CN110085811A - SiOx/ carbon composite and preparation method thereof, lithium ion battery - Google Patents
SiOx/ carbon composite and preparation method thereof, lithium ion battery Download PDFInfo
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- CN110085811A CN110085811A CN201810342260.5A CN201810342260A CN110085811A CN 110085811 A CN110085811 A CN 110085811A CN 201810342260 A CN201810342260 A CN 201810342260A CN 110085811 A CN110085811 A CN 110085811A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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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- 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
- H01M4/362—Composites
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- 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 present invention provides a kind of SiOxThe preparation method of/carbon composite, the following steps are included: under ball milling condition, silica and magnesium powder are subjected to ball-milling treatment, make silica and magnesium powder that magnesium thermit occur, then washed into detection eluate using hydrochloric acid without magnesium ion, it adopts and is washed with deionized to neutrality again, obtain SiOx；By SiOx, lignin, source of iron and organic solvent carry out mixing and ultrasonic treatment, obtain SiOx/ carbon precursor；By SiOx/ carbon precursor, which is placed in reducing atmosphere, carries out calcination processing, and source of iron is made to be reduced to iron, while iron is to playing catalytic action in the carbonisation of lignin, it is improved lignin degree of graphitization in carbonization, and iron is removed to carrying out washing treatment several times is carried out using acid solution, obtain SiOx/ carbon composite.The SiO that this method obtainsxThe chemical property of lithium ion battery can be improved in/carbon composite.
Description
Technical field
The invention belongs to lithium ion battery material technical fields, and in particular to a kind of SiOx/ carbon composite and its preparation
Method, lithium ion battery.
Background technique
Silicon is due to it has the characteristics that height ratio capacity (room temperature theoretical specific capacity 3580mAh/g), low de- lithium current potential, low cost
It is believed to the negative electrode material as next-generation lithium ion cell electrode.However, the scale use of silicium cathode material should solve
Two critical issues: (a) silicon particle causes in removal lithium embedded along with the expansion of volume and contraction (shrinking percentage is more than 300%)
Granule atomization, fall off and chemical property failure；(b) continued propagation of silicon particle surface solid electrolyte layer (SEI) is led
Cause the irreversible consumption of electrolyte and the lithium source from anode.The method for solving the above problem of silicium cathode material at present is main
It is by preparing Si-C composite material cathode.In Si-C composite material, silicon provides capacity mainly as active material；Carbon materials
Expect that the effect in charge and discharge process includes: (1) buffering and adjusts the variation of silicon active material volume, to prevent electrode material
It dusting and falls off；(2) movement that high conductivity promotes electronics and ion is provided；(3) active electrode material and electrolyte are reduced
Contact area forms stable SEI film at electrode/electrolyte interface, to improve the cyclical stability of material and reduce for the first time
Irreversible capacity.The preparation method of current existing Si-C composite material cathode, generallys use ball milling mixing nano silicon particles, stone
Ink and organic carbon source, by its fully dispersed rear heat treatment, effectively to solve silicon nanoparticle since granularity is small, surface energy Gao Ercun
Easily reunite the problems such as.In contrast, SiOx material has smaller compared to pure Si while playing height ratio capacity
Volume change, thus the more practical potentiality in terms of cycle life.
Industrial SiOxThe production of material is mainly by Si and SiO2It is deposited under high temperature high vacuum and (abbreviation vapor phase method) is made.
In addition to using Si and SiO2Outside for raw material, Si and O2、SiO2It also can be used as vapor phase method production SiO with CxRaw material；Synthesis atmosphere is removed
Outside using vacuum, inert atmosphere or mixed atmosphere also can be used, but all there is the disadvantages of high energy consumption high risk high cost.
