CN105070890A - Titanium oxide-coated porous hollow silicon ball composite electrode material and preparation method therefor - Google Patents
Titanium oxide-coated porous hollow silicon ball composite electrode material and preparation method therefor Download PDFInfo
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Abstract
A titanium oxide-coated porous hollow silicon ball composite electrode material and a preparation method therefor belong to the technical field of lithium ion battery electrode materials and preparation therefor. The internal of the composite electrode material is porous hollow silicon balls with the diameter of 200-500 nm; and the surfaces of the silicon balls are coated with titanium oxide with the thickness of 5-20 nm. The cooperation of the porous hollow silicon balls and titanium oxide enables the composite electrode material to show high specific capacity, high rate performance and high cycle stability. According to the titanium oxide-coated porous hollow silicon ball composite electrode material and the preparation method therefor, low-price silicon dioxide is taken as a silicon source and converted to a silicon material with electrochemical activity through a magnesiothermic reduction method; and the preparation method has the characteristics of simple preparation process, low cost, nontoxic reagent and convenience for large-scale production.
Description
Technical field
The invention belongs to lithium ion battery electrode material and preparing technical field thereof, particularly relate to a kind of titanium-oxide-coated Porous hollow silicon ball combination electrode material and preparation method thereof, this composite material can be used as lithium ion battery negative material.
Background technology
The demand of fast development to height ratio capacity, long circulation life and high security power lithium-ion battery of electric automobile is day by day urgent.Silicon based anode material has attracted the concern of researcher because of its height ratio capacity, high security.But volume change is up to 400% in electrochemistry cyclic process for silicium cathode material, and consequent huge stress easily causes electrode material local and even integrally-built destruction, storage lithium performance is caused to fall sharply.The conductivity that silicon is poor simultaneously also have impact on the high rate performance of material.The method of current solution silicium cathode height cubical expansivity mainly contains and reduces silicon materials size to nanoscale, design and synthesis porous silica material and silicon based composite material etc.
At document (1) ACSNano, in 2014,8:2977-2985, the people such as GoojinJeong utilize business silica flour and TiO
2calcining obtains nucleocapsid structure titanium-oxide-coated silicon nanowires under an argon atmosphere.Titanium oxide clad has good conductivity, but this structure can not overcome the material avalanche problem that silicon causes in charge and discharge process volumetric expansion.Also there are some common problems in nano silica fume simultaneously in actual applications, as very easily reunited and being oxidized, cause its transport and preserve difficulty, preparation process relates to the complex process such as laser splash and high temperature, cause its high cost etc., this all constrains the practical application of nano-silicon.
At document (2) Nature, in 2007,446:172-175, the people such as ZhihaoBao propose the new method adopting magnesiothermic reduction to prepare nano silicon material.The method is using metal magnesium powder as reducing agent, and the silicon dioxide of electrochemicaUy inert, as silicon source, just can be converted into the porous silica material with electro-chemical activity by silicon dioxide at 650 DEG C.The method cost is low, environmental friendliness, is considered to the new method preparing silicium cathode material having very much application prospect.But pure porous silica material still exists nano-silicon, and irreversible capacity is high first, cyclical stability is poor and the doubly problem such as forthright difference.
Summary of the invention
The object of the present invention is to provide a kind of titanium-oxide-coated Porous hollow silicon ball combination electrode material and preparation method thereof, solve pure porous silica material and still there is nano-silicon irreversible capacity is high first, cyclical stability is poor and the doubly problem such as forthright difference.The synergy of Porous hollow silicon ball and titanium oxide two kinds of components makes combination electrode material show height ratio capacity, high rate capability and high cyclical stability.Using the silicon dioxide of cheapness as silicon source, be translated into the silicon materials with electro-chemical activity by magnesium reduction process, have that preparation technology is simple, with low cost and reagent is nontoxic, be convenient to large-scale production.
