CN110474037A - A kind of preparation method of porous silicon-carbon composite cathode material - Google Patents
A kind of preparation method of porous silicon-carbon composite cathode material Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of porous silicon-carbon composite cathode material, comprising the following steps: prepares nano-silicon/silicon oxygen complex；Nano-silicon/silicon oxygen/carbon/carbon-copper composite material is prepared using magnetron sputtering method；Nano-silicon/silicon oxygen/copper/graphene composite material is prepared using chemical vapour deposition technique；It puts it into the mixed liquor of nitric/hydrofluoric, is impregnated, secondary distilled water cleaning, vacuum drying.The invention has the benefit that using magnetron sputtering method in nano-silicon/silicon oxygen complex surfaces vapor deposition consistency height, consistency height, the suitable Nanometer Copper of partial size, deposition Nanometer Copper is set to have the characteristics that stable structure, partial size are small, and graphene is deposited on its surface as hard template, corrode copper by acid soak and obtains porous structure, the feature strong using the electric conductivity of grapheme material itself, mechanical strength is high reduces the internal resistance of cell and its liquid-keeping property and cycle performance of material can be improved in expansion, the formation of porous structure.
Description
Technical field
The present invention relates to battery material technical fields, and in particular to a kind of preparation side of porous silicon-carbon composite cathode material
Method.
Background technique
Silicon is a kind of negative electrode material that lithium is stored up and forming alloy with lithium, and theoretical capacity is up to 4200mAh/g, meanwhile,
The discharge platform of silicon is slightly above carbon material, the security performance of battery can be improved, and material source is wide.But in charge and discharge cycles
In, lithium ion it is repeatedly embedding it is de- will cause the huge volume change of material (volume expansion > 300%), resulting machinery is answered
Power will lead to the collapse, dusting, peeling of material lattice structure, lose so as to cause between silicon particle, between particle and collector
Electrical contact, internal resistance increase, and ultimately cause reversible capacity rapid decrease.And material nanoization can then reduce the expansion of material, contracting
The embedding rate out of lithium ion, improves its high rate performance in short charge and discharge process.
Although researcher has the reunion for reducing material by template, for example patent (CN 103337612A) discloses one
Kind nanoporous Si-C composite material and preparation method thereof, mainly prepares nanoporous by being corroded to multicomponent alloy
The method of Si-C composite material, it is more that the ratio that this method passes through various components in control raw alloy piece can continuously adjust nanometer
The ratio of silicon in the Si-C composite material of hole, carbon component, thus reach the degree continuously adjusted to the composition adjustment of product, it can be right
The performance of material carries out microcosmic regulation, but this method is uniformly mixed difference due to metal and carbon material, it is caused to be formed
The structure distribution of hole is uneven.
Summary of the invention
The object of the present invention is to provide one kind to deposit Nanometer Copper in nano-silicon/silicon oxygen complex surfaces by magnetron sputtering method
And its graphene, it then erodes metal and obtains the silicon-carbon composite cathode material that hole configurations is evenly distributed.
A kind of preparation method of porous silicon-carbon composite cathode material, comprising the following steps:
(1) nano-silicon/silicon oxygen complex is prepared:
Nano-silicon, silane coupling agent, dispersing agent are sequentially added in organic solvent, are mixed evenly, is done by spraying
It is dry, mixed-powder；Mixed-powder is subjected to high temperature cabonization, ball milling obtains nano-silicon/silicon oxygen complex；
(2) nano-silicon/silicon oxygen/carbon/carbon-copper composite material is prepared using magnetron sputtering method:
It is target as cathode by substrate of nano-silicon/silicon oxygen complex as anode, copper oxide, nano-silicon/silicon oxygen is compound
The distance between body and copper oxide are 30-50cm, preheat fine copper backboard to 200-500 DEG C, holding sputtering power is direct current
10W-20W, deposition rate are 0.8-1.5 μm/min, sputtering pressure 0.5-2Pa, sputtering time 10-120min；
(3) nano-silicon/silicon oxygen/copper/graphene composite material is prepared using chemical vapour deposition technique:
Nano-silicon/silicon oxygen/carbon/carbon-copper composite material is added in vapor deposition tube furnace, by tubular type under the protection of inert gas
Furnace heating, closes inert gas, is passed through hydrogen/methane mixed gas, after a period of time, stops heating, and stop being passed through first
Alkane gas continues to be passed through hydrogen, is down to room temperature naturally, obtains nano-silicon/silicon oxygen/copper/graphene composite material；
(2) nano-silicon/silicon oxygen/copper/graphene composite material is put into the mixed liquor of nitric/hydrofluoric, is impregnated,
It finishes wait impregnate, is cleaned using secondary distilled water, be dried in vacuo to obtain porous silicon-carbon composite cathode material.
