CN109273694A - A kind of graphene/stannous oxide two-dimensional hetero-junction composite material and preparation method - Google Patents
A kind of graphene/stannous oxide two-dimensional hetero-junction composite material and preparation method Download PDFInfo
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- CN109273694A CN109273694A CN201811238998.3A CN201811238998A CN109273694A CN 109273694 A CN109273694 A CN 109273694A CN 201811238998 A CN201811238998 A CN 201811238998A CN 109273694 A CN109273694 A CN 109273694A
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- 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
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Abstract
The invention discloses a kind of graphene/stannous oxide two-dimensional hetero-junction composite material and preparation method and purposes, belong to lithium ion battery material technical field, and the composite material carries out layer assembly with stannous oxide nanometer sheet by graphene nanometer sheet and is combined；In the composite material, the weight fraction of graphene nanometer sheet is 20~95%, and the weight fraction of stannous oxide nanometer sheet is 80~5%.The purpose of the present invention is removing prepares graphene and SnO nanometer sheet from graphite cheap and easy to get and stannous oxide mineral, and the two dimension synergistic effect between graphene and stannous oxide nanometer sheet is constructed, prepares graphene/SnO two-dimensional nano heterojunction composite；Strengthen electronic and ionic transmission channel and volume expansion of the padded coaming in charge and discharge process in lithium ion cell electrode reaction, obtains a kind of high capacity, the novel cathode material for lithium ion battery of long-life.
Description
Technical field
The invention belongs to lithium ion battery material technical fields, and in particular to a kind of graphene/stannous oxide two dimension is heterogeneous
Tie composite material and preparation method and purposes.
Background technique
In recent years, lithium secondary battery is certainly with its excellent performance in multiple fields such as mobile electronic device, new-energy automobiles
It obtains and is widely applied.Increasingly serious with energy and environment problem, the development of New Energy Industry is to performance of lithium ion battery
More stringent requirements are proposed: existing battery material and device system have been unable to satisfy growing high capacity, long-life
Demand.Graphite is common commercial lithium cell cathode material, and theoretical specific capacity is only 372mAh/g, and research can replace graphite conduct
The material of negative electrode of lithium ion battery is research hotspot (Nano letters, 2008,8 (8), 2277-2282) in recent years.Graphite
Alkene be used as negative electrode of lithium ion battery shown good prospect, although its theoretical specific capacity height its capacity attenuation seriously etc. ask
Topic also limits it and develops (Journal of Power Sources, 2013,240 (10), 66-79).
Tin base cathode material has good electric conductivity, and when being used as lithium ion battery negative material, operation current potential is remote
Deposition potential higher than lithium is resolved the lithium deposition problems during high current charge-discharge, and is not present in charge and discharge process
Solvent is total to imbedding problem, smaller to the selectional restriction of electrolyte, and its capacity it is relatively high (Nano letters, 2012,12
(5), 2318-2323).But its volume expansion problem be still limit its performance performance internal factor, cyclical stability with
And capacity fade problem is (ACS nano, 2014,8 (2), 1728-1738) urgently to be resolved.
Tin base cathode material is mainly with Sn, SnO, SnO2To represent, theoretical capacity respectively reaches 990mAh/g (Sn) (ACS
Nano, 2014,8 (2), 1728-1738), 875mAh/g (SnO), 783mAh/g (SnO2)(ACS applied materials&
Interfaces, 2017,9 (40), 35030-35039), but with lithium alloying reaction, which occurs, for Sn in charge and discharge process generates
Larger volume expansion causes capacity attenuation with contraction.And SnO and SnO2Life can be first reacted with lithium ion before alloying reaction
At lithia (Li2O)(Journal of The Electrochemical Society,2011,158(12),1335-1339)
The consumption of lithium ion is caused, irreversible capacity is generated.With SnO2It compares, SnO theoretical specific capacity is higher than SnO2, while theoretically
For irreversible capacity it is lower, because of only one oxygen of SnO, reacting with lithium ion can ratio in the electrode reaction for generating lithia
SnO2Less lithium ion is consumed, lower irreversible capacity is generated.In conclusion SnO is being used as negative electrode of lithium ion battery material
There is greater advantage when material, is expected to realize its tremendous development in commercial Li-ion battery.Graphene is one kind by monolayer carbon
The New Two Dimensional material that atom is formed has the excellent performances such as its excellent electrical and thermal conductivity, big specific surface area.But it is applied to
In lithium ion battery, due to the excessive specific surface area of graphene, the SEI film excessive consumption lithium for causing it to be formed causes capacity to decline
Subtract the disadvantages such as fast, volume and capacity ratio is low.In the electrode reaction of SnO, volume expansion is to influence a main cause of its performance.
