CN104425802B - Silicon based composite material, preparation method, using and its lithium ion battery obtained - Google Patents
Silicon based composite material, preparation method, using and its lithium ion battery obtained Download PDFInfo
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- H01M4/00—Electrodes
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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
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/386—Silicon or alloys based on silicon
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses silicon based composite material, preparation method, using and its lithium ion battery obtained.Preparation method is：Base-material and conductive agent are mixed, spray drying obtains near-spherical particle, is sintered 6 10 hours under the conditions of 900 DEG C 1100 DEG C of temperature, you can；Wherein, the base-material includes：Silica flour slurry, graphite and emulsified asphalt；The content of silica flour in the silica flour slurry is 10% 20%, and the content of the graphite is 50% 70%, and the content of the emulsified asphalt is 10% 30%；The content of the conductive agent is 0.5% 3.0%；The percentage is the percentage for the gross mass for accounting for silica flour, graphite and emulsified asphalt.The present invention preparation method is simple for process, cost is relatively low, be suitable for industrialized production, silicon based composite material of the invention is largely near-spherical particle, gram volume and coulombic efficiency is higher for the first time.
Description
Technical field
The present invention relates to silicon based composite material, preparation method, using and its lithium ion battery obtained.
Background technology
Since the theoretical capacity of graphite is only 372mAh/g, and the theoretical capacity of silicon reaches 4200mAh/g, to improve lithium ion
Battery energy density, more and more to the research of siliceous negative material both at home and abroad in recent years, research has focused largely on again exists to silicon
In the research of the volume expansion generated in charge and discharge process.
To solve silicon charge and discharge process expansion issues, the usually used preparation method of silicon based anode material includes：Form silicon
Film, synthesis silicon alloy and silicon-carbon are compound etc..It is to prepare to be pyrolyzed the cladding that organic matter carries out amorphous carbon to silicon compound surface
On the one hand a kind of important method of silico-carbo compound, amorphous carbon can provide charge and discharge process ion channel, on the other hand may be used
It is fallen off with active material in the reunion and cyclic process after inhibiting Si powder to take off lithium.Chinese patent application
Using silicon, Si oxide it is initial feed after ball milling in CN201210303878.3, progress is mixed with graphite, conductive agent and pitch
Spray drying, obtains spherical particle, then carbonize being sintered and obtain silicon-carbon composite cathode material, in this application, is consolidated with conventional
Body asphalt powder is covering, by silicon-containing particles and graphite dispersion, is coated wherein, but since pitch used is solid powder
End is difficult that silicon particle and graphite coat is uniform, secured in carrying out spraying preparation process, it is not easy to obtain the production of near-spherical particle
Product, and because the presence containing part oxygen, oxygen will consume in battery system more in the silica used in the technical solution
Lithium causes the reduction of lithium moved between positive and negative anodes in system, and then the coulombic efficiency for the first time of battery is relatively low, and efficiency is low to be caused to want
More positive electrodes are consumed, battery cost etc. will be substantially increased.
Lithium ion battery negative material surface is modified in the prior art, usually to graphite surface using emulsified asphalt
It is modified, if emulsified asphalt is coated on outside graphite by Chinese patent CN200710181735.9, is formed with carbon after heat treatment
For the graphite material of clad, the material prepared in this way has excellent property as lithium ion battery negative material
Can, but the power-carrying of graphite is only 372mAh/g at present, even if graphite can be improved using modified methods such as emulsified asphalts
Performance, also unobvious, modified reversible gram volume are only capable of improving several milliampere hour effect（mAh）.
Invention content
Technical problem to be solved by the present invention lies in silicon and graphite in the existing silicon based composite material for overcoming the prior art
The problems such as dispersion effect is bad, surface cladding is uneven, first charge discharge efficiency is low, reversible capacity is low, provides a kind of silicon substrate composite wood
Material and preparation method thereof.Preparation method of the invention is simple for process, cost is relatively low, is suitable for industrialized production, silicon of the invention
Based composites are largely near-spherical particle, gram volume and coulombic efficiency is higher for the first time.
It is an object of the present invention to provide a kind of preparation method of silicon based composite material, the preparation method packet
Include following steps：Base-material and conductive agent are mixed, spray drying obtains near-spherical particle, under the conditions of 900 DEG C -1100 DEG C of temperature
Sintering 6-10 hours, you can；Wherein, the base-material includes：Silica flour slurry, graphite and emulsified asphalt；The silica flour slurry
In the content of silica flour be 10%-20%, the content of the graphite is 50%-70%, and the content of the emulsified asphalt is 10%-
30%；The content of the conductive agent is 0.5%-3.0%；The percentage is the gross mass for accounting for silica flour, graphite and emulsified asphalt
Percentage.
