CN107154483A - A kind of preparation method of graphene/ferric oxide/stannic oxide composite - Google Patents

A kind of preparation method of graphene/ferric oxide/stannic oxide composite Download PDF

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CN107154483A
CN107154483A CN201610132923.1A CN201610132923A CN107154483A CN 107154483 A CN107154483 A CN 107154483A CN 201610132923 A CN201610132923 A CN 201610132923A CN 107154483 A CN107154483 A CN 107154483A
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oxide
graphene
graphite
ferric oxide
raw material
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王晓清
赵爽
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Tianjin Polytechnic University
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Tianjin Polytechnic University
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
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    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
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Abstract

The present invention discloses a kind of by preparation method of the urea as graphene/ferric oxide/stannic oxide composite of precipitating reagent, and this method is completed by following steps：Graphite oxide, FeCl are synthesized by Hummers methods by raw material of graphite3·6H2O, graphite oxide are raw material, and deionized water is solvent, and magnetic agitation is well mixed it, and hydro-thermal reaction 3~6 hours at 100 DEG C~150 DEG C are passed through in autoclave, then in passing through SnCl under 25 DEG C~50 DEG C water bath conditions2·2H2O reduction, obtains Fe2O3/SnO2/ rGO presoma, finally calcining obtains Fe in 1 hour in 400 DEG C of Muffle furnaces2O3/SnO2/ rGO composites.The cost of raw material used in the present invention is relatively low, and requires low to consersion unit, easily operation.While Fe produced by the present invention2O3/SrnO2/ rGO composites have larger specific surface area, with excellent chemical property.