The two-dimentional synergistic effect for constructing graphene and SnO material, is prepared graphene/SnO heterogeneous structure material, is pressed down using graphene
System, the volume expansion for accommodating stannous oxide, and the electron transfer access of efficient stable is provided, it is expected to obtain a kind of novel high ratio
Hold the lithium ion battery negative material of long-life.
Summary of the invention
In order to solve the above problems existing in the present technology, can be used in lithium battery it is an object of that present invention to provide one kind to bear
The graphene of pole/stannous oxide two-dimensional hetero-junction composite material and preparation method.
The technical scheme adopted by the invention is as follows:
A kind of graphene/stannous oxide two-dimensional hetero-junction composite material, the composite material is by graphene nanometer sheet and oxygen
Change the progress layer assembly of stannous nanometer sheet to be combined；In the composite material, the weight fraction of graphene nanometer sheet is 20~
95%, the weight fraction of stannous oxide nanometer sheet is 80~5%.
Preferably, in the composite material, the weight fraction of graphene nanometer sheet is 25~67%, stannous oxide nanometer sheet
Weight fraction be 75~33%.
Preferably, for the graphene nanometer sheet with a thickness of 0.5~20nm, graphene nanometer sheet radial dimension is 0.1~10 μ
m；The stannous oxide nanometer sheet thickness is 0.484~5nm, and stannous oxide nanometer sheet radial dimension is 500nm~5 μm.
Further, the graphene nanometer sheet is with a thickness of 1~5nm；Graphene nanometer sheet radial dimension is 1~5 μm；Institute
Stating stannous oxide nanometer sheet thickness is 1~5nm, and stannous oxide nanometer sheet radial dimension is 1~5 μm.
Invention additionally discloses a kind of graphene/stannous oxide two-dimensional hetero-junction composite material preparation method, including it is following
Step:
1) stripping method is expanded by liquid phase intercalation using graphite and prepares graphene nanometer sheet；
2) stannous oxide nanometer sheet is prepared with liquid phase stripping method；
3) graphene/stannous oxide heterojunction composite is prepared, comprising the following steps:
3-1) graphene nanometer sheet and stannous oxide nanometer sheet are distributed to respectively in deionized water, dispersion concentration 1mg/
ml；
It is 3-2) 1~12 hour ultrasonic at room temperature；
It 3-3) is freeze-dried in freeze drier, obtains graphene/stannous oxide heterojunction structure composite wood
Material.
Preferably, the step 1) the following steps are included:
The concentrated sulfuric acid is stirred at room temperature with oleum 1-1) and is mixed, it is to be cooled to addition ammonium persulfate stirring after room temperature
5~15 minutes；
Graphite powder 1-2) is added to be reacted, reacts 40~80 minutes；
1-3) in 75~85 DEG C of progress water-baths, every water-bath ultrasound 3~10 minutes 15~45 minutes, repeat at least
Twice；
1-4) diluted with deionized water；
1-5) it is washed with deionized；
It 1-6) is freeze-dried to obtain graphene nanometer sheet.
Preferably, the step 2) the following steps are included:
2-1) make the dispersion liquid that dispersed phase prepares stannous oxide with the isopropanol water solution that volume fraction is 20~40%, point
Dispersion liquid concentration is 1mg/ml；
2-2) ultrasound is centrifugated sediment and obtains supernatant at room temperature after 10~14 hours；
2-3) supernatant is freeze-dried to obtain stannous oxide nanometer sheet.
Further, the step 2-2) in, isopropanol water solution is added in sediment, and ultrasonic again, centrifugation obtains supernatant
Liquid.