In the present invention, the silica flour slurry is the silica flour slurry of this field routine.Preferably, the silica flour slurry is
Silica flour progress wet ball grinding is made.The method and condition of the wet ball grinding is the method and condition of this field routine.Institute
The wet ball grinding stated is preferably that silica flour is milled to D50 grain sizes 100-350nm.The content of silica flour in the silica flour slurry
For 10%-30%, the percentage is the mass percent for accounting for silica flour slurry.
It is using the purpose of silica flour slurry in the present invention：The nano-silicon powder of the 100-350nm usually bought from market
Son is easy to reunite together during preserving, and the present invention directly carries out follow-up batch mixing, spray drying after using wet ball grinding silica flour,
Reduce nano pulp storage time, and slurry exist in liquid form also reduce to a certain extent silica flour particle reunion,
Increase dispersibility.
In the present invention, the grain size after silica flour ball milling is the result obtained by inventor's many experiments.The grain size of silicon is got over
Small, generation volume expansion variation is smaller, is conducive to circulating battery, but the Ball-milling Time needed for it is long, energy consumption is excessively high, is unfavorable for
Industrialized production；The grain size of silicon is excessive, and volume expansion changes greatly, and battery capacity can be caused to decay rapidly, therefore selects ball
The D50 grain sizes for being milled to silica flour, which are 100-350nm, can have both technique industrialization and reduce the purpose of cell expansion degree, realize more
Good technique effect.
In the present invention, the graphite is generally artificial graphite and/or natural graphite.The D of the graphite50Grain size is preferable
It is 3-20 μm, is more preferably 5-10 μm.
In the present invention, the emulsified asphalt refers to that the pitch of fusing is dispersed in the aqueous medium added with emulsifier to form
Emulsion.The oil-water ratio of the emulsified asphalt is preferably 1：2-7：10.Emulsifier in the emulsified asphalt
Quality is the 0.2%-3% of the quality of pitch.Fine grain grain size in the emulsified asphalt is preferably 3-10 μm.The breast
The content for changing the ash content in pitch is preferably 0.01%-0.1%, and the percentage is to account for fine grained gross mass in emulsified asphalt
Percentage.
Emulsifier in the emulsified asphalt is this field conventional emulsifier.Emulsifier in the emulsified asphalt compared with
Good includes cationic surfactant.Emulsifier in the emulsified asphalt more preferably includes cationic surfactant
（Basic emulsifier）And coemulsifier, the coemulsifier are nonionic surfactant.When the emulsified asphalt
In emulsifier include cationic surfactant（Basic emulsifier）When with coemulsifier, the breast in the emulsified asphalt
Agent is compound emulsifying agent.Further more preferably, the emulsifier in the emulsified asphalt is octadecyltrimethylammonium chloride
And nonylphenol polyoxyethylene ether.
Pitch in the emulsified asphalt is the pitch of this field routine.Pitch in the emulsified asphalt is preferable
For asphalt and/or coal tar pitch.The softening point of the pitch is preferably 50-150 DEG C.
The preparation method of the emulsified asphalt is the preparation method of this field routine.The preparation side of the emulsified asphalt
Method is preferably：Emulsifier is uniformly mixed to obtain mixed liquor with water, then the pitch of melting is uniformly mixed with the mixed liquor,
5-10min is stirred with the speed of 1000-3000rpm, you can.
When the emulsifier is octadecyltrimethylammonium chloride and nonylphenol polyoxyethylene ether, emulsification drip
Green preparation method is preferably：By the aqueous solution of the aqueous solution of octadecyltrimethylammonium chloride and nonylphenol polyoxyethylene ether
It is uniformly mixed to obtain mixed liquor, then the pitch of melting is added in above-mentioned mixed liquor, 5- is stirred with the speed of 1000-3000rpm
10min, you can；The quality of the octadecyltrimethylammonium chloride is the 0.1%-2% of asphalt quality, and the nonyl phenol is poly-
The quality of ethylene oxide ether is the 0.1%-1.0% of asphalt quality.
The conductive agent is the conductive agent of this field routine, preferably in carbon black, carbon nanotube and carbon nano-fiber
It is one or more.
In the present invention, the method for the mixing is the method for this field routine.The method of the mixing is preferably point
Step mixing, the substep mix the step of be：Silica flour slurry, graphite and conductive agent are first sufficiently mixed to obtain mixture, then will
Emulsified asphalt pours into the mixture, is uniformly dispersed, you can.The substep is mixed with conducive to emulsified asphalt when shorter
It is interior to be uniformly dispersed in mixed slurry.Preferably, it is described when pouring into, stir the mixture, the speed of the stirring
Degree is 30-100rpm, and the speed of the stirring is conducive to control the demulsification of emulsified asphalt.
In the present invention, the method for the spray drying is the method for this field routine.The spray drying is preferably being sprayed
It is carried out in mist drying machine.The inlet temperature of the spray dryer is preferably 250-380 DEG C, more preferably 300-350 DEG C；Institute
The outlet temperature for stating spray dryer is preferably 100-130 DEG C, more preferably 100-110 DEG C；The spray dryer
It is preferably 5-15Hz to be fed pump frequency；The atomizing disk frequency of the spray dryer is preferably 230-350Hz.
