CN105417543A - Process for preparing nano porous silicon electrode material - Google Patents

Process for preparing nano porous silicon electrode material Download PDF

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Publication number
CN105417543A
CN105417543A CN201510731316.2A CN201510731316A CN105417543A CN 105417543 A CN105417543 A CN 105417543A CN 201510731316 A CN201510731316 A CN 201510731316A CN 105417543 A CN105417543 A CN 105417543A
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nano
rice husk
porous silicon
silicon electrode
per minute
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CN105417543B (en
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焦连升
刘金玉
孟玲菊
王晓忠
卢明亮
陈中亚
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Hebei Normal University for Nationalities
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Hebei Normal University for Nationalities
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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
    • C01B33/025—Preparation by reduction of silica or free silica-containing material with carbon or a solid carbonaceous material, i.e. carbo-thermal process
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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 discloses a process for preparing a nano porous silicon electrode material. The process comprises the steps of washing rice hulls by water, then, drying the rice hulls, treating the rice hulls with an acid mixture of citric acid and tartaric acid under the action of ultrasound, then, carrying out high-temperature calcination, and then, carrying out reduction by magnesium powder, thereby obtaining the nano porous silicon electrode material. The nano porous silicon prepared by the process is large in capacity, high in rate capability and long in cycle service life; and meanwhile, the steps of the process are simple, so that industrialization is facilitated.

