CN104852024A - Iron trioxide monocrystal nanotube/graphene composite electrode material and preparation method thereof - Google Patents

Iron trioxide monocrystal nanotube/graphene composite electrode material and preparation method thereof Download PDF

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CN104852024A
CN104852024A CN201510159883.5A CN201510159883A CN104852024A CN 104852024 A CN104852024 A CN 104852024A CN 201510159883 A CN201510159883 A CN 201510159883A CN 104852024 A CN104852024 A CN 104852024A
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graphene
nanometer monocrystalline
pipe
electrode material
iron trioxide
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周忠福
王英国
王敬峰
鲁雄刚
俞健舒
王会利
王清露
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University of Shanghai for Science and Technology
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/366Composites as layered products
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M2004/021Physical characteristics, e.g. porosity, surface area
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention relates to an iron trioxide monocrystal nanotube/graphene composite electrode material and a preparation method thereof. The composite electrode material of the invention is formed by coating an iron trioxide monocrystal nanotube with graphene via Van der Waals' force, wherein the mass ratio of the graphene and ferric oxide is 1:(1 to 10); the iron trioxide monocrystal nanotube is an alpha-Fe2O3 monocrystal nanotube, and the length thereof is 300 to 500 nm, and the outer diameter is 60 to 90 nm while the inside diameter is 10 to 50 nm. The method designed by the invention is simple in synthetic process and low in cost, and can be applied to lithium ion battery cathode materials. The iron trioxide monocrystal nanotube/graphene composite electrode material has excellent stability and electrochemical performance.

Description

Di-iron trioxide nanometer monocrystalline pipe/graphene combination electrode material and preparation method thereof
Technical field
The present invention relates to a kind of di-iron trioxide nanometer monocrystalline pipe/graphene combination electrode material and preparation method thereof.
Technical background
From 2000, Tarascon etc. have reported transition group metallic oxide as since the chemical property of lithium ion battery negative material and reaction mechanism, researcher carries out structure to transition metal oxide and pattern controls, obtain very high specific capacity, the research for high performance lithium ionic cell cathode material opens a very important frontier.But, use the rapid decay of lithium battery on capacity of transition group metallic oxide seriously to hamper it further to apply, the main cause of this decay is caused to be transition group metallic oxide material to the embedding of lithium ion with deviate from volume in process significant change can occur, and conventional adhesive is also easy to expand in the electrolyte of lithium battery, thus cause cracking and the fragmentation of transition group metallic oxide electrode material.In order to overcome this problem, researcher adopts nanostructure transition group metallic oxide/graphene composite material, improves stability and the chemical property of lithium ion battery.
α-Fe 2o 3also known as bloodstone, being extensively present among rock and soil, is the iron ore that people know the earliest.α-Fe 2o 3there are six side's corundum structure, O in single cell configuration 2-exist with hexagonal closs packing spread pattern, and Fe 3+then be arranged in the space of octahedral structure 2/3.α-Fe 2o 3have the characteristic of II type semiconductor, energy gap is 2.2 eV.α-Fe 2o 3specific capacity is 1005 mAh/g, and has the advantages such as environmental friendliness, Heat stability is good and corrosion resistance are strong, is proved to be a kind of promising electrode material of lithium battery.
Graphene be a kind of by carbon atom with sp 2hybridized orbit composition hexangle type is the two-dimensional material of honeycomb lattice, and it has special monoatomic layer structure and novel physical property: thermal conductivity about 5000 J/ (mKs), carrier mobility reach 2 × 105 cm 2/ (Vs), specific area calculated value are 2630 m 2/ g, Young's modulus about 1100 GPa and fracture strength about 125 GPa.Due to these excellent specific properties of Graphene, in lithium ion battery electrode material field, researcher it can be used as α-Fe 2o 3performance enhancement phase, with α-Fe 2o 3compound, effectively alleviates the change in volume in charge and discharge process, improves stability and the chemical property of lithium ion battery.
