CN106252607B - Sea urchin shape nanometer TixSn1-xO2The preparation method of/graphene three-dimensional composite material and its application on negative electrode of lithium ion battery - Google Patents
Sea urchin shape nanometer TixSn1-xO2The preparation method of/graphene three-dimensional composite material and its application on negative electrode of lithium ion battery Download PDFInfo
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- CN106252607B CN106252607B CN201610656248.2A CN201610656248A CN106252607B CN 106252607 B CN106252607 B CN 106252607B CN 201610656248 A CN201610656248 A CN 201610656248A CN 106252607 B CN106252607 B CN 106252607B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- 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 sea urchin shape nanometer TixSn1‑xO2The preparation method of/graphene three-dimensional composite material and its application on negative electrode of lithium ion battery.The present invention is to prepare sea urchin shape nanometer Ti by a step hydrothermal synthesis technology self assembly using coordination principle and molecular self-assembling methodxSn1‑xO2/ graphene three-dimensional composite material.The preparation method is that：（1）Graphene oxide is prepared,（2）Prepare the electronegative graphite oxide colloidal sol in surface；（3）Sea urchin shape nanometer Ti is made in reductionxSn1‑xO2/ graphene three-dimensional composite material.Reaction process of the present invention carries out in aqueous solution, and without adding other reagents, simple for process, of low cost and energy conservation and environmental protection is easy to industrial volume production.As lithium ion battery anode material, this three dimensional composite structure is conducive to diffusion and electronics and ion of the electrolyte between composite material and transmits in the material, can effectively improve the performances such as charge/discharge capacity, cycle life and the multiplying power of composite material.
Description
Technical field
The invention belongs to nanometer material science and secondary power supply technical field, especially a kind of sea urchin shape nanometer TixSn1- xO2The preparation method of/graphene three-dimensional composite material and its application on negative electrode of lithium ion battery.
Background technology
Lithium ion battery occupies absolute leading position and is considered as next-generation heat in current various portable electronic devices
The power supply replacer of the most Commercial Prospect of door electric/hybrid automobile.In order to more effectively store and transport electricity
Can, researcher has been devoted to explore various high energy negative materials for next-generation rechargeable lithium ion batteries, such as theoretical ratio
Capacity is up to 782 mA h g respectively-1Stannic oxide (SnO2).However, the electric conductivity due to material itself is poor, it is unfavorable for
Charge transfer in charge and discharge process；In addition in charge and discharge process, Severe aggregation caused by the intercalation/deintercalation by lithium ion is imitated
Dusting and the rapid decay of capacity for easily causing electrode should be changed with enormousness, lead to the cycle performance and high rate performance of material
It is poor, to greatly hinder these materials further applying in lithium ion battery.Recently, extensive research has shown that content
Abundant, low cost, environmental protection, function admirable TiO2It is also potential next-generation lithium cell negative pole material.TiO2In lithium insertion, deviate from
Stable structure, safety in journey, while avoiding the electrochemical deposition of lithium（Such as SEI films）.The disadvantage is that its theoretical capacity is not high（About
170mAh g-1）It is not good enough with electronic conductivity.However Rutile Type SnO2With Rutile Type TiO2Crystal form is close, the two it is compound
Material is widely believed that the large-scale energy storage material of the most possible next generation.To solve these 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 in the single layer two dimensional crystal that hexagon cellular shape lattice arrangement is constituted, for example excellent with its unique performance
Different electric conductivity, good mechanical flexibility, huge specific surface area（2630m2 g-1）And the thermal stability and chemistry of superelevation are steady
Excellent carrier that is qualitative and becoming most attractive load electrochemical active material.Therefore, numerous metal oxide/graphite
Alkene nanocomposite, such as SnO2/ graphene, TiO2/ graphene, TiO2-SnO2/ graphene is in third party's nano particle or gold
Belong to and passes through being prepared by accumulation again between graphene layer under organic precursor effect.Relatively other carbon-based materials, such as graphite, charcoal
Black, carbon nanotube, graphene can more effectively buffer metal oxide in charge and discharge process due to the swelling stress of volume
To keep the satisfactory electrical conductivity of entire electrode.