In the present invention, the method for the sintering is the method for this field routine.The outside of nucleocapsid after the sintering
Pitch forms amorphous carbon.Preferably, the sintering carries out in retort.
By common sense in the field, the atmosphere of the sintering is inert atmosphere.The inert gas of the inert atmosphere is this
The gas of field routine not reacted with material, preferably nitrogen and/or argon gas.
The second object of the present invention is, provides silicon substrate composite wood made from the preparation method of above-mentioned silicon based composite material
Material.The grain size of the Si-C composite material is generally 10-25 μm.
The third object of the present invention is, provides above-mentioned silicon based composite material and is preparing lithium ion battery as negative material
In application.
The fourth object of the present invention is, provides a kind of lithium ion battery.The lithium ion battery includes above-mentioned silicon substrate
Composite material.
On the basis of common knowledge of the art, above-mentioned each optimum condition can be combined arbitrarily to get each preferable reality of the present invention
Apply example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that：
1, silicon based composite material of the invention is largely spherical particle, and tap density is high, since covered effect is good, silicon substrate
Silicon and graphite in composite material can be uniformly dispersed；
2, it is covering that silicon based composite material of the invention, which uses emulsified asphalt, is answered with silicon substrate prepared by spray dried form
Condensation material, silicon can be uniformly embedded in graphite material, and graphite is the electric conductivity that good conductor can not only improve silicon, can also be made
Volume expansion of the silicon in charge and discharge process is buffered for buffering matrix；
3, the sintered amorphous carbon of emulsified asphalt in silicon based composite material of the invention can be with as surface modifier
It is firmly coated on above-mentioned silicon, outside graphite mosaics, forms the nucleocapsid of silicon, graphite and amorphous carbon；
4, silicon based composite material of the invention makes that particle is more regular, covered effect is more preferable using liquid phase coating agent, nucleocapsid knot
The external amorphous carbon of structure can preferably ensure that internal silicon is not in direct contact with electrolyte, improve battery first charge discharge efficiency and shape
At preferable SEI films, be conducive to following cycle performance；
5, coulombic efficiency is high for the first time for lithium ion battery made from silicon based composite material of the invention, and up to 88.5%；Hold
Amount plays high, up to 955mAh/g or more；
6, preparation method of the invention is simple, at low cost, is suitble to industry chemical conversion production.
Description of the drawings
Fig. 1 is the scanning electron microscope of silicon based composite material made from embodiment 1（SEM）Figure.
Fig. 2 is the first charge-discharge curve graph of lithium ion battery made from embodiment 2.
Specific implementation mode
It is further illustrated the present invention below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
Product specification selects.
The purchase producer of the raw material used in the following embodiment of the present invention and its model are as follows：
Silica flour：Purchased from hair powder body Materials Co., Ltd of upper marine oil enterprise；
Artificial graphite and natural graphite：Purchased from Shanghai Shanshan Science and Technology Co., Ltd；Wherein graphite is 3H series, natural graphite
For MGS series；
Asphalt and coal tar pitch：Purchased from Sinosteel Corporation；The softening point of the asphalt and coal tar pitch is 50-150
℃。
Embodiment 1
（1）The preparation of silica flour slurry：1Kg silica flours are taken, it is 100nm that wet ball grinding to D50 grain sizes are carried out by medium of water, is obtained
Silica flour slurry；The content of silica flour is 20% in silica flour slurry, and the percentage is the mass percent for accounting for silica flour slurry；
（2）The preparation of emulsified asphalt：By the aqueous solution of octadecyltrimethylammonium chloride and nonylphenol polyoxyethylene ether
Aqueous solution is uniformly mixed to obtain mixed liquor, then the pitch of melting is added in above-mentioned mixed liquor, is stirred with the speed of 2000rpm
10min is made；The quality of the octadecyltrimethylammonium chloride is the 1.5% of asphalt quality, the polyoxyethylene nonyl phenyl second
The quality of alkene ether is the 0.5% of asphalt quality；The oil-water ratio of emulsified asphalt obtained is 6：4, thin in the emulsified asphalt
Grain grain size is 3 μm, and the content of ash content is 0.05%, and percentage is the percentage for accounting for fine grained gross mass in emulsified asphalt, softening point
50℃；
（3）By step（1）In silica flour slurry obtained, 6Kg D50The artificial graphite and 250g conductive blacks that grain size is 3 μm
It is sufficiently mixed uniformly, then by step（2）In emulsified asphalt 3.0Kg obtained slowly pour into wherein, while with 50rpm speed stir
Slurry is uniform to slurry；
（4）Spray drying, the inlet temperature for controlling spray dryer are 300 DEG C, and outlet temperature is 115 DEG C, supply disk frequency
Rate is 10Hz, and atomizing disk frequency is 250Hz, obtains near-spherical particle；
（5）By step（4）Described in near-spherical particle, in retort, under inert atmosphere（Nitrogen）, with 1000 DEG C
Temperature is sintered 9 hours, natural cooling, you can.