Authorization Notice No. is the preparation method that the Chinese patent literature of CN 103367720 A discloses a kind of Graphene and porous oxidation iron composite material.The principle of this invention is that react with graphene oxide, first the presoma of obtained Graphene and porous ferric oxide, carries out calcining obtained Graphene and porous oxidation iron composite material subsequently under air or inert gas with iron content inorganic salts for source of iron.Authorization Notice No. is that the Chinese patent literature of CN 103078108 A discloses a kind of graphene-supported rhombohedron ferric oxide composite material and hydrothermal synthesis method thereof.A kind of graphene-supported rhombohedron ferric oxide composite material is prepared in this invention, it is typically characterized as using Graphene as matrix skeleton, rhombohedron iron oxide is at graphene sheet layer two sides homoepitaxial, the particle size of rhombohedron iron oxide is 50 ~ 150nm, and each face is all the parallelogram of rule.Optimized production process, prepare morphology controllable, the composite material of size uniformity become researcher be concerned about problem.But α-Fe2O3 as during lithium cell cathode material in the embedding of lithium ion with deviate from volume in process significant change can occur, thus cause cracking and the fragmentation of electrode material.
Summary of the invention
An object of the present invention is to overcome α-Fe 2o 3as lithium cell cathode material Problems existing, provide a kind of di-iron trioxide nanometer monocrystalline pipe/graphene combination electrode material.
Two of object of the present invention is the preparation method providing this combination electrode material, prepares that a kind of novel pattern is unique, synthesis technique simple and the lithium ion battery negative material of stable electrochemical property.
For achieving the above object, the present invention adopts following technical scheme:
A kind of di-iron trioxide nanometer monocrystalline pipe/graphene combination electrode material, it is characterized in that this combination electrode material is that Graphene is coated on di-iron trioxide nanometer monocrystalline pipe by Van der Waals force and is formed, wherein the mass ratio of Graphene and iron oxide is 1:(1 ~ 10); Described di-iron trioxide nanometer monocrystalline pipe is α-Fe 2o 3nanometer monocrystalline pipe, its length is 300 ~ 500 nm, and external diameter is 60 ~ 90 nm, and internal diameter is 10 ~ 50 nm.
Prepare a method for above-mentioned di-iron trioxide nanometer monocrystalline pipe/graphene combination electrode material, it is characterized in that the concrete steps of the method are: by Graphene and α-Fe 2o 31:(1 ~ 10 pressed by nanometer monocrystalline pipe) mass ratio in deionized water dispersed, ultrasonic disperse 15 ~ 30 minutes, then mixes scattered solution, stir 5 ~ 7 days, leave standstill, outwell supernatant liquor, drying, finally obtains di-iron trioxide nanometer monocrystalline pipe/graphene combination electrode material.
Above-mentioned α-Fe 2o 3the preparation method of nanometer monocrystalline pipe is: the ammonium dihydrogen phosphate mixing of to be the liquor ferri trichloridi of 0.5 mol/L and concentration by concentration be 0.02mol/L; In mixed solution, add ionized water, rapid stirring, make it to form homogeneous mixed solution; Crystallization 45 ~ 52 h at 200 ~ 240 DEG C; Product, through centrifugation, repeatedly washs with ethanol and deionized water; Afterproduct will be washed dry, obtain α-Fe 2o 3nanometer monocrystalline pipe; The volume ratio of described liquor ferri trichloridi, ammonium dihydrogen phosphate and deionized water is 10:9:(225 ~ 235).
This composite material is the α-Fe of graphene coated 2o 3nanometer monocrystalline tube material, wherein α-Fe 2o 3the tubular structure that nanometer monocrystalline pipe is special, the embedding being applicable to lithium ion is deviate from, and has larger specific area.This kind of composite material not only can keep Graphene and α-Fe 2o 3primary characteristic, also can produce new cooperative effect.When it uses as lithium cell cathode material, can bulk effect be reduced, significantly improve electrochemical stability.
