CN106865494A - A kind of preparation method of hollow nano silicon spheres/graphene composite negative pole - Google Patents
A kind of preparation method of hollow nano silicon spheres/graphene composite negative pole Download PDFInfo
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Abstract
The invention belongs to technical field of inorganic material, more particularly, to a kind of preparation method of lithium ion battery negative material, and in particular to a kind of preparation method of hollow nano silicon spheres/graphene composite negative pole.The present invention prepares the hollow nanometer titanium dioxide silicon ball of small size using Stober method combinations soft template method first, under the auxiliary of surfactant, it is compound with graphene oxide, through the method for step heat treatment (including silica sintering, the reduction of graphene oxide and magnesiothermic reduction of silica), hollow nano silicon spheres/the graphene composite material of small size is prepared, silicon/graphene composite material is prepared for lithium ion battery negative.
Description
Technical field
The invention belongs to technical field of inorganic material, more particularly, to a kind of preparation side of lithium ion battery negative material
A kind of method, and in particular to preparation method of hollow nano silicon spheres/graphene composite negative pole.
Background technology
Lithium ion battery is due to being most to receive at present the advantages of its specific capacity is big, operating voltage is high, security is good, pollution is small
The energy storing device of concern, is mainly used in the fields such as smart mobile phone, panel computer and electric automobile.With smart mobile phone
Function is more and more, and screen is increasing, and power consumption is also increasing.At present, the lithium ion battery that smart mobile phone is used is only
Can maintain 1-2 days, the need for people far can not being met.The performance of electrode material is to determine the pass of lithium ion battery energy density
Key factor.Current nearly all commercialized lithium ion battery is all to use graphite cathode material, but the theoretical storage lithium of graphite holds
Amount only has 372mAhg-1, this is also that current lithium ion battery energy density is difficult to one of principal element for improving.Silicon has theory
On maximum specific capacity (4200mAh/g), and wide material sources substitute as potential negative material.But in charge/discharge
Cheng Zhong, the volume of silicon can occur great variety, cause electrode efflorescence, peel off and lose electrical contact with metal collector, and battery holds
Amount sharp-decay.This is the major obstacle for hindering silicon to be used for lithium ion battery.
In order to develop the silicon substrate lithium ion battery of high-capacity and long-life, it is necessary to design the silicon materials of new structure to accommodate silicon
Volume Changes without damaging the structure of electrode, and protect silicon to be difficult to be come off from metal collector surface during charge/discharge.
Report has the silicon substrate lithium ion battery of various structures, such as hollow-core construction, core shell structure, silicon/carbon, silicon/metal composite structure at present
Deng.Recently, Graphene due to its unique two-dimensional structure, high surface area, excellent chemical stability, remarkable electricity and
Thermal property and mechanical flexibility, it is considered to be build the ideal material of Graphene-silicon nanometer combined electrode.Graphene and silicon
On the one hand Material cladding can accommodate the Volume Changes of silicon, improve the stability of silicon electrode material, and another aspect Graphene can be with
The conductance of electrode material is significantly improved, improves the charge-discharge performance of electrode material.In current document it has been reported that numerous Graphenes-
Silicon composite cathode material.It will be appreciated, however, that the silicon that most of Graphene-silicon composite is used is the pure silicon of commercialization
Particle or the silicon nanoparticle prepared using vapour deposition process.Certainly, these silicon sources can be significantly increased composite
Preparation cost.In addition, although silicon nanoparticle can to a certain extent reduce the volumetric expansion of silicon, circulation repeatedly is still suffered from
The problem of material efflorescence.High power capacity, the Stability Analysis of Structures of good cycle are prepared by microstructure design and lower-cost is received
Rice silicon/graphene composite material is the effective way for improving performance of lithium ion battery and reduces cost.
The appearance of magnesiothermic reduction technology in 2007 greatly reduces the reduction temperature of silica, while can also prepare receiving
The silicon materials of meter ruler cun, have therefore suffered from extensive concern.In the structure design of nano silicon material, patent
201510011852.5 disclose a kind of method that magnesiothermic reduction prepares nano silicon material, raw materials used SiO2It is that length is 300
~800nm, width is the rod-like nano material of 20~40nm, and patent 201310059792.5 discloses a kind of magnesiothermic reduction and prepares
Order mesoporous silicon nano material with MCM-41 molecular sieve structures, raw materials used SiO2It is MCM-41 mesopore molecular sieves.Compare
These silicon materials, the hollow nano silicon spheres of small size have special advantage.On the one hand, using the teaching of the invention it is possible to provide specific surface area higher, separately
Outer one side, the hollow nano structure of itself can effectively alleviate nano-silicon Volume Changes in itself, when further with electric conductivity
Excellent Graphene compound tense, can effectively improve lithium storage content, stable circulation performance, have preferably application in lithium ion battery
Prospect.But the preparation of the hollow nano silicon spheres/graphene composite material of current small size is seldom reported.
