CN109411741A - A kind of composite negative pole material and its preparation method and application - Google Patents
A kind of composite negative pole material and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of composite negative pole materials, including CNT@Graphene and SnO2.The invention also discloses a kind of preparation method of composite negative pole material, includes the following steps: to stir multi-walled carbon nanotube, the concentrated sulfuric acid, obtain suspension；Oxidant is added into suspension to continue to stir, obtains prefabricated material；Prefabricated material is filtered, it is dry, obtain modified CNT@Graphene flexible base material；It will be modified CNT@Graphene flexible base material, water mixing dispersion, pink salt is added, regulation system pH value is 4-11, and stirring, filtering is washed, it is dry, obtain CNT@Graphene/SnO2Presoma；By CNT@Graphene/SnO2Presoma is heat-treated in inert gas, obtains composite negative pole material.The present invention can significantly alleviate SnO2Volume change in charge and discharge process improves the cycle life and high rate performance of material, the significant stability and chemical property for improving pole piece, technological parameter regulation is convenient, handling high, the uniformity height of modifying process, and it is at low cost, it is suitable for large-scale production.
Description
Technical field
The present invention relates to negative electrode material technical field more particularly to a kind of composite negative pole material and preparation method thereof and answer
With.
Background technique
In recent years, with the rise of electric automobile, energy storage power grid, lithium ion battery technology has obtained development at full speed.
And as the large-scale electric tool such as pure electric automobile is while requiring lithium battery high safety and long-life, to energy density and function
Rate density proposes higher index.The specific capacity of traditional carbon material is less than 400mAh/g, and high rate performance is poor, with electrolysis liquid phase
Capacitive is bad, and volume energy density is low, is unable to satisfy the requirement of next-generation lithium ion battery substantially.
Transition metal oxide material has high theoretical specific capacity, and bulk density is 5-7 times of traditional carbon material, well
High rate performance ensure that the ability of transition metal oxide material high power charging-discharging, can satisfy next-generation lithium ion battery
Needs.SnO2It is a kind of cheap, environmental-friendly transition metal oxide negative electrode material, its height ratio capacity and conduction
Property, it is widely concerned by researchers at home and abroad.SnO2The operating potential of negative electrode material is much higher than the deposition potential of lithium metal,
The lithium at interface can be inhibited to deposit in high-power charge and discharge process, which is embedded in altogether there is no solvent in charge and discharge process and asks
Topic, therefore can choose a greater variety of electrolyte, there is apparent advantage in application aspect.
SnO2The storage lithium mechanism of negative electrode material is complex, including two processes of conversion reaction and alloying, is charging
Cheng Zhong, lithium ion move to negative terminal surface from anode, with SnO2Li is generated by conversion reaction2O and metal Sn, metal Sn can be after
Continuous and lithium ion, which is combined, stores up lithium with LixSn alloy form.In this course, the volume change of material itself can be more than 300%,
The serious dusting or reunion of pole piece are caused, specific discharge capacity can decay rapidly.
Summary of the invention
Technical problems based on background technology, the invention proposes a kind of composite negative pole material and preparation method thereof and
Using the present invention can significantly alleviate SnO2Volume change in charge and discharge process, improve material cycle life and times
Rate performance significantly improves the stability and chemical property of pole piece, and technological parameter regulation is convenient, the handling height of modifying process,
Even property is high, at low cost, can be applicable to field of lithium ion battery, is suitable for large-scale production.
A kind of composite negative pole material proposed by the present invention, including CNT@Graphene and SnO2.Preferably, the SnO2For
Nano SnO2。
A kind of preparation method for composite negative pole material that the present invention also proposes, includes the following steps:
S1, multi-walled carbon nanotube, the concentrated sulfuric acid are stirred, obtains suspension；
S2, into suspension, addition oxidant continues to stir, and obtains prefabricated material；
S3, prefabricated material is filtered, it is dry, obtain modified CNT@Graphene flexible base material；
S4, it will be modified CNT@Graphene flexible base material, water mixing dispersion, and pink salt will be added, regulation system pH value will be
4-11 is stirred, and is filtered, and is washed, dry, obtains CNT@Graphene/SnO2Presoma；
S5, by CNT@Graphene/SnO2Presoma is heat-treated in inert gas, obtains composite negative pole material.