Titanium-oxide-coated Porous hollow silicon ball combination electrode material inside of the present invention is Porous hollow silicon ball MHSi, and diameter is 200 ~ 500 nanometers; Titanium oxide TiO
xbe coated on silicon ball surface, thickness is 5 ~ 20 nanometers; The chemical composition of this composite material can be described as MHSiTiO
x, wherein in TiOx, the span of x is 1.5 ~ 2.0.
The method preparing titanium-oxide-coated Porous hollow silicon ball combination electrode material of the present invention first prepares Porous hollow silica spheres MHSiO
2recycling magnesiothermic reduction method is translated into the Porous hollow silicon ball MHSi with electro-chemical activity, utilizes the calcining of butyl titanate under the hydrolysis and inert atmosphere on Porous hollow silicon ball MHSi surface to obtain titanium-oxide-coated Porous hollow silicon ball MHSiTiO further
x.The technological process of the inventive method as shown in Figure 1, comprises following concrete technology step:
(1) preparation ethanol and deionized water volume ratio are the mixed solvent of 0.3:1 ~ 0.8:1, according to mass fraction be 28% ammoniacal liquor and deionized water volume ratio be that ammoniacal liquor joins in above-mentioned ethanol/deionized water mixed solvent by the ratio of 3:200 ~ 1:40, softex kw CTAB is dispersed in above-mentioned containing in the ethanol/water solution of ammoniacal liquor according to the ratio that solid-to-liquid ratio is 1:750 ~ 1:250, solution is transferred in there-necked flask, bath temperature is kept to be 30 DEG C ~ 40 DEG C, with the rotating speed stirring reaction 5 ~ 10 minutes of 400 ~ 600 revs/min, the ratio being 3:200 ~ 1:40 in tetraethoxysilane and deionized water volume ratio adds tetraethoxysilane fast in above-mentioned solution, Keep agitation 12 ~ 36 hours, use deionized water and each centrifuge washing of ethanol 3 ~ 5 times afterwards, to remove unreacted tetraethoxysilane impurity, the centrifugal white solid obtained is dispersed in the beaker containing deionized water by solid-to-liquid ratio 1:200 ~ 1:100, ageing reaction 6 ~ 24 hours at 30 ~ 100 DEG C, use deionized water and each centrifuge washing of ethanol 3 ~ 5 times afterwards, to remove the impurity that ageing reaction produces, obtain pure hollow silica ball, according to mass fraction be 38% hydrochloric acid and absolute ethyl alcohol volume ratio be that hydrochloric acid joins in absolute ethyl alcohol by the ratio of 1:10000 ~ 3:10000, then be that 1:200 ~ 1:50 joins in the above-mentioned absolute ethyl alcohol containing hydrochloric acid by the centrifugal solid obtained by solid-to-liquid ratio, bath temperature is kept to be 50 ~ 80 DEG C, with the rotating speed Keep agitation 2 ~ 5 hours of 400 ~ 600 revs/min, use deionized water and each centrifuge washing of ethanol 3 ~ 5 times afterwards, to remove the softex kw CTAB in silicon dioxide, finally under 50 ~ 100 DEG C of conditions, namely vacuumize obtain Porous hollow silicon dioxide MHSiO for 10 ~ 20 hours
2white powder.
(2) white powder that step (1) obtains is mixed according to the ratio that mass ratio is 1:1 ~ 2:1 with magnesium powder, under an argon atmosphere with the ramp of 3 ~ 6 DEG C/min to 650 ~ 800 DEG C of magnesium thermit 5 ~ 8 hours, cool to room temperature with the furnace afterwards; Then the powder after magnesium heat is placed according to the ratio that solid-to-liquid ratio is 1:150 ~ 1:100 the hydrochloric acid that concentration is 1 ~ 2mol/L, soaks 12 ~ 24 hours, centrifugation, absolute ethanol washing 3 ~ 5 times is to remove unreacted hydrochloric acid; Then be placed in the HF solution of mass concentration 5 ~ 10%, soak 0.5 ~ 1.5 hour, centrifugation, absolute ethanol washing 3 ~ 5 times is to remove HF; Finally under 50 ~ 100 DEG C of conditions, namely vacuumize obtain hollow porous silicon MHSi brownish-yellow powder for 10 ~ 20 hours.
