Petroleum coke base porous carbon materials and preparation method thereof and silicon-carbon cathode material
Technical field
The present invention relates to carbon material preparation fields, more particularly, to a kind of petroleum coke base porous carbon materials and preparation method thereof
With silicon-carbon cathode material.
Background technique
Due to lithium ion battery have pollution-free, long service life, it is small in size, can be quickly charged and discharged outstanding advantages of,
Through being widely used in portable electronic device and electric car.In recent years, battery energy density is required with people
It increasingly improves, the material system of current battery is not able to satisfy high-energy density requirement gradually.For negative electrode material, graphite
Class negative electrode material has been widely used in commercial Li-ion battery, but the theoretical capacity of graphite negative electrodes material is only
372mAh/g can no longer meet the demand for development of lithium ion battery small-size light-weight, driving for a long time.Therefore novel bear is developed
Pole material system is always the emphasis and hot spot researched and developed.
Silicon based anode material is due to being following most promising bear with high specific capacity and low removal lithium embedded current potential
One of pole material system.However silicon generates huge volume change during removal lithium embedded, is easy to cause the destruction of electrode structure
Unstable SEI film, finally makes the capacity rapid decay of battery, the serious silicon based anode material that limits is in lithium ion with formation
Application in battery.Currently, carrying out compound obtained silicon-carbon cathode material with silicon using porous carbon is to solve silicon volume expansion to ask
One of preferred plan of topic, the hole in porous carbon are that silicon volume expansion reserves sufficient space, and silicon can be guaranteed in volume expansion
Still original pattern is maintained in journey, while the interaction between silicon particle can be effectively isolated in porous carbon, and buffers
The huge stress generated during silicon volume expansion.But current porous carbon is often with soft template method and hard template method system
Standby, complex technical process haves the shortcomings that high production cost and production efficiency are low, and the shape for the porous carbon materials being prepared
Mostly club shaped structure or fibrous structure lead to the lesser problem of its specific surface area.
Summary of the invention
The first object of the present invention is to provide a kind of preparation method of petroleum coke base porous carbon materials, to alleviate existing skill
The porous carbon high production cost and production efficiency of art be low and the existing lesser technical problem of porous carbon materials specific surface area.
The second object of the present invention is to provide a kind of petroleum coke base porous carbon materials obtained using above-mentioned preparation method,
The petroleum coke base porous carbon materials have the advantages that conductivity height and large specific surface area.
The third object of the present invention is to provide a kind of silicon-carbon cathode material, which has preferable circulation
Stability, and be conducive to improve the initial charge efficiency of battery.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
A kind of preparation method of petroleum coke base porous carbon materials, comprising the following steps:
The mixture of the petroleum coke obtained after ball milling and pore creating material is calcined, the petroleum coke base porous carbon is obtained
Material.
Further, the pore creating material is potassium hydroxide, phosphoric acid or zinc chloride, preferably potassium hydroxide, the petroleum coke
Weight ratio with the pore creating material is 1:(1-5).
Further, first petroleum coke is uniformly mixed with potassium hydroxide solution, is placed in ball milling in ball mill after drying, so
It is calcined again afterwards.
Further, the abrading-ball used in ball milling for the combination of different-diameter agate ball, distinguish by the diameter of the agate ball
For 4-6mm, 0.9-1.2cm and 1.4-1.6cm.
Further, the method for the calcining are as follows: under an inert atmosphere, be first warming up to the heating rate of 2-7 DEG C/min
Then 350-450 DEG C of calcining 1-3h is warming up to 850-950 DEG C of calcining 1-3h again with the heating rate of 2-7 DEG C/min.
Further, it is successively started the cleaning processing with acid solution, alcoholic solution and deionized water after calcining, after drying
Obtain the petroleum coke base porous carbon materials.
Further, the acid solution is dilute nitric acid solution or dilute hydrochloric acid solution, and the concentration of the dilute nitric acid solution is
2.5-3.5mol/L, the concentration of the dilute hydrochloric acid solution are 2.5-3.5mol/L.
Further, the alcoholic solution is ethanol solution or propanol solution, preferably ethanol solution, the ethanol solution
Concentration >=95%.
A kind of petroleum coke base porous carbon materials, are obtained using above-mentioned preparation method.
A kind of silicon-carbon cathode material, using silicon with above-mentioned petroleum coke base porous carbon materials are compound is prepared.
