CN106058233A - Preparation method of transition metal oxide/graphene nano composite material - Google Patents

Preparation method of transition metal oxide/graphene nano composite material Download PDF

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Publication number
CN106058233A
CN106058233A CN201610670704.9A CN201610670704A CN106058233A CN 106058233 A CN106058233 A CN 106058233A CN 201610670704 A CN201610670704 A CN 201610670704A CN 106058233 A CN106058233 A CN 106058233A
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transition metal
graphene
metal oxide
preparation
dispersion liquid
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CN201610670704.9A
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Inventor
陈伟凡
周文威
许云鹏
卓明鹏
郭兰玉
张文星
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Nanchang University
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Nanchang University
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    • 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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese 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
    • H01M4/36—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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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

Abstract

A preparation method of a transition metal oxide/graphene nano composite material comprises the following steps: (1) according to the loading amount of a transition metal oxide on graphene and the preparation amount of a target product, weighing transition metal nitrate, and dissolving the transition metal nitrate in an aqueous dispersion liquid of graphene oxide; (2) adding a proper amount of an organic fuel into the dispersion liquid of the step (1), and stirring and carrying out ultrasonic treatment to obtain an uniform dispersion liquid; and (3) heating and concentrating the dispersion liquid obtained in the step (2) to be viscous, then putting into a heating furnace with the temperature of 300-900 DEG C, igniting, and after completing combustion, cooling to room temperature to obtain a final product. The preparation method has the advantages of low synthesis temperature, short time, simple implementation, low cost, small particle size of transition metal oxide, uniform size and uniform dispersion in graphene, and is suitable for industrialized production.

