CN106252607A - Hemicentrotus seu Strongylocentrotus shape nanometer Tixsn1 xo2the preparation method of/Graphene three-dimensional composite material and the application on lithium ion battery negative thereof - Google Patents
Hemicentrotus seu Strongylocentrotus shape nanometer Tixsn1 xo2the preparation method of/Graphene three-dimensional composite material and the application on lithium ion battery negative thereof Download PDFInfo
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Abstract
The invention discloses a kind of Hemicentrotus seu Strongylocentrotus shape nanometer TixSn1‑xO2The preparation method of/Graphene three-dimensional composite material and the application on lithium ion battery negative thereof.The present invention is to utilize coordination principle and molecular self-assembling method, prepares Hemicentrotus seu Strongylocentrotus shape nanometer Ti by a step Hydrothermal Synthesis technology self assemblyxSn1‑xO2/ Graphene three-dimensional composite material.The preparation method is that: (1) prepares graphene oxide, (2) prepare surface electronegative graphite oxide colloidal sol；(3) reduction prepares Hemicentrotus seu Strongylocentrotus shape nanometer TixSn1‑xO2/ Graphene three-dimensional composite material.Course of reaction of the present invention is carried out in aqueous, it is not necessary to add other reagent, and technique is simple, with low cost and energy-conserving and environment-protective, it is easy to industrial volume production.As lithium ion battery anode material, this three dimensional composite structure is conducive to electrolyte diffusion between composite and electronics and ion to transmit in the material, can be effectively improved the performances such as the charge/discharge capacity of composite, cycle life and multiplying power.
Description
Technical field
The invention belongs to nanometer material science and secondary power supply technical field, particularly a kind of Hemicentrotus seu Strongylocentrotus shape nanometer TixSn1- xO2The preparation method of/Graphene three-dimensional composite material and the application on lithium ion battery negative thereof.
Background technology
In current various portable electric appts, lithium ion battery occupies absolute leading position and is considered heat of future generation
The power supply replacer most with Commercial Prospect of door electric/hybrid automobile.In order to enable more effectively to store and transport electricity
Can, researcher is devoted to explore various high energy negative materials, such as theory ratio for rechargeable lithium ion batteries of future generation always
Capacity is up to 782 mA h g respectively-1Tin ash (SnO2).But, owing to the electric conductivity of material itself is poor, it is unfavorable for
Charge transfer in charge and discharge process；Additionally in charge and discharge process, the intercalation/deintercalation of lithium ion the Severe aggregation effect caused
The efflorescence of electrode and the rapid decay of capacity should be easily caused with enormousness change, cause cycle performance and the high rate performance of material
Poor, thus greatly hinder the further application at lithium ion battery of these materials.Recently, research proves content widely
Abundant, low cost, environmental protection, function admirable TiO2Also it is potential lithium cell negative pole material of future generation.TiO2Embed at lithium, deviate from
Stability Analysis of Structures, safety in journey, avoid the electrochemical deposition (such as SEI film) of lithium simultaneously.Shortcoming is that its theoretical capacity is the highest (about
170mAh g-1) and electronic conductivity not good enough.But Rutile Type SnO2With Rutile Type TiO2Crystal formation is close, being combined of the two
Material is widely believed that the most possible next generation large-scale energy storage material.For solving these difficult problems, have high conductivity and
The carbonaceous material of ductility is widely used as the carrier of these active materials to improve its chemical property.Especially Graphene,
A kind of carbon atom is with sp2Hydridization is the monolayer two dimensional crystal that hexagon cellular shape lattice arrangement is constituted, and the performance with its uniqueness is the most excellent
Different electric conductivity, good mechanical flexibility, huge specific surface area (2630m2 g-1) and the heat stability of superelevation and chemistry steady
Qualitative and become the excellent carrier of the most attractive load electrochemical active material.Therefore, numerous metal-oxide/graphite
Alkene nano composite material, such as SnO2/ Graphene, TiO2/ Graphene, TiO2-SnO2/ Graphene is at third party's nano-particle or gold
Belong to and being prepared by the accumulation again between graphene layer under organic precursor effect.Other carbon-based material relatively, such as graphite, charcoal
Black, CNT, Graphene can more effectively buffer metal oxide in charge and discharge process due to the swelling stress of volume
Thus keep the satisfactory electrical conductivity of whole electrode.
