CN107959013A - The carbon-silicon composite material of graphene coated silicon grain and its preparation and application - Google Patents
The carbon-silicon composite material of graphene coated silicon grain and its preparation and application Download PDFInfo
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- CN107959013A CN107959013A CN201711157899.8A CN201711157899A CN107959013A CN 107959013 A CN107959013 A CN 107959013A CN 201711157899 A CN201711157899 A CN 201711157899A CN 107959013 A CN107959013 A CN 107959013A
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Abstract
The present invention provides a kind of carbon-silicon composite material of graphene coated silicon grain, is that the redox graphene of sheet and silicon grain are formed, redox graphene is coated on outside silicon grain at least in part, has gap between redox graphene and silicon grain；The particle diameter of the silicon grain is 30 50nm.The present invention also proposes the preparation method and application of the carbon-silicon composite material.It is negative electrode active material with carbon-silicon composite material provided by the invention, the battery formed, capacity is high and is not easy to decay, and cyclicity is good, and service life length, has good high rate performance and fast charging and discharging ability.According to an embodiment of the invention, battery initial specific capacities of the invention reach 1444.45mAh/g, and it is 993.06mAh/g to have reversible specific capacity after 500 charge and discharge cycles, and capacity retention ratio has good high rate performance and fast charging and discharging ability up to 68.75%.
Description
Technical field
The invention belongs to battery material field, and in particular to a kind of electrode material containing silicon, its preparation method and application.
Background technology
Lithium ion battery due to have the advantages that open-circuit voltage is high, energy density is big, self-discharge rate is small and it is pollution-free and
It is widely used in the fields such as electronic equipment, electronic traffic, aerospace, military affairs, medicine.The discharge and recharge of lithium ion battery
Journey, the embedded and deintercalation repeatedly based on lithium ion between positive and negative pole material.At present, commercialized lithium ion battery mainly uses
Carbon materials has obtained widest answer beneficial to insertion and the abjection of lithium ion as anode, graphite due to its layer structure
With.It is relatively low but the theoretical specific capacity of graphite is only 372mAh/g, it can not meet growing high power capacity, height
Power demand.Therefore, the material of new height ratio capacity is found, becomes the important probing direction of negative electrode of lithium ion battery research.
In non-carbon material, silicon is due to its higher theoretical specific capacity (4200mAh/g) and discharge potential is low, natural reserves
The advantage such as abundant, becomes the most potential lithium ion battery negative material for substituting graphite.However, body silicon materials are embedding in lithium ion
During entering and deviating from, up to 300% volume change is had, this can cause electrode structure to destroy, be electrically connected failure, active material
The problems such as material persistently consumes, ultimately results in battery capacity and decays rapidly, and cycle performance deteriorates.
At present, a kind of main method for improving silicium cathode is by silicon materials nanosizing, such as nano thin-film, nano wire, nanometer
Particle etc., the silicon of nanosizing can preferably discharge the stress of volume change generation, while provide the space of volumetric expansion, but
Since the intrinsic conductivity of silicon is low, the silicon of nanosizing still suffers from obvious capacity attenuation, and battery work(over numerous cycles
Rate density is relatively low.M.Holzapfel, N.Liu etc. are not only led using silicon and the composite material of carbon beneficial to the electronics of reinforcing material
Electrically, while the light weight of carbon material, ductile characteristic are also beneficial to stress release.But traditional carbon material is in silicon cycling
During, easy fragmentation, causes the capacity attenuation after more cycle-index to accelerate, and unbodied carbon material limits electronics
Conduction velocity.
Therefore, the material of lithium ion battery is prepared up for further research.Graphene has good as two-dimentional carbon material
Good electric conductivity and mechanical strength, can be good at helping releasing for stress by the use of graphene as the carbon material compound with silicon materials
Put.Graphene and silicon materials are effectively combined, lithium ion battery cyclical stability and power-performance can be greatly enhanced.