Invention additionally discloses another graphene/stannous oxide material two-dimensional layer layer heap pile complex method, including it is following
Step:
1) stripping method is expanded by liquid phase intercalation using graphite and prepares graphene nanometer sheet；
2) stannous oxide nanometer sheet is prepared with liquid phase stripping method；
3) graphene/stannous oxide heterojunction composite is prepared, comprising the following steps:
3-1) graphene nanometer sheet is distributed in deionized water, dispersion liquid concentration 1mg/ml；
After 3-2) ultrasonic disperse is uniform, PDDA aqueous solution is instilled under stirring conditions, instillation PDDA weight is graphite
The weight fraction of PDDA is 2% in 0.1~20%, the PDDA aqueous solution of alkene nanometer sheet weight, continues stirring 50 after being added dropwise to complete
~80 minutes, obtain the graphene nanometer sheet suspension of PDDA modification；
3-3) stannous oxide nanometer sheet is distributed in deionized water, ultrasound 1~12 hour, dispersion liquid concentration are at room temperature
1mg/ml；
3-4) graphene that PDDA modification is added in the dispersant liquid drop of stannous oxide nanometer sheet is hanged under the conditions of ultrasonic agitation
In nanometer sheet supernatant liquid；
It is freeze-dried after 3-5) being filtered by vacuum, obtains graphene/stannous oxide hetero-junctions composite wood of PDDA modification
Material.
The present invention points out simultaneously, graphene/stannous oxide heterojunction composite can be carried out marumerizer and carbon two
Secondary be coated with further increases its tap density and electrode performance, mainly comprises the steps of:
1) by obtained graphene/stannous oxide heterojunction composite dissolution, (water or water/ethyl alcohol mixing are molten in a solvent
Liquid), while a certain amount of carbon source polymer (glucose, polyvinyl alcohol, phenolic resin etc.) is dissolved in the solution.
2) mixed solution is sprayed dry progress marumerizer, the graphene/stannous oxide for obtaining polymer overmold is heterogeneous
Tie complex microsphere.
3) graphene of polymer overmold/stannous oxide hetero-junctions complex microsphere is heated to 650 DEG C in an inert atmosphere
Carbonization, obtains carbon-coated graphene/stannous oxide composite microsphere material.
Invention additionally discloses above-mentioned two kinds of graphenes/stannous oxide two-dimensional hetero-junction composite materials to prepare lithium-ion electric
The purposes of pond cathode.
The invention has the benefit that
1. the present invention uses liquid phase stripping method for main method, the two-dimensional sheet structure of nano-scale has been prepared.The party
Method is easy to operate, and green non-pollution is, it can be achieved that large scale preparation.
2. the graphene that the present invention prepares/stannous oxide heterojunction structure can realize that graphene and stannous oxide are made respectively
For the mutual supplement with each other's advantages of lithium ion battery negative material, the two-dimentional stack effect of stannous oxide nanometer sheet and graphene nanometer sheet is utilized
The reunion that can prevent graphene reduces its specific surface area and reduces capacity attenuation, and in turn, graphene improves stannous oxide material
The electric conductivity of material, it is suppressed that its volume expansion has shown the lithium ion battery negative material of high capacity, high circulation stability.
3. the material of technology of the present invention preparation, the processes such as the production of subsequent pole piece, battery assembly can with it is traditional
Pole piece production, battery assembly technology hardware compatibility are general, are suitable for heavy industrialization application.
4. a kind of preferred preparation method of the invention can be further improved two-dimensional nano piece heap by surface charge modification
The accurate control of folded behavior.It is not only a kind of preparation method of completely new heterojunction composite, while being also beneficial to electrochemistry
The regulation of behavior.
Detailed description of the invention
Fig. 1 is the SEM figure of the G/SnO two-dimensional hetero-junction composite material of embodiment 3；
Fig. 2 is the TEM figure of the G/SnO two-dimensional hetero-junction composite material of embodiment 3；
Fig. 3 is the cycle characteristics figure of the G/SnO two-dimensional hetero-junction composite material of embodiment 3；
Fig. 4 is the charging and discharging curve figure of the G/SnO two-dimensional hetero-junction composite material of embodiment 3；
Fig. 5 is the G/SnO two-dimensional hetero-junction composite material of embodiment 3 and the cycle performance pair of graphene and SnO particle
Than.
Wherein: G is graphene, and SnO is stannous oxide.