Further, in step (1), the silane coupling agent is alkylideneimino alkenyl dimethylsilane, two (alkylenes
Base imino group) enylmethyl silane, three (alkylideneimino) alkenyl silanes, arlydene imino group alkenyl dimethylsilane, two
(arlydene imino group) enylmethyl silane, three (arlydene imino group) alkenyl silanes, ammonia diaryl base alkenyl dimethylsilane,
One of two (ammonia diaryl base) enylmethyl silane.
Further, in step (1), the dispersing agent is the polyethylene glycol that molecular weight ranges are 500-3000.
Further, in step (1), the organic solvent is N-Methyl pyrrolidone, carbon tetrachloride, diphenylamines, first
One of benzene, acetone, diethanol or or mixtures thereof.
Further, in step (1), the temperature of the high temperature cabonization are as follows: 500-600 DEG C, when carbonization at this temperature
Between are as follows: 4-6h.
Further, in step (1), the weight ratio of nano-silicon, silane coupling agent, dispersing agent, organic solvent are as follows: 1-5:
1-5:0.1-1:100.
Further, in step (3), reach 800-1200 DEG C to the temperature in tube furnace, pressure reaches 0.1-
When 90Torr, inert gas is closed；It is passed through the hydrogen that flow is 500sccm and the methane that flow is 600sccm, and is passed through mixing
The when a length of 60-120min of gas.
Further, in step (4), the concentration of nitric/hydrofluoric mixed liquor is 1%-10%, nitric acid and hydrofluoric acid
Volume ratio is 1:1.
Further, in step (4), when immersion a length of 1-12h.
Further, in step (4), vacuum drying temperature is 80-120 DEG C, Zhen Kong Du≤100pa.
The invention has the benefit that a kind of preparation method of porous silicon-carbon composite cathode material of the present invention, passes through
It is vapor-deposited Nanometer Copper in nano-silicon/silicon oxygen complex surfaces, makes it have that deposition compact, particle are small, consistency is high and process
Controllable feature；And in nano-silicon/silicon oxygen/carbon/carbon-copper composite material surface coated graphite alkene, the electric conductivity of material itself can be improved
Energy, mechanical strength and high rate performance, obtain porous structure by immersion corrosion copper, and material can be improved in the formation of porous structure
Liquid-keeping property and cycle performance.And due to being controlled in nano-silicon/silicon oxygen deposit complexes Nanometer Copper by magnetron sputtering technique
The distribution of Nanometer Copper, i.e. presentation spot distribution, deposit graphene on its surface later, graphene a part is deposited on Nanometer Copper table
Face, a part are deposited on nano-silicon/silicon oxygen complex surfaces, carry out pore-creating to the corrosion of Nanometer Copper convenient for acid.
It can be seen in the drawings that porous structure is presented in porous silicon-carbon composite cathode material of the present invention, surface is received
Rice/micron hole, partial size is between 19-22 μm.
Detailed description of the invention
Fig. 1: the SEM figure of porous silicon-carbon composite cathode material of the present invention.