The content of the invention
For problems of the prior art, an object of the present invention is to provide a kind of specific discharge capacity height, follow
The lithium ion battery negative material that ring is good, service life is long and power is high, it is a kind of carbon silicon of graphene coated silicon grain
Composite material.
Second object of the present invention is to propose the preparation method of the carbon-silicon composite material.
Third object of the present invention is to propose the application of the carbon-silicon composite material.
To achieve the above object, the technical scheme is that：
A kind of carbon-silicon composite material of graphene coated silicon grain, is the redox graphene and silicon grain structure of sheet
Into redox graphene is coated on outside silicon grain at least in part, has sky between redox graphene and your particle
Gap；The particle diameter of the silicon grain is 30-50nm.
Surprisingly, it was found that redox graphene layer is coated on silicon grain surface, and with silicon grain it
Between there are certain interval, provide gap for nano silicon particles, during which is charging, discharging electric batteries, silicon volumetric expansion carries
Headspace has been supplied, has been conducive to keep the structural integrity of negative active core-shell material, so that, the capacity of battery is high and is not easy to decay, and follows
Ring is good, service life length.Meanwhile conductive network is formd between redox graphene, which fills, puts for battery
In electric process, the transmission of electronics provides passage, is conducive to shorten the transmission path of electronics, so that, the charge-discharge velocity of battery
It hurry up, power-performance is good.
The present invention also proposes the preparation method of the carbon-silicon composite material of the graphene coated silicon grain, including step：
1) silicon grain that particle diameter is 30-50nm is scattered in solvent, ammonium hydroxide, silicon source is added, in silicon grain surface hydrolysis
Oxidation generation silicon dioxide layer, the silicon source are double (triethoxy silicon substrate) methane or ethyl orthosilicate,
2) the composite particles solution that step 1) obtains is mixed with graphene oxide water solution, is then freezed, made molten
Agent congeals into ice completely.
3) in vacuum freeze drier, material is freezed, the ice that solvent condenses into all is directly sublimed into water
Steam,
4) high temperature reduction is carried out to material under 800-1000 DEG C, gas shield environment, graphene oxide is reduced into also
Former graphene oxide；
5) high temperature reduction resulting materials immerse etching agent, by the SiO of silicon grain superficial oxidation2Layer etching.
Further, in step 1), by silicon grain ultrasonic disperse in solvent, the solvent is 50-80 parts of organic solvents
With the mixture of 20 parts of water, the organic solvent is ethanol, ethylene glycol, n-butanol, glycerine, one kind in n-hexane or two
Kind.
Wherein, in step 1), the mass fraction of the ammonium hydroxide is 28%~30%, the silicon grain, solvent, ammonium hydroxide, silicon
The additional proportion in source is 300mg：(40-100)mL：(1-5) mL, 1-3mL.
Wherein, in step 1), for the feed postition of silicon source to be added dropwise, the time of hydrolysis is 10-15h.The silicon source is excellent
Elect ethyl orthosilicate (TEOS) as
Wherein, in step 2), the temperature of frost is -5 DEG C to -50 DEG C.
Step 4) takes 3 segmentation temperature-raising methods：From 0~300 DEG C, heating rate is slow, and in 3 DEG C/min or so, this process is delayed
It is slow to heat up gradually to discharge stress；From 300~600 DEG C, heating rate is fast slightly, in 5 DEG C/min or so, its speed of this process control
Rate is with gradually so that GO surface functional group dehydrating condensations；From 600~900 DEG C, then accelerate heating rate, in 7.5 DEG C/min or so,
Micro-structure is substantially stationary during this, and GO is converted into the higher rGO of reducing degree.
Specifically, the high temperature reduction process of step 4) takes three-stage to heat up：From -300 DEG C of room temperature, heating rate for 3 ±
0.5 DEG C/min, 0.5h is kept at 300 DEG C；From 300-600 DEG C, heating rate is 5 ± 0.5 DEG C/min, and 0.5h is kept at 600 DEG C；
From 600-950 DEG C, heating rate is 7.5 ± 0.5 DEG C/min, and 1h is kept at 850-950 DEG C.