(3) according to mass fraction be 28% ammoniacal liquor and absolute ethyl alcohol volume ratio be that ammoniacal liquor joins in absolute ethyl alcohol by the ratio of 3:200 ~ 1:40, brownish-yellow powder step (2) obtained is dispersed in above-mentioned ammoniacal liquor/alcohol mixed solution according to the ratio that solid-to-liquid ratio is 3:5000 ~ 3:2500, ultrasonic 5 ~ 10 minutes; 30 ~ 50 DEG C of water-baths, under the rotating speed of 400 ~ 600 revs/min, in above-mentioned solution, butyl titanate is added fast than for 3:1000 ~ 1:200 according to butyl titanate/ethanol contend, Keep agitation 12 ~ 36 hours, centrifugation, absolute ethanol washing 3 ~ 5 times, to remove unreacted butyl titanate, vacuumize 10 ~ 20 hours under 50 ~ 100 DEG C of conditions; Dried powder is reacted 2 ~ 5 hours to 650 ~ 900 DEG C with the ramp of 3 ~ 6 DEG C/min under an inert atmosphere, cools to room temperature afterwards with the furnace and namely obtain titanium-oxide-coated hollow porous ball MHSiTiO
x.Wherein, described inert atmosphere is the one in argon gas or nitrogen.
Adopt RigakuUItimaIII type x-ray diffractometer (XRD) to MHSi and MHSiTiO
xcharacterize, XRD spectra as shown in Figure 2, MHSi to go out peak position consistent with silicon standard card, MHSiTiO
xin except there is the characteristic diffraction peak of silicon, have also appeared the characteristic diffraction peak of titanium oxide.
Adopt the pattern of ZEISSSupra55 type field emission scanning electron microscope (FESEM) exosyndrome material, MHSiO
2fESEM picture as shown in Figure 3, particle diameter is in 200 ~ 500 nanometers, and as shown in Figure 4, uniform particle diameter, particle diameter is about 500nm to the FESEM picture of MHSi, MHSiTiO
xfESEM picture as shown in Figure 5, particle diameter is more homogeneous.HitachiH-800 type transmission electron microscope (TEM) microstructure to sample is adopted to observe, MHSiO
2tEM picture as shown in Figure 6, the TEM picture of MHSi as shown in Figure 7, MHSiTiO
xtEM picture as shown in Figure 8, clearly can observe the hollow-core construction of material internal from above-mentioned figure.
By MHSiTiO
xmix by the mass ratio of 60:20:20 with commercially available acetylene black conductor and Kynoar PVDF binding agent, be evenly coated in copper foil current collector with the thickness of 30 ~ 70 μm, 80 DEG C of vacuum dryings, carry out roll-in, the electrode slice that diameter is 1cm is obtained, in 120 DEG C of dry 24h of vacuum (<10Pa), using metal lithium sheet as negative pole with sheet-punching machine, adopt Celgard2400 barrier film, the LiPF of 1mol/L
6+ EC+DMC+DEC (EC/DMC/DEC volume ratio 1:1:1) is electrolyte, at German M.Braun company Unlab type dry argon gas glove box (H
2o<1ppm, O
2<1ppm) CR2032 button cell is assembled in.Adopt the blue electric CT2001A type cell tester in Wuhan to carry out electrochemical property test, charging/discharging voltage scope is 0.01 ~ 1.5V (vs.Li
+/ Li), test result as shown in Figure 9, MHSiTiO
xat 200mAg
-1current density under circulation 100 weeks afterwards specific capacity can reach 400mAhg
-1, and coulombic efficiency remains on more than 98% always.
