CN110474034A - A kind of nitrogen mixes porous nano-sheet Si-C composite material and its preparation method and application - Google Patents
A kind of nitrogen mixes porous nano-sheet Si-C composite material and its preparation method and application Download PDFInfo
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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
- H01M10/00—Secondary cells; Manufacture thereof
- 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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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/362—Composites
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
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- 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
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of nitrogen and mixes porous nano-sheet Si-C composite material and its preparation method and application, it the steps include: to be added dissolved organic matter in closed container as carbon source, then ammonium chloride is added, silica is eventually adding to be dispersed with stirring, in 100-250 DEG C of hydro-thermal reaction 2-24h, presoma is obtained through dry, 650-750 DEG C of calcining reduction of appropriate magnesium powder is added in presoma, finally obtains N doping porous nano-sheet Si-C composite material by washing, hf etching.As cell negative electrode material；The method of the present invention simple process, preparation process energy consumption are lower, the N doping porous nano-sheet Si-C composite material prepared using this method, structure feature is distinct, in porous nano sheet, with large specific surface area, structure feature is distinct, characteristic of electrochemical performance, and the negative electrode material chemical property being assembled by Si-C composite material prepared by the present invention is preferable.
Description
Technical field
The present invention relates to Si-C composite material technical field, in particular to a kind of nitrogen mixes porous nano-sheet Si-C composite material
And its preparation method and application.
Background technique
The energy is the basis that the mankind depend on for existence and development, traditional energy, such as: coal, petroleum, natural gas are faced with storage
The problems such as amount decline environmental pollution, it is unable to satisfy future society demand.Lithium ion battery has operating voltage height, energy density
Greatly, have extended cycle life, self-discharge rate is low and it is pollution-free the features such as, it is considered to be ideal energy storage and conversion tool.At present
To be widely used in various portable power tools, digital electronic goods.Continuous pursuit with people to electronic product function,
The energy density for further promoting lithium ion battery becomes research hotspot.
Although silicon has high theoretical specific capacity (4200mAh g-1), lower removal lithium embedded current potential (< 0.5V), rich reserves and
And the characteristics such as environmental-friendly, but since silicon materials generate huge volume expansion and contraction during removal lithium embedded, this can be led
The structure collapses of electrode material are caused, and then influence its specific capacity, stability and coulombic efficiency.
In order to alleviate bulk effect of the silicon materials in charge and discharge process, currently used method prepares nano material, mentions
The specific surface area of high material, such as the nano particle of zero dimension, one-dimensional nano line, nanotube, nanometer rods, two-dimensional nanobelt are received
Rice piece and three-dimensional porous nano material.And using nanometer spherical silicon dioxide as silicon source, the obtained nano material of magnesiothermic reduction
Generally Nanoparticulate, as Chinese patent CN106816590A discloses a kind of high-capacity lithium ion cell composite negative pole material
Preparation method.Although the above method alleviates the capacity attenuation of material to a certain extent, nano particle is easy to reunite, institute
Cannot fundamentally inhibit the bulk effect in charge and discharge process, capacity still can be faster with the increase of cycle-index
Decaying.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention provide a kind of nitrogen mix porous nano-sheet Si-C composite material and its
Preparation method and application, prepared Si-C composite material overall structure are stablized, and electric conductivity is good, as negative electrode of lithium ion battery
Volume expansion and contraction during removal lithium embedded can be effectively relieved in materials'use, so that battery has high specific capacity and good
Good cyclical stability.
The present invention is to be achieved through the following technical solutions:
A kind of nitrogen mixes the preparation method of porous nano-sheet Si-C composite material, includes the following steps:
Step 1, carbon source and ammonium chloride is soluble in water, silica is added, is dispersed with stirring uniformly, obtains precursor liquid；
Step 2, by precursor liquid in 100-250 DEG C of hydro-thermal reaction 2-24h, product is dried to obtain presoma；
Step 3, presoma is mixed, then calcining reduction with magnesium powder, finally obtains nitrogen by washing, hf etching and mix
Miscellaneous porous nano-sheet Si-C composite material.
Preferably, in step 1, the silica the preparation method comprises the following steps: by dehydrated alcohol, water and ammonium hydroxide mix, stirring
Uniformly, be added ethyl orthosilicate, continue to stir, be centrifuged, wash, dry after obtain the nano particle of silica.