Lot of experiments proves, by Graphene and TiO2-SnO2Nano-particle carries out the compound graphene modified obtained
Tin dioxide lithium ion battery negative pole material, can be greatly improved cycle performance and the high rate performance of lithium ion battery negative.And
Nanometer TixSn1-xO2Solid solution composite material is homogeneously combined at Ti-Sn-O atomic scale, significantly more efficient combines TiO2Height
Stability and SnO2The advantage of high power capacity, avoid TiO simultaneously2@SnO2Composite easily produces during charge and discharge cycles
The raw shortcoming causing capacity and life performance to decline that is separated.Pass through TixSn1-xO2Solid solution is permissible with Graphene LBL self-assembly
More effectively buffer metal oxide in charge and discharge process due to the swelling stress of volume thus keep the good of whole electrode
Electric conductivity.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of Hemicentrotus seu Strongylocentrotus shape nanometer TixSn1-xO2/ Graphene
The preparation method of three-dimensional composite material and the application on lithium ion battery negative thereof.
In order to achieve the above object, present invention employs following technical scheme:
A kind of Hemicentrotus seu Strongylocentrotus shape nanometer TixSn1-xO2/ Graphene three-dimensional composite material is to be 89.97～95.98% by weight/mass percentage composition
TixSn1-xO2Form with Graphene.
A kind of Hemicentrotus seu Strongylocentrotus shape nanometer TixSn1-xO2The preparation method of/Graphene three-dimensional composite material, comprises the steps:
(1) using the Hummers method improved to prepare graphene oxide, take the container of dried and clean, adding parts by volume is 60～90
Part concentration is the concentrated sulphuric acid of 98%, and container is placed on ice bath in frozen water；Weigh the crystalline flake graphite that weight portion is 1.5～2.5 parts to add
In the concentrated sulfuric acid solution carrying out ice-water bath, then carry out mechanical agitation 20～30min；Weighing weight portion is 8～10 parts high
Potassium manganate is slowly added in above-mentioned solution, adds fashionable slow as far as possible, treats that solution becomes green, after potassium permanganate adds completely,
Ice bath two hours again；Then move to 35 DEG C of thermostat water baths at the uniform velocity stir 12h, become the yellowish-brown slurry of thickness；?
Container removal water-bath, under stirring, divides 6 times, adds the water dilution that parts by volume is 44～50 parts every time, makes by sticky
Yellowish-brown slurry overstrike solution, after adding, moves into stirring 2h in the thermostat water bath of 35 DEG C；Measure parts by volume be 20～
28 parts of concentration are the H of 30%2O2Join in above-mentioned brown solution, treat that solution is become golden yellow by brown, with golden yellow lamellar
Thing；Being centrifuged with the rotating speed of 9000r/min, incline supernatant again, and precipitate dilute hydrochloric acid and deionization with concentration is 5% respectively is each
Wash three times, sample uniform spreading on surface plate, surface plate is placed on 24h lyophilizing in freeze drier, takes sample off, use agate
Nao mortar grinder, i.e. can get filemot graphite oxide powder；
(2) being dispersed in water by prepared graphene oxide powder ultrasonic, prepared mass ratio is 1～2.5%, surface bear electricity
Graphene oxide colloidal sol；
(3) under the conditions of continuously stirred, titanium potassium oxalate solid is added in the graphene oxide colloidal sol of preparation, treat that titanium potassium oxalate is solid
Body is slowly added dropwise the most continuously stirred 5～10 points of the butter of tin aqueous solution of 0.5 M that parts by volume is 10-25 part after being completely dissolved
Clock, then moves to carry out in water heating kettle hydro-thermal reaction, naturally cools to room temperature and obtain pitchy hydrogel post, warp after reaction completely
Wash, be dried, prepare Hemicentrotus seu Strongylocentrotus shape nanometer Ti through 400～600 DEG C of calcining reductions the most in a nitrogen atmospherexSn1-xO2/ Graphene three
Dimension composite.
Further, the tin ion in described step (3) is 1: 4 with the mol ratio of titanium.
Further, the Ti in described step (3)xSn1-xO2It is 1～2.5: 100 with the mass ratio of graphene oxide.
Further, dry in described step (3) refers to-56 DEG C of lyophilizations 12～24 hours.
A kind of Hemicentrotus seu Strongylocentrotus shape nanometer TixSn1-xO2The application on the lithium ion battery negative of/Graphene three-dimensional composite material.
Beneficial effect:
(1) course of reaction of the present invention only need to be carried out in aqueous, it is not necessary to the organic reagent such as template, surfactant, a step
Hydro-thermal.
