CN107112504A - Silicon-carbon compound, the method for preparing the compound and electrode material and battery comprising the compound - Google Patents
Silicon-carbon compound, the method for preparing the compound and electrode material and battery comprising the compound Download PDFInfo
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- CN107112504A CN107112504A CN201480084430.4A CN201480084430A CN107112504A CN 107112504 A CN107112504 A CN 107112504A CN 201480084430 A CN201480084430 A CN 201480084430A CN 107112504 A CN107112504 A CN 107112504A
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- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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Abstract
The present invention relates to silicon-carbon compound, it is present in the form of Multi-hole secondary particle and comprising nano silicon particles, one or more conductive carbonaceous additives and conductive carbon coating.The invention further relates to prepare the method for the compound and electrode material and battery comprising the compound.
Description
Technical field
The present invention relates to silicon-carbon compound, it exists in the form of Multi-hole secondary particle and includes nano silicon particles, one
Plant or a variety of conductive carbonaceous additives and conductive carbon coating.The invention further relates to prepare the method for the compound and comprising described
The electrode material and battery of compound.
Background technology
For for large-scale application such as electric car (EV) and static utility network there is high-energy-density and length to follow
The demand of the lithium ion battery of future generation (LIB) in ring life-span is increasing.Silicon is because its theoretical capacity is it in newest prior art
In 10 times of carbon homologue, so being noticeable lithium ion battery negative material.The significant challenge related to silicium cathode
It is that structure degradation and solid electrolyte interface (SEI) are unstable caused by during circulating due to big Volume Changes (about 300%)
It is fixed, cause the Si rapid decay of capacity and cycle life short.
People have paid substantial amounts of effort to solve these problems, the Si nano junctions generally limited in detail by designing
Structure, including nano wire, nanotube, nano particle, loose structure and their compounds with carbon material.In all these methods
In approach, because carbon has good electron conduction and stress buffer characteristic, the design of silicon/carbon complex has attracted quite big
Notice, to improve the stability of silicon-based anode.In recent years by various methods for preparing silicon/carbon complex, such as water
Hot method, CVD, high energy mechanical grinding (HEMM), spray drying (SD), pyrolysis and sol-gal process.In these methods, sol-gal process
It is not suitable for large-scale production, and mechanical lapping is looked can not provide high-quality carbon-coating.Pyrolysismethod can on Si surfaces shape
Into the quite complete carbon-coating with high conductivity, it easily expands scale in commercial point of view.CVD is because it is uniform, can
The high-quality carbon-coating of regulation, so being optimal carbon cladding process, but requires to implement in an inert atmosphere and at high temperature, this
It is that cost is at a relatively high.In chemical industry and food industry, SD is because its is with low cost, equipment simply and readily expands rule
Mould, so being widely used for nano particle encapsulating.Many research groups are primarily focused on the Si base negative poles by SD technologies
Material.
See How Ng et al. report the carbon by spray pyrolysis Si/ citric acids/alcohol suspension acquisition at 400 DEG C
The spherical silicon nano-complex of coating.The compound undergoes 20 circulations and shows 1489mAh g-1Reversible capacity.However, should
Composite structure is the Si nanostructureds that carbon is coated in the case of in the absence of the pore structure of the second particle level limited in detail
Simple assembling.In the charge and discharge process repeated, amorphous carbon layer can not buffer Si Volume Changes, therefore the compound is passed through
Cyclical stability when going through long-term circulation is poor.
The nano Si that Yu-Shi He et al. report the lily shape graphene platelet parcel obtained by simple SD methods is combined
Thing.It undergoes 30 circulations and shows 1525mAh g-1Reversible capacity.However, because wrapping up nano Si by graphene platelet
It can not ensure Si is completely covered by carbon, prevent the effect of nano Si and electrolyte contacts to be restricted, therefore it is steady to limit circulation
Qualitatively improve.
Miao Zhang et al. are reported by a series of high energy wet ball grindings, closing SD and subsequent chemical vapor deposition
Method synthesis silicon@carbon/CNT and carbon nano-fiber (Si@C/CNT＆CNF) compound, wherein CNT and carbon nano-fiber
Silicon (Si@C) the spherical compound coated with carbon is interweaved.The Si@C/CNT＆CNF compounds undergo 50 circulations and shown
1195mAh g-1Reversible capacity.However, the compound is prepared by a series of production process, cause production efficiency
It is low.
The common issue of the compound of above-mentioned three prior art references is the appearance being limited in short cycle-index
Conservation rate is measured, and their long-term cycle performance is not good.
The content of the invention
Therefore, it is an object of the present invention to provide novel silicon carbon complex, it shows good long-term cycle performance.