Preferably, in step 1, the carbon source be glucose, sucrose, maltose, fructose, lactose, citric acid, dopamine,
Any one in tannic acid and sodium acetate.
Preferably, in step 1, the mass ratio of the carbon source and ammonium chloride are as follows: (0.1-10): 1, the silica with
The mass ratio of carbon source are as follows: (0.01-0.3): 1.
Preferably, in step 3, the magnesium powder and presoma mass ratio are as follows: (0.1-2): 1.
Preferably, in step 3, the mass concentration of the hydrofluoric acid are as follows: 0.5%-10%, etch period are as follows: 0.5-10h.
Preferably, in step 3, calcination temperature is 650 DEG C -750 DEG C, time 2-10h.
The nitrogen that the preparation method is prepared mixes porous nano-sheet Si-C composite material.
The nitrogen mixes application of the porous nano-sheet Si-C composite material as negative electrode material in lithium ion battery.
Compared with prior art, the invention has the following beneficial technical effects:
The present invention obtains silica and nitrogen carbon dope composite material by addition carbon source and ammonium chloride in water-heat process,
Then magnesium powder is added, by magnesiothermic reduction, by reducing silica at silicon, and magnesium generates magnesia, the process are as follows: SiO2+
2Mg=2MgO+Si, then removed magnesia with hydrochloric acid, form material still unreduced silica etching with hydrofluoric acid
Porous structure.Firstly, ammonium chloride as nitrogen source, introduces nitrogen in the material can be improved the electric conductivity of material.Secondly, ammonium chloride exists
The heat of magnesium thermit release can be absorbed during magnesiothermic reduction.Magnesiothermic reduction process can make silicon oxide pellets become
Smaller nanometer silicon particle is self-assembled into nitrogen and mixes porous silicon carbon nanosheet under ammonium chloride and glucose collective effect
Composite material.Nitrogen mixes that porous silicon carbon nanosheet is not only easy to reunite, and stability is good, and the gap between nanometer sheet can be alleviated
Volume expansion and contraction during removal lithium embedded, so that battery has high specific capacity and good cyclical stability.In addition, carbon
Be added can reinforcing material toughness, alleviate structure collapses caused by bulk effect during removal lithium embedded；And porous knot
Structure can accommodate the volume expansion in process of intercalation, to inhibit bulk effect.In addition, nitrating can shorten lithium ion diffusion road
The characteristics of diameter effectively improves the electric conductivity of material, improves silicon materials poorly conductive.Raw material of the present invention is easy to get, at low cost, energy consumption
Low, preparation process is simple, and the Si-C composite material of preparation is nano-grade size material and controllable, can improve the usability of material
Can, the characteristics of being conducive to industrialized production.
The present invention ultimately generates the Si-C composite material of the three-dimensional porous structure by constituting containing foraminate nanometer sheet.
Detailed description of the invention
Fig. 1 is the powder diagram of N doping porous nano-sheet Si-C composite material prepared by embodiment 1.
Fig. 2 be the embodiment of the present invention 1 prepare N doping porous nano-sheet Si-C composite material scanning electron microscope (SEM) photograph and
Transmission electron microscope picture.
Fig. 3 is that the constant current charge-discharge of N doping porous nano-sheet Si-C composite material prepared by the embodiment of the present invention 1 is bent
Line chart.
Fig. 4 is that sample is dressed up battery, is tested by 250 constant current charge-discharges, then battery is dismantled to the scanning measured
Electron microscopic picture.
Fig. 5 is the scanning electron microscope (SEM) photograph of N doping porous nano-sheet Si-C composite material prepared by the embodiment of the present invention 1.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
A kind of nitrogen mixes the preparation method of porous nano-sheet Si-C composite material: dissolved organic matter being added in closed container
As carbon source, ammonium chloride is then added, is eventually adding silica and is dispersed with stirring, in 100-250 DEG C of hydro-thermal reaction 2-24h, warp
It is dry to obtain presoma, 650-750 DEG C of calcining reduction of appropriate magnesium powder is added in presoma, is finally carved by washing, hydrofluoric acid
Erosion obtains N doping porous nano-sheet Si-C composite material.
The silica the preparation method is as follows:
Dehydrated alcohol, water, ammonium hydroxide mixing, stir 30min at 25 DEG C, are rapidly added ethyl orthosilicate, continue to stir, from
The heart, washing, alcohol wash, dry after to obtain partial size be 200-300nm silica nanosphere.