Description

A kind of preparation method of graphene/ferric oxide/stannic oxide composite
Technical field
The invention belongs to electrochemical power source technical field of material, more particularly to a kind of graphite as anode material for lithium-ion battery alkene The preparation method of compound iron-tin oxide.Have in conventional secondary lithium battery and power source cell negative electrode material field It is widely applied prospect.
Background technology
Current commercialized lithium cell cathode material is mainly carbon negative pole material.But the SEI films produced in charge and discharge process, Lithium ion is had larger irreversible loss, influence the capacity of battery.Fe2O3And SnO2Because it has cost low, environmentally friendly without dirt Dye, tap density are larger, the advantages of higher charge and discharge platform voltage and outstanding theoretical specific capacity, have obtained more and more Research.But the deficiency of metal oxide materials generally existing is that Volume Changes are larger and material in material charge and discharge process Electronics and ionic conductivity are very low, for Volume Changes of the lightening material in charge and discharge process, improve the conductive capability of material, The irreversible capacity loss of material is reduced, the cycle performance of material is improved, metal oxide and electric conductivity is good, compare surface The larger lamellar graphite alkene of product is combined.
At present, the synthetic method of Fe-Sn quasi-metal oxides negative material mainly includes hydro-thermal method, coprecipitation and liquid-phase precipitation Method.Hydrothermal synthesis method can obtain the higher material of purity, by changing synthesis condition, can also control the structure and morphology of material, Compared with other methods, such a method is simple.Hydro-thermal method needs to react under high-temperature and high-pressure conditions, requirement to container compared with It is high.
The content of the invention
To overcome the deficiencies in the prior art, first Hummers methods are passed through using graphite as raw material it is an object of the invention to provide a kind of Graphite oxide is synthesized, then with graphite oxide, FeCl3·6H2O is raw material, and deionized water is mixed solvent, by adding urea And SnCl2·2H2O obtains Fe2O3/SnO2The method of/rGO composites.
The object of the present invention is achieved like this, using urea as precipitating reagent, after raw material are sufficiently mixed by magnetic agitation, in The presoma of ferric oxide/graphite oxide is obtained in autoclave by water-heat process, then passes through SnCl2·2H2O's goes back original work With obtaining Fe2O3/SnO2/ rGO presoma, finally obtains Fe in Muffle kiln roasting2O3/SnO2/rGO。
The present invention prepares comprising the following steps that for graphene/ferric oxide/stannic oxide composite：
(1) graphite oxide is synthesized by improved Hummers methods using graphite as raw material；
(2) graphite oxide ultrasound 30min is dispersed in appropriate amount of deionized water；
(3) FeCl is added into above-mentioned solution at room temperature3·6H2O and the abundant magnetic agitation of urea；
(4) solution is put into 100mL after dissolving has in the stainless steel autoclave of polytetrafluoroethyllining lining, 100 DEG C~150 DEG C Lower hydro-thermal reaction 3~6 hours；
(5) it is cooled to after room temperature, SnCl is added into above-mentioned solution2·2H2O, water bath with thermostatic control is stirred at 25 DEG C~50 DEG C, with steaming Respectively washing three times of distilled water and ethanol, are placed in 80 DEG C of baking ovens and dry 12h；
(6) dried product is calcined into 1h under nitrogen or argon gas atmosphere in tube furnace at 300~600 DEG C.
Further, under conditions of graphite oxide is not added with, Fe has been synthesized by same procedure2O3/SnO2。
The present invention utilizes graphite oxide, FeCl3·6H2O、SnCl2·2H2O, urea are raw material, and product is controlled by water-heat process Pattern, it is simple with equipment, the features such as easy to operate, be advantageously implemented large-scale industrial production.More importantly this hair Bright obtained material has very bigger serface, in the performance that lithium battery material application aspect is excellent.
Brief description of the drawings
Fig. 1 is ESEM (SEM) photo prepared by example 1.
Fig. 2 is ESEM (SEM) photo prepared by example 2.
Fig. 3 is the X ray diffracting spectrum prepared by example 1-2.
Embodiment
It is used for the method for further illustrating that the present invention is described below by way of specific embodiment, it is not intended that the present invention is limited to these Embodiment.
Embodiment 1：
A kind of preparation method of graphene/ferric oxide/stannic oxide composite, comprises the following steps：
(1) graphite oxide is made using graphite as raw material by improved Hummers methods.
(2) 0.1g graphite oxides are weighed in beaker, deionized water ultrasonic disperse 30min is added, graphite oxide is uniformly divided Dissipate in deionized water, concentration is 1mg/mL；
(3) 0.8gFeCl is added into above-mentioned solution at room temperature3·6H2The abundant magnetic agitation of O and 1.5g urea；
(4) solution is put into 100mL after dissolving has in the stainless steel autoclave of polytetrafluoroethyllining lining, water at 120 DEG C Thermal response 4 hours；
(5) it is cooled to after room temperature, 0.2gSnCl is added into above-mentioned solution2·2H2O, water bath with thermostatic control stirring 1h, is used at 30 DEG C Respectively washing three times of distilled water and ethanol, are placed in 80 DEG C of baking ovens and dry 12h；
(6) dried product is calcined into 1h in tube furnace at lower 400 DEG C of argon gas atmosphere.
Product obtained by preparing is scanned through electron microscope observation, as seen from Figure 1.Gained composite is prepared by X X ray diffraction analysis x, according to JCPDS 35-0609, has had more graphene peak compared with pure phase iron oxide.
Embodiment 2：
A kind of preparation method of graphene/ferric oxide/stannic oxide composite, comprises the following steps：
(1) graphite oxide is made using graphite as raw material by improved Hummers methods.
(2) 0.1g graphite oxides are weighed in beaker, deionized water ultrasonic disperse 30min is added, graphite oxide is uniformly divided Dissipate in deionized water, concentration is 1mg/mL；
(3) 0.8gFeCl is added into above-mentioned solution at room temperature3·6H2The abundant magnetic agitation of O and 1.5g urea；
(4) solution is put into 100mL after dissolving has in the stainless steel autoclave of polytetrafluoroethyllining lining, water at 120 DEG C Thermal response 4 hours；
(5) it is cooled to after room temperature, 0.2gSnCl is added into above-mentioned solution2·2H2O, water bath with thermostatic control stirring 1h, is used at 30 DEG C Respectively washing three times of distilled water and ethanol, are placed in 80 DEG C of baking ovens and dry 12h；
(6) dried product is calcined into 1h in tube furnace at lower 400 DEG C of nitrogen atmosphere.
Product obtained by preparing is scanned through electron microscope observation, as seen from Figure 2.