The purpose can be by existing and including nano silicon particles (Si NP), one in the form of Multi-hole secondary particle
Plant or the silicon-carbon compound of a variety of conductive carbonaceous additives and conductive carbon coating is realized.
The purpose can also realize that this method comprises the following steps by preparing the method for silicon-carbon compound：
1) provide comprising nano silicon particles, the dispersion of one or more conductive carbonaceous additives and carbon precursor in a solvent；
2) spray drying is implemented to the dispersion, so that the nano silicon particles and one or more conductive carbons be added
Agent is mixed in the form of Multi-hole secondary particle and coated with the carbon precursor；
3) product by 2) obtaining is heated, so that the carbon precursor is pyrolyzed to form conductive carbon coating.
There is provided comprising the silicon-carbon compound according to the present invention or by according to the present invention according to another aspect of the present invention
Method made from silicon-carbon compound electrode material.
There is provided comprising the silicon-carbon compound according to the present invention or by according to the present invention according to another aspect of the present invention
Method made from silicon-carbon compound battery.
The present invention is related to the purposes according to silicon-carbon compound of the invention as electrode active material according to another aspect.
Brief description of the drawings
Various aspects of the invention are explained in more detail with reference to accompanying drawing, wherein：
Fig. 1 show the Si/CNT@C of embodiment 1 schematic layout；
Fig. 2 show Si/CNT@C, (b) Si and (c) CNT of (a) embodiment 1 XRD spectrums；
Fig. 3 show (a, b) Si/CNT@PF and (c, d) Si/CNT@C of embodiment 1 SEM photograph；
Fig. 4 show the Si/CNT@C of embodiment 1 TEM photos, and wherein arrow show carbon-coating；
Fig. 5 show (a) simple Si NP and the Si/CNT@C of (b) embodiment 1 cycle performance；
Fig. 6 show the Si/CNT@C of (a) simple Si NP and (b) embodiment 1 the 1st time, the 3rd time, the 30th time, the
The charging and discharging curve of 50 times and the 100th time circulations；
Fig. 7 show (a) simple Si NP and the Si/CNT@C of (b) embodiment 1 high rate performance；
Fig. 8 show cycle performances of the Si/CNT@C of embodiment 1 under more high current density；
Fig. 9 show the Si/CNT@C of (a) embodiment 1, the Si/CNT@C of (b) embodiment 2 and (c) embodiment 3 Si/
CNT/Cu@C cycle performance；
Figure 10 show (a) Si/CNT/Cu salt@PF and (b) Si/CNT/Cu@C of embodiment 3 SEM photograph；
Figure 11 show the Si/CNT/Cu@C of (a) embodiment 3 and Si/CNT/Cu@C of (b) embodiment 4 XRD spectrums；
Figure 12 show the Si/CNT/Cu@C of embodiment 4 element mapping spectrum；
Figure 13 show the Si/CNT@C of (a) embodiment 1 and the Si/CNT/Cu@C of (b) embodiment 4 cycle performance；
Figure 14 show (a) Si/CNT/SnO of embodiment 52@PF and (b) Si/CNT/Sn@C XRD is composed；
Figure 15 show the Si/CNT/Sn@C of embodiment 5 cycle performance.
Embodiment
If without illustrating in addition, by publications all referred in this, patent application, patent and other bibliography
Full content is clearly incorporated herein by reference for all purposes, as fully illustrated.
Unless otherwise defined, all technologies as used herein and scientific terminology have and the technical field of the invention
Those of ordinary skill is common to understand identical implication.If there is conflict, it is defined by this specification, including definition.
If quantity, concentration or other numerical value or parameter scope or a series of preferred upper limits as scope, preferably and
It is preferred that lower limit provide, then should be understood to particularly discloses by any pair of any range upper limit or preferred numerical value with
Any range lower limit or all scopes of preferred numerical value formation, no matter whether these scopes are respectively disclosed.Carry herein
And numerical value scope when, unless otherwise indicated, it is meant that the scope includes its end points and all integers within the range
And fraction.
The present invention is related to silicon-carbon compound according to one aspect, and it exists in the form of Multi-hole secondary particle and received comprising silicon
Rice grain, one or more conductive carbonaceous additives and conductive carbon coating.
According to an embodiment of the silicon-carbon compound according to the present invention, the pore volume of the Multi-hole secondary particle for 0.1 to
1.5cm3/ g, preferably 0.3 to 1.2cm3/ g, more preferably 0.5 to 1.0cm3/g；Aperture be 1 to 200nm, preferably 10 to
180nm, more preferably 20 to 150nm；BET specific surface area is 30 to 300m2/ g, preferably 40 to 250m2/ g, more preferably 50
To 200m2/g。
According to another embodiment of the silicon-carbon compound according to the present invention, the particle diameter of the Multi-hole secondary particle for 1 to
10 μm, more preferably preferably 2 to 8 μm, 3 to 7 μm.