Compared with the prior art, the invention has the following beneficial effects:
It is to prepare raw material that the preparation method of petroleum coke base porous carbon materials provided by the invention, which is with petroleum coke, passes through ball
It grinds and carries out effectively being sufficiently mixed to obtain the mixture of the two by petroleum coke and pore creating material, then obtained again by calcining porous
Carbon material.Due to using petroleum coke as raw material, and ball-milling technology is utilized to carry out particle refinement, the ball of finally obtained porous carbon materials
Shape degree is very high, as shown in Figure 1, therefore, the specific surface area of the porous carbon materials obtained using the preparation method is also bigger.Benefit
It is carried out with the porous carbon materials of the high porosity and bigger serface with silicon compound, more silicon atoms can be accommodated, improve electricity
The capacity of pole material, while it being also beneficial to buffering silicon materials caused volume change in charge and discharge process, make silicon-carbon composite wood
Material keeps good stability.
In addition, can not only refine petroleum coke particles in mechanical milling process, while pore creating material and petroleum coke can also be increased
Contact area, porous carbon materials of available porosity height and even pore distribution after firing, as shown in Figure 2.From Fig. 2
As can be seen that the porous carbon materials obtained using preparation method provided by the invention, surface is evenly distributed with a large amount of holes.
In addition, preparation method synthetic route provided by the invention is simple, complicated instrument and equipment is not needed, when preparation
Between greatly shorten, production efficiency is higher;Meanwhile raw material petroleum coke used is simple and easy to get, lower production costs.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is that the petroleum coke base porous carbon materials that preparation method provided by the invention obtains amplify the scanning after 3000 multiplying powers
Electron microscope.
Fig. 2 is that the petroleum coke base porous carbon materials that preparation method provided by the invention obtains amplify the scanning after 12000 times
Electron microscope.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
On the one hand, the present invention provides a kind of preparation methods of petroleum coke base porous carbon materials, comprising the following steps:
The mixture of the petroleum coke obtained after ball milling and pore creating material is calcined, the petroleum coke base porous carbon is obtained
Material.
It is to prepare raw material that the preparation method of petroleum coke base porous carbon materials provided by the invention, which is with petroleum coke, passes through ball
It grinds and carries out effectively being sufficiently mixed to obtain the mixture of the two by petroleum coke and pore creating material, then obtained again by calcining porous
Carbon material.Due to using petroleum coke as raw material, and ball-milling technology is utilized to carry out particle refinement, the ball of finally obtained porous carbon materials
Shape degree is very high, as shown in Figure 1, therefore, the specific surface area of the porous carbon materials obtained using the preparation method is also bigger.Benefit
It is carried out with the porous carbon materials of the high porosity and bigger serface with silicon compound, more silicon atoms can be accommodated, improve electricity
The capacity of pole material, while it being also beneficial to buffering silicon materials caused volume change in charge and discharge process, make silicon-carbon composite wood
Material keeps good stability.
In addition, can not only refine petroleum coke particles in mechanical milling process, while pore creating material and petroleum coke can also be increased
Contact area, porous carbon materials of available porosity height and even pore distribution after firing, as shown in Figure 2.From Fig. 2
As can be seen that the porous carbon materials obtained using preparation method provided by the invention, surface is evenly distributed with a large amount of holes.
In addition, preparation method synthetic route provided by the invention is simple, complicated instrument and equipment is not needed, when preparation
Between greatly shorten, production efficiency is higher;Meanwhile raw material petroleum coke used is simple and easy to get, lower production costs.
In certain embodiments of the present invention, the pore creating material is potassium hydroxide, phosphoric acid or zinc chloride, preferably hydrogen-oxygen
The weight ratio of change potassium, the petroleum coke and the pore creating material is 1:(1-5).
When pore creating material is potassium hydroxide, phosphoric acid or when zinc chloride, the porosity of obtained porous carbon is relatively high, especially when
When pore creating material is potassium hydroxide, porosity highest.By optimizing the proportion of petroleum coke and pore creating material, can also further increase most
The porosity of the porous carbon obtained eventually.
Wherein, the weight ratio of petroleum coke and pore creating material be for example can be 1:1,1:2,1:3,1:4 or 1:5.
In certain embodiments of the present invention, first petroleum coke is uniformly mixed with potassium hydroxide solution, is set after drying
The ball milling 1-3h in ball mill, is then calcined again.