The above-mentioned preferred temperature of hydro-thermal reaction is 120-200 DEG C；It is preferred that the hydro-thermal time is 6-20h；Dry process uses
Freeze-drying, vacuum drying, supercritical drying, preferably freeze-drying or supercritical drying；Calcination time is 2-10h, calcining
Process is conducive to improve the degree of graphitization of carbon.
The carbon source is selected from glucose, sucrose, maltose, fructose, lactose, citric acid, dopamine, tannic acid and sodium acetate
In any one.
The mass ratio of the carbon source and ammonium chloride are as follows: (0.1-10): 1.
The mass ratio of the silica and carbon source are as follows: (0.01-0.3): 1, preferably are as follows: (0.05-0.2): 1.
The magnesium powder and presoma mass ratio are as follows: (0.1-2): 1, preferably are as follows: (0.3-1): 1.
The hydrofluoric acid mass concentration are as follows: 0.5%-10%, preferably are as follows: 1%-5%.
The hf etching time are as follows: 0.5-10h, preferably are as follows: 2-5h.
In following embodiment, silica the preparation method is as follows:
75mL dehydrated alcohol, 10mL water, 3.15mL ammonium hydroxide stir 30min at 25 DEG C, are rapidly added the positive silicic acid second of 6mL
Ester, continue stir 1h, centrifugation, washing, alcohol wash, dry after obtain partial size be 200-300nm nano SiO 2 particle.
Embodiment 1
5g glucose and 5g ammonium chloride are dissolved in 70ml water, then 1g silica is sufficiently stirred, and mixed liquor is shifted
Into closed reactor, 3.5h is reacted at 220 DEG C.After reaction through being dried to obtain presoma.Magnesium powder is added, quality is
1 times of forerunner's weight, 650 DEG C of calcining 10h under an argon atmosphere after grinding uniformly, then stirs 2 hours in 1M HCl, goes
Except impurity, washing filters drying, is 2%HF etching 6h with mass fraction, obtains Si-C composite material, powder after washing is dry
Diffraction pattern is shown in Fig. 1, sees from powder diagram, corresponds to cubic phase Si at 28.6,47.4 and 56.3 degree of three peaks
(111) of (JCPDS 27-1402), (200), (311) crystal face.In 35.6,60.0,71.8, the peak that corresponding peak is SiC, In
18.0, it is the peak C that 26.9,42.8,62.1 degree of peak is corresponding.A, b and Fig. 5 are prepared scanning electron microscope (SEM) photograph, scanning figure in Fig. 2
In as can be seen that prepared material be nano-particles self assemble at flaky nanometer structure, and have aperture in nanometer sheet, piece
There is gap between piece.C, d, e are the transmission electron microscope picture of sample in Fig. 2, and it is sheet that c figure, which can be seen that prepared sample, this
It is consistent with scanning result；It can be seen that lattice fringe, being measured interplanar distance is from the High-Resolution Map of figure d, e sample
0.31nm, (111) crystal face of corresponding silicon.It can be seen that Si, C, O, N element are equal from f, g, h, i, j, k transmission electron microscope energy spectrum diagram
Even distribution is in the sample.Fig. 3 is constant current charge-discharge curve graph.Fig. 4 is that sample is dressed up after battery by 250 constant current charge and discharges
Electrical testing dismantles the scanning electron microscope (SEM) photograph clapped after battery, in figure it can be seen that sample remains as laminated structure, illustrate this sheet tool
There is good structural stability.
Obtained Si-C composite material is uniformly mixed with acetylene black, Kynoar according to the mass ratio of 8:1:1, in copper
Smear on foil assembles button cell as lithium ion battery negative material.Electrolyte is LiPF6(1mol/L): EC:DMC=1:
1:1 (volume ratio).It is lithium piece to electrode.
It in voltage range is 0.01-3V by above-mentioned battery, current density is to recycle 10 times under 100mA/g, then in 200mA/g
Specific discharge capacity is 830mAh/g after recycling 240 times under current density.
