CN104009211B - Preparation method for porous silicon nanofiber/carbon composite material - Google Patents
Preparation method for porous silicon nanofiber/carbon composite material Download PDFInfo
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- H01M4/00—Electrodes
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention relates to a preparation method for a porous silicon nanofiber/carbon composite material, and belongs to the technical field of lithium ion battery. The preparation method comprises the steps: firstly, carrying out acid dipping, water washing, filtration and drying on chrysotile asbestos to obtain a silica nanofiber having alkali metal oxide impurities removed; adding a reductive metal into the silica nanofiber, mixing evenly, then carrying out a reduction reaction to obtain a reduzate, carrying out pickling, water washing and drying on the reduzate to obtain a porous silicon nanofiber; and evenly mixing the obtained porous silicon nanofiber with a carbon precursor to obtain a mixed material, then dissolving the mixed material in a solvent, dispersing to obtain a mixed solution under an ultrasonic condition, and carrying out pyrolysis carbonization or hydrothermal carbonization of the dispersed mixed solution under the inert gas protection to obtain the porous silicon nanofiber/carbon composite material. The method takes natural minerals as raw materials, is low in cost and simple; and the porous silicon nanofiber/carbon composite material has the characteristics of large capacity density, high first-time Kulun efficiency, stable cyclic performance and the like.
Description
Technical field
The present invention relates to a kind of preparation method of porous silicon nanofiber/carbon composite, belongs to lithium ion battery technology
Field.
Background technology
With the fast development of electronics and information industry, mobile communication, digital vedio recording and portable computer are obtained extensively
Using the development and exploitation of, electric automobile also in carrying out extensively and profoundly, so as to drive for the said equipment provide the device of the energy-
Lithium ion battery is developed rapidly.Compare with nickel-cadmium cell with traditional Ni-MH battery, lithium ion battery has energy density high,
Operating voltage is high, self discharge is little, can fast charging and discharging, the advantages of have a safety feature, be current with fastest developing speed, market prospects the most
A kind of bright secondary cell.
At present lithium ion battery research and development it is important that exploitation high power capacity and high-power power-type lithium ion battery and battery
Group.Now the negative pole of business-like lithium ion battery is mainly using carbon such as MCMB, modified natural graphite, Delaniums
Material.But the theoretical capacity of these graphitic carbonaceous materials only has 372mAh/g, battery whole volume is strongly limit
Further lifted.In order to meet the demand of high-capacity lithium ion cell, height ratio capacity non-carbon lithium ion battery negative is researched and developed
Material has become very urgent and necessary.
In non-carbon negative material, the theoretical specific capacity of silicon is up to 4200mAh/g, be 11 times of graphite cathode material it
Many, its intercalation potential is in below 0.5V, and silicon rich reserves, with low cost on earth, becomes current most promising lithium
Ion battery cathode material.But silicon is in charge and discharge process, because the alloying reaction of removal lithium embedded causes larger volume
Expansion, and in charge and discharge process, constantly corroded by the hydrofluoric acid to be formed is reacted with electrolyte contacts by SEI films, cause
The irreversible capacity first of silicon is larger and capacity attenuation is very fast.In recent years, researcher is modified to silicon systems negative material,
Including the nanosizing to silicon, loose structure, carbon coating and alloying etc., the appearance of silicon systems negative material is improved to a certain extent
Amount and cycle performance.
One dimension nano silicon material has the diameter of nanoscale, as silicium cathode material, can significantly inhibit the body of material
Product change, reduces Lithium-ion embeding distance, so as to improve the electrochemistry cycle performance of material.Cui Y, et al. is with silane work
For silicon source, using gold as catalyst, the silicon nanowires by gas-liquid-solid growth process on stainless steel.Silicon nanowires has
The theoretical charging capacity of silicon, discharge capacity reaches 75%, capacity attenuation very little in cyclic process [Chan CK, Peng HL,
Liu G, McIlwrath K, Zhang XF, Huggins RA, Cui Y. High-performance lithium
battery anodes using silicon nanowires. Nature nanotechnology, 2008, 3: 31-
35.]。Yoo JK et al.[ Yoo JK, Kim J, Lee H, Choi J. Porous silicon nanowires
for lithium rechargeable batteries. Nanotechnology, 2013, 24: (2013) 424008
(7pp)] then with tetraethyl orthosilicate (TEOS) as raw material, nanometer two is prepared using the method for electrospinning method and then burning-off organic matter
Silicon oxide line, then magnesiothermic reduction prepares one-dimensional nano, bag carbon and prepares one-dimensional nano/carbon compound cathode materials.
The preparation that can be seen that one-dimensional nano from method made above is prepared using method " from bottom to top ", although
The sample purity for synthesizing is higher, but haves the shortcomings that process complexity, high cost.And using it is poisonous costly
Silicon precursor is used as silicon source.All these practical applications for being unfavorable for one-dimensional nano.
