CN108172775A - A kind of lithium ion battery phosphorous doped silicon carbon negative pole material and preparation method thereof - Google Patents
A kind of lithium ion battery phosphorous doped silicon carbon negative pole material and preparation method thereof Download PDFInfo
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- CN108172775A CN108172775A CN201711184460.4A CN201711184460A CN108172775A CN 108172775 A CN108172775 A CN 108172775A CN 201711184460 A CN201711184460 A CN 201711184460A CN 108172775 A CN108172775 A CN 108172775A
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H01M4/02—Electrodes composed of, or comprising, active material
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Abstract
The invention discloses a kind of lithium ion battery phosphorous doped silicon carbon negative pole material, by being sintered after phosphorus doping nano silicon material and graphite and organic carbon source mist projection granulating.The invention also provides a kind of preparation method of lithium ion battery phosphorous doped silicon carbon negative pole material, including：Spray drying obtains phosphorus doping nano silicon material after nano silicon material is dispersed in phosphoric acid solution；Phosphorus doping nano silicon material is carried out once sintered；It will be uniformly dispersed through once sintered phosphorus doping nano silicon material in water, and add in graphite and organic carbon source, spray drying and double sintering after disperseing completely.Lithium ion battery proposed by the present invention is simple for process with the preparation method of phosphorous doped silicon carbon negative pole material, easy to operate, and raw material is naturally easy to get, at low cost, and subsequent processing mode is convenient, is easy to mass produce, and gained negative material electronic conductivity is high, and volume expansion is small.
Description
Technical field
The present invention relates to lithium ion battery material technical fields more particularly to a kind of lithium ion battery to be born with phosphorus doping silicon-carbon
Pole material and preparation method thereof.
Background technology
In recent years, as lithium ion battery should in the powerful devices such as electric tool, electronic/mixed electrical automobile, energy-accumulating power station
The continuous expansion used, conventional graphite cathode (372mAh/g) have been difficult to meet the needs of mankind are to high energy density cells,
Therefore the heat that can substitute the next-generation lithium ion battery anode material of graphite as current lithium ion battery correlative study is found
One of point.The theoretical specific capacity of silicon materials is 4200mAh/g, resourceful, solvent will not occur with electrolyte and be embedded in phenomenon altogether,
Intercalation potential is higher simultaneously, safer.However the volume that silicon anode material can undergo up to 300% in charge and discharge process becomes
Change, so high volume expansion is shunk, and is easily led to electrode material crushing, is disengaged with collector, electrodes conduct network, simultaneously
Volume change brings the generation on new surface, needs to be formed new solid-electrolyte interface (SEI) so as to cause to the big of electrolyte
Amount consumption, and then lead to being greatly lowered for cycle life.On the other hand, the conductivity of silicon, lithium ion diffusion velocity are below
Graphite, this will limit performance of the silicon under the conditions of high current is high-power.
Academic circles at present mainly optimizes material structure to be promoted by nanosizing, with means such as the mutually compound, pore-creating of inertia
Its chemical property.Such as houd (Chou S, Wang J, Choucair M, et al.Enhanced reversible
lithium storage in a nanosize silicon/graphene composite[J].Electrochemistry
Communications,2010,12(2):Silicon/graphene composite material of knowing clearly 303-306.) is prepared by simple liquid phase method,
Reversible capacity reaches 2158mAh/g for the first time.(Jo Y N, Kim Y, Kim J S, the et al.Si-graphite such as Kim
composites as anode materials for lithium secondary batteries[J].Journal of
Power Sources,2010,195(18):6031-6036.) silicon/graphite/agraphitic carbon is prepared for the method for mechanical ball mill
Material, material conductivity is good, and coulombic efficiency is up to 86.4% for the first time.Liu et al. (Liu N, Lu Z, Zhao J, et al.A
pomegranate-inspired nanoscale design for large-volume-change lithium battery
anodes[J].Nat Nanotechnol,2014,9(3):A kind of pomegranate 187-192.) is prepared using the method for polymer cracking
The nano silicon-based composite material of stone structure.Nano-silicon clustered particles surface coats one layer of resin pyrolytic carbon.This material is in 1A/g electricity
Reversible specific capacity reaches 2350mAh/g for the first time under current density.But these methods are carried using carbon material or conducting polymer
The electron conduction of high silica-base material is not improved the intrinsic electronic conductivity of silicon materials.
