CN102842710A - Preparation method of Co3O4/graphene nanocomposite material - Google Patents

Preparation method of Co3O4/graphene nanocomposite material Download PDF

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Publication number
CN102842710A
CN102842710A CN2012102480343A CN201210248034A CN102842710A CN 102842710 A CN102842710 A CN 102842710A CN 2012102480343 A CN2012102480343 A CN 2012102480343A CN 201210248034 A CN201210248034 A CN 201210248034A CN 102842710 A CN102842710 A CN 102842710A
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graphene
co3o4
composite material
preparation
solution
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潘兰英
董晓雯
赵宏滨
徐甲强
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

Belonging to the technical field of chemical material preparation, the invention relates to a preparation method of a Co3O4/graphene nanocomposite material. The method provided in the invention is characterized by: first employing a simple chemical method to synthesize Co3O4 nanoparticles under the protection of a surfactant, then adsorbing oxidized graphene on surfaces of the Co3O4 nanoparticles uniformly by means of the interaction between the surfactant and the oxidized graphene, and reducing the oxidized graphene, thus forming the uniform Co3O4/graphene nanocomposite material. Good electrical conductivity is achieved among Co3O4 nanoparticles through graphene, so that the electroconductibility of the composite material can be improved. The Co3O4 nanoparticles in the composite material have a size of 50-100 nanometers, and account for 60%-95% by weight. The method provided in the invention does not involve environmentally harmful materials, and the process is simple, practicable and easy to operate. The prepared Co3O4/graphene nanocomposite material has high specific capacity and capacitance, as well as good cycle performance, thus having good application prospects in the fields of lithium ion batteries and supercapacitors.

