CN109841814A - A kind of preparation method of silicon-carbon cathode material - Google Patents
A kind of preparation method of silicon-carbon cathode material Download PDFInfo
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Abstract
The present invention provides a kind of preparation methods of silicon-carbon cathode material comprising following steps: selection reaction mass, and is dried to reaction mass, blending processing；Wherein, silicon precursor material was at drying in oven 24-48 hours；Reaction mass is added in a kettle, in N2Or reacted under the atmosphere of Ar gas, the pressure of reaction kettle is 1-3MPa, and reaction temperature is 150-450 DEG C, and the reaction time is 6-60 hours, obtains reacting thorough silicium cathode material；Obtained silicium cathode material is washed, pickling, filtering, drying, obtains silicon materials；Packet carbon processing is carried out to obtained silicon materials, is then doped with graphite cathode material compound, obtains silicon-carbon cathode material.Using technical solution of the present invention, high-volume large-scale production silicon-carbon cathode material can be fully achieved, the low in cost of silicon materials is produced, last handling process is safe and harmless, and circulation volume is high, and first charge-discharge efficiency is high, has extended cycle life.
Description
Technical field
The invention belongs to battery material technical field more particularly to a kind of preparation methods of silicon-carbon cathode material.
Background technique
As the problem of energy and environment etc., becomes increasingly conspicuous, exploitation high-energy-density, high-specific-power, inexpensive new energy
Material and new type of energy storage device have important strategic importance and economic value.Silicon materials not only have highest theoretical specific capacity
(up to 4200mA h/g, Li5Si22), low removal lithium embedded platform (be lower than 0.5V vs Li/Li+) and persursor material it is resourceful
The advantages that, also there is the fast charging and discharging performance (performance is stablized under such as high speed charge-discharge magnification) better than carbon material, this answers it
It is most important for power battery in electric car.
However, silicon materials have the problem of extremely serious embedding lithium volume expansion in use, embedding lithium volume is swollen
It is swollen up to 370%.During being used for high-performance digital product battery or power battery of electric vehicle, this volume expansion not only can
The rupture and dusting inside silicon particle are caused, the contact with collector is also will cause and reduces, lead to falling off for electrode material.Electrode
Material falls off from collector will cause irreversible battery capacity reduction.Main direction of studying is to reduce the dimension of silicon materials at present
Degree, prepares nano particle, nano wire, the materials such as nanotube, or prepare porous silica material to alleviate embedding lithium volume expansion.
In addition, there are one the distinct disadvantages of poorly conductive for silicon.So the practical application of silicon materials, it is necessary to it is modified processing, and
Carbon negative pole material is cooperated to use.
Summary of the invention
Against the above technical problems, the invention discloses a kind of preparation methods of silicon-carbon cathode material, solve existing magnesium
Thermal method prepares the technical problem that silicon materials can not be mass produced, and feeding intake can be from several hectogram to several hundred kilograms；Silicon is abandoned
Material preparation has to hydrofluoric acid HF using highly corrosive, solves the high pollution in silicon materials production and asking not environmentally
Topic.Carbon coating and the compound problem of graphite are optimally handled, by Cell Performance Evaluation, it was demonstrated that obtained electrode material tool
There are good circulation stability and good high rate performance.
In this regard, the technical solution adopted by the present invention are as follows:
A kind of preparation method of silicon-carbon cathode material comprising following steps:
Step S1 selects reaction mass, including silicon precursor material, reaction reduction agent material and anhydrous chlorate, and to reaction
Material is dried, blending is handled；Wherein, silicon precursor material was at drying in oven 24-48 hours；Further, the baking
Temperature in case is 98 DEG C or more；It is further preferred that the temperature of the baking oven is 100 DEG C.Wherein, anhydrous chlorate is melting
Salt assitant.
Using improved fuse salt restoring method reaction mass is added, in inert gas atmosphere in step S2 in a kettle
Lower reaction, the pressure of reaction kettle are 1-3MPa, and reaction temperature is 150-450 DEG C, and the reaction time is 6-60 hours, obtain reacting thorough
The silicium cathode material at bottom；Here without SiO in the product that reaction thoroughly refers to2.The pressure of reaction kettle is critically important, pressure
Less than 1MPa, reaction not exclusively, is greater than 3Mpa, and the requirement to reaction kettle container is very high, and operation is dangerous, therefore finally by
Experimental selection is 1~3MPa.
Step S3 washes the silicium cathode material that step S2 is obtained, pickling, filtering, drying, obtains silicon materials；Its
In, pickling is using the acid solution in addition to HF, and further, the solution that the pickling uses is HCl solution, HNO3It is molten
Liquid or HCl and HNO3Mixed solution.Step S4 carries out packet carbon processing to obtained silicon materials, obtains the silicon material of carbon coated
Material；If having carried out the processing of packet carbon to the silicon precursor material after drying in step S1, then this step is omitted；Step S5 will be walked
The silicon materials for the carbon coated that rapid S4 is obtained are doped compound with graphite cathode material, obtain silicon-carbon cathode material.
