CN109802117A - A kind of γ-Fe2O3The porous graphene composite material and preparation method thereof of etching and application - Google Patents
A kind of γ-Fe2O3The porous graphene composite material and preparation method thereof of etching and application Download PDFInfo
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- CN109802117A CN109802117A CN201910056669.5A CN201910056669A CN109802117A CN 109802117 A CN109802117 A CN 109802117A CN 201910056669 A CN201910056669 A CN 201910056669A CN 109802117 A CN109802117 A CN 109802117A
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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
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- 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
The invention discloses a kind of γ-Fe2O3The porous graphene composite material and preparation method thereof of etching and application, comprising the following steps: (1) graphene oxide is added in deionized water and is configured to 60mL solution and ultrasound；(2) organic source of iron is added to 10mL organic solvent for ultrasonic；(3) under the conditions of 80-100 DEG C of temperature, step (2) is obtained liquid to be added drop-wise to dropwise in liquid obtained by step (1) with liquid-transfering gun, during dropwise addition, continues liquid obtained by whipping step (1), after being added dropwise to complete, stirred at 80-100 DEG C；(4) the resulting mixed liquor of step (3) is freeze-dried；(5) the 600-850 DEG C of calcining under tube furnace inert atmosphere protection by the sample after step (4) freeze-drying.The present invention obtains a kind of γ-Fe by punching in situ2O3There is excellent electric conductivity and hole path abundant to show the charging and discharging capacity and cyclical stability of superelevation when as lithium ion battery negative material for the porous graphene composite material of etching, the material.
Description
Technical field
The invention belongs to field of material technology, and in particular to a kind of γ-Fe2O3The porous graphene composite material system of etching
Preparation Method and application.
Background technique
The energy is the important material base of progress of human society and development.Rechargeable lithium ion batteries (LIB) Yin Qigao storage
Deposit energy density, long life cycle, memory-less effect and be widely used in the electronic device.Sony company trade since 1991
Since changing LIB, graphene has been used as the negative electrode material in business LIB, but its specific capacity only only has 372mAhg-1.Phase
Than under, transition metal oxide has higher charge and discharge theoretical specific capacity, energy density and cheap price to quilt
Research is used for LIB negative electrode material extensively.Wherein, γ-Fe2O3Due to its high theoretical specific capacity value (about 1000mAhg-1), storage
The features such as amount is abundant and highly-safe, causes the extensive concern of researcher.However γ-Fe2O3Volume in charge and discharge process
It changes greatly, and not excellent enough the discharge capacity that causes the presence of of electric conductivity is poor lower than theoretical value, cyclical stability.It realizes
Graphene and γ-Fe2O3The preparation of composite material, shown when as LIB negative electrode material higher charging and discharging capacity with
And cyclical stability.The rapid development of current science and technology, people are especially its high charge-discharge specific volume for good performance lithium ion battery
Amount and stable circulation performance, more stringent requirements are proposed.Common graphite alkene and γ-Fe2O3Composite material is as LIB cathode material
Current needs are had been unable to meet when material.
Summary of the invention
To solve the above-mentioned problems, one of the objects of the present invention is to provide a kind of γ-Fe2O3The porous graphene of etching
Composite material and preparation method thereof；The second object of the present invention is to provide a kind of γ-Fe2O3The porous graphene composite material of etching,
It is more uniform on the surface of graphene to inlay γ-Fe2O3Nanoparticle simultaneously etches porous structure in its in-situ surface, is realizing that this is compound
Effective mass transfer channel is provided while material high electrical conductivity energy；The third object of the present invention is to provide this kind of γ-Fe2O3It carves
The application field of the porous graphene composite material of erosion, this new material as new energy battery material especially as
There is potential significant application value when LIB negative electrode material.