Natural material with nanometer composition has the characteristic such as wide material sources, with low cost, using nano material therein
Prepare novel nano structure have process is simple, it is with low cost the features such as.As in recent years with crops rice husk as raw material, it is utilized
In nano silicon by preparing porous silicon by magnesiothermic reduction, as lithium ion battery negative.Chrysotile (Mg6
[Si4O10](OH)8) be a kind of natural nanofiber, its draw ratio is big, rich flexibility, fire resisting, alkaline-resisting, wear-resisting, thermal conductivity factor
It is low, it is a kind of desirable material of manufacture heat-insulating material, while also being used as the filler of humidification.Chrysotile
Belong to silicates mineral, its crystal structure unit layer is made up of one layer of silicon-oxy tetrahedron and brucite octahedron.Due to
Elementary layer is asymmetric, techonosphere bend to be formed it is octahedra outside, tetrahedron is in interior socket columnar structure.Choysotile fiber
Between 16-56nm, interior Jing is in 3.5-24nm for external diameter.The substantial amounts of OH of chrysotile fiber surface-It is easy to H+React and cause
Mg2+It is exposed, in H+In the case of enough, also by complete dissolution, reaction equation is MgO：
Mg6[Si4O10](OH)8+12H+→6Mg2++4SiO2+10H2O。
The content of the invention
The problem existed for above-mentioned prior art and deficiency, the present invention provides a kind of porous silicon nanofiber/carbon and is combined
The preparation method of material.The choysotile that the present invention is prepared using method " from top to bottom ", with Natural Chrysotile as raw material,
The nanoscale choysotile fiber in field is seen by its intermediary of pickling, dissolution MgO therein obtains fibrous nano titanium dioxide
Silicon；Then fibrous nano silica, acidleach as obtained by metallothermic reduction, obtains porous silicon nanofiber.Using carbon
Presoma hydrothermal carbonization, pyrolysis carbonization or chemical gaseous phase depositing process, carbon coated is applied on the porous silicon nanofiber for obtaining
Layer, obtains porous silicon nanofiber/carbon composite, as lithium ion battery negative material.Method process is simple, the low cost
It is honest and clean, asbestos tailings will be recycled for asbestos mine, enterprise is realized and the sustainable development of mineral resources provides condition, the present invention
It is achieved through the following technical solutions.
A kind of preparation method of porous silicon nanofiber/carbon composite, it is comprised the following steps that：
（1）Obtain removing alkali metal oxide impurity by choysotile asbestos acidleach, washing, filtration and after being dried first
It is silica nano fibrous；
（2）To step（1）After the silica nano fibrous addition reducing metal for obtaining is well mixed, in anaerobic, temperature
Spend and obtain reduzate, reduzate Jing pickling, washing, drying to carry out reduction reaction 1h～7h under the conditions of 500 DEG C～900 DEG C
After prepare porous silicon nanofiber；
（3）Prepare porous silicon nanofiber/carbon composite：By step（2）The porous silicon nanofiber of gained and carbon
Presoma in mass ratio 1：0.05～5 is well mixed and obtains mixed material, according to liquid-solid ratio is then 1 by mixed material：30～
80g/ml is dissolved in solvent, and disperses 2～8h to obtain mixed liquor under ultrasound condition, and the mixed liquor after dispersion is protected in indifferent gas
The lower pyrolysis carbonization of shield or hydrothermal carbonization prepare porous silicon nanofiber/carbon composite.
The choysotile asbestos includes following mass percent component：Si19～35%, Mg19～25%, Fe0.13～
2.4%th, Al0.03～0.32%, O42～53%.
The step（1）The solid-to-liquid ratio of middle acidleach process is 1：30～80g/ml, extraction temperature is 80～100 DEG C, is leached
Time is 1.5～4h, and mixing speed is 400～700r/min, and acid dip solution is H+The hydrochloric acid of 0.5～2mol/L of concentration, sulfuric acid
Or nitric acid.
The step（2）In reducing metal be magnesium powder, aluminium powder, potassium, lithium, sodium or calcium particle, addition is by dioxy
The theoretical amount that silica is restored completely in SiClx nanofiber.
The step（2）In reduzate acid cleaning process be first with HCl, HNO that concentration is 5wt%～40wt%3Or
H2SO4Washing, then with the hydrofluoric acid wash of 0.5wt%～40wt%, wash temperature is 20 DEG C～100 DEG C, and wash time is 0.2h
～7h.
The step（3）In carbon presoma be glucose, sucrose, starch, pitch or phenolic resin.
The step（3）In solvent be water, acetone, tetrahydrofuran, polyvinyl alcohol or polyethylene glycol.
The step（3）In pyrolysis carbonization process conditions be 600～1300 DEG C of temperature, 2～20h of temperature retention time.
The step（3）In the technique of hydrothermal carbonization be that mixed liquor is added in reactor to make mixed liquor account for the reaction
The 50%～90% of kettle product, is then 180～220 DEG C of 12～48h of insulation hydrothermal temperature is controlled, and is consolidated Jing after separation of solid and liquid
Body, finally under controlled atmosphere, solid is carbonized under the conditions of 400～1000 DEG C 2～24h.
The step（3）Prepare porous silicon nanofiber/carbon composite pyrolysis carbonization or hydrothermal carbonization can by with
Lower step is replaced：Porous silicon nanofiber is put into first is connected with the stove of inert gas and carbon-source gas, 600～
1000 DEG C of 0.5～10h of pyrolysis, obtain porous silicon nanofiber/carbon composite of the Carbon deposition on porous silicon nanofiber, its
Middle carbon-source gas include acetylene, ethene, benzene vapor, toluene, methane, ethane, propane, butane or hexamethylene；The inert gas
Including nitrogen, argon gas and/or helium.
Any combinations of any of the above described Parameter Conditions value can realize the present invention, prepare porous silicon nanofiber/carbon
Composite.