Feature of the present invention and advantage are: MHSiTiO
xexist with monodispersed form, for face contacts between the hollow silicon ball of titanium oxide and inside, make electronics and lithium ion rapidly from surface delivery to silicon ball, can greatly improve the transmission rate of electronics and lithium ion; The space of hollow silicon ball inside can cushion the change in volume of silicon materials in charge and discharge process effectively, ensure that the stability of composite structure; The titanium oxide of material surface can improve conductivity.Therefore this composite material has excellent electrochemical cycle stability as lithium ion battery negative material.In addition; the present invention take hollow silicon dioxide as silicon source; the silicon materials with electro-chemical activity are translated into by magnesiothermic reduction; the size of final composite material can be regulated and controled by the size controlling hollow silicon dioxide simultaneously, have with low cost, technique simple, be convenient to the advantages such as large-scale production.
Accompanying drawing explanation
Fig. 1 is the process flow diagram that the inventive method prepares titanium-oxide-coated Porous hollow silicon ball composite material.
Fig. 2 is MHSi and MHSiTiO prepared by embodiment 1
xxRD spectra.Abscissa is angle 2 θ, and unit is: degree (°); Ordinate is diffracted intensity, and unit is: absolute unit (a.u.).Curve a is the XRD spectra of MHSi, and curve b is MHSiTiO
xxRD spectra.
Fig. 3 is MHSiO prepared by embodiment 1
2fESEM photo.
Fig. 4 is the FESEM photo of MHSi prepared by embodiment 1.
Fig. 5 is MHSiTiO prepared by embodiment 1
xfESEM photo.
Fig. 6 is MHSiO prepared by embodiment 1
2tEM photo.
Fig. 7 is the TEM photo of MHSi prepared by embodiment 1.
Fig. 8 is MHSiTiO prepared by embodiment 1
xtEM photo.
Fig. 9 is MHSiTiO prepared by embodiment 1
xthe electrochemistry cycle performance of negative material and coulombic efficiency curve.Abscissa is circulating cycle number, and unit is: week; Left side ordinate is specific discharge capacity, and unit is: MAH gram
-1(mAhg
-1), right side ordinate is coulombic efficiency, and unit is: percentage (%).Curve a is the relation curve of specific discharge capacity and circulating cycle number; Curve b is the relation curve of coulombic efficiency and circulating cycle number.
Embodiment
Embodiment 1
Measure 60mL ethanol and 100mL deionized water is made into ethanol/water mixed solvent, then measure 2mL mass fraction be 28% ammoniacal liquor join in above-mentioned ethanol/water mixed solvent, get 0.3gCTAB and be dispersed in above-mentioned containing in the ethanol/water mixed solvent of ammoniacal liquor.Transfer in there-necked flask by above-mentioned solution, keep bath temperature to be 35 DEG C, adjustment rotating speed of agitator is 500 revs/min.Keep after rotating speed stirs 5 minutes, in solution, adding 2mL tetraethoxysilane fast, Keep agitation 24 hours, use deionized water and each centrifuge washing of ethanol 3 times afterwards, to remove the impurity such as unreacted tetraethoxysilane.By the sample dispersion that obtains in the beaker containing 320mL deionized water, at 70 DEG C, ageing reacts 12 hours, uses deionized water and each centrifuge washing of ethanol 3 times afterwards, to remove the impurity that ageing reaction produces, obtains pure hollow silica ball.Get 0.48mL mass fraction be 38% hydrochloric acid join in 240mL absolute ethyl alcohol, getting 2g acquisition hollow silica ball again joins in above-mentioned hydrochloric acid/ethanolic solution, bath temperature is kept to be 60 DEG C, mixing speed is 500 revs/min, Keep agitation 3 hours, use deionized water and each centrifuge washing of ethanol 3 times afterwards, to remove the softex kw CTAB deposited in silica, obtain Porous hollow silicon dioxide MHSiO
2white powder.