An object of the present invention is achieved through the following technical solutions:
A kind of γ-Fe2O3The porous graphene composite material and preparation method thereof of etching, comprising the following steps:
(1) quality is added to the solution and ultrasound that 60mL is configured in deionized water for 100-300mg graphene oxide
10-60min；
(2) organic source of iron is added to ultrasound 2-10min in 10mL acetonitrile；
(3) 80-100 DEG C, step (2) is obtained into liquid and is added drop-wise in liquid obtained by step (1) dropwise with liquid-transfering gun, is added dropwise
In the process, continue liquid obtained by whipping step (1), after being added dropwise to complete, stir 1-5h at 80-100 DEG C；
(4) the resulting mixed liquor of step (3) is freeze-dried；
(5) sample after step (4) freeze-drying is calcined into 1- at 600-850 DEG C in tube furnace inert atmosphere protection
5h；
Further, in step (1), the quality of graphene oxide is 200mg, ultrasonic time 30min；
Further, in step (2), organic source of iron is carbonyl iron, dosage are as follows: density 1.49gmL-1Carbonyl iron
77.86mL, organic solvent are acetonitrile, ultrasonic time 5min；
Further, in step (3), temperature is 90 DEG C, mixing time 3h；
Further, in step (5), inert atmosphere is argon atmosphere, and calcination temperature is respectively 600 DEG C, 750 DEG C, 850 DEG C.
The second object of the present invention is to what is be achieved through the following technical solutions:
γ-Fe made from foregoing preparation method2O3The porous graphene composite material of etching.
The third object of the present invention is achieved through the following technical solutions:
A kind of γ-Fe2O3The porous graphene composite material of etching can be applied in the field in high-performance LIB negative electrode material.
The beneficial effects of the present invention are:
The present invention prepares a kind of novel γ-Fe2O3The porous graphene composite material of etching, as LIB negative electrode material
Shi Yiqi excellent electric conductivity and relatively rich hole path show brilliant charging and discharging capacity and cyclical stability.Specifically
For, γ-Fe2O3As catalyst, etching graphene --- the carbon in catalytic graphite alkene is former in situ in a certain temperature conditions
Son is reacted with its surface functionalities group, i.e. γ-Fe2O3Original position is anchored on the pore structure side of etching, to obtain γ-Fe2O3It carves
The porous graphene composite material of erosion.It is 500mAg in current density when the material is as LIB negative electrode material-1Test-strips
Under part, after circulation 300 times, up to 1180mAhg is shown-1Charging and discharging capacity and its specific volume numerical quantity be able to maintain
It is recycled to 400.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram that material is prepared under the conditions of 1 calcination temperature of embodiment is 750 DEG C；
Fig. 2 is the scanning electron microscope diagram that material is prepared under the conditions of 1 calcination temperature of comparative examples is 600 DEG C；
Fig. 3 is the scanning electron microscope diagram that material is prepared under the conditions of 2 calcination temperature of comparative examples is 850 DEG C；
Fig. 4 is to prepare the charging and discharging capacity test chart of material under the conditions of different calcination temperatures.
Specific embodiment
It, below will be to preferred reality of the invention in order to keep the purpose of the present invention, technical scheme and beneficial effects clearer
Example is applied to be described in detail.
Embodiment one
A kind of γ-Fe2O3The preparation method and application of the porous graphene composite material of etching, comprising the following steps:
(1) graphene oxide of 200mg is added to the solution and ultrasound 30min that 60mL is configured in deionized water；
(2) by 77.86mL, 1.49gmL-1Carbonyl iron be added to ultrasound 5min in 10mL acetonitrile；
At (3) 90 DEG C, step (2) is obtained into liquid and is added drop-wise in liquid obtained by step (1) dropwise with liquid-transfering gun, was added dropwise
Cheng Zhong continues liquid obtained by whipping step (1), after being added dropwise to complete, stirs 3h at 90 DEG C；
(4) the resulting mixed liquor of step (3) is freeze-dried；
(5) sample after step (4) freeze-drying is protected in tube furnace argon atmosphere and calcines 1h at 750 DEG C；
(6) calcined sample is formed to button cell to be tested for the property in glove box.
