CN105481004B - A kind of high electric property tin dioxide nanometer tube and preparation method thereof - Google Patents
A kind of high electric property tin dioxide nanometer tube and preparation method thereof Download PDFInfo
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- CN105481004B CN105481004B CN201410475126.4A CN201410475126A CN105481004B CN 105481004 B CN105481004 B CN 105481004B CN 201410475126 A CN201410475126 A CN 201410475126A CN 105481004 B CN105481004 B CN 105481004B
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Abstract
The present invention relates to a kind of high electric property tin dioxide nanometer tube and preparation method thereof, methods described includes：1）Prepare the first mixed liquor containing Silica Nanotube and/or titania nanotube, alcoholic solution, pink salt and urea；2）First mixed liquor is placed in hydrothermal reaction kettle and reacted；3）The first mixed liquor that reaction is finished, which is centrifuged, obtains the first precipitum；4）By the calcining of the first precipitum；5）Burnt first precipitum is placed in strong base solution and obtains the second mixed liquor；6）Second mixed liquor is centrifuged and obtains the second precipitum, the cleaning of the second precipitum is finished, dried, the high electric property tin dioxide nanometer tube is produced.
Description
Technical field
The invention belongs to nano-functional material field, and in particular to a kind of high electric property tin dioxide nanometer tube and its system
Preparation Method.
Background technology
The fast development of novel high-energy power technology, higher requirement is proposed to lithium ion battery electrode material.Tool
It is scientists mesh to have high-energy-density, high power density, the lithium ion battery electrode material of good charge/discharge cycle characteristics
The emphasis of preceding research.At present, carbon material (graphene, amorphous carbon etc.) is the main negative pole material of commercialized lithium ion battery
Material.But the storage lithium ability of carbon material is relatively low (graphene theoretical capacity 372mAh/g), limits entering for capacity of lithium ion battery
One step is improved.Tin ash (SnO2) as the negative material of lithium ion battery, its theoretical capacity is 790mAh/g, much larger than stone
The theoretical capacity of black alkene.Therefore, SnO2It is considered as current most one of ion cathode material lithium of Commercial Prospect.But by
In huge Volume Changes in charge and discharge process, the efflorescence of stannic oxide electrode material can be caused, due to active material and collection
The separation of flow, its capacity can drastically decline, and cycle performance of battery is also deteriorated；In addition, stannic oxide electrode material fills first
Discharging efficiency is very low, and these all limit its commercial applications as lithium ion battery negative material.
At present, SnO is improved2The method of lithium ion battery negative material has general three kinds, and one kind is to prepare SnO2With other materials
The composite of material, such as C (CrystEngComm, 2014,16,517) (battery special capacity fade is 515mAh/g after 30 times),
Fe2O3(Advanced Functional Material, 2011,21,385) (battery special capacity fade is 200mAh/ after 30 times
G) etc..This preparation method, preparation process is cumbersome, and condition is harsh, but either to SnO2Battery capacity or circulation effect
Rate, its performance improves all very limited, it is impossible to reach the level of industrial applications；Another method is nano level by preparing
SnO2, SnO is prepared at present2Method mostly concentrate on hydro-thermal method prepare, it is necessary to add the 1B (patent No.：
200910084901.2), (first charge-discharge specific capacity is 1898 Hes to N- methylimidazoles (Nanoscale, 2013,5,3262)
1241mAh/g, battery special capacity fade is 718mAh/g after 60 times) etc. end-capping reagent, prepare the SnO of nano-grade size2Material.Also
It is to prepare SnO to have a kind of method2Hollow-core construction (small 2010,6,296), although specific surface area is increased, it is circulated
Battery specific capacity just decays to only 351mAh/g after 30 times.As can be seen that SnO2Hollow pipe has big specific surface area and sky
Chamber, has certain effect for improving its cycle performance of battery and battery capacity, but its cycle performance of battery and battery capacity
Industrial applications demand can not still be met.
The content of the invention
It is contemplated that overcoming existing SnO2Nano material be used as the performance deficiency in terms of cell negative electrode material, the present invention
There is provided a kind of high electric property tin dioxide nanometer tube and preparation method thereof.