Wherein, nitrogen, argon gas, neon, helium or other inert gases may be selected in inert gas.
It is further preferred that water content of the silicon precursor material after drying in oven is≤10%.
In above-mentioned technical proposal, by the optimization technique of step S1 and step S2, reaction can be carried out thoroughly, that is, do not had
There is unreacted SiO2, can be handled in this way without using HF, this is also a big characteristic of technical solution of the present invention.
In above-mentioned technical proposal, what material dampness was likely to result in obtains the violent moisture absorption when being blended with fuse salt chloride, draws
Smoke event is sent out, so needing to carry out drying and processing, strict control water content to material.If using the silica after packet carbon
As the presoma of reaction, drying and processing is equally also carried out.
As a further improvement of the present invention, in step S1, the silicon precursor material is amorphous silica or stone
Sand.The silicon precursor material can be silica of the partial size scale from several nanometers to several microns, and form can be for without fixed
Shape SiO2, or crystalline state SiO2。
As a further improvement of the present invention, the reaction reduction agent material is Mg powder or/and Al powder.In addition, other are high
Metal powder under the similar mesh number of reproducibility can also be with.It can be the mixing of two or more powder.Further, Ke Yixuan
Cooperation carbon dust is selected, also can choose and mismatch carbon dust.
As a further improvement of the present invention, the partial size for restoring agent material is 80-300 mesh.
As a further improvement of the present invention, the anhydrous chlorate is AlCl3Or AlCl3With the mixture of NaCl.Into
One step, the anhydrous chlorate is AlCl3With the mixture of NaCl.It is further preferred that AlCl3Mass ratio with NaCl is
5:1~100:1.It is further preferred that the AlCl3Mass ratio with NaCl is 20:1~50:1.
As a further improvement of the present invention, in step S1, first by the silicon precursor material of drying and reaction reducing agent material
Material carries out ball milling blending in the ball grinder under inert atmosphere protection, obtains the mixture of silicon precursor and reducing agent；Then will
The mixture of silicon precursor and reducing agent is mixed with anhydrous chlorate, incorporation time 20-60min.Further, wherein ball milling
Revolving speed be 50-250rpm, Ball-milling Time 60-120min, ratio of grinding media to material be 1:5~1:10.
As a further improvement of the present invention, in step S2, the atmosphere is Ar gas；Reaction temperature is 250-450 DEG C.
As a further improvement of the present invention, in step S3, the solution that the pickling uses is deionized water, 0.5~1M
HCl solution and ethyl alcohol mixture.
Further, deionized water, HCl solution, dehydrated alcohol mass ratio be 1:1:1.
As a further improvement of the present invention, in step S4, the packet carbon processing is using spray drying packet carbon or packet in situ
The mass ratio of the method for carbon, carbon coated and silicon is 1:1~10；
As a further improvement of the present invention, the carbon source of the spray drying packet carbon is citric acid, sucrose, glucose, pitch, urine
At least one of element or PVP.
As a further improvement of the present invention, the carbon source of the packet carbon in situ is conducting polymer or phenolic resin.
As a further improvement of the present invention, it in the processing of packet carbon, is sintered under atmosphere of inert gases after coating carbon source.
Further, in the processing of packet carbon, heating rate when sintering is 2-10 DEG C/min, and sintering temperature is 500-800 DEG C, the reaction time
For 2-6h.Further, sintering temperature is 600-800 DEG C, reaction time 3-5h；Wherein, nitrogen, argon may be selected in inert gas
Gas, neon, helium or other inert gases.
As a further improvement of the present invention, in step S5, in doped and compounded, the silicon materials of carbon coated account for silicon-carbon cathode material
The mass percent of material is 2.5-20%.Further, the silicon materials of carbon coated account for the mass percent of silicon-carbon cathode material and are
2.5-15%.
As a further improvement of the present invention, it in step S5, is doped using blended under agitation or ball milling blending compound.Into
One step, blended under agitation is to stir 2-4 hours at normal temperature；Ball milling is blended to be mixed using planetary ball mill, and revolving speed is
100-500rpm, time are 0.5-2 hours.
As a further improvement of the present invention, in step S5, carboxylated processing method is carried out to graphite, takes its surface
Uniform negative electrical charge obtains modified graphite；Amination processing is carried out to the silicon materials of the obtained carbon coated of step S4, makes it
The uniform positive charge of surface band, obtains modified Si-C composite material；Then modified graphite and modified silicon-carbon are answered
Condensation material stirs evenly into the water, then by spray drying, obtains silicon-carbon/graphite material.