Accompanying drawing explanation
Fig. 1 is α-Fe 2o 3the XRD spectra of nanometer monocrystalline pipe.
Fig. 2 is α-Fe 2o 3the SEM figure of nanometer monocrystalline pipe.
Fig. 3 is α-Fe 2o 3the SEM figure of nanometer monocrystalline pipe/graphene composite material.
Fig. 4 is α-Fe 2o 3the TEM figure of nanometer monocrystalline pipe.
Fig. 5 is α-Fe 2o 3the electron diffraction diagram of nanometer monocrystalline pipe.
Fig. 6 is α-Fe 2o 3the TEM figure of nanometer monocrystalline pipe/graphene composite material.
Fig. 7 is α-Fe 2o 3the isothermal adsorption of nanometer monocrystalline pipe/graphene composite material and desorption curve.
Fig. 8 is α-Fe 2o 3nanometer monocrystalline pipe/graphene composite material is as the cycle performance figure of negative pole.
Embodiment
The Graphene that the present invention is used and α-Fe 2o 3the preparation method of nanometer monocrystalline pipe please participate in following list of references:
[1]W. S. Hummers, R. E. Offeman. J. Am. Chem. Soc. 1958, 80: 1339-1340.
[2]Chun Jiang Jia, Ling Dong Sun, Zheng Guang Yan, Li Ping You, Feng Luo, Xiao Dong Han, Yu Cheng Pang, Ze Zhang, and Chun Hua Yan. Angew. Chem. Int. Ed. 2005, 44, 4328 –4333.
Embodiment 1:
1) preparation of Graphene
Under the condition that ice bath cools and stirs, toward the dense H of 69 mL 2sO 4in add 1.5 g NaNO 3(grinding), treats NaNO 3be dissolved in H completely 2sO 4in after, 3.0 g graphite are added wherein while stirring.Then 9.0 g KMnO are slowly added 4, add speed and strictly control, to ensure that temperature is lower than 20 DEG C, then removes ice bath, use water-bath and maintain the temperature at about 35 DEG C, being incubated 2 h.137 mL deionized waters are slowly added under stirring, be rapidly heated 98 DEG C, 15 minutes are kept afterwards with 98 DEG C of water-baths, then 420 mL are diluted to further with 60 DEG C of deionized waters, then add remaining potassium permanganate and manganese dioxide in 30% hydrogen peroxide 11 mL reduction system, obtain glassy yellow system.Filter while hot, then wash once with the hydrochloric acid solution that volume ratio is 1:10, distilled water washs three times.45 DEG C of dryings, obtain graphite oxide in an oven.By freshly prepd graphite oxide grind into powder, to ensure abundant expanded by heating, be progressively warming up to 200 DEG C, load in tube furnace, heating mouth of pipe place sealing (using glycerine oil sealing), thermocouple with contact bottom heating tube to ensure that thermometric is accurate.After thermal expansion terminates, obtain Graphene.
2) α-Fe 2o 3the preparation of nanometer monocrystalline pipe
Use FeCl 36H 2o solid and deionized water configuration concentration are the ferric chloride aqueous solutions of 0.5 mol/L, use NH 4h 2pO 4solid and deionized water configuration concentration are the ammonium dihydrogen phosphate aqueous solution of 0.02 mol/L; Pipette ferric chloride aqueous solutions (16.0 mL) and ammonium dihydrogen phosphate aqueous solution (14.4 mL) in the beaker of 500 mL, then in this beaker, add the deionized water of 369.6 mL, form mixed solution; This mixed solution of rapid stirring 20 ~ 30 minutes, forms homogeneous solution; Uniform solution after stirring is transferred in the band teflon-lined stainless steel autoclave of 100 mL, in air flotation oven, is incubated 48 h at the temperature of 220 DEG C; Centrifugation, repeatedly washs with ethanol and deionized water; By product vacuumize 12 h at the temperature of 80 DEG C, obtain α-Fe 2o 3nanometer monocrystalline pipe.
