CN106784680A - One-dimensional silicon-carbon cathode material and preparation method thereof - Google Patents
One-dimensional silicon-carbon cathode material and preparation method thereof Download PDFInfo
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- CN106784680A CN106784680A CN201611181142.8A CN201611181142A CN106784680A CN 106784680 A CN106784680 A CN 106784680A CN 201611181142 A CN201611181142 A CN 201611181142A CN 106784680 A CN106784680 A CN 106784680A
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- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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 one-dimensional silicon-carbon cathode material and preparation method thereof, the silicon-carbon cathode material is mainly made up of silicon nanowires, passivating film and Pintsch process carbon.The present invention carries out nanosizing for the shortcoming of elemental silicon to silicon, and it is silicon source to use one-dimensional silicon nanowires, and one layer of passivating film is formed on its surface in oxidizing atmosphere, and its volumetric expansion is suppressed as protective layer.And with Pintsch process carbon coating, on the one hand silicon nanowires can be protected as clad, it is to avoid its directly contact with electrolyte.On the other hand, the electrical conductivity of elemental silicon can be improved again.When the Si-C composite material of present invention synthesis is as lithium ion battery negative, excellent chemical property and good cyclical stability is shown.
Description
Technical field
The present invention relates to lithium ion battery negative material field, and in particular to a kind of lithium-ion battery silicon-carbon anode material
And preparation method thereof.
Background technology
As the lithium rechargeable battery of new green power, because it has many advantages, such as, and turn into it is strong in new energy and
One of strong candidate.Lithium ion battery negative material is the important component of lithium ion battery, the composition of negative material
There is conclusive influence on the chemical property of lithium ion battery with structure.The current commodity widely used graphite of lithium ion battery
Negative pole.But its theoretical energy density is only 372mAh/g, the development of graphite electrode is seriously constrained.
And the theoretical energy density of silicium cathode is up to 4200mAh/g, more than 10 times of graphite, it is considered as most having development potentiality
Cathode material of lithium ion battery.But, silicium cathode material has serious volumetric expansion, Yi Zao in charge and discharge process
Efflorescence, rupture into structure, so as to lose circulation ability.Therefore, to meet the demand of high-capacity lithium ion cell, by suppressing
The volumetric expansion of silicon, improves the structural stability and conductance of material to improve the cyclical stability of silicon materials will be future development
Main trend.It is general elementary silicon is modified using following methods for the problem that elementary silicon is present：Silicon grain nanometer
Change, the doping of silicon materials and Coated with Organic Matter and prepare composite.The present invention proposes a kind of new synthesis to be had well
Stability silicon-carbon cathode material preparation method.
The content of the invention
The purpose of the present invention is exactly that in prior art basis, solution silicon-carbon cathode material cyclical stability is poor, capacity declines
Subtract fast problem.
Another object of the present invention is to provide a kind of preparation method of above-mentioned one-dimensional silicon-carbon cathode material.
To achieve the above object, the technical solution adopted by the present invention is as follows：
One-dimensional silicon-carbon cathode material, the negative material is made up of silicon nanowires, passivating film and Pintsch process carbon, in three-layer sandwich
Structure, wherein innermost layer are silicon nanowires, account for the 5-50% of silicon-carbon cathode material gross mass, and intermediate layer is passivating film, account for silicon-carbon and bear
The 0.5-10% of pole material gross mass, outermost layer is Pintsch process carbon, accounts for the 40-85% of silicon-carbon cathode material gross mass.
The preparation method of above-mentioned one-dimensional silicon-carbon cathode material, using following steps：
（1）Silicon nanowires is listed in saggar according to certain thickness, is placed in the atmosphere containing oxidizing gases, insulation one
The section time, surface of silicon nanowires is set to produce passivation, afterwards, cooling is standby；
（2）Pintsch process carbon source is dissolved in solvent and forms carbon source solution, by step（1）Silicon nanowires adds above-mentioned solution after passivation
In, ultrasonic disperse 10-60min obtains the mixed solution that solid content is 10-50%；
（3）Above-mentioned mixed solution is spray-dried using spray dryer, is obtained Si-C composite material presoma；
（4）Si-C composite material presoma is placed in carbonization treatment in tube furnace, is ground, sieving obtains Si-C composite material.
Further, step（1）Middle silicon nanowires laying depth is 0.1-2cm, oxidizing gas be following one kind or
Several mixing：Oxygen, ozone, air, temperature are 200-700 DEG C, and soaking time is 0.1-2h.