The invention provides a kind of preparation method of high electric property tin dioxide nanometer tube, methods described includes：
1) first containing Silica Nanotube and/or titania nanotube, alcoholic solution, pink salt and urea is prepared
Mixed liquor, wherein, Silica Nanotube/and/or titania nanotube, three kinds of materials of pink salt and urea, mass ratio is 1：
(1-3)：(10-25), concentration of the nanotube in the first mixed liquor is 0.5-2g/L；
2) by step 1) prepare the first mixed liquor be placed in hydrothermal reaction kettle, at 140-240 DEG C react 0.5-12 it is small
When；
3) by step 2) in the first mixed liquor for finishing of reaction be centrifuged and obtain the first precipitum, and clean gained
First precipitum；
4) by step 3) the first precipitum is obtained, calcined 1-12 hours at 300-800 DEG C；
5) by step 4) in burnt first precipitum be placed in strong base solution and obtain the second mixed liquor, wherein, highly basic
Concentration be 0.1-2mol/L, the concentration of the first precipitum is 3-8g/L；
6) by step 5) the second mixed liquor for preparing is centrifuged and obtains the second precipitum, the second precipitum is cleaned
Finish, dry, produce the high electric property tin dioxide nanometer tube.
It is preferred that step 1) in, step 1) in, Silica Nanotube/and/or titania nanotube, pink salt and urine
The mass ratio of element is 1：(1.5-2.5)：(14-22.5).
It is preferred that step 1) in, alcohol is ethanol, normal propyl alcohol, isopropanol and/or n-butanol.
It is preferred that step 1) in, the pink salt is potassium stannate, sodium stannate, butter of tin, stannic chloride pentahydrate, dichloride
Tin and/or two water stannous chloride.
It is preferred that step 2) in, reaction temperature is 160-200 DEG C, and the reaction time is 0.5-4 hours.
It is preferred that step 4) in, 400-600 DEG C of calcining heat, calcination time is 2-8 hours.
Also, the invention provides high electric property tin dioxide nanometer tube prepared by a kind of above method, the titanium dioxide
The diameter 60-500nm of sijna mitron, 100-1000nm of internal diameter, 5-40um of length, specific surface area are 20-200m2g-1。
It is preferred that the lithium that the negative material of high electric property tin dioxide nanometer tube as the lithium ion battery is made
Ion battery is when current density is 160mA/g, and after 50 times circulate, charge and discharge specific capacity is still kept above 820mAh/g；
When current density is 800mA/g, after 50 times circulate, charge and discharge specific capacity is higher than 470mAh/g；It is in current density
During 1600mA/g, after 70 times circulate, charge and discharge specific capacity is higher than 440mAh/g；When current density is 3200mA/g, warp
Cross after 80 circulations, charge and discharge specific capacity is higher than 410mAh/g.
Beneficial effects of the present invention：
Relative to existing preparation SnO2The technology of preparing of hollow pipe (nanotube) shape material, the present invention has the advantage that：
1) preparation method is simple, easy, and method repeatability is high, and product batches are good.It is adapted to a large amount of productions；
2) SnO prepared by the present invention2Hollow pipe is after 140~240 DEG C of hydro-thermals are prepared for 0.5~12 hour, it is only necessary to 400
1~12h is calcined under~700 DEG C of low temperature, consumes energy extremely low, reduces industrialization cost；
3) SnO prepared using the present invention2Hollow pipe material prepares battery as the negative material of battery, its battery performance
It is very superior.Charge and discharge specific capacity can reach 924.1 and 2045.6mAh/g first, and charge-discharge performance is good：Electric current is close
When spending for 160mA/g, after 200 times circulate, charge and discharge specific capacity still maintains 580.7 and 585.8mAh/g, forthright again to fill
Discharge cycle performance is good；When current density is 800mA/g (1C), after 52 times circulate, charge and discharge specific capacity is still maintained
474.3 and 475.7mAh/g；When current density is 1600mA/g (2C), after 73 times circulate, charge and discharge specific capacity is still kept
There are 444.6 and 445.1mAh/g；When current density is 3200mA/g (4C), after 81 times circulate, charge and discharge specific capacity is
411.4 and 411.4mAh/g.