According to another embodiment of the silicon-carbon compound according to the present invention, the particle diameters of the nano silicon particles be less than
200nm, preferably 50 to 200nm, more preferably 80 to 150nm.
According to another embodiment of the silicon-carbon compound according to the present invention, nano silicon particles and conductive carbonaceous additive
Weight ratio is 1:2 and 90:Between 1, preferably 4:3 and 16:Between 1, more preferably 2:1 and 10:Between 1, particularly preferably 5:1
With 8:Between 1.
According to another embodiment of the silicon-carbon compound according to the present invention, the thickness of the conductive carbon coating for 1 to
10nm, preferably 2 to 8nm, more preferably 3 to 6nm, particularly preferably about 5nm.
According to another embodiment of the silicon-carbon compound according to the present invention, the conductive carbonaceous additive can be selected from following
In group：CNT, graphene and carbon black.Preferably, the external diameter of CNT is 10 to 50nm, preferably 15 to 40nm, more
Preferably 20 to 30nm；Length is 1 to 30 μm, more preferably preferably 5 to 25 μm, 10 to 20 μm.
According to another embodiment of the silicon-carbon compound according to the present invention, the silicon-carbon compound can also include one kind
Or a variety of metal materials for being not involved in embedding de- lithium, it is preferably one or more metal materials in the following group：Cu, Ni, no
Become rusty steel, Fe and Ti, more preferably Cu, exists in the form of the intermetallic compound of silicon and one or more metal materials.The gold
Compound has the middle property between ionic compound and alloy between category.One or more metal materials, especially
It is on the intermetallic compound of silicon and one or more metal materials, the surface that Si nano particles can be evenly distributed in.It is special
Not preferably, the metal material can be copper, exist in the form of the intermetallic compound of copper and silicon, such as Cu3Si and Cu5Si。
According to another embodiment of the silicon-carbon compound according to the present invention, the silicon-carbon compound can also include one kind
Or a variety of metal materials for participating in embedding de- lithium, it is preferably one or more metal materials in the following group：Ge、Sn、Al、
Mg, Ag, Zn and In, more preferably Sn.One or more metal materials can be evenly distributed in the table of Si nano particles
On face.
According to another embodiment of the silicon-carbon compound according to the present invention, the silicon-carbon compound can also include one kind
Or a variety of metal materials for being not involved in embedding de- lithium are together with one or more metal materials for participating in embedding de- lithium.
According to another embodiment of the silicon-carbon compound according to the present invention, the silicon-carbon compound can also include one kind
Or a variety of metal materials in the following group：Cu, Ni, stainless steel, Fe, Ti, Ge, Sn, Al, Mg, Ag, Zn and In.Described one
Plant or various metals material can be evenly distributed on the surface of Si nano particles.
Preferably, when the silicon-carbon compound includes one or more metal materials, the silicon in the silicon-carbon compound
The weight ratio of element and metallic element is 4:1 and 20:Between 1, preferably 5:1 and 15:Between 1, more preferably 6:1 and 13:1 it
Between.
According to the present invention, Si nano particles (Si NP) and conductive carbonaceous additive are uniformly mixed, and are wrapped completely by amorphous carbon layer
Envelope, so as to form 3D porous spherical second particles.Because Si nano particles are completely covered by conductive carbon coating, Si can be avoided to receive
Rice grain is directly contacted with electrolyte.Conductive carbon coating can be formed by spray drying and pyrolysis.Conductive carbon coating and conductive carbon add
Plus agent does not merely comprise continuous high conductivity 3D networks, and the void space of elasticity is provided with accommodate Si Volume Changes should
Become and stress, and avoid the Si NP during circulating from occurring aggregation and crush.Due to setting for porous nano/micron secondary structure
Meter, the compound (Si/CNT@C) of gained shows excellent cyclical stability and 78.3% conservation rate after being circulated at 110 times
And high reversible capacity.
The present invention is related to the method for preparing silicon-carbon compound according to another aspect, and this method comprises the following steps：
1) provide comprising nano silicon particles, the dispersion of one or more conductive carbonaceous additives and carbon precursor in a solvent；
2) spray drying is implemented to the dispersion, so that the nano silicon particles and one or more conductive carbons be added
Agent is mixed in the form of Multi-hole secondary particle and coated with the carbon precursor；
3) product by 2) obtaining is heated, so that the carbon precursor is pyrolyzed to form conductive carbon coating.
According to an embodiment of the method according to the invention, the particle diameters of the nano silicon particles is less than 200nm, preferably
For 50 to 200nm, more preferably 80 to 150nm.