Lot of experiments proves, by graphene and TiO2-SnO2Nano particle carries out compound obtained graphene modified
Tin dioxide lithium ion battery negative pole material can greatly improve the cycle performance and high rate performance of negative electrode of lithium ion battery.And
Nanometer TixSn1-xO2Solid solution composite material is homogeneously compound in Ti-Sn-O atomic scales, significantly more efficient to combine TiO2Height
Stability and SnO2High power capacity the advantages of, while avoiding TiO2@SnO2Composite material is easy production during charge and discharge cycles
The shortcomings that raw phase separation causes capacity and life performance to decline.Pass through TixSn1-xO2Solid solution and graphene LBL self-assembly can be with
More effectively buffer metal oxide in charge and discharge process due to the swelling stress of volume to keep the good of entire electrode
Electric conductivity.
Invention content
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of sea urchin shape nanometer TixSn1-xO2/ graphene
The preparation method of three-dimensional composite material and its application on negative electrode of lithium ion battery.
In order to achieve the above object, present invention employs following technical solutions：
A kind of sea urchin shape nanometer TixSn1-xO2/ graphene three-dimensional composite material be by mass percentage be 89.97~
95.98% TixSn1-xO2It is formed with graphene.
A kind of sea urchin shape nanometer TixSn1-xO2The preparation method of/graphene three-dimensional composite material, includes the following steps：
（1）Graphene oxide is prepared using improved Hummers methods, takes the container of dried and clean, it is 60 that parts by volume, which is added,
Container is placed on ice bath in ice water by~90 parts a concentration of 98% of the concentrated sulfuric acid；Weigh the crystalline flake graphite that parts by weight are 1.5~2.5 parts
It is added in the concentrated sulfuric acid solution for carrying out ice-water bath, then carries out 20~30min of mechanical agitation；It is 8~10 to weigh parts by weight
Part potassium permanganate is slowly added into above-mentioned solution, and when addition is as slow as possible, waits for that solution becomes green, potassium permanganate adds completely
Afterwards, then two hours of ice bath；Then it moves in 35 DEG C of thermostat water baths and at the uniform velocity stirs 12h, become sticky yellowish-brown slurry；
Container is removed water-bath, under stirring, is divided 6 times, the water that parts by volume is 44~50 parts is added every time and dilutes, makes by sticky
Yellowish-brown slurry become brown solution, after adding, move into 35 DEG C of thermostat water bath and stir 2h；It is 20 to measure parts by volume
~28 parts a concentration of 30% of H2O2It is added in above-mentioned brown solution, waits for that solution becomes golden yellow by brown, carry golden yellow color chips
Shape object；Again use 9000r/min rotating speed centrifuge, incline supernatant, sediment respectively with a concentration of 5% dilute hydrochloric acid and deionization
Each washing three times, is uniformly layered on sample on surface plate, surface plate is placed in freeze drier and is lyophilized for 24 hours, take sample off, uses
Agate mortar is ground, you can obtains filemot graphite oxide powder；
（2）By graphene oxide powder ultrasonic disperse obtained in water, it is 1~2.5% that mass ratio, which is made, surface bear
The graphene oxide colloidal sol of electricity；
（3）Under lasting stirring condition, titanium potassium oxalate solid is added in the graphene oxide colloidal sol prepared, waits for titanium oxalate
Potassium solid be slowly added dropwise after being completely dissolved parts by volume be 10-25 part 0.5 M butter of tin aqueous solution again persistently stir 5~
It 10 minutes, then moves to and carries out hydro-thermal reaction in water heating kettle, cooled to room temperature obtains dark brown hydrogel after the reaction was complete
Then through washing, drying sea urchin shape nanometer Ti is made through 400~600 DEG C of calcining reductions in a nitrogen atmosphere in columnxSn1-xO2/ stone
Black alkene three-dimensional composite material.
Further, the step（3）In tin ion and titanium molar ratio be 1: 4.
Further, the step（3）In TixSn1-xO2Mass ratio with graphene oxide is 1~2.5: 100.
Further, the step（3）In drying refer to -56 DEG C be freeze-dried 12~24 hours.
A kind of sea urchin shape nanometer TixSn1-xO2Application of/graphene the three-dimensional composite material on negative electrode of lithium ion battery.