Description

A kind of preparation method of transition metal oxide/graphene nanocomposite material
Technical field
The invention belongs to field of material synthesis technology, relate to preparation method prepared by carbon-based nano composite.
Technical background
Graphene-based have the electric conductivity more excellent than graphite type material, higher specific surface as lithium cell cathode material Long-pending, more preferable chemical stability, and wider electrochemical window, it has huge as ion secondary battery cathode material lithium Potentiality.But pure Graphene is with high costs when using Physical to prepare, hold during using the preparation of reduction-oxidation graphite method Stacking the most again, it is the most unfavorable to be completely embedded into lithium ion/deviate from.Therefore, Graphene as cell negative electrode material time generally add Enter other inorganic material, to improve its capacity character.Lithium ion is had stronger by the oxide of transition metal Co, Fe, Ni etc. Activity, has higher reversible capacity, thus can be as lithium ion battery negative material.But during discharge and recharge, Transition metal oxide electrode there will be huge change in volume, and then causes electrode to be pulverized, and electrode capacity is decayed rapidly.For Overcoming this obstacle, the carbonaceous material with high conductivity and preferable ductility is used as the base of transition metal oxide Matter, improves the cycle performance of electrode.Relative to carbonaceous materials such as graphite, carbon black, CNT, fullerenes, Graphene can The stress that more effectively buffer electrode occurs because of change in volume in charge and discharge process, and the conductance that whole electrode is high can be kept Rate.The most graphene-supported transition metal oxide can realize Graphene and transiting metal oxidation as lithium cell cathode material Thing is had complementary advantages, it is achieved synergistic enhancing effect: improve the transiting metal oxidation that can preferably suppress occur in charge and discharge process The reunion of composition granule;The change in volume preferably occurred in regulation charge and discharge process;Transition metal oxide can be made compound Weight ratio in material reaches the highest value;Whole electrode is kept to have high electrical conductivity；Lithium battery multiplying power is put by final realization Electricity and the improvement of cycle performance.
Summary of the invention
It is an object of the invention to propose the preparation method of a kind of transition metal oxide/graphene nanocomposite material, With solve that transition metal oxide/graphene nanocomposite material traditional preparation methods exists time-consuming long, purity is low, granularity relatively Greatly, product stability poor, yield is low, is unfavorable for the problems such as commercialization synthesis, and the method energy consumption is low, the shortest, easily operated, right Environmental nonpollution.
The preparation method of a kind of transition metal oxide/graphene nanocomposite material of the present invention, including following Step.
(1) according to transition metal oxide load capacity on Graphene and the preparation amount of target product, weigh corresponding The transition metal nitrate of amount, is dissolved in the graphene oxide aqueous dispersions that concentration is 0.5 ~ 5g/L of certain volume.
(2) adding appropriate organic-fuel in the dispersion liquid of step (1), stirring is also uniformly divided for ultrasonic 15 ~ 90 minutes Dissipate liquid.
(3) dispersion liquid heating step (2) obtained is concentrated into thickness, puts into the heating furnace that temperature is 300 ~ 900 DEG C Ignite, after having burnt, be cooled to room temperature, i.e. obtain end product.
In the step (1) of preparation method of the present invention, described transition metal is Co, Ni, Fe, Cu, Zn, Mn Or one or more of Cr.
In the step (1) of preparation method of the present invention, described transition metal oxide load capacity on Graphene It is 20 ~ 200%(mass ratio).
In the step (2) of preparation method of the present invention, described organic-fuel is in glycine, carbamide and ethylene glycol One or both, the molal quantity of added organic-fuel is in reactant 0.5 ~ 10 times of transition metal nitrate molal quantity summation.
The present invention prepare the method for transition metal oxide/graphene nanocomposite material be by transition metal nitrate, Graphene oxide solution, organic-fuel mixing sonic oscillation get a uniform mixture, and then heating mixed solution is to thick, Put into the heating furnace chamber that temperature is 300 ~ 900 DEG C to ignite, after having burnt, take out powder body and obtain end product.The present invention closes Temperature is low, the time is short for one-tenth, implements simple and with low cost, it is not necessary to the extra reducing agent that adds just can realize graphene oxide high temperature certainly Reduction obtains high-quality graphene, and transition metal oxide particle diameter is little, and size is uniform, and on Graphene, dispersibility is uniform, is one Kind quickly, high yield, be suitable to the novel preparation method of industrialized production transition metal oxide/graphene nanocomposite material.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of the embodiment of the present invention 1 sample, as it can be seen, these diffraction maximum of indexing and JCPDS Card number is the Fe of 39-13462O3Characteristic diffraction peak coincide, be 20 ~ 30 at 2 θoRegion have a diffraction maximum the most weak, corresponding Be the characteristic diffraction peak of Graphene, product indicated above is ferrum oxide/graphene composite material.
Fig. 2 is the transmission electron microscope photo of the embodiment of the present invention 1 sample, Fe2O3Nanoparticle be distributed in Graphene On, Fe2O3The mean diameter of particle is about 6 nm.
Fig. 3 be the embodiment of the present invention 2 sample XRD figure spectrum, as it can be seen, these indexing diffraction maximum with JCPDS card number is that the characteristic diffraction peak of the NiO of 47-1049 coincide, and it, be 20 ~ 30 at 2 θoRegion have spreads out the most weak Penetrating peak, corresponding is the characteristic diffraction peak of Graphene, and product indicated above is nickel oxide/graphene nanocomposite material.
Fig. 4 is the transmission electron microscope photo of the embodiment of the present invention 2 sample, and the nanoparticle of NiO is distributed on Graphene, The mean diameter of NiO particle is about 20 nm.
Fig. 5 is the XRD figure spectrum of the embodiment of the present invention 3 sample, as it can be seen, these diffraction maximum of indexing and JCPDS Card number is the Co of 43-10033O4Characteristic diffraction peak coincide, be 20 ~ 30 at 2 θoRegion have a diffraction maximum the most weak, corresponding Be the characteristic diffraction peak of Graphene, product indicated above be product be cobalt oxide/graphene composite.
Fig. 6 is the transmission electron microscope photo of the embodiment of the present invention 3 sample, Co3O4Nanoparticle be distributed on Graphene, Co3O4The mean diameter of particle is about 15 nm.
Detailed description of the invention
The present invention will be described further by following example.
Embodiment 1.
Weigh 1.010 g Fe (NO3)3·9H2O, joining 400 ml concentration is in 1g/L graphene oxide dispersion, so Rear addition 0.3145 g glycine, obtains uniform dispersion after stirring ultrasonic 30 minutes, heating is concentrated into thick, puts into temperature It is to ignite in the heating furnace of 500 DEG C, after having burnt, is cooled to room temperature, i.e. obtains ferrum oxide/graphene nanocomposite material.
Embodiment 2.
Weigh 0.7218g Ni (NO3)2·6H2O, joining 400ml concentration is in 1g/L graphene oxide dispersion, so Rear addition 0.208g glycine, obtains uniform dispersion after stirring ultrasonic 30 minutes, heating is concentrated into thick, and putting into temperature is Ignite in the heating furnace of 500 DEG C, after having burnt, be cooled to room temperature, i.e. obtain nickel oxide/graphene nano composite Nano material Material.
Embodiment 3.
Weigh 0.722g Co (NO3)2·6H2O, joining 400ml concentration is in 1g/L graphene oxide dispersion, then Adding 0.208g glycine, obtain uniform dispersion after stirring ultrasonic 30 minutes, heating is concentrated into thick, and putting into temperature is Ignite in the heating furnace of 500 DEG C, after having burnt, be cooled to room temperature, i.e. obtain the nano combined nanometer of cobalt oxide/graphene Material.