According to another embodiment of the method according to the invention, the weight ratio of nano silicon particles and conductive carbonaceous additive
1:2 and 90:Between 1, preferably 4:3 and 16:Between 1, more preferably 2:1 and 10:Between 1, particularly preferably 5:1 and 8:1
Between.
According to another embodiment of the method according to the invention, the carbon precursor can be in the following group：Phenolic aldehyde tree
Fat, citric acid, sucrose, epoxy resin and Kynoar.
According to another embodiment of the method according to the invention, the amount of carbon precursor can be selected so that the conduction
The thickness of carbon coating, to 6nm, is particularly preferably about 5nm for 1 to 10nm, preferably 2 to 8nm, more preferably 3.
According to another embodiment of the method according to the invention, the conductive carbonaceous additive can be in the following group：
CNT, graphene and carbon black.Preferably, the external diameter of CNT is more preferably for 10 to 50nm, preferably 15 to 40nm
20 to 30nm；Length is 1 to 30 μm, more preferably preferably 5 to 25 μm, 10 to 20 μm.
According to another embodiment of the method according to the invention, in step 1) in, the dispersion can also include with
One or more metal material precursors of lower metal material：One or more are not involved in the metal material of embedding de- lithium, preferably one
Plant or a variety of metal materials in the following group：Cu, Ni, stainless steel, Fe and Ti, more preferably Cu.Specifically, Ke Yitong
Crossing heating makes one or more metal material precursors be reacted with nano silicon particles, obtains silicon and one or more metal materials
Intermetallic compound.The intermetallic compound has the middle property between ionic compound and alloy.Described one kind
Or the intermetallic compound of various metals material, particularly silicon and one or more metal materials, Si can be evenly distributed in
On the surface of nano particle.It is particularly preferred that before the metal material precursors can be one or more copper in the following group
Body：Copper nano particles and organic copper salt, such as oacetic acid copper.
According to another embodiment of the method according to the invention, in step 1) in, the dispersion can also include with
One or more metal material precursors of lower metal material：One or more participate in the metal material of embedding de- lithium, are preferably one kind
Or a variety of metal materials in the following group：Ge, Sn, Al, Mg, Ag, Zn and In, more preferably Sn.The one or more
Metal material can be evenly distributed on the surface of Si nano particles.It is particularly preferred that the metal material precursors can be tin
Precursor, such as SnO2, it can be in step 3) according to equation SnO2+ 2C=Sn+2CO is reduced into Sn.
According to another embodiment of the method according to the invention, in step 1) in, the dispersion can also include one
Plant or one or more metal material precursors of a variety of metal materials for being not involved in embedding de- lithium participate in embedding de- together with one or more
One or more metal material precursors of the metal material of lithium.
According to another embodiment of the method according to the invention, in step 1) in, the dispersion can also include with
One or more metal material precursors of lower metal material：One or more metal materials in the following group：Cu, Ni, no
Become rusty steel, Fe, Ti, Ge, Sn, Al, Mg, Ag, Zn and In.One or more metal materials can be evenly distributed in Si nanometers
On the surface of particle.
Preferably, when the dispersion includes one or more metal material precursors of one or more metal materials,
The weight ratio of element silicon and metallic element is 4 in the silicon-carbon compound of gained:1 and 20:Between 1, preferably 5:1 and 15:1 it
Between, more preferably 6:1 and 13:Between 1.
According to another embodiment of the method according to the invention, in step 2) in, inlet temperature is 100 to 220 DEG C,
Preferably 120 to 200 DEG C, more preferably 150 to 180 DEG C, outlet temperature is 80 to 140 DEG C, preferably 90 to 130 DEG C, more excellent
Elect 100 to 120 DEG C as.
Another embodiment, step 3 according to the method according to the invention) can 800 to 1200 DEG C, preferably 850
To implementing 1 to 48 hour, preferably 5 to 24 hours at a temperature of 1100 DEG C, more preferably 900 to 1000 DEG C, it is more preferably 10 to 12 small
When.
The method according to the invention is simple and easy to apply, and there is provided the approach of large-scale production Si base complexes.
The present invention is related to comprising the silicon-carbon compound according to the present invention or by according to the present invention's according to another aspect
The electrode material of silicon-carbon compound made from method.
The present invention is related to comprising the silicon-carbon compound according to the present invention or by according to the present invention's according to another aspect
The battery of silicon-carbon compound made from method.
The present invention is related to the purposes according to silicon-carbon compound of the invention as electrode active material according to another aspect.