Application No. is 200810005625.1 Chinese invention patents to disclose a kind of negative electrode active based on silicon oxide sio x
Material and preparation method thereof is reacted particular by silane compound with lithium, prepares silica precursors, while in inert atmosphere
Lower sintering silica precursors need before silica precursors are sintered, in order to obtain the negative electrode active material containing carbon by carbonaceous
Material or carbon precursor are added in silica precursors, and this method and process is cumbersome, and energy consumption is high, and by the silicon oxide sioxCathode it is living
Property material be used in lithium ion battery in when, the capacity for the first time of lithium ion battery only has 900mAh/g or so, 50 circulation volumes
Conservation rate is 85% and hereinafter, capacity attenuation is very fast.
Application No. is 200810001626.9 Chinese invention patent disclose a kind of negative electrode active material, preparation method and
Cathode and lithium battery containing the material.Specifically using hydrogen silsesquioxane as raw material, calcined under an inert atmosphere to obtain cathode
Active material before calcining hydrogen silsesquioxane, needs that carbon is added thereto to obtain the negative electrode active material containing carbon
Material or carbonaceous material precursor.When the negative electrode active material is used in lithium ion battery, the capacity for the first time of lithium ion battery
Only 900mAh/g or so, 30 circulation volume conservation rates are 65% or so, and capacity attenuation is very fast, poor circulation.
Summary of the invention
Cumbersome for current silicon-carbon cathode material preparation process, capacity is low for the first time when for lithium ion battery, and capacity
The problems such as decaying is fast, poor circulation, the present invention provides a kind of SiOx/ carbon composite and preparation method thereof.
Further, the present invention also provides include SiO of the present inventionxThe lithium ion battery of/carbon composite.
For achieving the above object, technical scheme is as follows:
A kind of SiOxThe preparation method of/carbon composite, at least includes the following steps:
Step S01. carries out ball-milling treatment under ball milling condition, by silica and magnesium powder, makes the silica and magnesium
Magnesium thermit occurs for powder, and ball milling terminates, and is washed into detection eluate using hydrochloric acid without magnesium ion, then use deionized water
Washing obtains SiO to neutralityx；
Step S02. is by SiOx, lignin, source of iron and organic solvent carry out mixing and ultrasonic treatment, obtain SiOxBody before/carbon
Body；
Step S03. is by the SiOx/ carbon precursor, which is placed in reducing atmosphere, carries out calcination processing, is reduced source of iron
For iron, while the iron makes lignin graphitization in carbonization to catalytic action is played in the carbonisation of the lignin
Degree is improved, and is removed the iron to carrying out washing treatment several times is carried out using acid solution, obtains SiOx/ carbon composite wood
Material；
Wherein, the SiOxIn 0≤x < 2.
Correspondingly, a kind of SiOx/ carbon composite, the SiOx/ carbon composite is the nano material of core-shell structure, institute
Stating core part is with porous SiOx, the shell parts are amorphous carbon layer, and the amorphous carbon is filled in the SiOx's
In hole, the SiOx/ carbon composite is prepared using preparation method as described above.
Further, a kind of lithium ion battery, including negative electrode active material, the negative electrode active material are as described above
The SiO of preparation method preparationx/ carbon composite.
Technical effect of the invention are as follows: compared with the existing technology, the SiO of the above-mentioned offer of the present inventionxThe system of/carbon composite
Preparation Method is coated on porous SiO using lignin as carbon sourcexSurface, and be filled in inside hole, make under reducing atmosphere
At " island " particle Nanoscale Iron, lignin occurs source of iron growth in situ for the iron of formation to be graphitized catalysis work in carbonisation
With, the degree of graphitization of the amorphous carbon layer of formation is improved, the resource utilization of lignin is on the one hand realized, it is on the other hand wooden
Quality can be avoided SiO when carbonization determines carbon at the nothing with degree of graphitizationxReunion, and cover all SiOx, with
Avoid its exposed, to improve chemical property of the silicon carbon material in lithium ion battery.In addition, the technique letter of this preparation method
It is single, it is low for equipment requirements, it is suitble to large-scale production.