Further, step（2）Pintsch process carbon source is the following mixing of one or more：Glucose, polyethylene glycol,
Citric acid, sucrose, starch；The solvent of dissolving Pintsch process carbon source used is water, absolute ethyl alcohol, tetrahydrofuran, isopropanol, acetone
With one or more in cyclohexanone；Carbon source mass fraction accounts for 20-50% in carbon source solution.
Further, step（4）Middle carburizing temperature is 600-800 DEG C, and carbonization time is 2-8h, and protective atmosphere is nitrogen
One kind in gas, argon gas, neon.
Further, step（2）The power of described ultrasonic disperse is 200-600W；The temperature of ultrasonic disperse is 25 DEG C.
Further, step（3）Described Si-C composite material presoma is powdered.
Beneficial effect
The present invention has synthesized a kind of silicon-carbon cathode material of silicon nanowires-passivating film-Pintsch process carbon three-layer sandwich structure.Using
One-dimensional silicon nanowires is silicon source, and as " heart " of interlayer structure, makes its surface that passivation to occur and form one layer of passivating film, as guarantor
Sheath suppresses its volumetric expansion.The cladding of outermost layer Pintsch process carbon, acts not only as the another protection of silicon nanowires
Layer, it is to avoid its directly contact with electrolyte, and the electrical conductivity of silicon-carbon cathode material can be improved again.The silicon-carbon of present invention synthesis
Composite has good cyclical stability and excellent chemical property.
Brief description of the drawings
Fig. 1 schemes for the SEM of the lithium ion battery negative material of embodiment 1.
Fig. 2 is the XRD of the lithium ion battery negative material of embodiment 1.
Fig. 3 is the charging and discharging curve figure of the lithium ion battery negative material of embodiment 1.
Specific embodiment：
Preferably to embody the present invention, several case study on implementation are now enumerated, but the invention is not limited in following case.
Embodiment 1
（1）Silicon nanowires is listed in saggar according to the thickness of 0.1cm, is placed in 700 DEG C in air atmosphere, be incubated 0.1h, made
Surface of silicon nanowires is passivated, and afterwards, cooling is standby；
（2）Weigh 100g glucose to be dissolved in 100ml water, by step（1）The material for obtaining is added in above-mentioned glucose solution,
Ultrasonic disperse 10min, obtains mixed solution under the power of 600W；
（3）Above-mentioned mixed solution is spray-dried using spray dryer, is obtained powdered Si-C composite material forerunner
Body；
（4）Si-C composite material presoma is placed in 800 DEG C of carbonization treatment 2h in tube furnace, is ground, sieving obtains silicon-carbon and is combined
Material.
The silicon-carbon cathode of preparation is used as lithium ion battery negative material.Electrode preparation method is as follows：It is negative by silicon-carbon
Pole：Conductive agent：PTFE=80:15:5 weigh, mashing, after slurry is in dough, thin slice are pressed into twin rollers, through drying, beat
Hole, is obtained cathode pole piece.It is that, to electrode, microporous polypropylene membrane is barrier film, 1mol/LLiPF with metal lithium sheet6（=1:1:1）It is electricity
Solution liquid, is assembled into button cell in glove box, in the voltage range of 0.005 ~ 2V, with the charge-discharge magnification of 0.2C, carries out
Constant current charge-discharge test.Prepared silicon-carbon cathode material, the reversible capacity in 0.2C is 857.4mAh/g, after 50 circulations
Capability retention is 82.2%.
Embodiment 2
（1）Silicon nanowires is listed in saggar according to the thickness of 1cm, is placed in 600 DEG C in oxygen atmosphere, be incubated 1.5h, make silicon
Nanowire surface is passivated, and afterwards, cooling is standby；
（2）Weigh 50g polyethylene glycol and 100g sucrose is dissolved in 200ml water, by step（1）The material for obtaining adds above-mentioned carbon source
In solution, ultrasonic disperse 15min, obtains mixed solution under the power of 400W；
（3）Above-mentioned mixed solution is spray-dried using spray dryer, is obtained powdered Si-C composite material forerunner
Body；
（4）Si-C composite material presoma is placed in 600 DEG C of carbonization treatment 8h in tube furnace, is ground, sieving obtains silicon-carbon and is combined
Material.
The silicon-carbon cathode of preparation is used as lithium ion battery negative material.Electrode is prepared and method of testing and embodiment
1 is identical.Silicon-carbon cathode material prepared by embodiment 2, the reversible capacity in 0.2C is 806.0mAh/g, is held after 50 circulations
Amount conservation rate is 84.1%.
