CN105070894B - A kind of lithium ion battery porous silicon-base composite negative pole material, Preparation method and use - Google Patents
A kind of lithium ion battery porous silicon-base composite negative pole material, Preparation method and use Download PDFInfo
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- CN105070894B CN105070894B CN201510464295.2A CN201510464295A CN105070894B CN 105070894 B CN105070894 B CN 105070894B CN 201510464295 A CN201510464295 A CN 201510464295A CN 105070894 B CN105070894 B CN 105070894B
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- negative pole
- lithium ion
- ion battery
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Classifications
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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
- H01M4/00—Electrodes
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Abstract
The present invention relates to a kind of lithium ion battery porous silicon-base composite negative pole material, the negative material is capsule structure, and capsule-core is noncrystalline, porous silicon, and cyst wall is conductive carbon material；The particle diameter of the noncrystalline, porous silicon is 10~300nm, and the aperture of noncrystalline, porous silicon is 0.5~100nm；The thickness of the cyst wall is 0.5~10 μm.Lithium ion battery provided by the invention is high with porous silicon-base composite negative pole material specific capacitance capacity, and expansion is low, and compacted density is high, and processing characteristics is good, technique is simple, environment-friendly pollution-free.
Description
Technical field
The invention belongs to lithium ion battery negative material and electrochemical field, and in particular to a kind of porous silicon-base composite negative pole
Material and preparation method thereof, and the lithium ion battery prepared using the negative material.
Background technology
Lithium ion battery has that energy density is big, self discharge is small, memory-less effect, operating voltage range are wide, service life
The advantages that length, non-environmental-pollution, be the main electrical source of power of current new-energy automobile.Lithium ion battery key electrode material is electricity
The final deciding factor of pond performance, wherein raising of the negative material to performance of lithium ion battery play vital effect.
And conventional graphite cathode specific capacity is already close to 372mAh/g theoretical value, it is difficult to have the space of lifting again, so developing high property
Energy new electrode materials turn into study hotspot.
Silicon have superelevation theoretical specific capacity (4200mAh/g) and relatively low de- lithium current potential (<0.5V), and the voltage of silicon is put down
Platform is slightly above graphite, and in charging, difficulty causes surface to analyse lithium, and security performance is more preferable.Silicon turns into the carbon-based negative pole upgrading of lithium ion battery
One of rich potential selection of the replacement.But silicon also has shortcoming as lithium ion battery negative material：
(1) volumetric expansion and contraction easily occur for silicon materials, influence electric cycle performance：
Silicon is semi-conducting material, and the electrical conductivity of itself is relatively low, in electrochemistry cyclic process, the insertion and abjection of lithium ion
It can make material volume that more than 300% expansion and contraction occur, caused mechanicals efforts can make the gradual efflorescence of material, cause to tie
Structure caves in, and ultimately results in electrode active material and departs from collector, loses electrical contact, cause cycle performance of battery to substantially reduce；
(2) during use, silicon materials are perishable, capacity attenuation：
Due to the bulk effect of silicon materials, it is difficult to form stable solid electrolyte interface (SEI) film, companion in the electrolytic solution
With the destruction of electrode structure, new SEI films are constantly formed in the silicon face exposed, the corrosion and capacity for exacerbating silicon decline
Subtract.
CN103531760 discloses a kind of yolk-eggshell structural porous silicon-carbon complex microsphere and preparation method thereof, and it is provided
Microballoon core be porous sub-micron silicon ball, a diameter of 400~900nm, shell is porous carbon, and thickness is 10~60nm, cavity inside diameter
For 800~1400nm, its preparation method is with SiO2Carbon source cladding is carried out for core, is fired into the SiO of porous carbon coating2Powder,
Pass through alkali process part SiO again2Obtain the porous carbon coated Si O of yolk-eggshell structure2Powder, then pass through magnesiothermic reduction and HF
Handle SiO2Silica flour is reduced to, obtains the silicon-carbon complex microsphere of the coated porous silicon of porous carbon of yolk-eggshell structure, this method
Preparation section is complicated, the more difficult control of cavity inside diameter, additionally while assign silicon certain expansion space, but silicon grain carbon coating will not
Close, electric conductivity is poor, unfavorable to its long-term circulation.
Therefore, develop that a kind of technique is simple, excellent performance and environment-friendly amorphous nano porous silicon-base composite negative pole material
The preparation method of material is the important research direction of field of lithium ion battery.
