CN106025231A - Preparation method of hollow graphene ball/sulfur composite material - Google Patents
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Abstract
The invention discloses a preparation method of a hollow graphene ball/sulfur composite material and belongs to the technical field of chemical batteries. The preparation method comprises the following steps: an ethanol solution of tetraethyl orthosilicate is mixed with and reacts with the ethanol solution of ammonia water and the ammonia water, so as to obtain silica nanospheres; silica nanospheres and cetyltrimethylammonium bromide are dispersed in deionized water; an aqueous solution of graphene oxide is added; a mixture is centrifuged after stirring and reaction; a solid phase is taken to be washed, dried and placed in a vacuum tube furnace for reduction at a high temperature; an HF aqueous solution is added to perform corrosion reaction, so as to obtain the hollow graphene ball; finally, the hollow graphene ball and sulfur are mixed and subjected to the thermal melting and sulfur volatilization reaction so as to obtain the hollow graphene /sulfur composite material. The preparation method provided by the invention is low in production cost; the prepared product is favorable for forming a conductive network and improving the conductivity.
Description
Technical field
The invention belongs to chemical cell technical field, being specifically related to can be as the preparation method of a kind of hollow graphite alkene ball/sulfur composite of lithium sulfur positive electrode.
Background technology
The energy is one of fundamental maintaining social development.Before the mankind carry out the industrial revolution, the demand of the energy is the most urgent.And after the industrial revolution, for the most serious required by the energy.Nowadays, along with human society and the development of the productivity, energy problem has become a global matter of utmost importance, has also caused the extensive concern of national governments and scientific research personnel simultaneously.Reply energy problem, current solution route is broadly divided into three classes, and one is to develop the new available energy, such as solar energy, wind energy, geothermal energy etc..Its two for reduce the energy use, save non-renewable energy resources.Its three, for improving existing efficiency of energy utilization, are reduced energy loss.
The ratio circulation size of lithium-sulfur cell and the influence factor in service life are mainly anode composite material.Therefore, finding and develop new lithium sulfur battery anode material has been the problem needing solution badly[5].Elemental sulfur due to hypotoxicity, low cost and environmentally friendly feature, become the most promising positive electrode of one.But, lithium-sulfur cell is in discharge process, and elemental sulfur is reduced to S-2During have multiple intermediate state generate, wherein Li2Sn (4≤n≤8) is soluble in organic electrolyte, spreads from positive to negative pole, along with the carrying out of electric discharge, finally generates Li at negative pole2S deposits, and Li2S does not dissolves in organic electrolyte, causes the problems such as lithium-sulfur cell cyclicity is poor, coulombic efficiency is low, self-discharge rate is high, has delayed the paces that it is practical.
By contrasting with common Graphene sulfur composite, interconnect between Graphene in hollow graphite alkene ball/sulfur composite, advantageously form conductive network, improve electric conductivity, and play the effect of physics constraint polysulfide, there is high power capacity, the most forthright good and advantage that has extended cycle life, for lithium-sulfur cell theoretical research and further development offer reference, provide technical support for Graphene application in lithium-sulfur cell simultaneously.
Summary of the invention
In order to suppress the dissolving of polysulfide, improve the cycle performance of battery, it is an object of the invention to propose a kind of preparation method can made as the hollow graphite alkene ball of lithium sulfur battery anode material/sulfur.
The present invention comprises the following steps:
1) ethanol solution of the first tetraethyl orthosilicate is mixed with the ethanol solution of ammonia be stirred reaction, reaction adds ammonia after terminating, the ethanol solution continuation reaction adding the second tetraethyl orthosilicate again after reaction terminates to reaction, takes solid phase washing, acquirement silica nanosphere by centrifugation；
2) prepare hollow graphite alkene ball: under ultrasound condition, silica nanosphere and cetyl trimethylammonium bromide (CTAB) are scattered in deionized water, obtain finely dispersed mixed system；Graphene oxide water solution is added again in mixed system, react under stirring condition, reaction is centrifugal after terminating, take solid phase washing, be placed in vacuum tube furnace and carry out high temperature reduction after drying, then add HF aqueous solution and carry out corrosion reaction, reaction is centrifugal after terminating, and takes solid phase washing, is dried, obtains hollow graphite alkene ball；
3) hollow graphite alkene/sulfur composite is prepared: hollow graphite alkene ball and sulfur mixing are carried out heat fusing and waves reaction of Salmon-Saxl, obtain hollow graphite alkene/sulfur composite.