Wherein, in step 5), the etching agent is the ethanol composition of HF, 35-55wt% water of 2-6wt%, 40-60wt%
System.
Preparation in accordance with the present invention, during the redox graphene after high temperature reduction is formed on nano silicon particles surface
Empty top layer, there are gap between top layer and nano silicon particles, which is silicon volumetric expansion offer during charging, discharging electric batteries
Headspace, is conducive to keep the structural integrity of negative active core-shell material, so that, the capacity of battery is high and is not easy to decay, and circulates
Property it is good, service life length.Meanwhile conductive network is formd between redox graphene, which is charging, discharging electric batteries
During, the transmission of electronics provides passage, is conducive to shorten the transmission path of electronics, so that, the charge-discharge velocity of battery is fast,
Power-performance is good.
The lithium ion battery prepared using the carbon-silicon composite material, the carbon-silicon composite material are lived as the anode of battery
Property material.
The beneficial effects of the present invention are：
It is negative electrode active material with carbon-silicon composite material proposed by the present invention, the battery formed, capacity is high and is not easy to decline
Subtract, cyclicity is good, and service life length, has good high rate performance and fast charging and discharging ability.According to an embodiment of the invention, originally
The battery initial specific capacities of invention reach 1444.45mAh/g, and it is 993.06mAh/ to have reversible specific capacity after 500 charge and discharge cycles
G, capacity retention ratio (have high specific capacity and good cycle performance) up to 68.75%, and coulombic efficiency is high after stable circulation
Up to 98~99%.Under high magnification (5C) discharge and recharge, still with 802.13mAh/g, far above general commercial graphite cathode
Specific capacity 372mAh/g (has good high rate performance and fast charging and discharging ability).
Brief description of the drawings
The process flow chart of the silicon-carbon composite electrode material anode of Fig. 1 graphene coated silicon grains.
The composite particles SEM figures of Fig. 2 graphene oxides cladding silicon/silicon dioxide.
The silicon-carbon of graphene coated silicon grain of the composite particles after high temperature reduction, etching, washing is compound in Fig. 3 Fig. 2
Electrode material SEM schemes.
The carbon silicon combination electrode material cycle performance curve map of Fig. 4 graphene coated silicon grains.
The high rate performance curve of the silicon-carbon composite electrode material of Fig. 5 graphene coated silicon grains.
Embodiment
Following embodiments are used to illustrate the present invention, but are not limited to the scope of the present invention.
In embodiment, unless otherwise instructed, used means are means well known by persons skilled in the art.
It is prepared by the carbon silicon combination electrode material of 1 graphene coated silicon grain of embodiment
(1) by 0.3g silicon (Si) particle (30~50nm of average grain diameter) ultrasonic disperse in 40mL ethanol and 10mL ultra-pure waters
In system, 3mL ammonium hydroxide (commercially available, mass fraction 28%~30%) is then added, 2mL ethyl orthosilicates (TEOS) are added dropwise,
When persistently stirring 12 is small, in silica (SiO of the silicon grain surface hydrolysis oxidation generation rich in silanol group2) layer；
(2) by 20mg graphene oxide powders (GO) ultrasonic disperse in 20mL ultra-pure waters, configuration obtains the GO of 1mg/mL
Aqueous solution 20mL；
(3) (it is respectively the Si/SiO of 50mL by the above-mentioned two kinds of solution prepared2The GO water of composite particles solution and 20mL
Solution) ultrasonic mixing is carried out, under ultrasonication, the SiO of TEOS hydrolysis growths2The silanol group on surface and the hydroxyl on GO surfaces,
Carboxyl carries out dehydrating condensation so that GO lamellas are coated on particle surface, form the GO of spherical shell shape.
(4) the good material of ultrasonic mixing is freezed in subzero 28 degree of refrigerator-freezer, solvent is congealed into ice completely.
