CN106025231B - A kind of preparation method of hollow graphite alkene ball/sulphur composite material - Google Patents
A kind of preparation method of hollow graphite alkene ball/sulphur composite material Download PDFInfo
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Abstract
A kind of preparation method of hollow graphite alkene ball/sulphur composite material, belongs to chemical cell technical field, after the ethanol solution of tetraethyl orthosilicate and the ethanol solution of ammonium hydroxide, ammonium hydroxide hybrid reaction, obtains silica nanosphere；Silica nanosphere and cetyl trimethylammonium bromide are scattered in deionized water, add graphene oxide water solution, it is centrifuged after being stirred to react, solid phase washing, drying is taken to be placed in vacuum tube furnace after progress high temperature reduction, it adds HF aqueous solutions and carries out corrosion reaction, obtain hollow graphite alkene ball；Hollow graphite alkene ball and sulphur are finally mixed into progress heat fusing and wave reaction of Salmon-Saxl, obtains hollow graphite alkene/sulphur composite material.Production cost of the present invention is relatively low, and manufactured product advantageously forms conductive network, improves electric conductivity.
Description
Technical field
The invention belongs to chemical cell technical fields, and in particular to can be used as a kind of hollow graphite alkene of lithium sulphur positive electrode
The preparation method of ball/sulphur composite material.
Background technology
The energy is one of the fundamental for maintaining social development.Before the mankind carry out the industrial revolution, the demand of the energy is simultaneously
It is non-so urgent.And after the industrial revolution, for more serious required by the energy.Nowadays, with human society and productivity
Development, energy problem has become a global matter of utmost importance, while also having caused the wide of national governments and scientific research personnel
General concern.Energy problem is coped with, solution route is broadly divided into three classes at present, and one is to develop and use the new available energy,
Such as solar energy, wind energy, geothermal energy.Secondly being used to reduce the energy, non-renewable energy resources are saved.Its three are the existing energy of raising
Source utilization ratio reduces energy loss.
The ratio cycle size of lithium-sulfur cell and the influence factor of service life are mainly anode composite material.Therefore, it finds
And develop the problem of new lithium sulfur battery anode material has been urgent need to resolve[5].Elemental sulfur is due to hypotoxicity, low cost and environment
Friendly feature, becomes a kind of very promising positive electrode.However, lithium-sulfur cell, in discharge process, elemental sulfur is gone back
Originally it was S-2During have multiple intermediate states and generate, wherein Li2Sn (4≤n≤8) is soluble in organic electrolyte, from positive to
Cathode is spread, and with the progress of electric discharge, finally generates Li in cathode2S is deposited, and Li2S does not dissolve in organic electrolyte, causes
The problems such as lithium-sulfur cell cyclicity is poor, coulombic efficiency is low, self-discharge rate is high, the paces for having delayed it practical.
By with common graphene sulphur composite material comparison, graphene in hollow graphite alkene ball/sulphur composite material it
Between interconnect, advantageously form conductive network, improve electric conductivity, and play the role of physics constraint polysulfide, there is height
Capacity, it is forthright good again and the advantages of have extended cycle life, for lithium-sulfur cell theoretical research and further development offer reference, simultaneously
The application for being graphene in lithium-sulfur cell provides technical support.
Invention content
In order to inhibit the dissolving of polysulfide, the cycle performance of battery is improved, it is an object of the invention to propose that one kind can
The preparation method that hollow graphite alkene ball/sulphur as lithium sulfur battery anode material is made.
The present invention includes the following steps：
1）The ethanol solution of first tetraethyl orthosilicate is mixed with the ethanol solution of ammonium hydroxide and is stirred to react, reaction knot
Ammonium hydroxide is added after beam, then adds the ethanol solution of the second tetraethyl orthosilicate after reacting the reaction was continued terminates to reaction, through from
The heart takes solid phase to wash, and obtains silica nanosphere；
2）Prepare hollow graphite alkene ball：Under ultrasound condition, by silica nanosphere and cetyl trimethylammonium bromide
（CTAB）It is scattered in deionized water, obtains finely dispersed mixed system；Graphene oxide water is added into mixed system again
Solution is reacted under stirring condition, is centrifuged after reaction, and solid phase washing, dry be placed in vacuum tube furnace is taken to carry out
Then high temperature reduction adds HF aqueous solutions and carries out corrosion reaction, centrifuges after reaction, solid phase washing, drying are taken, in acquirement
Empty graphene ball；
3）Prepare hollow graphite alkene/sulphur composite material：Hollow graphite alkene ball and sulphur are mixed into progress heat fusing and wave reaction of Salmon-Saxl,
Obtain hollow graphite alkene/sulphur composite material.