Meanwhile, in preparing the document and patent of nano-silicon/graphene composite material by magnesiothermic reduction at present, the side of use
Method is mostly repeatedly heat treatment, is first thermally treated resulting in nano silicon, is thermally treated resulting in again after being combined with graphene oxide and received
Rice silica/graphene composite material, then obtain band nano-silicon/graphene composite material, this preparation side by magnesiothermic reduction
Method can consume mass energy, greatly increase the preparation cost of material.
The content of the invention
The purpose of the present invention is exactly that providing one kind can effectively improve lithium for the defect that overcomes above-mentioned prior art to exist
The preparation method of the specific capacity of ion battery and the hollow nano silicon spheres/graphene composite negative pole of cycle performance.
The present invention to achieve the above object and the technical scheme taken is：
A kind of preparation method of hollow nano silicon spheres/graphene composite negative pole of the present invention, comprises the following steps：
The first step, Stober method combinations soft template method prepares the hollow nanometer titanium dioxide silicon ball of small size：
(1) take polyvinylpyrrolidone stirring and dissolving and the solution that molar concentration is 0.01~1mmol/L is made in water, drip
Plus after the ammoniacal liquor that molar concentration is 0.001~1mol/L becomes clarification to above-mentioned solution, to addition cetyl three in settled solution
Methyl bromide ammonium to the molar concentration of cetyl trimethylammonium bromide is 0.001~0.1mol/L, is stirred to clarify；
(2) take during tetraethyl orthosilicate is added to ethanol and be made into the solution that molar concentration is 0.01~1mol/L, wherein positive silicon
Acetoacetic ester is 1 with the mol ratio of ammoniacal liquor：0.01~10, take tetraethyl orthosilicate be added in ethanol be made into molar concentration for 0.01~
The solution of 1mol/L, with vigorous stirring, adds in the solution of step (1), is stirred for 3~10h, is fitted into reactor, oil bath
Lower stirring reaction；
(3) after reaction terminates, directly freezed dried process obtains silica precursor powder, and 5h is heat-treated at 550 DEG C
Obtain silica；
Second step, is 1 according to the mass ratio of cetyl trimethylammonium bromide and silica:0.01~10 ratio takes
Cetyl trimethylammonium bromide, the mass ratio according still further to silica and graphene oxide is 1:0.1~10 ratio takes two
0.01~5mg/mL graphene oxide solutions that silica and concentration are, ultrasonic disperse, freeze-drying obtains small size hollow two
Siliconoxide precursor/graphene oxide composite material；
3rd step, is 1 according to mass ratio:1~3 ratio takes the small size hollow silica presoma/oxygen of second step
Graphite alkene composite and magnesium powder, after being well mixed, are obtained the hollow nanometer of small size after being heat-treated in an inert atmosphere
Silicon ball/graphene composite material；
4th step, conventionally removes magnesia or excessive magnesium powder, hydrofluoric acid removal unreacted using chlorohydric acid pickling
Silica, be centrifuged-wash and to obtain bottom precipitation, it is multiple to obtain final product i.e. dimension hollow nano silicon spheres/Graphene after drying
Condensation material.
Preferably, 12~48h of stirring reaction at 110~160 DEG C of oil bath in first step step (2) of the present invention.
Preferably, heat treatment condition is in the 3rd step of the invention, in an inert atmosphere, 1~10 DEG C/min of heating rate,
Temperature is 650~800 DEG C of 1~5h of heat treatment.
The present invention prepares the hollow nanometer titanium dioxide silicon ball of small size using Stober method combinations soft template method first, on surface
It is compound with graphene oxide under the auxiliary of activating agent, through step heat treatment (including silica sintering, graphene oxide also
The magnesiothermic reduction of former and silica) method, prepare the hollow nano silicon spheres/graphene composite material of small size, prepare silicon/stone
Black alkene composite is used for lithium ion battery negative.
Compared with prior art, the present invention has following beneficial effect：
1st, prepared small size hollow nanometer titanium dioxide silicon ball is that the bead heap of hollow 5~30nm of size is constituted
The microballoon of 100~300nm, with the hollow nano silicon spheres that this hollow nanometer titanium dioxide silicon ball is prepared as raw material, can preferably delay
The volumetric expansion of silicon is solved, preferable structural stability can and cycle performance can be simultaneously kept when lithium storage content higher is obtained.