Invention content
Technical problems based on background technology, the present invention propose a kind of lithium ion battery phosphorous doped silicon Carbon anode
Material and preparation method thereof, the preparation method is simple for process, easy to operate, and raw material is naturally easy to get, at low cost, subsequent processing mode
It is convenient, it is easy to mass produce, gained negative material electronic conductivity is high, and volume expansion is small.
A kind of lithium ion battery phosphorous doped silicon carbon negative pole material proposed by the present invention, the phosphorous doped silicon carbon negative pole material
By being sintered after phosphorus doping nano silicon material and graphite and organic carbon source mist projection granulating.
Preferably, in phosphorous doped silicon carbon negative pole material, the mass percent of phosphorus doping nano silicon material is 3%-95%,
Surplus is graphite and amorphous pyrolytic carbon.
A kind of preparation method of lithium ion battery phosphorous doped silicon carbon negative pole material that also proposes of the present invention, including with
Lower step：
S1, nano silicon material is dispersed in phosphoric acid solution, then carries out mist projection granulating, obtained after once sintered
Phosphorus doping nano silicon material；
S2, phosphorus doping nano silicon material is uniformly dispersed in water, adds in graphite and organic carbon source, carried out after disperseing completely
Then mist projection granulating carries out double sintering and obtains the lithium ion battery phosphorous doped silicon carbon negative pole material.
Preferably, in S1, a concentration of 0.1mol/L-1mol/L of the phosphoric acid solution.
Preferably, in S1, during once sintered, the temperature of sintering is 500-1000 DEG C, and the time of sintering is 1-
12h。
Preferably, in S1, phosphorus doping amount is 0.1wt%-10wt% in the phosphorus doping nano silicon material.
Preferably, in S2, the organic carbon source is citric acid, sucrose, starch, glucose, carboxymethyl chitosan, carboxylic first
One or more mixture in base sodium cellulosate；The graphite is native graphite, Delanium, spherical graphite, mesocarbon
One or more mixtures in microballoon.
Preferably, in S1 and S2, during mist projection granulating, sponging granulator intake air temperature is 140-170 DEG C,
Air outlet temperature is 100-120 DEG C.
Preferably, in S2, during double sintering, the temperature of sintering is 800 DEG C -1200 DEG C, and the time of sintering is
1h-12h。
Lithium ion battery of the present invention compared with prior art, is had the following advantages with phosphorous doped silicon carbon negative pole material：It is existing
Technology is mainly the electron conduction by improving silica-base material with conductive charcoal, conducting polymer or metal composite, of the invention
From the electronic conductivity of silicon materials in itself, using phosphoric acid as phosphorus source, by phosphorus atoms under the high temperature conditions to silicium cathode material
Gradually diffusion substitutes part silicon atom, forms instead type doping, so as to improve lone pair electrons concentration in nano silicon material, and then
Improve the native electronic conductivity of silicon materials.In addition, with graphite and organic carbon source mist projection granulating, the amorphous pyrolytic carbon of formation will
Phosphorus doping nano silicon material and graphite coat, not only can be into one so as to be an entirety by triplicity into near-spherical structure
Step improves the electron conduction of material, moreover it is possible to buffer the volume expansion of silicon.
The present invention prepares phosphorous doped silicon carbon negative pole material, preparation process letter by the way of high temperature sintering and mist projection granulating
Single, easy to operate, raw material is naturally easy to get, at low cost, and subsequent processing mode is convenient.
Phosphorous doped silicon material prepared by the present invention can be applied not only to negative electrode of lithium ion battery field, can also be applied to
The fields such as fieldtron, solar device, luminescent device and sensor component.