Description

A kind of Co 3O 4The preparation method of/graphene nano composite material
Technical field
The present invention relates to a kind of Co 3O 4The preparation method of/graphene composite material belongs to chemical material preparation process technical field.
Background technology
Along with the high speed development of mobile communication, portable electric appts, increasingly high to the performance requirement of electrode material.High-energy-density, high power density, low cost, environment amenable novel battery material are the emphasis of present and future studies.Current battery investigation of materials focus focuses mostly on new-type secondary battery material and fuel cell material.Lithium ion battery is development and the secondary cell of new generation that comes on the lithium metal secondary battery basis, advantage such as have that open circuit voltage height, energy density are big, long service life, memory-less effect, pollution-free and self-discharge rate are little.
P. Poizot etc. has reported that the earliest the oxide of transition metal Co, Fe, Ni etc. has activity to lithium ion, thereby can be used as lithium ion battery negative material.Afterwards, the higher reversible capacity of transition metal oxide has caused widely to be paid close attention to, and the report of a large amount of related fields research occurred.In the 3d transition group metallic oxide, Co 3O 4Can be used as lithium ion battery negative material, its theoretical specific capacity is 890mA h/g, is about 2～2.5 times of graphitized carbon material.But Li in charge and discharge process +Embedding is taken off the embedding meeting and is caused Co 3O 4Cracking, thereby make Co 3O 4Cycle performance relatively poor.One of method that solves is exactly with Co 3O 4Compound with material with carbon element, material with carbon element not only can be alleviated Co 3O 4Cracking and also itself also be the excellence conductor of electronics, make composite material have higher reversible capacity and cyclical stability preferably.In all material with carbon elements, Graphene is the ideal material of lithium ion battery, and this is because Graphene has better conductivity, bigger specific area and chemical stability.Along with going deep into of research, people adopt various physics and chemical method to prepare Co 3O 4With the composite material of Graphene, but under influence of surfactant, preparing Co 3O 4/ graphene nano composite process does not see that also report is arranged in the document at home and abroad.
Summary of the invention
The purpose of this invention is to provide a kind of Co 3O 4The simple method for preparing of/graphene nano composite material.
For achieving the above object, the present invention adopts following technical scheme:
1. prepare graphene oxide with existing chemical oxidation method;
2. under influence of surfactant, synthesize monodispersed Co 3O 4Nano particle;
3. coat Co with graphene oxide 3O 4Nano particle, and with reducing agent graphene oxide is reduced;
4. prepared material is characterized.
A kind of Co of the present invention 3O 4The preparation method of/graphene nano composite material is characterized in that this method has following processing step:
A. cobalt salt cobalt chloride or cobalt nitrate are dissolved in the deionized water, agitating solution is to clarification, and its concentration range is 0.01 ~ 0.04mol/L;
B. the surfactant polyvinylpyrrolidone is joined in the there-necked flask that above-mentioned solution is housed, stir under the room temperature, ultrasonic 30min makes it to dissolve fully and evenly mix with cobalt salt, and wherein the weight ratio of cobalt salt and surfactant is 1:2 ~ 1:6;
C. get certain amount of urea and be dissolved in the deionized water, agitating solution is to clarification, and its concentration range is 0.05 ~ 0.3mol/L;
D. slowly be added drop-wise to urea liquid in the cobalt salt solution; Ultrasonic mixing is placed on constant temperature 3h in 90 ~ 95 ℃ of oil baths; Slowly drip 100mL graphene oxide solution, mix, add a certain amount of reducing agent hydrazine hydrate or sodium borohydride; Be warmed up to 100 ℃ of continued constant temperature 4h, be cooled to room temperature;
E. with said mixture respectively with drying behind deionized water, the washing with acetone;
F. dried above-mentioned material is placed tube furnace, at N 2Under the protection, 600 ~ 650 ℃ of following heat treatment 3 ~ 6h place the Muffle furnace high-temperature process again after the cooling, and sintering temperature is 300 ~ 350 ℃, and sintering time is 3 ~ 6h, promptly obtains Co 3O 4/ graphene nano composite material, the Co in the composite material 3O 4Percentage by weight is 60% ~ 95%.
The Co of gained of the present invention 3O 4/ graphene nano composite material has material novelty, Co 3O 4Good dispersion, particle size little, with the compound advantage such as evenly of Graphene.
In order further to understand the present invention, specially elaborate, and provide accompanying drawing and describe Co involved in the present invention with instance 3O 4/ graphene nano composite material.
Description of drawings
Fig. 1 is the XRD comparison diagram of prepared graphene oxide, Graphene and graphite;
Fig. 2 is the SEM figure of prepared graphene oxide;
Fig. 3 is for the polyvinylpyrrolidone being the Co of surfactant preparation 3O 4XRD comparison diagram before and after the calcining of/graphene nano composite material;
Fig. 4 is for the polyvinylpyrrolidone being the Co of surfactant preparation 3O 4The SEM figure of/graphene nano composite material.
Embodiment
After specific embodiment of the present invention being described at present.
Embodiment one
With the cobalt chloride is feedstock production Co 3O 4/ graphene nano composite material, its process and step are following:
(1) preparation graphene oxide solution: adopt conventionally known Hummers chemical oxidation graphite method.Detailed process is following: be lower than under 0 ℃ the condition, with 100mL 98% H 2SO 4Join 2.0g KNO 3In 4.0g graphite, mixing slowly adds 15g KMnO after stirring 30min 4Afterwards system temperature is risen to 35 ± 3 ℃, under this temperature, react 2h.Drip 180mLH subsequently 2O is dripping H 2Can elevate the temperature in the process of O near 100 ℃, after stirring 30min under this temperature, add 14mL 30% H 2O 2To remove unnecessary KMnO 4, use 500mL 3% HCl and a large amount of H at last 2O washs, and through centrifugal, obtains graphite oxide after the vacuumize.Be dispersed in the deionized water graphite oxide is ultrasonic, be made into the graphene oxide solution of 1mg/mL.
(2) take by weighing the commercially available CoCl of 0.3g 2Be dissolved in the deionized water, agitating solution is mixed with the CoCl of 0.01 mol/L to clarification 2The aqueous solution, and add a certain amount of polyvinylpyrrolidone, CoCl 2With the mass ratio of polyvinylpyrrolidone be 1:5, stir under the room temperature, ultrasonic 30min, make it to dissolve fully and and CoCl 2Evenly mix.
(3) take by weighing the commercially available urea of 0.3g and be dissolved in the deionized water, agitating solution is mixed with the aqueous solution of urea of 0.2 mol/L to clarification.Aqueous solution of urea slowly is added drop-wise to CoCl 2Solution in, ultrasonic mixing is placed on constant temperature 3h in 90 ℃ of oil baths, slowly drips 100ml graphene oxide solution; Mix, add the hydrazine hydrate of 250 μ L, be warmed up to 100 ℃ of continued constant temperature 4h; Be cooled to room temperature, with drying behind deionized water, the washing with acetone;
(4) dried above-mentioned material is placed tube furnace, at N 2Under the protection, 600 ℃ of following heat treatment 6h place the Muffle furnace high-temperature process again after the cooling, and sintering temperature is 300 ℃, and sintering time is 6h, promptly obtains Co 3O 4/ graphene nano composite material.
Embodiment two
With the cobalt nitrate is feedstock production Co 3O 4/ graphene nano composite material, its process and step are following:
(1) preparation graphene oxide solution: adopt conventionally known Hummers chemical oxidation graphite method.Detailed process is following: be lower than under 0 ℃ the condition, with 100mL 98% H 2SO 4Join 2.0g KNO 3In 4.0g graphite, mixing slowly adds 15g KMnO after stirring 30min 4Afterwards system temperature is risen to 35 ± 3 ℃, under this temperature, react 2h.Drip 180mLH subsequently 2O is dripping H 2Can elevate the temperature in the process of O near 100 ℃, after stirring 30min under this temperature, add 14mL 30% H 2O 2To remove unnecessary KMnO 4, use 500mL 3% HCl and a large amount of H at last 2O washs, and through centrifugal, obtains graphite oxide after the vacuumize.Be dispersed in the deionized water graphite oxide is ultrasonic, be made into the graphene oxide solution of 1mg/mL.
(2) take by weighing the commercially available Co (NO of 0.367g 3) 2Be dissolved in the deionized water, agitating solution is mixed with the Co (NO of 0.01 mol/L to clarification 3) 2The aqueous solution, and add a certain amount of polyvinylpyrrolidone, Co (NO 3) 2With the mass ratio of polyvinylpyrrolidone be 1:5, stir under the room temperature, ultrasonic 30min, make it to dissolve fully and with Co (NO 3) 2Evenly mix.
(3) take by weighing the commercially available urea of 0.367g and be dissolved in the deionized water, agitating solution is mixed with the aqueous solution of urea of 0.2 mol/L to clarification.Aqueous solution of urea slowly is added drop-wise to Co (NO 3) 2Solution in, ultrasonic mixing is placed on constant temperature 3h in 90 ℃ of oil baths, slowly drips 100ml graphene oxide solution; Mix, add the hydrazine hydrate of 250 μ L, be warmed up to 100 ℃ of continued constant temperature 4h; Be cooled to room temperature, with drying behind deionized water, the washing with acetone;
(4) dried above-mentioned material is placed tube furnace, at N 2Under the protection, 600 ℃ of following heat treatment 6h place the Muffle furnace high-temperature process again after the cooling, and sintering temperature is 300 ℃, and sintering time is 6h, promptly obtains Co 3O 4/ graphene nano composite material.
  