2nd, step heat treatment completes the reduction of graphene oxide and the magnesiothermic reduction of silica simultaneously, greatly reduces energy
Amount is wasted.
3rd, product of the present invention is the hollow nano silicon spheres/graphene composite material of small size as lithium ion battery negative material
When using, under the current density of 100mA/g, lithium storage content can reach 500~2000mAh/g, and after 50 circulations, capacity is protected
Holdup is more than 80%.
4th, raw material is easy to get, with low cost, and method is simple, and chemical property preferably, is expected to large-scale promotion.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of prepared nanometer titanium dioxide silicon ball in embodiment 1；
Fig. 2 is the transmission electron microscope photo of prepared nanometer titanium dioxide silicon ball in embodiment 1；
Fig. 3 is the X ray diffracting spectrum of the magnesiothermic reduction product of prepared nanometer titanium dioxide silicon ball in embodiment 1；
Fig. 4 is the stereoscan photograph of prepared hollow nano silicon spheres/graphene composite material in embodiment 1；
Fig. 5 is the cycle performance of prepared hollow nano silicon spheres/graphene composite material in embodiment 1；
Fig. 6 be embodiment 1 in prepared hollow nano silicon spheres/graphene composite material in 100mAg-1Current density under
Charging and discharging curve.
Specific embodiment
Embodiments of the invention are elaborated below, the present embodiment is implemented under the premise of technical solution of the present invention,
Detailed implementation method and specific operation process is given, but protection scope of the present invention is not limited to following embodiments.
Embodiment 1
A kind of preparation method of hollow nano silicon spheres/graphene composite material, specifically includes following steps：
1st, 0.05g polyvinylpyrrolidones (K=28-32) and 0.5ml1% ammoniacal liquor are taken, stirring and dissolving is in 15mL deionizations
In water；
2nd, after solution clarification, 0.1g cetyl trimethylammonium bromides are taken and adds above-mentioned solution, stirring, 45 degrees Centigrades
To clarification；
3rd, it is stirred vigorously down, in dissolved with the 5mL ethanol solutions of the tetraethyl orthosilicate of 0.5mL, once adding above-mentioned solution,
It is stirred for 3h, 130 DEG C of stirring reaction 24h of oil bath；
4th, directly freezed dried process, obtains silica precursor powder；
5th, the silica precursor powder of above-mentioned steps 4 is heat-treated 5h in 550 DEG C of air；
6th, 0.1g cetyl trimethylammonium bromides are taken and adds stirring and dissolving in 30mL water, take 0.15g silica ultrasound
Dispersion, plus graphene oxide (4.2mg/ml) the stirring 10min after 9mL ultrasonic disperses, ultrasonic 1h, freeze-drying process are obtained
Small size hollow silica presoma/graphene oxide composite material；
7th, the small size hollow silica presoma of above-mentioned steps 6/graphene oxide composite material and magnesium powder (mass ratio are taken
1:2.5) it is well mixed, (heated up) heat treatment 3h 700 DEG C in argon gas with 5 DEG C/min；
8th, heat-treated products are placed in 1M hydrochloric acid, stir 3h, continuation uses 5wt.% hydrofluoric acid, 5min is stirred at room temperature, from
The heart-washing, collection is precipitated and dried, and obtains final product.
Understood with reference to Fig. 1 and Fig. 2, the silica prepared by the present invention is agglomerated into by numerous hollow nano beads
The microballoon of 100 rans, Fig. 3 shows, by magnesiothermic reduction, the feature broad peak of silica disappears, and occurs in that 28 ° of silicon
Characteristic spikes；Nano-silicon is relatively uniformly dispersed throughout graphite during Fig. 4 shows prepared hollow nano silicon spheres/graphene composite material
In alkene surface and hole, it is preferable that Fig. 5 and Fig. 6 shows that hollow nano silicon spheres/graphene composite material prepared by the present invention has
Cyclical stability.