Description

A kind of preparation technology of nano-structure porous silicon electrode materials
Technical field
The present invention relates to Material Field, in particular to a kind of preparation technology of the nano-structure porous silicon electrode materials for lithium cell.
Background technology
Lithium ion battery is widely used in portable electron device because of its higher energy density, excellent cycle performance and stronger retention of charge.But be limited by the lower specific storage of negative material and high rate performance, lithium ion battery can't meet high-energy-density, powerful requirement completely.The Li mainly containing graphitized carbon material, spinel type of current lithium ion battery negative material 4ti 5o 12, alloying negative material etc.Carbon material is most widely used a kind of negative material, is generally obtained by pyrolysis organic precursor under an inert atmosphere.Though graphitized carbon material has higher theoretical capacity, but the compatibility of itself and some electrolytic solution (as propylene carbonate and PC) is bad, PC molecule can insert graphite layers and be reduced generation gas molecule and graphite can be peeled off, and causes capacity of negative plates sharp-decay.The Li of spinel type 4ti 5o 12be another important lithium ion battery negative material, distinguishing feature is that unit cell parameters change is very little in charge and discharge process, is called as zero stress material, compared with graphitized carbon material, and Li 4ti 5o 12high embedding lithium voltage (1.6V) improves safety performance, but lower capacity (theoretical capacity 175mAh/g) limits its application.Alloying negative material can form the material of alloy, such as Si, Sn, Sb etc. with Li.Although Si has the highest specific storage and lower charging/discharging voltage platform, but because it also exists huge volume change (nearly the change of 300%) in slotting lithium and de-lithium process, cause electrode powder come off from collector and cause the cycle performance of Si very poor.And porous silicon had both remained high specific storage and low discharge and recharge flattening bench, effectively can alleviate again the pressure that volumetric expansion brings, be desirable lithium ion battery negative material.The preparation of current nano-structure porous silicon, the method such as galvanic corrosion, secondary chemical corrosion can be helped to make (Liu Jingjing etc. by light, prepared by the porous silica material for lithium ion battery negative, Xiamen University's journal (natural science edition), 52nd volume the 4th phase, 450-454 page), can also etching method, hydrothermal etching etc. be passed through.In general, the most complex process of making of current porous silicon, the porous silicon result of use of acquisition is not ideal enough, is unfavorable for industrialization.
Summary of the invention
The object of this invention is to provide a kind of preparation technology of nano-structure porous silicon electrode materials, the nano-structure porous silicon capacity that this technique is produced is large, and high rate performance is high, and service life cycle is long, and this processing step is succinct simultaneously, is convenient to industrialization.
To achieve these goals, the present invention takes following technical scheme:
A preparation technology for nano-structure porous silicon electrode materials, comprises the steps:
A the rice husk of 20 ~ 30 parts by weight washes by (), and dry at 100 ~ 105 DEG C, obtains dry rice husk;
B dry rice husk is put into container and is added the mixed acid solution of 400 ~ 500 parts by weight by (), then container is placed in ultrasonic cleaner, ultrasonic cleaner power 250W, frequency 25kHz, sonic oscillation filters after 30 ~ 45 minutes and rice husk is washed to neutrality, then 100 ~ 105 DEG C of dryings, obtain acid treatment rice husk, in described mixed acid solution, contain the tartrate of 4 ~ 5% citric acids and 5 ~ 6% by weight percentage;
C acid treatment rice husk adds in tube furnace by (), mixed gas is passed into the flow of per minute 20 ~ 25 milliliters, and heat up with the speed of per minute 5 DEG C, after being warming up to 550 DEG C, isothermal reaction obtains nano silicon in 2 hours, and described mixed gas to be made up of by volume oxygen and nitrogen at 9: 1;
(d) by nano silicon with etc. the magnesium powder of weight mix after be sealed in irony reactor, with isothermal reaction after the ramp to 600 of per minute 5 DEG C DEG C 2 hours, then magnesium oxide is removed with HCl treatment after being cooled to room temperature, remove unreacted nano silicon by hydrofluoric acid treatment again, be washed to neutral final vacuum drying and obtain nano-structure porous silicon electrode materials.
Preferably, step (d) hydrochloric acid substance withdrawl syndrome used is 1molL-1, and the mass percent concentration of hydrofluoric acid is 5%.
The present invention adopts rice husk to do raw material, make full use of the microvoid structure that rice husk self has, adopt weak acid and ultrasonicly to process, this step not only avoids the environmental pollution pressure using the strong acid such as hydrochloric acid to bring, and the coordination function of weak acid acid group and hyperacoustic cavatition are more conducive to the porous homogeneity removing other foreign metal ions and ensure the finished product, the thoroughness coordinating the gases used oxygen nitrogen proportioning of subsequent oxidation and calcining temperature to be conducive to silicon-dioxide and porous silicon to generate.The porous silicon theoretical capacity of test experiments display preparation is large, and high rate performance is high, and service life cycle is long.
Accompanying drawing explanation
Fig. 1 is the SEM figure of nano silicon;
Fig. 2 is the EDAX energy spectrogram of nano silicon;
Fig. 3 is the SEM figure of Porous Silicon Electrode material;
Fig. 4 is the TEM figure of Porous Silicon Electrode material;
Fig. 5 is Porous Silicon Electrode material properties test figure.
Embodiment
The preparation technology of this nano-structure porous silicon is further illustrated below by specific embodiment:
Embodiment 1:
A () is clean with distilled water flushing by the rice husk of 20 grams, then at 100 DEG C, be dried to constant weight, obtain dry rice husk;