Description of the drawings
Fig. 1 is the SEM figures that phosphorous doped silicon carbon negative pole material prepared by the embodiment of the present invention 1 amplifies 1000 times；
Fig. 2 is the SEM figures that phosphorous doped silicon carbon negative pole material prepared by the embodiment of the present invention 1 amplifies 5000 times；
Fig. 3 is the battery and comparative example negative material that phosphorous doped silicon carbon negative pole material prepared by the embodiment of the present invention 1 makes
The first charge-discharge curve graph of the battery of making；
Fig. 4 is that the battery that phosphorous doped silicon carbon negative pole material prepared by embodiment 1 makes makes with comparative example negative material
The cycle performance figure of battery.
Specific embodiment
In the following, technical scheme of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of lithium ion battery phosphorous doped silicon carbon negative pole material proposed by the present invention, the phosphorous doped silicon carbon negative pole material
By being sintered after phosphorus doping nano silicon material and graphite and organic carbon source mist projection granulating；
Wherein, in phosphorous doped silicon carbon negative pole material, the mass percent of phosphorus doping nano silicon material is 10%, and surplus is
Graphite and amorphous pyrolytic carbon.
The preparation method of a kind of lithium ion battery phosphorous doped silicon carbon negative pole material proposed by the present invention, including following
Step：
S1, the H that 10g nano silica fumes are dispersed in 1mol/L3PO4Spraying is carried out to it in solution, after stirring 0.5h to make
Grain, wherein, the intake air temperature of sponging granulator is 160 DEG C, and air outlet temperature is 110 DEG C, and then material is put into porcelain boat,
Be put into the tube furnace of logical nitrogen carry out it is once sintered, wherein, once sintered temperature is 900 DEG C, and time of sintering is 12h, room
Temperature discharging obtains phosphorus doping nano silicon material；
S2, phosphorus doping nano silicon material is uniformly dispersed in deionized water, adds in 85g spherical graphites and 10g glucose,
And mist projection granulating is carried out after homodisperse 1h, sponging granulator intake air temperature is 160 DEG C, and air outlet temperature is 110 DEG C, will
Material after granulation, which is put into the tube furnace of logical nitrogen, carries out double sintering, wherein, the temperature of double sintering is 1200 DEG C, sintering
Time for 2h, room temperature discharging can obtain phosphorous doped silicon carbon negative pole material.
SEM tests are carried out to phosphorous doped silicon carbon negative pole material manufactured in the present embodiment, as a result as depicted in figs. 1 and 2, by scheming
For 1 and Fig. 2 it is found that the phosphorous doped silicon carbon negative pole material is in spherical pattern, surface coats one layer of amorphous pyrolytic carbon；
By phosphorous doped silicon carbon negative pole material manufactured in the present embodiment according to active material：SP：LA133=8：1：1 weight ratio
Example carries out conjunction slurry, coating, assembles CR2016 button cells, and electrolyte uses the EC+DMC solution of 1mol/L LiPF6, and carries out
Electrochemical property test, test result is as shown in figure 3, from the figure 3, it may be seen that phosphorous doped silicon carbon negative pole material fills for the first time in this implementation
Electric specific capacity is 610.1mAh/g, and head effects are 91.7%.
Under 0.1C current densities, cycle performance survey is carried out to the battery that the embodiment phosphorous doped silicon carbon negative pole material makes
Examination, the results are shown in Figure 4, as shown in Figure 4, after 40 weeks the gram volume of material be 572.3mAh/g, capacity retention ratio 93.8%.
Comparative example
10g nano-silicons are uniformly dispersed in deionized water, add in 85g spherical graphites and 10g glucose, and uniformly divide
After dissipating 1h, mist projection granulating is carried out, sponging granulator intake air temperature is 160 DEG C, and air outlet temperature is 110 DEG C.After granulation
Material is put into the tube furnace of logical nitrogen, and 2h is sintered at 1200 DEG C, and room temperature discharging can obtain contrast sample.
Contrast sample prepared by comparative example is according to active material：SP：LA133=8:1:1 ratio carries out conjunction slurry, coating,
CR2016 button cells are assembled, electrolyte uses the EC+DMC solution of 1mol/L LiPF6, and carries out electrochemical property test, surveys
Test result is as shown in figure 3, from the figure 3, it may be seen that the initial charge specific capacity of undoped silicon carbon negative pole material is in comparative example
597.6mAh/g, head effect only 87.4%.