As a further improvement of the present invention, in step S4, the carbon source is graphene.Further, step S4 is specific
Encapsulation steps are as follows: the pure silicon powder that step S3 is prepared handles by amination, obtains positively charged silicon particle；Then and
Electronegative graphene is blended in aqueous solution, and after mixing evenly, by freeze-drying, collection obtains surface coated graphite alkene
Silicon materials.
As a further improvement of the present invention, by obtained silicon/graphene composite material and artificial plumbago negative pole material by
According to the ratio mixing of 5:95, obtained silicon-carbon/graphene/graphite cathode material.
As a further improvement of the present invention, by the silicon-carbon cathode material being prepared and high capacity graphite cathode material into
Row doped and compounded again after the silicon-carbon cathode material finally needed, adds conductive carbon black, binder is added, stirs evenly
Afterwards, roller process is carried out after lithium battery coating machine carries out uniform coating, obtains electrode material；The electrode material that will be prepared,
It is cut into the required shape of assembling button cell half-cell or soft-package battery full battery, then assembles lithium battery, evaluation electricity
Pond performance.
The technical scheme is that a kind of preparation method for the porous silicon that can be mass produced, has cooperated simple and environmentally-friendly
Processing method, optimize the graphite cathode material compounding technique of carbon coating technology and high capacity, it is steady to have obtained excellent performance
Fixed cell negative electrode material can satisfy the requirement of high-performance digital product battery and power battery of electric vehicle device.This
Silicon-carbon cathode material, which is mass produced, in patent has important practical usage.
Compared with prior art, the invention has the benefit that
Using technical solution of the present invention, high-volume large-scale production silicon-carbon cathode material can be fully achieved, produces silicon materials
It is low in cost, last handling process is safe and harmless, after the carbon coating of optimization and graphite combined processing, the battery performance of electrode
Circulation volume is high, and first charge-discharge efficiency is high, has extended cycle life.And whole preparation process environmental protection, it is easy to control.
Detailed description of the invention
Fig. 1 is the XRD comparison of the silicium cathode material of the carbon coated of the embodiment of the present invention and the silicium cathode material of uncoated carbon
Figure；It a) for the silicium cathode material of not no carbon coated, b) is wherein the silicium cathode material for carrying out fuse salt reduction reaction after carbon coated again
Material.
The Raman map of the silicium cathode material of 2 carbon coated of Fig. 2 embodiment of the present invention.
Fig. 3 is the SEM pattern of the porous silicon and the not silicon materials of carbon coated after the carbon coated that the embodiment of the present invention 1 obtains
Comparison diagram；It a) is wherein porous silica material after carbon coated for the silicon materials of not no carbon coated, b).
Fig. 4 is the thermogravimetric curve for the silicon materials that the embodiment of the present invention obtains carbon coated.
Fig. 5 is that the embodiment of the present invention obtains battery of the electrode material of rear carbon coated and preceding carbon coated under the conditions of 0.1C and follows
Ring curve graph, wherein be a) the obtained Si of magnesium heat of embodiment 1 using carbon coating, b) magnesium is warm again for the carbon coated of embodiment 2
The Si material arrived, wherein the mass ratio of carbon coating Si material and artificial graphite is 5:95.
Fig. 6 is the XRD diagram for the sample that comparative example 1-4 of the present invention is obtained, i.e., various not according to this patent specific implementation step
In the obtained XRD of the halfway sample of reaction of method.Fig. 6 a) it is the ball milling that comparative example 1 does not carry out step 1, it is simple total
Reaction obtains sample XRD diagram after mixed, and the raw material used is the silica of 8000 mesh；Fig. 6 b) it is that 2 pressure of comparative example does not reach
The preferred pressure that step 2 is previously mentioned, obtained sample XRD diagram, the raw material used are 8000 mesh silica；Fig. 6 c) it is comparison
3 reaction temperature of example is lower than the temperature that step 2 is previously mentioned, and the use of raw material is 8000 mesh silica；Fig. 6 d) it is that comparative example 4 does not have
Carry out the encapsulation step mentioned in step 1, the sample directly obtained under same temperature and pressure reaction condition, the raw material used
For the 100nm silica of carbon coated.
Specific embodiment
Preferably embodiment of the invention is described in further detail below.
A kind of method of large scale preparation silicon-carbon cathode material, comprising the following steps:
Step 1, reaction mass, the pretreatment to reaction mass, the drying including material, preceding packet carbon (optional), blending etc. are selected.