The scanning electron microscope of silicon based composite material obtained（SEM）Figure is as shown in Figure 1.
Embodiment 2
（1）By the water-soluble of silicon based composite material made from the method for 91 parts of embodiments 1 and 200 parts of CMC/Super-P/SBR
Liquid is uniformly mixed, and obtains slurry；Containing 9 parts of CMC/Super-P/SBR in the aqueous solution of CMC/Super-P/SBR, and CMC：
Super-P：The mass ratio of SBR is 4.5：2.0：2.5；
（2）By step（1）Described in slurry to be coated on thickness be, through drying, roll-forming, to obtain copper on 15 μm of copper foil
Foil electrode；It is that lithium rechargeable battery is formed with copper foil electrode to electrode with lithium foil；
Electrolyte used is the solution containing solvent and electrolyte, includes specifically following component：1. solvent：Ethylene carbon
Acid esters（EC）/ dimethyl carbonate（DMC）/ methyl ethyl carbonate（EMC）（The volume ratio of three is 1 in solvent：1：1）, 2. electrolyte：
1mol/L lithium hexafluoro phosphates（LiPF6）；Using polypropylene, polyethylene/polypropylene（PP/PE/PP）Three layers of micro-pore septum, thickness are
20μm。
Test charging and discharging currents density is 0.6mA/cm2, cut-off charging/discharging voltage is 0.005-2.000V.
Initial capacity and the coulombic efficiency for measuring the lithium ion battery are as shown in table 1.The head of lithium ion battery obtained
Secondary charging and discharging curve figure is as shown in Figure 2.
Embodiment 3
（1）The preparation of silica flour slurry：2Kg silica flours are taken, it is 200nm that wet ball grinding to D50 grain sizes are carried out by medium of water, is obtained
Silica flour slurry；The content of silica flour is 10% in silica flour slurry, and the percentage is the mass percent for accounting for silica flour slurry；
（2）The preparation of emulsified asphalt：By the aqueous solution of octadecyltrimethylammonium chloride and nonylphenol polyoxyethylene ether
Aqueous solution is uniformly mixed to obtain mixed liquor, then the asphalt of melting is added in above-mentioned mixed liquor, is stirred with the speed of 1500rpm
5min is made；The quality of the octadecyltrimethylammonium chloride is the 2% of asphalt quality, the Nonyl pheno
The quality of ether is the 0.1% of asphalt quality；The oil-water ratio of emulsified asphalt obtained is 1：1, the fine grained in the emulsified asphalt
Grain size is 5 μm, and the content of ash content is 0.01%, and percentage is the percentage for accounting for fine grained gross mass in emulsified asphalt, softening point 70
℃；
（3）By step（1）In silica flour slurry obtained, 7Kg D50The artificial graphite and 50g carbon nanotubes that grain size is 5 μm
It is sufficiently mixed uniformly, then by step（2）In cut oil pitch 1.0Kg obtained slowly pour into wherein, while with 30rpm speed
It is uniform to slurry to stir slurry；
（4）Spray drying, the inlet temperature for controlling spray dryer are 250 DEG C, and outlet temperature is 100 DEG C, supply disk frequency
Rate is 5Hz, and atomizing disk frequency is 230Hz, obtains near-spherical particle；
（5）By step（4）Described in near-spherical particle, in retort, under inert atmosphere（Nitrogen）, with 900 DEG C
Temperature is sintered 10 hours, natural cooling, you can.
According to 2 identical method assembled battery of embodiment and tested, the initial capacity of the lithium ion battery measured and
Coulombic efficiency is as shown in table 1.
Embodiment 4
（1）The preparation of silica flour slurry：1.5Kg silica flours are taken, it is 250nm that wet ball grinding to D50 grain sizes are carried out by medium of water,
Obtain silica flour slurry；The content of silica flour is 30% in silica flour slurry, and the percentage is the mass percent for accounting for silica flour slurry；
（2）The preparation of emulsified asphalt：By the aqueous solution of octadecyltrimethylammonium chloride and nonylphenol polyoxyethylene ether
Aqueous solution is uniformly mixed to obtain mixed liquor, then the coal tar pitch of melting is added in above-mentioned mixed liquor, is stirred with the speed of 3000rpm
8min is made；The quality of the octadecyltrimethylammonium chloride is the 0.1% of asphalt quality, the polyoxyethylene nonyl phenyl second
The quality of alkene ether is the 1% of asphalt quality.The oil-water ratio of the emulsified asphalt is 7：3, the fine grained grain in the emulsified asphalt
Diameter is 6 μm, and the content of ash content is 0.1%, and percentage is the percentage for accounting for fine grained gross mass in emulsified asphalt, softening point 90
℃；
（3）By step（1）In silica flour slurry obtained, 6.5Kg D50The artificial graphite and 300g that grain size is 10 μm are conductive
Carbon black is sufficiently mixed uniformly, then by step（2）In emulsification coal tar pitch 2.0Kg obtained slowly pour into wherein, while with 70rpm speed
Degree stirring slurry is uniform to slurry；
（4）Spray drying, the inlet temperature for controlling spray dryer are 350 DEG C, and outlet temperature is 120 DEG C, supply disk frequency
Rate is 7Hz, and atomizing disk frequency is 300Hz, obtains near-spherical particle；
（5）By step（4）Described in near-spherical particle, in retort, under inert atmosphere（Nitrogen）, with 1100 DEG C
Temperature is sintered 6 hours, natural cooling, you can.
