CN104332620A - Method for synthesizing silicon nano powder through hydrothermal reactions and applications of silicon nano powder - Google Patents
Method for synthesizing silicon nano powder through hydrothermal reactions and applications of silicon nano powder Download PDFInfo
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- CN104332620A CN104332620A CN201410424342.6A CN201410424342A CN104332620A CN 104332620 A CN104332620 A CN 104332620A CN 201410424342 A CN201410424342 A CN 201410424342A CN 104332620 A CN104332620 A CN 104332620A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
- C01B33/023—Preparation by reduction of silica or free silica-containing material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a method for synthesizing silicon nano powder through hydrothermal reactions, silicon nano powder prepared by the provided method, and applications of the silicon nano powder as the negative electrode material of lithium ion battery for lithium storage in the electrochemistry industry. Specifically, a water dispersion liquid of non-crystalline silicon oxide sol/amorphous powder is reduced through metal hydrothermal reactions at a temperature of 100 to 300 DEG C so as to synthesize the silicon nano powder. By controlling the reactant ratio, water dispersion liquid concentration, pH value and reaction temperature, the preparation of silicon nano powder can be achieved. The reaction conditions are mild, the reactant price is lower, the produced silicon nano powder has good electrochemical properties, the capacity of the silicon nano powder can reach 800 to 3000 mAh/g, and thus the provided silicon material can be used as the negative electrode material of high performance lithium battery and can be produced in a large scale.
Description
Technical field
The present invention relates to the preparations and applicatio field of silicon nano power, relate to a kind of metal hydro-thermal reduction colloidal sol of amorphous silicon oxide particularly and the aqueous dispersions of amorphous powder prepares the method for high performance silicon nano powder, the silicon nano power prepared by the method and as the application of lithium ion battery negative material in electrochemical lithium storage.
Background technology
Based on application important on function electronic equipment, the preparation of silicon nano material causes to be paid close attention to widely.Meanwhile, silicon nano material in lithium ion battery applications owing to having high theoretical capacity (~ 4200mAh/g) and low discharge potential (<0.5V, Li/Li
+) be considered to replace traditional negative pole best material.
Traditionally, silicon materials mainly adopt solid phase reduction silicon dioxide to prepare.Such as higher than the carbon thermal reduction silicon dioxide (document 1, Nagamori, M., Malinsky, I. & Claveau, A.Metall.Trans.B17,503 – 514 (1986)) of 2000 DEG C; Magnesiothermic reduction (document 2 when 650 DEG C, Bao Z, Weatherspoon M R, Shian S, et al., Nature, 446:172-175 (2007)) and electrochemical reduction (document 3, the Cho S K that is greater than under 850 DEG C of conditions, Fan F R F, Bard A J., AngewandteChemie, 124:12912-12916 (2012)).In the recent period, in order to synthesize the nano silicon material that can be applied to lithium cell cathode material, a large amount of synthetic methods is developed.Such as, by chemical vapour deposition technique, 400 DEG C of pyrolysis SiH in the reactor that pressure is 3Torr
4/ H
2and PH (50%)
3/ H
2(100ppm) gaseous mixture, and silicon nanowires is prepared under Woelm Alumina is assisting of template, this nano wire illustrates long cycle life (after 1100 circle charge and discharge circulations, capacity is 1029mAh/g) and high high rate performance (under 10 multiplying powers, capacity is ~ 956mAh/g) (document 4, Cho J H, Picraux S T.Nano letters, 13:5740-5747 (2013)).Silicon nano material better performances prepared by this technology, but method is very expensive, and output is less.For silicon nano material preparation in organic solvent, the people such as Heath reported first in 1992 in organic phase sodium reduction silicon tetrachloride prepare the method for silicon nanocluster, the method needs 385 DEG C of reactions, 3 to 7 days (documents 5 in steel bomb, Heath J R., Science, 258:1131-1133 (1992)).Subsequently, the people such as Jaephil Cho use similar preparation method to synthesize nano silicon particles, present high charging capacity (3535mAh/g) after this particle is coated