The method comprises the steps of firstly, preparing the silica nanosphere of diameter about 300nm, the CTAB adding positively charged modifies, stir 30min in deionized water, it is subsequently adding graphene oxide graphene solution, owing to surface of graphene oxide contains abundant electronegative functional group (hydroxyl, carboxyl), there is electrostatic interaction in easy and positively charged CTAB, it is coated on silica nanosphere surface, after centrifugal drying in tube furnace high temperature reduction graphene oxide, improve electric conductivity, finally with Fluohydric acid. erosion removal silicon dioxide, scrubbed, it is dried and just can obtain the most fluffy black hollow Graphene ball powder.Finally, use heat melting method that elemental sulfur and hollow graphite alkene ball powder are obtained composite.
The advantage of present invention process is: the Graphene using business-like Graphene is raw material, and production cost is relatively low,
And interconnect between the Graphene in hollow graphite alkene ball/sulfur composite, advantageously form conductive network, improve electric conductivity.Meanwhile, three-dimensional hollow graphite alkene ball has bigger specific surface, is possible to prevent Volumetric expansion, ties up the dissolving of suppression polysulfide in physical beam, has high power capacity, the most forthright advantage got well and have extended cycle life.
Further, in step 1) of the present invention, the mixed volume ratio of tetraethyl orthosilicate and ammonia is 0.36: 1.Ammonia volume under this ratio beneficially tetraethyl orthosilicate complete hydrolysis becomes silicon dioxide, and will not cross deep-etching silicon dioxide because of alkalescence again.
It addition, in described step 1), the ethanol solution of described first tetraethyl orthosilicate is mixed by the tetraethyl orthosilicate that volume ratio is 1: 27.5 and dehydrated alcohol and forms；The ethanol solution of described ammonia is mixed by the ammonia that volume ratio is 1: 4.4 and dehydrated alcohol and forms；The ethanol solution of described second tetraethyl orthosilicate is mixed by the tetraethyl orthosilicate that volume ratio is 1: 44 and dehydrated alcohol and forms.Under this proportioning, the silicon dioxide pattern of synthesis is homogeneous, and diameter is 300～400nm.
In described step 1), described centrifugal rotating speed is 7000r/min, and during washing, rotating speed is 6000r/min.Pattern can be prepared homogeneous under the conditions of this, the silica nanosphere of diameter about 300nm, when centrifugal rotational speed is more than 6000 r/min, completely can be centrifuged by product.
Step 2) in, the mass ratio that feeds intake of described silica nanosphere and cetyl trimethylammonium bromide is1.25 ~ 1.5 。Silica surface under this ratio is modified cetyl trimethylammonium bromide, is conducive to passing behind electrostatic interaction coated graphite alkene.
Step 2) in, in described graphene oxide water solution the concentration of graphene oxide be the mass ratio of 4mg/mL, graphene oxide and silica nanosphere be 1: 1.3～2.The graphene oxide added under this ratio coated silica completely of energy just, the hollow ball pattern formed after corrosion silicon dioxide is preferable.
Step 2) in, the condition of described high temperature reduction is: using argon as protection gas, with the heating rate of 5 DEG C/min, ambient temperature being warmed up to 1000 DEG C, constant temperature 2h reacts.Graphene oxide can be reduced under the conditions of this Graphene, improve electric conductivity.
Step 2) used by the mass concentration of HF aqueous solution be 5%.If the excessive concentration of HF, volatility is relatively strong, easily human respiratory is caused damage.
In step 3), the mass ratio of described hollow plumbago alkene ball and sulfur mixing is 1: 4.After the mixing of this ratio, the carrying capacity of sulfur is about 80%, and carrying capacity is higher.
It is 155 DEG C that step 3) carry out heat fusing to wave the temperature of sulfur, and the time is 20h.When temperature reaches 155 DEG C, sulfur has stronger mobility, enters the inside of hollow graphite alkene ball under capillary action.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of the hollow graphite alkene ball using the present invention to prepare.
Fig. 2 is the transmission electron microscope picture of the hollow graphite alkene ball/sulfur composite using the present invention to prepare.
Fig. 3 is the X-ray diffractogram of the hollow graphite alkene ball/sulfur composite using the present invention to prepare.
Fig. 4 is to use hollow graphite alkene ball/sulfur composite of preparing of the present invention as the charge-discharge performance figure of lithium sulfur battery anode material.
Detailed description of the invention
One, below in conjunction with embodiment, the present invention is described in detail preparation technology.