The method comprises the steps of firstly, preparing the silica nanospheres of diameter 300nm or so, and positively charged CTAB modifications are added,
30min is stirred in deionized water, then be added graphene oxide graphene solution, due to surface of graphene oxide contain it is abundant
Electronegative functional group（Hydroxyl, carboxyl）, it is easy that electrostatic interaction occurs with positively charged CTAB, is coated on silica nanosphere
Electric conductivity is improved in surface in tube furnace high temperature redox graphene after centrifugal drying, finally uses hydrofluoric acid erosion removal two
Silica, washed, drying just can obtain very fluffy black hollow graphene ball powder.Finally, using heat melting method
Elemental sulfur and hollow graphite alkene ball powder are obtained into composite material.
The advantages of present invention process is：Use the graphene of commercialized graphene for raw material, production cost is relatively low,
And interconnected between the graphene in hollow graphite alkene ball/sulphur composite material, conductive network is advantageously formed, is carried
High conductivity.Meanwhile three-dimensional hollow graphite alkene ball has larger specific surface, Volumetric expansion can be prevented, in physics
The dissolving for inhibiting polysulfide in constraint, has high power capacity, again forthright the advantages of getting well and having extended cycle life.
Further, step 1 of the present invention）In, the mixed volume ratio of tetraethyl orthosilicate and ammonium hydroxide is 0.36: 1.This
Ammonia volume under ratio is conducive to tetraethyl orthosilicate complete hydrolysis into silica, and will not cross deep-etching because of alkalinity again
Silica.
In addition, the step 1）In, the ethanol solution of first tetraethyl orthosilicate is 1: 27.5 just by volume ratio
Tetraethyl orthosilicate and absolute ethyl alcohol mixing composition；Ammonium hydroxide and anhydrous second of the ethanol solution of the ammonium hydroxide by volume ratio for 1: 4.4
Alcohol mixing composition；Tetraethyl orthosilicate and anhydrous second of the ethanol solution of second tetraethyl orthosilicate by volume ratio for 1: 44
Alcohol mixing composition.The lower silica pattern synthesized of proportioning is uniform herein, and diameter is 300~400nm.
The step 1）In, the rotating speed of the centrifugation is 7000r/min, and rotating speed is 6000r/min when washing.Under the conditions of this
It can be made that pattern is uniform, the silica nanosphere of diameter 300nm or so can when centrifugal rotational speed is more than 6000 r/min
Product to be centrifuged completely.
Step 2）In, the mass ratio that feeds intake of the silica nanosphere and cetyl trimethylammonium bromide is1.25~ 1.5。Silica surface under this ratio is modified upper cetyl trimethylammonium bromide, is conducive to pass behind electrostatic work
With coated graphite alkene.
Step 2）In, a concentration of 4mg/mL of graphene oxide in the graphene oxide water solution, graphene oxide and
The mass ratio of silica nanosphere is 1: 1.3~2.The graphene oxide being added under this ratio can coat titanium dioxide completely just
It is preferable to corrode the hollow ball pattern formed after silica for silicon.
Step 2）In, the condition of the high temperature reduction is：It, will with the heating rate of 5 DEG C/min using argon gas as protection gas
Environment temperature is warming up to 1000 DEG C, and constant temperature 2h is reacted.Graphene oxide can be reduced to graphene under the conditions of this, improved
Electric conductivity.
Step 2）The mass concentration of HF aqueous solutions used is 5%.If the excessive concentration of HF, volatility is stronger, is easy to people
Respiratory tract causes to damage.
Step 3）In, the mass ratio of the hollow plumbago alkene ball and sulphur mixing is 1: 4.The carrying capacity of sulphur after the mixing of this ratio
80% or so, carrying capacity is higher.
Step 3）It carries out heat fusing and waves the temperature of sulphur to be 155 DEG C, time 20h.When temperature reaches 155 DEG C, sulphur has
Stronger mobility enters the inside of hollow graphite alkene ball under capillary action.
Description of the drawings
Fig. 1 is the transmission electron microscope picture of the hollow graphite alkene ball prepared using the present invention.