Selected silicon precursor material can be amorphous silica, or quartz sand.React reducing agent selection
Metal powder under the similar mesh number of Mg powder, Al powder or other high reproducibilities is also possible to the mixed of two or more powder
It closes, can choose cooperation carbon dust, also can choose and mismatch carbon dust.Melting salt assitant mainly selects AlCl3, can also add
NaCl and other anhydrous chlorates.Material is needed by drying and processing, and the presoma of silicon can choose the processing of carbon coated in advance.
The silicon precursor of drying and excessive reproducibility magnesium powder, aluminium powder or carbon dust are carried out in the ball grinder under inert atmosphere protection
Ball milling blending, revolving speed 50-250rpm, Ball-milling Time 60-120min are carried out, ratio of grinding media to material is 1:5~1:10.By the forerunner of silicon
It is abundant in order to which reaction can be promoted to carry out later that body and reproducibility powder, which are sufficiently blended,.Then, by mixed reproducibility powder
It is mixed again with fuse salt with silicon precursor material, incorporation time 20-60min, mixing tank pays attention to dry and seals.Most
Afterwards, mixed raw material packing is vacuumized stand-by.
Step 2, it using improved fuse salt restoring method, obtains reacting thorough silicium cathode material.
Reaction puts into material using the high pressure resistant large-size reactor specially designed and produced, controls temperature and reaction time, most
The silicium cathode material thoroughly reacted eventually.Big reaction kettle is continually fed into high-purity N2Or Ar is adjusted after atmosphere displacement thoroughly in kettle
Low gas flow.Reaction temperature is 150-450 DEG C, and the reaction time continues 6-60 hours.
Step 3, the post-processing of product, including washing, pickling, alcohol are washed, dry and collection.Product after reaction needs
It is first washed, then pours into the HCl solution and ethyl alcohol of a certain proportion of deionized water, 0.5~1M again, settled to reaction product
Afterwards, supernatant is poured out, obtains final sample after vacuum drying at room temperature.Sample after drying at grinding pack drying by saving.
Step 4, packet carbon is handled after carrying out to obtained silicon materials, obtains the carbon coated that carbon is evenly coated at silicon materials surface
Silicon materials.Carbon-coated mainly includes two schemes, spray drying packet carbon and packet carbon method in situ.If step S1 is to drying
Silicon precursor material afterwards has carried out preceding packet carbon processing, then this step can delete.
The carbon source of spray drying includes but is not limited to citric acid, sucrose, glucose, pitch, urea, PVP etc..Packet carbon in situ
Method includes but is not limited to conducting polymer, phenolic resin etc..It after carbon coating, is sintered in high pure nitrogen tube furnace, reaction temperature
Degree is 600-800 DEG C, and 2-10 DEG C of heating rate, the reaction time is 3-6 hours.After the completion of carbon coating, the silicon materials of carbon coated are needed
Want the specific surface area of test sample, granularity and silicon-carbon ratio.
Step 5, doped and compounded again, the silicon-carbon cathode material finally needed are carried out with high capacity graphite cathode material
Material.
It is blended with high capacity graphite cathode material, normal agitation can be used and be blended and ball milling blending.Normal agitation is blended
It carries out, stirs 2-4 hours at normal temperature.The revolving speed of planetary ball mill is 100-500rpm, and the time is 0.5-2 hours.Carbon coated
The total electrode material of silicon materials Zhan mass percent be 2.5-20%.
It is further comprising the steps of in the test for carrying out being assembled into battery to obtained silicon-carbon cathode material:
Step 6, film is carried out to electrode material, adds conductive carbon black, binder is added, after mixing evenly, be coated in lithium battery
Machine carries out roller process after carrying out uniform coating.
Step 7, the electrode material that will be prepared is cut into the institute of assembling button cell half-cell or soft-package battery full battery
Then the shape needed assembles lithium battery, evaluate battery performance.
According to the method described above, it is further detailed below by different embodiments.
Embodiment 1
Silicon-carbon cathode material is prepared by raw material of quartz sand, comprising the following steps:
Select 8000 mesh quartz sand 2kg, 300 mesh magnesium powder 3kg, powdered anhydrous aluminum chloride 10kg, first by quartz sand at 100 DEG C
Drying in oven 24-48 hours；Then quartz sand, magnesium powder are uniformly mixed, progress ball milling blending, revolving speed 50-250rpm,
Ball-milling Time is 60-120min, and ratio of grinding media to material is 1:5~1:10；It is eventually adding powdered anhydrous aluminum chloride after mixing, puts
Enter in the high pressure resistant reaction kettle of nitrogen atmosphere, pressure is that 1~3Mpa is down to after reacting 48 hours under the conditions of 280 DEG C to temperature
Room temperature takes out reaction product.