Comparative examples one
(1) graphene oxide of 200mg is added to the solution and ultrasound 30min that 60mL is configured in deionized water；
(2) by 77.86mL, 1.49gmL-1Carbonyl iron be added to ultrasound 5min in 10mL acetonitrile；
At (3) 90 DEG C, step (2) is obtained into liquid and is added drop-wise in liquid obtained by step (1) dropwise with liquid-transfering gun, was added dropwise
Cheng Zhong continues liquid obtained by whipping step (1), after being added dropwise to complete, stirs 3h at 90 DEG C；
(4) the resulting mixed liquor of step (3) is freeze-dried；
(5) sample after step (4) freeze-drying is protected in tube furnace argon atmosphere and calcines 1h at 600 DEG C；
(6) calcined sample is formed to button cell to be tested for the property in glove box.
Comparative examples two
(1) graphene oxide of 200mg is added to the solution and ultrasound 30min that 60mL is configured in deionized water；
(2) by 77.86mL, 1.49gmL-1Carbonyl iron be added to ultrasound 5min in 10mL acetonitrile；
At (3) 90 DEG C, step (2) is obtained into liquid and is added drop-wise in liquid obtained by step (1) dropwise with liquid-transfering gun, was added dropwise
Cheng Zhong continues liquid obtained by whipping step (1), after being added dropwise to complete, stirs 3h at 90 DEG C；
(4) the resulting mixed liquor of step (3) is freeze-dried；
(5) sample after step (4) freeze-drying is protected in tube furnace argon atmosphere and calcines 1h at 850 DEG C；
(6) calcined sample is formed to button cell to be tested for the property in glove box.
The comparative analysis of embodiment one and one charging and discharging capacity of comparative examples: as the charge and discharge of Fig. 4, two samples exist
Preceding 20 circle left and right is in downward trend, is because battery produces irreversible product at discharge and recharge reaction initial stage；It opens below
Beginning rising is that the gradually activation and electron channel due to material are gradually opened.750 DEG C calcining sample charging and discharging capacity (from
Charging and discharging capacity is 900mAhg after 20 circulations-1Charging and discharging capacity after rising to 300 circulations is 1180mA
h·g-1, and its specific volume numerical quantity be able to maintain to 400 recycle) better than 600 DEG C calcining sample charging and discharging capacity (from
Charging and discharging capacity is 530mAhg after 20 circulations-1Charging and discharging capacity after rising to 300 circulations is 660mA
h·g-1, and its specific volume numerical quantity is able to maintain to 400 and recycles), it is because of (such as Fig. 1,2): γ-Fe in Fig. 22O3Particle one
Side non-porous structure, Fig. 1 γ-Fe abundant2O3Particle is more uniform on the surface of graphene, and γ-Fe2O3Particle side is dispersed with
Apparent hole configurations, this peomotes the infiltration of LIB electrolyte, electric charge transfer and effective mass transfer.
The comparative analysis of embodiment one and two charging and discharging capacity of comparative examples: as the charge and discharge of Fig. 4, two samples exist
Preceding 20 circle left and right is in downward trend, is because battery produces irreversible product at discharge and recharge reaction initial stage；It opens below
Beginning rising is that the gradually activation and electron channel due to material are gradually opened.750 DEG C calcining sample charging and discharging capacity (from
Charging and discharging capacity is 900mAhg after 20 circulations-1Charging and discharging capacity after rising to 300 circulations is 1180mA
h·g-1, and its specific volume numerical quantity is able to maintain to 400 and recycles) it is better than the sample charging and discharging capacity of 850 DEG C of calcinings (from 20
Charging and discharging capacity is 620mAhg after secondary circulation-1Charging and discharging capacity after rising to 300 circulations is 820mAh
g-1, and its specific volume numerical quantity is able to maintain to 400 and recycles), it is because of (such as Fig. 1,3): with γ-Fe in Fig. 12O3What is etched is more
Hole graphene composite material is compared, γ-Fe in Fig. 32O3Certain reunion has occurred in particle on graphene and partial size also becomes
Greatly, while certain destruction and collapsing has occurred in the structure of graphene, so as to cause charging and discharging capacity and cyclical stability
It reduces.
