop-wise to the Fe (NO stirred
3)
3, oxalic acid and carbon aerogels mixed liquor in, dropwise rear continuation stirring reaction and be about 3h.Centrifugation, utilizes ethanol that product is washed three times, is then placed in 85 DEG C of obtained black product of vacuum drying oven drying.Obtained black product is placed in porcelain boat, in 250 heat treatment 3h in air atmosphere, is placed on 500 DEG C of heat treatment 1h, obtained final product Fe
2o
3-carbon aerogel composite material.
By the Fe of preparation
2o
3/ carbon aerogels material is used as lithium ion battery negative material, is mixed to get slurry with acetylene black, PVDF according to the ratio of mass ratio 80:10:10.Evenly being coated on Copper Foil by slurry and obtaining work electrode, is to electrode with lithium sheet, and Celgard2325 polypropylene screen is barrier film, 1MLiPF
6/ EC+DMC (EC:DMC=1:1) is electrolyte, in the glove box being full of argon gas, be assembled into button cell.
Above-mentioned battery is carried out charge-discharge test on Land discharge and recharge instrument.Charging/discharging voltage scope 0.005 ~ 3.0V, current density is 100mAg
-1.Fig. 4 is prepared Fe
2o
3the cycle performance curve chart of-carbon aerogel composite material.
Embodiment 7
First, get 100mg commercialization BP2000, joined in 200mL ethanol, and utilize ultrasonic wave added dispersed with stirring 3h.Then, 0.60g FeCl is got respectively
39H
2o and 0.70g oxalic acid joins in the dispersion liquid of above-mentioned BP2000 successively, stirs and makes it dissolve.Get 0.4mL hydrazine hydrate solution and be dropwise added drop-wise to the FeCl stirred
3, oxalic acid and BP2000 mixed liquor in, dropwise rear continuation stirring reaction and be about 3h.Centrifugation, utilizes ethanol that product is washed three times, is then placed in 60 DEG C of obtained black product of vacuum drying oven drying.Obtained black product is placed in porcelain boat, 400 DEG C of heat treatment 1h in air atmosphere, obtained final product Fe
2o
3-BP2000 composite material.
Embodiment 8
First, get 100mg conductive carbon black, joined in 200mL deionized water and alcohol mixeding liquid, and adopt ultrasonic wave added dispersed with stirring 1h.Then, 0.80g Fe (NO is got respectively
3)
39H
2o and 0.90g oxalic acid joins in the dispersion liquid of above-mentioned mesoporous carbon successively, stirs and makes it dissolve.Get 0.5g potassium borohydride to be dissolved in about 5mL deionized water, and it is dropwise added drop-wise to the Fe (NO stirred
3)
3, oxalic acid and mesoporous carbon mixed liquor in, dropwise rear continuation stirring reaction and be about 1h.Centrifugation, utilizes ethanol that product is washed three times, is then placed in 85 DEG C of obtained black product of vacuum drying oven drying.Obtained black product is placed in porcelain boat, 300 DEG C of heat treatment 1h in air atmosphere, obtained final product Fe
2o
3-carbon composite.
By the Fe of preparation
2o
3/ conductive carbon black composite material is used as lithium ion battery negative material, is mixed to get slurry with acetylene black, PVDF according to the ratio of mass ratio 80:10:10.Evenly being coated on Copper Foil by slurry and obtaining work electrode, is to electrode with lithium sheet, and Celgard2325 polypropylene screen is barrier film, 1MLiPF
6/ EC+DMC (EC:DMC=1:1) is electrolyte, in the glove box being full of argon gas, be assembled into button cell.
Above-mentioned battery is carried out charge-discharge test on Land discharge and recharge instrument.Charging/discharging voltage scope 0.005 ~ 3.0V.Fig. 5 is prepared Fe
2o
3the high rate performance curve chart of-mesoporous carbon composite material.
Claims (13)
1. prepare Fe for one kind
2o
3the homogeneous precipitation method of nanobelt and the composite material with carbon thereof, is characterized in that:
Utilize complexing agent C
2o
4 2-with the Fe in solution
3+reaction generates [Fe (C
2o
4)
3]
3+complex compound, recycling reducing agent reduction Fe(III) be Fe(II), Fe(II) with solution in C
2o
4 2-reaction generates FeC
2o
4precipitation, or generate the FeC deposited equably on the carbonaceous material
2o
4precipitation, obtains ferrous oxalate or ferrous oxalate/carbon composite; Fe has been obtained again after uniform temperature calcination processing
2o
3nanobelt or Fe
2o
3nanobelt/carbon composite; Concrete steps are as follows:
1) dispersed carbon material: take required quality carbonaceous material and be dispersed in solvent and form suspension-turbid liquid;
Wherein, the dispersing mode of carbonaceous material is one or both in ultrasonic disperse, dispersed with stirring;
2) reaction solution is prepared: trivalent inorganic molysite and complexing agent are dissolved in solvent, then are added wherein by reducing agent, and continuous stirring reaction, be precipitated product;
Or trivalent inorganic molysite and complexing agent are dissolved in the suspension-turbid liquid containing material with carbon element, then reducing agent is added wherein, and continuous stirring reaction, be precipitated product;
3) by step 2) the centrifugal or isolated by filtration of the precipitated product that obtains, washing, and in 40 ~ 85 DEG C of vacuumizes, obtain FeC
2o
4or FeC
2o
4/ carbon composite;
4) FeC step 3) obtained
2o
4or FeC
2o
4/ carbon composite calcines 0.5 ~ 24h in protective atmosphere at 250 ~ 900 DEG C, obtained Fe
2o
3nanobelt or Fe
2o
3nanobelt/carbon composite.