Deionized water, 1M HCl solution and dehydrated alcohol, which are sequentially added, after stirring 30 minutes in reaction product stands 12-
48 hours.Supernatant is outwelled, the sample drying of precipitating, vacuum drying has obtained porous silica material.Obtained silicon materials
XRD curve is Fig. 1 a), it can be seen that the diffraction maximum of apparent silicon respectively corresponds different crystal faces.
Obtained porous silica material is uniformly mixed with glucose by the mass ratio of 1:1 in aqueous solution, is then sprayed
Mist drying-granulating obtains the silicon materials of packet carbon.The inlet temperature of spray drying is 150 DEG C, and charging rate is 200 μ L/min, is obtained
The particle size range of the particle arrived is at 10-20 μm.
Finally, by the graphite cathode MAG-10 of the silicon materials of obtained packet carbon processing and high capacity with 0.5:9.5 mass ratio
After mixing, binder is added, obtains electrode material, is assembled into battery and is tested.Test result are as follows: with the charge and discharge of 0.1C
Electric multiplying power is recycled, and coulombic efficiency is up to 93% for the first time, and Reversible Cycle capacity is 450mAh/g, as shown in Fig. 5 a), wherein
The silicon materials capacity contribution of carbon coated reaches 2160mAh/g.
Embodiment 2
On the basis of embodiment 1, the present embodiment carries out at preceding cladding using to silicon precursor material unlike the first embodiment
Reason does carbon source cladding quartz sand using citric acid and prepares silicon-carbon cathode material as raw material, comprising the following steps:
Using citric acid as carbon source, quartz sand surface is coated in the method for spray drying.Typically, using citric acid 5-20g, two
Raw silicon oxide material 10-20g, PVP 0.1-5g.The inlet temperature of spray drying is 180 DEG C, and wriggling pump speed is 100-500uL/
min.The carbon shell of cladding passes through thermogravimetric analysis, mass percent 5-20%.The silica of obtained carbon coated passes through
The reduction of fuse salt restoring method, obtains the carbon coating silicon materials with yolk-shell, the secondary knot that spray drying granulation obtains
Structure is opposite to keep good.
The XRD diagram of obtained silicon carbon material is as shown in Figure 1 b, shows the crystallographic plane diffraction peak of apparent silicon.It should be noted that
It is to show apparent indefinite form carbon packet at 20-30 °.It can see from the Raman map of Fig. 2, which shows obviously
Silicon Raman vibration peak (about 510cm-1) and carbon the unsetting (peak D 1361cm-1) and graphite-structure Raman vibration peak
(1596cm-1), it was demonstrated that obtained sample is that have carbon-coated silicon materials.The people of the silicon carbon material and high capacity that finally obtain
Make graphite cathode MAG-10 and binder be added after mixing with 0.5:9.5 mass ratio, obtain electrode material, be assembled into battery into
Row test.The result that the battery is tested are as follows: as shown in Figure 5 b, after capacity recycles 100 weeks under the charge-discharge magnification of 0.1C
It can stablize in 2000mAh/g, 100 circle capacity retention ratios are 80%.
Thermal weight loss test is carried out to the carbon coating silicon materials that the present embodiment obtains, as a result as shown in Figure 3, it is seen that obtain carbon-coating
Mass ratio is 13%.
Comparative example 1
Using the silica of 8000 mesh as raw material, with reproducibility magnesium powder without carrying out ball in the ball grinder under inert atmosphere protection
Mill is blended, and only passes through the XRD diagram of the sample of simple blend, as shown in Figure 6 a.It can be seen that spreading out without there is apparent silicon XRD
Peak is penetrated, sample shows many miscellaneous peaks, and 26 ° of position is the thorough silica material of unreacted.
Comparative example 2
After carrying out blending processing according to step 1 method of the present embodiment 1, but in reaction process, does not reach step 2 and be previously mentioned
Preferred pressure range, reaction pressure is only 0.2MPa, the XRD diagram of obtained sample, as shown in Figure 6 b.With the XRD diagram in Fig. 1
It compares, it can be seen that still could not access the sample of the XRD diffraction maximum with obvious Si.
Comparative example 3
On the basis of embodiment 1, pre-processed according to this patent step 1 method, but during the reaction, this comparative example with
Embodiment 1 is not all the preferable temperature for not reaching step 2 and being previously mentioned, and the reactor temperature of fuse salt reduction reaction is low
Silicium cathode material sample is obtained in 150 DEG C, the XRD diagram for obtaining sample is 6c.It can be seen that even if using same silicon source forerunner
Body, the sample for the XRD diffraction maximum with obvious Si that still must arrive.