Specific embodiment
Embodiment 1
A kind of preparation method of porous silicon-carbon composite cathode material, comprising the following steps:
(1) nano-silicon/silicon oxygen complex is prepared:
Nano-silicon, silane coupling agent, dispersing agent are sequentially added in organic solvent, are mixed evenly, is done by spraying
It is dry, mixed-powder；Mixed-powder is subjected to high temperature cabonization, ball milling obtains nano-silicon/silicon oxygen complex；
(2) nano-silicon/silicon oxygen/carbon/carbon-copper composite material is prepared using magnetron sputtering method:
It is target as cathode by substrate of nano-silicon/silicon oxygen complex as anode, copper oxide, nano-silicon/silicon oxygen is compound
The distance between body and copper oxide are 30cm, preheat fine copper backboard to 200 DEG C, holding sputtering power is direct current 10W, deposition rate
For 0.8 μm/min, sputtering pressure 0.5Pa, sputtering time 120min；
(3) nano-silicon/silicon oxygen/copper/graphene composite material is prepared using chemical vapour deposition technique:
Nano-silicon/silicon oxygen/carbon/carbon-copper composite material is added in vapor deposition tube furnace, by tubular type under the protection of inert gas
Furnace heating, closes inert gas, is passed through hydrogen/methane mixed gas, after a period of time, stops heating, and stop being passed through first
Alkane gas continues to be passed through hydrogen, is down to room temperature naturally, obtains nano-silicon/silicon oxygen/copper/graphene composite material；
(4) nano-silicon/silicon oxygen/copper/graphene composite material is put into the mixed liquor of nitric/hydrofluoric, is impregnated,
It finishes wait impregnate, is cleaned using secondary distilled water, be dried in vacuo to obtain porous silicon-carbon composite cathode material.
Embodiment 2
A kind of preparation method of porous silicon-carbon composite cathode material, comprising the following steps:
(1) nano-silicon/silicon oxygen complex is prepared:
By 1g nano-silicon, 1g alkylideneimino alkenyl dimethylsilane, 0.1g molecular weight be 500 polyethylene glycol successively
It is added in 100g organic solvent N-Methyl pyrrolidone, is mixed evenly, be spray-dried, obtain mixed-powder；It will mixing
For powder under conditions of temperature is 500 DEG C, high temperature cabonization 6h, ball milling obtain nano-silicon/silicon oxygen complex；
(2) nano-silicon/silicon oxygen/carbon/carbon-copper composite material is prepared using magnetron sputtering method:
It is target as cathode by substrate of nano-silicon/silicon oxygen complex as anode, copper oxide, nano-silicon/silicon oxygen is compound
The distance between body and copper oxide are 40cm, preheat fine copper backboard to 250 DEG C, holding sputtering power is direct current 15W, deposition rate
For 1.2 μm/min, sputtering pressure 1.2Pa, sputtering time 60min；
(3) nano-silicon/silicon oxygen/copper/graphene composite material is prepared using chemical vapour deposition technique:
Nano-silicon/silicon oxygen/carbon/carbon-copper composite material is added in vapor deposition tube furnace, by tubular type under the protection of inert gas
Furnace is warming up to 800 DEG C, but the pressure in tube furnace reaches 10Torr, closes inert gas, is passed through the hydrogen that flow is 500sccm
The methane mixed gas for being 600sccm with flow stops heating after being passed through 60min, and stops being passed through methane gas, continues to be passed through
Hydrogen is down to room temperature naturally, obtains nano-silicon/silicon oxygen/copper/graphene composite material；
(4) nano-silicon/silicon oxygen/copper/graphene composite material is put into nitric acid/hydrogen that concentration is 1%, volume ratio is 1:1
In the mixed liquor of fluoric acid, 1h is impregnated, finishes wait impregnate, is cleaned using secondary distilled water, and temperature is 100 DEG C, vacuum degree is
Porous silicon-carbon composite cathode material is dried in vacuo to obtain under conditions of 50pa.