Preferably, in S1, the w/v g:ml of multi-walled carbon nanotube and the concentrated sulfuric acid is 0.5-4:100.
Preferably, in S1, in whipping process, using ultrasonic agitation, mixing time 0.1-3h.
Preferably, in S2, the oxidant is potassium permanganate, at least one in potassium hyperchlorate, sodium perchlorate, ammonium persulfate
Kind；It is further preferred that the weight ratio of multi-walled carbon nanotube and oxidant is 1:1-6.
Preferably, in S2, in whipping process, using ultrasonic agitation, mixing time 1-6h.
Preferably, in S3, drying temperature is 60-150 DEG C, drying time 1-50h.
Preferably, in S4, using bronsted lowry acids and bases bronsted lowry regulation system pH value, it is described acid be nitric acid, hydrochloric acid, acetic acid and oxalic acid in extremely
Few one kind, the alkali are at least one of ammonium hydroxide, sodium hydroxide, potassium hydroxide.
Preferably, in S4, in whipping process, using stirring in water bath, mixing time 6-48h, bath temperature 50-
120℃；Preferably, the pink salt is at least one of nitric acid tin, tin acetate, STANNOUS SULPHATE CRYSTALLINE and stannic chloride；It is further preferred that pressing
According to multi-walled carbon nanotube and SnO2Weight ratio be 1:2-10 be added pink salt.
Preferably, in S4, in whipping process, using ultrasonic agitation, it is further preferred that will modified CNT@
Graphene flexible base material is divided using being modified CNT Graphene flexible base material as 5-20 times of weight water mixing of benchmark
It dissipates.
Preferably, in S5, the inert gas is nitrogen；
Preferably, heat treatment time 2-20h, heat treatment temperature are 200-600 DEG C.
The invention also provides a kind of application of composite negative pole material in lithium ion battery.
In composite negative pole material of the invention, SnO can be improved by the high conductivity using CNT@Graphene substrate2
The electronic conductance of particle, CNT@Graphene can form the skeleton of good mechanical performance, alleviate SnO2Particle is in charge and discharge
Volume change in journey, the significant stability and chemical property for improving pole piece.Compared to single CNT, CNT@of the present invention
Graphene can significantly improve electronic conductance；And compared to single Graphene, CNT@Graphene and SnO of the present invention2
Compounding, the excellent mechanical performance of structure can significantly alleviate the volume change in charge and discharge process, improve the circulation of material
Service life and high rate performance, present invention specific discharge capacity under the current density of 500mA/g reach 800mAh/g or more, follow for 100 times
Ring capacity retention ratio is 70% or more.
In the preparation process of composite negative pole material of the present invention, compound using using strong acid and strong oxidizer from multi-wall carbon nano-tube
Pipe surface strips out graphene film, then using the more oxygen-content active group induction Sn ion in graphene film surface in the dilute table of graphite
Face absorption and supersaturation precipitation, finally obtain CNT@Graphene and SnO using high-temperature calcination2Composite negative pole material, wherein
By using low-temperature assembled technology it is lower without harsh conditions, the energy consumption such as high temperature and pressure, Sn in solution4+Ion is in modification
Supersaturation is precipitated in CNT@Graphene substrate, forms ultra-fine SnO2It is nanocrystalline, it is nanocrystalline in reservation by high-temperature calcination processing
Size and shape under the premise of make SnO2Crystallization, allows ultra-fine nanoscale SnO2It is nanocrystalline can be with CNT@Graphene substrate
It being combined together well, technological parameter regulation is convenient, and the handling height of modifying process, uniformity is high, and it is at low cost, it is suitable for big rule
The production of mould.