Petroleum coke is mixed with potassium hydroxide using the form of potassium hydroxide solution, in addition to can make potassium hydroxide sufficiently and
Outside uniformly contacting with petroleum coke surface, potassium hydroxide can also be made to infiltrate into the inside of petroleum coke material, improve its internal hole
Gap rate.
In certain embodiments of the present invention, the abrading-ball used in ball milling is described for the combination of different-diameter agate ball
The diameter of agate ball is respectively 4-6mm, 0.9-1.2cm and 1.4-1.6cm.It, can using the agate ball of different-diameter as abrading-ball
To improve the smashing fineness of petroleum coke, come into full contact with it with pore creating material.Wherein, when the diameter of agate ball for example can be respectively
When the combination that tri- kinds of 5mm, 1cm and 1.5cm, the grinding effect of obtained petroleum coke and pore creating material is preferable.
In certain embodiments of the present invention, the method for the calcining are as follows: under an inert atmosphere, first with 2-7 DEG C/min
Heating rate be warming up to 350-450 DEG C of calcining 1-3h, be then warming up to 850-950 DEG C again with the heating rate of 2-7 DEG C/min
Calcine 1-3h.
Illustrate the reaction mechanism of above-mentioned method for calcinating using potassium hydroxide as pore creating material below:
(1) when low temperature, i.e., in 350 DEG C or less ranges when, potassium hydroxide itself dehydration and petroleum coke surface functional group
It is reacted, enough activation energy cannot be provided since activation temperature is lower makes potassium hydroxide and weakly acidic methyl and methine
Reaction;
(2) medium temperature radial direction activation stage, i.e., within the scope of 350-450 DEG C when, the methyl of potassium hydroxide and petroleum coke surface,
Methine etc. disappears carbon reaction, i.e., converts the discharge of CO gas for petroleum coke surface carbonaceous material on petroleum coke surface
Carry out pore-creating;
(3) high temperature transverse direction activation stage, i.e., within the scope of 850-950 DEG C when, amorphous carbon and hydroxide in petroleum coke
Potassium priming reaction consumes, so as to form micropore;
Reaction is initial, and based on radial activation pore-creating, a large amount of micropore is formd on the surface of petroleum coke;With activation
The raising of temperature, the increase of activation time, so that the degree of activation significantly improves.Although at this point, also there is diameter in activation process
To activation, still, priming reaction obviously become with laterally activate reaming activation process, a large amount of micropore this stage by
In hole wall destruction and be converted to macropore and mesoporous.
6KOH+2C→2K+3H2+2K2CO3
K2CO3→K2O+CO2
CO2+C→2CO
K2CO3+2C→2K+3CO
C+K2O→2K+CO
In above embodiment, calcine technology is using staged calcine technology and uses a method for calcinating, passes through control
Heating rate and calcination temperature processed carry out the transformation of pore-creating and pattern to petroleum coke.Wherein it is possible to by being passed through argon gas, neon
Or the inert gases such as helium form inert atmosphere.Above-mentioned calcination temperature provides for petroleum coke with reacting for pore creating material potassium hydroxide
Reaction condition, then the flow by controlling the inert gas (such as argon gas) being passed through change environment temperature to the size shape of device to hole
Looks are adjusted, and so that petroleum coke base porous carbon materials is had various sizes of hole with this.This method time-consuming is short, can save big
The resource of amount is more advantageous to the industrialized production of lithium ion battery electrode material to reduce economic cost.
In certain embodiments of the present invention, it is successively carried out with acid solution, alcoholic solution and deionized water after calcining
Cleaning treatment obtains the petroleum coke base porous carbon materials after drying.
By starting the cleaning processing the porous carbon materials that can be effectively removed with acid solution, alcoholic solution and deionized water
The impurity on surface and remaining pore creating material, avoid impurity and pore creating material from having a negative impact the electrical property of subsequent electrode material.
Wherein, acid solution can be dilute nitric acid solution or dilute hydrochloric acid solution, and the concentration of dilute hydrochloric acid solution is 2.5-3.5mol/
L, the concentration of dilute nitric acid solution are 2.5-3.5mol/L.Alcoholic solution can be ethanol solution or propanol solution, preferably ethyl alcohol, choosing
Concentration >=95% of ethanol solution, such as can be 95%, 96%, 97%, 98% or 99%.
Second aspect, the present invention provides a kind of petroleum coke base porous carbon materials, are obtained using above-mentioned preparation method.
