CN107425184A - A kind of silicon porous carbon electrode material and its preparation method and application - Google Patents
A kind of silicon porous carbon electrode material and its preparation method and application Download PDFInfo
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- CN107425184A CN107425184A CN201710573128.0A CN201710573128A CN107425184A CN 107425184 A CN107425184 A CN 107425184A CN 201710573128 A CN201710573128 A CN 201710573128A CN 107425184 A CN107425184 A CN 107425184A
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- 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
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- 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
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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Abstract
The invention discloses a kind of silicon porous carbon electrode material and its preparation method and application.Described silicon porous carbon electrode material is that silicon nanoparticle is dispersed on porous carbon template, and silicon porous carbon electrode material has the pore passage structure that aperture is 4 500nm, the 400m of specific surface area 1802/g.The preparation method, including：By the mixture ultrasonic disperse of nano silica fume and nano oxidized magnesium dust in sucrose solution, being heated after drying makes sucrose be carbonized, and then washes away nano magnesia with HCl solution, produces silicon porous carbon electrode material.Present invention also offers application of the described silicon porous carbon electrode material in negative electrode of lithium ion battery.Silicon porous carbon electrode material of the present invention, good cycling stability, high rate performance are high, are produced on a large scale.
Description
Technical field
The invention belongs to battery material field, more particularly to a kind of capacity height, good rate capability, the silicon-porous of low cost
Carbon electrode material, further relate to the preparation method of the electrode material.
Background technology
The superior function of lithium ion battery makes it in portable electric appts, electric tool, the vehicles, Aero-Space etc.
Aspect all has broad application prospects.
Commercial negative material still based on the carbon material of carbon element of graphite class, only have by its theoretical maximum specific capacity at present
372mAh/g, constrain the further raising of lithium battery capacity.Silicon has the advantages that lithium storage content is high, earth resource is abundant, has
The negative material as lithium ion battery of future generation is hoped, the appearance of battery can be substantially improved by being used as the negative pole of lithium ion battery
Amount.The theoretical capacity of silicon is up to 4200mAh/g, is more than 10 times of carbon negative material capacity.But conventional research table
It is bright, silicon based electrode during charge and discharge cycles, i.e., Lithium-ion embeding, abjection electrode during, Volume Changes it is huge (>
300%), cause the avalanche of material structure and the peeling of electrode, efflorescence, the decline of electrical conductivity, and then cause battery capacity to fall sharply.
Simultaneously as silicon is semiconductor, intrinsic conductivity is low, and the high-rate charge-discharge capability of pure silicon material is poor.
In recent years, by the method with carbon material composite lifting silicon based electrode material circulation performance and high rate performance by wide
General concern.The Si-C composite material of a variety of special constructions shows good cyclical stability and high rate capability.But these
The preparation method of material often has some shortcomings, such as preparation technology is tediously long, cost is high, has pollution to environment, is difficult to advise greatly
Mould production etc..
The content of the invention
Technical problem：For overcome the deficiencies in the prior art, the invention provides a kind of silicon-porous carbon electrode material and its system
Preparation Method and application, the material circulation stability is good, good rate capability, cost are low, it is environment-friendly, be produced on a large scale.This hair
Another bright purpose is to provide the preparation method and application of the silicon-porous carbon electrode material.
Technical scheme：A kind of silicon-porous carbon electrode material of the present invention is dispersed on porous carbon template for silicon nanoparticle,
Silicon-porous carbon electrode material has the pore passage structure that aperture is 4-500nm, specific surface area 180-400m2/g。
The preparation method of silicon-porous carbon electrode material of the present invention is：By the mixed of nano silica fume and nano oxidized magnesium dust
For compound ultrasonic disperse in sucrose solution, being heated after drying makes sucrose be carbonized, and then washes away nano magnesia with HCl solution, i.e.,
Obtain silicon-porous carbon electrode material.
Wherein：
The mass ratio of the silica flour and magnesia powder is 1：(1.0-4.0).
The mass ratio of silica flour and sucrose is 1：(1.0-5.0).
The particle diameter of the magnesia powder is 10-500nm.
The concentration of the sucrose solution is 0.02-0.50g/mL.