Get the white powder that 300mg above-mentioned steps obtains to mix with 240mg magnesium powder, under an argon atmosphere with the ramp of 5 DEG C/min to 650 DEG C, magnesium thermit 6 hours, cools to room temperature with the furnace afterwards; Then it is the HCl of 2mol/L that the powder got after magnesium heat is placed in 60mL concentration, soaks 12 hours, centrifugation, and absolute ethanol washing 3 times is to remove HCl; Then be placed in the HF solution that 40mL mass fraction is 10%, soak 1 hour, centrifugation, absolute ethanol washing 3 times is to remove HF; Finally under 80 DEG C of conditions, namely vacuumize obtain hollow porous silicon MHSi brownish-yellow powder for 10 hours.
Measure 0.3mL mass fraction be 28% ammoniacal liquor join in 100mL absolute ethyl alcohol, then get the brownish-yellow powder that 80mg above-mentioned steps obtains and be dispersed in above-mentioned ammoniacal liquor/ethanolic solution, ultrasonic 5 minutes; 45 DEG C of water-baths, under 500rpm rotating speed, in above-mentioned solution, add 0.3mL butyl titanate fast, Keep agitation 24 hours, centrifugation, absolute ethanol washing 3 times, to remove unreacted butyl titanate, vacuumize 10 hours under 80 DEG C of conditions; By dried powder under argon gas with the ramp of 5 DEG C/min to 800 DEG C, react 3 hours, cool to room temperature afterwards with the furnace and namely obtain titanium oxide coated hollow porous ball MHSiTiO
x.
Embodiment 2
Measure 50mL ethanol and 100mL deionized water is made into ethanol/water mixed solvent, then measure 1.5mL mass fraction be 28% ammoniacal liquor join in above-mentioned ethanol/water mixed solvent, get 0.4gCTAB and be dispersed in above-mentioned containing in the ethanol/water mixed solvent of ammoniacal liquor.Transfer in there-necked flask by above-mentioned solution, keep bath temperature to be 30 DEG C, adjustment rotating speed of agitator is 400 revs/min.Keep after rotating speed stirs 8 minutes, in solution, adding 1.5mL tetraethoxysilane fast, Keep agitation 12 hours, use deionized water and each centrifuge washing of ethanol 5 times afterwards, to remove the impurity such as unreacted tetraethoxysilane.By the sample dispersion that obtains in the beaker containing 250mL deionized water, at 90 DEG C, ageing reacts 24 hours, uses deionized water and each centrifuge washing of ethanol 5 times afterwards, to remove the impurity that ageing reaction produces, obtains pure hollow silica ball.Get 0.2mL mass fraction be 38% hydrochloric acid join in 200mL absolute ethyl alcohol, getting 1.8g acquisition hollow silica ball again joins in above-mentioned hydrochloric acid/ethanolic solution, bath temperature is kept to be 80 DEG C, mixing speed is 400 revs/min, Keep agitation 2 hours, use deionized water and each centrifuge washing of ethanol 5 times afterwards, to remove the softex kw CTAB deposited in silica, obtain Porous hollow silicon dioxide MHSiO
2white powder.
Get the white powder that 300mg above-mentioned steps obtains to mix with 300mg magnesium powder, under an argon atmosphere with the ramp of 4 DEG C/min to 650 DEG C, magnesium thermit 8 hours, cools to room temperature with the furnace afterwards; Then be the HCl that 1:150 is placed in that 60mL concentration is 1.5mol/L by the powder after magnesium heat according to solid-to-liquid ratio, soak 24 hours, centrifugation, absolute ethanol washing 5 times is to remove HCl; Then be placed in the HF solution that 40mL mass fraction is 5%, soak 0.5 hour, centrifugation, absolute ethanol washing 5 times is to remove HF; Finally under 60 DEG C of conditions, namely vacuumize obtain hollow porous silicon MHSi brownish-yellow powder for 15 hours.
Measure 0.25mL mass fraction be 28% ammoniacal liquor join in 100mL absolute ethyl alcohol, then get the brownish-yellow powder that 100mg above-mentioned steps obtains and be dispersed in above-mentioned ammoniacal liquor/ethanolic solution, ultrasonic 8 minutes; 35 DEG C of water-baths, under the rotating speed of 400 revs/min, in above-mentioned solution, add 0.5mL butyl titanate fast, Keep agitation 18 hours, centrifugation, absolute ethanol washing 5 times, to remove unreacted butyl titanate, vacuumize 15 hours under 60 DEG C of conditions; By dried powder under argon gas with the ramp of 3 DEG C/min to 650 DEG C, react 5 hours, cool to room temperature afterwards with the furnace and namely obtain titanium oxide coated hollow porous ball MHSiTiO
x.