by further carbon and after 40 circles that circulate capacity keep 96% (document 6, Kim H, Seo M, Park M H, et al.Angew.Chem.Inter.Ed., 49:2146-2149 (2010)).The people such as Brian A.Korgel are at 490 DEG C, silicon nanowires has been prepared by pyrolysis phenylsilane in organic phase, when carry out further carbon coated after, after this silicon nanowires circulation 30 circle, reversible capacity still reaches 1500mAh/g (document 7, Chan C K, Patel R N, O ' Connell M J, et al., ACS nano, 4:1443-1450 (2010)).Up to the present, only have the people such as Lee successfully to realize preparing silicon nano material in aqueous phase, its method is by silicon nitrogen coupling agent (C
6h
17nO
3si) and trisodium citrate react under microwave radiation technology, product is the nano silicon particles (document 8, Zhong Y, Peng F, Bao F, et al., J.Am.Chem.Soc., 135:8350-8356 (2013)) of ~ 2.2 nanometers.The lithium electrical property of nano particle prepared by the method is not yet studied.Recently, we use metal direct-reduction Na
2siO
39H
2o Opacity in lens porous silica microsphere ground rice, further with Graphene compound after, after 300 circles that circulate under 3.6A/g current density, capacity remains on 576mAh/g (document 9, Liang Jianwen, Zhu Yongchun, Li Xiaona, Qian Yitai, Chem.Commun., 50,6856-6859 (2014)).The eco-friendly low-temperature synthetic method of development silicon nano power, to the preparation of the scale of silicon nano material and silicon significant as the practical application of high-performance lithium ion negative material.
Summary of the invention
Present applicant proposes a kind of method that hydro-thermal reaction prepares silicon nano power, synthesized silicon nano power is as lithium ion battery negative material, compared with the graphite-like commodity negative material being 372mAh/g with theoretical capacity, chemical property is better, and capacity can reach 800-3000mAh/g.Compared with the silicon materials of bibliographical information, required temperature is lower, and environment is comparatively friendly, and productive rate is higher, and production cost is lower, efficiently solves the key issue that silicon materials are produced as high-performance lithium cell negative electrode material magnanimity.
The present invention is achieved through the following technical solutions: by selecting colloidal sol such as silica hydrosol, the sodium metasilicate hydrosol and waterglass or amorphous silicon oxide powder such as aerosil, the silicic acid of amorphous silicon oxide to be silicon source, utilize hydrothermal reduction to react, adopt metal to reduce.By controlling reactant ratio, the concentration of aqueous dispersions, pH value and reaction temperature etc. realize the preparation of silicon nano power.
Particularly, the present invention relates to the following:
1. prepare a method for silicon nano power, it is characterized in that, with metal hydro-thermal reduction amorphous silicon oxide aqueous dispersions, synthesis silicon nano power.
2. the method according to 1, described amorphous silicon oxide comprises the colloidal sol of Si oxide and amorphous powder, and the colloidal sol of wherein said Si oxide comprises silica hydrosol, the sodium metasilicate hydrosol and waterglass; The amorphous powder of described Si oxide comprises aerosil and silicic acid.
3. the method according to 1, described metal comprises magnesium, sodium, potassium, aluminium, zinc or its alloy.
4. the method according to 1, after in described aqueous dispersions, amorphous silicon oxide is converted into silicon dioxide, its content is 5 ~ 80wt%, is preferably 10 ~ 40wt%; Described aqueous dispersions pH is 3 ~ 14, is preferably 6 ~ 14.
5. the method according to 1, the proportioning of wherein said metal and amorphous silicon oxide aqueous dispersions is 1g:0.2mL ~ 4mL, is preferably 1g:0.6mL ~ 1.5mL.
6. the method according to 1, wherein said hydrothermal reduction reaction need be carried out in the stainless steel autoclave of sealing, and the volume of described autoclave is 20mL ~ 50L.
7. the method according to 1, the temperature of described hydrothermal reduction reaction between 100 DEG C ~ 300 DEG C, preferably between 150 ~ 300 DEG C; Reaction time between 2 hours ~ 3 days, preferably between 2 ~ 20h.
8. the method according to any one of 1-7, described method also comprises the step of removing impurity and filtration drying, and the step of described removing impurity comprises washing, pickling.