According to 2 identical method assembled battery of embodiment and tested, the initial capacity of the lithium ion battery measured and
Coulombic efficiency is as shown in table 1.
Embodiment 5
（1）The preparation of silica flour slurry：2Kg silica flours are taken, it is 300nm that wet ball grinding to D50 grain sizes are carried out by medium of water, is obtained
Silica flour slurry；The content of silica flour is 15% in silica flour slurry, and the percentage is the mass percent for accounting for silica flour slurry；
（2）By step（1）In silica flour slurry obtained, 5.5Kg D50The natural graphite and 150g that grain size is 20 μm are conductive
Carbon black is sufficiently mixed uniformly, then the emulsification coal tar pitch 2.5Kg of 120 DEG C of softening point well prepared in advance is slowly poured into wherein, together
When with 90rpm speed stirring slurry it is uniform to slurry；
（3）Spray drying, the inlet temperature for controlling spray dryer are 320 DEG C, and outlet temperature is 130 DEG C, supply disk frequency
Rate is 12Hz, and atomizing disk frequency is 350Hz, obtains near-spherical particle；
（4）By step（3）Described in near-spherical particle, in retort, under inert atmosphere（Nitrogen）, with 950 DEG C
Temperature is sintered 7 hours, natural cooling, you can.
According to 2 identical method assembled battery of embodiment and tested, the initial capacity of the lithium ion battery measured and
Coulombic efficiency is as shown in table 1.
Embodiment 6
（1）The preparation of silica flour slurry：2.0Kg silica flours are taken, it is 350nm that wet ball grinding to D50 grain sizes are carried out by medium of water,
Obtain silica flour slurry；The content of silica flour is 25% in silica flour slurry, and the percentage is the mass percent for accounting for silica flour slurry；
（2）By step（1）In silica flour slurry obtained, 5.0Kg D50Grain size is 15 μm of natural graphite and 100g nanometers
Carbon fiber is sufficiently mixed uniformly, then the cut oil pitch 3.0Kg of 150 DEG C of softening point well prepared in advance is slowly poured into it
In, while it is uniform to slurry with 100rpm speed stirring slurry；
（3）Spray drying, the inlet temperature for controlling spray dryer are 280 DEG C, and outlet temperature is 110 DEG C, supply disk frequency
Rate is 9Hz, and atomizing disk frequency is 270Hz, obtains near-spherical particle；
（4）By step（3）Described in near-spherical particle, in retort, under inert atmosphere（Nitrogen）, with 1050 DEG C
Temperature is sintered 8 hours, natural cooling, you can.
According to 2 identical method assembled battery of embodiment and tested, the initial capacity of the lithium ion battery measured and
Coulombic efficiency is as shown in table 1.
Embodiment 7
（1）The preparation of silica flour slurry：1.7Kg silica flours are taken, it is 350nm that wet ball grinding to D50 grain sizes are carried out by medium of water,
Obtain silica flour slurry；The content of silica flour is 20% in silica flour slurry, and the percentage is the mass percent for accounting for silica flour slurry；
（2）By step（1）In silica flour slurry obtained, 6.8Kg D50The natural graphite and 200g that grain size is 15 μm are conductive
Carbon black is sufficiently mixed uniformly, then the cut oil pitch 1.5Kg of 60 DEG C of softening point well prepared in advance is slowly poured into wherein, together
When with 40rpm speed stirring slurry it is uniform to slurry；
（3）Spray drying, the inlet temperature for controlling spray dryer are 280 DEG C, and outlet temperature is 105 DEG C, supply disk frequency
Rate is 9Hz, and atomizing disk frequency is 270Hz, obtains near-spherical particle；
（4）By step（3）Described in near-spherical particle, in retort, under inert atmosphere（Argon gas）, with 1050 DEG C
Temperature is sintered 8 hours, natural cooling, you can.
According to 2 identical method assembled battery of embodiment and tested, the initial capacity of the lithium ion battery measured and
Coulombic efficiency is as shown in table 1.