Embodiment 3
Measure 80mL ethanol and 100mL deionized water is made into ethanol/water mixed solvent, then measure 2.5mL mass fraction be 28% ammoniacal liquor join in above-mentioned ethanol/water mixed solvent, get 0.25gCTAB and be dispersed in above-mentioned containing in the ethanol/water mixed solvent of ammoniacal liquor.Transfer in there-necked flask by above-mentioned solution, keep bath temperature to be 40 DEG C, adjustment rotating speed of agitator is 600 revs/min.Keep after rotating speed stirs 10 minutes, in solution, adding 2.5mL tetraethoxysilane fast, Keep agitation 36 hours, use deionized water and each centrifuge washing of ethanol 4 times afterwards, to remove the impurity such as unreacted tetraethoxysilane.By the sample dispersion that obtains in the beaker containing 350mL deionized water, at 35 DEG C, ageing reacts 6 hours, uses deionized water and each centrifuge washing of ethanol 4 times afterwards, to remove the impurity that ageing reaction produces, obtains pure hollow silica ball.Get 0.5mL mass fraction be 38% hydrochloric acid join in 200mL absolute ethyl alcohol, getting 1.6g acquisition hollow silica ball again joins in above-mentioned hydrochloric acid/ethanolic solution, bath temperature is kept to be 70 DEG C, mixing speed is 600 revs/min, Keep agitation 5h, use deionized water and each centrifuge washing of ethanol 4 times afterwards, to remove the softex kw CTAB deposited in silica, obtain Porous hollow silicon dioxide MHSiO
2white powder.
Get the white powder that 270mg above-mentioned steps obtains to mix with 150mg magnesium powder, under an argon atmosphere with the ramp of 6 DEG C/min to 750 DEG C, magnesium thermit 5 hours, cools to room temperature with the furnace afterwards; Then be the HCl that 1:150 is placed in that 60mL concentration is 1mol/L by the powder after magnesium heat according to solid-to-liquid ratio, soak 18 hours, centrifugation, absolute ethanol washing 4 times is to remove HCl; Then be placed in the HF solution that 40mL mass fraction is 7%, soak 1.2 hours, centrifugation, absolute ethanol washing 4 times is to remove HF; Finally under 100 DEG C of conditions, namely vacuumize obtain hollow porous silicon MHSi brownish-yellow powder for 18 hours.
Measure 0.2mL mass fraction be 28% ammoniacal liquor join in 100mL absolute ethyl alcohol, then get the brownish-yellow powder that 120mg above-mentioned steps obtains and be dispersed in above-mentioned ammoniacal liquor/ethanolic solution, ultrasonic 10 minutes; 50 DEG C of water-baths, under the rotating speed of 600 revs/min, in above-mentioned solution, add 0.4mL butyl titanate fast, Keep agitation 36 hours, centrifugation, absolute ethanol washing 4 times, to remove unreacted butyl titanate, vacuumize 18 hours under 100 DEG C of conditions; By dried powder under argon gas with the ramp of 5 DEG C/min to 900 DEG C, react 2 hours, cool to room temperature afterwards with the furnace and namely obtain titanium oxide coated hollow porous ball MHSiTiO
x.
