CN103165874A - Porous silicon negative material of lithium ion battery and preparation method and application of material - Google Patents
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- CN103165874A CN103165874A CN2013101228114A CN201310122811A CN103165874A CN 103165874 A CN103165874 A CN 103165874A CN 2013101228114 A CN2013101228114 A CN 2013101228114A CN 201310122811 A CN201310122811 A CN 201310122811A CN 103165874 A CN103165874 A CN 103165874A
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Abstract
The invention discloses a porous silicon negative material of a lithium ion battery, and a preparation method and application of the material. The method comprises the following steps of: reacting silicon alloy powder, which is taken as a raw material, with inorganic acid to generate porous silicon particles; and washing the porous silicon particles by an HF (Hydrogen Fluoride) acid solution to eliminate surface silicon oxide, and washing and drying the washed porous silicon particles so as to obtain the porous silicon material. The porous silicon material prepared by the method has a sponge-shaped structure which is formed by linking nano silicon particles; the particle sizes of the particles of the porous silicon negative material range from 0.01 micron to 50 microns; the specific surface area of the material is 30-600cm<2>/g; the porous silicon negative material can be taken as a negative material of a lithium ion battery; and in a lithium ion battery electrolyte, the porous silicon powder shows high specific discharge capacity and charge-discharge circulation stability. The porous silicon negative material has the advantages of low cost, simplicity and convenience in method and high electrochemical property, and can be applied to production of silicon negative materials of high-performance lithium ion batteries.
Description
Technical field
The invention belongs to new energy field, relate to a kind of lithium ion battery, specifically, relate to a kind of lithium ion battery porous silicon negative material and preparation method thereof.
The present invention is a new energy field., As a new energy batteries, lithium-ion battery is the highest energy density, wide range of uses can charge and discharge the battery, is the most promising electric vehicle batteries, lithium for the current practical low ion battery cathode active material graphite discharge capacity (372, mAh / g) issues the patent invented acid etching silicon alloy powder prepared by high-performance lithium-ion battery porous silicon method, a lithium-ion battery cathode active substances, the porous silicon has a higher than 2000, mAh / g discharge capacity., after 150 charge-discharge cycles, the discharge capacity is still higher than 1500, mAh / g. performance of porous silicon material 5 times graphite materials used in the now. and graphite, like, when prepared porous silicon material for lithium ion batteries, the battery voltage is constant, and has the same security. facilitate the production of the present invention, a low cost, outstanding material properties , this is a breakthrough invention., using the present process of porous silicon material will greatly improve the performance of lithium-ion batteries.
Background technology
Along with the development of electric automobile and electronics industry, the performance of lithium ion battery is had higher requirement.Due to the theoretical specific discharge capacity lower (372 mAh/g) of practical at present lithium ion battery negative pole active materials graphite, develop the focus that the new negative material with height ratio capacity becomes research and development.Although lithium metal has very high theoretical specific discharge capacity (3862 mAh/g), owing to existing insoluble being easy in charge and discharge process to generate the unsafe factors such as dendrite, efflorescence, develop so far unhappyly, bottleneck is arranged.Another kind of possible method is to utilize to generate the material of alloy with lithium, as Si, Al, Sn, Mg and oxide thereof etc., makes the lithium alloy negative pole.Wherein Si is the material that practical prospect is arranged most.Silicon and lithium can generate Li
4.4Si.Press silicon and calculate, its specific discharge capacity can reach 4200 mAh/g.But due to the embedding of lithium, the volumetric expansion of silicon material reaches 3.2 times in charging process.The sharp drastic change of volume, can cause the efflorescence of silicon grain in charge and discharge process, thereby make loose contact, and electrode performance descends very soon.Exist in addition the diffusion coefficient of lithium in the lithium silicon alloy less, and as the shortcoming such as the conductivity of Semiconducting Silicon Materials is relatively poor.For these problems, several different methods has been proposed, as employing nano-silicon, nano cilicon fibre and nano carbon tube, mesoporous and porous nano silicon materials, and nano-silicone wire/carbon composite material etc.Generally speaking, these material preparation method more complicated, cost are higher, are difficult for large-scale production.
Summary of the invention
The purpose of this invention is to provide a kind of easy new method of utilizing acid etch silicon alloy powder preparation porous silica material, the material of the method gained has quite high specific discharge capacity and discharges and recharges stability as lithium ion battery negative, and practical prospect is arranged very much.