Fig. 2 is the transmission electron microscope picture of the hollow graphite alkene ball/sulphur composite material prepared using the present invention.
Fig. 3 is the X-ray diffractogram of the hollow graphite alkene ball/sulphur composite material prepared using the present invention.
Fig. 4 is that the hollow graphite alkene ball/sulphur composite material prepared using the present invention is filled as lithium sulfur battery anode material
Discharge cycle performance figure.
Specific implementation mode
One, preparation process is described in detail to the present invention with reference to embodiments.
Embodiment 1
1）Prepare silica nanosphere：By 1.6mL tetraethyl orthosilicates（TEOS）It is dissolved in 44mL absolute ethyl alcohols and is used as A
Liquid.10mL ammonium hydroxide is dissolved in 44mL absolute ethyl alcohols and is used as B liquid.By 2mL tetraethyl orthosilicates（TEOS）It is dissolved in the anhydrous second of 88mL
C liquid is used as in alcohol.
A liquid and B liquid are added with stirring is started simultaneously in churned mechanically three-necked flask, rotating speed is 350r/min left
After reacting 30min 8mL ammonium hydroxide is added from three-necked flask side port, then after reacting 5~10min, C is added into system in the right side
Liquid, the reaction was continued 2h.
Centrifuging and taking solid phase is washed with deionized water after reaction, obtains silica nanosphere 0.3g.
2）Prepare hollow graphite alkene ball：The silica nanosphere that 0.2g is prepared will be taken to pour into 50mL deionized waters to surpass
Sound disperses, then is transferred to beaker, and 250mg cetyl trimethylammonium bromides are then added（CTAB）, stir 10min.Wait for it
After being uniformly dispersed, a concentration of 4mg/mL graphene oxide water solutions of 25mL are added into system, are reacted under agitation
30min.It centrifuges after reaction, takes solid phase washing, drying, then product is put into vacuum tube furnace, using argon gas as protection
Gas, 5 DEG C/min of heating rate are warming up to 1000 DEG C, carry out high temperature reduction and react 2h.It is 5% that 50mL mass concentrations, which are then added,
HF aqueous solutions, stirring carry out corrosion reaction 30min, are then centrifuged, and take solid phase washing, dry, acquirement hollow graphite alkene ball
100mg。
3）Prepare hollow graphite alkene/sulphur composite material：The ratio of hollow graphite alkene ball and sulphur in mass ratio 1: 4 is mixed,
Be then placed in reaction kettle, environment temperature be 155 DEG C condition carry out heat fusing wave reaction of Salmon-Saxl 20h, after obtain it is hollow
Graphene/sulphur composite material.
Embodiment 2
1）Prepare silica nanosphere：By 3.2mL tetraethyl orthosilicates（TEOS）It is dissolved in 88mL absolute ethyl alcohols and is used as A
Liquid.20mL ammonium hydroxide is dissolved in 88mL absolute ethyl alcohols and is used as B liquid.By 4mL tetraethyl orthosilicates（TEOS）It is dissolved in the anhydrous second of 176mL
C liquid is used as in alcohol.
A liquid and B liquid are added with stirring is started simultaneously in churned mechanically three-necked flask, rotating speed is 350r/min left
After reacting 30min 8mL ammonium hydroxide is added from three-necked flask side port, then after reacting 5~10min, C is added into system in the right side
Liquid, the reaction was continued 2h.
Centrifuging and taking solid phase is washed with deionized water after reaction, obtains silica nanosphere 0.6g.
2）Prepare hollow graphite alkene ball：The silica nanosphere that 0.4g is prepared will be taken to pour into 100mL deionized waters
Ultrasonic disperse, then it is transferred to beaker, 500mg cetyl trimethylammonium bromides are then added（CTAB）, stir 10min.It waits for
After it is uniformly dispersed, a concentration of 4mg/mL graphene oxide water solutions of 50mL are added into system, carry out under agitation anti-
Answer 30min.It centrifuges after reaction, takes solid phase washing, drying, then product is put into vacuum tube furnace, using argon gas as guarantor
Gas is protected, 5 DEG C/min of heating rate is warming up to 1000 DEG C, carries out high temperature reduction and reacts 2h.It is 5% that 100mL mass concentrations, which are then added,
HF aqueous solutions, stirring carries out corrosion reaction 30min, then centrifuged, and takes solid phase washing, dry, obtains hollow graphite alkene
Ball 200mg.