Embodiment 1：
First by 0.73 gram of Si NP (size is 50-200nm, Alfa-Aesar), (OD is 10-20nm to 0.11 gram of CNT, long
Spend for 10-30 μm, Chengdu organic chemistry Co., Ltd) and 0.37 gram of PF (Shandong holy well Shenquan groups) be dispersed in 150mL
In absolute ethanol, stirring and ultrasonication 1 hour.Secondly, the mixture is spray-dried (inlet temperature：170℃；Outlet
Temperature：100 DEG C) with formed PF parcel Si NP and CNT (Si/CNT@PF) compound microparticle.Finally, by the Si/ of gained
CNT@PF compounds are heated to 900 DEG C with 5 DEG C/min in argon atmospher and last 2 hours, and PF pyrolysis turns into amorphous carbon.Gained
Compound is Si/CNT@C.Because PF residual carbon ratio is 58%, the Si NP in Si/CNT@C compounds are calculated:CNT:C
The weight ratio of coating is 69:10:21.
Structural appraisal：
Fig. 1 show Si/CNT@C schematic layout.Si/CNT@C structure can be described as follows：Micron-sized ball by
The silicon grain composition of CNT nano-scale is distributed with inside.Thickness is uniformly coated on Si/CNT balls for several nanometers of carbon-coating
Surface on.
Fig. 2 show (a) Si/CNT@C, (b) Si and (c) CNT X-ray diffraction (XRD) is composed.Si/CNT@C show height
The structure of crystallization is spent, it meshes well into standard Si peaks (JCPDS27-1402).Peak at 28 °, 47 °, 56 °, 69 ° and 76 °
(111), (220), (311), (400) and (331) face of Si crystal can be respectively labeled as.It has also appeared in Si/CNT@C
CNT main peak.Correspond to unbodied PF pyrolytic carbons by 20 to 25 ° of wide diffraction maximums.
Using SEM (SEM) and transmission electron microscope (TEM) characterize product size and structure (referring to
Fig. 3 and 4).
The detailed structure of the compound is porous nano/micron second particle, as shown in SEM and TEM photos.Si
In NP and CNT insertion amorphous carbon layers, 3D porous spherical secondary structures are formed.
As shown in figure 3, sample keeps identical spherical structure before and after pyrolysis, show that pyrolytic process does not change sample and existed
Pattern after spraying.The scope of second particle is 1 to 7 μm.
By Fig. 4 b it was determined that the thickness of the PF pyrolytic carbons on Si NP is about 5nm.
Battery is assembled and electrochemistry is assessed：
The chemical property of obtained compound is assessed using bipolar electrode button cell.By dextrinizing activity material,
Super P conductive blacks (40nm, Timical) and as adhesive butadiene-styrene rubber/sodium carboxymethylcellulose (SBR/SCMC,
Weight compares 3:5, be dissolved in distilled water) weight ratio be 60:20:20 mixture preparation work electrode.By the mixture
After being coated on Cu paper tinsels, by pole drying, Ф 12mm disk is cut into, is suppressed with 3MPa, finally in vacuum at 50 DEG C
Middle drying 4 hours.The assembling CR2016 button cells in the glove box (MB-10compact, MBraun) filled with argon gas, wherein
The use of the volume ratio in dimethyl carbonate (DMC) and ethylene carbonate (EC) is 1:1 include 2 weight % vinylene carbonates
(VC) the 1M LiPF of in the mixed solvent6As electrolyte, using PE films (TEKLON UH2045.5) as barrier film, lithium is used
Metal is as to electrode.With perseverance at 25 DEG C on LAND battery test systems (CT2007A, Wuhan Jin Nuo Electronics Co., Ltd.s)
Fixed current density assessments performance.(embedding Li) blanking voltage discharge relative to Li+/ Li is 0.01V, charging (de- Li) cut-off
Voltage is relative to Li+/ Li is 1.2V.Weight based on Si/CNT@C compounds calculates specific capacity.The active material in each electrode
The quality loading capacity for expecting (Si and C) is about 0.5mg/cm2。
Fig. 5 show (a) simple Si NP and (b) Si/CNT@C cycle performance.Button cell is relative to Li/Li+
With 0.1A g in initial circulation twice between 0.01 and 1.2V-1Discharge and in following cycle with 0.3A g-1Electric discharge.
As shown in figure 5, compared with simple Si NP, the cycle performance of Si/CNT@C compounds is greatly improved, wherein
Stable reversible capacity is about 1800mAh g after 110 circulations-1.Excellent cycle performance is attributable to porous nano/micron two
Secondary structure and the carbon coating on Si NP, its can suppress caused by the alloying due to Li and Si particle volume change with
And Si is fluorinated the corrosion of thing salt electrolyte, more stable conductive network and interface performance is produced in the electrodes.
Fig. 6 show (a) simple Si NP and (b) Si/CNT@C at the 1st time, the 3rd time, the 30th time, the 50th time and the
Charging and discharging curve during 100 circulations.Button cell is relative to Li/Li+In initial circulation twice between 0.01 and 1.2V
In with 0.1A g-1Discharge and in following cycle with 0.3A g-1Electric discharge.