(2) principle of the invention is simple, simple operation, and abundant raw material is cheap, economic and environment-friendly, is suitable for industry metaplasia
Produce.
(3) present invention utilize titanium potassium oxalate for titanium source, do not use titanium chloride, sulfate titanium and tetrabutyl titanate etc. inorganic,
Organic titanium source, it is to avoid its hydrolysis rate is soon to self-assembled material structure and the uncontrollability of pattern, by utilizing titanium potassium oxalate
Carboxylic acid group and surface of graphene oxide active group (carboxyl, hydroxyl, epoxy radicals etc.) and metal ion stannum (Sn4+) weak coordination work
With, use growth in situ controlled self assembly TixSn1-xO2/ graphene three-dimensional structure composite.
(4) Ti in three-dimensional composite material prepared by the present inventionxSn1-xO2Crystal is Hemicentrotus seu Strongylocentrotus spherical morphology, particle diameter be 120～
150nm, specific surface area is big, is evenly distributed closely, and is firmly supported on laminated structure surface between graphene layer between graphene layer,
Adjusting TixSn1-xO2Under the conditions of graphene oxide colloidal sol suitable proportion, active material TixSn1-xO2Content through thermogravimetric survey
Examination may be up to 95.98%；
(5) Hemicentrotus seu Strongylocentrotus shape nanometer Ti that prepared by the present inventionxSn1-xO2The battery-active of/Graphene three-dimensional lithium cell negative pole material is high,
100 mA g-1Under charging or discharging current, charge/discharge specific capacity first is respectively 784,1184 mA h g-1, charge ratio after 100 weeks
Capacity is still up to 580 mA h g-1, capability retention > and 97%.Through 100,200,500,1000,2000 mA g-1Different multiplying is filled
Discharge test, after 100 weeks, when charge/discharge flow back into 100mA/g, its charge specific capacity is still up to 600 mA h g-1；
(6) present invention, Hemicentrotus seu Strongylocentrotus shape nanometer Ti are usedxSn1-xO2The active substance Ti of/Graphene three-dimensional composite negative pole materialxSn1- xO2The component ratio of/Graphene is prone to Morphological control.
Accompanying drawing explanation
Fig. 1 is Hemicentrotus seu Strongylocentrotus shape nanometer Ti of embodiment 1 preparationxSn1-xO2The X-ray diffractogram of/Graphene three-dimensional composite material.
Fig. 2 is Hemicentrotus seu Strongylocentrotus shape nanometer Ti of embodiment 2 preparationxSn1-xO2The transmission electron microscope picture of/Graphene three-dimensional composite material.
Fig. 3 is Hemicentrotus seu Strongylocentrotus shape nanometer Ti of embodiment 3 preparationxSn1-xO2The thermal multigraph of/Graphene three-dimensional composite material.
Fig. 4 is Hemicentrotus seu Strongylocentrotus shape nanometer Ti of embodiment 4 preparationxSn1-xO2The battery charging and discharging of/Graphene three-dimensional composite material times
Rate performance map.
Fig. 5 is Hemicentrotus seu Strongylocentrotus shape nanometer Ti of embodiment 4 preparationxSn1-xO2The battery charging and discharging of/Graphene three-dimensional composite material follows
Ring performance map.
Fig. 6 is Hemicentrotus seu Strongylocentrotus shape nanometer Ti of embodiment 5 preparationxSn1-xO2The specific surface area figure of/Graphene three-dimensional composite material.
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme is described in further detail, but the protection model of the present invention
Enclose and be not limited thereto.