The invention has the beneficial effects as follows：（1）In the method for preparing porous silicon nanofiber/carbon composite of the present invention,
Rich raw material resource, preparation technology are with low cost；（2）As lithium ion battery negative material, the porous silicon for preparing
Nanofiber/carbon composite has capacity density big, good rate capability, and first coulombic efficiency is high, the spy such as stable cycle performance
Point；（3）Nanometer titanium dioxide silica fibre is extracted in the invention from choysotile, initiates many by metallothermic reduction preparation with this fiber
Hole silicon nanofiber, and lithium ion battery negative material is applied to, widen the application of choysotile.
Specific embodiment
With reference to specific embodiment, the invention will be further described.
Embodiment 1
The preparation method of the porous silicon nanofiber/carbon composite, it is comprised the following steps that：
（1）Obtain removing alkali metal oxide impurity by 1g choysotile asbestos acidleach, washing, filtration and after being dried first
It is silica nano fibrous, wherein choysotile asbestos include following mass percent component：Si35%、Mg19%、Fe2.4%、
Al0.29%, O42.7%, the solid-to-liquid ratio of acidleach process is 1：30g/ml, extraction temperature is 96 DEG C, and extraction time is 127min, is stirred
It is 400r/min to mix speed, and acid dip solution is H+The hydrochloric acid of concentration 2mol/L；
（2）To step（1）After the silica nano fibrous addition reducing metal for obtaining is well mixed, in anaerobic, temperature
Spend and obtain reduzate to carry out reduction reaction 7h under the conditions of 550 DEG C, reduzate is prepared Jing pickling, washing, after being dried
Porous silicon nanofiber, wherein reducing metal are magnesium powder, and addition is that silica nano fibrous middle silica is complete
The theoretical amount for restoring；Reduzate acid cleaning process is first to be washed with the HCl that concentration is 40wt%, afterwards with the hydrogen fluorine of 0.5wt%
Acid elution, wash temperature is 20 DEG C, and wash time is 0.2h；
（3）Prepare porous silicon nanofiber/carbon composite：By step（2）Gained 0.1g porous silicons nanofiber with
The presoma of carbon in mass ratio 1：2 are well mixed and obtain mixed material, according to liquid-solid ratio are then 1 by mixed material:80g/ml
In being dissolved in solvent, and under ultrasound condition disperse 2h obtain mixed liquor, by the mixed liquor after dispersion under controlled atmosphere hydro-thermal
Carbonization prepares porous silicon nanofiber/carbon composite, and the wherein presoma of carbon is sucrose, and solvent is water；Hydrothermal carbonization
Technique be that mixed liquor is added in reactor make mixed liquor account for the reactor volume 50%, then control hydrothermal temperature
For 180 DEG C insulation 24h, solid is obtained Jing after separation of solid and liquid, finally under controlled atmosphere, by solid under the conditions of 400 DEG C carbon
Change 24h.
Using the porous silicon nanofiber/carbon composite of the preparation as the negative pole of lithium ion battery, and it is filled
Specific discharge capacity and cycle performance can be tested：1-dimention nano porous silicon and conductive agent, binding agent in mass ratio 8:1:1 is mixed
Working electrode pole piece, lithium metal is that, to electrode, electrolyte is EC, DEC and DMC (volume ratio 1:1:1) mixed liquor, 1M's
Used as electrolytic salt, barrier film is Celgard2400 to LiFP6, and in argon gas atmosphere glove box button cell is assembled into.Button cell
Charging/discharging voltage be 0.01V～1.4V (vs.Li+/Li), current density is 100mA/g.
Test result：The initial charge capacity of 1-dimention nano porous silicon is 1900mAh/g, and first coulombic efficiency is 80%, Jing
It is 1460mAh/g to cross charging capacity after 30 circulations.
Embodiment 2
The preparation method of the porous silicon nanofiber/carbon composite, it is comprised the following steps that：
（1）First by 10g choysotile asbestos acidleach, washing, filtration and obtain removal alkali metal oxide after being dried miscellaneous
Matter it is silica nano fibrous, wherein choysotile asbestos include following mass percent component：Si19%、Mg25%、
Fe1.6%、Al0.32%、O53%；The solid-to-liquid ratio of acidleach process is 1：60g/ml, extraction temperature is 80 DEG C, and extraction time is 3h, is stirred
It is 700r/min to mix speed, and acid dip solution is H+The hydrochloric acid of concentration 2mol/L；
（2）To step（1）After the silica nano fibrous addition reducing metal for obtaining is well mixed, in anaerobic, temperature
Spend and obtain reduzate to carry out reduction reaction 5h under the conditions of 600 DEG C, reduzate is prepared Jing pickling, washing, after being dried
Porous silicon nanofiber, wherein reducing metal are aluminium powder, and addition is that fiber silica in silica nanometer is complete
The theoretical amount for restoring；Reduzate acid cleaning process is first with the HNO that concentration is 5wt%3Washing, then with the hydrogen of 0.5wt%
Fluoric acid is washed, and wash temperature is 100 DEG C, and wash time is 7h；
（3）Prepare porous silicon nanofiber/carbon composite：By step（2）Gained 0.2g porous silicons nanofiber with
The presoma of carbon in mass ratio 1：2.5 are well mixed and obtain mixed material, according to liquid-solid ratio are then 1 by mixed material:30g/
Ml is dissolved in solvent, and disperses 8h to obtain mixed liquor under ultrasound condition, and the mixed liquor after dispersion is warm under controlled atmosphere
Solution carbonization prepares porous silicon nanofiber/carbon composite, and the wherein presoma of carbon is phenolic resin, and solvent is acetone；
Pyrolysis carbonization process conditions be 800 DEG C of temperature, temperature retention time 5h.