(5) in vacuum freeze drier, material is freezed, the ice that solvent condenses into material all directly distillations
Into vapor, so that remaining nano particle maintains the structure of spherical shell shape GO cladding nano-silicon/silica dioxide granules.
(6) high temperature reduction is carried out to material under Ar environmental protections, GO is reduced into rGO, takes 3 segmentation temperature-raising methods：From normal
- 300 DEG C of temperature, heating rate is 3 DEG C/min, and 0.5h is kept at 300 DEG C；From 300-600 DEG C, heating rate is 5 DEG C/min,
600 DEG C of holding 0.5h；From 600-950 DEG C, heating rate is 7.5 DEG C/min, and 1h is kept at 900 DEG C.
(7) resulting materials are immersed in 4wt%HF, 46wt% water, 50wt% ethanol systems, the SiO of silicon grain superficial oxidation2
Layer is etched；
(8) silicon-carbon composite electrode material of the graphene coated silicon grain is obtained.
Flow is referring to Fig. 1.Fig. 3 show the silicon-carbon compound electric of the graphene coated silicon grain of gained after above-mentioned technological process
The SEM figures of pole material, are compared to not etched Fig. 2 patterns, it can be seen that silicon grain is dispersed and reduced oxygen graphite
Alkene layer coats, and forms spheroidal structure, is the swollen of silicon grain there are a fixed gap between redox graphene and silicon grain
Swollen offer space.And redox graphene forms good conductive network between each other, conductive well make is played
With.
In order to carry out electro-chemical test, button-shaped half-cell is made, test result is as follows：
Fig. 4 show lithium ion half-cell of the silicon-carbon composite electrode material as anode of above-mentioned graphene coated silicon grain
Cycle performance curve.As can be seen that the button-shaped half-cell prepared based on the material, it circulates specific capacity first to reach
1444.45mAh/g, still remains with 993.06mAh/g after 500 circulations, and cycle efficieny is basicly stable after being circulated at second
Between 99%~100%.Fig. 4 as a comparison be silicon grain (SiNPs, 30~50nm of average grain diameter).
Fig. 5 show the high rate performance curve of above-mentioned silicon-carbon composite electrode material.As can be seen that under 5C multiplying powers,
The specific discharge capacity of chondritic silicon-carbon composite electrode material still has 802.13mAh/g, is born far above general commercial graphite
The specific capacity 372mAh/g of pole, illustrates good high rate performance and fast charging and discharging ability.
It is prepared by the carbon silicon combination electrode material of 2 graphene coated silicon grain of embodiment
The present embodiment preparation method removes following two step, other operations and embodiment 1 are identical.
(1) by 0.3g silicon (Si) particle (30~50nm of average grain diameter) ultrasonic disperse in 40mL ethanol and 10mL ultra-pure waters
In system, 3mL ammonium hydroxide (commercially available, mass fraction 28%~30%) is then added, 1mL ethyl orthosilicates (TEOS) are added dropwise,
When persistently stirring 12 is small, in silica (SiO of the silicon grain surface hydrolysis oxidation generation rich in silanol group2) layer；
(4) the good material of ultrasonic mixing is freezed in the refrigerator-freezer of minus 20 degrees, solvent is congealed into ice completely.
Result of the test shows that 1 silicon source of embodiment adds 2mL, the product obtained compared to the present embodiment silicon source 1mL, pattern base
This is identical, but existing gap is some larger between the redox graphene and silicon grain of 1 product of embodiment.
Step (4) does not influence product significantly as long as the temperature of frost can realize icing.
It the above is only the preferred embodiment of the present invention, it is noted that come for those skilled in the art
Say, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should be regarded as
Protection scope of the present invention.
Claims (10)
- A kind of 1. carbon-silicon composite material of graphene coated silicon grain, it is characterised in that for sheet redox graphene and Silicon grain is formed, and redox graphene is coated on outside silicon grain at least in part, redox graphene and silicon grain it Between there is gap；The particle diameter of the silicon grain is 30-50nm.