Claims (1)

1. a preparation method for transition metal oxide/graphene nanocomposite material, is characterized in that comprising the following steps:
(1) according to transition metal oxide load capacity on Graphene and the preparation amount of target product, respective amount is weighed Transition metal nitrate, is dissolved in the graphene oxide aqueous dispersions that concentration is 0.5 ~ 5g/L of certain volume；
(2) adding appropriate organic-fuel in the dispersion liquid of step (1), stirring also obtains uniform dispersion in ultrasonic 15 ~ 90 minutes；
(3) dispersion liquid heating step (2) obtained is concentrated into thickness, puts into the heating furnace that temperature is 300 ~ 900 DEG C and ignites, After having burnt, it is cooled to room temperature, i.e. obtains end product；
Described in step (1) transition metal is Co, Ni, Fe, Cu, Zn, Mn or Cr one or more；
The transition metal oxide described in step (1) load capacity on Graphene is mass ratio 20 ~ 200%；
Organic-fuel described in step (2) is one or both in glycine, carbamide and ethylene glycol, added organic-fuel Molal quantity is in reactant 0.5 ~ 10 times of transition metal nitrate molal quantity summation.
CN201610670704.9A 2016-08-16 2016-08-16 Preparation method of transition metal oxide/graphene nano composite material Pending CN106058233A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106564892A (en) * 2016-11-04 2017-04-19 华中科技大学 Method for conducting oxygen vacancy introduction on transition metal oxide in intrinsic modification manner
CN107619045A (en) * 2017-09-21 2018-01-23 中国科学院合肥物质科学研究院 A kind of method in situ for preparing small sized metallic oxide on graphene
CN108690919A (en) * 2018-05-15 2018-10-23 昆明理工大学 A kind of method that nano metallurgical method prepares carbon nanotube and/or graphene enhancing lead base composite anode

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103145199A (en) * 2013-03-08 2013-06-12 南昌大学 Preparation method of cobalt oxide/graphene composite nano material
CN103524128A (en) * 2013-10-12 2014-01-22 南昌大学 Preparation method of yttria-stabilized zirconia tetragonal nano powder with high specific surface area
CN103553594A (en) * 2013-10-12 2014-02-05 南昌大学 Preparation method for terbium oxide and yttrium oxide co-stabilized zirconia nano fluorescent ceramic powder

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103145199A (en) * 2013-03-08 2013-06-12 南昌大学 Preparation method of cobalt oxide/graphene composite nano material
CN103524128A (en) * 2013-10-12 2014-01-22 南昌大学 Preparation method of yttria-stabilized zirconia tetragonal nano powder with high specific surface area
CN103553594A (en) * 2013-10-12 2014-02-05 南昌大学 Preparation method for terbium oxide and yttrium oxide co-stabilized zirconia nano fluorescent ceramic powder

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106564892A (en) * 2016-11-04 2017-04-19 华中科技大学 Method for conducting oxygen vacancy introduction on transition metal oxide in intrinsic modification manner
CN107619045A (en) * 2017-09-21 2018-01-23 中国科学院合肥物质科学研究院 A kind of method in situ for preparing small sized metallic oxide on graphene
CN108690919A (en) * 2018-05-15 2018-10-23 昆明理工大学 A kind of method that nano metallurgical method prepares carbon nanotube and/or graphene enhancing lead base composite anode

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