Embodiment 1
A kind of Hemicentrotus seu Strongylocentrotus shape nanometer TixSn1-xO2The preparation method of/Graphene three-dimensional composite material, comprises the steps:
(1) using the Hummers method improved to prepare graphene oxide, take the container of dried and clean, adding 70ml concentration is 98%
Concentrated sulphuric acid, is placed on ice bath in frozen water container；The crystalline flake graphite weighing 2g joins in the concentrated sulfuric acid solution carrying out ice-water bath,
Then mechanical agitation 20～30min is carried out；Weighing weight portion is that 8g potassium permanganate is slowly added in above-mentioned solution, adds fashionable most
May be slow, treat that solution becomes green, after potassium permanganate adds completely, then ice bath two hours；Then 35 DEG C of waters bath with thermostatic control are moved to
At the uniform velocity stir 12h in Guo, become the yellowish-brown slurry of thickness；Container is removed water-bath, under stirring, points 6 times, often
The water dilution of secondary addition 46ml, makes, by sticky yellowish-brown slurry overstrike solution, after adding, to move into the thermostatted water of 35 DEG C
Bath stirs 2h；Measure the H that 25ml concentration is 30%2O2Join in above-mentioned brown solution, treat that solution is become golden yellow by brown
Color, with golden yellow tablet；Being centrifuged with the rotating speed of 9000r/min, incline supernatant again, and precipitate is 5% by concentration respectively
Dilute hydrochloric acid and deionization respectively wash three times, sample uniform spreading on surface plate, surface plate is placed on 24h in freeze drier and freezes
Dry, take sample off, grind with agate mortar, i.e. can get filemot graphite oxide powder；
(2), the ultrasonic 30min of graphene oxide 300W that weighs 0.1000g be scattered in 100mL water, can obtain pH be 7, concentration be 1
Mg/mL graphene oxide colloidal sol；
(3), under stirring condition, joining in above-mentioned graphene oxide colloidal sol by 5.000g bis-oxalic acid hydrate titanium potassium, stirring is to grass
After acid titanium potassium is completely dissolved, under stirring condition, by SnCl4Solution instills graphene oxide/titanium potassium oxalate with the speed of 1 per second
In colloidal sol, after dropping the most continuously stirred 5～10 minutes, then move to water heating kettle is carried out hydro-thermal reaction, after reaction completely
Naturally cool to that room temperature obtains pitchy hydrogel post, washing, lyophilization obtain Hemicentrotus seu Strongylocentrotus shape nanometer TixSn1-xO2/ Graphene is three-dimensional
Composite；Hemicentrotus seu Strongylocentrotus shape nanometer Ti is prepared the most in a nitrogen atmosphere through 400～600 DEG C of calcining reductionsxSn1-xO2/ Graphene three
Dimension composite lithium ion battery cathode material.
Fig. 1 is Hemicentrotus seu Strongylocentrotus shape nanometer Ti obtained by embodiment 1xSn1-xO2The X-ray diffraction of/Graphene three-dimensional composite material
Figure, from fig. 1, it can be seen that the composition of institute's prepared material is defined as TixSn1-xO2Solid solution/Graphene.
Embodiment 2
A kind of Hemicentrotus seu Strongylocentrotus shape nanometer TixSn1-xO2The preparation method of/Graphene three-dimensional composite material, comprises the steps:
(1) using the Hummers method improved to prepare graphene oxide, take the container of dried and clean, adding 60ml concentration is 98%
Concentrated sulphuric acid, is placed on ice bath in frozen water container；The crystalline flake graphite weighing 1.5g joins the concentrated sulfuric acid solution carrying out ice-water bath
In, then carry out mechanical agitation 20～30min；Weighing weight portion is that 8g potassium permanganate is slowly added in above-mentioned solution, adds
Time slow as far as possible, treat that solution becomes green, after potassium permanganate adds completely, then ice bath two hours；Then 35 DEG C of constant temperature are moved to
Water-bath at the uniform velocity stirs 12h, becomes the yellowish-brown slurry of thickness；Container is removed water-bath, under stirring, divides 6
Secondary, add the water dilution of 50ml every time, make, by sticky yellowish-brown slurry overstrike solution, after adding, to move into 35 DEG C
Thermostat water bath stirs 2h；Measure the H that 20ml concentration is 30%2O2Join in above-mentioned brown solution, treat that solution is become by brown
Become golden yellow, with golden yellow tablet；Being centrifuged with the rotating speed of 9000r/min, incline supernatant, and precipitate uses concentration respectively again
Be 5% dilute hydrochloric acid and deionization respectively wash three times, sample uniform spreading on surface plate, surface plate is placed on freeze drier
Middle 24h lyophilizing, takes sample off, grinds with agate mortar, i.e. can get filemot graphite oxide powder；
(2), the ultrasonic 30min of graphene oxide 300W that weighs 0.1500g be scattered in 100mL water, can obtain pH be 7, concentration be
1.5 mg/mL graphene oxide colloidal sols；
Under (3) stirring condition, joining in above-mentioned graphene oxide colloidal sol by 5.000g bis-oxalic acid hydrate titanium potassium, stirring is to grass
After acid titanium potassium is completely dissolved, under stirring condition, by SnCl4Solution instills graphene oxide/titanium potassium oxalate with the speed of 1 per second
In colloidal sol, after dropping the most continuously stirred 5～10 minutes, then move to water heating kettle is carried out hydro-thermal reaction, after reaction completely
Naturally cooling to room temperature and obtain pitchy hydrogel post, washing, lyophilization obtain Hemicentrotus seu Strongylocentrotus shape nanometer TixSn1-xO2/ Graphene is layer by layer
Self assembly 3-dimensional composite；Hemicentrotus seu Strongylocentrotus shape nanometer Ti is prepared the most in a nitrogen atmosphere through 400～600 DEG C of calcining reductionsxSn1-xO2/
Graphene three-dimensional composite lithium ion battery cathode material.