Silicon nano power prepared by method described in any one of 9.1-8.
Silicon nano power described in 10.9 is as the application of lithium ion battery negative material in electrochemical lithium storage.
In a word, the invention provides a kind of method that hydro-thermal reaction prepares silicon nano power, and the silicon nano power prepared of the method and this silicon nano power are as the application of lithium ion battery negative material in electrochemical lithium storage.At 100-300 DEG C, use cheap raw material, solve and prepare silicon nano material severe reaction conditions at present, the problems such as expensive starting materials.Therefore this silicon nano power is applied to lithium ion battery and effectively can solves the actual application problem of silicon as high-performance lithium ion negative material.
Detailed Description Of The Invention
Below technical scheme of the present invention is elaborated further.It should be pointed out that each embodiment of the present invention can combine as required by any way.
First aspect of the present invention provides a kind of hydro-thermal reaction to prepare the method for silicon nano power.
In one embodiment, described method is with metal hydro-thermal reduction amorphous silicon oxide aqueous dispersions, thus completes the method.
In one embodiment, described amorphous silicon oxide comprises the colloidal sol of Si oxide and amorphous powder.Wherein the colloidal sol of Si oxide comprises silica hydrosol, the sodium metasilicate hydrosol and waterglass; The amorphous powder of Si oxide comprises aerosil and silicic acid.
In one embodiment, described metal includes but not limited to magnesium, sodium, potassium, aluminium, zinc and alloy thereof.
In a specific embodiment, described method comprises the steps:
A. with water described amorphous silicon oxide carried out disperseing and the dioxide-containing silica being made into conversion at 5 ~ 80wt%, pH be 3 ~ 14 amorphous silicon oxide aqueous dispersions;
B. metal and the amorphous silicon oxide aqueous dispersions described in a are that 1g:0.2mL ~ 4mL mixes by proportioning, be sealed in the autoclave of 20mL ~ 50L, in 100 DEG C ~ 300 DEG C reactions 2 hours to 3 days, head product was through washing, after the step removing impurity such as pickling, namely filtration drying obtains silicon nano power.
In a preferred embodiment, the dioxide-containing silica converted in described amorphous silicon oxide aqueous dispersions is 10 ~ 40wt%; PH value is 6 ~ 14;
In a preferred embodiment, the proportioning of metal and amorphous silicon oxide aqueous dispersions is 1g:0.6mL ~ 1.5mL;
In a preferred embodiment, reaction temperature is 150 ~ 300 DEG C; Reaction time is 2 ~ 20h.
Second aspect of the present invention provides the silicon nano power prepared by the method described in the present invention first aspect.
Concrete, the nano powder of silicon prepared by the inventive method can reach 40% even higher productive rate.Silicon nano power prepared by the inventive method has better micro-nano structure.
3rd aspect of the present invention provides silicon nano power described in the present invention second aspect as the application of lithium ion battery negative material in electrochemical lithium storage.
In one embodiment, using the silicon nano power described in the present invention second aspect as negative material, be assembled into lithium ion battery, when described silicon nano power is as lithium ion battery negative material, show the cycle life of high lithium storage content and coulombic efficiency and length.This silicon nano power is containing a small amount of impurity, and particularly during silicon dioxide, the impact of chemical property is little.After carbon compound, performance can further be optimized.
Advantage and the feature of hinge structure of the present invention are:
In synthetic method, with existing carbon heat, the technology such as magnesiothermic reduction silica are compared, and the temperature needed for method of the present invention is lower and productive rate is higher; Compared with the technology such as existing organic liquid phase reduction, method raw material of the present invention is cheap nontoxic, environmental friendliness.Generally speaking, source, the silicon source cheapness that the present invention is used, the simple environmental protection of preparation flow, is beneficial to amplify and produces.
In the silicon nano power obtained, this silicon nano power is the particle of micro-nano structure, and size is adjustable, mostly is loose structure, and aperture is mainly distributed in 10 nanometers.
Be used in lithium ion battery at the silicon nano power obtained, this silicon nano power demonstrates the lithium storage content far above commercial graphite class negative pole, under 0.2C (1C=3.6A/g) charging and discharging currents density, its capacity is higher than 2300mAh/g, improve more than 6 times compared with the 372mAh/g of graphite negative electrodes, and there is long cycle life.