Advantageous effect：
（1）Reaction process of the present invention need to only carry out in aqueous solution, be not necessarily to the organic reagents such as template, surfactant,
One step hydro-thermal.
（2）The principle of the invention is simple, simple operation, and abundant raw material is cheap, economic and environment-friendly, is suitable for industrial metaplasia
Production.
（3）The present invention is titanium source using titanium potassium oxalate, inorganic without using titanium chloride, sulfate titanium and tetrabutyl titanate etc.,
Organic titanium source avoids uncontrollability of its hydrolysis rate soon to self-assembled material structure and pattern, by using titanium potassium oxalate
Carboxylic acid group and surface of graphene oxide active group（Carboxyl, hydroxyl, epoxy group etc.）With metal ion tin（Sn4+）Weak coordination is made
With using the controllable self assembly Ti of growth in situxSn1-xO2/ graphene three-dimensional structure composite material.
（4）Ti in three-dimensional composite material prepared by the present inventionxSn1-xO2Crystal be in sea urchin spherical morphology, grain size be 120~
150nm, large specific surface area are evenly distributed close between graphene layer, and are securely supported on laminated structure surface between graphene layer,
In adjustment TixSn1-xO2Under the conditions of graphene oxide colloidal sol suitable proportion, active material TixSn1-xO2Content surveyed through thermogravimetric
Examination up to 95.98%；
（5）Sea urchin shape nanometer Ti prepared by the present inventionxSn1-xO2The battery-active of/graphene three-dimensional lithium cell negative pole material is high,
In 100 mA g-1Under charging or discharging current, charge/discharge specific capacity is respectively 784,1184 mA h g for the first time-1, charge after 100 weeks
Specific capacity is still up to 580 mA h g-1, Rong Liangbaochishuai >97%.Through 100,200,500,1000,2000 mA g-1Different multiplying
Charge-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）Using the present invention, sea urchin shape nanometer TixSn1-xO2The active material of/graphene three-dimensional composite negative pole material
TixSn1-xO2The component ratio of/graphene is easy to Morphological control.
Description of the drawings
Fig. 1 is sea urchin shape nanometer Ti prepared by embodiment 1xSn1-xO2The X-ray diffractogram of/graphene three-dimensional composite material.
Fig. 2 is sea urchin shape nanometer Ti prepared by embodiment 2xSn1-xO2The transmission electron microscope picture of/graphene three-dimensional composite material.
Fig. 3 is sea urchin shape nanometer Ti prepared by embodiment 3xSn1-xO2The thermal multigraph of/graphene three-dimensional composite material.
Fig. 4 is sea urchin shape nanometer Ti prepared by embodiment 4xSn1-xO2The battery charging and discharging of/graphene three-dimensional composite material times
Rate performance map.
Fig. 5 is sea urchin shape nanometer Ti prepared by embodiment 4xSn1-xO2The battery charging and discharging of/graphene three-dimensional composite material follows
Ring performance map.
Fig. 6 is sea urchin shape nanometer Ti prepared by embodiment 5xSn1-xO2The specific surface area figure of/graphene three-dimensional composite material.
Specific implementation mode
Technical scheme of the present invention is described in further detail with reference to specific embodiment, but the protection model of the present invention
It encloses and is not limited thereto.