For achieving the above object, the invention provides a kind of preparation method of lithium ion battery porous silicon negative material, the method is take the silicon alloy powder as raw material, generates the porous silicon particulate with inorganic acid reaction; After the Surface Oxygen SiClx was removed in the cleaning of HF acid solution, washing was dried and is obtained porous silica material again.
The preparation method of above-mentioned lithium ion battery porous silicon negative material, wherein, described silicon alloy powder is sial, ferrosilicon or Si-Mg alloy powder.
The preparation method of above-mentioned lithium ion battery porous silicon negative material, wherein, the particle diameter of described silicon alloy powder is 0.01 μ m-50 μ m, the silicon content of described silicon alloy powder is 5% to 90% by mass percentage.
The preparation method of above-mentioned lithium ion battery porous silicon negative material, wherein, described inorganic acid is hydrochloric acid or sulfuric acid, the mass percent concentration of described inorganic acid is 0.1%-30%.
The preparation method of above-mentioned lithium ion battery porous silicon negative material, wherein, the mass percent concentration of described HF acid solution is 0.5%-20%.
The present invention also provides a kind of lithium ion battery porous silicon negative material according to the said method preparation, described porous silicon negative material has the spongelike structure that is formed by the connection of nano-silicon particulate, the particle diameter of this porous silicon negative material particulate is 0.01 μ m-50 μ m, and specific area is 30-600cm
2/ g.
The present invention also provides a kind of purposes of the lithium ion battery porous silicon negative material according to said method preparation, and this porous silicon negative material is used for lithium ion battery negative, and the electrolyte of this lithium ion battery is LiPF
6/ ethylene carbonate (EC)+dimethyl carbonate (DMC), LiPF
6/ ethylene carbonate (EC)+diethyl carbonate (DEC), and LiPF
6Any one in/ethylene carbonate (EC)+dimethyl carbonate (DMC)+diethyl carbonate (DEC).Wherein, the meaning of "/" representative " being dissolved in " is as " LiPF
6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) " the expression solute is LiPF
6, solvent is the mixed solvent of EC and DMC, i.e. LiPF
6Be dissolved in EC and DMC.
Above-mentioned purposes, wherein, LiPF in described lithium-ion battery electrolytes
6Concentration be 0.5-1.5mol/L.
Above-mentioned purposes, wherein, also adding in described lithium-ion battery electrolytes has additive, and described additive refers to the perfluorocarbon acid vinyl acetate, and its concentration is 1-30% by mass percentage.
Above-mentioned purposes, wherein, also adding in described lithium-ion battery electrolytes has additive, and described additive refers to vinylene carbonate, and its concentration is 1-30% by mass percentage.
The present invention has initiated a kind of preparation method of new lithium ion battery negative silicon materials, the method utilizes silicon alloy powder (sial, ferrosilicon, silicon magnesium etc.) as raw material, utilize acid-etched method, make itself and acid reaction, can make the porous silicon powder after cleaning and drying, the particle diameter of this porous silicon powder is 0.01 μ m-50 μ m, and porosity (that is, the ratio of the hole of porous mass possessive volume in whole object) is 10%-90%; As lithium ion battery negative material, in lithium-ion battery electrolytes, the porous silicon powder has shown high specific discharge capacity and charge and discharge cycles stability: more than first specific discharge capacity can reach 2000mAh/g, more than still remaining on 1500mAh/g after discharging and recharging 150 times.Interpolation perfluorocarbon acid vinyl acetate (FEC) and/or vinylene carbonate (VC) can effectively improve specific discharge capacity and the charge and discharge cycles stability of porous silicon powder in electrolyte.Further, adopt the organic compound thermal decomposition can significantly improve the conductivity of porous silica material in the method for the surperficial bag of porous silicon powder carbon, thereby improve specific discharge capacity and charge and discharge cycles stability.Adopt method of the present invention to prepare the lithium ion battery negative silicon materials and have that cost is low, method is easy, the advantage that the resulting materials chemical property is high can be applicable to the production of high performance lithium ion battery silicium cathode material.
Description of drawings
Fig. 1 is scanning electron microscopy (scanning electron microscope the is called for short SEM) figure of the porous silicon powder of a kind of lithium ion battery porous silicon negative material of the present invention.