Brief description of the drawings
Fig. 1 shows the SnO prepared in an embodiment of the invention2The ESEM of hollow pipe (nanotube) shines
Piece；
Fig. 2 shows the SnO prepared in an embodiment of the invention2The transmission electron microscope photo of hollow pipe；
Fig. 3 shows the SnO prepared in an embodiment of the invention2The XRD spectrum of quantum dot；
Fig. 4 shows the tin ash hollow pipe prepared in an embodiment of the invention as lithium ion battery negative
The charge and discharge cycles curve map of lithium ion battery prepared by material；
Fig. 5 shows the tin ash hollow pipe prepared in an embodiment of the invention as lithium ion battery negative
The charge-discharge magnification cyclic curve figure of lithium ion battery prepared by material；
Fig. 6 shows the tin ash nitrogen adsorption desorption figure prepared in an embodiment of the invention and its aperture point
Butut.
Embodiment
The present invention is further illustrated below in conjunction with accompanying drawing and following embodiments, it should be appreciated that accompanying drawing and following embodiments
The present invention is merely to illustrate, is not intended to limit the present invention.
The invention discloses a kind of high electric property tin ash hollow pipe and its preparation method.The SnO2Hollow pipe is used as lithium
Ion electrode negative material, the lithium ion capacity of preparation is high, and charge-discharge performance is good, for example with two prepared in the present invention
The performance parameter of lithium battery prepared by tin oxide hollow pipe is：When current density is 160mA/g, after 50 times circulate, fills, put
Electric specific capacity is still kept above 820mAh/g, and forthright charge-discharge performance is good again；When current density is 800mA/g (1C),
After 50 times circulate, charge and discharge specific capacity is higher than 470mAh/g；When current density is 1600mA/g (2C), followed by 70 times
After ring, charge and discharge specific capacity is higher than 440mAh/g；When current density is 3200mA/g (4C), after 80 times circulate, fills, put
Electric specific capacity is higher than 410mAh/g.This SnO2The preparation method of hollow pipe is：By pink salt, urea and silicon dioxide hollow pipe die
Plate material configures alcohol, water mixed solution by a certain percentage, and hydro-thermal reaction for a period of time, is then centrifuged for separation at a certain temperature,
Dry and calcined a few hours in air atmosphere at a certain temperature, then mould material is removed with certain density NaOH, obtain
Tin ash hollow pipe material.The present invention, as mould material, prepares tin ash hollow pipe using silicon dioxide hollow pipe, should
Method is simple and easy to apply, and energy consumption is low, and raw material are cheap, is adapted to large-scale production.
High electric property tin ash hollow pipe in the present invention, diameter is in 60~500nm, and powder dispersity is good.This hair
Bright tin dioxide nanometer tube due to specific surface area it is big the characteristics of, gas sensor, solar cell, electrically conducting transparent electricity
Important application is respectively provided with terms of pole and lithium ion battery.The invention provides one kind by means of silicon dioxide hollow pipe be template
Prepare with capacity, cycle performance and the pure SnO of forthright cycle performance again2The method of hollow pipe material.
It is as follows the step of this method the invention provides a kind of preparation method of high electric property tin ash hollow pipe：
A) the method that silicon dioxide hollow pipe (nanotube) is prepared using early stage；
A, the method that the sodium chloride crystal of nanocube pattern is prepared using early stage prepares the sodium chloride that concentration is 2.0M
Glycerite, 0.5ml sodium chloride glycerite is added into 100ml aqueous isopropanols, and (25 DEG C) are reacted 5 points at normal temperatures
Clock；
B, a certain amount of tetraethyl orthosilicate (TEOS) 2.0ml, ammoniacal liquor (NH4OH) 1.0m and water 5ml are all added in two times
Enter in step a solution, reaction is 8 hours altogether under room temperature (25 DEG C)；
C, 10ml deionized water is added dropwise into step b solution；
D, step c resulting solutions are centrifuged, and are cleaned with ethanol, are then centrifuged, are so repeated several times again；
E, by powder obtained by step d as being dried 3 hours in the case where temperature is 100 DEG C and 300 DEG C respectively in baking oven, obtains dioxy
SiClx nanotube；
B) take certain mass step A) prepare silicon dioxide hollow pipe be placed in certain volume alcohol and water mixed solution
In, the pink salt and urea of certain volume are proportionally added into, certain time is stirred at room temperature；Wherein alcohol can be ethanol, normal propyl alcohol,
Isopropanol and n-butanol, preferred alcohol and isopropanol；Volume ratio wherein in the mixed solution of alcohol and water shared by alcohol 1%~
Between 99%, the volume ratio shared by alcohol is preferably 50%~70%；The quality of silicon dioxide hollow pipe die plate, pink salt and urea