Embodiment 1
A kind of sea urchin shape nanometer TixSn1-xO2The preparation method of/graphene three-dimensional composite material, includes the following steps：
（1）Graphene oxide is prepared using improved Hummers methods, takes the container of dried and clean, it is a concentration of that 70ml is added
Container is placed on ice bath in ice water by 98% concentrated sulfuric acid；Weigh 2g crystalline flake graphite be added to carried out ice-water bath the concentrated sulfuric acid it is molten
In liquid, 20~30min of mechanical agitation is then carried out；It is that 8g potassium permanganate is slowly added into above-mentioned solution to weigh parts by weight, is added
It is fashionable as slow as possible, wait for that solution becomes green, after potassium permanganate adds completely, then two hours of ice bath；Then 35 DEG C of perseverances are moved to
12h is at the uniform velocity stirred in warm water bath, becomes sticky yellowish-brown slurry；Container is removed water-bath, under stirring, point
6 times, the water dilution of 46ml is added every time, makes to become brown solution by sticky yellowish-brown slurry, after adding, moves into 35 DEG C
2h is stirred in thermostat water bath；Measure the H of 25ml a concentration of 30%2O2It is added in above-mentioned brown solution, waits for that solution is become by brown
At golden yellow, with golden yellow tablet；The rotating speed of 9000r/min is used to centrifuge again, incline supernatant, and sediment uses concentration respectively
It is respectively washed three times for 5% dilute hydrochloric acid and deionization, sample is uniformly layered on surface plate, surface plate is placed on freeze drier
In be lyophilized for 24 hours, take sample off, ground with agate mortar, you can obtain filemot graphite oxide powder；
（2）, the graphene oxide 300W ultrasounds 30min that weighs 0.1000g be scattered in 100mL water, can obtain pH be 7, it is dense
Degree is 1 mg/mL graphene oxide colloidal sols；
（3）, under stirring condition, bis- oxalic acid hydrate titanium potassium of 5.000g is added in above-mentioned graphene oxide colloidal sol, stir
After being completely dissolved to titanium potassium oxalate, under stirring condition, by SnCl4Solution instills graphene oxide/oxalic acid with the speed of 1 drop per second
In titanium potassium colloidal sol, is persistently stirred 5~10 minutes again after being added dropwise, then move to and carry out hydro-thermal reaction in water heating kettle, reacted
Cooled to room temperature obtains dark brown water-setting rubber column gel column, washing, is freeze-dried to obtain sea urchin shape nanometer Ti after completexSn1-xO2/ graphene
Three-dimensional composite material；Then sea urchin shape nanometer Ti is made through 400~600 DEG C of calcining reductions in a nitrogen atmospherexSn1-xO2/ graphite
Alkene three-dimensional composite lithium ion battery cathode material.
Fig. 1 is the sea urchin 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 ingredient of institute's prepared material is determined as TixSn1-xO2Solid solution/graphene.
Embodiment 2
A kind of sea urchin shape nanometer TixSn1-xO2The preparation method of/graphene three-dimensional composite material, includes the following steps：
（1）Graphene oxide is prepared using improved Hummers methods, takes the container of dried and clean, it is a concentration of that 60ml is added
Container is placed on ice bath in ice water by 98% concentrated sulfuric acid；The crystalline flake graphite for weighing 1.5g is added to the concentrated sulfuric acid for carrying out ice-water bath
In solution, 20~30min of mechanical agitation is then carried out；It is that 8g potassium permanganate is slowly added into above-mentioned solution to weigh parts by weight,
It is as slow as possible when addition, wait for that solution becomes green, after potassium permanganate adds completely, then two hours of ice bath；Then 35 DEG C are moved to
12h is at the uniform velocity stirred in thermostat water bath, becomes sticky yellowish-brown slurry；Container is removed water-bath, under stirring,
Divide 6 times, the water dilution of 50ml is added every time, makes to become brown solution by sticky yellowish-brown slurry, after adding, moves into 35 DEG C
Thermostat water bath in stir 2h；Measure the H of 20ml a concentration of 30%2O2It is added in above-mentioned brown solution, waits for solution by brown
Become golden yellow, with golden yellow tablet；The rotating speed of 9000r/min is used to centrifuge again, incline supernatant, and sediment is respectively with dense
Degree respectively washs three times for 5% dilute hydrochloric acid and deionization, and sample is uniformly layered on surface plate, surface plate is placed on freeze-drying
It is lyophilized for 24 hours in instrument, takes sample off, ground with agate mortar, you can obtain filemot graphite oxide powder；
（2）, the graphene oxide 300W ultrasounds 30min that weighs 0.1500g be scattered in 100mL water, can obtain pH be 7, it is dense
Degree is 1.5 mg/mL graphene oxide colloidal sols；
（3,）Under stirring condition, bis- oxalic acid hydrate titanium potassium of 5.000g is added in above-mentioned graphene oxide colloidal sol, is stirred
After being completely dissolved to titanium potassium oxalate, under stirring condition, by SnCl4Solution instills graphene oxide/oxalic acid with the speed of 1 drop per second
In titanium potassium colloidal sol, is persistently stirred 5~10 minutes again after being added dropwise, then move to and carry out hydro-thermal reaction in water heating kettle, reacted
Cooled to room temperature obtains dark brown water-setting rubber column gel column after complete, washes, is freeze-dried to obtain sea urchin shape nanometer TixSn1-xO2/ graphene
LBL self-assembly 3 ties up composite material；Then sea urchin shape nanometer is made through 400~600 DEG C of calcining reductions in a nitrogen atmosphere
TixSn1-xO2/ graphene three-dimensional composite lithium ion battery cathode material.