The Integration Assembly And Checkout of battery, test result are carried out according to identical method in embodiment 1：Porous silicon nanofiber/
The initial charge capacity of carbon composite is 1500mAh/g, and first coulombic efficiency is 83%, the charging capacity after 30 circulations
For 1230mAh/g.
Embodiment 3
The preparation method of the porous silicon nanofiber/carbon composite, it is comprised the following steps that：
（1）First by 10g choysotile asbestos acidleach, washing, filtration and obtain removal alkali metal oxide after being dried miscellaneous
Matter it is silica nano fibrous, wherein choysotile asbestos include following mass percent component：Si27%、Mg22%、
Fe1.3%、Al0.18%、O48%；The solid-to-liquid ratio of acidleach process is 1：60g/ml, extraction temperature is 90 DEG C, and extraction time is 4h, is stirred
It is 600r/min to mix speed, and acid dip solution is H+The sulfuric acid of concentration 0.5mol/L；
（2）To step（1）After the silica nano fibrous addition reducing metal for obtaining is well mixed, in anaerobic, temperature
Spend and obtain reduzate to carry out reduction reaction 3h under the conditions of 700 DEG C, reduzate is prepared Jing pickling, washing, after being dried
Porous silicon nanofiber, wherein reducing metal are magnesium powder, and addition is that silica nano fibrous middle silica is complete
The theoretical amount for restoring；Reduzate acid cleaning process is first with the H that concentration is 30wt%2SO4Washing, then with the hydrogen of 25wt%
Fluoric acid is washed, and wash temperature is 80 DEG C, and wash time is 5h；
（3）Prepare porous silicon nanofiber/carbon composite：By step（2）Gained 0.3g porous silicons nanofiber with
The presoma of carbon in mass ratio 1：5 are well mixed and obtain mixed material, according to liquid-solid ratio are then 1 by mixed material:55g/ml
In being dissolved in solvent, and disperse 5h to obtain mixed liquor under ultrasound condition, the mixed liquor after dispersion is pyrolyzed under controlled atmosphere
Carbonization prepares porous silicon nanofiber/carbon composite, and the wherein presoma of carbon is pitch, and solvent is tetrahydrofuran；Heat
Solution carbonization process conditions be 800 DEG C of temperature, temperature retention time 5h.
The Integration Assembly And Checkout of battery, test result are carried out according to identical method in embodiment 1：Porous silicon nanofiber/
The initial charge capacity of carbon composite is 1370mAh/g, and first coulombic efficiency is 84%, the charging capacity after 30 circulations
For 1130mAh/g.
Embodiment 4
The preparation method of the porous silicon nanofiber/carbon composite, it is comprised the following steps that：
（1）First by 10g choysotile asbestos acidleach, washing, filtration and obtain removal alkali metal oxide after being dried miscellaneous
Matter it is silica nano fibrous, wherein choysotile asbestos include following mass percent component：Si19.5%、Mg25.0%、
Fe1.6%、Al0.32%、O52.7%；The solid-to-liquid ratio of acidleach process is 1：40g/ml, extraction temperature is 80 DEG C, and extraction time is 3h,
Mixing speed is 600r/min, and acid dip solution is H+The sulfuric acid of concentration 1mol/L；
（2）To step（1）After the silica nano fibrous addition reducing metal for obtaining is well mixed, in anaerobic, temperature
Spend and obtain reduzate to carry out reduction reaction 6h under the conditions of 800 DEG C, reduzate is prepared Jing pickling, washing, after being dried
Porous silicon nanofiber, wherein reducing metal are lithium particle, and addition is that silica nano fibrous middle silica is complete
The theoretical amount for restoring entirely；Reduzate acid cleaning process is first to be washed with the HCl that concentration is 35wt%, then with the hydrogen of 10wt%
Fluoric acid is washed, and wash temperature is 60 DEG C, and wash time is 4h；
（3）Prepare porous silicon nanofiber/carbon composite：By step（2）The 1g porous silicons nanofiber and carbon of gained
Presoma in mass ratio 1：0.05 is well mixed and obtains mixed material, according to liquid-solid ratio is then 1 by mixed material:55g/ml
In being dissolved in solvent, and under ultrasound condition disperse 3h obtain mixed liquor, by the mixed liquor after dispersion under controlled atmosphere hydro-thermal
Carbonization prepares porous silicon nanofiber/carbon composite, and the wherein presoma of carbon is glucose, and solvent is polyethylene glycol；
The technique of hydrothermal carbonization is that mixed liquor is added in reactor make mixed liquor account for the reactor volume 90%, then in control
Hydrothermal temperature is 220 DEG C of insulation 48h, solid is obtained Jing after separation of solid and liquid, finally under controlled atmosphere, by solid at 500 DEG C
Under the conditions of be carbonized 4h.
The Integration Assembly And Checkout of battery, test result are carried out according to identical method in embodiment 1：Porous silicon nanofiber/
The initial charge capacity of carbon composite is 1800mAh/g, and first coulombic efficiency is 85%, the charging capacity after 30 circulations
For 1520mAh/g.