Specific embodiment
Further explaination is done to the present invention combined with specific embodiments below.
Embodiment 1:
The present embodiment provides a kind of graphene/stannous oxide two-dimensional hetero-junction composite material and preparation methods, by dense sulphur
Acid is stirred at room temperature with oleum to be mixed, to be cooled to stir 5 minutes to addition ammonium persulfate after room temperature；Be added graphite powder into
Row reaction, reacts 40 minutes；In 75 DEG C of progress water-baths, every water-bath 15 minutes 3 minutes ultrasonic, in triplicate；It spends
Ionized water dilution；It is washed with deionized；It is freeze-dried to obtain graphene nanometer sheet.The graphene is uniformly dispersed in water
In.Make the dispersion liquid that dispersed phase prepares stannous oxide with the isopropanol water solution that volume fraction is 20%, dispersion liquid concentration is
1mg/ml；Ultrasound is centrifuged after 10 hours at room temperature, and taking supernatant is the dispersion liquid of stannous oxide nanometer sheet, and sediment (is not shelled
From stannous oxide) can disperse again after ultrasound-centrifugation and be recycled；Supernatant, which is freeze-dried to obtain stannous oxide, to be received
Rice piece；By this, stannous oxide nanometer sheet is uniform is dispersed in water.Graphene and stannous oxide nanometer sheet are according to mass ratio 2:1 in water
It is mixed 12 hours under the conditions of middle ultrasonic agitation, freeze-drying obtains G/SnO two-dimensional hetero-junction composite material.
In mass ratio by the G/SnO two-dimensional hetero-junction composite material, conductive black and sodium carboxymethylcellulose (CMC) of preparation
8:1:1 mixed dissolution is uniformly coated on copper foil in deionized water, and 80 ° of vacuum drying 12h are obtained in a vacuum drying oven
Pole piece is cut into the disk of Φ 14mm by pole piece, is anode with composite material pole piece in glove box, metal lithium sheet be to electrode,
Electrolyte used is EC:DEC:EMC=1:1:1,5%FEC, 1MLiPF6, compound with tri- layers of Cellgard 2320PP/PE/PP
Film is diaphragm, and using CR2025 battery case, 0.5mm gasket, 1.1mm elastic slice is assembled into button cell.Use LAND battery testing
System, with different current densities (50mA/g, 100mA/g, 200mA/g, 400mA/g, 800mA/g, 1000mA/g) to assembling
Button cell carry out cycle performance test and multiplying power test, voltage window be 0.01V~2.5V.Electrode is close in 50mA/g electric current
Spending lower reversible capacity is 550mAh/g, and cycle life is 200 times.
Embodiment 2:
The present embodiment provides a kind of graphene/stannous oxide two-dimensional hetero-junction composite material and preparation methods, by dense sulphur
Acid is stirred at room temperature with oleum to be mixed, to be cooled to stir 15 minutes to addition ammonium persulfate after room temperature；Graphite powder is added
It is reacted, is reacted 80 minutes；In 85 DEG C of progress water-baths, every water-bath 45 minutes 10 minutes ultrasonic, in triplicate；With
Deionized water dilution；It is washed with deionized；It is freeze-dried to obtain graphene nanometer sheet.The graphene is uniformly dispersed in
In water.Make the dispersion liquid that dispersed phase prepares stannous oxide with the isopropanol water solution that volume fraction is 40%, dispersion liquid concentration is
1mg/ml；Ultrasound is centrifuged after 14 hours at room temperature, and taking supernatant is the dispersion liquid of stannous oxide nanometer sheet, and sediment (is not shelled
From stannous oxide) can disperse again after ultrasound-centrifugation and be recycled；Supernatant, which is freeze-dried to obtain stannous oxide, to be received
Rice piece；By this, stannous oxide nanometer sheet is uniform is dispersed in water.Graphene and stannous oxide nanometer sheet are according to mass ratio 1:1 in water
It is mixed 12 hours under the conditions of middle ultrasonic agitation, freeze-drying obtains G/SnO two-dimensional hetero-junction composite material.