Embodiment 2
5.5g sucrose and 4.5g ammonium chloride are dissolved in 70ml water, then 1.2g silica is sufficiently stirred, by mixed liquor
It is transferred in closed reactor, reacts 4h at 200 DEG C.After reaction through being dried to obtain presoma.Magnesium powder, quality is added
It is 1.5 times of forerunner's weight, then it is small to stir 2 in 1M HCl by 690 DEG C of calcining 6h under an argon atmosphere after grinding uniformly
When, impurity is removed, washing filters drying, is 0.5%HF etching 10h with mass fraction, obtains silicon-carbon composite wood after washing is dry
Material obtains Si-C composite material.
Obtained Si-C composite material is uniformly mixed with acetylene black, Kynoar according to the mass ratio of 8:1:1, in copper
Smear on foil assembles button cell as lithium ion battery negative material.Electrolyte is LiPF6(1mol/L): EC:DMC=1:
1:1 (volume ratio).It is lithium piece to electrode.
It in voltage range is 0.01-3V by above-mentioned battery, current density is to recycle 10 times under 100mA/g, then in 200mA/g
Specific discharge capacity is 840mAh/g after recycling 240 times under current density.
Embodiment 3
10g maltose and 6g ammonium chloride are dissolved in 120ml water, then 0.1g silica is sufficiently stirred, by mixed liquor
It is transferred in closed reactor, reacts 5h at 180 DEG C.After reaction through being dried to obtain presoma.Magnesium powder, quality is added
It is 0.1 times of forerunner's weight, then it is small to stir 2 in 1M HCl by 740 DEG C of calcining 3h under an argon atmosphere after grinding uniformly
When, impurity is removed, washing filters drying, is 10%HF etching 0.5h with mass fraction, obtains silicon-carbon composite wood after washing is dry
Material obtains Si-C composite material.
Obtained Si-C composite material is uniformly mixed with acetylene black, Kynoar according to the mass ratio of 8:1:1, in copper
Smear on foil assembles button cell as lithium ion battery negative material.Electrolyte is LiPF6(1mol/L): EC:DMC=1:
1:1 (volume ratio).It is lithium piece to electrode.
It in voltage range is 0.01-3V by above-mentioned battery, current density is to recycle 10 times under 100mA/g, then in 200mA/g
Specific discharge capacity is 400mAh/g after recycling 240 times under current density.
Embodiment 4
5g dopamine and 0.5g ammonium chloride are dissolved in 50ml water, then 1.5g silica is sufficiently stirred, by mixed liquor
It is transferred in closed reactor, reacts 6h at 160 DEG C.After reaction through being dried to obtain presoma.Magnesium powder, quality is added
It is 2 times of forerunner's weight, then 680 DEG C of calcining 7h under an argon atmosphere after grinding uniformly are stirred 2 hours in 1M HCl,
Impurity is removed, washing filters drying, is 6%HF etching 2h with mass fraction, obtains Si-C composite material after washing is dry and obtain
Si-C composite material.
Obtained Si-C composite material is uniformly mixed with acetylene black, Kynoar according to the mass ratio of 8:1:1, in copper
Smear on foil assembles button cell as lithium ion battery negative material.Electrolyte is LiPF6(1mol/L): EC:DMC=1:
1:1 (volume ratio).It is lithium piece to electrode.
It in voltage range is 0.01-3V by above-mentioned battery, current density is to recycle 10 times under 100mA/g, then in 200mA/g
Specific discharge capacity is 820mAh/g after recycling 240 times under current density.
Embodiment 5
7g dopamine and 1g ammonium chloride are dissolved in 60ml water, then 1g silica is sufficiently stirred, and mixed liquor is shifted
Into closed reactor, 10h is reacted at 140 DEG C.After reaction through being dried to obtain presoma.Magnesium powder is added, quality is
1.2 times of forerunner's weight, 660 DEG C of calcining 9h under an argon atmosphere after grinding uniformly, are then stirred 2 hours in 1M HCl,
Impurity is removed, washing filters drying, is 7%HF etching 1.5h with mass fraction, obtains Si-C composite material after washing is dry and obtain
To Si-C composite material.
Obtained Si-C composite material is uniformly mixed with acetylene black, Kynoar according to the mass ratio of 8:1:1, in copper
Smear on foil assembles button cell as lithium ion battery negative material.Electrolyte is LiPF6(1mol/L): EC:DMC=1:
1:1 (volume ratio).It is lithium piece to electrode.
It in voltage range is 0.01-3V by above-mentioned battery, current density is to recycle 10 times under 100mA/g, then in 200mA/g
Specific discharge capacity is 780mAh/g after recycling 240 times under current density.