Visible according to transmission electron microscope Fig. 2, Ti in obtained three-dimensional composite materialxSn1-xO2For Hemicentrotus seu Strongylocentrotus shape ball, Hemicentrotus seu Strongylocentrotus shape is received
Rice TixSn1-xO2Crystal diameter is about 120～150nm, is evenly distributed closely, and is firmly supported on Graphene between graphene layer
Interlayer laminated structure surface.
Embodiment 3
A kind of Hemicentrotus seu Strongylocentrotus shape nanometer TixSn1-xO2The preparation method of/Graphene three-dimensional composite material, comprises the steps:
(1) using the Hummers method improved to prepare graphene oxide, take the container of dried and clean, adding 70ml concentration is 98%
Concentrated sulphuric acid, is placed on ice bath in frozen water container；The crystalline flake graphite weighing 1.5g joins the concentrated sulfuric acid solution carrying out ice-water bath
In, then carry out mechanical agitation 20～30min；Weighing weight portion is that 8g potassium permanganate is slowly added in above-mentioned solution, adds
Time slow as far as possible, treat that solution becomes green, after potassium permanganate adds completely, then ice bath two hours；Then 35 DEG C of constant temperature are moved to
Water-bath at the uniform velocity stirs 12h, becomes the yellowish-brown slurry of thickness；Container is removed water-bath, under stirring, divides 6
Secondary, add the water dilution of 48ml every time, make, by sticky yellowish-brown slurry overstrike solution, after adding, to move into 35 DEG C
Thermostat water bath stirs 2h；Measure the H that 25ml concentration is 30%2O2Join in above-mentioned brown solution, treat that solution is become by brown
Become golden yellow, with golden yellow tablet；Being centrifuged with the rotating speed of 9000r/min, incline supernatant, and precipitate uses concentration respectively again
Be 5% dilute hydrochloric acid and deionization respectively wash three times, sample uniform spreading on surface plate, surface plate is placed on freeze drier
Middle 24h lyophilizing, takes sample off, grinds with agate mortar, i.e. can get filemot graphite oxide powder；
(2), the ultrasonic 30min of graphene oxide 300W that weighs 0.200g be scattered in 100mL water, can obtain pH be 7, concentration be
2.0 mg/mL graphene oxide colloidal sols；
(3), under stirring condition, joining in above-mentioned graphene oxide colloidal sol by 5.000g bis-oxalic acid hydrate titanium potassium, stirring is to grass
After acid titanium potassium is completely dissolved, under stirring condition, by SnCl4Solution instills graphene oxide/titanium potassium oxalate with the speed of 1 per second
In colloidal sol, after dropping the most continuously stirred 5～10 minutes, then move to water heating kettle is carried out hydro-thermal reaction, after reaction completely
Naturally cool to that room temperature obtains pitchy hydrogel post, washing, lyophilization obtain Hemicentrotus seu Strongylocentrotus shape nanometer TixSn1-xO2/ Graphene is three-dimensional
Composite；Hemicentrotus seu Strongylocentrotus shape nanometer Ti is prepared the most in a nitrogen atmosphere through 400-600 DEG C of calcining reductionxSn1-xO2/ Graphene is layer by layer
Self assembly 3-dimensional composite lithium ion battery cathode material.
