CN109585834A - A kind of mesoporous silicon-tin composite electrode material and its preparation method and application - Google Patents
A kind of mesoporous silicon-tin composite electrode material and its preparation method and application Download PDFInfo
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- CN109585834A CN109585834A CN201811502751.8A CN201811502751A CN109585834A CN 109585834 A CN109585834 A CN 109585834A CN 201811502751 A CN201811502751 A CN 201811502751A CN 109585834 A CN109585834 A CN 109585834A
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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
- 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
- H01M4/38—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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
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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 invention discloses a kind of mesoporous silicon-tin composite electrode materials and its preparation method and application.The mesoporous silicon-tin combination electrode material has the cellular structure of 5~40nm, and the mass fraction of tin accounts for 5~20%.The preparation method includes: to carry out magnesium thermit to the mixture of magnesium powder and mesoporous silicon oxide mesoporous silicon is made；Mesoporous silicon-tin composite is prepared using dipping-hydrogen reduction method.The present invention also provides the mesoporous silicon-tin electrode materials to prepare the application in negative electrode of lithium ion battery.Mesoporous silicon of the present invention-tin combination electrode material has many advantages, such as reversible capacity height, good cycling stability, good rate capability, is produced on a large scale.
Description
Technical field
The invention belongs to lithium ion battery negative material field, in particular to a kind of high capacity, the long-life, low cost Jie
Hole silicon-tin composite electrode material and its preparation method and application.
Background technique
As the emerging markets such as electric car (EV), mixed power electric car (HEV) occur, to lithium ion battery
(LIB) great demand is generated.
Commercial negative electrode material still based on the carbon material of carbon element of graphite class, only have by theoretical maximum specific capacity at present
372mAh/g constrains further increasing for lithium battery capacity.Silicon is considered as most promising electrode material, theoretical capacity
Up to 4200mAh/g (Li4.4Si alloy).In addition, the lithiumation platform voltage of silicon electrode is higher than the platform voltage of graphite electrode, energy
The formation for effectively avoiding dendrite, promotes the safety of lithium ion battery.But it is previous studies have shown that silicon based electrode is in charge and discharge
It in electric cyclic process, will lead to the great variety (> 300%) of silicon electrode volume, lead to avalanche and the electrode of silicon material structure
Peeling, dusting, the decline of conductivity, and then battery capacity is caused to fall sharply.
For Volumetric expansion of the silicon based electrode in charge and discharge process, people propose magnesiothermic reduction mesoporous two in recent years
The method that silica synthesizes porous silicon, the cellular structure of prepared porous silicon can be silicon in embedding lithium/de- lithium process volume
Variation provides cushion space, offsets part internal stress, has preferable electrochemical cycle stability.But simple porous silicon is led
Electrically poor, high-rate discharge capacity is poor, and repeatedly inducing capacity fading is still more serious after circulation.
Summary of the invention
Goal of the invention: poor to solve porous silicon electric conductivity in the prior art, high-rate discharge capacity is poor, and repeatedly circulation
The still more serious problem of inducing capacity fading afterwards, the present invention provides a kind of mesoporous silicon-tin composite electrode materials, and of the invention is another
One purpose is to provide preparation method and application.
Technical solution:
A kind of mesoporous silicon-tin composite electrode material, the material have the cellular structure of 5~40nm, the mass fraction of tin
It is 5~15%.Further, which has the cellular structure of 5~15nm, and the mass fraction of tin is 10~15%.
The present invention also provides the mesoporous silicon-tin composite electrode material preparation methods, comprising: uses SnCl4It is molten
After liquid impregnates mesoporous silicon, mesoporous silicon-tin composite electrode material is prepared using the method for hydro-reduction.
The mesoporous silicon is prepared by magnesium powder and meso-porous titanium dioxide silicon powder through magnesium thermit.
The temperature of the magnesium thermit is 400~700 DEG C, can be 400~600 DEG C, 600~700 DEG C etc., soaking time
For 1~5h, heating rate is 0.5~10 DEG C/min.Reaction temperature is 400~600 DEG C of by-product Mg2Si content is higher, quality
Percentage 10% or so, as temperature increases, by-product Mg2Si content gradually decreases, when reaction temperature is 650 DEG C, Mg2Si contains
Amount is 4.2% or so, when being increased to 700 DEG C, Mg2Si content is less than 1%.
The mass ratio of the magnesium powder and mesoporous silicon oxide is 0.8~1.2:1.Under the conditions of pyroreaction, the Mg meeting of part
It is lost in the form of Mg steam, thus Mg is generally excessive when ingredient, when excess is more than 50%, Mg can form a large amount of by-products with Si
Object Mg2The yield of Si, Si reduce.Therefore after preferably, determine that the mass ratio of the magnesium powder and mesoporous silicon oxide is 0.88~1:
1。
The magnesium powder is 80-600 mesh, is further 300-350 mesh.But it is not limited to this.