According to transmission electron microscope Fig. 2 as it can be seen that Ti in obtained three-dimensional composite materialxSn1-xO2For sea urchin shape ball, sea urchin shape is received
Rice TixSn1-xO2Crystal diameter is about 120~150nm, is evenly distributed between graphene layer close, and be securely supported on graphene
Interlayer laminated structure surface.
Embodiment 3
A kind of sea urchin shape nanometer TixSn1-xO2The preparation method of/graphene three-dimensional composite material, includes the following steps：
（1）Graphene oxide is prepared using improved Hummers methods, takes the container of dried and clean, it is a concentration of that 70ml is added
Container is placed on ice bath in ice water by 98% concentrated sulfuric acid；The crystalline flake graphite for weighing 1.5g is added to the concentrated sulfuric acid for carrying out ice-water bath
In solution, 20~30min of mechanical agitation is then carried out；It is that 8g potassium permanganate is slowly added into above-mentioned solution to weigh parts by weight,
It is as slow as possible when addition, wait for that solution becomes green, after potassium permanganate adds completely, then two hours of ice bath；Then 35 DEG C are moved to
12h is at the uniform velocity stirred in thermostat water bath, becomes sticky yellowish-brown slurry；Container is removed water-bath, under stirring,
Divide 6 times, the water dilution of 48ml is added every time, makes to become brown solution by sticky yellowish-brown slurry, after adding, moves into 35 DEG C
Thermostat water bath in stir 2h；Measure the H of 25ml a concentration of 30%2O2It is added in above-mentioned brown solution, waits for solution by brown
Become golden yellow, with golden yellow tablet；The rotating speed of 9000r/min is used to centrifuge again, incline supernatant, and sediment is respectively with dense
Degree respectively washs three times for 5% dilute hydrochloric acid and deionization, and sample is uniformly layered on surface plate, surface plate is placed on freeze-drying
It is lyophilized for 24 hours in instrument, takes sample off, ground with agate mortar, you can obtain filemot graphite oxide powder；
（2）, the graphene oxide 300W ultrasounds 30min that weighs 0.200g be scattered in 100mL water, it is 7, concentration that can obtain pH
For 2.0 mg/mL graphene oxide colloidal sols；
（3）, under stirring condition, bis- oxalic acid hydrate titanium potassium of 5.000g is added in above-mentioned graphene oxide colloidal sol, stir
After being completely dissolved to titanium potassium oxalate, under stirring condition, by SnCl4Solution instills graphene oxide/oxalic acid with the speed of 1 drop per second
In titanium potassium colloidal sol, is persistently stirred 5~10 minutes again after being added dropwise, then move to and carry out hydro-thermal reaction in water heating kettle, reacted
Cooled to room temperature obtains dark brown water-setting rubber column gel column, washing, is freeze-dried to obtain sea urchin shape nanometer Ti after completexSn1-xO2/ graphene
Three-dimensional composite material；Then sea urchin shape nanometer Ti is made through 400-600 DEG C of calcining reduction in a nitrogen atmospherexSn1-xO2/ graphene
LBL self-assembly 3 ties up composite lithium ion battery cathode material.