Embodiment 1
1) silica nanosphere is prepared: be dissolved in 44mL dehydrated alcohol 1.6mL tetraethyl orthosilicate (TEOS) as A liquid.10mL ammonia is dissolved in 44mL dehydrated alcohol as B liquid.2mL tetraethyl orthosilicate (TEOS) is dissolved in 88mL dehydrated alcohol as C liquid.
Adding A liquid and B liquid with starting simultaneously at stirring in churned mechanically there-necked flask, rotating speed is about 350r/min, after question response 30min, adds 8mL ammonia from there-necked flask side port, then after reacting 5～10min, adds C liquid, continue reaction 2h in system.
Reaction terminates rear centrifuging and taking solid phase with deionized water wash, acquirement silica nanosphere 0.3g.
2) hollow graphite alkene ball is prepared: pour ultrasonic disperse in 50mL deionized water into by taking the silica nanosphere that 0.2g prepares, then proceeded to beaker, be subsequently adding 250mg cetyl trimethylammonium bromide (CTAB), stir 10min.After it is uniformly dispersed, adding 25mL concentration in system is 4mg/mL graphene oxide water solution, carries out under agitation reacting 30min.Reaction is centrifugal after terminating, and takes solid phase washing, is dried, then is put into by product in vacuum tube furnace, and using argon as protection gas, 5 DEG C/min of heating rate is warmed up to 1000 DEG C, carries out high temperature reduction reaction 2h.Being subsequently added the HF aqueous solution that 50mL mass concentration is 5%, stirring carries out corrosion reaction 30min, is then centrifuged, and takes solid phase washing, is dried, obtains hollow graphite alkene ball 100mg.
3) hollow graphite alkene/sulfur composite is prepared: the ratio of hollow graphite alkene ball and sulfur in mass ratio 1: 4 mixed, it is then placed in reactor, carry out heat fusing in the condition that ambient temperature is 155 DEG C and wave reaction of Salmon-Saxl 20h, after terminating, obtain hollow graphite alkene/sulfur composite.
Embodiment 2
1) silica nanosphere is prepared: be dissolved in 88mL dehydrated alcohol 3.2mL tetraethyl orthosilicate (TEOS) as A liquid.20mL ammonia is dissolved in 88mL dehydrated alcohol as B liquid.4mL tetraethyl orthosilicate (TEOS) is dissolved in 176mL dehydrated alcohol as C liquid.
Adding A liquid and B liquid with starting simultaneously at stirring in churned mechanically there-necked flask, rotating speed is about 350r/min, after question response 30min, adds 8mL ammonia from there-necked flask side port, then after reacting 5～10min, adds C liquid, continue reaction 2h in system.
Reaction terminates rear centrifuging and taking solid phase with deionized water wash, acquirement silica nanosphere 0.6g.
2) hollow graphite alkene ball is prepared: pour ultrasonic disperse in 100mL deionized water into by taking the silica nanosphere that 0.4g prepares, then proceeded to beaker, be subsequently adding 500mg cetyl trimethylammonium bromide (CTAB), stir 10min.After it is uniformly dispersed, adding 50mL concentration in system is 4mg/mL graphene oxide water solution, carries out under agitation reacting 30min.Reaction is centrifugal after terminating, and takes solid phase washing, is dried, then is put into by product in vacuum tube furnace, and using argon as protection gas, 5 DEG C/min of heating rate is warmed up to 1000 DEG C, carries out high temperature reduction reaction 2h.Being subsequently added the HF aqueous solution that 100mL mass concentration is 5%, stirring carries out corrosion reaction 30min, is then centrifuged, and takes solid phase washing, is dried, obtains hollow graphite alkene ball 200mg.
3) hollow graphite alkene/sulfur composite is prepared: the ratio of hollow graphite alkene ball and sulfur 1:4 in mass ratio mixed, it is then placed in reactor, carry out heat fusing in the condition that ambient temperature is 155 DEG C and wave reaction of Salmon-Saxl 20h, after terminating, obtain hollow graphite alkene/sulfur composite.
Embodiment 3
1) silica nanosphere is prepared: be dissolved in 132mL dehydrated alcohol 4.8mL tetraethyl orthosilicate (TEOS) as A liquid.30mL ammonia is dissolved in 132mL dehydrated alcohol as B liquid.6mL tetraethyl orthosilicate (TEOS) is dissolved in 264mL dehydrated alcohol as C liquid.