Although pure Si shows higher initial charge capacity, its capacity reduces rapidly and voltage during circulating
Polarization becomes very serious.Unlike this, the capability retention and voltage polarizing of the Si/CNT@C compounds of embodiment 1 obtain bright
Improve aobviously.In 100 times circulate, its specific capacity is substantially stablized in about 1800mAh g-1.Si/CNT@C initial coulomb effect
Rate (CE) is 82.0%, slightly below Si (85.2%).Reason is probably：(1) Multi-hole secondary structure has bigger surface area, its
Form more irreversible SEI；(2) there is low-down CE by being pyrolyzed the carbon from PF, because its amorphous knot
Structure has substantial amounts of defect, and it can capture and consume embedded lithium.
Fig. 7 show (a) simple Si NP and (b) Si/CNT@C high rate performance.Button cell is close with different electric currents
Spend charge/discharge.As seen from Figure 7, although compared with Si/CNT@C, Si is in 0.1A g-1Low current density under show
Higher capacity, and then rapid reduction at higher current densities.Unlike this, Si/CNT@C are even in 5A g-1Under still show
Go out 1248mAh/g high power capacity.Si/CNT@C good high rate performance be attributable to by CNT and carbon coating formation it is good
Conductive network.
Fig. 8 show Si/CNT@C in 2A g-1Cycle performance under (=1C).Button cell is relative to Li/Li+0.01
With 0.1A g in initial circulation twice between 1.2V-1Discharge and in following cycle with 2A g-1Electric discharge.Can be with by Fig. 8
Find out, even in 2A g-1Under the high current multiplying power of (=1C), Si/CNT@C capacity undergoes 300 circulations and may remain in about
1000mAh g-1。
In the present embodiment, design and synthesized the agglomerated structures of Si/CNT@C compounds.Existed by CNT and carbon coating
Carbon conductive network is formd in aggregate.Volume Changes in charge and discharge process can pass through aggregate and the hole of carbon-coating
Buffered.
Cycle performance is better than above-mentioned three prior art references.With point in above-mentioned three prior art references
The 1489mAh g that Jing Li do not circulate for 20 times-1, experience 30 times circulation 1525mAh g-1And the 1195mAh g of 50 circulations of experience-1Compare, the present embodiment realizes 110 circulation 1826mAh g of experience-1Reversible capacity.After 110 times circulate, capacity is protected
Holdup is 78.3%.The present embodiment additionally uses 2Ag-1High current multiplying power, and realize 300 times circulate after about
1000mAh g-1Stable reversible capacity.Height is not given in See How Ng et al. and Miao Zhang et al. document
Cycle performance under current ratio, and in Yu-Shi He et al. document, maximum current multiplying power is 0.6Ag-1。
Document of the Si weight content higher than See How Ng et al. and Miao Zhang et al..In See How Ng et al.
Document in Si weight content be 44%, and in the present embodiment Si weight content be 69%.Because the carbon in compound
Content the decrease of power density and can reduce capacity, thus should be controlled by so as to controllable energy density and capacity into
Originally maximize volume buffering effect.Reversible capacity is about 1800mAh g-1, higher than above-mentioned three prior art references.
Embodiment 2：
Implement embodiment 2 similar to Example 1ly, difference is：Calculate the Si in the Si/CNT@C compounds of gained
NP:CNT:The weight ratio of C coatings is 54:10:36.
Fig. 9 show the Si/CNT@C of (b) embodiment 2 cycle performance.
Embodiment 3：
Implement embodiment 3 similar to Example 1ly, difference is：Oacetic acid copper (Cu salt) is originated as copper
Material is extraly dispersed in absolute ethanol, step 2) intermediate product be PF parcel Si NP+CNT+Cu salt (Si/CNT/Cu
Salt@PF), calculate the Si NP in the compound (Si/CNT/Cu@C) of gained:CNT:Cu:The weight ratio of C coatings is 60:10:
10:20。
Fig. 9 show the Si/CNT/Cu@C of (c) embodiment 3 cycle performance；Figure 10 show (a) Si/ of embodiment 3
CNT/Cu salt@PF and (b) Si/CNT/Cu@C SEM photograph；Figure 11 show the Si/CNT/Cu@C of (a) embodiment 3 XRD
Spectrum.
As seen from Figure 9, by adding the circulation that copper further improves the Si/CNT/Cu@C compounds of embodiment 3
Performance.