Can obtain according to transmission electron microscope picture, the Ti that the present embodiment preparesxSn1-xO2/ Graphene three-dimensional composite material, wherein
TixSn1-xO2For Hemicentrotus seu Strongylocentrotus shape, Hemicentrotus seu Strongylocentrotus shape TixSn1-xO2Crystal diameter is about 110 ~ 140nm, is distributed sparse between graphene layer,
But being uniformly firmly supported on laminated structure surface between graphene layer, Fig. 3 is Hemicentrotus seu Strongylocentrotus shape nanometer Ti obtained by embodiment 3xSn1- xO2The thermal multigraph of/Graphene three-dimensional composite material, as can be known from Fig. 3, Ti in resulting materialsxSn1-xO2Content be 95.13
wt%。
Embodiment 4
A kind of Hemicentrotus seu Strongylocentrotus shape nanometer TixSn1-xO2The preparation method of/Graphene three-dimensional composite material, comprises the steps:
(1) using the Hummers method improved to prepare graphene oxide, take the container of dried and clean, adding 80ml concentration is 98%
Concentrated sulphuric acid, is placed on ice bath in frozen water container；The crystalline flake graphite weighing 2g joins in the concentrated sulfuric acid solution carrying out ice-water bath,
Then mechanical agitation 20～30min is carried out；Weighing weight portion is that 9g potassium permanganate is slowly added in above-mentioned solution, adds fashionable most
May be slow, treat that solution becomes green, after potassium permanganate adds completely, then ice bath two hours；Then 35 DEG C of waters bath with thermostatic control are moved to
At the uniform velocity stir 12h in Guo, become the yellowish-brown slurry of thickness；Container is removed water-bath, under stirring, points 6 times, often
The water dilution of secondary addition 45ml, makes, by sticky yellowish-brown slurry overstrike solution, after adding, to move into the thermostatted water of 35 DEG C
Bath stirs 2h；Measure the H that 26ml concentration is 30%2O2Join in above-mentioned brown solution, treat that solution is become golden yellow by brown
Color, with golden yellow tablet；Being centrifuged with the rotating speed of 9000r/min, incline supernatant again, and precipitate is 5% by concentration respectively
Dilute hydrochloric acid and deionization respectively wash three times, sample uniform spreading on surface plate, surface plate is placed on 24h in freeze drier and freezes
Dry, take sample off, grind with agate mortar, i.e. can get filemot graphite oxide powder；
(2), the ultrasonic 30min of graphene oxide 300W that weighs 0.2500g be scattered in 100mL water, can obtain pH be 7, concentration be
2.5 mg/mL graphene oxide colloidal sols；
(3), under stirring condition, joining in above-mentioned graphene oxide colloidal sol by 5.000g bis-oxalic acid hydrate titanium potassium, stirring is to grass
After acid titanium potassium is completely dissolved, under stirring condition, by SnCl4Solution instills graphene oxide/titanium potassium oxalate with the speed of 1 per second
In colloidal sol, after dropping the most continuously stirred 5～10 minutes, then move to water heating kettle is carried out hydro-thermal reaction, after reaction completely
Naturally cool to that room temperature obtains pitchy hydrogel post, washing, lyophilization obtain Hemicentrotus seu Strongylocentrotus shape nanometer TixSn1-xO2/ Graphene is three-dimensional
Composite；Hemicentrotus seu Strongylocentrotus shape nanometer Ti is prepared the most in a nitrogen atmosphere through 400～600 DEG C of calcining reductionsxSn1-xO2/ Graphene three
Dimension composite lithium ion battery cathode material.
Embodiment 5
A kind of Hemicentrotus seu Strongylocentrotus shape nanometer TixSn1-xO2The preparation method of/Graphene three-dimensional composite material, comprises the steps:
(1) using the Hummers method improved to prepare graphene oxide, take the container of dried and clean, adding 90ml concentration is 98%
Concentrated sulphuric acid, is placed on ice bath in frozen water container；The crystalline flake graphite weighing 2.5g joins the concentrated sulfuric acid solution carrying out ice-water bath
In, then carry out mechanical agitation 20～30min；Weighing weight portion is that 10g potassium permanganate is slowly added in above-mentioned solution, adds
Time slow as far as possible, treat that solution becomes green, after potassium permanganate adds completely, then ice bath two hours；Then 35 DEG C of constant temperature are moved to
Water-bath at the uniform velocity stirs 12h, becomes the yellowish-brown slurry of thickness；Container is removed water-bath, under stirring, divides 6
Secondary, add the water dilution of 44ml every time, make, by sticky yellowish-brown slurry overstrike solution, after adding, to move into 35 DEG C
Thermostat water bath stirs 2h；Measure the H that 28ml concentration is 30%2O2Join in above-mentioned brown solution, treat that solution is become by brown
Become golden yellow, with golden yellow tablet；Being centrifuged with the rotating speed of 9000r/min, incline supernatant, and precipitate uses concentration respectively again
Be 5% dilute hydrochloric acid and deionization respectively wash three times, sample uniform spreading on surface plate, surface plate is placed on freeze drier
Middle 24h lyophilizing, takes sample off, grinds with agate mortar, i.e. can get filemot graphite oxide powder；
(2), the ultrasonic 30min of graphene oxide 300W that weighs 0.1500g be scattered in 100mL water, can obtain pH be 7, concentration be
1.5 mg/mL graphene oxide colloidal sols；
(3), under stirring condition, joining in above-mentioned graphene oxide colloidal sol by 3.3333g bis-oxalic acid hydrate titanium potassium, stirring is extremely
After titanium potassium oxalate is completely dissolved, under stirring condition, by SnCl4Solution instills graphene oxide/titanium oxalate with the speed of 1 per second
In potassium colloidal sol, after dropping the most continuously stirred 5～10 minutes, then moving to carry out in water heating kettle hydro-thermal reaction, reaction is completely
After naturally cool to that room temperature obtains pitchy hydrogel post, washing, lyophilization obtain Hemicentrotus seu Strongylocentrotus shape nanometer TixSn1-xO2/ Graphene three
Dimension composite；Hemicentrotus seu Strongylocentrotus shape nanometer Ti is prepared the most in a nitrogen atmosphere through 400～600 DEG C of calcining reductionsxSn1-xO2/ Graphene
LBL self-assembly 3-dimensional composite lithium ion battery cathode material.