Comparative example 4
On the basis of embodiment 2, equally use the 100nm silica of carbon coated as raw material, this comparative example and embodiment 2
Be not all not carry out the encapsulation step in step 1, the sample directly obtained under same temperature and pressure reaction condition,
The XRD diagram for obtaining sample is 6d.Discovery is compared with Fig. 1 b, does not obtain the XRD diffraction maximum with apparent silicon, it was demonstrated that is anti-
It should be not thorough.In conclusion as shown in figures 1 to 6, passing through sample obtained in Examples 1 and 2 and XRD pairs of comparative example 1-4
Than as it can be seen that should be carried out in strict accordance with this patent specific implementation step in reaction process.When pretreated mixing and encapsulation process
It omits in the case that perhaps reaction pressure temperature is not achieved and is all difficult to obtain the silicon for reacting thorough silicon materials or carbon coated
Material.
Embodiment 3
On the basis of embodiment 1, the present embodiment is unlike the first embodiment: preparing silicon by raw material of aerosil
Carbon negative pole material, comprising the following steps:
Using partial size for 100nm or so aerosil as fuse salt reduction reaction raw material, with Mg powder, chlorination
Aluminium, sodium chloride ratio be 1:1.2:4:6.It is mixed after fuse salt reduction drying with Mg powder, aluminium chloride, sodium chloride, sample is uniform
It after mixing, is put into the high pressure resistant reaction kettle of nitrogen atmosphere and is reacted, reaction temperature is 280 DEG C, reaction time 12h.It obtains
Nano silicone material is handled, obtained silicon-carbon cathode material using packet carbon.
Finally obtained silicon-carbon cathode material is mixed with the graphite cathode MAG-10 of high capacity with 0.5:9.5 mass ratio
After even, binder is added, obtains electrode material, is assembled into battery and is tested.The result that the battery is tested are as follows: in 0.1C
Under the conditions of charge and discharge, the capacity after 100 circle of circulation is maintained at 2100mAh/g or so.
Embodiment 4
On the basis of embodiment 1, the present embodiment is unlike the first embodiment: using the aerosil of packet carbon as raw material
The silicon-carbon cathode material of preparation is handled using preceding packet carbon, comprising the following steps:
Select the SiO of vapor phase method preparation2Aeroge 30g weighs 10g cetyl trimethylammonium bromide CTAB, and 1000mL is added
In deionized water, uniform mixture is obtained after stirring 1h.Then 1000mL dehydrated alcohol, phenol 30g, ammonium hydroxide are sequentially added
5mL is again stirring for uniform 1h.The formaldehyde of 10mL is added later, in 50 DEG C of water-bath, after heating stirring 12h, it is heavy to stand
Drop, centrifugation washing, after vacuum drying, calcines in nitrogen atmosphere, carbon-coating is evenly coated at SiO2Aeroge surface.With this kind
Raw material of the carbon coating silicon materials as magnesium thermit, the ratio with Al powder, Mg powder, aluminium chloride, sodium chloride is 1:0.5:0.5:
6:4.Sample after evenly mixing, is put into the high pressure resistant reaction kettle of special nitrogen atmosphere and is reacted, and reaction temperature is 320 DEG C,
Reaction time is for 24 hours.Deionized water, 1M HCl and dehydrated alcohol are sequentially added later, and its ratio be 8:1:4.Sample pellet is thorough
Behind bottom, supernatant is outwelled, precipitating vacuum drying has obtained carbon-coated silicon materials, this kind of material equally also has after drying
Yolk-shell structure.
This kind of material is pressed to 15% doping, compound with the graphite cathode material of high capacity, roll-in after slurrying film obtains
The battery performance of the electrode material arrived are as follows: recycled by charge-discharge magnification of 0.1C, cycle efficieny is up to 94% for the first time, can
Inverse circulation volume is 620mAh/g, and the contribution of silicon carbon material is 2093mAh/g.
Embodiment 5
On the basis of embodiment 1, the present embodiment is unlike the first embodiment: the carbon coating silicon of N is mixed using PVP as carbon source preparation
Negative electrode material, that is, cladding is handled after using, comprising the following steps:
Polyvinylpyrrolidone is a kind of macromolecule carbon source containing N, can obtain mixing the carbon of N using PVP as carbon source, molten for coating
Melt the silicon nano material that salt magnesiothermic reduction obtains, can effectively improve the storage lithium battery performance of material.Select spherical 500nm's
SiO2As silicon source, fuse salt reduction reaction is carried out, reduction obtains spherical Si nano particle.Use the mass percentage of PVP
For 5-25%, it is made into aqueous solution with suitable nano Si particle, after mist projection granulating and carbonization treatment, obtains to surface and is coated with
Mix the carbon-coated Si material of N.
The graphite cathode MAG-10 of the carbon-coated Si material for mixing N and high capacity that finally obtain is with 0.5:9.5 mass ratio
After mixing, binder is added, obtains electrode material, is assembled into battery and is tested.Test result are as follows: this kind of silicon carbon material
Under 0.1C charge-discharge magnification, recycling 100 reversible specific capacities can achieve 2400mA h/g or so.