It can be obtained according to transmission electron microscope picture, Ti made from the present embodimentxSn1-xO2/ graphene three-dimensional composite material, wherein
TixSn1-xO2For sea urchin shape, sea urchin shape TixSn1-xO2Crystal diameter is about 110 ~ 140nm, be distributed between graphene layer it is sparse,
But it is uniformly securely supported on laminated structure surface between graphene layer, Fig. 3 is the sea urchin 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 sea urchin shape nanometer TixSn1-xO2The preparation method of/graphene three-dimensional composite material, includes the following steps：
（1）Graphene oxide is prepared using improved Hummers methods, takes the container of dried and clean, it is a concentration of that 80ml is added
Container is placed on ice bath in ice water by 98% concentrated sulfuric acid；Weigh 2g crystalline flake graphite be added to carried out ice-water bath the concentrated sulfuric acid it is molten
In liquid, 20~30min of mechanical agitation is then carried out；It is that 9g potassium permanganate is slowly added into above-mentioned solution to weigh parts by weight, is added
It is fashionable as slow as possible, wait for that solution becomes green, after potassium permanganate adds completely, then two hours of ice bath；Then 35 DEG C of perseverances are moved to
12h is at the uniform velocity stirred in warm water bath, becomes sticky yellowish-brown slurry；Container is removed water-bath, under stirring, point
6 times, the water dilution of 45ml is added every time, makes to become brown solution by sticky yellowish-brown slurry, after adding, moves into 35 DEG C
2h is stirred in thermostat water bath；Measure the H of 26ml a concentration of 30%2O2It is added in above-mentioned brown solution, waits for that solution is become by brown
At golden yellow, with golden yellow tablet；The rotating speed of 9000r/min is used to centrifuge again, incline supernatant, and sediment uses concentration respectively
It is respectively washed three times for 5% dilute hydrochloric acid and deionization, sample is uniformly layered on surface plate, surface plate is placed on freeze drier
In be lyophilized for 24 hours, take sample off, ground with agate mortar, you can obtain filemot graphite oxide powder；
（2）, the graphene oxide 300W ultrasounds 30min that weighs 0.2500g be scattered in 100mL water, can obtain pH be 7, it is dense
Degree is 2.5 mg/mL graphene oxide colloidal sols；
（3）, under stirring condition, bis- oxalic acid hydrate titanium potassium of 5.000g is added in above-mentioned graphene oxide colloidal sol, stir
After being completely dissolved to titanium potassium oxalate, under stirring condition, by SnCl4Solution instills graphene oxide/oxalic acid with the speed of 1 drop per second
In titanium potassium colloidal sol, is persistently stirred 5~10 minutes again after being added dropwise, then move to and carry out hydro-thermal reaction in water heating kettle, reacted
Cooled to room temperature obtains dark brown water-setting rubber column gel column, washing, is freeze-dried to obtain sea urchin shape nanometer Ti after completexSn1-xO2/ graphene
Three-dimensional composite material；Then sea urchin shape nanometer Ti is made through 400~600 DEG C of calcining reductions in a nitrogen atmospherexSn1-xO2/ graphite
Alkene three-dimensional composite lithium ion battery cathode material.
Embodiment 5
A kind of sea urchin shape nanometer TixSn1-xO2The preparation method of/graphene three-dimensional composite material, includes the following steps：
（1）Graphene oxide is prepared using improved Hummers methods, takes the container of dried and clean, it is a concentration of that 90ml is added
Container is placed on ice bath in ice water by 98% concentrated sulfuric acid；The crystalline flake graphite for weighing 2.5g is added to the concentrated sulfuric acid for carrying out ice-water bath
In solution, 20~30min of mechanical agitation is then carried out；It is that 10g potassium permanganate is slowly added into above-mentioned solution to weigh parts by weight,
It is as slow as possible when addition, wait for that solution becomes green, after potassium permanganate adds completely, then two hours of ice bath；Then 35 DEG C are moved to
12h is at the uniform velocity stirred in thermostat water bath, becomes sticky yellowish-brown slurry；Container is removed water-bath, under stirring,
Divide 6 times, the water dilution of 44ml is added every time, makes to become brown solution by sticky yellowish-brown slurry, after adding, moves into 35 DEG C
Thermostat water bath in stir 2h；Measure the H of 28ml a concentration of 30%2O2It is added in above-mentioned brown solution, waits for solution by brown
Become golden yellow, with golden yellow tablet；The rotating speed of 9000r/min is used to centrifuge again, incline supernatant, and sediment is respectively with dense
Degree respectively washs three times for 5% dilute hydrochloric acid and deionization, and sample is uniformly layered on surface plate, surface plate is placed on freeze-drying
It is lyophilized for 24 hours in instrument, takes sample off, ground with agate mortar, you can obtain filemot graphite oxide powder；
（2）, the graphene oxide 300W ultrasounds 30min that weighs 0.1500g be scattered in 100mL water, can obtain pH be 7, it is dense
Degree is 1.5 mg/mL graphene oxide colloidal sols；
（3）, under stirring condition, bis- oxalic acid hydrate titanium potassium of 3.3333g is added in above-mentioned graphene oxide colloidal sol, is stirred
It mixes to titanium potassium oxalate after being completely dissolved, under stirring condition, by SnCl4Solution instills graphene oxide/grass with the speed of 1 drop per second
It in sour titanium potassium colloidal sol, is persistently stirred 5~10 minutes again after being added dropwise, then moves to and carry out hydro-thermal reaction in water heating kettle, reacted
Cooled to room temperature obtains dark brown water-setting rubber column gel column, washing, is freeze-dried to obtain sea urchin shape nanometer Ti after completelyxSn1-xO2/ graphite
Alkene three-dimensional composite material；Then sea urchin shape nanometer Ti is made through 400~600 DEG C of calcining reductions in a nitrogen atmospherexSn1-xO2/ stone
Black alkene LBL self-assembly 3 ties up composite lithium ion battery cathode material.