Embodiment 3
（1）Silicon nanowires is listed in saggar according to the thickness of 2cm, is placed in 200 DEG C in oxygen atmosphere, be incubated 2h, silicon is received
Nanowire surface is passivated, and afterwards, cooling is standby；
（2）Weigh 50g starch and 100g citric acids are dissolved in 200ml absolute ethyl alcohols, by step（1）The material for obtaining adds above-mentioned
In carbon source solution, ultrasonic disperse 60min, obtains mixed solution under the power of 200W；
（3）Above-mentioned mixed solution is spray-dried using spray dryer, is obtained powdered Si-C composite material forerunner
Body；
（4）Si-C composite material presoma is placed in 700 DEG C of carbonization treatment 5h in tube furnace, is ground, sieving obtains silicon-carbon and is combined
Material.
The silicon-carbon cathode of preparation is used as lithium ion battery negative material.Electrode is prepared and method of testing and embodiment
1 is identical.Silicon-carbon cathode material prepared by embodiment 3, the reversible capacity in 0.2C is 862.3mAh/g, is held after 50 circulations
Amount conservation rate is 81.8%.
Comparative example 1
（1）Weigh 50g polyethylene glycol and 62g glucose is dissolved in 150ml water, during silicon nanowires added into above-mentioned carbon source solution,
Ultrasonic disperse 40min, obtains mixed solution under the power of 500W；
（2）Above-mentioned mixed solution is spray-dried using spray dryer, is obtained powdered Si-C composite material forerunner
Body；
（3）Si-C composite material presoma is placed in 600 DEG C of carbonization treatment 2h in tube furnace, is ground, sieving obtains silicon-carbon and is combined
Material.
Silicon-carbon cathode prepared by comparative example 1 is used as lithium ion battery negative material.Its electrode is prepared and test side
Method is carried out according to embodiment 1.Silicon-carbon cathode material prepared by comparative example 1, the reversible capacity in 0.2C is 818.2mAh/g,
Capability retention is 72.5% after 50 circulations.
Claims (7)
1. one-dimensional silicon-carbon cathode material, it is characterised in that the negative material is by silicon nanowires, passivating film and Pintsch process carbon group
Into in three-layer sandwich structure, wherein innermost layer is silicon nanowires, accounts for the 5-50% of silicon-carbon cathode material gross mass, and intermediate layer is blunt
Change film, account for the 0.5-10% of silicon-carbon cathode material gross mass, outermost layer is Pintsch process carbon, accounts for silicon-carbon cathode material gross mass
40-85%。
2. the preparation method of the one-dimensional silicon-carbon cathode material described in claim 1, it is characterised in that use following steps：
（1）Silicon nanowires is listed in saggar according to certain thickness, is placed in the atmosphere containing oxidizing gases, insulation one
The section time, surface of silicon nanowires is set to produce passivation, afterwards, cooling is standby；
（2）Pintsch process carbon source is dissolved in solvent and forms carbon source solution, by step（1）Silicon nanowires adds above-mentioned solution after passivation
In, ultrasonic disperse 10-60min obtains the mixed solution that solid content is 10-50%；
（3）Above-mentioned mixed solution is spray-dried using spray dryer, is obtained Si-C composite material presoma；
（4）Si-C composite material presoma is placed in carbonization treatment in tube furnace, is ground, sieving obtains Si-C composite material.
3. preparation method according to claim 2, it is characterised in that：Step（1）Middle silicon nanowires laying depth is 0.1-
2cm, oxidizing gas are the following mixing of one or more：Oxygen, ozone, air, temperature are 200-700 DEG C, during insulation
Between be 0.1-2h.
4. preparation method according to claim 2, it is characterised in that：Step（2）Pintsch process carbon source is following one kind
Or several mixing：Glucose, polyethylene glycol, citric acid, sucrose, starch；It is used dissolving Pintsch process carbon source solvent for water,
One or more in absolute ethyl alcohol, tetrahydrofuran, isopropanol, acetone and cyclohexanone；Carbon source mass fraction is accounted in carbon source solution
20-50%。
5. preparation method according to claim 2, it is characterised in that：Step（4）Middle carburizing temperature is 600-800 DEG C, carbon
The change time is 2-8h, and protective atmosphere is the one kind in nitrogen, argon gas, neon.
6. preparation method according to claim 2, it is characterised in that step（2）The power of described ultrasonic disperse is
200-600W；The temperature of ultrasonic disperse is 25 DEG C.
7. preparation method according to claim 2, it is characterised in that step（3）Described Si-C composite material presoma
For powdered.
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Cited By (1)
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| CN107732192A (en) * | 2017-09-30 | 2018-02-23 | 中国有色桂林矿产地质研究院有限公司 | Used as negative electrode of Li-ion battery Si-C composite material and preparation method thereof |
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