Detailed description of the invention
Fig. 1 is the CNT@Graphene/SnO that the embodiment of the present invention 9 synthesizes2The SEM photograph of negative electrode material；
Fig. 2 is the CNT@Graphene/SnO that the embodiment of the present invention 9 synthesizes2The TEM photo of negative electrode material；
Fig. 3 is the CNT@Graphene/SnO that the embodiment of the present invention 9 synthesizes2The cycle performance figure of negative electrode material 1C multiplying power.
Specific embodiment
In the following, technical solution of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of composite negative pole material, including CNT@Graphene and SnO2。
Embodiment 2
A kind of composite negative pole material, including CNT@Graphene and SnO2, the SnO2For nano SnO2。
Embodiment 3
A kind of preparation method of composite negative pole material, includes the following steps:
S1, multi-walled carbon nanotube, the concentrated sulfuric acid are stirred, obtains suspension；
S2, into suspension, addition oxidant continues to stir, and obtains prefabricated material；
S3, prefabricated material is filtered, it is dry, obtain modified CNT@Graphene flexible base material；
S4, it will be modified CNT@Graphene flexible base material, water mixing dispersion, and pink salt will be added, regulation system pH value will be
4-11 is stirred, and is filtered, and is washed, dry, obtains CNT@Graphene/SnO2Presoma；
S5, by CNT@Graphene/SnO2Presoma is heat-treated in inert gas, obtains composite negative pole material.
Embodiment 4
A kind of preparation method of composite negative pole material, includes the following steps:
S1, multi-walled carbon nanotube, the concentrated sulfuric acid are stirred, obtains suspension；
S2, into suspension, addition oxidant continues to stir, and obtains prefabricated material；
S3, prefabricated material is filtered, it is dry, obtain modified CNT@Graphene flexible base material；
S4, it will be modified CNT@Graphene flexible base material, water mixing dispersion, and pink salt will be added, regulation system pH value will be
4-11 is stirred, and is filtered, and is washed, dry, obtains CNT@Graphene/SnO2Presoma；
S5, by CNT@Graphene/SnO2Presoma is heat-treated in inert gas, and heat treatment temperature is 400 DEG C, is obtained
Composite negative pole material.
Embodiment 5
A kind of preparation method of composite negative pole material, includes the following steps:
S1, multi-walled carbon nanotube, the concentrated sulfuric acid are stirred, obtains suspension；
S2, into suspension, addition oxidant continues to stir, and obtains prefabricated material；
S3, prefabricated material is filtered, it is dry, obtain modified CNT@Graphene flexible base material；
S4, it will be modified CNT@Graphene flexible base material, water mixing dispersion, and pink salt will be added, regulation system pH value will be
4-11 is stirred, and is filtered, and is washed, dry, obtains CNT@Graphene/SnO2Presoma；
S5, by CNT@Graphene/SnO2Presoma is heat-treated in inert gas, and heat treatment temperature is 600 DEG C, is obtained
Composite negative pole material.
Embodiment 6
A kind of preparation method of composite negative pole material, includes the following steps:
S1,0.1h is stirred by ultrasonic in multi-walled carbon nanotube, the concentrated sulfuric acid, obtains suspension, wherein multi-walled carbon nanotube and dense
The w/v g:ml of sulfuric acid is 4:100；
S2, into suspension be added potassium permanganate continue be stirred by ultrasonic 1h, obtain prefabricated material, wherein multi-walled carbon nanotube and
The weight ratio of oxidant is 1:6；
S3, prefabricated material is filtered, in the dry 50h of temperature 60 C, obtains modified CNT@Graphene flexible base material；
S4, CNT@Graphene flexible base material will be modified, to be modified CNT@Graphene flexible base material as base
Quasi- 5 times of weight waters mix ultrasonic disperse 100min, and stannic chloride is added, and use nitric acid and sodium hydroxide regulation system pH value for 4, water
Bath stirring 48h, bath temperature are 50 DEG C, filter, wash, dry, obtain CNT@Graphene/SnO2Presoma；
Wherein according to multi-walled carbon nanotube and SnO2Weight ratio be 1:10 be added pink salt；
S5, by CNT@Graphene/SnO2Presoma is heat-treated 2h in nitrogen atmosphere, and heat treatment temperature is 600 DEG C, obtains
Composite negative pole material.