The content of the invention
In view of the shortcomings of the prior art, an object of the present invention is that provide a kind of lithium ion battery is answered with porous silicon-base
Negative material is closed, the negative material is capsule structure, and capsule-core is noncrystalline, porous silicon, and cyst wall is conductive carbon material.
The particle diameter of the noncrystalline, porous silicon is 10~300nm, for example, 20nm, 50nm, 80nm, 120nm, 150nm,
180nm, 200nm, 240nm, 260nm, 280nm etc., the aperture of noncrystalline, porous silicon are 0.5-100nm, such as 1nm, 10nm,
30nm, 40nm, 55nm, 70nm, 90nm, 240nm etc.；
The thickness of the cyst wall is 0.5~10 μm, such as 0.8 μm, 2 μm, 4 μm, 6 μm, 7 μm, 9 μm etc..
Well known to a person skilled in the art, in lithium ion battery the increase of silicone content can improve the ratio of lithium ion battery
Electric capacity, but corresponding dilation effect can be brought, the lithium ion battery porous silicon-base of the invention by designing capsule structure
Composite negative pole material, while silicon carbon material advantage is combined, by the way that capsule-core is arranged into noncrystalline, porous silicon so that it has
There are bigger specific surface area and abundant pore passage structure, effectively alleviate volumetric expansion of the silicon in charge and discharge process and shrink effect
Answer, improve the combination property of material；In addition, the setting of cyst wall is avoided that nano particle reunites in cyclic process, obstructs silicon
Directly contacted with electrolyte, greatly improve material circulation performance and efficiency first.And to noncrystalline, porous silicon grain footpath and aperture
Selection also have decided on whether that the reduction of preferable specific capacitance and volumetric expansion blockage effect can be obtained simultaneously；To wall thickness
Setting determine and can obtain firm capsule structure and preferable specific capacitance.
Noncrystalline, porous silicon containing 5~60wt%, 40~95wt% conductive carbon material in negative material of the present invention
Material, the mass percent sum of the noncrystalline, porous silicon and conductive carbon material is 100wt%.
Preferably, the median particle diameter of the negative material is 1~30 μm, such as 2 μm, 6 μm, 12 μm, 15 μm, 22 μm, 26 μ
M etc., preferably 2~20 μm, further preferred 4~15 μm.
Preferably, the specific surface area of the negative material is 1~20m2/ g, such as 3m2/g、6m2/g、13m2/g、18m2/g
Deng preferably 2~10m2/g。
Preferably, the powder body compacted density of the negative material is 0.5~2.5g/cm3, such as 0.8g/cm3、1g/cm3、
1.1g/cm3、1.6g/cm3、2g/cm3、2.3g/cm3Deng preferably 0.8~2g/cm3。
The second object of the present invention is to provide one kind lithium ion battery porous silicon-base Compound Negative as described in the first purpose
The preparation method of pole material, comprises the following steps：
(1) silicon alloy raw material Si-M is taken, extra-fine grinding is carried out, obtains silicon alloy particle；
(2) silicon alloy particle is etched, metallic element therein is removed, obtains noncrystalline, porous silicon grain；
(3) it is noncrystalline, porous silicon is homogeneously compound with carbon source material, obtain negative material presoma；
(4) negative material presoma is subjected to mechanical fusion, after sintered, obtains porous silicon-base composite negative pole material.
Step (1) the silicon alloy raw material Si-M is any 1 in crystalline state silicon alloy Si-M or amorphous silicon alloy Si-M
Kind or at least two kinds of combinations, the metallic element M in the silicon alloy raw material be selected from aluminium, titanium, nickel, tin, tungsten, iron, copper, manganese, cobalt,
Germanium, zinc, magnesium, sow any a kind or at least two kinds of combinations in metal simple-substance.
Preferably, any a kind in dry ball milling or wet ball grinding of the extra-fine grinding.
Preferably, the ball-grinding machine be selected from high-speed stirred mill, planetary ball mill, tube mill, type taper grinder, rod mill and
Any a kind in sand mill, preferably planetary ball mill.
Preferably, the material of the ball milling pearl in described mechanical milling process is selected from stainless steel, agate, ceramics, zirconium oxide, oxidation
Aluminium, any a kind in hard alloy.
Preferably, the median particle diameter of the silicon alloy particle is 0.1~100 μm, such as 2 μm, 6 μm, 12 μm, 25 μm, 42 μ
M, 56 μm, 72 μm, more preferably 87 μm, 95 μm etc., preferably 0.5~50 μm, 1~15 μm.