The petroleum coke base porous carbon materials have large specific surface area, porosity height and conductivity is good and electrochemistry circulation is steady
Qualitative good advantage.
The third aspect, the present invention provides a kind of silicon-carbon cathode materials, utilize silicon and above-mentioned petroleum coke base porous carbon materials
It is compound to be prepared.
Silicon-carbon cathode material provided by the invention has all advantages of above-mentioned petroleum coke base porous carbon materials, due to above-mentioned
Petroleum coke base porous carbon materials can accommodate more silicon atom, improve the capacity of electrode material, while be also beneficial to buffering silicon
Material caused volume change in charge and discharge process makes Si-C composite material keep good stability.Therefore, the silicon is utilized
The lithium ion battery that carbon negative pole material is prepared has stable charge-discharge performance, and with higher capacity and for the first time
Charge efficiency.
Below in conjunction with embodiment and comparative example, the present invention will be further described in detail.
Wherein, material as used in the following examples, reagent and instrument can be bought by commercial sources.Agents useful for same
It is that analysis is pure.It is Milli-Q high purity water used in experimentation (its resistance is 18.2M Ω).
Embodiment 1
The present embodiment is a kind of preparation method of petroleum coke base porous carbon materials, comprising the following steps:
A) petroleum coke is dried first, dried petroleum coke and potassium hydroxide is blended in one by 1:3 mass ratio
It rises, wherein potassium hydroxide is mixed with petroleum coke as a solution;It is sufficiently dry at 60 DEG C after mixing;
B) agate ball of different-diameter is chosen, wherein the diameter of agate ball is respectively 5mm, 1cm and 1.5cm;
C) mixture and load weighted agate ball of the petroleum coke mixed and potassium hydroxide are put into ball in ball mill
2h is ground, the product after collecting ball milling is loaded into be put into tube furnace and calcine under an argon atmosphere after material is sufficiently dry;
It sets furnace when calcining to rise to 400 DEG C with the heating rate of 5 DEG C/min and keep the temperature 1h, later again with same heating rate
Temperature is increased to 900 DEG C of heat preservation 1h, completes calcination process;
D) sample is taken out after stove cooled to room temperature to be fully ground, sample is successively then used into dust technology again
Solution, ethanol solution and deionized water start the cleaning processing, and adjust the pH value of sample to neutrality, are finally dried to obtain the petroleum
Burnt base porous carbon materials.
Embodiment 2
The present embodiment is a kind of preparation method of petroleum coke base porous carbon materials, difference from example 1 is that, this
Petroleum coke and potassium hydroxide quality ratio are 1:1 in embodiment, other are all the same with embodiment 1.
Embodiment 3
The present embodiment is a kind of preparation method of petroleum coke base porous carbon materials, difference from example 1 is that, this
Petroleum coke and potassium hydroxide quality ratio are 1:2 in embodiment, other are all the same with embodiment 1.
Embodiment 4
The present embodiment is a kind of preparation method of petroleum coke base porous carbon materials, difference from example 1 is that, this
Petroleum coke and potassium hydroxide quality ratio are 1:4 in embodiment, other are all the same with embodiment 1.
Embodiment 5
The present embodiment is a kind of preparation method of petroleum coke base porous carbon materials, difference from example 1 is that, this
Petroleum coke and potassium hydroxide quality ratio are 1:5 in embodiment, other are all the same with embodiment 1.
Embodiment 6
The present embodiment is a kind of preparation method of petroleum coke base porous carbon materials, difference from example 1 is that, this
Heating rate in embodiment in calcination process is 3 DEG C/min, other are all the same with embodiment 1.
Embodiment 7
The present embodiment is a kind of preparation method of petroleum coke base porous carbon materials, difference from example 1 is that, this
Heating rate in embodiment in calcination process is 7 DEG C/min, other are all the same with embodiment 1.
Embodiment 8
The present embodiment is a kind of preparation method of petroleum coke base porous carbon materials, difference from example 1 is that, this
In embodiment in calcination process, furnace rises to 400 DEG C with the heating rate of 5 DEG C/min and keeps the temperature 2h, later again with same
Heating rate increase temperature to 900 DEG C of heat preservation 2h, completion calcination process;Other are all the same with embodiment 1.