Fig. 2 is X-ray diffraction (XRD) figure of the porous silicon powder of a kind of lithium ion battery porous silicon negative material of the present invention.
Fig. 3 is the charging and discharging curve of the Porous Silicon Electrode of a kind of lithium ion battery porous silicon negative material of the present invention, and wherein, electrolyte is 1mol/L LiPF
6/ EC+DMC (1:1)+15% FEC(perfluorocarbon acid vinyl acetate), current density is 100 mA/g.
Fig. 4 is the cycle performance of the Porous Silicon Electrode of a kind of lithium ion battery porous silicon negative material of the present invention, electrolyte 1mol/L LiPF
6/ EC+DMC (1:1)+15% FEC, current density is 100 mA/g.
Embodiment
Porous nano silicon materials of the present invention are made by hydrochloric acid etching silicon alloy powder (comprising sial, ferrosilicon, silicon magnesium etc.): (composition: the silicon content of silicon alloy powder is that mass percent counts 5% to 90% to take the silicon alloy of certain mass, powder diameter: 0.01 μ m-50 μ m), add in batches excessive HCl, or H
2SO
4In (analyzing pure) aqueous solution (mass percent concentration 0.1%-30%), and constantly stir with magnetic stirring apparatus.Product through washed with de-ionized water repeatedly.Then be placed in HF solution (mass percent concentration 0.5%-10%) and stirred several hours, with the SiO on dissolves silicon surface
2Use respectively deionized water, absolute ethanol washing repeatedly again.Be placed at last vacuum drying oven, oven dry under 80 ℃.The particle of gained porous silica material is approximately less than 30 μ m, and has the spongy loose structure that significantly is gathered into by nanoparticle.Be distributed in whole particle to fine and closely woven porous nickel in particle, this is formed by the acid reaction loss by dissolution.The X-ray structural analysis shows, porous silica material has crystallinity preferably.
Adopt conductive materials carbon black (Super P, i.e. conductive black) and water-soluble adhesive glue to prepare Porous Silicon Electrode: the composition of water-soluble adhesive glue is to contain the hydrosol that mass percent is counted the styrene butadiene rubbers of 10-80% (SBR)+sodium carboxymethylcellulose (CMC).Porous silicon, carbon black, adhesive glue be furnishing electrode sizing material according to a certain ratio.This sizing material is coated on Copper Foil equably, dries under 80 ℃ of vacuum, make the negative electrode for lithium ion battery sheet.
Positive electrode in lithium ion battery take Porous Silicon Electrode as negative pole is LiCoO
2, LiMn
2O
4, or LiFePO
4, take microporous polypropylene membrane as barrier film, electrolyte is LiPF
6/ ethylene carbonate (EC)+dimethyl carbonate (DMC), LiPF
6/ ethylene carbonate (EC)+diethyl carbonate (DEC), and LiPF
6/ ethylene carbonate (EC)+dimethyl carbonate (DMC)+diethyl carbonate (DEC), and contain the solution of organic additive; LiPF in electrolyte
6Concentration be 0.5-1.5mol/L; Additive is perfluorocarbon acid vinyl acetate (FEC), and its concentration is 1-30%; And vinylene carbonate (VC), concentration is 1-30%.
Below in conjunction with drawings and Examples, technical scheme of the present invention is described further.
Embodiment
The porous nano silicon materials are made by hydrochloric acid etching SiAl alloy powder.Take silicon-aluminum (composition: 80% Al, 20% Si, particle diameter the be 15 μ m approximately) powder of certain mass, add in batches 8% excessive HCl(AR) in the aqueous solution, and constantly stir with magnetic stirring apparatus.Product is through washed with de-ionized water three times, to remove AlCl
3Then be placed in 2% HF ethanolic solution and stir 2h, with the SiO on dissolves silicon surface
2Use respectively deionized water, absolute ethanol washing repeatedly again.Be placed at last vacuum drying oven, oven dry makes the porous nano Si powder under 80 ℃.As shown in Figure 1, be the SEM figure of porous silicon powder, as seen, the particle of material is approximately less than 20 μ m, and has the obvious spongy loose structure that is gathered into by nanoparticle.Fine and closely woven hole in particle is by forming after al composition in silicon-aluminum and hydrochloric acid reaction loss by dissolution.Pore is evenly distributed in whole particle.The specific area that records porous silicon is 102.7cm
2/ g.Fig. 2 is the XRD figure of porous silicon powder.Be 28.5 °, 47.4 °, 56.2 °, 69.3 °, 76.5 ° and 88.2 ° of characteristic diffraction peaks of locating to occur crystalline silicon at 2 θ in figure, and there is no other impurity crystal diffraction peak appearance.Illustrate that the porous silicon powder that makes has good crystal structure and purity.