Under 0.1C current densities, cycle performance survey is carried out to the battery that comparative example undoped silicon carbon negative pole material makes
Examination, the results are shown in Figure 4, as shown in Figure 4, after 40 weeks the gram volume of material be 509mAh/g, capacity retention ratio 85.2%.
It is compared by example 1 and comparative example it can be found that the battery that the phosphorous doped silicon carbon negative pole material in embodiment 1 makes
No matter improve on gram volume for the first time, for the first time coulombic efficiency and following cycle very significantly, this is because phosphorus doping is material
Electronic conductivity is higher, and material polarization smaller, performance is obviously improved during loop test.
Embodiment 2
A kind of lithium ion battery phosphorous doped silicon carbon negative pole material proposed by the present invention, the phosphorous doped silicon carbon negative pole material
By being sintered after phosphorus doping nano silicon material and graphite and organic carbon source mist projection granulating；
Wherein, in phosphorous doped silicon carbon negative pole material, the mass percent of phosphorus doping nano silicon material is 95%, and surplus is
Graphite and amorphous pyrolytic carbon.
The preparation method of a kind of lithium ion battery phosphorous doped silicon carbon negative pole material proposed by the present invention, including following
Step：
S1, the H that 10g nano silica fumes are dispersed in 0.1mol/L3PO4In solution, spray after stirring 0.5h to it
It is granulated, wherein, sponging granulator intake air temperature is 160 DEG C, and air outlet temperature is 110 DEG C, and then material is put into porcelain boat,
Be put into the tube furnace of logical nitrogen carry out it is once sintered, wherein, once sintered temperature be 1000 DEG C, time 1h, room temperature goes out
Material obtains phosphorus doping nano silicon material；
S2, phosphorus doping nano silicon material is uniformly dispersed in deionized water, adds in 0.3g graphite and 0.5g glucose, and
And mist projection granulating is carried out after homodisperse 1h, wherein, sponging granulator intake air temperature is 160 DEG C, air outlet temperature 110
DEG C, the material after granulation is put into the tube furnace of logical nitrogen and carries out double sintering, wherein, the temperature of double sintering is 800 DEG C,
Time is 2h, and room temperature discharging can obtain phosphorous doped silicon carbon negative pole material.
Embodiment 3
A kind of lithium ion battery phosphorous doped silicon carbon negative pole material proposed by the present invention, the phosphorous doped silicon carbon negative pole material
By being sintered after phosphorus doping nano silicon material and graphite and organic carbon source mist projection granulating；
Wherein, in phosphorous doped silicon carbon negative pole material, the mass percent of phosphorus doping nano silicon material is 3%, and surplus is
Graphite and amorphous pyrolytic carbon.
The preparation method of a kind of lithium ion battery phosphorous doped silicon carbon negative pole material proposed by the present invention, including following
Step：
S1, the H that 10g nano silica fumes are dispersed in 1mol/L3PO4Spraying is carried out to it in solution, after stirring 0.5h to make
Grain, wherein, sponging granulator intake air temperature is 160 DEG C, and air outlet temperature is 110 DEG C, and material is put into porcelain boat, is put into logical
It is 500 DEG C that once sintered, once sintered temperature is carried out in the tube furnace of nitrogen, and the time of sintering is 1h, and room temperature discharges to obtain
Phosphorus doping nano silicon material；
S2, phosphorus doping nano silicon material is uniformly dispersed in deionized water, adds in 325g spherical graphites and 10g grapes
Sugar, and after homodisperse 1h, mist projection granulating is carried out, wherein, the intake air temperature of comminutor is 160 DEG C, and air outlet temperature is
110 DEG C, the material after granulation is put into the tube furnace of logical nitrogen and carries out double sintering, wherein, the temperature of double sintering is
1200 DEG C, the time of sintering is 1h, and room temperature discharging can obtain phosphorous doped silicon carbon negative pole material.