In mass ratio by the G/SnO two-dimensional hetero-junction composite material, conductive black and sodium carboxymethylcellulose (CMC) of preparation
8:1:1 peace is assembled into button cell according to the method in embodiment 1.Using LAND battery test system, with different current densities
(50mA/g, 100mA/g, 200mA/g, 400mA/g, 800mA/g, 1000mA/g) carries out cycle performance to the button cell of assembling
Test and multiplying power test, voltage window are 0.01V~2.5V.Impedance is carried out with ten thousand energization chem workstation of Switzerland and CV curve is surveyed
Examination, voltage window is 0V~3V, scanning speed 0.1mV/s.Electrode reversible capacity under 50mA/g current density is 580mAh/
G, can stablize circulation 200 times.
Embodiment 3:
The present embodiment provides a kind of graphene/stannous oxide two-dimensional hetero-junction composite material and preparation methods, by dense sulphur
Acid is stirred at room temperature with oleum to be mixed, to be cooled to stir 10 minutes to addition ammonium persulfate after room temperature；Graphite powder is added
It is reacted, is reacted 60 minutes；In 80 DEG C of progress water-baths, every water-bath 30 minutes 5 minutes ultrasonic, in triplicate；With
Deionized water dilution；It is washed with deionized；It is freeze-dried to obtain graphene nanometer sheet.The graphene is uniformly dispersed in
In water.Make the dispersion liquid that dispersed phase prepares stannous oxide with the isopropanol water solution that volume fraction is 30%, dispersion liquid concentration is
1mg/ml；Ultrasound is centrifuged after 12 hours at room temperature, and taking supernatant is the dispersion liquid of stannous oxide nanometer sheet, and sediment (is not shelled
From stannous oxide) can disperse again after ultrasound-centrifugation and be recycled；Supernatant, which is freeze-dried to obtain stannous oxide, to be received
Rice piece；By this, stannous oxide nanometer sheet is uniform is dispersed in water.Graphene and stannous oxide nanometer sheet are according to mass ratio 1:2 in water
It is mixed 12 hours under the conditions of middle ultrasonic agitation, freeze-drying obtains G/SnO two-dimensional hetero-junction composite material.
In mass ratio by the G/SnO two-dimensional hetero-junction composite material, conductive black and sodium carboxymethylcellulose (CMC) of preparation
8:1:1 peace is assembled into button cell according to the method in embodiment 1.Using LAND battery test system, with different current densities
(50mA/g, 100mA/g, 200mA/g, 400mA/g, 800mA/g, 1000mA/g) carries out cycle performance to the button cell of assembling
Test and multiplying power test, voltage window are 0.01V~2.5V.Impedance is carried out with ten thousand energization chem workstation of Switzerland and CV curve is surveyed
Examination, voltage window is 0V~3V, scanning speed 0.1mV/s.Electrode reversible capacity under 50mA/g current density is 608mAh/
G, can stablize circulation 200 times.
As shown in figure 4, the charging and discharging curve figure of the G/SnO two-dimensional hetero-junction composite material of embodiment 3, after single charge and discharge
Specific capacity is shown in Table 1.
Table 1
Embodiment 4:
The present embodiment provides a kind of graphene/stannous oxide two-dimensional hetero-junction composite material and preparation methods, by dense sulphur
Acid is stirred at room temperature with oleum to be mixed, to be cooled to stir 15 minutes to addition ammonium persulfate after room temperature；Graphite powder is added
It is reacted, is reacted 60 minutes；In 80 DEG C of progress water-baths, every water-bath 30 minutes 5 minutes ultrasonic, in triplicate；With
Deionized water dilution；It is washed with deionized；It is freeze-dried to obtain graphene nanometer sheet.The graphene is uniformly dispersed in
In water.Make the dispersion liquid that dispersed phase prepares stannous oxide with the isopropanol water solution that volume fraction is 30%, dispersion liquid concentration is
1mg/ml；Ultrasound is centrifuged after 12 hours at room temperature, and taking supernatant is the dispersion liquid of stannous oxide nanometer sheet, and sediment (is not shelled
From stannous oxide) can disperse again after ultrasound-centrifugation and be recycled；Supernatant, which is freeze-dried to obtain stannous oxide, to be received
Rice piece；By this, stannous oxide nanometer sheet is uniform is dispersed in water.Graphene and stannous oxide nanometer sheet are according to mass ratio 1:3 in water
It is mixed 12 hours under the conditions of middle ultrasonic agitation, freeze-drying obtains G/SnO two-dimensional hetero-junction composite material.