Than 1:1:10~1:3:Between 25, each material mass ratio preferably 1:1.5:14~1:2.5:22.5；Wherein pink salt can be
Potassium stannate, sodium stannate, butter of tin, stannic chloride pentahydrate, stannous chloride and two water stannous chloride etc., pink salt is preferably stannic acid
Potassium, sodium stannate and stannic chloride pentahydrate；
C) by step B) mixed solution of configuration is placed in hydrothermal reaction kettle and reacted.Temperature is in 140~240oC, instead
It is between seasonable 0.5~12 hour (h), natural cooling after reaction completely；Wherein, preferably 160~200 DEG C of reaction temperature, during reaction
Between be preferably 0.5~4h；
D) by step C) solution centrifugal separation, and respectively washed 3 times with ethanol and deionized water, powder be placed in tube furnace
In, certain time is calcined in air atmosphere.Temperature is 300~800 DEG C, and the time is 1~12 hour, naturally cold after calcining terminates
But；Wherein preferably 400~600 DEG C of reaction temperature, the reaction time is preferably 2~8h；
E) by step D) prepare powder be placed in certain density sodium hydroxide solution, naoh concentration is 0.1M/
L, the concentration of composite granule is 3~8g/L；
F) by step E) powder for preparing centrifuges, and cleaned 3 times with deionized water, powder is placed in baking oven in 80
DEG C drying 24 hours, obtain tin ash hollow pipe material；
Performance of lithium ion battery method of testing and step
1) by the SnO of preparation2Hollow pipe lithium ion battery negative material gathers inclined two as electrode active material with binding agent
PVF (PVDF) and conductive acetylene is black presses 80：10：10 mass ratio mixing, obtains compound, plus appropriate amount of deionized water
Slurry is stirred into, aluminium foil surface is coated uniformly on coating machine, pole piece is then dried into 24h at 85 DEG C.Cutting be made lithium from
The negative plate of sub- battery；
2) negative plate of the lithium ion battery of preparation is assembled into lithium ion half-cell and carries out performance detection, be used as lithium ion
The negative pole of battery, metal Li pieces are used as positive pole.Electrolyte is the LiPF containing 1mol/L6DEC (carbonic acid diethyl ester)+EC (carbonic acid
Ethene fat) (volume ratio Dec：Ec=7：3), barrier film polypropylene Celgard2300.Battery assembling process is whole in vacuum hand behaviour
Completed in case.The battery assembled is placed and constant current charge-discharge test is carried out after 12h, and charging/discharging voltage is 0.2~2V, in environment temperature
Spend at 25 DEG C ± 2 DEG C, current density is 160mA/g (multiplying powers：Constant current charge-discharge loop test is carried out under 0.2C), dioxy is measured
Change reversible capacity and charge-discharge performance that tin quantum dot prepares lithium ion battery as electrode active material.Forthright charge and discharge again
Electric cyclic test, respectively current density be 80mAh/g, 400mAh/g, 800mAh/g, 1600mAh/g, 3200mAh/g,
Charge and discharge cycles experiment is carried out under 80mAh/g, test tin ash hollow pipe prepares lithium ion battery as electrode active material
Reversible capacity and forthright charge and discharge cycles experiment again.
Relative to existing preparation SnO2The technology of preparing of hollow tubular material, the present invention has the advantage that：
1) preparation method is simple, easy, and method repeatability is high, and product batches are good.It is adapted to a large amount of productions；
2) SnO prepared by the present invention2Hollow pipe is after 140~240 DEG C of hydro-thermals are prepared for 0.5~12 hour, it is only necessary to 400
1~12h is calcined under~700 DEG C of low temperature, consumes energy extremely low, reduces industrialization cost；
3) SnO prepared using the present invention2Hollow pipe material prepares battery as the negative material of battery, its battery performance
It is very superior.Charge and discharge specific capacity is 924.1 and 2045.6mAh/g first, and charge-discharge performance is good；Current density is
During 160mA/g, after 200 times circulate, charge and discharge specific capacity still maintains 580.7 and 585.8mAh/g, again forthright discharge and recharge
Good cycle；When current density is 800mA/g (1C), after 52 times circulate, charge and discharge specific capacity is 474.3 Hes
475.7mAh/g；When current density is 1600mA/g (2C), after 73 times circulate, charge and discharge specific capacity is 444.6 Hes
445.1mAh/g；When current density is 3200mA/g (4C), after 81 times circulate, charge and discharge specific capacity is 411.4 Hes
411.4mAh/g。
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described, it is impossible to be interpreted as limiting the scope of the invention.Those skilled in the art are according to the present invention
Some nonessential modifications and adaptations for making of the above belong to protection scope of the present invention.Following examples are specifically warm
Degree, time etc. are also only an examples in OK range, i.e., those skilled in the art can be done properly by this paper explanation
In the range of select, and be not limited to the concrete numerical value of hereafter example.