It can be obtained according to transmission electron microscope picture, Ti made from the present embodimentxSn1-xO2/ graphene three-dimensional composite material, wherein
TixSn1-xO2For sea urchin shape ball, sea urchin shape ball TixSn1-xO2Crystal diameter is about 80~120nm, between graphene layer distribution compared with
It is sparse, but it is securely uniformly supported on laminated structure surface between graphene layer, thermogravimetric analysis shows Ti made from the present embodimentxSn1- xO2Ti in/graphene three-dimensional composite materialxSn1-xO2Mass percent be 90.04%, Fig. 6 surface analysis show this implementation
Ti made from examplexSn1-xO2The specific surface area of/graphene three-dimensional composite material is 161.9 m2 g-1。
Application examples
A kind of sea urchin shape nanometer TixSn1-xO2Application of/graphene the three-dimensional composite material on negative electrode of lithium ion battery：
It can be obtained according to transmission electron microscope picture, Ti made from embodiment 4xSn1-xO2/ graphene three-dimensional composite material, wherein
TixSn1-xO2For sea urchin shape, sea urchin shape TixSn1-xO2Crystal diameter is about 100~140nm, is distributed between graphene layer diluter
It dredges, but is uniformly securely supported on laminated structure surface between graphene layer, Fig. 4 is the sea urchin shape nanometer obtained by embodiment 4
TixSn1-xO2The charge-discharge magnification curve graph of the battery of/graphene three-dimensional composite material, Fig. 5 are sea urchin shape prepared by embodiment 4
Nanometer TixSn1-xO2The battery charging and discharging cycle performance figure of/graphene three-dimensional composite material.By scheme it is upper as it can be seen that through 100,200,
500、1000 mA g-1Different multiplying charge-discharge test, when charge/discharge flow back into 100mA g-1When its charge specific capacity be still up to
630 mA h g-1.In 1000 mA g-1Current density under, to sample carried out 504 weeks charge and discharge cycles test（First 4 weeks
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
Five weeks capacity are 454.7 mA h g-1, capacity at 504 weeks is 488.9 mA h g-1, 1000 mA g-1High current it is close
Capacity retention ratio after lower 500 circle of cycle of degree is 107.5 % and cyclic curve is steady, shows good cyclical stability
Energy.The experimental results showed that the battery multiplying power and cycle performance of active material are excellent, it is suitable for high performance lithium ionic cell cathode
Material.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (5)
1. a kind of sea urchin shape nanometer TixSn1-xO2The preparation method of/graphene three-dimensional composite material, which is characterized in that the material
Material be by mass percentage be 89.97~95.98% TixSn1-xO2It is formed with graphene；
The preparation method includes the following steps：
（1）Graphene oxide is prepared using improved Hummers methods, takes the container of dried and clean, it is 60~90 that parts by volume, which is added,
Container, is placed on ice bath in ice water by the concentrated sulfuric acid of part a concentration of 98%；The crystalline flake graphite that parts by weight are 1.5~2.5 parts is weighed to be added
Into the concentrated sulfuric acid solution for carrying out ice-water bath, 20~30min of mechanical agitation is then carried out；It is 8~10 parts of height to weigh parts by weight
Potassium manganate is slowly added into above-mentioned solution, and when addition is as slow as possible, waits for that solution becomes green, after potassium permanganate adds completely,
Two hours of ice bath again；Then it moves in 35 DEG C of thermostat water baths and at the uniform velocity stirs 12h, become sticky yellowish-brown slurry；
Container removes water-bath, under stirring, divides 6 times, and the water that parts by volume is 44~50 parts is added every time and dilutes, makes by sticky