Can obtain according to transmission electron microscope picture, the Ti that the present embodiment preparesxSn1-xO2/ Graphene three-dimensional composite material, wherein
TixSn1-xO2For Hemicentrotus seu Strongylocentrotus shape ball, Hemicentrotus seu Strongylocentrotus shape ball TixSn1-xO2Crystal diameter is about 80～120nm, is distributed relatively between graphene layer
Sparse, but uniformly firmly it is supported on laminated structure surface between graphene layer, thermogravimetric analysis shows the Ti that the present embodiment preparesxSn1- xO2Ti in/Graphene three-dimensional composite materialxSn1-xO2Mass percent be 90.04%, Fig. 6 surface analysis shows this enforcement
The Ti that example preparesxSn1-xO2The specific surface area of/Graphene three-dimensional composite material is 161.9 m2 g-1。
Application examples
A kind of Hemicentrotus seu Strongylocentrotus shape nanometer TixSn1-xO2The application on the lithium ion battery negative of/Graphene three-dimensional composite material:
Can obtain according to transmission electron microscope picture, the Ti that embodiment 4 preparesxSn1-xO2/ Graphene three-dimensional composite material, wherein TixSn1-xO2
For Hemicentrotus seu Strongylocentrotus shape, Hemicentrotus seu Strongylocentrotus shape TixSn1-xO2Crystal diameter is about 100～140nm, is distributed sparse between graphene layer, but uniformly jail
Admittedly be supported on laminated structure surface between graphene layer, Fig. 4 is Hemicentrotus seu Strongylocentrotus shape nanometer Ti obtained by embodiment 4xSn1-xO2/ Graphene
The charge-discharge magnification curve chart of the battery of three-dimensional composite material, Fig. 5 is Hemicentrotus seu Strongylocentrotus shape nanometer Ti of embodiment 4 preparationxSn1-xO2/ stone
The battery charging and discharging cycle performance figure of ink alkene three-dimensional composite material.Upper, through 100,200,500,1000 mA g from figure-1No
Test with rate charge-discharge, when charge/discharge flow back into 100mA g-1Time its charge specific capacity still be up to 630 mA h g-1.?
1000 mA g-1Electric current density under, sample has been carried out 504 weeks charge and discharge cycles test (within first 4 weeks, electric current density is 100
mA g-1), first Zhou Rongliang is 1123.3 mA h g-1, the capacity of the second circle is 676.4 mA h g-1, the capacity of the 5th week is
454.7 mA h g-1, capacity when 504 weeks is 488.9 mA h g-1, 1000 mA g-1High current density under circulate 500
Capability retention after circle is 107.5 % and cyclic curve is steady, shows good stable circulation performance.Experimental result table
The battery multiplying power of bright active material and cycle performance are excellent, are adapted as high performance lithium ionic cell cathode material.
Although, the present invention is described in detail the most with a general description of the specific embodiments, but
On the basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to the scope of protection of present invention.
Claims (6)
1. Hemicentrotus seu Strongylocentrotus shape nanometer TixSn1-xO2/ Graphene three-dimensional composite material, it is characterised in that be to be by weight/mass percentage composition
89.97～the Ti of 95.98%xSn1-xO2Form with Graphene.
