CN108878824A - A kind of preparation method of core-shell structure graphene coated micron silicon - Google Patents
A kind of preparation method of core-shell structure graphene coated micron silicon Download PDFInfo
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Abstract
The invention belongs to lithium ion battery material technical field more particularly to a kind of preparation methods of core-shell structure graphene coated micron silicon, include the following steps：Step 1 generates SiO2The uniformly composite material of cladding micron silicon；Step 2 obtains SiO2/ micron silicon/graphene oxide；Step 3 obtains the SiO of graphene coated2/ micron silicon materials；Step 4 obtains the graphene coated micron silicon materials of core-shell structure.Compared with the prior art, preparation process of the present invention is simple, low in cost and be easily achieved mass production；The core-shell structure graphene coated micron silicon materials that the present invention obtains, can reduce silicon in cyclic process as dilation cause cycle performance caused by crystal dusting deteriorate, promote the coulombic efficiency of battery；In addition to this, the superior electric conductivity of graphene itself is capable of forming the conductive network of good plane-plane contact, effectively promotes the power-performance of battery.
Description
Technical field
The invention belongs to lithium ion battery material technical field more particularly to a kind of core-shell structure graphene coated micron silicons
Preparation method.
Background technique
Currently, commercialized power single battery core energy density is 170-200Wh/kg, the energy of power battery module is close
Degree reaches the developing goal that 300Wh/kg is this field next stage power battery, therefore the weight energy for promoting power battery core is close
It is imperative to spend.
The power battery core negative electrode material of Current commercial is mainly graphite negative electrodes material, but its energy density is only
372mAh/g is no longer satisfied industry for the demand of power battery core energy density.Therefore exploitation height ratio capacity, high power energy
The novel anode material of power and long circulation life becomes the hot spot of current research.
When silicon is as negative electrode material, silicon lithium alloy is formed since more lithium ions can be embedded in same atoms number
(Si+4.4e-+4.4Li+→Li4.4Si), theoretical capacity is up to 4200mAh/g, more than ten times of current commodity graphite.Together
When, content of the silicon in the earth's crust is only second to oxygen (O), accounts for about the 26.4% of gross mass.Therefore silicon is in power battery cathode material
With very big application prospect.But silicon as material still have it is insufficient and in the application aspect of power battery cathode material
It is restricted, it is specific as follows：1) due to the physicochemical characteristics of silicon materials itself, first charge-discharge efficiency is relatively low, usually
It is 60~70%；2) silicon in charge and discharge it is embedding while take off more lithium ions along with bigger volume expansion and contraction (highest
Up to 300%), huge volume expansion leads to material dusting, and variation is contacted with collector, forms new interface and continues and be electrolysed
Liquid reaction, consumes active lithium, cycle performance of battery is caused sharply to deteriorate；3) silicon itself is semiconductor material, itself electric conductivity
It can be not so good as graphite, power-performance is insufficient.
Summary of the invention
It is an object of the invention to：In view of the deficiencies of the prior art, a kind of core-shell structure graphene coated micron is provided
The preparation method of silicon, to solve silicon, applied to first charge discharge efficiency in negative electrode material, low, huge volume expansion and power-performance are poor
The problem of.
To achieve the goals above, the present invention uses following technical scheme：
A kind of preparation method of core-shell structure graphene coated micron silicon, includes the following steps：
Step 1 grows SiO in micron silicon face2Layer generates SiO2The uniformly composite material of cladding micron silicon；
Step 2, the SiO that step 1 is obtained2Uniformly the composite material of cladding micron silicon is scattered in deionized water, side
It is slowly stirred side and graphene oxide is added, then carry out mechanical stirring, then filter, be dried to obtain SiO2/ micron silicon/graphite oxide
Alkene；
Step 3, the SiO that step 2 is obtained2/ micron silicon/graphene oxide is placed in the pyroreaction of nitrogen atmosphere protection
It is sintered in kettle, obtains the SiO of graphene coated2/ micron silicon materials；
Step 4, the SiO for the graphene coated that step 3 is obtained2/ micron silicon materials are scattered in deionized water, while stirring
It mixes side and instills HF solution, then suction filtration, cleaning are in neutrality to aqueous solution pH, obtain the graphene coated micron silicon material of core-shell structure
Material.
It should be noted that in step 2, due to SiO2Per se with faint negative electrical charge, and graphene oxide itself
With faint positive charge, therefore, graphene oxide is adsorbed almost uniformly in SiO in dispersion process2/ micron silicon face.