Embodiment 5
The preparation method of the porous silicon nanofiber/carbon composite, it is comprised the following steps that：
（1）Obtain removing alkali metal oxide impurity by choysotile asbestos acidleach, washing, filtration and after being dried first
Silica nano fibrous, wherein choysotile asbestos includes following mass percent component：Si19%、Mg20%、Fe0.13%、
Al0.03%、O53%；The solid-to-liquid ratio of acidleach process is 1：40g/ml, extraction temperature is 80 DEG C, and extraction time is 3h, mixing speed
For 600r/min, acid dip solution is H+The nitric acid of concentration 0.5mol/L；
（2）To step（1）After the silica nano fibrous addition reducing metal for obtaining is well mixed, in anaerobic, temperature
Spend and obtain reduzate to carry out reduction reaction 2.5h under the conditions of 700 DEG C, reduzate is prepared into Jing pickling, washing, after being dried
To porous silicon nanofiber, wherein reducing metal is k particle, and addition is by silica nano fibrous middle silica
The theoretical amount for restoring completely；Reduzate acid cleaning process is first with the H that concentration is 25wt%2SO4Washing, then uses 40wt%
Hydrofluoric acid wash, wash temperature be 80 DEG C, wash time is 6h；
（3）Prepare porous silicon nanofiber/carbon composite：By step（2）The 1g porous silicons nanofiber and carbon of gained
Presoma in mass ratio 1：4 are well mixed and obtain mixed material, according to liquid-solid ratio are then 1 by mixed material:55g/ml is molten
In solvent, and disperse 2h to obtain mixed liquor under ultrasound condition, the mixed liquor after dispersion is hydrolyzed into carbon under controlled atmosphere
Change prepares porous silicon nanofiber/carbon composite, and the wherein presoma of carbon is sucrose, and solvent is water, hydrothermal carbonization
Technique is that mixed liquor is added in reactor make mixed liquor account for the reactor volume 80%, is then controlling hydrothermal temperature
190 DEG C of insulation 12h, solid is obtained Jing after separation of solid and liquid, finally under controlled atmosphere, solid is carbonized under the conditions of 1000 DEG C
24h。
The Integration Assembly And Checkout of battery, test result are carried out according to identical method in embodiment 1：Porous silicon nanofiber/
The initial charge capacity of carbon composite is 2100mAh/g, and first coulombic efficiency is 85%, the charging capacity after 30 circulations
For 1770mAh/g.
Embodiment 6
The preparation method of the porous silicon nanofiber/carbon composite, it is comprised the following steps that：
（1）First by 10g choysotile asbestos acidleach, washing, filtration and obtain removal alkali metal oxide after being dried miscellaneous
Matter it is silica nano fibrous, wherein choysotile asbestos include following mass percent component：Si21%、Mg25.3%、
Fe0.13%、Al0.03%、O42%；The solid-to-liquid ratio of acidleach process is 1：40g/ml, extraction temperature is 70 DEG C, and extraction time is 3h,
Mixing speed is 500r/min, and acid dip solution is H+The nitric acid of concentration 1mol/L；
（2）To step（1）After the silica nano fibrous addition reducing metal for obtaining is well mixed, in anaerobic, temperature
Spend and obtain reduzate to carry out reduction reaction 1.5h under the conditions of 850 DEG C, reduzate is prepared into Jing pickling, washing, after being dried
To porous silicon nanofiber, wherein reducing metal is sodium particle, and it is that silica nano fibrous middle silica is complete to enter amount
The theoretical amount for restoring entirely；Reduzate acid cleaning process is first to be washed with the HCl that concentration is 10wt%, then with the hydrogen of 20wt%
Fluoric acid is washed, and wash temperature is 80 DEG C, and wash time is 5h；
（3）Prepare porous silicon nanofiber/carbon composite：By step（2）The porous silicon nanofiber of gained and carbon
Presoma in mass ratio 1：4 are well mixed and obtain mixed material, according to liquid-solid ratio are then 1 by mixed material:55g/ml is dissolved in
In solvent, and disperse 6h to obtain mixed liquor under ultrasound condition, the mixed liquor after dispersion is pyrolyzed under controlled atmosphere carbonization
Porous silicon nanofiber/carbon composite is prepared, the wherein presoma of carbon is glucose, and solvent is water, pyrolysis carbonization
Process conditions be 800 DEG C of temperature, temperature retention time 16h.
The Integration Assembly And Checkout of battery, test result are carried out according to identical method in embodiment 1：Porous silicon nanofiber/
The initial charge capacity of carbon composite is 1370mAh/g, and first coulombic efficiency is 84%, the charging capacity after 30 circulations
For 1130mAh/g.
Embodiment 7
The preparation method of the porous silicon nanofiber/carbon composite, it is comprised the following steps that：
（1）First by 10g choysotile asbestos acidleach, washing, filtration and obtain removal alkali metal oxide after being dried miscellaneous
Matter it is silica nano fibrous, wherein choysotile asbestos include following mass percent component：Si19.5%、Mg25.0%、
Fe1.6%、Al0.32%、O52.7%；The solid-to-liquid ratio of acidleach process is 1：80g/ml, extraction temperature is 100 DEG C, and extraction time is
1.5, mixing speed is 500r/min, and acid dip solution is H+The hydrochloric acid of concentration 1.5mol/L；
（2）To step（1）After the silica nano fibrous addition reducing metal for obtaining is well mixed, in anaerobic, temperature
Spend and obtain reduzate to carry out reduction reaction 1h under the conditions of 900 DEG C, reduzate is prepared Jing pickling, washing, after being dried
Porous silicon nanofiber, wherein reducing metal are calcium particle, and addition is that silica nano fibrous middle silica is complete
The theoretical amount for restoring entirely；Reduzate acid cleaning process is first with the HNO that concentration is 30wt%3Washing, then with 30wt%'s
Hydrofluoric acid wash, wash temperature is 80 DEG C, and wash time is 5h；
（3）Prepare porous silicon nanofiber/carbon composite：By step（2）Gained 0.1g porous silicons nanofiber with
The presoma of carbon in mass ratio 1：4 are well mixed and obtain mixed material, according to liquid-solid ratio are then 1 by mixed material：55g/ml
In being dissolved in solvent, and disperse 6h to obtain mixed liquor under ultrasound condition, the mixed liquor after dispersion is pyrolyzed under controlled atmosphere
Carbonization prepares porous silicon nanofiber/carbon composite, and the wherein presoma of carbon is starch, and solvent is water；Pyrolysis carbonization
Process conditions be 1300 DEG C of temperature, temperature retention time 2h.