The mesoporous silicon oxide is SBA-15, but not limited to this, other kinds of meso-porous titanium dioxide can also be used
Silicon.
Reaction product need to generally be post-processed after magnesium thermit, the post-processing is to use reaction product respectively
Hydrochloric acid (washes away reaction product MgO and Mg2Si) and hydrofluoric acid clean (removal react remaining mesoporous silicon oxide), cross and be filtered dry
It is dry.
The SnCl4The concentration of solution is 50~400g/L, and mesoporous silicon is in SnCl4Additional amount in solution is 30~50g/
L。SnCl4Solution concentration is excessively high, then Theil indices are high in the sample restored, can reduce the capacity of material, by experimental study, preferably
, the SnCl4The concentration of solution is 70~100g/L, and aforementioned proportion is best.Wherein, SnCl4The solvent of solution by ethyl alcohol with
Water 1:1~5 by volume further obtain for the preparation of 1:1~3.
The dip time is 0.5~5h.Dip time length can make SnCl4The more full and uniform filling mesoporous silicon of solution
Duct, generally in 0.5h or more.
Dipping ultrasonic treatment.
After dipping, mesoporous silicon needs filtration drying.
When hydro-reduction, the volume flow of hydrogen is 5~50sccm, further preferably 20~30sccm, the body of argon gas
Product flow is 5~50sccm, further preferably 5~10sccm.
The temperature of the hydro-reduction is greater than 200 DEG C, and heating rate is 0.5~10 DEG C/min.
Further, when hydro-reduction, temperature is 300~400 DEG C, keeps the temperature 0.5~5h.It can make SnCl at this temperature4
Hydro-reduction is obtained, longer soaking time can make SnCl4What is restored is more abundant, it is preferred that when hydro-reduction, temperature is
350 DEG C, keep the temperature 0.5h.
The present invention also provides the mesoporous silicon-tin composite electrode materials to prepare answering in negative electrode of lithium ion battery
With.
Compared with prior art, the invention has the benefit that
Mesoporous silicon provided by the invention-tin electrode material reversible capacity is high, and capacity can achieve 2184.8mAhg for the first time-1,
Good cycling stability still keeps 1128.6mAhg in 100 circulations-1, high-rate discharge capacity is good, in 0.2 to 0.5,1,2A g-1Current density, range is interior to provide 1605,1280,941,530mAhg-1Capacity, when current density switches back into 0.2Ag-1When, it is extensive
1441mAhg is arrived again-1。
The present invention utilizes mesoporous silicon alternate internal connection, uniform cellular structure, buffers silicon materials in process of intercalation
Volume change offsets part internal stress；It is receipts of silicon materials during de- lithium meanwhile in mesoporous silicon surface modification tin particles
Contracting provides effectively support, and two aspects inhibit the dusting of silicon materials, promote the cyclical stability of silicon based electrode.On the other hand, tin
The electric conductivity of grain is preferable, provides more conductive paths for electronics, the high magnification for reducing electronics transfer impedance, promoting silicon based electrode
Discharge capability, and tin has high theoretical capacity.Inventor passes through a large amount of the study found that comparing mesoporous silicon-copper complex,
Mesoporous silicon-tin composite is with the obvious advantage, is embodied in: firstly, Sn and Si have storage lithium ability, and having the volume being closer to swollen
Swollen rate, the former be 250~300%, the latter be 300~400%, so the two embedding lithium-take off lithium during, volume matched
Compatibility is all relatively good；And Cu does not have storage lithium ability, so the compatibility of the two volume expansion during embedding lithium-takes off lithium
It is bad, it is easily separated from each other, energy density declines rapidly after cycle-index increase.Secondly because Sn and Si have storage lithium energy
Power, therefore the initial energy density of electrode and first circulation coulombic efficiency will be higher than Cu-Sn electrode, high rate performance is also above rear
Person.