- 2. the preparation method of the carbon-silicon composite material of the graphene coated silicon grain described in claim 1, it is characterised in that including Step：1) silicon grain that particle diameter is 30-50nm is scattered in solvent, adds ammonium hydroxide, silicon source, aoxidized in silicon grain surface hydrolysis Silicon dioxide layer is generated, the silicon source is double (triethoxy silicon substrate) methane or ethyl orthosilicate,2) the composite particles solution that step 1) obtains is mixed with graphene oxide water solution, is then freezed, make solvent complete Congeal into ice entirely.3) in vacuum freeze drier, material is freezed, the ice that solvent condenses into all is directly sublimed into vapor,4) high temperature reduction is carried out to material under 800-1000 DEG C, gas shield environment, graphene oxide is reduced into oxygen reduction Graphite alkene；5) high temperature reduction resulting materials immerse etching agent, and the silicon dioxide layer of silicon grain superficial oxidation is etched.
- 3. preparation method according to claim 2, it is characterised in that in step 1), by silicon grain ultrasonic disperse in solvent In, the solvent is 50-80 parts of organic solvents and the mixture of 20 parts of water, and the organic solvent is ethanol, ethylene glycol, positive fourth One kind in alcohol, glycerine, n-hexane or two kinds.
- 4. preparation method according to claim 2, it is characterised in that in step 1), the mass fraction of the ammonium hydroxide is 28%~30%, the silicon grain, solvent, ammonium hydroxide, the additional proportion of silicon source are 300mg：(40-100)mL：(1-5) mL, 1- 3mL。
- 5. preparation method according to claim 2, it is characterised in that in step 1), the feed postition of silicon source is is added dropwise, water The time of solution reaction is 10-15h, and the silicon source is ethyl orthosilicate.
- 6. preparation method according to claim 2, it is characterised in that in step 2), composite particles that step 1) is obtained The volume ratio that solution is mixed with graphene oxide water solution is 5：(1-3)；The concentration of the graphene oxide water solution is 0.5-2mg/mL。
- 7. preparation method according to claim 2, it is characterised in that in step 2), the temperature of frost is -5 DEG C to -50 ℃。
- 8. according to claim 2-7 any one of them preparation methods, it is characterised in that in step 3), the high temperature of step 4) is also Former process takes three-stage to heat up：From -300 DEG C of room temperature, heating rate is 3 ± 0.5 DEG C/min, and 0.5h is kept at 300 DEG C；From 300-600 DEG C, heating rate is 5 ± 0.5 DEG C/min, and 0.5h is kept at 600 DEG C；From 600-950 DEG C, heating rate for 7.5 ± 0.5 DEG C/min, 1h is kept at 850-950 DEG C.
- 9. according to claim 2-7 any one of them preparation methods, it is characterised in that in step 5), the etching agent is 2- The system of HF, 35-55wt% water of 6wt%, the ethanol composition of 40-60wt%.
- 10. lithium ion battery prepared by carbon-silicon composite material described in application claim 1, it is characterised in that the carbon silicon is compound Negative active core-shell material of the material as battery.
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| CN110931746A (en) * | 2019-12-03 | 2020-03-27 | 东南大学 | Silicon-tin-graphene composite electrode material and preparation method and application thereof |
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| CN114497483B (en) * | 2021-12-31 | 2023-07-04 | 惠州锂威新能源科技有限公司 | Negative plate, preparation method thereof and lithium ion battery |
| CN116002660A (en) * | 2022-12-28 | 2023-04-25 | 太原科技大学 | Preparation method of carbon-silicon composite material, carbon-silicon composite material and lithium battery |
| CN116002660B (en) * | 2022-12-28 | 2023-07-18 | 太原科技大学 | Preparation method of carbon-silicon composite material, carbon-silicon composite material and lithium battery |
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