Embodiment 4
Measure 50mL ethanol and 100mL deionized water is made into ethanol/water mixed solvent, then measure 2.5mL mass fraction be 28% ammoniacal liquor join in above-mentioned ethanol/water mixed solvent, get 0.2gCTAB and be dispersed in above-mentioned containing in the ethanol/water mixed solvent of ammoniacal liquor.Transfer in there-necked flask by above-mentioned solution, keep bath temperature to be 30 DEG C, adjustment rotating speed of agitator is 500 revs/min.Keep after rotating speed stirs 10 minutes, in solution, adding 2.5mL tetraethoxysilane fast, Keep agitation 18 hours, use deionized water and each centrifuge washing of ethanol 4 times afterwards, to remove the impurity such as unreacted tetraethoxysilane.By the sample dispersion that obtains in the beaker containing 350mL deionized water, at 50 DEG C, ageing reacts 6 hours, uses deionized water and each centrifuge washing of ethanol 4 times afterwards, to remove the impurity that ageing reaction produces, obtains pure hollow silica ball.Get 0.6mL mass fraction be 38% hydrochloric acid join in 200mL absolute ethyl alcohol, getting 3.6g acquisition hollow silica ball again joins in above-mentioned hydrochloric acid/ethanolic solution,, keep bath temperature to be 50 DEG C, mixing speed is 600 revs/min, Keep agitation 4 hours, use deionized water and each centrifuge washing of ethanol 4 times afterwards, to remove the softex kw CTAB deposited in silica, obtain Porous hollow silicon dioxide MHSiO
2white powder.
Get the white powder that 300mg above-mentioned steps obtains to mix with 150mg magnesium powder, under an argon atmosphere with the ramp of 3 DEG C/min to 800 DEG C, magnesium thermit 6 hours, cools to room temperature with the furnace afterwards; Then be the HCl that 1:150 is placed in that 60mL concentration is 1.2mol/L by the powder after magnesium heat according to solid-to-liquid ratio, soak 15 hours, centrifugation, absolute ethanol washing 4 times is to remove HCl; Then be placed in the HF solution that 40mL mass fraction is 9%, soak 1.5 hours, centrifugation, absolute ethanol washing 4 times is to remove HF; Finally under 50 DEG C of conditions, namely vacuumize obtain hollow porous silicon MHSi brownish-yellow powder for 20 hours.
Measure 0.4mL mass fraction be 28% ammoniacal liquor join in 100mL absolute ethyl alcohol, then get the brownish-yellow powder that 90mg above-mentioned steps obtains and be dispersed in above-mentioned ammoniacal liquor/ethanolic solution, ultrasonic 6 minutes; 40 DEG C of water-baths, under the rotating speed of 600 revs/min, in above-mentioned solution, add 0.45mL butyl titanate fast, Keep agitation 36 hours, centrifugation, absolute ethanol washing 4 times, to remove unreacted butyl titanate, vacuumize 12 hours under 100 DEG C of conditions; By dried powder under argon gas with the ramp of 6 DEG C/min to 700 DEG C, react 4 hours, cool to room temperature afterwards with the furnace and namely obtain titanium oxide coated hollow porous ball MHSiTiO
x.
Claims (3)
1. a titanium-oxide-coated Porous hollow silicon ball combination electrode material, is characterized in that: this combination electrode material inside is Porous hollow silicon ball MHSi, and diameter is 200 ~ 500 nanometers; Titanium oxide TiO
xbe coated on silicon ball surface, thickness is 5 ~ 20 nanometers; The chemical composition of this composite material is described as MHSiTiO
x, wherein in TiOx, the span of x is 1.5 ~ 2.0.