Detailed description of the invention
Fig. 1 is the scanning electron microscopic picture that magnesiothermic reduction prepares mesoporous silicon material；
Fig. 2 is the transmission electron microscope picture that magnesiothermic reduction prepares mesoporous silicon material；
Fig. 3 is dipping-hydrogen reduction method preparation mesoporous silicon-tin composite transmission electron microscope picture；
Fig. 4 is mesoporous silicon and dipping-hydrogen reduction method preparation mesoporous silicon-tin composite pore-size distribution picture；
Fig. 5 is dipping-mesoporous silicon-tin composite of hydrogen reduction method preparation and the electrochemical cycle stability of simple mesoporous silicon
Comparison；
Fig. 6 is the high rate performance comparison of dipping-hydrogen reduction method preparation mesoporous silicon-tin composite and simple mesoporous silicon；
Fig. 7 is the AC impedance comparison of dipping-hydrogen reduction method preparation mesoporous silicon-tin composite and mesoporous silicon；
Fig. 8 is dipping-hydrogen reduction method preparation mesoporous silicon-tin composite XRD diagram piece.
Specific embodiment
Combined with specific embodiments below, the present invention is furture elucidated, it should be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the invention, after the present invention has been read, those skilled in the art are to various equivalences of the invention
The modification of form falls within the application range as defined in the appended claims.
The present invention is further illustrated With reference to embodiment.
The partial size for the magnesium powder that following embodiment uses is 325 mesh, mesoporous silicon oxide SBA-15.
Embodiment 1
A kind of mesoporous silicon-tin composite electrode material the preparation method is as follows:
Magnesium powder and meso-porous titanium dioxide Si powder 1:1 in mass ratio that partial size is 325 mesh are ground, 0.5g mixed powder is taken
End.Mix powder is packed into quartz boat, is put into tube furnace, under an argon atmosphere, is warming up to 1 degree/min of speed
700 DEG C, 5 hours are kept the temperature, furnace cooling.The sample in tube furnace is taken out, is cleaned respectively with 1M HCl solution and 10%HF solution,
Resulting materials are mesoporous silicon material (see Fig. 1, Fig. 2).
By ethyl alcohol: the volume ratio of deionized water is that 1:3 prepares mixed solution, adds SnCl4·6H2O solid, is made into
The SnCl of 100g/L concentration4Solution.Appropriate mesoporous silicon (additional amount is 30~50mg) is poured into 10ml SnCl4In solution, ultrasound
Shake 60min.Vacuum oven is put into after suction filtration, with 100 DEG C of dry 10h to get arrive SnCl4The mesoporous silicon compound of dipping.
By gained SnCl4The mesoporous silicon compound of dipping, which is put into tube calciner, carries out hydrogen reduction, with 5 DEG C/min heating
To 350 DEG C, and keep the temperature 1h.In During Hydrogen Reducing, whole process is passed through the H of 20sccm2With the Ar mixed gas of 10sccm, furnace cooling
To room temperature to get to mesoporous silicon-tin composite (see Fig. 3).
Mesoporous silicon-tin composite transmission electron microscope results are shown in Fig. 3.Spherical tin particles be evenly distributed on mesoporous silicon surface and
Inside duct.And it is tested and is found by BET, mesoporous silicon specific surface area is 337.2m2/ g, tin-mesopore surface area are
114.782m2/ g, the doping of tin reduce the specific surface area of mesoporous silicon.Mesoporous silicon and mesoporous silicon-tin composite pore-size distribution
As shown in figure 4, the aperture of mesoporous silicon is mainly distributed on 15.16nm, mesoporous silicon-tin composite aperture is mainly distributed on
9.53nm。
Take out mesoporous silicon obtained-tin composite powder, conductive black super P and binder polyvinyladine floride
(PVDF) 3:1:1 in mass ratio is mixed, and appropriate N-Methyl pyrrolidone (NMP) is added and is tuned into uniform slurry, (thickness is about for coating
5 μm) on copper foil of affluxion body.The copper foil for being coated with sample is put into vacuum oven, 10 hours dry in vacuum environment.
Sample after taking out drying, rushes electrode slice, and electrode slice diameter is 13mm.
The charge-discharge performance of sample is to test to obtain on new prestige charging/discharging apparatus.Electro-chemical test is in 2032 type buttons
It is carried out in battery system, electrolyte is 1M LiPF6It is dissolved in the EC/DEC (ethylene carbonate of addition 2%VC (vinylene carbonate)
Ester/diethyl carbonate, volume ratio 1:1) solution is metal lithium sheet to electrode.Above-mentioned button cell is connected to new prestige equipment
On, at room temperature, carry out constant current charge-discharge test.Stopping potential 0.01V is first discharged to the current density of 200mA/g
(vs.Li/Li+), after standing 2min, then stopping potential 3.0V (vs.Li/Li charged to the current density of 200mA/g+), it obtains
To circulation volume (see Fig. 5).
Mesoporous silicon prepared by the present embodiment-tin sample, 100 times circulation after specific discharge capacity be 1128.6mAh/g, put
Capacitance fall-off rate is respectively 51.7%；It is obviously improved compared to simple mesoporous silicon (88.7%), it is compound compared to mesoporous silicon-copper
Object material performance boost nearly 40%.