The SiO of above method preparation of the present inventionx/ carbon composite, the mixture containing silicon such as silicon, silica, and these
Mixture is evenly dispersed without reuniting, and SiOxSurface cladding have certain degree of graphitization amorphous carbon layer and
SiOxHole in equally be filled with certain degree of graphitization amorphous carbon so that SiOx/ carbon composite is relative to single silicon
The electric conductivity of material is improved, and the presence that graphited amorphous carbon layer occurs makes SiOxCompletely cut off completely with extraneous,
By the SiOxWhen/carbon composite is as lithium ion battery anode active material, on the one hand, SiOxIt can not directly be connect with electrolyte
On the other hand touching since the content of pure silicon reduces, significantly reduces expansion rate, silicon-based anode active material is effectively relieved
Pulverizing problem, and the SEI film that negative terminal surface is formed is attached directly to carbon-coating surface, so that SEI is stabilized, finally improves battery
Coulombic efficiency for the first time and cyclical stability.
Lithium ion battery provided by the invention, since negative electrode active material uses SiO prepared by the present inventionx/ carbon composite wood
Material, SiOxSurface cladding has the amorphous carbon layer and SiO of certain degree of graphitizationxHole in equally be filled with certain stone
The amorphous carbon of blackization degree, so that SiOx/ carbon composite is improved relative to the electric conductivity of single silicon materials, and is sent out
The presence of raw graphited amorphous carbon layer makes SiOxCompletely cut off completely with extraneous, by the SiOx/ carbon composite is as lithium ion
When battery cathode active material, on the one hand, SiOxIt can not directly and electrolyte contacts, on the other hand, since the content of pure silicon drops
It is low, expansion rate is significantly reduced, is effectively relieved the pulverizing problem of silicon-based anode active material, and the SEI that negative terminal surface is formed
Film is attached directly to carbon-coating surface, so that SEI is stabilized, the final coulombic efficiency for the first time and cyclical stability for improving battery.
Detailed description of the invention
It to describe the technical solutions in the embodiments of the present invention more clearly, below will be to needed in the embodiment
Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for ability
For the those of ordinary skill of domain, without creative efforts, it can also be obtained according to these attached drawings other attached
Figure.
Fig. 1 is the SiO that the embodiment of the present invention 1 obtainsxTEM figure；
Fig. 2 is SiO prepared by the embodiment of the present invention 2xThe TEM of/carbon composite schemes；
Fig. 3 is the SiO obtained in the embodiment of the present invention 1xEDS Elemental redistribution scanning figure；
Fig. 4 is SiO prepared by the embodiment of the present invention 2 and comparative example 1xThe Raman spectrogram of/carbon composite；
Fig. 5 is the SiO that step S02 is obtained in the embodiment of the present invention 1xCirculation as lithium ion battery anode active material
Curve and coulombic efficiency curve graph；
Fig. 6 is SiO prepared by the embodiment of the present invention 2 and comparative example 1x/ carbon composite is living as negative electrode of lithium ion battery
Property material and the cyclic curve and coulombic efficiency curve graph for being assembled into lithium ion battery.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, not
For limiting the present invention.
In the present invention, lignin occur charing generate amorphous carbon when, due to the catalytic action of iron, generation it is amorphous
Carbon is graphitized, therefore SiO of the present inventionxIn/carbon composite, it is coated on SiOxThe carbon on surface is with certain graphitization journey
The amorphous carbon of degree has higher electric conductivity relative to amorphous carbon.
Present example provides a kind of SiOxThe preparation method of/carbon composite, at least includes the following steps:
Step S01. carries out ball-milling treatment under ball milling condition, by silica and magnesium powder, makes the silica and magnesium
Magnesium thermit occurs for powder, and ball-milling treatment terminates, and is washed into detection eluate using hydrochloric acid without magnesium ion, and using go from
Sub- water washing obtains SiO to neutralityx；
Step S02. is by SiOx, lignin, source of iron and organic solvent carry out mixing and ultrasonic treatment, obtain SiOxBody before/carbon
Body；
Step S03. is by the SiOx/ carbon precursor, which is placed in reducing atmosphere, carries out calcination processing, is reduced source of iron
For iron, while the iron makes lignin graphitization in carbonization to catalytic action is played in the carbonisation of the lignin
Degree is improved, and is removed the iron to carrying out washing treatment several times is carried out using acid solution, obtains SiOx/ carbon composite wood
Material；
Wherein, the SiOxIn 0≤x < 2.