Embodiment 4：
Implement embodiment 4 similar to Example 1ly, difference is：It regard copper nano particles (Cu NP) as copper source material
Extraly be dispersed in absolute ethanol, step 2) intermediate product be PF wrap up Si NP+CNT+Cu NP (Si/CNT/Cu@
PF), the Si NP in the compound (Si/CNT/Cu@C) of gained are calculated:CNT:Cu:The weight ratio of C coatings is 65:10:5:
20。
Figure 11 show the Si/CNT/Cu@C of (b) embodiment 4 XRD spectrums；Figure 12 show the Si/CNT/ of embodiment 4
Cu@C element mapping spectrum；Figure 13 show the Si/CNT/Cu@C of (b) embodiment 4 cycle performance.
As seen from Figure 12, copper is spread evenly across on Si NP.In addition, being further improved by adding copper
The cycle performance of the Si/CNT/Cu@C compounds of embodiment 4 (referring to Figure 13).
Embodiment 5：
Implement embodiment 5 similar to Example 1ly, difference is：By SnO2Nano particle is extra as tin source material
Ground is dispersed in absolute ethanol, step 2) intermediate product be PF wrap up Si NP+CNT+SnO2(Si/CNT/SnO2@PF), meter
Calculate the Si NP in the compound (Si/CNT/Sn@C) of gained:CNT:Sn:The weight ratio of C coatings is 65:10:5:20.
Figure 14 show (a) Si/CNT/SnO of embodiment 52@PF and (b) Si/CNT/Sn@C XRD is composed；Shown in Figure 15
For the Si/CNT/Sn@C of embodiment 5 cycle performance.
As seen from Figure 15, by adding the circulation that tin further improves the Si/CNT/Sn@C compounds of embodiment 5
Performance.
Although describing specific embodiment, these embodiments are only provided in an exemplary fashion, are not meant to
Limit the scope of the present invention.Appended appended claims and their equivalents mean that covering is fallen within the spirit and scope of the invention
All modifications, replace and change scheme.
Claims (26)
1. silicon-carbon compound, it is characterised in that the silicon-carbon compound exists in the form of Multi-hole secondary particle and includes silicon
Nano particle, one or more conductive carbonaceous additives and conductive carbon coating.
2. silicon-carbon compound according to claim 1, it is characterised in that the pore volume of the Multi-hole secondary particle be 0.1 to
1.5cm3/ g, aperture is 1 to 200nm, and BET specific surface area is 30 to 300m2/g。
3. according to the silicon-carbon compound of claim 1 or 2, it is characterised in that the particle diameter of the Multi-hole secondary particle is 1 to 10 μ
m。
4. according to the silicon-carbon compound of one of claims 1 to 3, it is characterised in that the particle diameter of the nano silicon particles is less than
200nm。
5. according to the silicon-carbon compound of one of Claims 1-4, it is characterised in that the nano silicon particles and the conductive carbon
The weight ratio of additive is 1:2 and 90:Between 1, preferably 4:3 and 16:Between 1.
6. according to the silicon-carbon compound of one of claim 1 to 5, it is characterised in that the thickness of the conductive carbon coating be 1 to
10nm。
7. according to the silicon-carbon compound of one of claim 1 to 6, it is characterised in that the conductive carbonaceous additive is selected from the following group
In：CNT, graphene and carbon black.
8. silicon-carbon compound according to claim 7, it is characterised in that the external diameter of CNT is 10 to 50nm, length be 1 to
30μm。
9. according to the silicon-carbon compound of one of claim 1 to 8, it is characterised in that the silicon-carbon compound further includes one
Plant or a variety of metal materials in the following group：Cu, Ni, stainless steel, Fe, Ti, Ge, Sn, Al, Mg, Ag, Zn and In.
10. silicon-carbon compound according to claim 9, it is characterised in that element silicon and metal member in the silicon-carbon compound
The weight ratio of element is 4:1 and 20:Between 1, preferably 5:1 and 15:Between 1.
11. according to the silicon-carbon compound of one of claim 1 to 10, it is characterised in that the nano silicon particles are by the conduction
Carbon coating is completely covered.
12. according to the silicon-carbon compound of one of claim 1 to 11, it is characterised in that the conductive carbon coating is by spray drying
Formed with pyrolysis.
13. preparing the method for silicon-carbon compound, it the described method comprises the following steps：
1) provide comprising nano silicon particles, the dispersion of one or more conductive carbonaceous additives and carbon precursor in a solvent；
2) spray drying is implemented to the dispersion, thus by the nano silicon particles and one or more conductive carbonaceous additive with
The form of Multi-hole secondary particle mixes and uses the carbon precursor to coat；
3) product by 2) obtaining is heated, so that the carbon precursor is pyrolyzed to form conductive carbon coating.
14. method according to claim 13, it is characterised in that the particle diameter of the nano silicon particles is less than 200nm.
15. according to the method for claim 13 or 14, it is characterised in that the nano silicon particles and the conductive carbonaceous additive
Weight ratio is 1:2 and 90:Between 1, preferably 4:3 and 16:Between 1.