Embodiment 2
A kind of preparation method of hollow nano silicon spheres/graphene composite material, specifically includes following steps
1st, 0.005g polyvinylpyrrolidone K=28-32 are taken) and 0.5ml5% ammoniacal liquor, stirring and dissolving is in 15ml water；
2nd, after solution clarification, 0.1g cetyl trimethylammonium bromides are taken and adds above-mentioned solution, stirring, 30 degrees Centigrades
To clarification；
3rd, it is stirred vigorously down, by dissolved with the 45ml ethanol solutions of the tetraethyl orthosilicate of 0.1ml, is stirred vigorously and adds next time
In above-mentioned solution, 5h, 110 DEG C of stirring 48h of oil bath are stirred for；
4th, freeze-drying process；
5th, the product of above-mentioned steps 4 is heat-treated 5h in 550 DEG C of air；
6th, 0.05g cetyl trimethylammonium bromides are taken and adds stirring and dissolving in 30ml water, take 0.15g silica ultrasound
Dispersion, plus graphene oxide (5.0mg/ml) stirring 10min, ultrasonic 1h, freeze-drying process after 30ml ultrasonic disperses；
7th, the product of above-mentioned steps 6 and magnesium powder (1 are taken:2.5) it is well mixed, (heated up) heat 700 DEG C in argon gas with 10 DEG C/min
Treatment 3h；
8th, heat-treated products are placed in 1M hydrochloric acid, stir 3h, continuation uses 5wt.% hydrofluoric acid, 5min is stirred at room temperature.From
The heart-washing, collection is precipitated and dried, and obtains final product.
Embodiment 3
A kind of preparation method of hollow nano silicon spheres/graphene composite material, specifically includes following steps
1st, 0.5g polyvinylpyrrolidones (K=28-32) and 1ml25% ammoniacal liquor are taken, stirring and dissolving is in 15ml water；
2nd, after solution clarification, 0.5g cetyl trimethylammonium bromides are taken and adds above-mentioned solution, stirring, 45 degrees Centigrades
To clarification；
3rd, it is stirred vigorously down, dissolved with the 10ml ethanol solutions of the tetraethyl orthosilicate of 1ml, will be stirred vigorously add next time
State in solution, be stirred for 10h, 160 DEG C of stirring 24h of oil bath；
4th, freeze-drying process；
5th, the product of above-mentioned steps 4 is heat-treated 5h in 550 DEG C of air；
6th, 0.1g cetyl trimethylammonium bromides are taken and adds stirring and dissolving in 30ml water, take 0.15g silica ultrasound
Dispersion, plus graphene oxide (1mg/ml) stirring 10min, ultrasonic 1h, freeze-drying process after 15ml ultrasonic disperses；
7th, the product of above-mentioned steps 6 and magnesium powder (1 are taken:2.5) it is well mixed, (heated up) heat 800 DEG C in argon gas with 10 DEG C/min
Treatment 3h；
8th, heat-treated products are placed in 1M hydrochloric acid, stir 3h, continuation uses 5wt.% hydrofluoric acid, 5min is stirred at room temperature.From
The heart-washing, collection is precipitated and dried, and obtains final product.
Embodiment 4
A kind of preparation method of hollow nano silicon spheres/graphene composite material, specifically includes following steps
1st, 0.05g polyvinylpyrrolidones (K=28-32) and 0.25ml1% ammoniacal liquor are taken, stirring and dissolving is in 150ml water；
2nd, after solution clarification, 0.005g cetyl trimethylammonium bromides are taken and adds above-mentioned solution, stirred, 45 degrees Celsius add
Heat is extremely clarified；
3rd, it is stirred vigorously down, by dissolved with the 5ml ethanol solutions of the tetraethyl orthosilicate of 1.1ml, is stirred vigorously and adds next time
In above-mentioned solution, 3h, 160 DEG C of stirring 24h of oil bath are stirred for；
4th, freeze-drying process；
5th, the product of above-mentioned steps 4 is heat-treated 5h in 550 DEG C of air；
6th, 0.025g cetyl trimethylammonium bromides are taken and adds stirring and dissolving in 30ml water, taken 0.05g silica and surpass
Sound disperses, plus graphene oxide (5mg/ml) stirring 10min, ultrasonic 1h, freeze-drying process after 100ml ultrasonic disperses；
7th, the product of above-mentioned steps 6 and magnesium powder (1 are taken:1) it is well mixed, (heated up) heat treatment 700 DEG C in argon gas with 3 DEG C/min
3h；
8th, heat-treated products are placed in 1M hydrochloric acid, stir 3h, continuation uses 5wt.% hydrofluoric acid, 5min is stirred at room temperature.From
The heart-washing, collection is precipitated and dried, and obtains final product.