Embodiment 1
1) method that silicon dioxide hollow pipe is prepared using early stage
A, the method that the sodium chloride crystal of nanocube pattern is prepared using early stage prepares the sodium chloride that concentration is 2.0M
Glycerite, 0.5ml sodium chloride glycerite is added into 100ml aqueous isopropanols, and (25 DEG C) are reacted 5 points at normal temperatures
Clock；
B, a certain amount of tetraethyl orthosilicate (TEOS) 2.0ml, ammoniacal liquor (NH4OH) 1.0m and water 5ml are all added in two times
Enter in step a solution, reaction is 8 hours altogether under room temperature (25 DEG C)；C, 10ml deionization is added dropwise into step b solution
Water；
D, step c resulting solutions are centrifuged, and are cleaned with ethanol, are then centrifuged, are so repeated several times again；
E, by powder obtained by step d as being dried 3 hours in the case where temperature is 100 DEG C and 300 DEG C respectively in baking oven, obtains dioxy
SiClx nanotube；
2) certain mass step 1 is taken) the silicon dioxide hollow pipe 60mg for preparing is placed in 25ml isopropanol and 15ml water
In mixed solution, 110mg potassium stannates and 0.85g urea are added, 10min is stirred at room temperature；
3) by step 2) configuration mixed solution be transferred to capacity be 100ml hydrothermal reaction kettle in, be put in hydro-thermal reaction
Reacted in stove.Temperature is at 170 DEG C, and the reaction time is 1h, natural cooling after reaction completely；
4) by step 3) solution centrifugal separation, and respectively washed 3 times with ethanol and deionized water, powder be placed in tube furnace
In, certain time is calcined in air atmosphere.Calcining heat is 500 DEG C, and the time is 4 hours, after calcining terminates, natural cooling；
5) by step 4) prepare powder be placed in certain density sodium hydroxide solution, naoh concentration is 0.1M/
L, the concentration of composite granule is 5g/L；
6) by step 5) powder for preparing centrifuges, and cleaned 3 times with deionized water, powder is placed in baking oven in 80
DEG C drying 24 hours, obtain tin ash hollow pipe material；
Fig. 1 is the SnO for preparing in the embodiment2The stereoscan photograph of hollow pipe；
Fig. 2 is the SnO for preparing in the embodiment2The transmission electron microscope photo of hollow pipe；
Fig. 3 is the SnO prepared in the embodiment2The XRD spectrum of hollow pipe, with SnO2Standard card (JCPDS：41-
1445) fit like a glove, it is pure SnO to illustrate product2；
Fig. 4 is SnO2The cycle performance of battery picture of lithium ion battery prepared by hollow pipe lithium ion battery negative material.