2. Hemicentrotus seu Strongylocentrotus shape nanometer TixSn1-xO2The preparation method of/Graphene three-dimensional composite material, it is characterised in that: include as follows
Step:
(1) using the Hummers method improved to prepare graphene oxide, take the container of dried and clean, adding parts by volume is 60～90
Part concentration is the concentrated sulphuric acid of 98%, and container is placed on ice bath in frozen water；Weigh the crystalline flake graphite that weight portion is 1.5～2.5 parts to add
In the concentrated sulfuric acid solution carrying out ice-water bath, then carry out mechanical agitation 20～30min；Weighing weight portion is 8～10 parts high
Potassium manganate is slowly added in above-mentioned solution, adds fashionable slow as far as possible, treats that solution becomes green, after potassium permanganate adds completely,
Ice bath two hours again；Then move to 35 DEG C of thermostat water baths at the uniform velocity stir 12h, become the yellowish-brown slurry of thickness；?
Container removal water-bath, under stirring, divides 6 times, adds the water dilution that parts by volume is 44～50 parts every time, makes by sticky
Yellowish-brown slurry overstrike solution, after adding, moves into stirring 2h in the thermostat water bath of 35 DEG C；Measure parts by volume be 20～
28 parts of concentration are the H of 30%2O2Join in above-mentioned brown solution, treat that solution is become golden yellow by brown, with golden yellow lamellar
Thing；Being centrifuged with the rotating speed of 9000r/min, incline supernatant again, and precipitate dilute hydrochloric acid and deionization with concentration is 5% respectively is each
Wash three times, sample uniform spreading on surface plate, surface plate is placed on 24h lyophilizing in freeze drier, takes sample off, use agate
Nao mortar grinder, i.e. can get filemot graphite oxide powder；
(2) being dispersed in water by prepared graphene oxide powder ultrasonic, prepared mass ratio is 1～2.5%, surface bear electricity
Graphene oxide colloidal sol；
(3) under the conditions of continuously stirred, titanium potassium oxalate solid is added in the graphene oxide colloidal sol of preparation, treat that titanium potassium oxalate is solid
Body is slowly added dropwise the most continuously stirred 5～10 points of the butter of tin aqueous solution of 0.5 M that parts by volume is 10-25 part after being completely dissolved
Clock, then moves to carry out in water heating kettle hydro-thermal reaction, naturally cools to room temperature and obtain pitchy hydrogel post, warp after reaction completely
Wash, be dried, prepare Hemicentrotus seu Strongylocentrotus shape nanometer Ti through 400～600 DEG C of calcining reductions the most in a nitrogen atmospherexSn1-xO2/ Graphene three
Dimension composite.
A kind of Hemicentrotus seu Strongylocentrotus shape nanometer Ti the most according to claim 2xSn1-xO2The preparation method of/Graphene three-dimensional composite material,
It is characterized in that: the tin ion in described step (3) is 1: 4 with the mol ratio of titanium.
A kind of Hemicentrotus seu Strongylocentrotus shape nanometer Ti the most according to claim 2xSn1-xO2The preparation method of/Graphene three-dimensional composite material,
It is characterized in that: the Ti in described step (3)xSn1-xO2It is 1～2.5: 100 with the mass ratio of graphene oxide.
A kind of Hemicentrotus seu Strongylocentrotus shape nanometer Ti the most according to claim 2xSn1-xO2The preparation method of/Graphene three-dimensional composite material,
It is characterized in that: dry in described step (3) refers to-56 DEG C of lyophilizations 12～24 hours.
6. a kind of Hemicentrotus seu Strongylocentrotus shape nanometer Ti as claimed in claim 1 or 2xSn1-xO2/ Graphene three-dimensional composite material lithium from
Application in sub-battery cathode.
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| CN107579241A (en) * | 2017-09-22 | 2018-01-12 | 上海工程技术大学 | A kind of preparation method of three-dimensional tent type graphene metal oxide nano composite material |
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| CN109187690A (en) * | 2018-09-17 | 2019-01-11 | 洛阳理工学院 | A kind of preparation method and application of GR/PSS/Pt/GCE electrochemical sensor |
| CN110655809A (en) * | 2019-10-29 | 2020-01-07 | 江苏华光粉末有限公司 | Polyamide wax modified sea urchin-shaped graphene and preparation method thereof, and anticorrosive powder coating and preparation process thereof |
| CN114538426A (en) * | 2022-03-04 | 2022-05-27 | 深圳石墨烯创新中心有限公司 | Preparation method of graphene |
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