3）Prepare hollow graphite alkene/sulphur composite material：By hollow graphite alkene ball and sulphur in mass ratio 1：4 ratio mixing,
Be then placed in reaction kettle, environment temperature be 155 DEG C condition carry out heat fusing wave reaction of Salmon-Saxl 20h, after obtain it is hollow
Graphene/sulphur composite material.
Embodiment 3
1）Prepare silica nanosphere：By 4.8mL tetraethyl orthosilicates（TEOS）It is dissolved in conduct in 132mL absolute ethyl alcohols
A liquid.30mL ammonium hydroxide is dissolved in 132mL absolute ethyl alcohols and is used as B liquid.By 6mL tetraethyl orthosilicates（TEOS）It is anhydrous to be dissolved in 264mL
C liquid is used as in ethyl alcohol.
A liquid and B liquid are added with stirring is started simultaneously in churned mechanically three-necked flask, rotating speed is 350r/min left
After reacting 30min 8mL ammonium hydroxide is added from three-necked flask side port, then after reacting 5~10min, C is added into system in the right side
Liquid, the reaction was continued 2h.
Centrifuging and taking solid phase is washed with deionized water after reaction, obtains silica nanosphere 0.9g.
2）Prepare hollow graphite alkene ball：The silica nanosphere that 0.5g is prepared will be taken to pour into 150mL deionized waters
Ultrasonic disperse, then it is transferred to beaker, 750mg cetyl trimethylammonium bromides are then added（CTAB）, stir 10min.It waits for
After it is uniformly dispersed, a concentration of 4mg/mL graphene oxide water solutions of 75mL are added into system, carry out under agitation anti-
Answer 30min.It centrifuges after reaction, takes solid phase washing, drying, then product is put into vacuum tube furnace, using argon gas as guarantor
Gas is protected, 5 DEG C/min of heating rate is warming up to 1000 DEG C, carries out high temperature reduction and reacts 2h.It is 5% that 150mL mass concentrations, which are then added,
HF aqueous solutions, stirring carries out corrosion reaction 30min, then centrifuged, and takes solid phase washing, dry, obtains hollow graphite alkene
Ball 300mg.
3）Prepare hollow graphite alkene/sulphur composite material：By hollow graphite alkene ball and sulphur in mass ratio 1：4 ratio mixing,
Be then placed in reaction kettle, environment temperature be 155 DEG C condition carry out heat fusing wave reaction of Salmon-Saxl 20h, after obtain it is hollow
Graphene/sulphur composite material.
Two, product is verified：
As shown in Figure 1, for the transmission electron microscope picture of the hollow graphite alkene ball prepared using the method for the present invention.As it can be seen that prepare
Hollow graphite alkene ball has hollow spheres structure, a diameter of 300 ~ 400nm.It is observed that hollow ball surface there are many curling and
Pleated structure, this is the typical pattern of graphene.
As shown in Fig. 2, for the transmission electron microscope picture of the hollow graphite alkene ball/sulphur composite material prepared using the method for the present invention.
It can be seen from the figure that black portions are elemental sulfurs, because it has been embedded in graphene ball, protected by graphene ball
Shield acts on, and the time is difficult volatilization.It is therefore intended that hollow graphite alkene ball can play good object as the carrier of elemental sulfur
Constraint effect is managed, inhibits the dissolving of polysulfide, improves the cyclical stability and coulombic efficiency of battery.
Fig. 3 is the X-ray powder diffraction figure of the hollow graphite alkene ball/sulphur composite material prepared using the method for the present invention.From
It can be seen from the figure that, elemental sulfur belong to monoclinic crystal S8, and the XRD diffraction maximums for passing through the hollow graphite alkene ball of high temperature reduction are
25.8 °, reproducibility is higher, is conducive to improve electric conductivity, and peak is wider, is shown to be nano material.When hollow graphene ball and list
After matter sulphur, elemental sulfur therein is still monoclinic crystal S8, chemical property stabilization.