A kind of improvement of preparation method as core-shell structure graphene coated micron silicon of the present invention, step 1 tool
Body includes following operation：
1) silicon particle is taken to be scattered in appropriate amount of deionized water, mechanical stirring forms the aqueous solution containing silicon powder；
2) appropriate Na is taken2SiO3It is dissolved in the resulting aqueous solution containing silicon powder of step 1), and places it in 70~100
It is heated in DEG C water-bath, is slowly introducing CO while stirring2Gas grows one layer of uniform SiO in micron silicon face2Layer；
3) step 2) acquired solution is filtered, obtains much filtrate, then cleaned with deionized water and remove Na2CO3, do
It is dry to obtain SiO2The uniformly composite material of cladding micron silicon.
A kind of improvement of preparation method as core-shell structure graphene coated micron silicon of the present invention, in step 1)
In, the churned mechanically time is 10~30min.
A kind of improvement of preparation method as core-shell structure graphene coated micron silicon of the present invention, in step 2)
In, the flow velocity of CO2 gas is 5~10m/s, and the reaction time is 45~90min.
A kind of improvement of preparation method as core-shell structure graphene coated micron silicon of the present invention, in step 3)
In, dry temperature is 60~80 DEG C.
A kind of improvement of preparation method as core-shell structure graphene coated micron silicon of the present invention, in step 2
In, the churned mechanically time is 20~40min.
A kind of improvement of preparation method as core-shell structure graphene coated micron silicon of the present invention, in step 3
In, the temperature of sintering is 900~1200 DEG C, and the time of sintering is 3~5h.
A kind of improvement of preparation method as core-shell structure graphene coated micron silicon of the present invention, in step 4
In, the time of stirring is 15~45min.
A kind of improvement of preparation method as core-shell structure graphene coated micron silicon of the present invention, in step 4
In, the volume ratio of deionized water and HF solution is 3:1.
Compared with the prior art, the beneficial effects of the present invention are：
1) raw material micron silicon employed in the present invention is cheap, preparation process is simple, it is easy to accomplish batch metaplasia
It produces.
2) certain volumetric spaces are reserved in the expansion that the present invention is formed by that core-shell structure is silicon, be can reduce silicon and are being recycled
In the process as dilation cause cycle performance caused by crystal dusting deteriorate, promote the coulombic efficiency of battery.
3) graphene layer on core-shell structure surface of the present invention has good electron conduction and ion permeability, and promotion is led
Electrically simultaneously guarantee the inside silicon particle electro-chemical activity, and the graphene layer on surface reacted with electrolyte to be formed it is good
SEI film avoids the continuous contact of silicon particle and electrolyte, promotes coulombic efficiency and cycle performance.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of the core-shell structure graphene coated micron silicon of embodiment 1.
Fig. 2 is that gram volume plays comparison diagram.
Fig. 3 is first charge discharge efficiency comparison diagram.
Fig. 4 is coulombic efficiency comparison diagram.
Specific embodiment
With reference to embodiment and Figure of description, the present invention is described in further detail, but the present invention
Embodiment be not limited to this.
Embodiment 1
The present embodiment provides a kind of preparation methods of core-shell structure graphene coated micron silicon, include the following steps：
Step 1, micron silicon face grow SiO2Layer generates SiO2The composite material of micron silicon is coated, concrete operations are as follows：
1) 28g silicon particle is taken to be scattered in 1000g deionized water, mechanical stirring 20min, formation contains the water-soluble of silicon powder
Liquid；
2) 10g Na is taken2SiO3It is dissolved in the aqueous solution containing silicon powder, and places it in 85 DEG C of water-baths and heat, then
It is slowly introducing CO while stirring2Gas, the flow velocity for controlling gas is 8m/s, reacts 60min, coats one layer in micron silicon face
Even SiO2Layer；
3) step 2) acquired solution is filtered, obtains much filtrate, then cleaned with deionized water and remove Na2SiO3, 70
SiO is obtained after DEG C dry2The uniformly composite material of cladding micron silicon.
Step 2, the SiO that step 1 is obtained2The micron silicon composite of cladding is scattered in deionized water, and side is slow
It stirs side and graphene oxide is added, then mechanical stirring 30min is filtered, is dried to obtain SiO2/ micron silicon/graphene oxide；
Step 3, the SiO that step 2 is obtained2/ micron silicon/graphene oxide is placed in the high temperature of nitrogen atmosphere protection
In reaction kettle, it is sintered 4h in 1050 DEG C of environment, obtains the SiO by graphene coated2/ micron silicon materials；
Step 4, the graphene coated SiO that step 3 is obtained2/ micron silicon composite, is scattered in deionized water,
HF solution (V is instilled while stirringWater：VHF=3：1) 30min, is stirred, then suction filtration, cleaning are in neutrality to aqueous solution pH, obtain core
The graphene coated micron silicon materials of shell structure.