Technical solution of the present invention is further explained in detail below.
The silica of one of raw material of the present invention, can be diatomite, sea sand and other main components is silica
Material.By carrying out ball milling with magnesium powder, the SiO of Nano grade is obtainedx.The SiOxFor a kind of mixture, contain silicon, silica
The compound of equal silicon, and in dilute hydrochloric acid washing process, the compound for the magnesium being mixed therein is removed, and is formed with porous
The SiO of structurex。
Preferably, in mass ratio for the ingredient proportion of the silica and magnesium powder is (0.5~2): 1.
Preferably, during ball-milling treatment, the diameter of ball milling pearl is 0.5~10mm, and ratio of grinding media to material is 5:1~50:1.
Preferably, the time of ball-milling treatment is 30min~5h, and Ball-milling Time is too short, and temperature is not achieved needed for magnesium thermit
The temperature wanted, and Ball-milling Time is too long, can not finally form porous structure.
In above-mentioned steps S01, ball milling is obtained containing SiOx, unreacted silica, magnesium powder, Mg2SiO4Or Mg2Si etc.
Equal mixtures.
The concentration of hydrochloric acid for washing is 0.5~5mol/L, washes off unreacted magnesium powder, Mg by hydrochloric acid2SiO4Or
Mg2Si etc..It there is a need to be dried after washing to neutrality.
The target product of above-mentioned steps S01 is SiOx, and 0≤x < 2.
Preferably, it is wooden to can be alkali lignin, lignosulfonates, sulfonation alkali for one of raw material of the invention lignin
Element, sulfonation enzymolysis xylogen, carboxylated alkali lignin, carboxylated enzymolysis xylogen, ammonium choline lignin, ammonium enzymolysis xylogen
At least one of.Used lignin is finally carbonized into amorphous carbon, but also can adulterate the elements such as nitrogen.
Preferably, source of iron is the carbonization of ferrous salt perhaps molysite ferrous salt or molysite itself not Catalytic lignin, still
Ferrous salt or molysite are reduced to the iron of Nano grade under the action of reducibility gas, and growth in situ is in SiOxTable
Face (surface here includes in outer surface and hole), and be distributed in " island ", it can be used as lignin conversion Cheng Wuding
The catalytic media that degree of graphitization is improved when shape carbon.Certainly, it is not limited to which ferrous salt or molysite can also be other
Source of iron is uniformly mixed, and can be gone back under reducing atmosphere as long as can be mutually dissolved with other raw materials of the invention
Original belongs to source of iron of the invention.
It is further preferred that ferrous salt is any one of frerrous chloride, ferrous sulfate, certainly since ferrous sulfate is easy
Water suction, so being added generally in the form of ferrous sulfate heptahydrate；Or molysite is ferric nitrate.With chloride ion or sulfate ion
Or SiO is being made as subsidiary ion in nitrate ionxWhen/carbon composite, it is easy to be eluted；And it is a small amount of remaining
Ion will not be to SiOxThe chemical property of/carbon composite has a negative impact.Certainly source of iron of the invention is not limited to
It states and enumerates several, can also be that other can be reduced to the source of iron of iron.
Preferably, organic solvent is any one of the mixed solvent of tetrahydrofuran and ethyl alcohol, tetrahydrofuran.This several class has
Solvent can evaporate the favorable solubility of lignin, source of iron at slightly higher temperature.
Preferably, equipment used in being ultrasonically treated can be ultrasonic cell disruptor, and it is common super to be also possible to other
Acoustic equipment, ultrasonic purpose is mainly so that SiOxIt is evenly dispersed, and uniformly coated for lignin.
In step S02, including removal organic solvent, specific removing method mainly using heat be evaporated by the way of,
Stirring at normal temperature can be used, so that organic solvent volatilizees under state of disturbance.