16. according to the method for one of claim 13 to 15, it is characterised in that the carbon precursor is in the following group：Phenolic aldehyde tree
Fat, citric acid, sucrose, epoxy resin and Kynoar.
17. according to the method for one of claim 13 to 16, it is characterised in that the amount of the selection carbon precursor, so that described
The thickness of conductive carbon coating is 1 to 10nm.
18. according to the method for one of claim 13 to 17, it is characterised in that the conductive carbonaceous additive is in the following group：
CNT, graphene and carbon black.
19. method according to claim 18, it is characterised in that the external diameter of CNT is 10 to 50nm, length is 1 to 30 μ
m。
20. according to the method for one of claim 13 to 19, it is characterised in that in step 2) in, inlet temperature is 100 to 220
DEG C, outlet temperature is 80 to 140 DEG C.
21. according to the method for one of claim 13 to 20, it is characterised in that step 3) it is real at a temperature of 800 to 1200 DEG C
Apply 1 to 24 hour.
22. according to the method for one of claim 13 to 21, it is characterised in that in step 1) described in dispersion further include
One or more are selected from Cu, Ni, stainless steel, the one or more of Fe, Ti, Ge, Sn, Al, Mg, Ag, Zn and In metal material
Metal material precursors.
23. method according to claim 22, it is characterised in that the weight of element silicon and metallic element in the silicon-carbon compound
Ratio is measured 4:1 and 20:Between 1, preferably 5:1 and 15:Between 1.
24. electrode material, it is characterised in that comprising the silicon-carbon compound according to one of claim 1 to 12 or by according to right
It is required that silicon-carbon compound made from one of 13 to 23 method.
25. battery, it is characterised in that comprising the silicon-carbon compound according to one of claim 1 to 12 or by according to claim
Silicon-carbon compound made from one of 13 to 23 method.
26. according to the silicon-carbon compound of one of claim 1 to 12 or pass through the method system according to one of claim 13 to 23
Silicon-carbon compound as electrode active material purposes.
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| CN112310363A (en) * | 2019-07-31 | 2021-02-02 | 华为技术有限公司 | Silicon-carbon composite material, preparation method thereof and lithium ion battery |
| US11063253B2 (en) | 2018-11-30 | 2021-07-13 | National Cheng Kung University | Composite particle for electrode |
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| DE112016002671T5 (en) * | 2016-10-19 | 2018-07-19 | Tec One Co., Ltd. | Carbon-silicon composite, negative electrode, secondary battery, and carbon-silicon composite manufacturing method |
| CN106410204A (en) * | 2016-11-22 | 2017-02-15 | 天津赫维科技有限公司 | Preparation method of carbon nanotube/silicon cathode material |
| JP6229245B1 (en) * | 2017-04-27 | 2017-11-15 | テックワン株式会社 | Carbon-silicon composite material, negative electrode, secondary battery |
| GB2563455B (en) * | 2017-06-16 | 2019-06-19 | Nexeon Ltd | Particulate electroactive materials for use in metal-ion batteries |
| CN107768626B (en) * | 2017-09-30 | 2019-12-03 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of high capacity rate C-base composte material, preparation method and the purposes in lithium ion battery |
| KR102321502B1 (en) | 2017-12-19 | 2021-11-02 | 주식회사 엘지에너지솔루션 | Anode active material for lithium secondary battery, Method of making the same and Lithium secondary battery comprising the same |
| EP3776694A4 (en) * | 2018-03-30 | 2021-12-22 | The Board of Trustees of the Leland Stanford Junior University | Silicon sealing for high performance battery anode materials |
| CN109148851B (en) * | 2018-08-16 | 2021-07-06 | 武汉理工大学 | Silicon-carbon composite negative electrode material modified by double carbon structure and preparation method thereof |
| CN109411713B (en) * | 2018-09-10 | 2022-07-22 | 江苏正力新能电池技术有限公司 | Mechanical co-coating method of silicon-containing base material, silicon-containing base material and lithium ion battery |
| CN109449423A (en) * | 2018-11-13 | 2019-03-08 | 东莞市凯金新能源科技股份有限公司 | Hollow/porous structure the silicon based composite material of one kind and its preparation method |
| EP3654413A1 (en) | 2018-11-14 | 2020-05-20 | Université de Liège | Silicon-carbon composite anode material |
| KR102243610B1 (en) * | 2018-12-17 | 2021-04-27 | 주식회사 티씨케이 | Negative active material, method for preparing the same and lithium secondary battery comprising the same |
| CN111244417B (en) * | 2020-01-17 | 2022-04-15 | 天津大学 | Preparation method of micron silicon-carbon composite negative electrode material with long cycle life |
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