The Integration Assembly And Checkout of battery, test result are carried out according to identical method in embodiment 1：Porous silicon nanofiber/
The initial charge capacity of carbon composite is 1500mAh/g, and first coulombic efficiency is 85%, the charging capacity after 30 circulations
For 1256mAh/g.
Embodiment 8
The preparation method of the porous silicon nanofiber/carbon composite, it is comprised the following steps that：
（1）Obtain removing alkali metal oxide impurity by choysotile asbestos acidleach, washing, filtration and after being dried first
Silica nano fibrous, wherein choysotile asbestos includes following mass percent component：Si19.5%、Mg25.0%、
Fe1.6%、Al0.32%、O52.7%；The solid-to-liquid ratio of acidleach process is 1：40g/ml, extraction temperature is 90 DEG C, and extraction time is 3h,
Mixing speed is 600r/min, and acid dip solution is H+The sulfuric acid of concentration 1mol/L；
（2）To step（1）After the silica nano fibrous addition reducing metal for obtaining is well mixed, in anaerobic, temperature
Spend and obtain reduzate to carry out reduction reaction 6h under the conditions of 500 DEG C, reduzate is prepared Jing pickling, washing, after being dried
Porous silicon nanofiber, wherein reducing metal are magnesium powder, and addition is that silica nano fibrous middle silica is complete
The theoretical amount for restoring；
（3）Prepare porous silicon nanofiber/carbon composite：By step（2）The porous silicon nanofiber of gained and carbon
Presoma in mass ratio 1：0.05 is well mixed and obtains mixed material, according to liquid-solid ratio is then 1 by mixed material:40g/ml is molten
In solvent, and under ultrasound condition disperse 4h obtain mixed liquor, by the mixed liquor after dispersion under controlled atmosphere pyrolytic carbon
Change prepares porous silicon nanofiber/carbon composite, and wherein solvent is polyvinyl alcohol；The process conditions of pyrolysis carbonization are temperature
600 DEG C of degree, temperature retention time 20h.
The Integration Assembly And Checkout of battery, test result are carried out according to identical method in embodiment 1：Porous silicon nanofiber/
The initial charge capacity of carbon composite is 2200mAh/g, and first coulombic efficiency is 80%, the charging capacity after 30 circulations
For 1700mAh/g.
Embodiment 9
The preparation method of the porous silicon nanofiber/carbon composite, it is comprised the following steps that：
（1）Obtain removing alkali metal oxide impurity by choysotile asbestos acidleach, washing, filtration and after being dried first
Silica nano fibrous, wherein choysotile asbestos includes following mass percent component：Si19.5%、Mg25.0%、
Fe1.6%、Al0.32%、O52.7%；The solid-to-liquid ratio of acidleach process is 1：40g/ml, extraction temperature is 90 DEG C, and extraction time is 3h,
Mixing speed is 600r/min, and acid dip solution is H+The sulfuric acid of concentration 1mol/L；
（2）To step（1）After the silica nano fibrous addition reducing metal for obtaining is well mixed, in anaerobic, temperature
Spend and obtain reduzate to carry out reduction reaction 6h under the conditions of 500 DEG C, reduzate is prepared Jing pickling, washing, after being dried
Porous silicon nanofiber, wherein reducing metal are magnesium powder, and addition is that silica nano fibrous middle silica is complete
The theoretical amount for restoring；
（3）Prepare porous silicon nanofiber/carbon composite：Porous silicon nanofiber is put into and is connected with nitrogen and acetylene gas
In the tube furnace of body, 0.5h is pyrolyzed at 600 DEG C, obtains porous silicon nanofiber/carbon of the Carbon deposition on porous silicon nanofiber
Composite.
The Integration Assembly And Checkout of battery, test result are carried out according to identical method in embodiment 1：Porous silicon nanofiber/
The initial charge capacity of carbon composite is 2000mAh/g, and first coulombic efficiency is 81%, the charging capacity after 30 circulations
For 1596mAh/g.
Embodiment 10
The preparation method of the porous silicon nanofiber/carbon composite, it is comprised the following steps that：
（1）Obtain removing alkali metal oxide impurity by choysotile asbestos acidleach, washing, filtration and after being dried first
Silica nano fibrous, wherein choysotile asbestos includes following mass percent component：Si19.5%、Mg25.0%、
Fe1.6%、Al0.32%、O52.7%；The solid-to-liquid ratio of acidleach process is 1：40g/ml, extraction temperature is 90 DEG C, and extraction time is 3h,
Mixing speed is 600r/min, and acid dip solution is H+The sulfuric acid of concentration 1mol/L；
（2）To step（1）After the silica nano fibrous addition reducing metal for obtaining is well mixed, in anaerobic, temperature
Spend and obtain reduzate to carry out reduction reaction 6h under the conditions of 500 DEG C, reduzate is prepared Jing pickling, washing, after being dried
Porous silicon nanofiber, wherein reducing metal are magnesium powder, and addition is that silica nano fibrous middle silica is complete
The theoretical amount for restoring；
（3）Prepare porous silicon nanofiber/carbon composite：Porous silicon nanofiber is put into and is connected with argon gas and methane gas
In the tube furnace of body, 10h is pyrolyzed at 1000 DEG C, obtains porous silicon nanofiber/carbon of the Carbon deposition on porous silicon nanofiber
Composite.