Preferably, the reducibility gas that the reducing atmosphere is related to is hydrogen, the mixture of hydrogen and argon gas, an oxidation
Any one of carbon, hydrogen sulfide, methane.Iron ion or ferrous ion under the action of above-mentioned reducibility gas, in source of iron
It is reduced, and lignin is made effectively to be converted into the amorphous carbon that degree of graphitization improves.
Preferably, the calcination temperature is 600~900 DEG C, and at such a temperature, lignin is carbonized, and is changed into without fixed
Shape carbon, and the catalytic action of iron is combined, newly-generated amorphous carbon degree of graphitization improves, so that being coated on porous SiOx
Amorphous carbon degree of graphitization with higher in surface and hole, since the graphite of higher degree occurs for amorphous carbon
Change, so that SiOxThe electric conductivity of/carbon composite is improved.
In a preferred embodiment, it is the iron: silicon=1:(40~200 according to atomic ratio), it is described according to mass ratio
Lignin: SiOx: organic solvent=(0.5~2): 1:(100~500).Calcining terminates, and is carried out by the way of natural cooling cold
But.It is cooled to room temperature, with acid solution to the SiO of acquisitionx/ carbon composite carries out carrying out washing treatment.Acid solution is by iron from SiOx/ carbon is multiple
It is eluted in condensation material, iron is avoided to remain in carbon coating layer.
Preferably, the acid solution is any one of dilute sulfuric acid, dilute hydrochloric acid, dust technology.Dilute sulfuric acid, dilute hydrochloric acid, dust technology
Any one of chemically reacted with the iron simple substance on carbon coating layer, so that it is become ferrous ion and dissolve into dilute hydrochloric acid or dilute sulphur
In acid or dust technology, to achieve the purpose that elution.
And due to using acid solution to SiOxWhen/carbon composite is eluted, SiOx/ carbon composite becomes acid, can not
It uses, in order to enable it can be used as ion cathode material lithium, it further include using deionized water to the SiO after acid solution washingx/ carbon
Composite material is cleaned repeatedly, and cleaning to eluate is in neutrality, then it is assumed that SiOx/ carbon composite reaches the matter that can be used
Amount standard.
The SiO of the above-mentioned offer of the present inventionxThe preparation method of/carbon composite is coated on porous using lignin as carbon source
SiOxSurface, form core-shell structure, and carbon source is filled in porous SiOxHole inside, make source of iron former under reducing atmosphere
Position grows into " island " particle Nanoscale Iron, and the iron of formation occurs lignin to be graphitized catalytic action in carbonisation, mention
The degree of graphitization for the amorphous carbon layer that height is formed, on the one hand realizes the resource utilization of lignin, another aspect lignin
When carbonization determines carbon at the nothing with degree of graphitization, SiO can be avoidedxReunion, and cover all SiOx, to avoid
Its is exposed, to improve chemical property of the silicon carbon material in lithium ion battery.In addition, this preparation method simple process, right
Equipment requirement is low, is suitble to large-scale production.
The SiO prepared by above-mentioned preparation methodx/ carbon composite is the nano material of porous core-shell structure, described
Core part is the SiO with porous structurex, the shell parts are amorphous carbon layer, and the amorphous carbon is also filled up in described
SiOxHole in.
In specific lithium ion battery applications, and specific lithium ion battery is including anode, cathode and for being isolated
The diaphragm of the anode and cathode, the cathode includes negative current collector and the cathode for being adhered to the negative current collector surface
Material, the negative electrode material include negative electrode active material, cathode conductive agent, binder, and the negative electrode active material is the present invention
SiOxThe SiO of the preparation method preparation of/carbon compositex/ carbon composite.
Preferably, the cathode conductive agent be acetylene black, Super P, carbon nanotube, be also possible to other suitable for lithium from
The conductive agent of sub- battery.
Preferably, the negative current collector is copper foil.
The diaphragm is common polyethylene, the diaphragm based on polypropylene is also possible to make pottery such as 2400 diaphragm of Celgard
Porcelain diaphragm.
It is described that just extremely lithium ion battery routine techniques and conventional material are no longer discussed in detail herein to save length.