2. prepare Fe according to described in claim 1
2o
3the homogeneous precipitation method of nanobelt and the composite material with carbon thereof, is characterized in that: the carbonaceous material described in step 1) is one or more in carbon nano-tube, carbon aerogels, mesoporous carbon, expanded graphite, Graphene, conductive carbon black, Cabot Super-conductive carbon BP2000, active carbon;
The conductivity of carbonaceous material is more than or equal to 0.1Scm
-1, specific area is more than or equal to 50m
2g
-1, pore volume is more than or equal to 0.2cm
3g
-1.
3. prepare Fe according to described in claim 1
2o
3the homogeneous precipitation method of nanobelt and the composite material with carbon thereof, is characterized in that: the ultrasonic disperse described in step 1) is for adopting supersonic wave cleaning machine or cell disruptor ultrasonic disperse, and ultrasonic power is 25 ~ 1000W, and ultrasonic time is 0.1 ~ 3h;
Described dispersed with stirring is magnetic agitation or mechanical agitation, and the speed of stirring is 400 ~ 1000rmp, and mixing time is 0.1 ~ 3h.
4. prepare Fe according to described in claim 1
2o
3the homogeneous precipitation method of nanobelt and the composite material with carbon thereof, is characterized in that: step 1) and step 2) described in solvent be deionized water, methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, ethylene glycol one or more.
5. prepare Fe according to described in claim 1
2o
3the homogeneous precipitation method of nanobelt and the composite material with carbon thereof, is characterized in that: step 2) described in trivalent inorganic molysite be ferric nitrate, iron chloride, ferric sulfate one or more;
Wherein, the mol ratio of iron ion and carbonaceous material is 1:1.5 ~ 100.
6. prepare Fe according to described in claim 1
2o
3the homogeneous precipitation method of nanobelt and the composite material with carbon thereof, is characterized in that: step 2) described in complexing agent be potassium oxalate, sodium oxalate, lithium oxalate, ammonium oxalate, oxalic acid one or more;
Wherein, the mol ratio of the iron ion in trivalent inorganic molysite and complexing agent oxalate ion is 1:0.5 ~ 6.
7. prepare Fe according to described in claim 1
2o
3the homogeneous precipitation method of nanobelt and the composite material with carbon thereof, is characterized in that: step 2) described in reducing agent be one or more in sodium borohydride, potassium borohydride, hydrazine hydrate, inferior sodium phosphate, ascorbic acid;
Wherein, the iron ion in trivalent inorganic molysite and the mol ratio of reducing agent are 1:0.5 ~ 3.
8. prepare Fe according to described in claim 1
2o
3the homogeneous precipitation method of nanobelt and the composite material with carbon thereof, is characterized in that: step 2) in add reducing agent after, mixing speed is 400 ~ 1000rmp, and reaction temperature is 0 ~ 90 DEG C, and the reaction time is 0.1 ~ 3h.
9. prepare Fe according to described in claim 1
2o
3the homogeneous precipitation method of nanobelt and the composite material with carbon thereof, is characterized in that: the calcining heat described in step 4) is 300 ~ 700 DEG C.
10. prepare Fe according to described in claim 1
2o
3the homogeneous precipitation method of nanobelt and the composite material with carbon thereof, is characterized in that: the protective atmosphere described in step 4) be air, oxygen, argon gas, nitrogen one or more.
11. prepare Fe according to described in claim 1
2o
3the homogeneous precipitation method of nanobelt and the composite material with carbon thereof, is characterized in that: the Fe of described preparation
2o
3nanobelt and with the Fe in the composite material of carbon
2o
3mass fraction is 5% ~ 98%.
12. prepare Fe according to described in claim 11
2o
3the homogeneous precipitation method of nanobelt and the composite material with carbon thereof, is characterized in that: the Fe of described preparation
2o
3nanobelt and with the Fe in the composite material of carbon
2o
3mass fraction is 25% ~ 90%.
The Fe that described in 13. claims 1 prepared by method
2o
3nanobelt and be applied to the negative material in the electrochemical energy storage device of lithium ion battery or asymmetric type supercapacitor with the composite material of carbon.
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| CN106025263A (en) * | 2016-05-17 | 2016-10-12 | 安徽师范大学 | Ferric oxide nano material, preparation method of ferric oxide nano material, lithium ion battery negative pole and lithium ion battery |
| CN106025263B (en) * | 2016-05-17 | 2018-10-30 | 安徽师范大学 | A kind of ferric oxide nano-material and preparation method thereof, negative electrode of lithium ion battery and lithium ion battery |
| CN107195891A (en) * | 2017-06-30 | 2017-09-22 | 绍兴文理学院 | A kind of preparation method of lithium battery graphene composite negative pole |
| CN109950457A (en) * | 2017-12-21 | 2019-06-28 | 北京金羽新能科技有限公司 | A kind of water system ion energy storage device |
| CN112973702A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | Catalyst for producing high-carbon olefin from carbon dioxide and hydrogen mixed gas and preparation and application methods thereof |
| CN112973702B (en) * | 2019-12-13 | 2022-05-06 | 中国科学院大连化学物理研究所 | Catalyst for producing high-carbon olefin from carbon dioxide and hydrogen mixed gas and preparation and application methods thereof |
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