Embodiment 9
The present embodiment is a kind of preparation method of petroleum coke base porous carbon materials, difference from example 1 is that, this
In embodiment in calcination process, furnace rises to 450 DEG C with the heating rate of 5 DEG C/min and keeps the temperature 1h, later again with same
Heating rate increase temperature to 850 DEG C of heat preservation 1h, completion calcination process;Other are all the same with embodiment 1.
Embodiment 10
The present embodiment is a kind of preparation method of petroleum coke base porous carbon materials, difference from example 1 is that, this
Pore creating material used in the examples is phosphoric acid, other are all the same with embodiment 1.
Embodiment 11
The present embodiment is a kind of preparation method of petroleum coke base porous carbon materials, difference from example 1 is that, this
Ball-milling Time is 1h in embodiment, other are all the same with embodiment 1.
Comparative example 1
This comparative example is a kind of preparation method of porous carbon materials, uses artificial graphite for carbon source in this comparative example, former material
Expect without ball milling, difference from example 1 is that, in the present embodiment in calcination process, furnace is with 5 DEG C/min's
Heating rate rises to 400 DEG C and keeps the temperature 2h, increases temperature to 900 DEG C of heat preservation 2h with same heating rate again later, completes to forge
Burning process;Other are all the same with embodiment 1.
Comparative example 2
This comparative example is a kind of preparation method of porous carbon materials, uses natural graphite for carbon source in this comparative example.Former material
Expect without ball milling, difference from example 1 is that, in the present embodiment in calcination process, furnace is with 5 DEG C/min's
Heating rate rises to 400 DEG C and keeps the temperature 2h, increases temperature to 900 DEG C of heat preservation 2h with same heating rate again later, completes to forge
Burning process;Other are all the same with embodiment 1.
The porous carbon materials that provide respectively embodiment 1-10 and comparative example 1-2 is provided are tested for the property, test item
Mesh has: porosity and specific surface area.Test result is listed in table 1.
The performance test results of the different porous carbon materials of table 1
Test item |
Porosity |
Specific surface area/m2/g |
Embodiment 1 |
89% |
580 |
Embodiment 2 |
85% |
530 |
Embodiment 3 |
83% |
490 |
Embodiment 4 |
86% |
550 |
Embodiment 5 |
84% |
520 |
Comparative example 1 |
27% |
227 |
Comparative example 2 |
23% |
216 |
It can be seen that from the data in table 1 using preparation method provided by the invention, i.e., be prepared by raw material of petroleum coke
The porous carbon materials arrived, porosity is all 80% or more, and specific surface area is in 490m2/ g or more, and respectively with artificial graphite and
Natural graphite is the porous carbon materials that raw material is prepared, and porosity and specific surface area are lower, and porosity is respectively 27%
With 23%, specific surface area is only respectively 227m2/ g and 216m2/g.Therefore, it can be obtained using preparation method provided by the invention
Porosity and the biggish porous carbon materials of specific surface area.
Porous carbon materials embodiment 1-10 offer and that comparative example 1-2 is provided are provided and prepare silicon-carbon cathode material,
Wherein, the mass ratio of silicon and porous carbon materials is 1:9, and the silicon-carbon cathode material for then each group being recycled to obtain assembles button-shaped lithium
Ion battery it is all the same to assemble other raw materials used in lithium ion battery, wherein positive material in addition to silicon-carbon cathode material is different
Material is ferric phosphate lithium cell, and collector is aluminium foil.The specific capacity and stable circulation of each group lithium ion battery are tested after assembling
Property.
The electric performance test result of 2 each group battery of table
From the data in table 2 can be seen that using porous carbon materials provided by the invention with silicon is compound that silicon-carbon is prepared
Negative electrode material recycles the silicon-carbon cathode material that lithium ion battery is prepared, and specific capacity can reach 350mAh/g or more,
Highest can reach 410mAh/g, and capacity retention ratio can be got at 79% or more up to 87% after circulation 50 times.And utilization pair
The lithium ion battery that the porous carbon materials that ratio 1 and comparative example 2 provide are prepared, specific capacity can be respectively 295mAh/g
And 260mAh/g, capacity retention ratio is respectively 63% and 60% after recycling 50 times.Illustrate to carry out using the porous carbon materials and silicon
Compound obtained silicon carbon material, can accommodate more silicon atoms, improve the capacity of electrode material, while be also beneficial to buffering silicon
Material caused volume change in charge and discharge process makes Si-C composite material keep good stability.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations;To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement;And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.