Embodiment 6
7.5g dopamine and 5g ammonium chloride are dissolved in 80ml water, then 0.8g silica is sufficiently stirred, by mixed liquor
It is transferred in closed reactor, reacts 2h at 250 DEG C.After reaction through being dried to obtain presoma.Magnesium powder, quality is added
It is 0.25 times of forerunner's weight, then it is small to stir 2 in 1M HCl by 700 DEG C of calcining 5h under an argon atmosphere after grinding uniformly
When, impurity is removed, washing filters drying, is 3%HF etching 5h with mass fraction, obtains Si-C composite material after washing is dry and obtain
To Si-C composite material.
Obtained Si-C composite material is uniformly mixed with acetylene black, Kynoar according to the mass ratio of 8:1:1, in copper
Smear on foil assembles button cell as lithium ion battery negative material.Electrolyte is LiPF6(1mol/L): EC:DMC=1:
1:1 (volume ratio).It is lithium piece to electrode.
It in voltage range is 0.01-3V by above-mentioned battery, current density is to recycle 10 times under 100mA/g, then in 200mA/g
Specific discharge capacity is 755mAh/g after recycling 240 times under current density.
Embodiment 7
5g tannic acid and 6g ammonium chloride are dissolved in 75ml water, then 0.25g silica is sufficiently stirred, and mixed liquor is turned
It moves in closed reactor, is reacted for 24 hours at 100 DEG C.After reaction through being dried to obtain presoma.Magnesium powder, quality is added
It is 0.15 times of forerunner's weight, then it is small to stir 2 in 1M HCl by 740 DEG C of calcining 3h under an argon atmosphere after grinding uniformly
When, impurity is removed, washing filters drying, is 5%HF etching 3h with mass fraction, obtains Si-C composite material after washing is dry and obtain
To Si-C composite material.
Obtained Si-C composite material is uniformly mixed with acetylene black, Kynoar according to the mass ratio of 8:1:1, in copper
Smear on foil assembles button cell as lithium ion battery negative material.Electrolyte is LiPF6(1mol/L): EC:DMC=1:
1:1 (volume ratio).It is lithium piece to electrode.
It in voltage range is 0.01-3V by above-mentioned battery, current density is to recycle 10 times under 100mA/g, then in 200mA/g
Specific discharge capacity is 550mAh/g after recycling 240 times under current density.
Embodiment 8
4.5g tannic acid and 7g ammonium chloride are dissolved in 75ml water, then 1g silica is sufficiently stirred, and mixed liquor is turned
It moves in closed reactor, reacts 14h at 140 DEG C.After reaction through being dried to obtain presoma.Magnesium powder, quality is added
It is 1 times of forerunner's weight, then 750 DEG C of calcining 2h under an argon atmosphere after grinding uniformly are stirred 2 hours in 1M HCl,
Impurity is removed, washing filters drying, is 4%HF etching 4h with mass fraction, obtains Si-C composite material after washing is dry and obtain
Si-C composite material.
Obtained Si-C composite material is uniformly mixed with acetylene black, Kynoar according to the mass ratio of 8:1:1, in copper
Smear on foil assembles button cell as lithium ion battery negative material.Electrolyte is LiPF6(1mol/L): EC:DMC=1:
1:1 (volume ratio).It is lithium piece to electrode.
It in voltage range is 0.01-3V by above-mentioned battery, current density is to recycle 10 times under 100mA/g, then in 200mA/g
Specific discharge capacity is 795mAh/g after recycling 240 times under current density.
Embodiment 9
4g citric acid and 7.5g ammonium chloride are dissolved in 70ml water, then 1.2g silica is sufficiently stirred, by mixed liquor
It is transferred in closed reactor, reacts 16h at 120 DEG C.After reaction through being dried to obtain presoma.Magnesium powder, matter is added
Amount is 1.2 times of forerunner's weight, then 730 DEG C of calcining 3.5h under an argon atmosphere after grinding uniformly stir 2 in 1M HCl
Hour, impurity is removed, washing filters drying, is 0.8%HF etching 9h with mass fraction, obtains silicon-carbon composite wood after washing is dry
Material obtains Si-C composite material.