Embodiment 6
On the basis of embodiment 5, the present embodiment as different from Example 5: mix N's by carbon source preparation of urea and glucose
Carbon coating silicium cathode material, that is, cladding is handled after using, comprising the following steps:
Using urea and glucose as carbon source, the carbon material for mixing N can also be prepared, is a kind of low-cost method.Take implementation
The fuse salt reduction reaction of example 1 obtains silicon nano material, and particle size is in 50-500nm 10g.Using urea 10g, glucose
10g is made into 100mL solution, after 30min is mixed with silicon nano material, is dried in vacuo after centrifugation, by high temperature N2Under atmosphere
Annealing carries out packet carbon in situ, obtains the carbon coating Si negative electrode material for mixing N.
The graphite cathode MAG-10 of the carbon-coated Si material for mixing N and high capacity that finally obtain is with 0.5:9.5 mass ratio
Film after mixing, the electrode material of acquisition are assembled into battery and are tested.Test result are as follows: under 0.1C charge and discharge
After circulation 100 times, reversible specific capacity can achieve 2400mA h/g or so.
Embodiment 7
On the basis of embodiment 5, the present embodiment as different from Example 5: using water soluble chitosan as carbon source preparation mix N's
Carbon coating silicium cathode material, that is, cladding is handled after using, comprising the following steps:
The chitosan aqueous solution of 2-20% is configured, fuse salt reduction reaction in embodiment 1 or embodiment 3 is added and obtains silicon powder
In, the quality of chitosan and silicon powder is 1:1~1:10 than range.After stirring 1 hour, centrifuge washing is dry, then by mixture
It is put into porcelain boat to be made annealing treatment, annealing temperature is 700 DEG C, keeps the temperature 3 hours, obtains the doping carbon-coated silicon-carbon cathode material of N.
By the graphite cathode MAG-10 of the obtained carbon-coated silicon-carbon cathode material for mixing N and high capacity with 0.5:9.5 matter
It measures ratio after mixing, binder is added, obtain electrode material, be assembled into battery and tested.Test result are as follows: this kind of silicon-carbon
Material after circulation 100 times under 0.1C, reversible specific capacity can achieve 2500mA h/g or so.
Embodiment 8
By charge adsorption with graphite is compound prepares silicon-carbon/graphite cathode material.
Using electrostatic absorption principle, by synthetic graphite particles' carboxylated processing method, by synthetic graphite particles surface band
Upper uniform negative electrical charge, the graphite after obtaining caping.Use the silicon-carbon composite wood being prepared in embodiment 2 or embodiment 4
Then material is obtained to a certain extent using the fuse salt restoring method of embodiment 1 again that is, to packet carbon processing is first carried out on silica
Si-C composite material with Yolk-shell structure, is then carried out amination processing, makes its uniform positive charge of surface band,
Obtain modified Si-C composite material.Entire silicon-carbon/graphite cathode material quality of materials percentage is accounted for according to Si-C composite material
Than stirring evenly into the water for 2.5-15%, then by being spray-dried again, a kind of silicon-carbon/graphite material is obtained.For
Silicon carbon material is doped to silicon-carbon/graphite material of the ratio of 5wt%, and binder is added and obtains positive electrode, be assembled into battery into
Row test, test result are as follows: after circulation 100 times under 0.1C charge-discharge magnification, be doped to silicon-carbon/stone of the ratio of 5wt%
The reversible specific capacity of black composite material can achieve 480mAh/g or so, and the capacity contribution of corresponding silicon carbon material reaches 2760mAh/g.
Embodiment 9
On the basis of embodiment 8, unlike the present embodiment: by charge adsorption and graphene, the compound preparation of graphite silicon/
Graphene/graphite cathode material.
The pure silicon powder being prepared using the fuse salt reduction reaction of embodiment 1, is handled by amination, is obtained positively charged
Silicon particle, be then blended with electronegative graphene in aqueous solution, after mixing evenly, by freeze-drying, collection obtained
The silicon materials of surface coated graphite alkene.By this silicon/graphene composite material and artificial plumbago negative pole material according to the ratio of 5:95
Example mixing, obtained silicon-carbon/graphene/graphite cathode material.To using silicon-carbon/graphene/graphite cathode material as cathode material
The battery of material is tested, test result are as follows: after circulation 100 times under 0.1C charge-discharge magnification, reversible specific capacity can reach
To 500mA h/g or more.
Data through the foregoing embodiment are as it can be seen that the silicon-carbon cathode material obtained using preparation method of the invention, reaction
Thoroughly, i.e., no unreacted SiO2, so reaction process does not need the hydrofluoric acid HF using highly corrosive, solve silicon materials
High pollution in production and not environmentally the problem of.And obtained silicon-carbon cathode material is after multiple charge and discharge cycles, still
With very high reversible specific capacity, it was demonstrated that obtained electrode material has good circulation stability and good high rate performance.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, exist
Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to of the invention
Protection scope.