Experiment adopts Philip Philips XL300 type ESEM to measure the microscopic appearance of material.Adopt the crystal structure of the Brooker Bruker D8 of company type X-ray diffractometer working sample.Adopt the specific area of specific area and pore size distribution determining instrument (Micromeritics ASAP 2010 types) working sample.
Further, in some more excellent embodiment, the above-mentioned porous nano Si powder that makes is processed through bag carbon method.Bag carbon method refers to that the carbon sources such as a porous Si and citric acid are mixed in organic solvent in certain proportion, stir.Mixture is put into tube furnace, under the argon atmosphere that flows, heat-treat under uniform temperature.Process the conductivity that can significantly improve porous silica material through bag carbon method, thereby improve specific discharge capacity and charge and discharge cycles stability.
Adopt conductive materials carbon black (Super P) and water-soluble adhesive glue to prepare Porous Silicon Electrode.The composition of water-soluble adhesive glue is to contain 50% SBR+CMC(mass ratio 1: 1) the hydrosol.Porous Silicon Electrode component proportioning is, porous silicon: carbon black: binding agent=1: 1: 1 is made into glue.Glue is coated on Copper Foil equably, dries under 80 ℃ of vacuum, be washed into the pole piece of diameter 14mm.Contain approximately 0.3mg of porous silicon in every pole piece.Continuation is at 80 ℃ of lower vacuumize 8h.After temperature is down to room temperature, be assembled into button cell (CR2016) in argon gas glove box (Super 1220/750, that Mikrouna of Mi Kailuo).In battery is metal lithium sheet to electrode, and microporous polypropylene membrane (Celgard 2300) is barrier film, and electrolyte is to contain the 1mol/L LiPF that mass percent is 15% FEC
6/ EC+DMC (volume ratio of EC and DMC is 1:1) solution (available from Guotai Huarong Chemical New Material Co., Ltd., Zhangjiagang City), the LiPF6 solute that is 1mol is dissolved in the EC+DMC mixed solvent of 1L, and in mixed solvent, the volume ratio of EC and DMC is 1:1.
Constant current charge-discharge test is carried out discharging and recharging on instrument system of Land Instr Ltd., and charging and discharging currents density is 100 mA/g.The cell voltage that discharges and recharges is interval is 0.01V-1.5V.Fig. 3 is that Porous Silicon Electrode is at 1mol/L LiPF
6Charging and discharging curve figure in/EC+DMC (1:1)+15% FEC electrolyte, wherein, C1 represents charging curve for the first time, and C2 represents charging curve for the second time, and D1 represents discharge curve for the first time, and D2 represents discharge curve for the second time.Individual current potential level ground section is arranged at the 1.4V place, and this is corresponding to the decomposition of FEC on the Si surface, to generate different SEI film (solid electrolyte interface, solid electrolyte interface film).Total electric weight of initial charge is 3450 mAh/g, and discharge capacity is 2072mAh/g, and efficiency for charge-discharge is 60%.And discharge curve almost overlaps with curve first for the second time.The charge-discharge performance curve of the Porous Silicon Electrode of showing from Fig. 4 as can be known (wherein, the c curve represents charging curve, d represents discharge curve), the pseudo-discharge capacity curve of Porous Silicon Electrode is comparatively steady, have fine institute charge-discharge performance. at the 152nd circulation time, its discharge capacity still can remain on 1540mAh/g, and the capacity retention is 74.4%.The high charge-discharge stability of material is attributable to nano particle and the porousness of material.Nano particle is conducive to Li
+The diffusion of ion.The porousness of material makes between enough microvoids to bear sharp acute expansion of silicon in charging process.And each nano-silicon particulate joins together, and spongelike structure is difficult for rupturing because of the expansion in charge and discharge process, contraction.