3) α-Fe 2o 3the preparation of nanometer monocrystalline pipe/graphene composite material
With the α-Fe of electronic balance weighing 1.5 g 2o 3nanometer monocrystalline pipe is dispersed in 250 mL deionized waters, ultrasonic 15 minutes, makes it disperse completely; By the graphene dispersion of electronic balance weighing 0.5 g in 250 mL deionized waters, ultrasonic 15 minutes, it is made to disperse completely.Continue ultrasonic 10 minutes again, stirred at ambient temperature 7 days by after two kinds of solution mixing after ultrasonic, in 60 DEG C of baking ovens, dry 24 h, obtain α-Fe 2o 3nanometer monocrystalline pipe/graphene composite material.
Fig. 1 is α-Fe 2o 3the XRD spectra of nanometer monocrystalline pipe, product is α-Fe 2o 3(bloodstone) (JCPDS:33-6604), six side's corundum structure, space group is R c; Fig. 2 is α-Fe 2o 3the scanning electron microscope (SEM) photograph of nanometer monocrystalline pipe, as can be seen from Figure 2 α-Fe 2o 3for nanotube-shaped, length is 300 ~ 500 nm, and external diameter is 60 ~ 90 nm, and internal diameter is 10 ~ 50 nm; Fig. 3 is α-Fe 2o 3the scanning electron microscope (SEM) photograph of nanometer monocrystalline pipe/graphene composite material, as can be seen from Figure 3 α-Fe 2o 3nanometer monocrystalline pipe is by graphene coated; Fig. 4 is α-Fe 2o 3the transmission electron microscope picture of nanometer monocrystalline pipe, the color of material side wall is deeper than mid portion as can be seen from Figure 4, and testimonial material is tubulose; Fig. 5 is α-Fe 2o 3the electron diffraction diagram of nanometer monocrystalline pipe, electron diffraction spot is the isolated point of dispersion as can be seen from Figure 5, and testimonial material is monocrystal; Fig. 6 is α-Fe 2o 3the transmission electron microscope picture of nanometer monocrystalline pipe/graphene composite material, as seen from Figure 6 α-Fe 2o 3nanometer monocrystalline pipe is covered by Graphene.Fig. 7 is α-Fe 2o 3the isothermal adsorption of nanometer monocrystalline pipe/graphene composite material and desorption curve, as can be seen from the figure this composite material is mesoporous material, and this composite material has larger specific area, is 31.8424 m 2/ g, mesoporous average diameter is 116.9030.Fig. 8 is α-Fe 2o 3nanometer monocrystalline pipe/graphene composite material as the cycle performance figure of lithium ion battery negative, at 0.2 A g -1current density condition under, discharge and recharge 100 times, α-Fe 2o 3nanometer monocrystalline pipe/graphene composite material shows stable cycle performance, and capacity remains on 1000 mAh g -1left and right.
Embodiment 2:
1) preparation method of Graphene is with 1 in embodiment 1) step.
2) α-Fe 2o 3the preparation of nanometer monocrystalline pipe
Use FeCl 36H 2o solid and deionized water configuration concentration are the ferric chloride aqueous solutions of 0.5 mol/L, use NH 4h 2pO 4solid and deionized water configuration concentration are the ammonium dihydrogen phosphate aqueous solution of 0.02 mol/L; Pipette ferric chloride aqueous solutions (10.0 mL) and ammonium dihydrogen phosphate aqueous solution (9.0 mL) in the beaker of 300 mL, then in this beaker, add the deionized water of 235 mL, form mixed solution; This mixed solution of rapid stirring 20 ~ 30 minutes, forms homogeneous solution; Uniform solution after stirring is moved in the band teflon-lined stainless steel autoclave of 100 mL, in air flotation oven, is incubated 50 h at the temperature of 210 DEG C; Centrifugation, repeatedly washs with ethanol and deionized water; By product vacuumize 12 h at the temperature of 80 DEG C, obtain α-Fe 2o 3nanometer monocrystalline pipe.