B dry rice husk is put into beaker and is added the mixed acid solution of 400 parts by (), then container is placed in ultrasonic cleaner, ultrasonic cleaner power 250W, frequency 25kHz, sonic oscillation filters after 30 minutes and rice husk is washed to neutrality, then 100 DEG C of dryings, obtain acid treatment rice husk, in described mixed acid solution, contain the tartrate of 4% citric acid and 5% by weight percentage;
C acid treatment rice husk adds in tube furnace by (), mixed gas is passed into the flow of per minute 20 milliliters, and heat up with the speed of per minute 5 DEG C, after being warming up to 550 DEG C, isothermal reaction obtains nano silicon in 2 hours, and described mixed gas to be made up of by volume oxygen and nitrogen at 9: 1;
(d) by nano silicon with etc. the magnesium powder of weight mix after be sealed in irony reactor, with isothermal reaction after the ramp to 600 of per minute 5 DEG C DEG C 2 hours, after being then cooled to room temperature, use 1molL -1hCl treatment removes magnesium chloride, then removes unreacted nano silicon by the hydrofluoric acid treatment that mass percent concentration is 5%, and after being washed to neutrality, under 60 DEG C and 0.5 normal atmosphere, vacuum-drying obtains nano-structure porous silicon electrode materials in 12 hours.
Fig. 1 is that the obtained nano silicon SEM of embodiment step (c) schemes, and as can be seen from this figure, the nanometer silicon dioxide material adopting the process of this patent method to obtain keeps better raw-material mesoporous characteristic.Fig. 2 is the EDAX energy spectrogram of nano silicon, illustrates that this method can obtain highly purified nano silicon.Fig. 3 is the SEM figure of the nano-structure porous silicon motor material that step (d) obtains, and the nano-structure porous silicon configuration obtained as can be seen from Fig. is very even.Fig. 4 is the TEM figure of nano-structure porous silicon electrode materials, more clearly can see the meso-hole structure of nano-structure porous silicon, have the feature of the regular order of arrangement mode and the uniformity consistency of aperture structure from TEM figure.
Embodiment 2:
A () is clean with distilled water flushing by the rice husk of 30 grams, then at 105 DEG C, be dried to constant weight, obtain dry rice husk;
B dry rice husk is put into beaker and is added the mixed acid solution of 500 parts by (), then container is placed in ultrasonic cleaner, ultrasonic cleaner power 250W, frequency 25kHz, sonic oscillation filters after 45 minutes and rice husk is washed to neutrality, then 105 DEG C of dryings, obtain acid treatment rice husk, in described mixed acid solution, contain the tartrate of 5% citric acid and 6% by weight percentage;
C acid treatment rice husk adds in tube furnace by (), mixed gas is passed into the flow of per minute 25 milliliters, and heat up with the speed of per minute 5 DEG C, after being warming up to 550 DEG C, isothermal reaction obtains nano silicon in 2 hours, and described mixed gas to be made up of by volume oxygen and nitrogen at 9: 1;
(d) by nano silicon with etc. the magnesium powder of weight mix after be sealed in irony reactor, with isothermal reaction after the ramp to 600 of per minute 5 DEG C DEG C 2 hours, after being then cooled to room temperature, use 0.5molL -1hCl treatment removes magnesium oxide, then removes unreacted nano silicon by the hydrofluoric acid treatment that mass percent concentration is 4%, and after being washed to neutrality, under 50 DEG C and 0.1 normal atmosphere, vacuum-drying obtains nano-structure porous silicon electrode materials in 10 hours.
Silicon-dioxide obtained by the present embodiment and nano-structure porous silicon spectral data substantially the same manner as Example 1.
Embodiment 3:
A () is clean with distilled water flushing by the rice husk of 25 grams, then at 103 DEG C, be dried to constant weight, obtain dry rice husk;
B dry rice husk is put into beaker and is added the mixed acid solution of 450 parts by (), then container is placed in ultrasonic cleaner, ultrasonic cleaner power 250W, frequency 25kHz, sonic oscillation filters after 30 minutes and rice husk is washed to neutrality, then 103 DEG C of dryings, obtain acid treatment rice husk, in described mixed acid solution, contain the tartrate of 4.5% citric acid and 5.5% by weight percentage;
C acid treatment rice husk adds in tube furnace by (), mixed gas is passed into the flow of per minute 22 milliliters, and heat up with the speed of per minute 5 DEG C, after being warming up to 550 DEG C, isothermal reaction obtains nano silicon in 2 hours, and described mixed gas to be made up of by volume oxygen and nitrogen at 9: 1;
(d) by nano silicon with etc. the magnesium powder of weight mix after be sealed in irony reactor, with isothermal reaction after the ramp to 600 of per minute 5 DEG C DEG C 2 hours, after being then cooled to room temperature, use 1.5molL -1hCl treatment removes magnesium oxide, then removes unreacted nano silicon by the hydrofluoric acid treatment that mass percent concentration is 6%, and after being washed to neutrality, vacuum-drying obtains nano-structure porous silicon electrode materials in 12 hours under 0.1 normal atmosphere at normal temperatures.
Silicon-dioxide obtained by the present embodiment and nano-structure porous silicon spectral data substantially the same manner as Example 1.
Embodiment 4:
The nano-structure porous silicon obtained to embodiment 1 carries out performance test, and test event is with obtained nano-structure porous silicon for negative material, and under the high current density of 1A/g, cycle charge-discharge 200 times, experimental result as shown in Figure 5.Result shows, and carry out 200 discharge and recharges under powerful current density like this after, last capacity still has 600mAh/g, is 2 times of graphite theoretical capacity.This result illustrates that the nano-structure porous silicon capacity that this technique obtains is large, and high rate performance is high, and service life cycle is long, is the negative material of excellent property.
As fully visible, biological waste rice husk is turned waste into wealth by the present invention, make full use of the porosity characteristic that rice husk self has, utilize mixed weak acids and ultrasonic wave to match to react under mild conditions, the foreign ion of abundant removal rice husk also ensures porous homogeneity by ultrasonic cavitation, eventually passes oxidation and nano-structure porous silicon electrode materials has been prepared in displacement.Nano-structure porous silicon capacity prepared by this technique is large, and high rate performance is high, and service life cycle is long, and this processing step is succinct simultaneously, is convenient to industrialization.