Lithium ion battery further includes electrolyte, and applicable electrolyte is that electrolyte is LiPF6, solvent EC, PC, EMC,
At least one of DMC and DEC, the electrolyte concentration are 0.8~1.5mol/L, specific such as 1mol/L LiPF6EC, EMC
(v/v=1:1) mixed solution.The production method of lithium ion battery makes according to method common to those skilled in the art,
Therefore, it in order to save length, no longer discusses in detail herein.
More effectively to illustrate technical solution of the present invention, technology of the invention is illustrated below by multiple specific embodiments
Scheme.
Embodiment 1
A kind of SiOx/ carbon composite, is prepared using following steps:
(a) taking diameter is the ball milling pearl of 10mm, diatomite, magnesium powder, wherein ratio of grinding media to material 20:1, diatomite and magnesium powder
Ratio is 1:1, carries out ball milling together, and Ball-milling Time 45min obtains the first product；
(b) concentration is used to wash for the hydrochloric acid of 1mol/L to the first product, washing can't detect magnesium into eluate
Ion then continues to wash using deionized water, washing to neutrality, then dry at 80 DEG C, obtains SiOx；For use.
Embodiment 2
A kind of SiOx/ carbon composite, is prepared using following steps:
(a) taking diameter is the ball milling pearl of 10mm, diatomite, magnesium powder, wherein ratio of grinding media to material 20:1, diatomite and magnesium powder
Ratio is 1:1, carries out ball milling together, and Ball-milling Time 45min obtains the first product；
(b) concentration is used to wash for the hydrochloric acid of 1.0mol/L to the first product, washing can't detect into eluate
Magnesium ion then continues to wash using deionized water, washing to neutrality, then dry at 80 DEG C, obtains SiOx；
(c) SiO for obtaining 5g alkali lignin, 5g step (b)x, 1.25g ferrous sulfate heptahydrate, 500g tetrahydrofuran sets
Mixing treatment is carried out in the beaker that volume is 1000mL, while being ultrasonically treated using ultrasonic cell disruptor, is obtained
SiOx/ carbon precursor solution；
(d) step (c) is obtained into SiOx/ carbon precursor solution is stirred at 25 DEG C, so that tetrahydrofuran volatilizees, obtains alkali wood
The SiO of quality claddingxMixture is fully ground using mixture of the ball mill to acquisition；
(f) material after step (d) grinding is placed in the tube furnace with hydrogen atmosphere, 700 DEG C of calcining 6h are obtained
SiOx/ carbon composite, cooled to room temperature；
(g) product that step (f) obtains is washed using the hydrochloric acid of 1M, is washed 5 times, in the hydrochloric acid after detection washing
It without ferrous ion, is then cleaned 3 times using deionized water, pH test paper, which is detected, obtains qualified SiO to neutrality, naturally dryx/
Carbon composite, for use.
Comparative example 1
A kind of SiOx/ carbon composite, is prepared using following steps:
(a) taking diameter is the ball milling pearl of 10mm, diatomite, magnesium powder, wherein ratio of grinding media to material 20:1, diatomite and magnesium powder
Ratio is 1:1, carries out ball milling together, and Ball-milling Time 45min obtains the first product；
(b) concentration is used to wash for the hydrochloric acid of 1.0mol/L to the first product, washing can't detect into eluate
Magnesium ion then continues to wash using deionized water, washing to neutrality, then dry at 80 DEG C, obtains SiOx；
(c) SiO for obtaining 5g alkali lignin, 5g step (b)x, 500g tetrahydrofuran be placed in volume be 1000mL burning
Mixing treatment is carried out in cup, while being ultrasonically treated using ultrasonic cell disruptor, and SiO is obtainedx/ carbon precursor solution；
(d) step (c) is obtained into SiOx/ carbon precursor solution is stirred at 25 DEG C, so that tetrahydrofuran volatilizees, obtains alkali wood
The SiO of quality claddingxMixture is fully ground using mixture of the ball mill to acquisition；
(f) material after step (d) grinding is placed in the tube furnace with hydrogen atmosphere, 700 DEG C of calcining 6h are obtained
SiOx/ carbon composite, cooled to room temperature, for use.