In mass ratio by the G/SnO two-dimensional hetero-junction composite material, conductive black and sodium carboxymethylcellulose (CMC) of preparation
8:1:1 peace is assembled into button cell according to the method in embodiment 1.Using LAND battery test system, with different current densities
(50mA/g, 100mA/g, 200mA/g, 400mA/g, 800mA/g, 1000mA/g) carries out cycle performance to the button cell of assembling
Test and multiplying power test, voltage window are 0.01V~2.5V.Electrode reversible capacity under 50mA/g current density is 710mAh/
G, can stablize circulation 200 times.
Embodiment 5:
The present embodiment provides a kind of graphene/stannous oxide two-dimensional hetero-junction composite material and preparation methods, by dense sulphur
Acid is stirred at room temperature with oleum to be mixed, to be cooled to stir 10 minutes to addition ammonium persulfate after room temperature；Graphite powder is added
It is reacted, is reacted 60 minutes；In 80 DEG C of progress water-baths, every water-bath 30 minutes 5 minutes ultrasonic, in triplicate；With
Deionized water dilution；It is washed with deionized；It is freeze-dried to obtain graphene nanometer sheet.The graphene is uniformly dispersed in
In water.Make the dispersion liquid that dispersed phase prepares stannous oxide with the isopropanol water solution that volume fraction is 30%, dispersion liquid concentration is
1mg/ml；Ultrasound is centrifuged after 12 hours at room temperature, and taking supernatant is the dispersion liquid of stannous oxide nanometer sheet, and sediment (is not shelled
From stannous oxide) can disperse again after ultrasound-centrifugation and be recycled；Supernatant, which is freeze-dried to obtain stannous oxide, to be received
Rice piece.Graphene nanometer sheet is distributed in deionized water, dispersion liquid concentration 1mg/ml；After ultrasonic disperse is uniform, by PDDA
Aqueous solution instills under stirring conditions, instills PDDA in 2%, the PDDA aqueous solution that PDDA weight is graphene nano sheet weight
Weight fraction be 2%, continue after being added dropwise to complete stirring 60 minutes, obtain PDDA modification graphene nanometer sheet suspension；It will
Stannous oxide nanometer sheet is distributed in deionized water, at room temperature ultrasound 12 hours, dispersion liquid concentration 1mg/ml；It is being stirred by ultrasonic
Under the conditions of the graphene that PDDA modification is added in the dispersant liquid drop of stannous oxide nanometer sheet is hanged in nanometer sheet supernatant liquid, graphene and oxygen
Change stannous nanometer sheet according to mass ratio 1: 2；It is freeze-dried after vacuum filtration, the graphene/oxidation for obtaining PDDA modification is sub-
Tin heterojunction composite is dissolved in 30% ethanol water by heterojunction composite and PVA according to 3:1 mass ratio, spray
650 DEG C of carbonizations, obtain carbon-coated second particle heterojunction composite after mist is dry.
By carbon-coated second particle heterojunction composite, conductive black and the sodium carboxymethylcellulose of preparation
(CMC) peace of 8:1:1 in mass ratio is assembled into button cell according to the method in embodiment 1.Using LAND battery test system, with not
Button cell of the same current density (50mA/g, 100mA/g, 200mA/g, 400mA/g, 800mA/g, 1000mA/g) to assembling
Cycle performance test and multiplying power test are carried out, voltage window is 0.01V~2.5V.Electrode reversible appearance under 50mA/g current density
Amount is 696mAh/g, can stablize circulation 200 times.