Embodiment 3
A kind of preparation method of porous silicon-carbon composite cathode material, comprising the following steps:
(1) nano-silicon/silicon oxygen complex is prepared:
By 3g nano-silicon, (alkylideneimino) enylmethyl of 3g bis- silane, the polyethylene glycol that 0.5g molecular weight is 1200
It sequentially adds in 100g organic solvent-acetone, is mixed evenly, be spray-dried, obtain mixed-powder；Mixed-powder is existed
Under conditions of temperature is 550 DEG C, high temperature cabonization 5h, ball milling obtain nano-silicon/silicon oxygen complex；
(2) nano-silicon/silicon oxygen/carbon/carbon-copper composite material is prepared using magnetron sputtering method:
It is target as cathode by substrate of nano-silicon/silicon oxygen complex as anode, copper oxide, nano-silicon/silicon oxygen is compound
The distance between body and copper oxide are 40cm, preheat fine copper backboard to 350 DEG C, holding sputtering power is direct current 18W, deposition rate
For 1.3 μm/min, sputtering pressure 1.6Pa, sputtering time 80min；
(3) nano-silicon/silicon oxygen/copper/graphene composite material is prepared using chemical vapour deposition technique:
Nano-silicon/silicon oxygen/carbon/carbon-copper composite material is added in vapor deposition tube furnace, by tubular type under the protection of inert gas
Furnace is warming up to 1000 DEG C, but the pressure in tube furnace reaches 60Torr, closes inert gas, is passed through the hydrogen that flow is 500sccm
The methane mixed gas that gas and flow are 600sccm stops heating after being passed through 80min, and stops being passed through methane gas, continues to lead to
Enter hydrogen, be down to room temperature naturally, obtains nano-silicon/silicon oxygen/copper/graphene composite material；
(4) nano-silicon/silicon oxygen/copper/graphene composite material is put into nitric acid/hydrogen that concentration is 6%, volume ratio is 1:1
In the mixed liquor of fluoric acid, 6h is impregnated, finishes wait impregnate, is cleaned using secondary distilled water, and temperature is 80 DEG C, vacuum degree is
Porous silicon-carbon composite cathode material is dried in vacuo to obtain under conditions of 100pa.
Embodiment 4
A kind of preparation method of porous silicon-carbon composite cathode material, comprising the following steps:
(1) nano-silicon/silicon oxygen complex is prepared:
By 5g nano-silicon, 5g bis- (arlydene imino group) enylmethyl silane, 1g molecular weight be 3000 polyethylene glycol according to
It in secondary addition 100g organic solvent diethanol, is mixed evenly, is spray-dried, obtains mixed-powder；Mixed-powder is existed
Under conditions of temperature is 600 DEG C, high temperature cabonization 4h, ball milling obtain nano-silicon/silicon oxygen complex；
(2) nano-silicon/silicon oxygen/carbon/carbon-copper composite material is prepared using magnetron sputtering method:
It is target as cathode by substrate of nano-silicon/silicon oxygen complex as anode, copper oxide, nano-silicon/silicon oxygen is compound
The distance between body and copper oxide are 50cm, preheat fine copper backboard to 500 DEG C, holding sputtering power is direct current 20W, deposition rate
For 1.5 μm/min, sputtering pressure 2Pa, sputtering time 120min；
(3) nano-silicon/silicon oxygen/copper/graphene composite material is prepared using chemical vapour deposition technique:
Nano-silicon/silicon oxygen/carbon/carbon-copper composite material is added in vapor deposition tube furnace, by tubular type under the protection of inert gas
Furnace is warming up to 1200 DEG C, but the pressure in tube furnace reaches 90Torr, closes inert gas, is passed through the hydrogen that flow is 500sccm
The methane mixed gas that gas and flow are 600sccm stops heating after being passed through 120min, and stops being passed through methane gas, continues
It is passed through hydrogen, is down to room temperature naturally, obtains nano-silicon/silicon oxygen/copper/graphene composite material；
(4) nano-silicon/silicon oxygen/copper/graphene composite material is put into nitric acid/hydrogen that concentration is 10%, volume ratio is 1:1
In the mixed liquor of fluoric acid, 1h is impregnated, finishes wait impregnate, is cleaned using secondary distilled water, and temperature is 120 DEG C, vacuum degree is
Porous silicon-carbon composite cathode material is dried in vacuo to obtain under conditions of 10pa.Comparative example 1
Silicon-carbon composite cathode material described in comparative example 1 the preparation method comprises the following steps: by 3 nano-silicons, 3g alkylideneimino alkenyl
Dimethylsilane, 0.5g polyethylene glycol are added in 100mlN- methyl pyrrolidone organic solvent, later after mixing evenly, into
Row spray drying, and 550 DEG C of high temperature sintering 5h, ball millings under an argon atmosphere to obtain the final product.