Accompanying drawing explanation
Fig. 1 is the silicon nano power X-ray diffractogram that embodiment 1 obtains; A, b, the c respectively X-ray diffractogram of gained silicon nano power under corresponding 150,200,300 DEG C of reaction conditions in figure;
Fig. 2 is the silicon nano power transmission electron microscope picture that embodiment 1 obtains; A, b, the c respectively transmission electron microscope picture of gained silicon nano power under corresponding 150,200,300 DEG C of reaction conditions in figure;
Fig. 3 is the silicon nano power X-ray diffractogram that embodiment 2 obtains;
Fig. 4 is the silicon nano power X-ray diffractogram that embodiment 3 obtains;
Fig. 5 is the silicon nano power X-ray diffractogram that embodiment 4 obtains;
Fig. 6 is the silicon nano power X-ray diffractogram that embodiment 5 obtains;
Fig. 7 is the feature charging and discharging curve figure of button cell under 0.2C charging and discharging currents density that embodiment 6 obtains;
Fig. 8 is the electrochemical cycle stability figure of button cell under 0.2C charging and discharging currents density that embodiment 6 obtains;
Fig. 9 is the electrochemical cycle stability figure of button cell under 0.1C charging and discharging currents density that embodiment 6 obtains;
Figure 10 is the electrochemical cycle stability figure of button cell under 1C charging and discharging currents density that embodiment 6 obtains.
Embodiment
Carry out clear below in conjunction with embodiment to technical scheme of the present invention, detailed description.But should be appreciated that described embodiment is only a part of the present invention, instead of whole embodiment.Based on the embodiment in the present invention, the technical work personnel of this area, not making the every other embodiment obtained under creative work prerequisite, belong to protection scope of the present invention.
The chemical reagent adopted in the embodiment of the present invention is market and buys.
Embodiment 1: be silicon source with the alkaline silicon dioxide hydrosol (jx-30, pH value about 9, purchased from Guangzhou Sui Ze Environmental Protection Technology Co., Ltd) that dioxide-containing silica is 30%, prepares silicon nano power by hydro-thermal reaction.
Get after this silica hydrosol of 10mL mixes with 10g magnesium powder and put into 50mL stainless steel autoclave, seal and be placed in electrical crucible, at 150,200,300 DEG C, reacting 10h respectively, then naturally cool to room temperature; After driving still, products therefrom is through washing, and centrifugation after 1M watery hydrochloric acid 2h soaking and washing, then washes centrifugal drying further, namely obtain silicon nano power.
Adopt X light powder diffraction instrument to carry out X light diffracting analysis, in Fig. 1, a, b, c are this embodiment X-ray diffraction spectrum of gained silicon nano power under 150,200,300 DEG C of reaction conditions respectively.As seen from the figure, have apparent diffraction maximum in x-ray diffraction spectra, all diffraction maximums all can the index Si (JPCDS 77-2111) that is cube.Adopt electronic balance to carry out productive rate estimation, the middle dioxide-containing silica that feeds intake is about 3g, and product silicon nano power is about 0.15 ~ 0.22g, and productive rate is ~ 20%.
It is nano-porous structure that the projection Electronic Speculum figure (Fig. 2 a, gained silicon nano power under corresponding 150,200, the 300 DEG C of reaction conditions of b, c difference) of product shows the silica flour prepared in this embodiment, and hole is evenly distributed in 10 nanometer range.And also can change along with the change particle size of temperature and pore-size distribution.
Embodiment 2:
Scheme as described in Example 1, difference is the pH value to 8 adopting hydrochloric acid to regulate silicon solution in embodiment 1, and the amount of magnesium is corresponding is simultaneously increased to 11.44g, reacts 20h, prepare silicon nano power at 300 DEG C.Productive rate is promoted to further ~ and 40%.Fig. 3 is the characteristic X ray diffracting spectrum of this embodiment gained silicon nano power.It is Emission in Cubic silicon (JPCDS 77-2111) that spectrogram shows this silicon nano power.