Fig. 4 is the property that the hollow graphite alkene ball/sulphur composite positive pole prepared using the present invention recycles 95 circles at 0.5C
It can figure.It can be seen from the figure that it is 1227mAh/g to put a specific capacity for the first time, preceding 20 circle capacity attenuation is larger, mainly due to one
Part elemental sulfur is distributed in the surface of hollow graphite alkene ball, carries out forming polysulfide with charge and discharge, is gradually dissolved in electricity
Capacitance loss is caused in solution liquid.After 95 circle of cycle, specific capacity is still 782 mAh/g, and specific capacity conservation rate is 63.73%.
Claims (9)
1. a kind of preparation method of hollow graphite alkene ball/sulphur composite material, it is characterised in that include the following steps：
1）The ethanol solution of first tetraethyl orthosilicate is mixed with the ethanol solution of ammonium hydroxide and is stirred to react, after reaction
Ammonium hydroxide is added, then adds the ethanol solution of the second tetraethyl orthosilicate after reacting the reaction was continued terminates to reaction, through centrifuging and taking
Solid phase is washed, and silica nanosphere is obtained；
2）Prepare hollow graphite alkene ball：Under ultrasound condition, silica nanosphere and cetyl trimethylammonium bromide are disperseed
In deionized water, finely dispersed mixed system, the silica nanosphere and cetyl trimethylammonium bromide are obtained
Feed intake mass ratio be 1: 1.25~1.5；Graphene oxide water solution is added into mixed system again, is carried out under stirring condition anti-
It answers, centrifuges after reaction, take solid phase washing, dry be placed in vacuum tube furnace to carry out high temperature reduction, then add HF
Aqueous solution carries out corrosion reaction, centrifuges after reaction, takes solid phase washing, dry, acquirement hollow graphite alkene ball；
3）Prepare hollow graphite alkene/sulphur composite material：Hollow graphite alkene ball and sulphur are mixed into progress heat fusing and wave reaction of Salmon-Saxl, is obtained
Hollow graphite alkene/sulphur composite material.
2. preparation method according to claim 1, it is characterised in that the step 1）In, tetraethyl orthosilicate and ammonium hydroxide
Mixed volume ratio is 0.36: 1.
3. preparation method according to claim 1 or 2, it is characterised in that the step 1）In, the first positive silicic acid four
Tetraethyl orthosilicate and the absolute ethyl alcohol mixing that the ethanol solution of ethyl ester is 1: 27.5 by volume ratio form；The ethyl alcohol of the ammonium hydroxide
Ammonium hydroxide and the absolute ethyl alcohol mixing that solution is 1: 4.4 by volume ratio form；The ethanol solution of second tetraethyl orthosilicate by
Tetraethyl orthosilicate and absolute ethyl alcohol the mixing composition that volume ratio is 1: 44.
4. preparation method according to claim 1, it is characterised in that the step 1）In, the rotating speed of the centrifugation is
7000r/min, rotating speed is 6000r/min when washing.
5. preparation method according to claim 1, it is characterised in that step 2）In, oxygen in the graphene oxide water solution
The mass ratio of a concentration of 4mg/mL of graphite alkene, graphene oxide and silica nanosphere is 1: 1.3~2.
6. preparation method according to claim 1, it is characterised in that step 2）In, the condition of the high temperature reduction is：With
Environment temperature is warming up to 1000 DEG C, constant temperature 2h is reacted by argon gas as protection gas with the heating rate of 5 DEG C/min.
7. preparation method according to claim 1, it is characterised in that step 2）The mass concentration of HF aqueous solutions used is 5%.
8. preparation method according to claim 1, it is characterised in that step 3）In, it is described sky graphene ball and sulphur mixing
Mass ratio is 1: 4.
9. preparation method according to claim 1, it is characterised in that step 3）The middle temperature condition for carrying out heat fusing and waving sulphur
It is 155 DEG C, reaction time 20h.
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| CN101867038A (en) * | 2010-06-08 | 2010-10-20 | 南开大学 | Method for preparing anode composite material for lithium sulfur secondary batteries |
| CN102969487A (en) * | 2012-11-23 | 2013-03-13 | 南开大学 | Carbon-sulfur composite material used for positive pole of lithium-sulfur battery and preparation method of material |
| CN104882594A (en) * | 2015-04-16 | 2015-09-02 | 中国人民解放军国防科学技术大学 | Three-dimensional graphene-hollow carbon sphere nano composite and preparation method thereof |
| CN105013439A (en) * | 2015-06-26 | 2015-11-04 | 同济大学 | Preparation method of nitrogen and sulfur functionalized carbon foam magnetic microspheres |
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