Comparative example 1
Use solid powder pitch for covering, remaining is the same as embodiment 1；Specifically, preparation method includes following step
Suddenly：
（1）The preparation of silica flour slurry：1Kg silica flours are taken, wet ball grinding is carried out to D by medium of water50Grain size is 100nm, is obtained
Silica flour slurry；The content of silica flour is 20% in silica flour slurry, and the percentage is the mass percent for accounting for silica flour slurry；
（2）By step（1）In silica flour slurry obtained, 6Kg D50Artificial graphite that grain size is 3 μm, 50 DEG C of softening point
Solid coal tar pitch powder 3.0Kg and 250g conductive black is sufficiently mixed uniformly；
（3）Spray drying, the inlet temperature for controlling spray dryer are 300 DEG C, and outlet temperature is 110 DEG C, supply disk frequency
Rate is 10Hz, and atomizing disk frequency is 250Hz, obtains random powder；
（4）By step（3）Described in random powder in retort, under inert atmosphere（Nitrogen）, burnt with 1000 DEG C
Knot 9 hours, natural cooling, you can.
It according to 2 identical method assembled battery of embodiment and is tested, the results are shown in Table 2.
Comparative example 2
Use solid powder pitch for covering, remaining is the same as embodiment 4；Specifically, preparation method includes following step
Suddenly：
（1）The preparation of silica flour slurry：1.5Kg silica flours are taken, wet ball grinding is carried out to D by medium of water50Grain size is 350nm,
Obtain silica flour slurry；The content of silica flour is 30% in silica flour slurry, and the percentage is the mass percent for accounting for silica flour slurry；
（2）By step（1）In silica flour slurry obtained, 6.5Kg D50The artificial graphite and 300g that grain size is 10 μm are conductive
Carbon black is sufficiently mixed uniformly, then the solid coal tar pitch powder 2.0Kg of 90 DEG C of softening point well prepared in advance is slowly poured into wherein,
It is uniform to slurry with 70rpm speed stirring slurry simultaneously；
（3）Spray drying, the inlet temperature for controlling spray dryer are 350 DEG C, and outlet temperature is 120 DEG C, supply disk frequency
Rate is 7Hz, and atomizing disk frequency is 300Hz, must obtain random powder；
（4）By step（3）Described in random powder in retort, it is 6 small with 1100 DEG C of sintering under inert atmosphere
When, natural cooling, you can.
It according to 2 identical method assembled battery of embodiment and is tested, the results are shown in Table 2.
Comparative example 3
Spray drying is replaced using cladding kettle cladding, remaining is the same as embodiment 3；Specifically, preparation method includes following
Step：
（1）The preparation of silica flour slurry：2Kg silica flours are taken, wet ball grinding is carried out to D by medium of water50Grain size is 200nm, is obtained
Silica flour slurry；The content of silica flour is 10% in silica flour slurry, and the percentage is the mass percent for accounting for silica flour slurry；
（2）The preparation of emulsified asphalt：By the aqueous solution of octadecyltrimethylammonium chloride and nonylphenol polyoxyethylene ether
Aqueous solution is uniformly mixed to obtain mixed liquor, then the asphalt of melting is added in above-mentioned mixed liquor, is stirred with the speed of 1500rpm
5min is made；The quality of the octadecyltrimethylammonium chloride is the 2% of asphalt quality, the Nonyl pheno
The quality of ether is the 0.1% of asphalt quality；The oil-water ratio of emulsified asphalt obtained is 1：1, the fine grained in the emulsified asphalt
Grain size is 5 μm, ash content 0.01%, 70 DEG C of softening point；
（3）By step（1）In silica flour slurry obtained, 7Kg D50Grain size be 5 μm artificial graphite, 50g carbon nanotubes and
1.0Kg is by step（2）In cut oil pitch 1.0Kg obtained cladding kettle in be sufficiently mixed uniformly；
（4）In cladding kettle, 150 DEG C are warming up under inert gas shielding while stirring and keeps the temperature 3 hours, is then continued
It is warming up to 500 DEG C and keeps the temperature 5 hours, be cooled to room temperature, obtain random powder；
（5）By step（4）Described in powder in retort, under inert atmosphere（Nitrogen）, it is sintered with 900 DEG C of temperature
10 hours, natural cooling, you can.
It according to 2 identical method assembled battery of embodiment and is tested, the results are shown in Table 3.
Effect example 1
By embodiment 1,3-7 silicon based composite material made from lithium ion battery initial discharge capacity and coulombic efficiency such as
Shown in table 1.
1 embodiment 1 of table, 3-7 silicon based composite material made from lithium ion battery initial discharge capacity and coulomb effect
Rate
As seen from the above table：Preparation method preparation silicon substrate composite negative pole material performance obtained of the present invention is good, uses the silicon substrate
Capacity is big for the first time for lithium rechargeable battery made from composite negative pole material, and initial discharge capacity peak capacity reaches 955mAh/g, library
Logical sequence efficiency is up to 88.5%.