Embodiment 3:
Scheme as described in Example 1, difference adopts aerosil (aerosil r106 wins wound Degussa purchased from Germany) to be silicon source.Being dispersed in by 0.6g aerosil in 1.8mL water and being mixed with dioxide-containing silica is 25%, the silica aqueous dispersion of pH value about 7, add 2.3g magnesium powder subsequently carry out mixing and put into 20mL stainless steel autoclave, seal and be placed in electrical crucible, react 2h under 200 DEG C of conditions, then naturally cool to room temperature; After driving still, products therefrom is through washing, and centrifugation after 1M watery hydrochloric acid 2h soaking and washing, then washes centrifugal drying further, namely obtain silicon nano power.Fig. 4 is the X-ray diffraction spectrum of this embodiment gained silicon nano power.It is Emission in Cubic silicon (JPCDS 77-2111) that spectrogram shows this silicon nano power.
Embodiment 4:
Scheme as described in Example 1, difference adopts silicic acid (20035518, purchased from Shanghai traditional Chinese medicines group) to be silicon source.Getting water that 0.57g silicic acid adds 2.8mL, to be made into the dioxide-containing silica be converted into be ~ 10%, pH value is the dispersion liquid of 6, puts into 20mL stainless steel autoclave after mixing with 2.2g magnesium powder, seals and is placed in electrical crucible, under 300 DEG C of conditions, react 5h, then naturally cool to room temperature; After driving still, products therefrom is through washing, and centrifugation after 1M watery hydrochloric acid 2h soaking and washing, then washes centrifugal drying further, namely obtain silicon nano power.Fig. 5 is the X-ray diffraction spectrum of this embodiment gained silicon nano power.It is Emission in Cubic silicon (JPCDS 77-2111) that spectrogram shows this powder, simultaneously containing a small amount of silica impurity.
Embodiment 5:
Scheme as described in Example 1, difference be silicon source do not adopt silica hydrosol but directly use modulus be 3.3 waterglass (T3401, purchased from Linyi Lv Sen Chemical Co., Ltd.).(dioxide-containing silica be converted into is 22wt% to get this waterglass of 1.4mL, pH value is about the sodium metasilicate hydrosol of 14) mix with 1.5g magnesium powder after put into 20mL stainless steel autoclave, seal and be placed in electrical crucible, under 200 DEG C of conditions, react 2h, then naturally cool to room temperature; After driving still, products therefrom is through washing, and centrifugation after 1M watery hydrochloric acid 2h soaking and washing, then washes centrifugal drying further, namely obtain silicon nano power.Fig. 6 is the X-ray diffraction spectrum that this embodiment reacts 2h gained silicon nano power at 200 DEG C.It is Emission in Cubic silicon (JPCDS 77-2111) that spectrogram shows this silicon nano power
Embodiment 6:
Product in above-described embodiment 1 to 5 is assembled into CR2016 button cell respectively, is to electrode with lithium sheet, and polyolefin porous membrane (Celgard 2500) is barrier film, with LiPF
6ethylene carbonate (EC) and the mixed solution of dimethyl carbonate (DMC) (volume ratio 1:1) as electrolyte, CR2016 battery pack is contained in the glove box of argon gas atmosphere and completes.Silicon electrode adopts the sodium alginate gluing agent of the silicon nano power in the embodiment of 70wt%, 10wt%, conductive black, the water of 20% mixes, and the substrate of electrode film is metal copper foil.Electric performance test is carried out at probe temperature is 25 DEG C.Fig. 7-9 is the electrochemical lithium storage performance map of the button cell that the silicon nano power of above-described embodiment gained is assembled into.Fig. 7 is the electrochemical characteristic curve chart of button cell under 0.2C that embodiment 1 gained silicon nano power is assembled into, and demonstrates the feature charging and discharging curve figure of silicon in figure.Fig. 8 is the electrochemical lithium storage stable circulation figure of button cell under 0.2C that embodiment 1 gained silicon nano power is assembled into, and lithium storage content figure showing this silica flour, higher than 2300mAh/g, improves more than 6 times compared with the theoretical capacity 372mAh/g of graphite negative electrodes; Fig. 9 is the electrochemical lithium storage stable circulation figure of button cell under 0.1C that embodiment 1 gained silicon nano power is assembled into, and figure shows the lithium storage content of this silica flour higher than 3000mAh/g.Figure 10 is the electrochemical lithium storage cyclical stability figure of button cell under 1C that embodiment 1 gained silicon nano power is assembled into, and lithium storage content figure shown after this silicon nano power circulation 100 circle still can be stabilized in 1000mAh/g.From above each map analysis, this silicon nano power chemical property is better, and capacity can reach 800-3000mAh/g, and coulombic efficiency is higher and have longer cycle life.