Obtained Si-C composite material is uniformly mixed with acetylene black, Kynoar according to the mass ratio of 8:1:1, in copper
Smear on foil assembles button cell as lithium ion battery negative material.Electrolyte is LiPF6(1mol/L): EC:DMC=1:
1:1 (volume ratio).It is lithium piece to electrode.
It in voltage range is 0.01-3V by above-mentioned battery, current density is to recycle 10 times under 100mA/g, then in 200mA/g
Specific discharge capacity is 770mAh/g after recycling 240 times under current density.
Embodiment 10
3.5g citric acid and 8g ammonium chloride are dissolved in 70ml water, then 0.5g silica is sufficiently stirred, by mixed liquor
It is transferred in closed reactor, reacts 15h at 130 DEG C.After reaction through being dried to obtain presoma.Magnesium powder, matter is added
Amount is 0.2 times of forerunner's weight, then it is small to stir 2 in 1M HCl by 740 DEG C of calcining 3h under an argon atmosphere after grinding uniformly
When, impurity is removed, washing filters drying, is 1.5%HF etching 8h with mass fraction, obtains Si-C composite material after washing is dry
Obtain Si-C composite material.
Obtained Si-C composite material is uniformly mixed with acetylene black, Kynoar according to the mass ratio of 8:1:1, in copper
Smear on foil assembles button cell as lithium ion battery negative material.Electrolyte is LiPF6(1mol/L): EC:DMC=1:
1:1 (volume ratio).It is lithium piece to electrode.
It in voltage range is 0.01-3V by above-mentioned battery, current density is to recycle 10 times under 100mA/g, then in 200mA/g
Specific discharge capacity is 610mAh/g after recycling 240 times under current density.
Embodiment 11
3g fructose and 8.5g ammonium chloride are dissolved in 70ml water, then 0.8g silica is sufficiently stirred, and mixed liquor is turned
It moves in closed reactor, reacts 16h at 120 DEG C.After reaction through being dried to obtain presoma.Magnesium powder, quality is added
It is 0.3 times of forerunner's weight, then it is small to stir 2 in 1M HCl by 710 DEG C of calcining 4.5h under an argon atmosphere after grinding uniformly
When, impurity is removed, washing filters drying, is 2.5%HF etching 7h with mass fraction, obtains Si-C composite material after washing is dry
Obtain Si-C composite material.
Obtained Si-C composite material is uniformly mixed with acetylene black, Kynoar according to the mass ratio of 8:1:1, in copper
Smear on foil assembles button cell as lithium ion battery negative material.Electrolyte is LiPF6(1mol/L): EC:DMC=1:
1:1 (volume ratio).It is lithium piece to electrode.
It in voltage range is 0.01-3V by above-mentioned battery, current density is to recycle 10 times under 100mA/g, then in 200mA/g
Specific discharge capacity is 705mAh/g after recycling 240 times under current density.
Embodiment 12
1g fructose and 10g ammonium chloride are dissolved in 70ml water, then 0.3g silica is sufficiently stirred, and mixed liquor is shifted
Into closed reactor, 20h is reacted at 110 DEG C.After reaction through being dried to obtain presoma.Magnesium powder is added, quality is
0.15 times of forerunner's weight, 670 DEG C of calcining 8h under an argon atmosphere after grinding uniformly, is then stirred 2 hours in 1M HCl,
Impurity is removed, washing filters drying, is 1%HF etching 8h with mass fraction, obtains Si-C composite material after washing is dry and obtain
Si-C composite material.
Obtained Si-C composite material is uniformly mixed with acetylene black, Kynoar according to the mass ratio of 8:1:1, in copper
Smear on foil assembles button cell as lithium ion battery negative material.Electrolyte is LiPF6(1mol/L): EC:DMC=1:
1:1 (volume ratio).It is lithium piece to electrode.
It in voltage range is 0.01-3V by above-mentioned battery, current density is to recycle 10 times under 100mA/g, then in 200mA/g
Specific discharge capacity is 415mAh/g after recycling 240 times under current density.
Embodiment 13
8g maltose and 3g ammonium chloride are dissolved in 70ml water, then 0.7g silica is sufficiently stirred, and mixed liquor is turned
It moves in closed reactor, reacts 3h at 240 DEG C.After reaction through being dried to obtain presoma.Magnesium powder is added, quality is
0.25 times of forerunner's weight, 650 DEG C of calcining 9h under an argon atmosphere after grinding uniformly, is then stirred 2 hours in 1M HCl,
Impurity is removed, washing filters drying, is 2%HF etching 6h with mass fraction, obtains Si-C composite material after washing is dry and obtain
Si-C composite material.