According to this field routine, since the theoretical capacity of silicon is very high, maximum, different silicone content is acted on played in material
The Index Influences such as the capacity to material are very big.Therefore, in following effect example, battery obtained after being changed with unitary variant
Initial discharge capacity and coulombic efficiency, with the positive effect further illustrated the present invention.
Effect example 2
Influence of the emulsified asphalt to silicon based composite material.By embodiment 2 and comparative example 1 and embodiment 4 and comparative example 2
It makes comparisons, to further illustrate initial discharge capacity and coulombic efficiency of the emulsified asphalt for battery made from silicon based composite material
Influence.The results are shown in Table 2 for it：
The initial discharge capacity and coulombic efficiency of 2 battery of table
The covering used in comparative example 1 is solid powder pitch, remaining raw material and preparation process and condition are the same as implementation
Example 2（That is the preparation method of silicon based composite material is other than covering is solid powder pitch, remaining is with embodiment 1, and battery
Assemble method with embodiment 2）；The covering used in comparative example 2 is solid powder pitch, remaining raw material and preparation process and
Condition is the same as embodiment 4.As shown in Table 2：Under conditions of other parameters all same, obtained using general solid powder pitch
Negative material, the initial discharge capacity and coulombic efficiency of battery obtained are significantly lower than the silicon substrate prepared using emulsified asphalt
Composite material.
Effect example 3
It is spray-dried the influence for silicon based composite material.Embodiment 3 is made comparisons with comparative example 3, to further illustrate
It is spray-dried the influence of the initial discharge capacity and coulombic efficiency for battery made from silicon based composite material.Its result such as table 3
It is shown：
The initial discharge capacity and coulombic efficiency of 3 battery of table
| Battery performance | Embodiment 3 | Comparative example 3 |
| Initial discharge capacity（mAh/g） | 955 | 835 |
| Coulombic efficiency（%） | 85.4 | 84.4 |
Replace spray drying, remaining raw material and preparation process and condition equal by the way of cladding kettle cladding in comparative example 3
With embodiment 3.As shown in Table 3：The initial discharge capacity of battery made from the silicon based composite material of comparative example 3 is only 835mAh/
G, coulombic efficiency is 84.4% for the first time, the initial discharge capacity of battery made from the silicon based composite material of corresponding embodiment 3
Up to 955mAh/g, the two capacity differ 100mAh/g or more.While battery made from the silicon based composite material in embodiment 3
Coulombic efficiency is also above comparative example 3 for the first time.Under conditions of other parameters all same, obtained using general spray dried form
Negative material, the initial discharge capacity and coulombic efficiency of battery obtained are apparently higher than to be made using general cladding kettle cladding
Standby silicon based composite material.
It should be understood that after the above for having read the present invention, those skilled in the art can make the present invention various
Change or modification, these equivalent forms also fall within the scope of the appended claims of the present application.
Claims (16)
1. a kind of preparation method of silicon based composite material, it is characterised in that：The preparation method includes the following steps：By base-material
It is mixed with conductive agent, spray drying obtains near-spherical particle, is sintered 6-10 hours under the conditions of 900 DEG C -1100 DEG C of temperature, you can；
Wherein, the base-material includes：Silica flour slurry, graphite and emulsified asphalt；The silica flour slurry is that silica flour is carried out wet method ball
It grinds；The content of silica flour in the silica flour slurry is 10%-20%, and the content of the graphite is 50%-70%, institute
The content for the emulsified asphalt stated is 10%-30%；The content of the conductive agent is 0.5%-3.0%；The percentage is to account for
The percentage of the gross mass of silica flour, graphite and emulsified asphalt；
Wherein, the method for the mixing is that the step of substep mixes, and the substep mixes is：First by silica flour slurry, graphite
It is sufficiently mixed to obtain mixture with conductive agent, then emulsified asphalt is poured into the mixture, is uniformly dispersed, you can；Described
When pouring into, the mixture is stirred, the speed of the stirring is 30-100rpm.
2. preparation method as described in claim 1, it is characterised in that：The wet ball grinding is D of the wet ball grinding to silica flour50
Grain size 100-350nm；The content of silica flour in the silica flour slurry is 10%-30%, and the percentage is to account for silica flour slurry
Mass percent；
The graphite is artificial graphite and/or natural graphite.
3. preparation method as claimed in claim 2, it is characterised in that：The D of the graphite50Grain size is 3-20 μm.
4. preparation method as claimed in claim 3, it is characterised in that：The D of the graphite50Grain size is 5-10 μm.