In order to verify the SiO that embodiment 1,2 and comparative example 1 are preparedxThe characteristic of/carbon composite, below to its into
The relevant performance test of row.
(1) TEM is scanned
The SiO that embodiment 1 is preparedxTEM surface sweeping is carried out, as a result as shown in Figure 1；Embodiment 2 is prepared
SiOx/ carbon composite carries out TEM scanning, as a result as shown in Figure 2.
After from Fig. 1,2 it is found that silica and magnesium powder are carried out ball milling, SiO is obtainedx, SiOxIn the oxygen containing silicon, silicon
Compound etc.；And after being mixed and being calcined with lignin, lignin-base carbon is in SiOxCoated with uniform forms 5-10nm
The carbon-coating of thickness, to play during circulating battery and avoid SiOxWith the effect of electrolyte contacts, and active material is improved
Electric conductivity.
(2) EDS power spectrum surface sweeping
The SiO that 1 step (b) of embodiment is preparedxThe surface sweeping of EDS power spectrum is carried out, as a result as shown in Figure 3.
As can be seen from Figure 3, SiOxIn containing silicon, oxide of silicon etc. mix mixed distribution under minimum nano-scale.
(3) Raman spectrum
The SiO that embodiment 2 and comparative example 1 are obtainedx/ carbon composite carries out the test of Raman spectrum, test knot respectively
Fruit is as shown in Figure 4.
As can be seen from Figure 4, I in embodiment 2G: ID=0.674, and the I of comparative example 1G: ID=0.803.The peak G is relative to the peak D
Peak intensity (IG: ID) higher, show that the degree of graphitization of carbon coating layer is higher, to illustrate that the molysite being added in embodiment 2 can pass through
Reducing atmosphere calcining significantly improves carbon-coating degree of graphitization, and more 2 degrees of graphitization of embodiment of molysite are higher than comparative example
1。
(4) battery performance test
The SiO that the present embodiment 1 is prepared respectivelyx, the SiO that is prepared of embodiment 2x/ carbon composite and comparative example 1
Obtained SiOxLithium ion battery is made as negative electrode active material and other materials in/carbon composite, to the lithium ion of acquisition
Battery is tested, specific as follows:
Wherein, negative electrode binder PPA is binder: Super P: negative electrode active material=10:10 according to mass ratio:
80 are mixed, and obtain contain SiO respectivelyxNegative electrode slurry embodiment 1, embodiment 2, comparative example 1 negative electrode slurry, and by institute
It states negative electrode slurry to be respectively coated in copper foil current collector, the electrode slice that diameter is 12mm is made with sheet-punching machine after 110 DEG C of drying；It will
Obtained electrode slice is to electrode, 2400 diaphragm of Celgard, with 1mol/L LiPF with metal lithium sheet as cathode6EC,
EMC (v/v=1:1) mixed solution is electrolyte solution, in the inert atmosphere glove box (O of Chinese vigor company production2And H2O
Content be respectively less than 0.1ppm) in assembling obtain the CR2025 type button half-cell of embodiment 1, the CR2025 type of embodiment 2 is buckled
The CR2025 type button half-cell of formula half-cell and comparative example 1.
After CR2025 type button half-cell obtained above is stood for 24 hours respectively, using the type of Wuhan Lan electricity company production
Number electrochemical property test being carried out for the battery test system of CT 2001A, the voltage range of test condition is 0.01~2.0V,
Test result is as shown in Figure 5,6.
As shown in Figure 5, SiO described in embodiment 1xFabulous long circulating stability energy is shown, it is close in the electric current of 4A/g
Lower 2000 circle of circulation of degree, capacity still have 600mAh/g, capacity retention ratio 68.3%.As a result it proves due to SiOxIts own is more
Permeability and nano silicone region are distributed with conducive to its macrocyclic stabilization.SiOxPorosity be conducive to buffer silicon in charge and discharge
Volume expansion in the process can also promote contact of the electrode material with electrolyte to improve cycle performance, reduce lithium ion
Radius is transmitted, high rate performance is improved.And the dispersed distribution of silicon nano-area can further decrease the body of bulky grain silicon aggregation
Product expands brought material pulverizing problem, improves its structural stability.