Claims (4)

1. a kind of preparation method of graphene/ferric oxide/stannic oxide composite, it comprises the following steps：
(1) graphite oxide is synthesized by improved Hummers methods；
(2) by graphite oxide, iron chloride and urea in deionized water, then surpass again according to certain mol ratio stirring and dissolving Sound scattered a period of time；
(3) by the dispersion liquid in step 2 in stainless steel autoclave, hydro-thermal reaction 3~6 hours at 100 DEG C~150 DEG C Afterwards, take out and be cooled to room temperature；
(4) under 25 DEG C~50 DEG C of water bath condition, SnCl is added into above-mentioned solution2·2H2O solid medicines, stir one section After time, centrifugation, washing, drying, grinding are taken out；
(5) solid powder obtained above in nitrogen or argon gas atmosphere, is calcined 1 hour in tube furnace at 300~600 DEG C.
2. the method according to claim 1 for preparing graphene/ferric oxide/stannic oxide composite, it is characterised in that Medicine used is that analysis is pure.
3. the method according to claim 1 for preparing graphene/ferric oxide/stannic oxide composite, it is characterised in that The gas purity of nitrogen or argon gas used is 99.99%.
4. it is mixed phase graphene/ferric oxide/stannic oxide nano composite material by the product obtained by claim 1.
CN201610132923.1A 2016-03-04 2016-03-04 A kind of preparation method of graphene/ferric oxide/stannic oxide composite Pending CN107154483A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108034407A (en) * 2017-12-07 2018-05-15 上海电机学院 A kind of preparation method of absorbing material
CN108123126A (en) * 2017-12-20 2018-06-05 厦门紫阳科技产业发展有限公司 A kind of preparation method of high-capacity lithium ion cell stannic oxide/nitrogen-doped graphene composite negative pole material
CN108365190A (en) * 2018-01-19 2018-08-03 浙江衡远新能源科技有限公司 A kind of iron oxide/titanium carbide composite negative pole material and preparation method thereof
CN109208321A (en) * 2018-09-10 2019-01-15 山东理工大学 A kind of SnO2/Ni3Sn2The preparation method of composite graphite alkene cladding cotton carbon fibre material
CN109348696A (en) * 2018-10-15 2019-02-15 安徽理工大学 A kind of preparation method of Fe2O3 doping stannic oxide/nano combined absorbing material of redox graphene
CN111697205A (en) * 2019-03-13 2020-09-22 南京理工大学 High-performance lithium battery negative electrode material r-GO/Fe2O3-MoO3Preparation method of (1)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108034407A (en) * 2017-12-07 2018-05-15 上海电机学院 A kind of preparation method of absorbing material
CN108123126A (en) * 2017-12-20 2018-06-05 厦门紫阳科技产业发展有限公司 A kind of preparation method of high-capacity lithium ion cell stannic oxide/nitrogen-doped graphene composite negative pole material
CN108365190A (en) * 2018-01-19 2018-08-03 浙江衡远新能源科技有限公司 A kind of iron oxide/titanium carbide composite negative pole material and preparation method thereof
CN109208321A (en) * 2018-09-10 2019-01-15 山东理工大学 A kind of SnO2/Ni3Sn2The preparation method of composite graphite alkene cladding cotton carbon fibre material
CN109348696A (en) * 2018-10-15 2019-02-15 安徽理工大学 A kind of preparation method of Fe2O3 doping stannic oxide/nano combined absorbing material of redox graphene
CN109348696B (en) * 2018-10-15 2020-08-07 安徽理工大学 Preparation method of iron-doped tin dioxide/reduced graphene oxide nano composite wave-absorbing material
CN111697205A (en) * 2019-03-13 2020-09-22 南京理工大学 High-performance lithium battery negative electrode material r-GO/Fe2O3-MoO3Preparation method of (1)
CN111697205B (en) * 2019-03-13 2022-04-15 南京理工大学 High-performance lithium battery negative electrode material r-GO/Fe2O3-MoO3Preparation method of (1)

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Application publication date: 20170912