Embodiment 2
The present embodiment provides a kind of preparation methods of core-shell structure graphene coated micron silicon, include the following steps：
Step 1, micron silicon face grow SiO2Layer generates SiO2The composite material of micron silicon is coated, concrete operations are as follows：
1) 20g silicon particle is taken to be scattered in 1000g deionized water, mechanical stirring 10min, formation contains the water-soluble of silicon powder
Liquid；
2) 10g Na is taken2SiO3It is dissolved in the aqueous solution containing silicon powder, and places it in 70 DEG C of water-baths and heat, then
It is slowly introducing CO while stirring2Gas, the flow velocity for controlling gas is 10m/s, reacts 45min, coats one layer in micron silicon face
Uniform SiO2Layer；
3) step 2) acquired solution is filtered, obtains much filtrate, then cleaned with deionized water and remove Na2SiO3, 60
SiO is obtained after DEG C dry2The uniformly composite material of cladding micron silicon.
Step 2, the SiO that step 1 is obtained2The micron silicon composite of cladding is scattered in deionized water, and side is slow
It stirs side and graphene oxide is added, then mechanical stirring 20min is filtered, is dried to obtain SiO2/ micron silicon/graphene oxide；
Step 3, the SiO that step 2 is obtained2/ micron silicon/graphene oxide is placed in the high temperature of nitrogen atmosphere protection
In reaction kettle, it is sintered 5h in 900 DEG C of environment, obtains the SiO by graphene coated2/ micron silicon materials；
Step 4, the graphene coated SiO that step 3 is obtained2/ micron silicon composite, is scattered in deionized water,
HF solution (V is instilled while stirringWater：VHF=3：1) 15min, is stirred, then suction filtration, cleaning are in neutrality to aqueous solution pH, obtain core
The graphene coated micron silicon materials of shell structure.
Embodiment 3
The present embodiment provides a kind of preparation methods of core-shell structure graphene coated micron silicon, include the following steps：
Step 1, micron silicon face grow SiO2Layer generates SiO2The composite material of micron silicon is coated, concrete operations are as follows：
1) 32g silicon particle is taken to be scattered in 1000g deionized water, mechanical stirring 30min, formation contains the water-soluble of silicon powder
Liquid；
2) 12g Na is taken2SiO3It is dissolved in the aqueous solution containing silicon powder, and places it in 100 DEG C of water-baths and heat, then
It is slowly introducing CO while stirring2Gas, the flow velocity for controlling gas is 5m/s, reacts 90min, coats one layer in micron silicon face
Even SiO2Layer；
3) step 2) acquired solution is filtered, obtains much filtrate, then cleaned with deionized water and remove Na2SiO3, 80
SiO is obtained after DEG C dry2The uniformly composite material of cladding micron silicon.
Step 2, the SiO that step 1 is obtained2The micron silicon composite of cladding is scattered in deionized water, and side is slow
It stirs side and graphene oxide is added, then mechanical stirring 40min is filtered, is dried to obtain SiO2/ micron silicon/graphene oxide；
Step 3, the SiO that step 2 is obtained2/ micron silicon/graphene oxide is placed in the high temperature of nitrogen atmosphere protection
In reaction kettle, it is sintered 3h in 1200 DEG C of environment, obtains the SiO by graphene coated2/ micron silicon materials；
Step 4, the graphene coated SiO that step 3 is obtained2/ micron silicon composite, is scattered in deionized water,
HF solution (V is instilled while stirringWater：VHF=3：1) 45min, is stirred, then suction filtration, cleaning are in neutrality to aqueous solution pH, obtain core
The graphene coated micron silicon materials of shell structure.
Performance test
1) pattern of core-shell structure graphene coated micron silicon made from embodiment 1 is characterized, is obtained as shown in Figure 1
Scanning electron microscope (SEM) photograph.
2) respectively using core-shell structure graphene coated micron silicon, silicon particle and graphite made from embodiment 1 as cathode
Battery is prepared, electrochemical property test is carried out to three classes battery, data measured includes electric discharge gram volume, first charge discharge efficiency and coulomb
Efficiency, concrete outcome is as shown in figs. 2 to 4.
Test result
As seen from Figure 2, the gram volume of electric discharge for the first time of core-shell structure graphene coated micron silicon reaches 3500mAh/g,
It is suitable with pure silicon particle；And at core-shell structure graphene coated micron silicon cycling 600 weeks, capacity retention ratio is initial holds
The 60% of amount, hence it is evident that due to the capacity retention ratio of micron silicon.