Embodiment 2
The charge-discharge performance of 1 sample of embodiment is to test to obtain on new prestige charging/discharging apparatus.Electro-chemical test exists
It is carried out in 2032 type button cell systems, electrolyte is 1M LiPF6It is dissolved in the EC/ of addition 2%VC (vinylene carbonate)
DEC (ethylene carbonate/diethyl carbonate, volume ratio 1:1) solution, is metal lithium sheet to electrode.Above-mentioned button cell is connected
It connects in new prestige equipment, at room temperature, carries out rate charge-discharge test.Detailed process is first to be put with the current density of 200mA/g
Electricity is to stopping potential 0.01V (vs.Li/Li+), after standing 2min, then stopping potential charged to the current density of 200mA/g
3.0V(vs.Li/Li+), it recycles ten times.Current density becomes 500,1000,2000mA/g according to this later, finally returns
200mA/g, every grade of current density recycle ten times, obtain high rate performance (see Fig. 6).Sn-Si composite electrode embodies excellent
High rate performance.0.5,1,2A g is arrived 0.2-1Current density, range is interior to provide 1605,1280,941,530mAhg-1Appearance
Amount, when current density switches back into 0.2Ag-1When, it is restored to 1441mAhg-1.Compared to mesoporous silicon-copper complex material, the performance has
It is obviously improved, promotes nearly 50%.
Embodiment 3
The electrochemical impedance spectroscopy of sample is tested by the CHI604E type Electrochemical Comprehensive Tester of Shanghai Chen Hua instrument company
It arrives, test frequency obtains ac impedance spectroscopy from 100kHz to 1Hz (see Fig. 7).The Charge-transfer resistance of mesoporous silicon is 835.6 Ω,
Mesoporous silicon-tin composite material Charge-transfer resistance is 117.68 Ω.
Embodiment 4
XRD (X-ray diffraction) test is carried out to mesoporous silicon-tin sample is prepared, test result is shown in Fig. 8.The peak of test result
It is all directed to Sn and Si, shows that the Success in Experiment has synthesized Sn-Si composite material.And by soft by Topas to the XRD spectrum
Part refine can obtain, and silicone content is in 85%wt, Theil indices 15%wt.
Claims (9)
1. a kind of mesoporous silicon-tin composite electrode material, which is characterized in that the material has the cellular structure of 5~40nm, tin
Mass fraction is 5~15%.
2. mesoporous silicon according to claim 1-tin composite electrode material preparation method characterized by comprising use
SnCl4After solution impregnates mesoporous silicon, mesoporous silicon-tin composite electrode material is prepared using the method for hydro-reduction
Material.
3. mesoporous silicon according to claim 2-tin composite electrode material preparation method, which is characterized in that described
SnCl4The concentration of solution is 50~400g/L, and mesoporous silicon is in SnCl4Additional amount in solution is 30~50g/L.
4. mesoporous silicon according to claim 2-tin composite electrode material preparation method, which is characterized in that when dipping
Between be 0.5~5h.
5. mesoporous silicon according to claim 2-tin composite electrode material preparation method, which is characterized in that hydrogenation is also
When former, the volume flow of hydrogen is 5~50sccm, and the volume flow of argon gas is 5~50sccm.
6. mesoporous silicon according to claim 2-tin composite electrode material preparation method, which is characterized in that hydrogenation is also
Former temperature is greater than 200 DEG C, and heating rate is 0.5~10 DEG C/min.
7. mesoporous silicon according to claim 6-tin composite electrode material preparation method, which is characterized in that hydrogenation is also
When former, temperature is 300~400 DEG C, keeps the temperature 1~5h.
8. mesoporous silicon according to claim 2-tin composite electrode material preparation method, which is characterized in that given an account of
Hole silicon is prepared by magnesium powder and meso-porous titanium dioxide silicon powder through magnesium thermit.
9. mesoporous silicon according to claim 1-tin composite electrode material is preparing the application in negative electrode of lithium ion battery.
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| CN110931746B (en) * | 2019-12-03 | 2022-04-26 | 东南大学 | Silicon-tin-graphene composite electrode material and preparation method and application thereof |
| CN111785951A (en) * | 2020-08-07 | 2020-10-16 | 昆明理工大学 | Preparation method of Sn-doped Si/C negative electrode material of lithium ion battery |
| CN115188955A (en) * | 2022-06-28 | 2022-10-14 | 中国科学院青岛生物能源与过程研究所 | Composite magnesium metal negative electrode active material with multiphase material and application thereof |
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