Embodiment 4
The preparation method of a kind of lithium ion battery phosphorous doped silicon carbon negative pole material proposed by the present invention, including following
Step：
S1, the H that 10g nano silica fumes are dispersed in 1mol/L3PO4Spraying is carried out to it in solution, after stirring 0.5h to make
Grain, wherein, the intake air temperature of sponging granulator is 160 DEG C, and air outlet temperature is 110 DEG C, and material is put into porcelain boat, is put into
It is 900 DEG C that once sintered, once sintered temperature is carried out in the tube furnace of logical nitrogen, and the time of sintering is 1h, and room temperature discharges
To phosphorus doping nano silicon material；
S2, phosphorus doping nano silicon material is uniformly dispersed in deionized water, adds in 85g spherical graphites and 10g glucose,
And after homodisperse 1h, mist projection granulating is carried out, wherein, the intake air temperature of sponging granulator is 160 DEG C, and air outlet temperature is
110 DEG C, the material after granulation is put into the tube furnace of logical nitrogen and carries out double sintering, the temperature of double sintering is 800 DEG C, is burnt
The time of knot is 12h, and room temperature discharging can obtain phosphorous doped silicon carbon negative pole material.
Embodiment 5
The preparation method of a kind of lithium ion battery phosphorous doped silicon carbon negative pole material proposed by the present invention, including following
Step：
S1, the H that 5g silicon nanoparticles are dispersed in 1mol/L3PO4In solution, spray after stirring 0.5h to it
It is granulated, wherein, the intake air temperature of sponging granulator is 160 DEG C, and air outlet temperature is 110 DEG C, and material is put into porcelain boat, is put
It is 900 DEG C to enter to carry out once sintered, once sintered temperature in the tube furnace of logical nitrogen, and time 1h, room temperature discharges to obtain phosphorus
Dopen Nano silicon materials；
S2, phosphorus doping nano silicon material is uniformly dispersed in deionized water, adds in 90g spherical graphites and 10g glucose,
And after homodisperse 1h, mist projection granulating is carried out, wherein, the intake air temperature of sponging granulator is 160 DEG C, and air outlet temperature is
110 DEG C, the material after granulation being put into the tube furnace of logical nitrogen and carries out double sintering, the temperature of double sintering is 1200 DEG C,
Time is 2h, and room temperature discharging can obtain phosphorous doped silicon carbon negative pole material.
Embodiment 6
The preparation method of a kind of lithium ion battery phosphorous doped silicon carbon negative pole material proposed by the present invention, including following
Step：
S1, the H that 3g silicon nanoparticles are dispersed in 1mol/L3PO4In solution, mist projection granulating is carried out to it after stirring 0.5h,
Wherein, the intake air temperature of sponging granulator is 160 DEG C, and air outlet temperature is 110 DEG C, and then material is put into porcelain boat, is put
It is 900 DEG C to enter to carry out once sintered, once sintered temperature in the tube furnace of logical nitrogen, and the time of sintering is 1h, and room temperature discharges
Obtain phosphorus doping nano silicon material；
S2, phosphorus doping nano silicon material is uniformly dispersed in deionized water, adds in 92g spherical graphites and 10g pitches, and
And after homodisperse 1h, mist projection granulating is carried out, the intake air temperature of sponging granulator is 160 DEG C, and air outlet temperature is 110 DEG C,
Material after granulation is put into the tube furnace of logical nitrogen and carries out double sintering, the temperature of double sintering is 1200 DEG C, and the time is
2h, room temperature discharging can obtain phosphorous doped silicon carbon negative pole material.