In addition, as seen from Figure 3, the first charge discharge efficiency of core-shell structure graphene coated micron silicon is 92.8%, graphite
First charge discharge efficiency is 93.8%, and the first charge discharge efficiency of pure silicon particle is 73%；It can be seen that core-shell structure graphene coated micron silicon
First charge discharge efficiency be substantially better than pure silicon particle.In addition to this, the core-shell structure graphene coated micron silicon it can be seen from body 4
Subsequent coulombic efficiency reach 99.93%, meet application requirement.
In conclusion core-shell structure graphene coated micron silicon produced by the present invention can improve the cycle performance of battery, mention
Coulombic efficiency is risen, practical application request is able to satisfy.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and is modified.Therefore, the invention is not limited to above-mentioned specific embodiment, all those skilled in the art exist
Made any conspicuous improvement, replacement or modification all belong to the scope of protection of the present invention on the basis of the present invention.This
Outside, although using some specific terms in this specification, these terms are merely for convenience of description, not to the present invention
Constitute any restrictions.
Claims (9)
1. a kind of preparation method of core-shell structure graphene coated micron silicon, which is characterized in that include the following steps：
Step 1 grows SiO in micron silicon face2Layer generates SiO2The uniformly composite material of cladding micron silicon；
Step 2, the SiO that step 1 is obtained2Uniformly the composite material of cladding micron silicon is scattered in deionized water, and side is slowly stirred
It mixes side and graphene oxide is added, then carry out mechanical stirring, then filter, be dried to obtain SiO2/ micron silicon/graphene oxide；
Step 3, the SiO that step 2 is obtained2/ micron silicon/graphene oxide is placed in the pyroreaction kettle of nitrogen atmosphere protection
Sintering, obtains the SiO of graphene coated2/ micron silicon materials；
Step 4, the SiO for the graphene coated that step 3 is obtained2/ micron silicon materials are scattered in deionized water, while stirring
HF solution is instilled, then suction filtration, cleaning are in neutrality to aqueous solution pH, obtain the graphene coated micron silicon materials of core-shell structure.
2. the preparation method of core-shell structure graphene coated micron silicon according to claim 1, which is characterized in that step 1
Specifically include following operation：
1) silicon particle is taken to be scattered in appropriate amount of deionized water, mechanical stirring forms the aqueous solution containing silicon powder；
2) appropriate Na is taken2SiO3It is dissolved in the resulting aqueous solution containing silicon powder of step 1), and places it in 70~100 DEG C of water
It is heated in bath, is slowly introducing CO while stirring2Gas grows one layer of uniform SiO in micron silicon face2Layer；
3) step 2) acquired solution is filtered, obtains much filtrate, then cleaned with deionized water and remove Na2CO3, dry
To SiO2The uniformly composite material of cladding micron silicon.
3. the preparation method of core-shell structure graphene coated micron silicon according to claim 2, it is characterised in that：In step
1) in, the churned mechanically time is 10~30min.
4. the preparation method of core-shell structure graphene coated micron silicon according to claim 2, it is characterised in that：In step
2) in, CO2The flow velocity of gas is 5~10m/s, and the reaction time is 45~90min.
5. the preparation method of core-shell structure graphene coated micron silicon according to claim 2, it is characterised in that：In step
3) in, dry temperature is 60~80 DEG C.
6. the preparation method of core-shell structure graphene coated micron silicon according to claim 1, it is characterised in that：In step
In two, the churned mechanically time is 20~40min.
7. the preparation method of core-shell structure graphene coated micron silicon according to claim 1, it is characterised in that：In step
In three, the temperature of sintering is 900~1200 DEG C, and the time of sintering is 3~5h.
8. the preparation method of core-shell structure graphene coated micron silicon according to claim 1, it is characterised in that：In step
In four, the time of stirring is 15~45min.
9. the preparation method of core-shell structure graphene coated micron silicon according to claim 1, it is characterised in that：In step
In four, the volume ratio of deionized water and HF solution is 3:1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113659122A (en) * | 2021-08-16 | 2021-11-16 | 四川金汇能新材料股份有限公司 | Silicon-carbon negative electrode material, preparation method and application |
| CN115057442A (en) * | 2022-06-23 | 2022-09-16 | 北京卫蓝新能源科技有限公司 | Spherical micron silicon, preparation method thereof, core-shell structure composite material, electrode and battery |
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| CN101306309A (en) * | 2008-06-26 | 2008-11-19 | 浙江大学 | Preparation method of nano-calcium base carbon dioxide absorbent modified by silica precipitation |
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| CN113659122A (en) * | 2021-08-16 | 2021-11-16 | 四川金汇能新材料股份有限公司 | Silicon-carbon negative electrode material, preparation method and application |
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