It will be appreciated from fig. 6 that the SiO of the embodiment of the present invention 2x/ carbon composite can show good cycle performance.And it is real
Example 2 is applied compared to comparative example 1, the doping of molysite effectively improves SiOxThe specific capacity of/carbon composite, this is attributed to the fact that its carbon
The higher degree of graphitization of shell (Fig. 4 verifying), it is electro to enhance leading for material.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc. within mind and principle should all include within protection scope of the present invention.
Claims (10)
1. a kind of SiOxThe preparation method of/carbon composite, which is characterized in that at least include the following steps:
Step S01. carries out ball-milling treatment under ball milling condition, by silica and magnesium powder, sends out the silica and magnesium powder
Raw magnesium thermit, ball-milling treatment is terminated, is washed using hydrochloric acid into eluate without magnesium ion, then is adopted and be washed with deionized
To neutrality, SiO is obtainedx；
Step S02. is by SiOx, lignin, source of iron and organic solvent carry out mixing and ultrasonic treatment, obtain SiOx/ carbon precursor；
Step S03. is by the SiOx/ carbon precursor, which is placed in reducing atmosphere, carries out calcination processing, and source of iron is made to be reduced to iron,
The iron obtains lignin degree of graphitization in carbonization to catalytic action is played in the carbonisation of the lignin simultaneously
It is removed the iron to carrying out washing treatment several times is carried out to raising, and using acid solution, obtains SiOx/ carbon composite；
Wherein, the SiOxIn 0≤x < 2.
2. SiO as described in claim 1xThe preparation method of/carbon composite, which is characterized in that according to mass ratio be the wood
Quality: SiOx: organic solvent=(0.5~2): 1:(100~500)；It is the iron: silicon=1:(40~200 according to atomic ratio).
3. such as the described in any item SiO of claim 1~2xThe preparation method of/carbon composite, which is characterized in that described wooden
Element is alkali lignin, lignosulfonates, sulfonated wheat-strew lignin, sulfonation enzymolysis xylogen, carboxylated alkali lignin, carboxylated enzyme
Solve at least one of lignin, ammonium choline lignin, ammonium enzymolysis xylogen.
4. such as the described in any item SiO of claim 1~2xThe preparation method of/carbon composite, which is characterized in that the source of iron
For ferrous salt or molysite.
5. such as the described in any item SiO of claim 1~2xThe preparation method of/carbon composite, which is characterized in that the calcining
Temperature is 600~900 DEG C.
6. such as the described in any item SiO of claim 1~2xThe preparation method of/carbon composite, which is characterized in that the reduction
Property atmosphere be any one of hydrogen, the mixture of hydrogen and argon gas, carbon monoxide, hydrogen sulfide, methane.
7. such as the described in any item SiO of claim 1~2xThe preparation method of/carbon composite, which is characterized in that the acid solution
For any one of dilute hydrochloric acid, dilute sulfuric acid, dust technology.
8. such as the described in any item SiO of claim 1~2xThe preparation method of/carbon composite, which is characterized in that described organic
Solvent is any one of the mixed solvent of tetrahydrofuran and ethyl alcohol, tetrahydrofuran.
9. a kind of SiOx/ carbon composite, which is characterized in that the SiOx/ carbon composite is the nano material of core-shell structure,
The core part is with porous SiOx, the shell parts are amorphous carbon layer, and the amorphous carbon is filled in the SiOx
Hole in, the SiOx/ carbon composite is prepared using preparation method as described in any one of claims 1 to 8.
10. a kind of lithium ion battery, including negative electrode active material, which is characterized in that the negative electrode active material is claim 1
The SiO of any one of~8 preparation method preparationx/ carbon composite.
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