Embodiment 7
The preparation method of a kind of lithium ion battery phosphorous doped silicon carbon negative pole material proposed by the present invention, including following
Step：
S1, the H that 10g nano silica fumes are dispersed in 1mol/L3PO4Spraying is carried out to it in solution, after stirring 0.5h to make
Grain, wherein, the intake air temperature of sponging granulator is 160 DEG C, and air outlet temperature is 110 DEG C, and then material is put into porcelain boat,
It is 900 DEG C to be put into the tube furnace of logical nitrogen and carry out once sintered, once sintered temperature, and time 1h, room temperature discharges to obtain
Phosphorus doping nano silicon material；
S2, phosphorus doping nano silicon material is uniformly dispersed in deionized water, adds in 85g spherical graphites and 10g carboxymethyls
Chitosan, and after homodisperse 1h, mist projection granulating is carried out, the intake air temperature of sponging granulator is 160 DEG C, air outlet temperature
It is 110 DEG C, the material after granulation is put into the tube furnace of logical nitrogen and carries out double sintering, the temperature of double sintering is 1200
DEG C, time 2h, room temperature discharging can obtain phosphorous doped silicon carbon negative pole material.
Embodiment 8
A kind of preparation method of lithium ion battery phosphorous doped silicon carbon negative pole material that also proposes of the present invention, including with
Lower step：
S1, nano silicon material is dispersed in phosphoric acid solution, then carries out mist projection granulating, obtained after once sintered
Phosphorus doping nano silicon material；
S2, phosphorus doping nano silicon material is uniformly dispersed in water, adds in graphite and organic carbon source, carried out after disperseing completely
Then mist projection granulating carries out double sintering and obtains the lithium ion battery phosphorous doped silicon carbon negative pole material.
Embodiment 9
A kind of preparation method of lithium ion battery phosphorous doped silicon carbon negative pole material that also proposes of the present invention, including with
Lower step：
S1, nano silicon material is dispersed in phosphoric acid solution, then carries out mist projection granulating, obtained after once sintered
Phosphorus doping nano silicon material；Wherein, a concentration of 1mol/L of the phosphoric acid solution；During once sintered, the temperature of sintering
It it is 500 DEG C, the time of sintering is 12h；Phosphorus doping amount is 0.1wt% in the phosphorus doping nano silicon material；
S2, phosphorus doping nano silicon material is uniformly dispersed in water, adds in graphite and organic carbon source, carried out after disperseing completely
Then mist projection granulating carries out double sintering and obtains the lithium ion battery phosphorous doped silicon carbon negative pole material；Wherein, it is described organic
Carbon source is citric acid；The graphite is Delanium, the mixture of spherical graphite, and the weight ratio of Delanium, spherical graphite
It is 4：3；During double sintering, the temperature of sintering is 800 DEG C, and the time of sintering is 1h；
In S1 and S2, during mist projection granulating, sponging granulator intake air temperature is 170 DEG C, air outlet temperature
It is 100 DEG C.
Embodiment 10
A kind of preparation method of lithium ion battery phosphorous doped silicon carbon negative pole material that also proposes of the present invention, including with
Lower step：
S1, nano silicon material is dispersed in phosphoric acid solution, then carries out mist projection granulating, obtained after once sintered
Phosphorus doping nano silicon material；Wherein, a concentration of 1mol/L of the phosphoric acid solution；During once sintered, the temperature of sintering
It it is 1000 DEG C, the time of sintering is 1h；Phosphorus doping amount is 10wt% in the phosphorus doping nano silicon material；
S2, phosphorus doping nano silicon material is uniformly dispersed in water, adds in graphite and organic carbon source, carried out after disperseing completely
Then mist projection granulating carries out double sintering and obtains the lithium ion battery phosphorous doped silicon carbon negative pole material；Wherein, it is described organic
Carbon source is sucrose, the mixture of starch, and the weight ratio of sucrose, starch is 1：4；The graphite is native graphite；In secondary burning
During knot, the temperature of sintering is 1200 DEG C, and the time of sintering is 12h；
In S1 and S2, during mist projection granulating, sponging granulator intake air temperature is 140 DEG C, air outlet temperature
It is 120 DEG C.