The physicochemical property and its button cell of porous silicon-carbon composite cathode material of the present invention are tested
According to national standards GBT-245332009 " silicon/carbon/graphite in lithium ion batteries class negative electrode material " testing example 1-4 with
The specific surface area and tap density of the composite negative pole material of comparative example preparation:
Respectively with silicon-carbon composite cathode material described in porous silicon-carbon composite cathode material described in embodiment 1-4 and comparative example
Prepare pole piece；
Specific steps are as follows: weigh 9g negative electrode material, 0.5g conductive agent SP, 132 binder of 0.5g LA respectively and be added to
Film is in being made into diaphragm after mixing evenly on copper foil in the deionized water of 220ml, using lithium piece as cathode, celegard2400 be every
Film, electrolyte solute are the LiPF of 1mol/L6, solvent be ethylene carbonate (EC) and diethyl carbonate (DMC) (volume ratio 1:
1) mixed solution is assembled into button cell in the glove box that oxygen and water content are below 0.1ppm, later by button
Battery is attached on blue electric tester, and with the rate charge-discharge of 0.1C, voltage range 0.05V-2.0V, circulation stops after 3 weeks；
The high rate performance of button cell is tested, with 1.0C charging, 1.0C and 10.0C electric discharge, voltage range are as follows: 0.05V-
2.0V；
Cycle performance test: with charging and discharging currents 1.0C/1.0C, voltage range 0.05-2.0V, 23 ± 5 DEG C of temperature, into
100 charge and discharge cycles of row, the capacity retention ratio after testing its circulation；
The physicochemical property of silicon-carbon composite cathode material described in 1 1-4 of the embodiment of the present invention of table and comparative example
As can be seen from Table 1, the porous silicon-carbon composite cathode material of embodiment 1-4 is in first charge discharge efficiency and its gram volume side
Face is better than comparative example, that is, copper oxide is used to have imbibition liquid-keeping property strong, swollen for the porous Si-C composite material that matrix is prepared
The features such as swollen rate is low, so that the gram volume for improving its material plays and its first charge discharge efficiency, while porous material has high imbibition
Ability improves the ability that its material accommodates lithium ion, and then improves the multiplying power and cycle performance of its material.The oxidation of acid corrosion simultaneously
The porous silicon-carbon cathode material that copper leaves reduces the tap density of material with biggish specific surface area.
The present invention is not limited to above-mentioned preferred forms, anyone can show that other are various under the inspiration of the present invention
The product of form, however, make any variation in its details, it is all that there is technical solution identical or similar to the present application,
It is within the scope of the present invention.