Embodiment 7
A kind of preparation method of composite negative pole material, includes the following steps:
S1,3h is stirred by ultrasonic in multi-walled carbon nanotube, the concentrated sulfuric acid, obtains suspension, wherein multi-walled carbon nanotube and dense sulphur
The w/v g:ml of acid is 0.54:100；
S2, into suspension, addition oxidant continues that 6h is stirred by ultrasonic, and obtains prefabricated material, wherein multi-walled carbon nanotube and oxygen
The weight ratio of agent is 1:1；
The oxidant includes potassium hyperchlorate, sodium perchlorate；
S3, prefabricated material is filtered, in 150 DEG C of temperature dry 10h, obtains modified CNT@Graphene flexible base material；
S4, CNT@Graphene flexible base material will be modified, to be modified CNT@Graphene flexible base material as base
Quasi- 20 times of weight waters mix ultrasonic disperse 10min, and pink salt is added, uses bronsted lowry acids and bases bronsted lowry regulation system pH value for 11, stirring in water bath 6h,
Bath temperature is 120 DEG C, is filtered, and is washed, dry, obtains CNT@Graphene/SnO2Presoma；
Wherein according to multi-walled carbon nanotube and SnO2Weight ratio be 1:2 be added pink salt；
The acid includes nitric acid, hydrochloric acid, and the alkali includes ammonium hydroxide, sodium hydroxide；
The pink salt includes nitric acid tin, STANNOUS SULPHATE CRYSTALLINE；
S5, by CNT@Graphene/SnO2Presoma is heat-treated 20h in nitrogen atmosphere, and heat treatment temperature is 200 DEG C, obtains
To composite negative pole material.
Embodiment 8
A kind of preparation method of composite negative pole material, includes the following steps:
S1,0.5h is stirred by ultrasonic in multi-walled carbon nanotube, the concentrated sulfuric acid, obtains suspension, wherein multi-walled carbon nanotube and dense
The w/v g:ml of sulfuric acid is 3:100；
S2, into suspension be added oxidant continue be stirred by ultrasonic 1-6h, obtain prefabricated material, wherein multi-walled carbon nanotube and
The weight ratio of oxidant is 1:4；
The oxidant includes potassium permanganate, potassium hyperchlorate, sodium perchlorate, ammonium persulfate；
S3, prefabricated material is filtered, in 120 DEG C of temperature dry 23h, obtains modified CNT@Graphene flexible base material；
S4, CNT@Graphene flexible base material will be modified, to be modified CNT@Graphene flexible base material as base
Quasi- 14 times of weight waters mix ultrasonic disperse 30min, and pink salt is added, and use bronsted lowry acids and bases bronsted lowry regulation system pH value for 7.2, stirring in water bath
For 24 hours, bath temperature is 110 DEG C, is filtered, and is washed, dry, obtains CNT@Graphene/SnO2Presoma；
Wherein according to multi-walled carbon nanotube and SnO2Weight ratio be 1:8 be added pink salt；
The acid includes nitric acid, hydrochloric acid, acetic acid and oxalic acid, and the alkali includes ammonium hydroxide, sodium hydroxide, potassium hydroxide；
The pink salt includes nitric acid tin, tin acetate, STANNOUS SULPHATE CRYSTALLINE and stannic chloride；
S5, by CNT@Graphene/SnO2Presoma is heat-treated 14h in nitrogen atmosphere, and heat treatment temperature is 400 DEG C, obtains
To composite negative pole material.