It is 160mA/g (0.2C) in current density, after circulating 200 times, SnO2The charging and discharging capacity of hollow pipe still maintains 580.7,
585.8mAh/g, tends towards stability substantially, no longer decays；
Fig. 5 is SnO2The charge and discharge cycles figure forthright again of lithium ion battery prepared by hollow pipe lithium ion battery negative material
Piece.As can be seen from the figure forthright charge-discharge performance is good again for its high battery.Forthright charge-discharge performance is good again：Work as electricity
When current density is 800mA/g (1C), charge and discharge specific capacity is 474.3 and 475.7mAh/g, and current density is 1600mA/g (2C)
When, charge and discharge specific capacity is 444.6 and 445.1mAh/g, and when current density is 3200mA/g (4C), charge and discharge specific capacity is
411.4 and 411.4mAh/g；
Fig. 6 is SnO2The nitrogen adsorption desorption figure of hollow pipe material, the SnO as can be seen from the figure prepared2The ratio of hollow pipe
Surface area is 123.6m2g-1；
A diameter of 120-620nm of tin dioxide nanometer tube in the embodiment, 100-600nm of internal diameter, length 5-
20um, specific surface area is 123.6m2g-1。
Embodiment 2
1) method that silicon dioxide hollow pipe is prepared using early stage
A, the method that the sodium chloride crystal of nanocube pattern is prepared using early stage prepares the sodium chloride that concentration is 2.0M
Glycerite, 0.5ml sodium chloride glycerite is added into 100ml aqueous isopropanols, and (25 DEG C) are reacted 5 points at normal temperatures
Clock；
B, a certain amount of tetraethyl orthosilicate (TEOS) 2.0ml, ammoniacal liquor (NH4OH) 1.0m and water 5ml are all added in two times
Enter in step a solution, reaction is 8 hours altogether under room temperature (25 DEG C)；C, 10ml deionization is added dropwise into step b solution
Water；
D, step c resulting solutions are centrifuged, and are cleaned with ethanol, are then centrifuged, are so repeated several times again；
E, by powder obtained by step d as being dried 3 hours in the case where temperature is 100 DEG C and 300 DEG C respectively in baking oven, obtains dioxy
SiClx nanotube；
2) certain mass step 1 is taken) the silicon dioxide hollow pipe 60mg for preparing is placed in 30ml isopropanol and 10ml water
In mixed solution, 130mg stannic chloride pentahydrates and 1g urea are added, 10min is stirred at room temperature；
3) by step 2) configuration mixed solution be transferred to capacity be 100ml hydrothermal reaction kettle in, be put in hydro-thermal reaction
Reacted in stove.Temperature is at 190 DEG C, and the reaction time is 0.5h, natural cooling after reaction completely；
4) by step 3) solution centrifugal separation, and respectively washed 3 times with ethanol and deionized water, powder be placed in tube furnace
In, certain time is calcined in air atmosphere.Calcining heat is 600 DEG C, and the time is 3 hours, after calcining terminates, natural cooling；
5) by step 4) prepare powder be placed in certain density sodium hydroxide solution, naoh concentration is 0.1M/
L, the concentration of composite granule is 5g/L；
6) by step 5) powder for preparing centrifuges, and cleaned 3 times with deionized water, powder is placed in baking oven in 80
DEG C drying 24 hours, obtain tin ash hollow pipe material；
A diameter of 130-630nm of tin dioxide nanometer tube in the embodiment, 100-600nm of internal diameter, length 5-
20um, specific surface area is 108m2g-1。
Embodiment 3
1) the commercially available titania nanotube of certain mass (diameter about 100nm) 50mg is taken to be placed in 30ml isopropanol and 10ml
In the mixed solution of water, 130mg stannic chloride pentahydrates and 1g urea are added, 10min is stirred at room temperature；
2) by step 2) configuration mixed solution be transferred to capacity be 100ml hydrothermal reaction kettle in, be put in hydro-thermal reaction
Reacted in stove.Temperature is at 190 DEG C, and the reaction time is 0.5h, natural cooling after reaction completely；
3) by step 3) solution centrifugal separation, and respectively washed 3 times with ethanol and deionized water, powder be placed in tube furnace
In, certain time is calcined in air atmosphere.Calcining heat is 600 DEG C, and the time is 3 hours, after calcining terminates, natural cooling；
4) by step 4) prepare powder be placed in certain density sodium hydroxide solution, naoh concentration is 0.1M/
L, the concentration of composite granule is 5g/L；
5) by step 5) powder for preparing centrifuges, and cleaned 3 times with deionized water, powder is placed in baking oven in 80
DEG C drying 24 hours, obtain tin ash hollow pipe material；
A diameter of 125-625nm of tin dioxide nanometer tube in the embodiment, 100-600nm of internal diameter, length 5-
20um, specific surface area is 156m2g-1。
Claims (8)
1. a kind of preparation method of high electric property tin dioxide nanometer tube, it is characterised in that methods described includes：