The Integration Assembly And Checkout of battery, test result are carried out according to identical method in embodiment 1：Porous silicon nanofiber/
The initial charge capacity of carbon composite is 1800mAh/g, and first coulombic efficiency is 80%, the charging capacity after 30 circulations
For 1410mAh/g.
Embodiment 11
The preparation method of the porous silicon nanofiber/carbon composite, it is comprised the following steps that：
（1）Obtain removing alkali metal oxide impurity by choysotile asbestos acidleach, washing, filtration and after being dried first
Silica nano fibrous, wherein choysotile asbestos includes following mass percent component：Si19.5%、Mg 25.0%、
Fe1.6%、Al0.32%、O52.7%；The solid-to-liquid ratio of acidleach process is 1：40g/ml, extraction temperature is 90 DEG C, and extraction time is 3h,
Mixing speed is 600r/min, and acid dip solution is H+The sulfuric acid of concentration 1mol/L；
（2）To step（1）After the silica nano fibrous addition reducing metal for obtaining is well mixed, in anaerobic, temperature
Spend and obtain reduzate to carry out reduction reaction 6h under the conditions of 500 DEG C, reduzate is prepared Jing pickling, washing, after being dried
Porous silicon nanofiber, wherein reducing metal are magnesium powder, and addition is that silica nano fibrous middle silica is complete
The theoretical amount for restoring；
（3）Prepare porous silicon nanofiber/carbon composite：Porous silicon nanofiber is put into and is connected with helium and toluene steaming
In the tube furnace of gas, 5h is pyrolyzed at 800 DEG C, obtains porous silicon nanofiber/carbon of the Carbon deposition on porous silicon nanofiber multiple
Condensation material.
The Integration Assembly And Checkout of battery, test result are carried out according to identical method in embodiment 1：Porous silicon nanofiber/
The initial charge capacity of carbon composite is 1900mAh/g, and first coulombic efficiency is 82%, the charging capacity after 30 circulations
For 1525mAh/g.
Embodiment 12
The preparation method of the porous silicon nanofiber/carbon composite, it is comprised the following steps that：
（1）Obtain removing alkali metal oxide impurity by choysotile asbestos acidleach, washing, filtration and after being dried first
Silica nano fibrous, wherein choysotile asbestos includes following mass percent component：Si19.5%、Mg25.0%、
Fe1.6%、Al0.32%、O52.7%；The solid-to-liquid ratio of acidleach process is 1：40g/ml, extraction temperature is 90 DEG C, and extraction time is 3h,
Mixing speed is 600r/min, and acid dip solution is H+The sulfuric acid of concentration 1mol/L；
（2）To step（1）After the silica nano fibrous addition reducing metal for obtaining is well mixed, in anaerobic, temperature
Spend and obtain reduzate to carry out reduction reaction 6h under the conditions of 500 DEG C, reduzate is prepared Jing pickling, washing, after being dried
Porous silicon nanofiber, wherein reducing metal are magnesium powder, and addition is that silica nano fibrous middle silica is complete
The theoretical amount for restoring；
（3）Prepare porous silicon nanofiber/carbon composite：Porous silicon nanofiber is put into and is connected with helium and propane flammable gas
In the tube furnace of body, 0.5h is pyrolyzed at 900 DEG C, obtains porous silicon nanofiber/carbon of the Carbon deposition on porous silicon nanofiber
Composite.
The Integration Assembly And Checkout of battery, test result are carried out according to identical method in embodiment 1：Porous silicon nanofiber/
The initial charge capacity of carbon composite is 1700mAh/g, and first coulombic efficiency is 87%, the charging capacity after 30 circulations
For 1460mAh/g.
Embodiment 13
The preparation method of the porous silicon nanofiber/carbon composite, it is comprised the following steps that：
（1）Obtain removing alkali metal oxide impurity by choysotile asbestos acidleach, washing, filtration and after being dried first
Silica nano fibrous, wherein choysotile asbestos includes following mass percent component：Si19.5%、Mg25.0%、
Fe1.6%、Al0.32%、O52.7%；The solid-to-liquid ratio of acidleach process is 1：40g/ml, extraction temperature is 90 DEG C, and extraction time is 3h,
Mixing speed is 600r/min, and acid dip solution is H+The sulfuric acid of concentration 1mol/L；
（2）To step（1）After the silica nano fibrous addition reducing metal for obtaining is well mixed, in anaerobic, temperature
Spend and obtain reduzate to carry out reduction reaction 6h under the conditions of 500 DEG C, reduzate is prepared Jing pickling, washing, after being dried
Porous silicon nanofiber, wherein reducing metal are magnesium powder, and addition is that silica nano fibrous middle silica is complete
The theoretical amount for restoring；
（3）Prepare porous silicon nanofiber/carbon composite：Porous silicon nanofiber is put into and is connected with argon gas and ethylene gas
In the tube furnace of body, 10h is pyrolyzed at 600 DEG C, obtains porous silicon nanofiber/carbon of the Carbon deposition on porous silicon nanofiber multiple
Condensation material.