Obtained Si-C composite material is uniformly mixed with acetylene black, Kynoar according to the mass ratio of 8:1:1, in copper
Smear on foil assembles button cell as lithium ion battery negative material.Electrolyte is LiPF6(1mol/L): EC:DMC=1:
1:1 (volume ratio).It is lithium piece to electrode.
It in voltage range is 0.01-3V by above-mentioned battery, current density is to recycle 10 times under 100mA/g, then in 200mA/g
Specific discharge capacity is 685mAh/g after recycling 240 times under current density.
Embodiment 14
10g lactose and 1g ammonium chloride are dissolved in 70ml water, then 2.5g silica is sufficiently stirred, and mixed liquor is shifted
Into closed reactor, 4.5h is reacted at 190 DEG C.After reaction through being dried to obtain presoma.Magnesium powder is added, quality is
1.8 times of forerunner's weight, 750 DEG C of calcining 2h under an argon atmosphere after grinding uniformly, are then stirred 2 hours in 1M HCl,
Impurity is removed, washing filters drying, is 3%HF etching 5h with mass fraction, obtains Si-C composite material after washing is dry and obtain
Si-C composite material.
Obtained Si-C composite material is uniformly mixed with acetylene black, Kynoar according to the mass ratio of 8:1:1, in copper
Smear on foil assembles button cell as lithium ion battery negative material.Electrolyte is LiPF6(1mol/L): EC:DMC=1:
1:1 (volume ratio).It is lithium piece to electrode.
It in voltage range is 0.01-3V by above-mentioned battery, current density is to recycle 10 times under 100mA/g, then in 200mA/g
Specific discharge capacity is 820mAh/g after recycling 240 times under current density.
Claims (9)
1. the preparation method that a kind of nitrogen mixes porous nano-sheet Si-C composite material, which comprises the steps of:
Step 1, carbon source and ammonium chloride is soluble in water, silica is added, is dispersed with stirring uniformly, obtains precursor liquid；
Step 2, by precursor liquid in 100-250 DEG C of hydro-thermal reaction 2-24h, product is dried to obtain presoma；
Step 3, presoma is mixed with magnesium powder, then calcining reduction, it is more that finally process is washed, hf etching obtains N doping
Hole nanometer sheet Si-C composite material.
2. the preparation method that nitrogen according to claim 1 mixes porous nano-sheet Si-C composite material, which is characterized in that step
In 1, the silica the preparation method comprises the following steps: by dehydrated alcohol, water and ammonium hydroxide mix, stir evenly, be added ethyl orthosilicate,
Continue to stir, be centrifuged, wash, dry after obtain the nano particle of silica.
3. the preparation method that nitrogen according to claim 1 mixes porous nano-sheet Si-C composite material, which is characterized in that step
In 1, the carbon source is appointing in glucose, sucrose, maltose, fructose, lactose, citric acid, dopamine, tannic acid and sodium acetate
It anticipates one kind.
4. the preparation method that nitrogen according to claim 1 mixes porous nano-sheet Si-C composite material, which is characterized in that step
In 1, the mass ratio of the carbon source and ammonium chloride are as follows: (0.1-10): 1, the mass ratio of the silica and carbon source are as follows:
(0.01-0.3):1。
5. the preparation method that nitrogen according to claim 1 mixes porous nano-sheet Si-C composite material, which is characterized in that step
In 3, the magnesium powder and presoma mass ratio are as follows: (0.1-2): 1.
6. the preparation method that nitrogen according to claim 1 mixes porous nano-sheet Si-C composite material, which is characterized in that step
In 3, the mass concentration of the hydrofluoric acid are as follows: 0.5%-10%, etch period are as follows: 0.5-10h.
7. the preparation method that nitrogen according to claim 1 mixes porous nano-sheet Si-C composite material, which is characterized in that step
In 3, calcination temperature is 650 DEG C -750 DEG C, time 2-10h.
8. the nitrogen that the described in any item preparation methods of claim 1-7 are prepared mixes porous nano-sheet Si-C composite material.
9. nitrogen according to any one of claims 8 mix porous nano-sheet Si-C composite material as negative electrode material answering in lithium ion battery
With.
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