The temperature of the high temperature cabonization is more than 700 DEG C, is incubated 3-10 hours.
Silicon-the porous carbon electrode material is applied in negative electrode of lithium ion battery.
Beneficial effect：Compared with prior art, beneficial effects of the present invention are：
Silicon provided by the invention-porous carbon electrode material good cycling stability, high rate performance are excellent, preparation cost is low and ring
Border is friendly.
The present invention is by magnesium oxide template pore-creating, and silicon-porous carbon electrode material of acquisition, capability retention and high magnification fill
The Si-C composite material that discharge performance is above pure silicon granules and prepared by unused magnesium oxide template pore-creating.
Brief description of the drawings
Fig. 1 is the transmission electron microscope picture of the silicon-porous carbon materials prepared using magnesium oxide template pore-creating；
Fig. 2 is the transmission electron microscope picture that silico-carbo material prepared by magnesium oxide template is not used；
Fig. 3 be prepared using magnesium oxide template pore-creating silicon-porous carbon materials, be not used magnesium oxide template prepare silicon-
The pore size distribution curve of carbon material；
Fig. 4 is the silicon-porous carbon materials and commodity silicon nanoparticle, unused oxidation prepared using magnesium oxide template pore-creating
The electrochemical cycle stability contrast of silico-carbo material prepared by magnesium template；
Fig. 5 is the silicon-porous carbon materials and commodity silicon nanoparticle, unused oxidation prepared using magnesium oxide template pore-creating
The high rate performance contrast of silico-carbo material prepared by magnesium template.
Embodiment
Silicon-porous carbon electrode material of the present invention, described silicon-porous carbon electrode material disperse for silicon nanoparticle
On porous carbon template, there is 4-500nm pore structure, specific surface area 180-400m2/g。
Present invention also offers the preparation method of described silicon-porous carbon electrode material, is specially：By nano silica fume with receiving
For the mixture ultrasonic disperse of rice magnesium oxide powder in sucrose solution, being heated after drying makes sucrose be carbonized, and is then washed with HCl solution
Nano magnesia is removed, produces silicon-porous carbon electrode material.
The mass ratio of the nano silica fume and sucrose is 1：1.0-5.0.It is compound when the ratio increase of sample nano silica fume
The charge/discharge capacity of electrode material improves, but when the ratio of silicon and sucrose is higher than 1:When 1, the carbon content in combination electrode material
It is too low, it is not easy to form the network structure of contact.The preferred mass ratio of the nano silica fume and sucrose is 1：1.5-3.0.
The mass ratio of the silica flour and magnesia powder is 1:1.0-4.0.Magnesia powder is pore-creating template, works as content of magnesia
When too low, the pore volume of composite is smaller, it is impossible to enough expansion spaces are provided for silicon.When content of magnesia is too high, prepare
The composite specific surface area gone out is excessive, and coulombic efficiency is very low first.Preferably, the mass ratio of the silica flour and magnesia powder is
1:2.0-3.0。
The magnesia powder is 10-500nm, is further 30-200nm.But it is not limited to this.
The temperature of the high temperature cabonization is >=700 DEG C, can be 700-800 DEG C, 830-900 DEG C etc., soaking time 3-
10 hours.Carburizing temperature is less than 700 DEG C or soaking time is less than 3 hours, and sucrose carbonization is incomplete.Soaking time is long, then
It is likely to form silicon carbon compound.It is preferred that soaking time is 5-8 hours.
High temperature cabonization needs to be post-processed product after terminating, and the post processing is to clean product with hydrochloric acid solution, with
Removing template magnesia is removed, then filtration drying.
Present invention also offers application of the described silicon-porous carbon electrode material in negative electrode of lithium ion battery is prepared.
The present invention is further explained with reference to embodiment.
The particle diameter for the silica flour that following examples use is 100nm, and magnesia powder particle diameter is 50nm.