Claims (2)

1. a preparation technology for nano-structure porous silicon electrode materials, comprises the steps:
A the rice husk of 20 ~ 30 parts by weight washes by (), and dry at 100 ~ 105 DEG C, obtains dry rice husk;
B dry rice husk is put into container and is added the mixed acid solution of 400 ~ 500 parts by weight by (), then container is placed in ultrasonic cleaner, ultrasonic cleaner power 250W, frequency 25kHz, sonic oscillation filters after 30 ~ 45 minutes and rice husk is washed to neutrality, then 100 ~ 105 DEG C of dryings, obtain acid treatment rice husk, in described mixed acid solution, contain the tartrate of 4 ~ 5% citric acids and 5 ~ 6% by weight percentage;
C acid treatment rice husk adds in tube furnace by (), mixed gas is passed into the flow of per minute 20 ~ 25 milliliters, and heat up with the speed of per minute 5 DEG C, after being warming up to 550 DEG C, isothermal reaction obtains nano silicon in 2 hours, and described mixed gas to be made up of by volume oxygen and nitrogen at 9: 1;
(d) by nano silicon with etc. the magnesium powder of weight mix after be sealed in irony reactor, with isothermal reaction after the ramp to 600 of per minute 5 DEG C DEG C 2 hours, then magnesium oxide is removed with HCl treatment after being cooled to room temperature, remove unreacted nano silicon by hydrofluoric acid treatment again, be washed to neutral final vacuum drying and obtain nano-structure porous silicon electrode materials.
2. the preparation technology of nano-structure porous silicon electrode materials according to claim 1, is characterized in that, step (d) hydrochloric acid substance withdrawl syndrome used is 1molL -1, the mass percent concentration of hydrofluoric acid is 5%.
CN201510731316.2A 2015-10-26 2015-10-26 Preparation process of nano porous silicon electrode material Active CN105417543B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107742715A (en) * 2017-10-25 2018-02-27 山东大学 A kind of preparation method of lithium cell cathode material nano-structure porous silicon
CN112467125A (en) * 2020-12-29 2021-03-09 山东硅纳新材料科技有限公司 Method for preparing novel silicon-carbon negative electrode material by using rice hull ash

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JP2004300051A (en) * 2003-03-31 2004-10-28 Royal Industries Kk Fruit tree thinning agent and thinning method
CN101528601A (en) * 2006-10-27 2009-09-09 株式会社栗本铁工所 Amorphous silica and process for production thereof
CN103579596A (en) * 2013-11-08 2014-02-12 合肥国轩高科动力能源股份公司 Preparation method of lithium ion battery cathode material
CN103771392A (en) * 2014-02-09 2014-05-07 湘潭大学 Preparation method of shape-controllable ordered layer porous chromium carbide skeleton carbon material for supercapacitor
CN104009235A (en) * 2014-05-13 2014-08-27 昆明理工大学 Preparation method of porous silicon/graphene composite material
CN104518209A (en) * 2014-12-09 2015-04-15 江西正拓新能源科技股份有限公司 Lithium ion battery silicon composite material and preparation method thereof
CN104692388A (en) * 2013-12-05 2015-06-10 沈阳宜盛瓷新型材料有限公司 Method for preparing high-purity nanometer three-dimensional porous structure silicon from rice hulls
CN104787770A (en) * 2015-04-22 2015-07-22 哈尔滨工业大学 Method using circulating fluidized bed for rice hull organic acid pretreatment and combustion to prepare nanometer SiO2

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004300051A (en) * 2003-03-31 2004-10-28 Royal Industries Kk Fruit tree thinning agent and thinning method
CN101528601A (en) * 2006-10-27 2009-09-09 株式会社栗本铁工所 Amorphous silica and process for production thereof
CN103579596A (en) * 2013-11-08 2014-02-12 合肥国轩高科动力能源股份公司 Preparation method of lithium ion battery cathode material
CN104692388A (en) * 2013-12-05 2015-06-10 沈阳宜盛瓷新型材料有限公司 Method for preparing high-purity nanometer three-dimensional porous structure silicon from rice hulls
CN103771392A (en) * 2014-02-09 2014-05-07 湘潭大学 Preparation method of shape-controllable ordered layer porous chromium carbide skeleton carbon material for supercapacitor
CN104009235A (en) * 2014-05-13 2014-08-27 昆明理工大学 Preparation method of porous silicon/graphene composite material
CN104518209A (en) * 2014-12-09 2015-04-15 江西正拓新能源科技股份有限公司 Lithium ion battery silicon composite material and preparation method thereof
CN104787770A (en) * 2015-04-22 2015-07-22 哈尔滨工业大学 Method using circulating fluidized bed for rice hull organic acid pretreatment and combustion to prepare nanometer SiO2

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107742715A (en) * 2017-10-25 2018-02-27 山东大学 A kind of preparation method of lithium cell cathode material nano-structure porous silicon
CN107742715B (en) * 2017-10-25 2021-02-26 山东大学 Preparation method of lithium battery negative electrode material nano porous silicon
CN112467125A (en) * 2020-12-29 2021-03-09 山东硅纳新材料科技有限公司 Method for preparing novel silicon-carbon negative electrode material by using rice hull ash

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