Embodiment 9
A kind of preparation method of composite negative pole material, includes the following steps:
S1, the multi-walled carbon nanotube for weighing 0.5g are put into beaker, and the 100ml concentrated sulfuric acid is added, and ultrasonic agitation 0.5h is formed
Evenly dispersed solution；
S2, according to multi-walled carbon nanotube: oxidant be 1:4 mass ratio weigh oxidant, be added in the solution of S1, ultrasound
Stir 6h；
S3, black powder will be obtained by filtration after the dilution of the solution in S2, black powder is dried for 24 hours at 80 DEG C, is changed
Property CNT@Graphene flexible base material；
S4, it will be modified the CNT@Graphene flexible base material deionized water ultrasonic disperse 30min of 8 times of quality, pressed
According to CNT:SnO2SnCl2 is added for the mass ratio of 1:4, uses NH3·H2After O adjusts pH to 7.5,80 DEG C of constant temperature water baths are with 80rpm
Speed stirring, reaction is filtered afterwards for 24 hours, is washed, dry, obtains CNT@Graphene/SnO2Presoma.
S5, by CNT@Graphene/SnO2Presoma is heat-treated under N2 atmosphere, and heat treatment temperature is 450 DEG C, heat treatment
Time is 15h, obtains the SnO of CNT@Graphene load2Negative electrode material, i.e. composite negative pole material.As shown in FIG. 1, FIG. 1 is this
The CNT@Graphene/SnO that embodiment 9 synthesizes2The SEM photograph of negative electrode material；As shown in Fig. 2, Fig. 2 is the synthesis of the present embodiment 9
CNT@Graphene/SnO2The TEM photo of negative electrode material；As shown in figure 3, Fig. 3 is the CNT@synthesized in the present embodiment 9
Graphene/SnO2The cycle performance figure of the 1C multiplying power of negative electrode material.
The present embodiment product specific discharge capacity under the current density of 500mA/g reaches 1036mAh/g, and 100 times circulation is held
Measuring conservation rate is 77% or more.
Embodiment 10
A kind of preparation method of composite negative pole material, includes the following steps:
S1, the multi-walled carbon nanotube for weighing 4g are put into beaker, and the 100ml concentrated sulfuric acid is added, and ultrasonic agitation 0.5h is formed
The solution of even dispersion；
S2, according to multi-walled carbon nanotube: oxidant be 1:6 mass ratio weigh oxidant, be added in the solution of S1, ultrasound
Stir 1h；
S3, black powder will be obtained by filtration after the dilution of the solution in S2, black powder is dried for 24 hours at 90 DEG C, is changed
Property CNT@Graphene flexible base material；
S4, it will be modified the CNT@Graphene flexible base material deionized water ultrasonic disperse 30min of 20 times of quality, pressed
According to CNT:SnO2SnSO is added for the mass ratio of 1:6.54, use HNO3And CH3After COOH adjusts pH to 5,120 DEG C of constant temperature water baths
It is stirred with the speed of 300rpm, is filtered after reacting 6h, washed, it is dry, obtain CNT@Graphene/SnO2Presoma.
S5, by CNT@Graphene/SnO2Presoma is in N2It is heat-treated under atmosphere, heat treatment temperature is 600 DEG C, heat treatment
Time is 2h, obtains the SnO of CNT@Graphene load2Negative electrode material, i.e. composite negative pole material.
The present embodiment product specific discharge capacity under the current density of 500mA/g reaches 1008mAh/g, and 100 times circulation is held
Measuring conservation rate is 72% or more.
Embodiment 11
A kind of preparation method of composite negative pole material, includes the following steps:
S1, the multi-walled carbon nanotube for weighing 1g are put into beaker, and the 100ml concentrated sulfuric acid is added, and ultrasonic agitation 0.5h is formed
The solution of even dispersion；
S2, according to multi-walled carbon nanotube: oxidant be 1:2.5 mass ratio weigh oxidant, be added in the solution of S1, surpass
Sound stirs 5h；
S3, black powder will be obtained by filtration after the dilution of the solution in S2, black powder is dried for 24 hours at 120 DEG C, is changed
Property CNT@Graphene flexible base material；
S4, it will be modified the CNT@Graphene flexible base material deionized water ultrasonic disperse 30min of 15 times of quality, pressed
According to CNT:SnO2SnAc is added for the mass ratio of 1:4.52, use KOH and NH3·H2After O adjusts pH to 10,60 DEG C of constant temperature water baths
It is stirred with the speed of 50rpm, is filtered after reacting 36h, washed, it is dry, obtain CNT@Graphene/SnO2Presoma.