The result shows that the present invention is using organic source of iron and dry by freezing by punching in situ in material preparation process
Dry and high-temperature process method, realizes γ-Fe2O3It is evengranular to be mounted to graphene surface, while realizing γ-Fe2O3
Particle etches to obtain porous graphene composite material in its surface in situ.When the composite material is as LIB negative electrode material, in electric current
Density is 500mAg-1Under conditions of recycle 300 times after, show up to 1180mAhg-1Charging and discharging capacity, and
And its specific capacity value is able to maintain to 400 and recycles.Therefore the material has the charging and discharging capacity and cyclical stability of superelevation, this
The novel LIB negative electrode material of kind has important potential using value.
Finally, it is stated that preferred embodiment above is only used to illustrate the technical scheme of the present invention and not to limit it, although logical
It crosses above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (7)
1. a kind of γ-Fe2O3The porous graphene composite material and preparation method thereof of etching, it is characterised in that: the following steps are included:
(1) quality is added to the solution and ultrasound 10- that 60mL is configured in deionized water for 100-300mg graphene oxide
60min；
(2) organic source of iron is added to 10mL organic solvent for ultrasonic 2-10min；
(3) under the conditions of 80-100 DEG C of temperature, step (2) is obtained into liquid and is added drop-wise to liquid obtained by step (1) dropwise with liquid-transfering gun
In, during dropwise addition, continues liquid obtained by whipping step (1), after being added dropwise to complete, stir 1-5h under the conditions of 80-100 DEG C of temperature；
(4) the resulting mixed liquor of step (3) is freeze-dried；
(5) by step (4) freeze-drying after sample under tube furnace inert atmosphere protection 600-850 DEG C of calcining 1-3h.
2. a kind of γ-Fe according to claim 12O3The porous graphene composite material and preparation method thereof of etching, feature exist
In: in the step (1), the quality of graphene oxide is 200mg, ultrasonic time 30min.
3. a kind of γ-Fe according to claim 12O3The porous graphene composite material and preparation method thereof of etching, feature exist
In: in the step (2), organic source of iron is carbonyl iron, dosage are as follows: density 1.49gmL-1Carbonyl iron 77.86mL, You Jirong
Agent is acetonitrile, ultrasonic time 5min.
4. a kind of γ-Fe according to claim 12O3The porous graphene composite material and preparation method thereof of etching, feature exist
In: in the step (3), temperature is 90 DEG C, mixing time 3h.
5. a kind of γ-Fe according to claim 12O3The porous graphene composite material and preparation method thereof of etching, feature exist
In: in the step (5), inert atmosphere is argon atmosphere, and calcination temperature is respectively 600 DEG C, 750 DEG C, 850 DEG C, calcination time
For 1h.
6. γ-Fe made from a kind of preparation method according to any one of claims 1 to 52O3The porous graphite of etching
Alkene composite material.
7. γ-Fe made from a kind of preparation method according to any one of claims 1 to 52O3The porous graphite of etching
Application of the alkene composite material in high performance electrode material field.
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Citations (3)
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| CN103449427A (en) * | 2013-09-09 | 2013-12-18 | 东南大学 | Preparation method of porous graphene-ferric oxide composite material |
| CN106450197A (en) * | 2016-10-19 | 2017-02-22 | 清华大学深圳研究生院 | Graphene/oxide based electrode material and lithium-sulfur battery comprising electrode material |
| CN108726514A (en) * | 2017-04-19 | 2018-11-02 | 四川大学 | porous graphene material and preparation method thereof |
-
2019
- 2019-01-24 CN CN201910056669.5A patent/CN109802117A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103449427A (en) * | 2013-09-09 | 2013-12-18 | 东南大学 | Preparation method of porous graphene-ferric oxide composite material |
| CN106450197A (en) * | 2016-10-19 | 2017-02-22 | 清华大学深圳研究生院 | Graphene/oxide based electrode material and lithium-sulfur battery comprising electrode material |
| CN108726514A (en) * | 2017-04-19 | 2018-11-02 | 四川大学 | porous graphene material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| HAILIANG CAO等: ""Metal etching method for preparing porous graphene as high performance anode material for lithium-ion batteries"", 《CARBON》 * |
| LIAN YING ZHANG等: ""γ-Fe2O3 nanocrystals-anchored macro/meso-porous graphene as a highly efficient adsorbent toward removal of methylene blue"", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
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Application publication date: 20190524 |