Embodiment result shows, the present invention under the hydro-thermal reaction of 100-300 DEG C, can use cheap silica hydrosol, the sodium metasilicate hydrosol and waterglass, aerosil, silicic acid etc. to be raw material, realize the preparation of silicon nano power.Because reaction condition is gentle, environmental friendliness, is beneficial to enlarged experiment experiment, amplifies when producing and does not have substantive difficulty.When this silicon nano power is applied to lithium ion battery negative material, demonstrate the lithium storage content far above graphite cathode and good cyclical stability.After carbon compound, performance can be optimized further.Can be used as high performance lithium ionic cell cathode material of future generation.
Claims (10)
1. prepare a method for silicon nano power, it is characterized in that, with metal hydro-thermal reduction amorphous silicon oxide aqueous dispersions, synthesis silicon nano power.
2. method according to claim 1, described amorphous silicon oxide comprises the colloidal sol of Si oxide and amorphous powder, and the colloidal sol of wherein said Si oxide comprises silica hydrosol, the sodium metasilicate hydrosol and waterglass; The amorphous powder of described Si oxide comprises aerosil and silicic acid.
3. method according to claim 1, described metal comprises magnesium, sodium, potassium, aluminium, zinc or its alloy.
4. method according to claim 1, after in described aqueous dispersions, amorphous silicon oxide is converted into silicon dioxide, its content is 5 ~ 80wt%, is preferably 10 ~ 40wt%; Described aqueous dispersions pH is 3 ~ 14, is preferably 6 ~ 14.
5. method according to claim 1, the proportioning of wherein said metal and amorphous silicon oxide aqueous dispersions is 1g:0.2mL ~ 4mL, is preferably 1g:0.6mL ~ 1.5mL.
6. method according to claim 1, wherein said hydrothermal reduction reaction need be carried out in the stainless steel autoclave of sealing, and the volume of described autoclave is 20mL ~ 50L.
7. method according to claim 1, the temperature of described hydrothermal reduction reaction between 100 DEG C ~ 300 DEG C, preferably between 150 ~ 300 DEG C; Reaction time between 2 hours ~ 3 days, preferably between 2 ~ 20h.
8. the method according to any one of claim 1-7, described method also comprises the step of removing impurity and filtration drying, and the step of described removing impurity comprises washing, pickling.
9. the silicon nano power prepared by the method described in any one of claim 1-8.
10. silicon nano power according to claim 9 is as the application of lithium ion battery negative material in electrochemical lithium storage.
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| CN106602028A (en) * | 2016-12-30 | 2017-04-26 | 东莞市佳乾新材料科技有限公司 | Preparation method for high-energy-density lithium ion power battery |
| CN106602028B (en) * | 2016-12-30 | 2019-08-30 | 联动天翼新能源有限公司 | A kind of preparation method of the lithium-ion-power cell of high-energy density |
| CN107331847A (en) * | 2017-07-12 | 2017-11-07 | 天津巴莫科技股份有限公司 | The preparation method of the sulphur composite positive pole of silicon substrate support |
| CN107681131A (en) * | 2017-08-28 | 2018-02-09 | 河南工程学院 | A kind of preparation method of inexpensive nano silica fume and silicon carbon material |
| CN107681131B (en) * | 2017-08-28 | 2020-11-17 | 河南卓谷科技有限公司 | Preparation method of low-cost nano silicon powder and silicon carbon material |
| CN113097462A (en) * | 2021-03-29 | 2021-07-09 | 中国科学院广州地球化学研究所 | Petal-shaped micro-nano composite structure silicon material and preparation method and application thereof |
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