S5, by CNT@Graphene/SnO2Presoma is in N2It is heat-treated under atmosphere, heat treatment temperature is 400 DEG C, heat treatment
Time is 8h, obtains the SnO of CNT@Graphene load2Negative electrode material, i.e. composite negative pole material.
The present embodiment product specific discharge capacity under the current density of 500mA/g reaches 1080mAh/g, and 100 times circulation is held
Measuring conservation rate is 71.5% or more.
Embodiment 12
A kind of preparation method of composite negative pole material, includes the following steps:
S1, the multi-walled carbon nanotube for weighing 2g are put into beaker, and the 100ml concentrated sulfuric acid is added, and ultrasonic agitation 0.5h is formed
The solution of even dispersion；
S2, according to multi-walled carbon nanotube: oxidant be 1:2 mass ratio weigh oxidant, be added in the solution of S1, ultrasound
Stir 3h；
S3, black powder will be obtained by filtration after the dilution of the solution in S2, black powder is dried for 24 hours at 150 DEG C, is changed
Property CNT@Graphene flexible base material；
S4, it will be modified the CNT@Graphene flexible base material deionized water ultrasonic disperse 30min of 8 times of quality, pressed
According to CNT:SnO2Sn (NO is added for the mass ratio of 1:93)4, after adjusting pH to 6 using HCl, 60 DEG C of constant temperature water baths are with 200rpm's
Speed stirring, filters after reacting 6h, washs, dry, obtains CNT@Graphene/SnO2Presoma.
S5, by CNT@Graphene/SnO2Presoma is in N2It is heat-treated under atmosphere, heat treatment temperature is 350 DEG C, heat treatment
Time is 15h, obtains the SnO of CNT@Graphene load2Negative electrode material, i.e. composite negative pole material.
The present embodiment product specific discharge capacity under the current density of 500mA/g reaches 1180mAh/g, and 100 times circulation is held
Measuring conservation rate is 73% or more.
Embodiment 13
A kind of preparation method of composite negative pole material, includes the following steps:
S1, the multi-walled carbon nanotube for weighing 3g are put into beaker, and the 100ml concentrated sulfuric acid is added, and ultrasonic agitation 0.5h is formed
The solution of even dispersion；
S2, according to multi-walled carbon nanotube: oxidant be 1:3.5 mass ratio weigh oxidant, be added in the solution of S1, surpass
Sound stirs 2.5h；
S3, black powder will be obtained by filtration after the dilution of the solution in S2, black powder is dried for 24 hours at 150 DEG C, is changed
Property CNT@Graphene flexible base material；
S4, it will be modified the CNT@Graphene flexible base material deionized water ultrasonic disperse 30min of 10 times of quality, pressed
According to CNT:SnO2SnCl is added for the mass ratio of 1:72, use NaOH and NH3·H2After O adjusts pH to 8.5,100 DEG C of constant temperature water baths
It is stirred with the speed of 150rpm, is filtered after reacting 10h, washed, it is dry, obtain CNT@Graphene/SnO2Presoma.
S5, by CNT@Graphene/SnO2Presoma is in N2It is heat-treated under atmosphere, heat treatment temperature is 550 DEG C, heat treatment
Time is 4h, obtains the SnO of CNT@Graphene load2Negative electrode material, i.e. composite negative pole material.
The present embodiment product specific discharge capacity under the current density of 500mA/g reaches 1008mAh/g, and 100 times circulation is held
Measuring conservation rate is 80% or more.