Referring to accompanying drawing 1, Fig. 1 is the XRD comparison diagram with graphene oxide, Graphene and the graphite of existing chemical oxidation method preparation.A among Fig. 1 is the XRD figure spectrum of graphite.As can be seen from the figure a very very strong diffraction maximum of point appears in graphite near 26 ° of 2 θ ≈, and promptly the diffraction maximum of graphite (002) face explains that the spatial arrangements of pure graphite microcrystal lamella is very regular.B among Fig. 1 is the XRD figure spectrum of graphene oxide.Therefrom can find out at 2 θ ≈ characteristic peak to occur for 10 °, i.e. the diffraction maximum of (001) face of graphene oxide, crystal formation of this explanation graphite is destroyed, and a large amount of defective functional groups makes the interlamellar spacing of graphite change, and has caused generating new crystal structure.C among Fig. 1 is the XRD figure spectrum of Graphene.As can be seen from the figure Graphene diffraction maximum occurs for 25 ° at 2 θ ≈, and the diffraction maximum position of this and graphite is close, but diffraction maximum broadens strength reduction.This is that the integrality of crystal structure descends because after the reduction, the graphite flake layer size is dwindled more, and the degree of disorder increases.
Referring to accompanying drawing 2, Fig. 2 is the SEM figure of graphene oxide.We see that synthetic graphene oxide is the sheet pattern that curls, and a large amount of folding and folds occurred.
Referring to accompanying drawing 3, Fig. 3 is for the polyvinylpyrrolidone being the Co of surfactant preparation 3O 4XRD comparison diagram before and after the calcining of/graphene nano composite material.A among Fig. 3 is Co 3O 4XRD figure spectrum before the calcining of/graphene nano composite material, the b among Fig. 3 is Co 3O 4XRD figure spectrum after the calcining of/graphene nano composite material.Can find the Co on the graphene film of calcining back through contrasting us 3O 4Degree of crystallinity be greatly improved, and from figure we can see Graphene (rGO) and Co simultaneously 3O 4Characteristic peak, Graphene and Co are described 3O 4Be combined with each other well.
Referring to accompanying drawing 4, Fig. 4 is for the polyvinylpyrrolidone being the Co of surfactant preparation 3O 4The SEM figure of/graphene nano composite material.As can be seen from the figure, a large amount of Co 3O 4The nano particle random deposition on the Graphene lamella, even particle size.