Adding A liquid and B liquid with starting simultaneously at stirring in churned mechanically there-necked flask, rotating speed is about 350r/min, after question response 30min, adds 8mL ammonia from there-necked flask side port, then after reacting 5～10min, adds C liquid, continue reaction 2h in system.
Reaction terminates rear centrifuging and taking solid phase with deionized water wash, acquirement silica nanosphere 0.9g.
2) hollow graphite alkene ball is prepared: pour ultrasonic disperse in 150mL deionized water into by taking the silica nanosphere that 0.5g prepares, then proceeded to beaker, be subsequently adding 750mg cetyl trimethylammonium bromide (CTAB), stir 10min.After it is uniformly dispersed, adding 75mL concentration in system is 4mg/mL graphene oxide water solution, carries out under agitation reacting 30min.Reaction is centrifugal after terminating, and takes solid phase washing, is dried, then is put into by product in vacuum tube furnace, and using argon as protection gas, 5 DEG C/min of heating rate is warmed up to 1000 DEG C, carries out high temperature reduction reaction 2h.Being subsequently added the HF aqueous solution that 150mL mass concentration is 5%, stirring carries out corrosion reaction 30min, is then centrifuged, and takes solid phase washing, is dried, obtains hollow graphite alkene ball 300mg.
3) hollow graphite alkene/sulfur composite is prepared: the ratio of hollow graphite alkene ball and sulfur 1:4 in mass ratio mixed, it is then placed in reactor, carry out heat fusing in the condition that ambient temperature is 155 DEG C and wave reaction of Salmon-Saxl 20h, after terminating, obtain hollow graphite alkene/sulfur composite.
Two, product checking:
As it is shown in figure 1, the transmission electron microscope picture of the hollow graphite alkene ball prepared for employing the inventive method.Visible, the hollow graphite alkene ball of preparation has hollow spheres structure, a diameter of 300 ~ 400nm.It is observed that there are many curlings and pleated structure in hollow ball surface, this is the typical pattern of Graphene.
As in figure 2 it is shown, the transmission electron microscope picture of the hollow graphite alkene ball/sulfur composite prepared for employing the inventive method.It can be seen that black part is elemental sulfur, because it embedded in Graphene ball, by the protective effect of Graphene ball, the time is difficult to volatilization.It is therefore intended that hollow graphite alkene ball can play good physics constraint effect, the dissolving of suppression polysulfide as the carrier of elemental sulfur, improve cyclical stability and the coulombic efficiency of battery.
Fig. 3 is the X-ray powder diagram of the hollow graphite alkene ball/sulfur composite using the inventive method to prepare.It can be seen that elemental sulfur belongs to monoclinic crystal S8, and be 25.8 ° through the XRD diffraction maximum of the hollow graphite alkene ball of high temperature reduction, reproducibility is higher, is conducive to improving electric conductivity, and peak is wider, is shown to be nano material.When, after hollow Graphene ball and elemental sulfur, elemental sulfur therein is still monoclinic crystal S8, stable chemical nature.
Fig. 4 is the performance map that the hollow graphite alkene ball/sulfur composite positive pole using the present invention to prepare circulates 95 circles under 0.5C.As can be seen from the figure, putting a specific capacity first is 1227mAh/g, and front 20 circle capacity attenuations are relatively big, are distributed in the surface of hollow graphite alkene ball mainly due to a part of elemental sulfur, along with the carrying out of discharge and recharge forms polysulfide, it is gradually dissolved in electrolyte and causes capacitance loss.After circulation 95 circle, specific capacity is still 782 mAh/g, and specific capacity conservation rate is 63.73%.
Claims (10)
1. the preparation method of hollow graphite alkene ball/sulfur composite, it is characterised in that comprise the following steps:
1) ethanol solution of the first tetraethyl orthosilicate is mixed with the ethanol solution of ammonia be stirred reaction, reaction adds ammonia after terminating, the ethanol solution continuation reaction adding the second tetraethyl orthosilicate again after reaction terminates to reaction, takes solid phase washing, acquirement silica nanosphere by centrifugation；
2) prepare hollow graphite alkene ball: under ultrasound condition, silica nanosphere and cetyl trimethylammonium bromide are scattered in deionized water, obtain finely dispersed mixed system；Graphene oxide water solution is added again in mixed system, react under stirring condition, reaction is centrifugal after terminating, take solid phase washing, be placed in vacuum tube furnace and carry out high temperature reduction after drying, then add HF aqueous solution and carry out corrosion reaction, reaction is centrifugal after terminating, and takes solid phase washing, is dried, obtains hollow graphite alkene ball；
3) hollow graphite alkene/sulfur composite is prepared: hollow graphite alkene ball and sulfur mixing are carried out heat fusing and waves reaction of Salmon-Saxl, obtain hollow graphite alkene/sulfur composite.