Embodiment 6:
The present embodiment provides a kind of graphene/stannous oxide two-dimensional hetero-junction composite material and preparation methods, by dense sulphur
Acid is stirred at room temperature with oleum to be mixed, to be cooled to stir 10 minutes to addition ammonium persulfate after room temperature；Graphite powder is added
It is reacted, is reacted 60 minutes；In 80 DEG C of progress water-baths, every water-bath 30 minutes 5 minutes ultrasonic, in triplicate；With
Deionized water dilution；It is washed with deionized；It is freeze-dried to obtain graphene nanometer sheet.The graphene is uniformly dispersed in
In water.Make the dispersion liquid that dispersed phase prepares stannous oxide with the isopropanol water solution that volume fraction is 30%, dispersion liquid concentration is
1mg/ml；Ultrasound is centrifuged after 12 hours at room temperature, and taking supernatant is the dispersion liquid of stannous oxide nanometer sheet, and sediment (is not shelled
From stannous oxide) can disperse again after ultrasound-centrifugation and be recycled；Supernatant, which is freeze-dried to obtain stannous oxide, to be received
Rice piece.Graphene nanometer sheet is distributed in deionized water, dispersion liquid concentration 1mg/ml；After ultrasonic disperse is uniform, by PDDA
Aqueous solution instills under stirring conditions, instills PDDA in 2%, the PDDA aqueous solution that PDDA weight is graphene nano sheet weight
Weight fraction be 2%, continue after being added dropwise to complete stirring 60 minutes, obtain PDDA modification graphene nanometer sheet suspension；It will
Stannous oxide nanometer sheet is distributed in deionized water, at room temperature ultrasound 12 hours, dispersion liquid concentration 1mg/ml；It is being stirred by ultrasonic
Under the conditions of the graphene that PDDA modification is added in the dispersant liquid drop of stannous oxide nanometer sheet is hanged in nanometer sheet supernatant liquid, graphene and oxygen
Change stannous nanometer sheet according to mass ratio 1: 3；It is freeze-dried after vacuum filtration, the graphene/oxidation for obtaining PDDA modification is sub-
Tin heterojunction composite is dissolved in 30% ethanol water by heterojunction composite and PVA according to 3:1 mass ratio, spray
650 DEG C of carbonizations, obtain carbon-coated second particle heterojunction composite after mist is dry.
Graphene/stannous oxide heterojunction composite, conductive black and carboxymethyl cellulose that the PDDA of preparation is modified
Plain sodium (CMC) 8:1:1 in mass ratio peace is assembled into button cell according to the method in embodiment 1.Using LAND battery test system,
With different current densities (50mA/g, 100mA/g, 200mA/g, 400mA/g, 800mA/g, 1000mA/g) to the button of assembling
Battery carries out cycle performance test and multiplying power test, and voltage window is 0.01V~2.5V.Electrode can under 50mA/g current density
Inverse capacity is 718mAh/g, can stablize circulation 200 times.
Can be seen that graphene/stannous oxide heterojunction structure that the present invention prepares in conjunction with Fig. 1 to Fig. 5 can realize stone
Black alkene and stannous oxide utilize stannous oxide nanometer sheet and graphene respectively as the mutual supplement with each other's advantages of lithium ion battery negative material
The two-dimentional stack effect of nanometer sheet can prevent the reunion of graphene, meanwhile, graphene improves the conduction of stannous oxide material
Property, it is suppressed that its volume expansion has shown the lithium ion battery negative material of high capacity, high circulation stability.Pass through surface electricity
Lotus modification can be further improved the accurate control that two-dimensional nano piece stacks behavior.It is not only a kind of completely new hetero-junctions composite wood
The preparation method of material, while being also beneficial to the regulation of electrochemical behavior.
The present invention is not limited to above-mentioned optional embodiment, anyone can show that other are each under the inspiration of the present invention
The product of kind form.Above-mentioned specific embodiment should not be understood the limitation of pairs of protection scope of the present invention, protection of the invention
Range should be subject to be defined in claims, and specification can be used for interpreting the claims.
Claims (10)
1. a kind of graphene/stannous oxide two-dimensional hetero-junction composite material, it is characterised in that: the composite material is received by graphene
Rice piece carries out layer assembly with stannous oxide nanometer sheet and is combined；In the composite material, the weight point of graphene nanometer sheet
Number is 20~95%, and the weight fraction of stannous oxide nanometer sheet is 80~5%.
2. a kind of graphene according to claim 1/stannous oxide two-dimensional hetero-junction composite material, it is characterised in that: institute
It states in composite material, the weight fraction of graphene nanometer sheet is 25~67%, the weight fraction of stannous oxide nanometer sheet is 75~
33%.