Embodiment 1
The nano Si particle of commercialization and nano-MgO particle are put into water/ethanol solution (water and the ethanol of the sucrose configured
By volume 3:1 configuration), the mass ratio of nano Si particle, nano-MgO particle and sucrose is 1:2:2；By the beaker equipped with sample
It is put into Ultrasound Instrument, is ultrasonically treated 30 minutes, makes nano Si particle and nano-MgO even particulate dispersion in sucrose solution；Will
Sample is put into vacuum drying chamber, is dried in vacuo 10 hours, is then transferred in tube furnace at 100 DEG C, with 2 DEG C/min of heatings
To 900 DEG C, 6 hours are incubated, sucrose is carbonized；Sample after carbonization is put into 3 hours of magnetic agitation in 1M HCl solutions, with
The MgO particles in sample are removed, obtain pore structure, after deionization cleaning for several times, are filtered, resulting materials are silicon-porous carbon
Material (see Fig. 1).
Silico-carbo composite prepared by non-oxidation magnesium template：Magnesium oxide powder is not added, other preparation processes are same as above.
Gained silicon-porous carbon materials (see Fig. 2).
The specific surface area that nitrogen adsorption tests to obtain silicon-porous carbon materials is 207m2/ g, pore volume 1.02cc/g, aperture
Distribution is 4-13nm and 50-200nm (see Fig. 3)；And silico-carbo composite prepared by non-oxidation magnesium template, specific surface area
For 167m2/ g, pore volume 0.187cc/g, there is no obvious peak on pore size distribution curve (see Fig. 3).
Taking-up obtained silicon-porous carbon materials, conductive black super P and binding agent sodium alginate in mass ratio 1~
6:1~6:1~6 mixing, add appropriate amount of deionized water and be tuned into uniform slurry, coating (about 5 μm of thickness) is on copper foil of affluxion body.
The copper foil for being coated with sample is put into vacuum drying chamber, is dried 10 hours in vacuum environment.Dried sample is taken out, is rushed
Electrode slice, a diameter of 13mm of electrode slice.
The charge-discharge performance of sample is to test to obtain on Land (blue electricity) charging/discharging apparatus.Electro-chemical test is 2032
Carried out in type button cell system, electrolyte is 1M LiPF6It is dissolved in addition 2%VC (vinylene carbonate) EC/DEC (carbon
Vinyl acetate/diethyl carbonate, volume ratio 1:1) solution, it is metal lithium sheet to electrode.Above-mentioned button cell is connected to
In Land equipment, at room temperature, constant current charge-discharge test is carried out.First with 200mAg-1Current density be discharged to stopping potential
0.01V(vs.Li/Li+), after standing 2min, then with 200mAg-1Current density charge to stopping potential 1.0V (vs.Li/
Li+), obtained circulation volume (see Fig. 4).40 circulations of silicon-porous carbon materials that after tabletting of the present invention prepared by magnesium thermit
Capability retention be 86.5%, than commodity nano silica fume (78.6%) and non-oxidation magnesium template preparation silico-carbo material
(68%) it is significantly improved.
The high rate performance test of sample is carried out on Land (blue electricity) charging/discharging apparatus.The mistake of rate charge-discharge test
Cheng Wei：Electrode uses 200mAg successively-1, 500mAg-1, 1000mAg-1, 2000mA g-1, 4000mAg-1Current density carry out
Cycle charge-discharge, each stage are respectively 10 charge and discharge cycles.Charge cutoff current potential is 1V, and electric discharge stopping potential is 0.01V, is filled
Time of repose between discharge process is arranged to 2 minutes, obtains multiplying power test curve (see Fig. 5).Magnesium heat is anti-after tabletting of the present invention
Silicon-the porous carbon materials that should be prepared are 1000mA g in current density-1, 2000mA g-1With 4000mA g-1When, discharge capacity point
Wei not 947mAh g-1, 670mAh g-1With 394mAh g-1, (it is respectively 667mAh g than business nano-silicon-1, 268mAh g-1,
10.5mAh g-1) and non-oxidation magnesium template prepare silico-carbo material (be respectively 516mAh g-1, 327mAh g-1, 172mAh g-1) it is much higher.
Embodiment 2
When weighing raw material, the mass ratio of nano Si particle, nano-MgO particle and carbon source sucrose is 1:2:3, remaining is the same as implementation
Example 1.
Embodiment 3
When weighing raw material, the mass ratio of nano Si particle, nano-MgO particle and carbon source sucrose is 1:3:2, remaining is the same as implementation
Example 1.