Claims (2)

1. Co 3O 4The preparation method of/graphene nano composite material, the processing step and the condition of this method are following:
A. cobalt salt cobalt chloride or cobalt nitrate are dissolved in the deionized water, agitating solution is to clarification, and its concentration range is 0.01 ~ 0.04mol/L;
B. the surfactant polyvinylpyrrolidone is joined in the there-necked flask that above-mentioned solution is housed, stir under the room temperature, ultrasonic 30min makes it to dissolve fully and evenly mix with cobalt salt, and wherein the weight ratio of cobalt salt and surfactant is 1:2 ~ 1:6;
C. get certain amount of urea and be dissolved in the deionized water, agitating solution is to clarification, and its concentration range is 0.05 ~ 0.3mol/L;
D. urea liquid slowly is added drop-wise in the cobalt salt solution, ultrasonic mixing is placed on constant temperature 3h in 90 ~ 95 ℃ of oil baths, slowly drips 100mL graphene oxide solution; Mix; Add a certain amount of reducing agent hydrazine hydrate or sodium borohydride, be warmed up to 100 ℃ of continued constant temperature 4h, be cooled to room temperature;
E. with said mixture respectively with drying behind deionized water, the washing with acetone;
F. dried above-mentioned material is placed tube furnace, at N 2Under the protection, 600 ~ 650 ℃ of following heat treatment 3 ~ 6h place the Muffle furnace high-temperature process again after the cooling, and sintering temperature is 300 ~ 350 ℃, and sintering time is 3 ~ 6h, promptly obtains Co 3O 4/ graphene nano composite material, the Co in the composite material 3O 4Percentage by weight is 60% ~ 95%.
2. a kind of Co as claimed in claim 1 3O 4The preparation method of/graphene nano composite material is characterized in that described graphene oxide is selected from Hummers chemical oxidation graphite method and improves resulting 3 ~ 10 layers of graphene oxide of Hummers method.
CN2012102480343A 2012-07-18 2012-07-18 Preparation method of Co3O4/graphene nanocomposite material Pending CN102842710A (en)

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CN103199219A (en) * 2013-04-08 2013-07-10 朱苗红 Method for preparing graphene-cobaltous stannate-cobaltosic oxide composite negative electrode material
CN103606656A (en) * 2013-12-02 2014-02-26 华南师范大学 Preparation method of lead oxide/graphene nanocomposite material for lead carbon super battery
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CN114496396B (en) * 2021-12-21 2022-11-29 浙江大学 Preparation method of pomegranate seed-like structure high-elastic-modulus conductive assembly

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Application publication date: 20121226