Embodiment 11
A kind of preparation method of lithium ion battery phosphorous doped silicon carbon negative pole material that also proposes of the present invention, including with
Lower step：
S1, nano silicon material is dispersed in phosphoric acid solution, then carries out mist projection granulating, obtained after once sintered
Phosphorus doping nano silicon material；Wherein, a concentration of 0.7mol/L of the phosphoric acid solution；During once sintered, the temperature of sintering
It is 700 DEG C to spend, and the time of sintering is 8h；Phosphorus doping amount is 6wt% in the phosphorus doping nano silicon material；
S2, phosphorus doping nano silicon material is uniformly dispersed in water, adds in graphite and organic carbon source, carried out after disperseing completely
Then mist projection granulating carries out double sintering and obtains the lithium ion battery phosphorous doped silicon carbon negative pole material；Wherein, it is described organic
Carbon source is citric acid, the mixture of sucrose, starch, glucose, carboxymethyl chitosan, sodium carboxymethylcellulose, and citric acid, sugarcane
Sugar, starch, glucose, carboxymethyl chitosan, sodium carboxymethylcellulose weight ratio be 3：2：1：4：5：1；The graphite is day
Right graphite, Delanium, spherical graphite, carbonaceous mesophase spherules mixture, and native graphite, Delanium, spherical graphite, in
Between phase carbosphere weight ratio be 3:4:2:3；During double sintering, the temperature of sintering is 1000 DEG C, and the time of sintering is
8h；
In S1 and S2, during mist projection granulating, sponging granulator intake air temperature is 150 DEG C, air outlet temperature
It is 110 DEG C.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (9)
1. a kind of lithium ion battery phosphorous doped silicon carbon negative pole material, which is characterized in that the phosphorous doped silicon carbon negative pole material by
It is sintered after phosphorus doping nano silicon material and graphite and organic carbon source mist projection granulating.
2. lithium ion battery phosphorous doped silicon carbon negative pole material according to claim 1, which is characterized in that in phosphorus doping silicon-carbon
In negative material, the mass percent of phosphorus doping nano silicon material is 3%-95%, and surplus is graphite and amorphous pyrolytic carbon.
3. a kind of preparation method of lithium ion battery as claimed in claim 1 or 2 phosphorous doped silicon carbon negative pole material, feature exist
In including the following steps：
S1, nano silicon material is dispersed in phosphoric acid solution, then carries out mist projection granulating, phosphorus is obtained after once sintered and is mixed
Miscellaneous nano silicon material；
S2, phosphorus doping nano silicon material is uniformly dispersed in water, adds in graphite and organic carbon source, spray after dispersion completely
It is granulated, then carries out double sintering and obtain the lithium ion battery phosphorous doped silicon carbon negative pole material.
4. the preparation method of lithium ion battery phosphorous doped silicon carbon negative pole material according to claim 3, which is characterized in that
In S1, a concentration of 0.1mol/L-1mol/L of the phosphoric acid solution.
5. according to the preparation method of the lithium ion battery phosphorous doped silicon carbon negative pole material of claim 3 or 4, feature exists
In in S1, during once sintered, the temperature of sintering is 500-1000 DEG C, and the time of sintering is 1-12h.
6. according to the preparation method of any one of claim 3-5 lithium ion battery phosphorous doped silicon carbon negative pole materials,
It is characterized in that, in S1, phosphorus doping amount is 0.1wt%-10wt% in the phosphorus doping nano silicon material.
7. according to the preparation method of any one of claim 3-6 lithium ion battery phosphorous doped silicon carbon negative pole materials,
It is characterized in that, in S2, the organic carbon source is citric acid, sucrose, starch, glucose, carboxymethyl chitosan, carboxymethyl cellulose
One or more mixture in plain sodium；The graphite is native graphite, in Delanium, spherical graphite, carbonaceous mesophase spherules
One or more mixtures.
8. according to the preparation method of any one of claim 3-7 lithium ion battery phosphorous doped silicon carbon negative pole materials,
It is characterized in that, in S1 and S2, during mist projection granulating, sponging granulator intake air temperature is 140-170 DEG C, air outlet
Temperature is 100-120 DEG C.
9. according to the preparation method of any one of claim 3-8 lithium ion battery phosphorous doped silicon carbon negative pole materials,
It is characterized in that, in S2, during double sintering, the temperature of sintering is 800 DEG C -1200 DEG C, and the time of sintering is 1h-12h.
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