Embodiment 4
During heating carbonization, temperature setting is 700 degree, and soaking time is 8 hours, and remaining is the same as embodiment 1.
Embodiment 5
During heating carbonization, temperature setting is 1000 degree, and soaking time is 5 hours, and remaining is the same as embodiment 1.
Silicon-porous carbon electrode material prepared by embodiment 2-5, cyclical stability, high rate capability are superior to corresponding conditionses
Under the silico-carbo composite for preparing of unused magnesium oxide template pore-creating.
Claims (8)
1. a kind of silicon-porous carbon electrode material, it is characterised in that described silicon-porous carbon electrode material disperses for silicon nanoparticle
On porous carbon template, silicon-porous carbon electrode material has the pore passage structure that aperture is 4-500nm, specific surface area 180-
400m2/g。
A kind of 2. preparation method of silicon-porous carbon electrode material as claimed in claim 1, it is characterised in that：By nano silica fume
For mixture ultrasonic disperse with nano oxidized magnesium dust in sucrose solution, being heated after drying makes sucrose be carbonized, then molten with HCl
Liquid washes away nano magnesia, produces silicon-porous carbon electrode material.
3. the preparation method of silicon-porous carbon electrode material according to claim 2, it is characterised in that the silica flour and oxygen
The mass ratio for changing magnesium powder is 1：(1.0-4.0).
4. the preparation method of silicon-porous carbon electrode material according to claim 2, it is characterised in that silica flour and sucrose
Mass ratio is 1：(1.0-5.0).
5. the preparation method of silicon-porous carbon electrode material according to claim 2, it is characterised in that the magnesia powder
Particle diameter be 10-500nm.
6. the preparation method of silicon-porous carbon electrode material according to claim 2, it is characterised in that the sucrose solution
Concentration be 0.02-0.50g/mL.
7. the preparation method of silicon-porous carbon electrode material according to claim 2, it is characterised in that the high temperature cabonization
Temperature be more than 700 DEG C, be incubated 3-10 hours.
A kind of 8. application of silicon-porous carbon electrode material as claimed in claim 1, it is characterised in that the silicon-porous carbon electricity
Pole materials application is in negative electrode of lithium ion battery.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109638270A (en) * | 2018-12-29 | 2019-04-16 | 内蒙古杉杉科技有限公司 | A kind of silicon-graphene-porous carbon composite electrode material and its preparation method and application |
| CN113036109A (en) * | 2021-03-12 | 2021-06-25 | 广州巨湾技研有限公司 | Preparation method of high-rate silicon-carbon negative electrode microspheres and high-rate silicon-carbon negative electrode microspheres |
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| CN102709565A (en) * | 2012-05-30 | 2012-10-03 | 力芯（青岛）新能源材料有限公司 | Preparation method of lithium ion battery porous silicon carbon composite negative material |
| CN105489867A (en) * | 2016-01-21 | 2016-04-13 | 泰山医学院 | Porous carbon and silicon material and preparation method thereof |
| CN106450192A (en) * | 2016-10-14 | 2017-02-22 | 浙江天能能源科技股份有限公司 | Silicon/carbon composite material for lithium ion battery and preparation method and application thereof |
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2017
- 2017-07-14 CN CN201710573128.0A patent/CN107425184A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102709565A (en) * | 2012-05-30 | 2012-10-03 | 力芯（青岛）新能源材料有限公司 | Preparation method of lithium ion battery porous silicon carbon composite negative material |
| CN105489867A (en) * | 2016-01-21 | 2016-04-13 | 泰山医学院 | Porous carbon and silicon material and preparation method thereof |
| CN106450192A (en) * | 2016-10-14 | 2017-02-22 | 浙江天能能源科技股份有限公司 | Silicon/carbon composite material for lithium ion battery and preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109638270A (en) * | 2018-12-29 | 2019-04-16 | 内蒙古杉杉科技有限公司 | A kind of silicon-graphene-porous carbon composite electrode material and its preparation method and application |
| CN113036109A (en) * | 2021-03-12 | 2021-06-25 | 广州巨湾技研有限公司 | Preparation method of high-rate silicon-carbon negative electrode microspheres and high-rate silicon-carbon negative electrode microspheres |
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Application publication date: 20171201 |