Claims (10)
1. a kind of preparation method of porous silicon-carbon composite cathode material, which comprises the following steps:
(1) nano-silicon/silicon oxygen complex is prepared:
Nano-silicon, silane coupling agent, dispersing agent are sequentially added in organic solvent, are mixed evenly, be spray-dried,
Mixed-powder；Mixed-powder is subjected to high temperature cabonization, ball milling obtains nano-silicon/silicon oxygen complex；
(2) nano-silicon/silicon oxygen/carbon/carbon-copper composite material is prepared using magnetron sputtering method:
Be target as cathode by substrate of nano-silicon/silicon oxygen complex as anode, copper oxide, nano-silicon/silicon oxygen complex with
The distance between copper oxide is 30-50cm, preheats fine copper backboard to 200-500 DEG C, holding sputtering power is direct current 10W-
20W, deposition rate are 0.8-1.5 μm/min, sputtering pressure 0.5-2Pa, sputtering time 10-120min；
(3) nano-silicon/silicon oxygen/copper/graphene composite material is prepared using chemical vapour deposition technique:
Nano-silicon/silicon oxygen/carbon/carbon-copper composite material is added in vapor deposition tube furnace, by tube furnace liter under the protection of inert gas
Temperature closes inert gas, is passed through hydrogen/methane mixed gas, after a period of time, stops heating, and stop being passed through methane gas
Body continues to be passed through hydrogen, is down to room temperature naturally, obtains nano-silicon/silicon oxygen/copper/graphene composite material；
(4) nano-silicon/silicon oxygen/copper/graphene composite material is put into the mixed liquor of nitric/hydrofluoric, is impregnated, wait soak
It finishes complete, is cleaned using secondary distilled water, be dried in vacuo to obtain porous silicon-carbon composite cathode material.
2. a kind of preparation method of porous silicon-carbon composite cathode material according to claim 1, which is characterized in that step (1)
In, the silane coupling agent is alkylideneimino alkenyl dimethylsilane, two (alkylideneimino) enylmethyl silane, three
(alkylideneimino) alkenyl silanes, arlydene imino group alkenyl dimethylsilane, two (arlydene imino group) enylmethyl silicon
Alkane, three (arlydene imino group) alkenyl silanes, ammonia diaryl base alkenyl dimethylsilane, two (ammonia diaryl base) enylmethyl silicon
One of alkane.
3. a kind of preparation method of porous silicon-carbon composite cathode material according to claim 1, which is characterized in that step (1)
In, the dispersing agent is the polyethylene glycol that molecular weight ranges are 500-3000.
4. a kind of preparation method of porous silicon-carbon composite cathode material according to claim 1, which is characterized in that step (1)
In, the organic solvent be one of N-Methyl pyrrolidone, carbon tetrachloride, diphenylamines, toluene, acetone, diethanol or or
Its mixture.
5. a kind of preparation method of porous silicon-carbon composite cathode material according to claim 1, which is characterized in that step (1)
In, the temperature of the high temperature cabonization are as follows: 500-600 DEG C, carbonization time at this temperature are as follows: 4-6h.
6. a kind of preparation method of porous silicon-carbon composite cathode material according to claim 1, which is characterized in that step (1)
In, the weight ratio of nano-silicon, silane coupling agent, dispersing agent, organic solvent are as follows: 1-5:1-5:0.1-1:100.
7. a kind of preparation method of porous silicon-carbon composite cathode material according to claim 1, which is characterized in that step (3)
In, reach 800-1200 DEG C, when pressure reaches 0.1-90Torr to the temperature in tube furnace, closes inert gas；It is passed through stream
The methane that the hydrogen and flow that amount is 500sccm are 600sccm, and it is passed through the when a length of 60-120min of mixed gas.
8. a kind of preparation method of porous silicon-carbon composite cathode material according to claim 1, which is characterized in that step (4)
In, the concentration of nitric/hydrofluoric mixed liquor is 1%-10%, and the volume ratio of nitric acid and hydrofluoric acid is 1:1.
9. a kind of preparation method of porous silicon-carbon composite cathode material according to claim 1, which is characterized in that step (4)
In, when immersion a length of 1-12h.
10. a kind of preparation method of porous silicon-carbon composite cathode material according to claim 1, which is characterized in that step (4)
In, vacuum drying temperature is 80-120 DEG C, Zhen Kong Du≤100pa.
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| CN201910811954.3A CN110474037B (en) | 2019-08-30 | 2019-08-30 | Preparation method of porous silicon-carbon composite negative electrode material |
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| CN201910811954.3A CN110474037B (en) | 2019-08-30 | 2019-08-30 | Preparation method of porous silicon-carbon composite negative electrode material |
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