Yellowish-brown slurry becomes brown solution, after adding, moves into 35 DEG C of thermostat water bath and stirs 2h；Measure parts by volume be 20~
28 parts a concentration of 30% of H2O2It is added in above-mentioned brown solution, waits for that solution becomes golden yellow by brown, with golden yellow sheet
Object；The rotating speed of 9000r/min is used to centrifuge again, incline supernatant, and sediment is each with a concentration of 5% dilute hydrochloric acid and deionization respectively
Washing three times, is uniformly layered on sample on surface plate, surface plate is placed in freeze drier and is lyophilized for 24 hours, takes sample off, uses agate
Nao mortar grinders, you can obtain filemot graphite oxide powder；
（2）By graphene oxide powder ultrasonic disperse obtained in water, it is 1~2.5% that mass ratio, which is made, surface bear electricity
Graphene oxide colloidal sol；
（3）Under lasting stirring condition, titanium potassium oxalate solid is added in the graphene oxide colloidal sol prepared, waits for that titanium potassium oxalate is solid
0.5 M that parts by volume is 10-25 parts is slowly added dropwise in body butter of tin aqueous solution after being completely dissolved persistently stirs 5~10 points again
Then clock moves to and carries out hydro-thermal reaction in water heating kettle, cooled to room temperature obtains dark brown water-setting rubber column gel column after the reaction was complete, passes through
Washing, drying, are then made sea urchin shape nanometer Ti through 400~600 DEG C of calcining reductions in a nitrogen atmospherexSn1-xO2/ graphene three
Tie up composite material.
2. a kind of sea urchin shape nanometer Ti according to claim 1xSn1-xO2The preparation method of/graphene three-dimensional composite material,
It is characterized in that：The step（3）In tin ion and titanium molar ratio be 1:4.
3. a kind of sea urchin shape nanometer Ti according to claim 1xSn1-xO2The preparation method of/graphene three-dimensional composite material,
It is characterized in that：The step（3）In TixSn1-xO2Mass ratio with graphene oxide is 1~2.5:100.
4. a kind of sea urchin shape nanometer Ti according to claim 1xSn1-xO2The preparation method of/graphene three-dimensional composite material,
It is characterized in that：The step（3）In drying refer to -56 DEG C be freeze-dried 12~24 hours.
5. a kind of a kind of sea urchin shape nanometer Ti prepared by preparation method as described in claim 1xSn1-xO2/ graphene three-dimensional is multiple
Application of the condensation material on negative electrode of lithium ion battery.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104218232A (en) * | 2014-09-16 | 2014-12-17 | 郑州大学 | Preparation method of graphene-modified tin oxide lithium ion battery negative material |
| CN105551828A (en) * | 2015-12-11 | 2016-05-04 | 郑州大学 | Nano titanium dioxide/graphene composite material and preparation method thereof |
| CN105540657A (en) * | 2016-01-14 | 2016-05-04 | 浙江大学 | Nanosheet-assembling core-shell structure anatase titanium dioxide microsphere and preparation method thereof |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104218232A (en) * | 2014-09-16 | 2014-12-17 | 郑州大学 | Preparation method of graphene-modified tin oxide lithium ion battery negative material |
| CN105551828A (en) * | 2015-12-11 | 2016-05-04 | 郑州大学 | Nano titanium dioxide/graphene composite material and preparation method thereof |
| CN105540657A (en) * | 2016-01-14 | 2016-05-04 | 浙江大学 | Nanosheet-assembling core-shell structure anatase titanium dioxide microsphere and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Anchoring ultra-fine TiO2–SnO2 solid solution particles onto graphene by one-pot ball-milling for long-life lithium-ion batteries;Sheng Li et.al;《Journal of Materials Chemistry A》;20150323(第3期);第9700-9706页 * |
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