3) α-Fe 2o 3the preparation of nanometer monocrystalline pipe/graphene composite material
With the α-Fe of electronic balance weighing 1.0 g 2o 3nanometer monocrystalline pipe is dispersed in 250 mL deionized waters, ultrasonic 15 minutes, makes it disperse completely; By the graphene dispersion of electronic balance weighing 0.2 g in 250 mL deionized waters, ultrasonic 15 minutes, it is made to disperse completely.Continue ultrasonic 10 minutes again, stirred at ambient temperature 6 days by after two kinds of solution mixing after ultrasonic, in 60 DEG C of baking ovens, dry 24 h, obtain α-Fe 2o 3nanometer monocrystalline pipe/graphene composite material.
Embodiment 3:
1) preparation method of Graphene is with 1 in embodiment 1) step.
2) α-Fe 2o 3the preparation of nanometer monocrystalline pipe
Use FeCl 36H 2o solid and deionized water configuration concentration are the ferric chloride aqueous solutions of 0.5 mol/L, use NH 4h 2pO 4solid and deionized water configuration concentration are the ammonium dihydrogen phosphate aqueous solution of 0.02 mol/L; Pipette ferric chloride aqueous solutions (5.0 mL) and ammonium dihydrogen phosphate aqueous solution (4.5 mL) in the beaker of 200 mL, then in this beaker, add the deionized water of 113 mL, form mixed solution; This mixed solution of rapid stirring 20 ~ 30 minutes, forms homogeneous solution; Uniform solution after stirring is moved in the band teflon-lined stainless steel autoclave of 100 mL, in air flotation oven, is incubated 46 h at the temperature of 230 DEG C; Centrifugation, repeatedly washs with ethanol and deionized water; By product vacuumize 12 h at the temperature of 80 DEG C, obtain α-Fe 2o 3nanometer monocrystalline pipe.
3) α-Fe 2o 3the preparation of nanometer monocrystalline pipe/graphene composite material
With the α-Fe of electronic balance weighing 1.0 g 2o 3nanometer monocrystalline pipe is dispersed in 250 mL deionized waters, ultrasonic 15 minutes, makes it disperse completely; By the graphene dispersion of electronic balance weighing 0.1 g in 250 mL deionized waters, ultrasonic 15 minutes, it is made to disperse completely.Continue ultrasonic 10 minutes again, stirred at ambient temperature 5 days by after two kinds of solution mixing after ultrasonic, in 60 DEG C of baking ovens, dry 24 h, obtain α-Fe 2o 3nanometer monocrystalline pipe/graphene composite material.

Claims (3)

1. di-iron trioxide nanometer monocrystalline pipe/graphene combination electrode material, it is characterized in that this combination electrode material is that Graphene is coated on di-iron trioxide nanometer monocrystalline pipe by Van der Waals force and is formed, wherein the mass ratio of Graphene and iron oxide is 1:(1 ~ 10); Described di-iron trioxide nanometer monocrystalline pipe is α-Fe 2o 3nanometer monocrystalline pipe, its length is 300 ~ 500 nm, and external diameter is 60 ~ 90 nm, and internal diameter is 10 ~ 50 nm.
2. prepare a method for di-iron trioxide nanometer monocrystalline pipe/graphene combination electrode material according to claim 1, it is characterized in that the concrete steps of the method are: by Graphene and α-Fe 2o 31:(1 ~ 10 pressed by nanometer monocrystalline pipe) mass ratio in deionized water dispersed, ultrasonic disperse 15 ~ 30 minutes, then mixes scattered solution, stir 5 ~ 7 days, leave standstill, outwell supernatant liquor, drying, finally obtains di-iron trioxide nanometer monocrystalline pipe/graphene combination electrode material.