The Integration Assembly And Checkout of battery, test result are carried out according to identical method in embodiment 1：Porous silicon nanofiber/
The initial charge capacity of carbon composite is 1850mAh/g, and first coulombic efficiency is 86.5%, charges after 30 circulations and holds
Measure as 1576mAh/g.
Claims (10)
1. a kind of preparation method of porous silicon nanofiber/carbon composite, it is characterised in that comprise the following steps that：
（1）Obtain removing the dioxy of alkali metal oxide impurity first by choysotile asbestos acidleach, washing, filtration and after being dried
SiClx nanofiber；
（2）To step（1）After the silica nano fibrous addition reducing metal for obtaining is well mixed, it is in anaerobic, temperature
Reduction reaction 1h～7h is carried out under the conditions of 500 DEG C～900 DEG C and obtains reduzate, reduzate is made Jing pickling, washing, after being dried
It is standby to obtain porous silicon nanofiber；
（3）Prepare porous silicon nanofiber/carbon composite：By step（2）The porous silicon nanofiber of gained and the forerunner of carbon
Body in mass ratio 1：0.05～5 is well mixed and obtains mixed material, according to liquid-solid ratio is then 1 by mixed material：30～80g/
Ml is dissolved in solvent, and disperses 2～8h to obtain mixed liquor under ultrasound condition, by the mixed liquor after dispersion under controlled atmosphere
Pyrolysis carbonization or hydrothermal carbonization prepare porous silicon nanofiber/carbon composite.
2. the preparation method of porous silicon nanofiber/carbon composite according to claim 1, it is characterised in that：It is described
Choysotile asbestos includes following mass percent component：Si19～35%, Mg19～25%, Fe0.13～2.4%, Al0.03～
0.32%th, O42～53%.
3. the preparation method of porous silicon nanofiber/carbon composite according to claim 1, it is characterised in that：It is described
Step（1）The solid-to-liquid ratio of middle acidleach process is 1：30～80g/ml, extraction temperature be 80～100 DEG C, extraction time be 1.5～
4h, mixing speed is 400～700r/min, and acid dip solution is H+The hydrochloric acid of 0.5～2mol/L of concentration, sulfuric acid or nitric acid.
4. the preparation method of porous silicon nanofiber/carbon composite according to claim 1, it is characterised in that：It is described
Step（2）In reducing metal be magnesium powder, aluminium powder, potassium, lithium, sodium or calcium particle, addition is will be silica nano fibrous
The theoretical amount that middle silica is restored completely.
5. the preparation method of porous silicon nanofiber/carbon composite according to claim 1, it is characterised in that：It is described
Step（2）In reduzate acid cleaning process be first with HCl, HNO that concentration is 5wt%～40wt%3Or H2SO4Washing, Ran Houyong
The hydrofluoric acid wash of 0.5wt%～40wt%, wash temperature is 20 DEG C～100 DEG C, and wash time is 0.2h～7h.
6. the preparation method of porous silicon nanofiber/carbon composite according to claim 1, it is characterised in that：It is described
Step（3）In carbon presoma be glucose, sucrose, starch, pitch or phenolic resin.
7. the preparation method of porous silicon nanofiber/carbon composite according to claim 1, it is characterised in that：It is described
Step（3）In solvent be water, acetone, tetrahydrofuran, polyvinyl alcohol or polyethylene glycol.
8. the preparation method of porous silicon nanofiber/carbon composite according to claim 1, it is characterised in that：It is described
Step（3）In pyrolysis carbonization process conditions be 600～1300 DEG C of temperature, 2～20h of temperature retention time.
9. the preparation method of porous silicon nanofiber/carbon composite according to claim 1, it is characterised in that：It is described
Step（3）In the technique of hydrothermal carbonization be that mixed liquor is added in reactor make mixed liquor account for the reactor volume 50%
～90%, it is then 180～220 DEG C of 12～48h of insulation hydrothermal temperature is controlled, solid is obtained Jing after separation of solid and liquid, finally lazy
Under property gas shielded, solid is carbonized under the conditions of 400～1000 DEG C 2～24h.
10. the preparation method of porous silicon nanofiber/carbon composite according to claim 1, it is characterised in that：It is described
Step（3）Prepare porous silicon nanofiber/carbon composite to be replaced by following steps：First by porous silicon nanofiber
It is put into and is connected with the stove of inert gas and carbon-source gas, at 600～1000 DEG C 0.5～10h is pyrolyzed, obtains Carbon deposition in porous silicon
Porous silicon nanofiber/carbon composite on nanofiber.
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| CN113571685B (en) * | 2021-06-11 | 2022-10-28 | 信骅(上海)器材有限公司 | Preparation process of high-performance lithium ion battery silicon negative electrode material using serpentine powder and graphene |
| CN115092924B (en) * | 2022-07-22 | 2023-08-18 | 中南大学 | Serpentine-derived porous silicon nano-sheet negative electrode active material, preparation thereof and application thereof in lithium ion battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| GB2464158B (en) * | 2008-10-10 | 2011-04-20 | Nexeon Ltd | A method of fabricating structured particles composed of silicon or a silicon-based material and their use in lithium rechargeable batteries |
| CN102352435A (en) * | 2011-10-27 | 2012-02-15 | 中南大学 | Efficient leaching technology of metal ions in chrysotile nanofiber |
| CN102969489B (en) * | 2012-12-05 | 2016-08-17 | 奇瑞汽车股份有限公司 | A kind of Si-C composite material and preparation method thereof, lithium ion battery containing this material |
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