1）The first mixed liquor containing Silica Nanotube, alcoholic solution, pink salt and urea is prepared, wherein, silica is received
Mitron, three kinds of materials of pink salt and urea, mass ratio is 1：（1-3）：（10-25）, concentration of the nanotube in the first mixed liquor
For 0.5-2g/L, the Silica Nanotube is prepared via a method which：
A, prepares the sodium chloride glycerite that concentration is 2.0M, 0.5ml sodium chloride glycerine is added into 100ml aqueous isopropanols
Solution, reacts 5 minutes at normal temperatures；
B, a certain amount of tetraethyl orthosilicate, ammoniacal liquor and moisture is all added in step a solution twice, reaction at room temperature has altogether
For 8 hours；
C, 10ml deionized water is added dropwise into step b solution；
D, step c resulting solutions are centrifuged, and are cleaned with ethanol, are then centrifuged, are so repeated several times again；
E, powder obtained by step d is placed in baking oven and dried 3 hours in the case where temperature is 100 DEG C and 300 DEG C respectively, silica is obtained
Nanotube；
2）By step 1）The first mixed liquor prepared is placed in hydrothermal reaction kettle, is reacted 0.5-12 hours at 140-240 DEG C；
3）By step 2）The first mixed liquor that middle reaction is finished, which is centrifuged, obtains the first precipitum, and cleans gained first
Precipitum；
4）By step 3）The first precipitum is obtained, is calcined 1-12 hours at 300-800 DEG C；
5）By step 4）In burnt first precipitum be placed in strong base solution and obtain the second mixed liquor, wherein, highly basic it is dense
Spend for 0.1-2mol/L, the concentration of the first precipitum is 3-8 g/L；
6）By step 5）The second mixed liquor prepared, which is centrifuged, obtains the second precipitum, and the second precipitum has been cleaned
Finish, dry, produce the high electric property tin dioxide nanometer tube,
The lithium ion battery that the negative material of high electric property tin dioxide nanometer tube as the lithium ion battery is made exists
When current density is 160mA/g, after 50 times circulate, charge and discharge specific capacity is still kept above 820mAh/g.
2. preparation method according to claim 1, it is characterised in that step 1）In, Silica Nanotube, pink salt and
The mass ratio of urea is 1：（1.5-2.5）：（14-22.5）.
3. preparation method according to claim 1, it is characterised in that step 1）In, alcohol is ethanol, normal propyl alcohol, isopropanol
And/or n-butanol.
4. preparation method according to claim 1, it is characterised in that step 1）In, the pink salt is potassium stannate, stannic acid
Sodium, butter of tin, and/or stannous chloride.
5. preparation method according to claim 1, it is characterised in that step 2）In, reaction temperature is 160-200 DEG C, instead
It is 0.5-4 hours between seasonable.
6. according to any described preparation method in claim 1-5, it is characterised in that step 4）In, calcining heat 400-600
DEG C, calcination time is 2-8 hours.
7. the high electric property tin dioxide nanometer tube that in a kind of claim 1-6 prepared by any methods described, it is characterised in that
The diameter 120-630nm of the tin dioxide nanometer tube, 100-600nm of internal diameter, 5-40um of length, specific surface area be 20-
200 m2g-1, the lithium-ion electric that the negative material of high electric property tin dioxide nanometer tube as the lithium ion battery is made
Pond is when current density is 160mA/g, and after 50 times circulate, charge and discharge specific capacity is still kept above 820mAh/g.
8. high electric property tin dioxide nanometer tube according to claim 7, it is characterised in that by the high electric property
The lithium ion battery that tin dioxide nanometer tube is made as the negative material of lithium ion battery when current density is 800mA/g,
After 50 times circulate, charge and discharge specific capacity is higher than 470mAh/g；When current density is 1600 mA/g, by 70 circulations
Afterwards, charge and discharge specific capacity is higher than 440 mAh/g；When current density is 3200 mA/g, after 80 times circulate, charge and discharge
Specific capacity is higher than 410mAh/g.
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| CN106299294A (en) * | 2016-09-13 | 2017-01-04 | 天津大学 | A kind of preparation method of tin dioxide nanocrystal/titania nanotube composite |
| CN108666562B (en) * | 2018-04-17 | 2021-03-26 | 宁波大学 | Cobalt-manganese-doped tin dioxide nanotube and preparation method thereof |
| CN111874940B (en) * | 2020-07-13 | 2022-12-06 | 滁州学院 | Preparation method and application of tubular tin dioxide and carbon-coated tubular tin dioxide nanocomposite |
| CN112811473B (en) * | 2021-01-06 | 2022-09-30 | 安徽师范大学 | Nano bracelet iron sesquioxide/graphene quantum dot/tin dioxide core-shell structure composite material, preparation method thereof and battery application |
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