5. preparation method as described in claim 1, it is characterised in that：The oil-water ratio of the emulsified asphalt is 1：2-7：
10；The quality of emulsifier in the emulsified asphalt is the 0.2%-3% of the quality of pitch；Thin in the emulsified asphalt
The grain size of grain is 3-10 μm；The content of ash content in the emulsified asphalt is 0.01%-0.1%, and the percentage is to account for breast
Change the percentage of fine grained gross mass in pitch；
Emulsifier in the emulsified asphalt includes cationic surfactant
Pitch in the emulsified asphalt is asphalt and/or coal tar pitch, and the softening point of the pitch is 50-150 DEG C；
The preparation method of the emulsified asphalt is：Emulsifier is uniformly mixed to obtain mixed liquor with water, then by the pitch of melting with
The mixed liquor is uniformly mixed, and 5-10min is stirred with the speed of 1000-3000rpm, you can.
6. preparation method as claimed in claim 5, it is characterised in that：Emulsifier in the emulsified asphalt includes cation
Surfactant and coemulsifier, the coemulsifier are nonionic surfactant.
7. preparation method as claimed in claim 6, it is characterised in that：Emulsifier in the emulsified asphalt is octadecyl
Trimethyl ammonium chloride and nonylphenol polyoxyethylene ether.
8. preparation method as claimed in claim 7, it is characterised in that：The preparation method of the emulsified asphalt is：By 18
The aqueous solution of alkyl trimethyl ammonium chloride and the aqueous solution of nonylphenol polyoxyethylene ether are uniformly mixed to obtain mixed liquor, then by melting
Pitch is added in above-mentioned mixed liquor, and 5-10min is stirred with the speed of 1000-3000rpm, you can；The octadecyl front three
The quality of ammonium chloride is the 0.1%-2% of asphalt quality, and the quality of the nonylphenol polyoxyethylene ether is asphalt quality
0.1%-1.0%.
9. preparation method as described in claim 1, it is characterised in that：The conductive agent is carbon black, carbon nanotube and nano-sized carbon
It is one or more in fiber.
10. preparation method as described in claim 1, it is characterised in that：The spray drying carries out in spray dryer；Institute
The inlet temperature for stating spray dryer is 250-380 DEG C；The outlet temperature of the spray dryer is 100-130 DEG C；Described
The feed pump frequency of spray dryer is 5-15Hz；The atomizing disk frequency of the spray dryer is 230-350Hz；
The sintering carries out in retort；The atmosphere of the sintering is inert atmosphere, the inertia of the inert atmosphere
Gas is nitrogen and/or argon gas.
11. preparation method as claimed in claim 10, it is characterised in that：The inlet temperature of the spray dryer is 300-
350℃。
12. preparation method as claimed in claim 10, it is characterised in that：The outlet temperature of the spray dryer is 100-
110℃。
13. silicon based composite material made from the preparation method as described in any one of claim 1-12.
14. silicon based composite material as claimed in claim 13, it is characterised in that：The grain size of the silicon based composite material is
10-25μm。
15. silicon based composite material according to claim 13 or 14 answering in preparing lithium ion battery as negative material
With.
16. a kind of lithium ion battery, it is characterised in that：The lithium ion battery includes silicon according to claim 13 or 14
Based composites.
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| CN108428879A (en) * | 2018-03-30 | 2018-08-21 | 河北民族师范学院 | A kind of preparation method and application of New Type of Carbon silicon based composite material |
| CN109461921B (en) * | 2018-11-09 | 2021-01-05 | 广东省稀有金属研究所 | Preparation method of modified silicon-based alloy composite negative electrode material of lithium ion battery |
| CN112186140B (en) * | 2019-07-04 | 2022-01-28 | 江苏天奈科技股份有限公司 | Silicon-based active composite conductive slurry applied to silicon-carbon cathode and cathode slurry mixing method |
| CN112635741A (en) * | 2020-12-29 | 2021-04-09 | 虎皇新材料科技集团有限公司 | Emulsified asphalt coated silicon-carbon negative electrode material and preparation method thereof |
| CN113380992A (en) * | 2021-04-07 | 2021-09-10 | 万向一二三股份公司 | Silicon monoxide/graphite composite material and preparation method and application thereof |
| CN113644252B (en) * | 2021-08-04 | 2024-06-14 | 西北工业大学 | Silicon-carbon negative electrode material and preparation method thereof |
| CN114142011B (en) * | 2021-11-29 | 2023-06-16 | 蜂巢能源科技有限公司 | Hard carbon composite material and preparation method and application thereof |
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| CN102891297A (en) * | 2012-11-10 | 2013-01-23 | 江西正拓新能源科技有限公司 | Silicon-carbon composite material for lithium ion battery and preparation method thereof |
| CN103208615A (en) * | 2012-10-25 | 2013-07-17 | 郴州杉杉新材料有限公司 | Silicon-carbon composite material, and preparation method and application thereof |
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| CN103208615A (en) * | 2012-10-25 | 2013-07-17 | 郴州杉杉新材料有限公司 | Silicon-carbon composite material, and preparation method and application thereof |
| CN102891297A (en) * | 2012-11-10 | 2013-01-23 | 江西正拓新能源科技有限公司 | Silicon-carbon composite material for lithium ion battery and preparation method thereof |
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