Preparation method the most according to claim 1, it is characterised in that in described step 1), the mixed volume ratio of tetraethyl orthosilicate and ammonia is 0.36: 1.
Preparation method the most according to claim 1 and 2, it is characterised in that in described step 1), the ethanol solution of described first tetraethyl orthosilicate is mixed by the tetraethyl orthosilicate that volume ratio is 1: 27.5 and dehydrated alcohol and forms；The ethanol solution of described ammonia is mixed by the ammonia that volume ratio is 1: 4.4 and dehydrated alcohol and forms；The ethanol solution of described second tetraethyl orthosilicate is mixed by the tetraethyl orthosilicate that volume ratio is 1: 44 and dehydrated alcohol and forms.
Preparation method the most according to claim 1, it is characterised in that in described step 1), described centrifugal rotating speed is 7000r/min, and during washing, rotating speed is 6000r/min.
Preparation method the most according to claim 1, it is characterised in that step 2) in, the mass ratio that feeds intake of described silica nanosphere and cetyl trimethylammonium bromide is 1: 1.25～1.5.
Preparation method the most according to claim 1, it is characterised in that step 2) in, in described graphene oxide water solution the concentration of graphene oxide be the mass ratio of 4mg/mL, graphene oxide and silica nanosphere be 1: 1.3～2.
Preparation method the most according to claim 1, it is characterised in that step 2) in, the condition of described high temperature reduction is: using argon as protection gas, with the heating rate of 5 DEG C/min, ambient temperature being warmed up to 1000 DEG C, constant temperature 2h reacts.
Preparation method the most according to claim 1, it is characterised in that step 2) used by the mass concentration of HF aqueous solution be 5%.
Preparation method the most according to claim 1, it is characterised in that in step 3), the mass ratio of described empty Graphene ball and sulfur mixing is 1: 4.
Preparation method the most according to claim 1, it is characterised in that carry out heat fusing in step 3) waving the temperature conditions of sulfur is 155 DEG C, and the response time is 20h.
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| CN106898759A (en) * | 2017-04-25 | 2017-06-27 | 张廷祥 | The preparation method and graphene lithium ion battery group of graphene lithium ion battery cathode pole piece |
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| CN109088055A (en) * | 2017-10-24 | 2018-12-25 | 胡小玲 | Sulphur lithium battery |
| US11611066B2 (en) | 2017-10-30 | 2023-03-21 | Lg Energy Solution, Ltd. | Sulfur-carbon composite and method for preparing same |
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| CN110835423A (en) * | 2019-12-10 | 2020-02-25 | 中国科学院金属研究所 | Graphene-based composite filler and preparation method thereof |
| CN110835423B (en) * | 2019-12-10 | 2021-08-31 | 中国科学院金属研究所 | Graphene-based composite filler and preparation method thereof |
| CN111740093A (en) * | 2020-06-11 | 2020-10-02 | 扬州大学 | Method for preparing reduced graphene/aminated column [5] arene/sulfur serving as lithium-sulfur positive electrode material |
| CN112625370A (en) * | 2020-12-31 | 2021-04-09 | 四川六九一二科技有限公司 | Preparation method of high-strength and light-weight graphene/silicon dioxide fiber composite material |
| CN112625370B (en) * | 2020-12-31 | 2021-09-17 | 四川六九一二通信技术股份有限公司 | Preparation method of high-strength and light-weight graphene/silicon dioxide fiber composite material |
| CN116093292A (en) * | 2023-02-17 | 2023-05-09 | 三一红象电池有限公司 | Method for preparing carbon-coated sodium iron sulfate material, carbon-coated sodium iron sulfate material and battery |
| CN116093292B (en) * | 2023-02-17 | 2024-03-01 | 三一红象电池有限公司 | Method for preparing carbon-coated sodium iron sulfate material, carbon-coated sodium iron sulfate material and battery |
| CN117410479A (en) * | 2023-12-13 | 2024-01-16 | 河南鑫泉能源科技有限公司 | Lithium ion battery composite positive electrode material, preparation method thereof and assembled battery |
| CN117410479B (en) * | 2023-12-13 | 2024-03-01 | 河南鑫泉能源科技有限公司 | Lithium ion battery composite positive electrode material, preparation method thereof and assembled battery |
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