Embodiment 14
A kind of preparation method of composite negative pole material, includes the following steps:
S1, the multi-walled carbon nanotube for weighing 2g are put into beaker, and the 100ml concentrated sulfuric acid is added, and ultrasonic agitation 0.5h is formed
The solution of even dispersion；
S2, according to multi-walled carbon nanotube: oxidant be 1:4.5 mass ratio weigh oxidant, be added in the solution of S1, surpass
Sound stirs 4h；
S3, black powder will be obtained by filtration after the dilution of the solution in S2, black powder is dried for 24 hours at 100 DEG C, is changed
Property CNT@Graphene flexible base material；
S4, it will be modified the CNT@Graphene flexible base material deionized water ultrasonic disperse 30min of 15 times of quality, pressed
According to CNT:SnO2SnAc is added for the mass ratio of 1:82, after adjusting pH to 9 using NaOH, 90 DEG C of constant temperature water baths are with the speed of 280rpm
Degree stirring, filters after reacting 48h, washs, dry, obtains CNT@Graphene/SnO2Presoma.
S5, by CNT@Graphene/SnO2Presoma is in N2It is heat-treated under atmosphere, heat treatment temperature is 300 DEG C, heat treatment
Time is 20h, obtains the SnO of CNT@Graphene load2Negative electrode material, i.e. composite negative pole material.
The present embodiment product specific discharge capacity under the current density of 500mA/g reaches 980mAh/g, 100 circulation volumes
Conservation rate is 72% or more.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of composite negative pole material, which is characterized in that including CNT@Graphene substrate and be supported on CNT@Graphene base
SnO on bottom2。
2. composite negative pole material according to claim 1, which is characterized in that the SnO2For nano SnO2。
3. a kind of preparation method of composite negative pole material according to claim 1 or 2, which is characterized in that including walking as follows
It is rapid:
S1, multi-walled carbon nanotube, the concentrated sulfuric acid are stirred, obtains suspension；
S2, into suspension, addition oxidant continues to stir, and obtains prefabricated material；
S3, prefabricated material is filtered, it is dry, obtain modified CNT@Graphene flexible base material；
S4, it will be modified CNT@Graphene flexible base material, water mixing dispersion, pink salt is added, regulation system pH value is 4-11,
Stirring is filtered, and is washed, dry, obtains CNT@Graphene/SnO2Presoma；
S5, by CNT@Graphene/SnO2Presoma is heat-treated in inert gas, obtains composite negative pole material.
4. the preparation method of composite negative pole material according to claim 3, which is characterized in that in S1, multi-wall carbon nano-tube
The w/v g:ml of pipe and the concentrated sulfuric acid is 0.5-4:100.
5. the preparation method of composite negative pole material according to claim 3, which is characterized in that in S2, the oxidant
For at least one of potassium permanganate, potassium hyperchlorate, sodium perchlorate, ammonium persulfate；
Preferably, the weight ratio of multi-walled carbon nanotube and oxidant is 1:1-6.
6. the preparation method of composite negative pole material according to claim 3, which is characterized in that in S3, drying temperature is
60-150 DEG C, drying time 1-50h.
7. the preparation method of composite negative pole material according to claim 3, which is characterized in that in S4, using bronsted lowry acids and bases bronsted lowry
Regulation system pH value, the acid are at least one of nitric acid, hydrochloric acid, acetic acid and oxalic acid, and the alkali is ammonium hydroxide, sodium hydroxide, hydrogen
At least one of potassium oxide.
8. the preparation method of composite negative pole material according to claim 3, which is characterized in that in S4, in whipping process
In, using stirring in water bath, mixing time 6-48h, bath temperature is 50-120 DEG C；
Preferably, the pink salt is at least one of nitric acid tin, tin acetate, STANNOUS SULPHATE CRYSTALLINE and stannic chloride；It is further preferred that according to
Multi-walled carbon nanotube and SnO2Weight ratio be 1:2-10 be added pink salt.
9. according to the preparation method of the described in any item composite negative pole materials of claim 3-8, which is characterized in that in S5, institute
Stating inert gas is nitrogen；
Preferably, heat treatment time 2-20h, heat treatment temperature are 200-600 DEG C.
10. a kind of application of composite negative pole material according to claim 1 or 2 in lithium ion battery.
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