Embodiment 5
A kind of preparation method of hollow nano silicon spheres/graphene composite material, specifically includes following steps
1st, 0.05g polyvinylpyrrolidones (K=28-32) and 0.5ml1% ammoniacal liquor are taken, stirring and dissolving is in 15ml water；
2nd, after solution clarification, 0.1g cetyl trimethylammonium bromides are taken and adds above-mentioned solution, stirring, 45 degrees Centigrades
To clarification；
3rd, it is stirred vigorously down, by dissolved with the 5ml ethanol solutions of the tetraethyl orthosilicate of 0.5ml, is stirred vigorously and adds next time
In above-mentioned solution, 3h, oil bath stirring 24h are stirred for；
4th, freeze-drying process；
5th, the product of above-mentioned steps 4 is heat-treated 5h in 550 DEG C of air；
6th, 0.013g cetyl trimethylammonium bromides are taken and adds stirring and dissolving in 30ml water, taken 0.02g silica and surpass
Sound disperses, plus graphene oxide (0.1mg/ml) stirring 10min, ultrasonic 1h, freeze-drying process after 20ml ultrasonic disperses；
7th, the product of above-mentioned steps 6 and magnesium powder (1 are taken:3) it is well mixed, (heated up) heat treatment 650 DEG C in argon gas with 1 DEG C/min
5h；
8th, heat-treated products are placed in 1M hydrochloric acid, stir 3h, continuation uses 5wt.% hydrofluoric acid, 5min is stirred at room temperature.From
The heart-washing, collection is precipitated and dried, and obtains final product.
Claims (3)
1. a kind of preparation method of hollow nano silicon spheres/graphene composite negative pole, it is characterised in that comprise the following steps：
The first step, Stober method combinations soft template method prepares the hollow nanometer titanium dioxide silicon ball of small size：
(1) take polyvinylpyrrolidone stirring and dissolving and the solution that molar concentration is 0.01~1mmol/L is made in water, dropwise addition rubs
Your concentration be 0.001~1mol/L ammoniacal liquor become clarification to above-mentioned solution after, to adding cetyl trimethyl in settled solution
Ammonium bromide to the molar concentration of cetyl trimethylammonium bromide is 0.001~0.1mol/L, is stirred to clarify；
(2) take during tetraethyl orthosilicate is added to ethanol and be made into the solution that molar concentration is 0.01~1mol/L, wherein positive silicic acid second
Ester is 1 with the mol ratio of ammoniacal liquor：0.01~10, take tetraethyl orthosilicate be added in ethanol be made into molar concentration for 0.01~
The solution of 1mol/L, with vigorous stirring, adds in the solution of step (1), is stirred for 3~10h, is fitted into reactor, oil bath
Lower stirring reaction；
(3) after reaction terminates, directly freezed dried process obtains silica precursor powder, and being heat-treated 5h at 550 DEG C obtains
Silica；
Second step, is 1 according to the mass ratio of cetyl trimethylammonium bromide and silica:0.01~10 ratio takes 16
Alkyl trimethyl ammonium bromide, the mass ratio according still further to silica and graphene oxide is 1:0.1~10 ratio takes titanium dioxide
0.01~5mg/mL graphene oxide solutions that silicon and concentration are, ultrasonic disperse, freeze-drying obtains the hollow titanium dioxide of small size
Silicon precursor/graphene oxide composite material；
3rd step, is 1 according to mass ratio:1~3 ratio takes the small size hollow silica presoma/oxidation stone of second step
Black alkene composite and magnesium powder, be obtained after being well mixed, after being heat-treated in an inert atmosphere small size hollow nano silicon spheres/
Graphene composite material；
4th step, conventionally removes magnesia or excessive magnesium powder, hydrofluoric acid removal unreacted two using chlorohydric acid pickling
Silica, is centrifuged-washes and to obtain bottom precipitation, and final product i.e. dimension hollow nano silicon spheres/Graphene composite wood is obtained after drying
Material.
2. a kind of preparation method of hollow nano silicon spheres/graphene composite negative pole according to claim 1, its feature
It is 12~48h of stirring reaction at 110~160 DEG C of oil bath in the first step step (2).
3. a kind of preparation method of hollow nano silicon spheres/graphene composite negative pole according to claim 1, its feature
Be that heat treatment condition is in the 3rd step, in an inert atmosphere, 1~10 DEG C/min of heating rate, temperature be 650~
800 DEG C of 1~5h of heat treatment.
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| CN111082035A (en) * | 2019-12-20 | 2020-04-28 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of sheet-graphene @ silicon @ amorphous carbon-sandwich structure composite material, and product and application thereof |
| CN111082035B (en) * | 2019-12-20 | 2022-09-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of sheet-graphene @ silicon @ amorphous carbon-sandwich structure composite material, and product and application thereof |
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