As mentioned above, utilize acid etch SiAl alloy to prepare that the method for porous silicon powder powder material is easy and simple to handle, cost is lower.As lithium ion battery negative material, gained porous silicon powder has quite high specific discharge capacity and well discharges and recharges stability in the electrolyte that contains the FEC additive.
The present invention proposes to utilize the method for acid etch Si alloy (preferred SiAl alloy contains Al 80%) powder to prepare porous silica material first.The analysis showed that material is crystal, and have the spongy loose structure that is integrated into by nano particle.The particle diameter of porous silicon powder is about 15 μ m, and specific area is about 100cm
2/ g.Nano particle is conducive to Li
+The diffusion of ion, the porousness of material make sharp acute expansion that can bear silicon in charging process between enough microvoids, are conducive to the negative material as lithium ion battery.And the nano-silicon particulate joins together, and whole being difficult for ruptures because expanding, shrinking.At the 1mol/L LiPF that adds 15% FEC
6In/EC+DMC (1:1) electrolyte, discharge and recharge under the 100mA/g current density, the first discharge specific capacity of Porous Silicon Electrode is higher, greater than 2000mAh/g.After circulation, more than its discharge capacity still can remain on 1500mAh/g, shown the high stability that discharges and recharges after discharging and recharging for 152 times.The new method of this preparation lithium ion battery porous silicon negative material has easy and simple to handle, lower-cost advantage, and outstanding application prospect is arranged.
Although content of the present invention has been done detailed introduction by above preferred embodiment, will be appreciated that above-mentioned description should not be considered to limitation of the present invention.After those skilled in the art have read foregoing, for multiple modification of the present invention with to substitute will be all apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (10)
1. the preparation method of a lithium ion battery porous silicon negative material, is characterized in that, the method is take the silicon alloy powder as raw material, generates the porous silicon particulate with inorganic acid reaction; After the Surface Oxygen SiClx was removed in the cleaning of HF acid solution, washing was dried and is obtained porous silica material again.
2. the preparation method of lithium ion battery porous silicon negative material as claimed in claim 1, is characterized in that, described silicon alloy powder is sial, ferrosilicon Huo Gui Magnesium alloy powder.
3. the preparation method of lithium ion battery porous silicon negative material as claimed in claim 2, is characterized in that, the particle diameter of described silicon alloy powder is 0.01 μ m-50 μ m, and the silicon content of described silicon alloy powder is 5% to 90% by mass percentage.
4. the preparation method of lithium ion battery porous silicon negative material as claimed in claim 1, is characterized in that, described inorganic acid is hydrochloric acid or sulfuric acid, and the mass percent concentration of described inorganic acid is 0.1%-30%.
5. the preparation method of lithium ion battery porous silicon negative material as claimed in claim 1, is characterized in that, the mass percent concentration of described HF acid solution is 0.5%-20%.
6. the lithium ion battery porous silicon negative material of the described method preparation of any one in a kind according to claim 1-5, it is characterized in that, described porous silicon negative material has the spongelike structure that is formed by the connection of nano-silicon particulate, the particle diameter of this porous silicon negative material particulate is 0.01 μ m-50 μ m, and specific area is 30-600cm
2/ g.
7. the purposes of the lithium ion battery porous silicon negative material of a method preparation according to claim 1, is characterized in that, this porous silicon negative material is used for lithium ion battery negative, and the electrolyte of this lithium ion battery is: solute LiPF
6Be dissolved in the solution that forms in the mixed solvent of ethylene carbonate and dimethyl carbonate, solute LiPF
6Be dissolved in the solution that forms in the mixed solvent of ethylene carbonate and diethyl carbonate, and, solute LiPF
6Be dissolved in any one in the solution that forms in the mixed solvent of ethylene carbonate, dimethyl carbonate and diethyl carbonate.
8. purposes as claimed in claim 7, is characterized in that, LiPF in described lithium-ion battery electrolytes
6Concentration be 0.5-1.5mol/L.
9. purposes as claimed in claim 7, is characterized in that, also adding in described lithium-ion battery electrolytes has additive, and described additive refers to the perfluorocarbon acid vinyl acetate, and its concentration is 1-30% by mass percentage.
10. purposes as claimed in claim 7, is characterized in that, also adding in described lithium-ion battery electrolytes has additive, and described additive refers to vinylene carbonate, and its concentration is 1-30% by mass percentage.
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