2. prepare a method for titanium-oxide-coated Porous hollow silicon ball combination electrode material described in claim 1, it is characterized in that, comprise the steps:
(1) preparation ethanol and deionized water volume ratio are the mixed solvent of 0.3:1 ~ 0.8:1, according to mass fraction be 28% ammoniacal liquor and deionized water volume ratio be that ammoniacal liquor joins in above-mentioned ethanol/deionized water mixed solvent by the ratio of 3:200 ~ 1:40, softex kw CTAB is dispersed in above-mentioned containing in the ethanol/water solution of ammoniacal liquor according to the ratio that solid-to-liquid ratio is 1:750 ~ 1:250, solution is transferred in there-necked flask, bath temperature is kept to be 30 DEG C ~ 40 DEG C, with the rotating speed stirring reaction 5 ~ 10 minutes of 400 ~ 600 revs/min, the ratio being 3:200 ~ 1:40 in tetraethoxysilane and deionized water volume ratio adds tetraethoxysilane fast in above-mentioned solution, Keep agitation 12 ~ 36 hours, use deionized water and each centrifuge washing of ethanol 3 ~ 5 times afterwards, to remove unreacted tetraethoxysilane impurity, the centrifugal white solid obtained is dispersed in the beaker containing deionized water by solid-to-liquid ratio 1:200 ~ 1:100, ageing reaction 6 ~ 24 hours at 30 ~ 100 DEG C, use deionized water and each centrifuge washing of ethanol 3 ~ 5 times afterwards, to remove the impurity that ageing reaction produces, obtain pure hollow silica ball, according to mass fraction be 38% hydrochloric acid and absolute ethyl alcohol volume ratio be that hydrochloric acid joins in absolute ethyl alcohol by the ratio of 1:10000 ~ 3:10000, then be that 1:200 ~ 1:50 joins in the above-mentioned absolute ethyl alcohol containing hydrochloric acid by the centrifugal solid obtained by solid-to-liquid ratio, bath temperature is kept to be 50 ~ 80 DEG C, with the rotating speed Keep agitation 2 ~ 5 hours of 400 ~ 600 revs/min, use deionized water and each centrifuge washing of ethanol 3 ~ 5 times afterwards, to remove the CTAB in silicon dioxide, finally under 50 ~ 100 DEG C of conditions, namely vacuumize obtain Porous hollow silicon dioxide MHSiO for 10 ~ 20 hours
2white powder,
(2) white powder that step (1) obtains is mixed according to the ratio that mass ratio is 1:1 ~ 2:1 with magnesium powder, under an argon atmosphere with the ramp of 3 ~ 6 DEG C/min to 650 ~ 800 DEG C of magnesium thermit 5 ~ 8 hours, cool to room temperature with the furnace afterwards; Then the powder after magnesium heat is placed according to the ratio that solid-to-liquid ratio is 1:150 ~ 1:100 the hydrochloric acid that concentration is 1 ~ 2mol/L, soaks 12 ~ 24 hours, centrifugation, absolute ethanol washing 3 ~ 5 times is to remove unreacted hydrochloric acid; Then be placed in the HF solution of mass concentration 5 ~ 10%, soak 0.5 ~ 1.5 hour, centrifugation, absolute ethanol washing 3 ~ 5 times is to remove HF; Finally under 50 ~ 100 DEG C of conditions, namely vacuumize obtain hollow porous silicon MHSi brownish-yellow powder for 10 ~ 20 hours;
(3) according to mass fraction be 28% ammoniacal liquor and absolute ethyl alcohol volume ratio be that ammoniacal liquor joins in absolute ethyl alcohol by the ratio of 3:200 ~ 1:40, brownish-yellow powder step (2) obtained is dispersed in above-mentioned ammoniacal liquor/alcohol mixed solution according to the ratio that solid-to-liquid ratio is 3:5000 ~ 3:2500, ultrasonic 5 ~ 10 minutes; 30 ~ 50 DEG C of water-baths, under the rotating speed of 400 ~ 600 revs/min, in above-mentioned solution, butyl titanate is added fast than for 3:1000 ~ 1:200 according to butyl titanate/ethanol contend, Keep agitation 12 ~ 36 hours, centrifugation, absolute ethanol washing 3 ~ 5 times, to remove unreacted butyl titanate, vacuumize 10 ~ 20 hours under 50 ~ 100 DEG C of conditions; Dried powder is reacted 2 ~ 5 hours to 650 ~ 900 DEG C with the ramp of 3 ~ 6 DEG C/min under an inert atmosphere, cools to room temperature afterwards with the furnace and namely obtain titanium-oxide-coated hollow porous ball MHSiTiO
x.
3. preparation method according to claim 2, is characterized in that, in step (3), described inert atmosphere is the one in argon gas or nitrogen.
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