3. a kind of graphene according to claim 1 or 2/stannous oxide two-dimensional hetero-junction composite material, it is characterised in that:
For the graphene nanometer sheet with a thickness of 0.5~20nm, graphene nanometer sheet radial dimension is 0.1~10 μm；The stannous oxide
Nanometer sheet thickness is 0.484~5nm, and stannous oxide nanometer sheet radial dimension is 500nm~5 μm.
4. a kind of graphene according to claim 3/stannous oxide two-dimensional hetero-junction composite material, it is characterised in that: institute
Graphene nanometer sheet is stated with a thickness of 1~5nm；Graphene nanometer sheet radial dimension is 1~5 μm；The stannous oxide nanometer sheet is thick
Degree is 1~5nm, and stannous oxide nanometer sheet radial dimension is 1~5 μm.
5. the preparation method of composite material as described in claim 1-4 any one, it is characterised in that the following steps are included:
1) stripping method is expanded by liquid phase intercalation using graphite and prepares graphene nanometer sheet；
2) stannous oxide nanometer sheet is prepared with liquid phase stripping method；
3) graphene/stannous oxide heterojunction composite is prepared, comprising the following steps:
3-1) graphene nanometer sheet and stannous oxide nanometer sheet are distributed in deionized water, dispersion concentration 1mg/ml；
It is 3-2) 1~12 hour ultrasonic at room temperature；
It 3-3) is freeze-dried in freeze drier, obtains graphene/stannous oxide heterojunction structure composite material.
6. preparation method according to claim 5, which is characterized in that the step 1) the following steps are included:
The concentrated sulfuric acid is stirred at room temperature with oleum 1-1) and is mixed, it is to be cooled to be added after room temperature ammonium persulfate stirring 5~
15 minutes；
Graphite powder 1-2) is added to be reacted, reacts 40~80 minutes；
1-3) in 75~85 DEG C of progress water-baths, every water-bath ultrasound 3~10 minutes 15~45 minutes, at least two are repeated
It is secondary；
1-4) diluted with deionized water；
1-5) it is washed with deionized；
It 1-6) is freeze-dried to obtain graphene nanometer sheet.
7. preparation method according to claim 5, which is characterized in that the step 2) the following steps are included:
2-1) make the dispersion liquid that dispersed phase prepares stannous oxide, dispersion liquid with the isopropanol water solution that volume fraction is 20~40%
Concentration is 1mg/ml；
2-2) ultrasound is centrifugated sediment and obtains supernatant at room temperature after 10~14 hours；
2-3) supernatant is freeze-dried to obtain stannous oxide nanometer sheet.
8. preparation method according to claim 7, which is characterized in that the step 2-2) in, isopropanol is added in sediment
Aqueous solution, ultrasonic again, centrifugation obtains supernatant.
9. the preparation method of composite material as described in claim 1-4 any one, it is characterised in that the following steps are included:
1) stripping method is expanded by liquid phase intercalation using graphite and prepares graphene nanometer sheet；
2) stannous oxide nanometer sheet is prepared with liquid phase stripping method；
3) graphene/stannous oxide heterojunction composite is prepared, comprising the following steps:
3-1) graphene nanometer sheet is distributed in deionized water, dispersion liquid concentration 1mg/ml；
After 3-2) ultrasonic disperse is uniform, PDDA aqueous solution is instilled under stirring conditions, instills PDDA weight and received for graphene
The weight fraction of PDDA is 2% in 0.1~20%, the PDDA aqueous solution of rice sheet weight, continues stirring 50~80 after being added dropwise to complete
Minute, obtain the graphene nanometer sheet suspension of PDDA modification；
3-3) stannous oxide nanometer sheet is distributed in deionized water, at room temperature ultrasound 1~12 hour, dispersion liquid concentration 1mg/
ml；
The graphene that PDDA modification is added in the dispersant liquid drop of stannous oxide nanometer sheet 3-4) is hanged into nanometer under the conditions of ultrasonic agitation
In piece supernatant liquid；
It is freeze-dried after 3-5) being filtered by vacuum, obtains graphene/stannous oxide heterojunction composite of PDDA modification.
10. composite material is in the purposes for preparing negative electrode of lithium ion battery as described in claim 1-4 any one.
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| CN110670023A (en) * | 2019-09-18 | 2020-01-10 | 华南理工大学 | Method for preparing high-quality few-layer stannous oxide crystal by thermal evaporation method |
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