Claims (10)
1. a kind of preparation method of silicon-carbon cathode material, it is characterised in that: itself the following steps are included:
Step S1 selects reaction mass, including silicon precursor material, reaction reduction agent material and anhydrous chlorate, and to reaction
Material is dried, blending is handled；Wherein, silicon precursor material was at drying in oven 24-48 hours；
Using improved fuse salt restoring method reaction mass is added, under inert gas atmosphere instead in step S2 in a kettle
It answers, the pressure of reaction kettle is 1-3MPa, and reaction temperature is 150-450 DEG C, and the reaction time is 6-60 hours, obtains silicium cathode material
Material；
Step S3 washes the silicium cathode material that step S2 is obtained, pickling, filtering, drying, obtains silicon materials；Wherein, institute
The solution that pickling uses is stated as HCl solution, HNO3Solution or HCl and HNO3Mixed solution；
Step S4 carries out packet carbon processing to obtained silicon materials, obtains the silicon materials of carbon coated；If in step S1 to drying after
Silicon precursor material has carried out the processing of packet carbon, then this step is omitted；
Step S5, the silicon materials of the obtained carbon coated of step S4 is doped with graphite cathode material compound, and it is negative to obtain silicon-carbon
Pole material.
2. the preparation method of silicon-carbon cathode material according to claim 1, it is characterised in that: in step S1, before the silicon
Driving body material is amorphous silica or quartz sand；The reaction reduction agent material is Mg powder or/and Al powder；Restore agent material
Partial size be 80-300 mesh；The anhydrous chlorate is AlCl3Or AlCl3With the mixture of NaCl.
3. the preparation method of silicon-carbon cathode material according to claim 2, it is characterised in that: the reduction agent material also wraps
Include carbon dust.
4. the preparation method of silicon-carbon cathode material according to claim 2, it is characterised in that: the anhydrous chlorate is
AlCl3With the mixture of NaCl, AlCl3Mass ratio with NaCl is 5:1 ~ 100:1.
5. the preparation method of silicon-carbon cathode material according to claim 4, it is characterised in that: the AlCl3With the matter of NaCl
Amount is than being 20:1 ~ 50:1.
6. the preparation method of silicon-carbon cathode material according to claim 1, it is characterised in that:, first will drying in step S1
Silicon precursor material and reaction reduction agent material ball milling blending is carried out in the ball grinder under inert atmosphere protection, before obtaining silicon
The mixture of body and reducing agent is driven, wherein the revolving speed of ball milling is 50-250 rpm, Ball-milling Time 60-120min, and ratio of grinding media to material is
1:5 ~ 1:10；Then the mixture of silicon precursor and reducing agent is mixed with anhydrous chlorate, incorporation time is 20-60 min.
7. the preparation method of silicon-carbon cathode material according to claim 1, it is characterised in that: in step S2, the atmosphere
For Ar gas；Reaction temperature is 250-450 DEG C.
8. the preparation method of silicon-carbon cathode material according to claim 8, it is characterised in that: in step S3, the pickling
The solution used is deionized water, the mixture of the HCl solution of 0.5 ~ 1M and ethyl alcohol.
9. the preparation method of silicon-carbon cathode material according to claim 8, it is characterised in that: in step S4, the packet carbon
The mass ratio of the method that processing uses spray drying packet carbon or packet carbon in situ, carbon coated and silicon is 1:1 ~ 10；
The carbon source of the spray drying packet carbon is at least one of citric acid, sucrose, glucose, pitch, urea or PVP；Institute
The carbon source for stating packet carbon in situ is conducting polymer or phenolic resin；In the processing of packet carbon, after cladding carbon source under atmosphere of inert gases
It is sintered, heating rate is 2-10 DEG C/min, and sintering temperature is 500-800 DEG C, reaction time 2-6h；
In step S5, in doped and compounded, it is 2.5- that the silicon materials of carbon coated, which account for silicon-carbon/graphite cathode material mass percent,
15%。
10. the preparation method of silicon-carbon cathode material described in any one according to claim 1 ~ 9, it is characterised in that: step S5
In, carboxylated processing method is carried out to graphite, so that its surface is taken uniform negative electrical charge, obtains modified graphite；To step
The silicon materials for the carbon coated that S4 is obtained carry out amination processing, make its uniform positive charge of surface band, and it is multiple to obtain modified silicon-carbon
Condensation material；Then modified graphite and modified Si-C composite material are stirred evenly into the water, then by spraying
It is dry, obtain silicon-carbon/graphite material.
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