3. method according to claim 2, is characterized in that described α-Fe 2o 3the preparation method of nanometer monocrystalline pipe is: the ammonium dihydrogen phosphate mixing of to be the liquor ferri trichloridi of 0.5 mol/L and concentration by concentration be 0.02mol/L; In mixed solution, add deionized water, rapid stirring, make it to form homogeneous mixed solution; Crystallization 45 ~ 52 h at 200 ~ 240 DEG C; Product, through centrifugation, repeatedly washs with ethanol and deionized water; Afterproduct will be washed dry, obtain α-Fe 2o 3nanometer monocrystalline pipe; The volume ratio of described liquor ferri trichloridi, ammonium dihydrogen phosphate and deionized water is 10:9:(225 ~ 235).
CN201510159883.5A 2015-04-07 2015-04-07 Iron trioxide monocrystal nanotube/graphene composite electrode material and preparation method thereof Pending CN104852024A (en)

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CN108199014A (en) * 2017-12-07 2018-06-22 银隆新能源股份有限公司 A kind of porous nitrogen-doped carbon/Fe2O3/ grapheme foam flexible composite, preparation method and applications
CN108390046A (en) * 2018-03-16 2018-08-10 福州大学 A kind of preparation method of rodlike α-di-iron trioxide/GN lithium cell negative pole materials
CN108807882A (en) * 2018-05-24 2018-11-13 江西师范大学 A kind of Fe with porous octahedral structure2O3/Fe3O4The preparation method of@C/G composite materials
WO2019243614A1 (en) * 2018-06-21 2019-12-26 Cambridge Enterprise Limited Electrode active materials and method for their manufacture
CN114094075A (en) * 2021-11-15 2022-02-25 江苏科技大学 Iron selenide-iron oxide nanotube/graphene aerogel composite anode material and preparation method and application thereof
CN114335496A (en) * 2021-12-29 2022-04-12 上海纳米技术及应用国家工程研究中心有限公司 Preparation of iron oxide single crystal nanotube and nitrogen-doped graphene axial composite nanomaterial, product and application
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CN106199448A (en) * 2016-07-22 2016-12-07 北京农业信息技术研究中心 Farmland wireless sensor network node performance of lithium ion battery method of testing
CN106199448B (en) * 2016-07-22 2019-02-22 北京农业信息技术研究中心 Farmland wireless sensor network node performance of lithium ion battery test method
CN108199014A (en) * 2017-12-07 2018-06-22 银隆新能源股份有限公司 A kind of porous nitrogen-doped carbon/Fe2O3/ grapheme foam flexible composite, preparation method and applications
CN108390046A (en) * 2018-03-16 2018-08-10 福州大学 A kind of preparation method of rodlike α-di-iron trioxide/GN lithium cell negative pole materials
CN108390046B (en) * 2018-03-16 2020-06-12 福州大学 Preparation method of rod-shaped α -ferric oxide/GN lithium battery negative electrode material
CN108807882A (en) * 2018-05-24 2018-11-13 江西师范大学 A kind of Fe with porous octahedral structure2O3/Fe3O4The preparation method of@C/G composite materials
WO2019243614A1 (en) * 2018-06-21 2019-12-26 Cambridge Enterprise Limited Electrode active materials and method for their manufacture
CN114094075A (en) * 2021-11-15 2022-02-25 江苏科技大学 Iron selenide-iron oxide nanotube/graphene aerogel composite anode material and preparation method and application thereof
CN114094075B (en) * 2021-11-15 2023-05-26 江苏科技大学 Iron selenide-iron oxide nanotube/graphene aerogel composite anode material and preparation method and application thereof
CN114335496A (en) * 2021-12-29 2022-04-12 上海纳米技术及应用国家工程研究中心有限公司 Preparation of iron oxide single crystal nanotube and nitrogen-doped graphene axial composite nanomaterial, product and application
CN115386955A (en) * 2022-08-31 2022-11-25 上海旦元新材料科技有限公司 Mesoporous ferric oxide single crystal and hydrothermal preparation method thereof
CN115386955B (en) * 2022-08-31 2023-09-05 上海旦元新材料科技有限公司 Mesoporous ferric oxide monocrystal and hydrothermal preparation method thereof

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