A diameter of 0.1~the 20mm of ball milling pearl of the dry ball milling, ratio of grinding media to material are (10~200):1；Rotational speed of ball-mill is 100
~3000rpm, Ball-milling Time are 1~100h.
Preferably, a diameter of 0.01~20mm of ball milling pearl of the wet ball grinding, ratio of grinding media to material are (10~200):1, rotating speed
For 100~3000rpm, Ball-milling Time is 1~50h.
Preferably, the wet ball grinding solvent for use is organic solvent and/or water.
Preferably, the organic solvent is any a kind or at least two kinds of of combination in tetrahydrofuran, acid amides, alcohol and ketone,
It is preferred that any a kind or at least two kinds of of combination in tetrahydrofuran, dimethyl acetamide, C1-C6 alcohol and C3-C8 ketone.
Preferably, the C1-C6 alcohol is methanol, ethanol, ethylene glycol, propyl alcohol, isopropanol, 1,2-PD, 1,3- the third two
Any a kind in alcohol, glycerine, n-butanol, 1,2- butanediols, 1,3 butylene glycol, 1,4- butanediols, n-amyl alcohol and 2- hexanols or
At least two kinds of combinations；The C3-C8 ketone is acetone, methyl ethyl ketone, methyl propyl ketone, 1-METHYLPYRROLIDONE, ethyl propyl
Any a kind or at least two kinds of in ketone, methyl butyl ketone, ethyl n-butyl ketone, methyl amyl ketone and methyl hexyl ketone
Combination.
Step (2) etching is acid etch, is specially：Silicon alloy particle is immersed in the first etching acid solution, stirred
Mix, etching metallic element M；Transfer them in the second etching acid solution, stir afterwards, etch metal oxide；
Preferably, it is described first etching acid selected from can with metallic element M react more active acid, preferably hydrochloric acid, nitric acid,
Appointing in nitrous acid, sulfuric acid, sulfurous acid, carbonic acid, boric acid, phosphoric acid, hydrofluoric acid, hydrogen cyanide, perchloric acid, acetic acid, benzoic acid, selenic acid
The combination of a kind or at least two kinds of of meaning；
Preferably, the second etching acid is more active acid that can be with reactive metal oxide, preferably hydrochloric acid, nitre
In acid, nitrous acid, sulfuric acid, sulfurous acid, carbonic acid, boric acid, phosphoric acid, hydrofluoric acid, hydrogen cyanide, perchloric acid, acetic acid, benzoic acid, selenic acid
Any a kind or at least two kinds of of combination；
Preferably, the solvent in the first etching acid solution and the second etching acid solution independently selected from for water and/or
Organic solvent；
Preferably, the organic solvent is any a kind or at least two kinds of of combination in tetrahydrofuran, acid amides, alcohol and ketone；
1 kind or at least two kinds of of combination preferably in tetrahydrofuran, dimethyl acetamide, C1-C6 alcohol and C3-C8 ketone；
Preferably, the C1-C6 alcohol is methanol, ethanol, ethylene glycol, propyl alcohol, isopropanol, 1,2-PD, 1,3- the third two
Any a kind in alcohol, glycerine, n-butanol, 1,2- butanediols, 1,3 butylene glycol, 1,4- butanediols, n-amyl alcohol and 2- hexanols or
At least two kinds of combinations；The C3-C8 ketone is acetone, methyl ethyl ketone, methyl propyl ketone, 1-METHYLPYRROLIDONE, ethyl propyl
1 kind or at least two kinds of of group in ketone, methyl butyl ketone, ethyl n-butyl ketone, methyl amyl ketone and methyl hexyl ketone
Close.
The step (3) the homogeneous composite amorphous state porous silicon and the mass ratio of conductive carbon source are 1:2~1:20；
Preferably, it is described it is homogeneous it is compound be preferably that solid phase is compound or liquid phase is compound；
Preferably, the compound processing step of the solid phase is：By it is described it is non-through porous silicon grain and particle diameter be 5~20 μm
Carbon source mixes, and mixing quality ratio is 1:2~1:20, it is subsequently placed in VC mixers, 5~50Hz of regulating frequency, mixing is at least
30min, obtain noncrystalline, porous silicon grain；
Preferably, the compound processing step of the liquid phase is：By it is described it is non-through porous silicon grain and particle diameter be 5~20 μm
Carbon source mixes, and mixing quality ratio is 1:2~1:20, it is dispersed in water or organic solvent, dries, obtain noncrystalline, porous silicon
Grain；
Preferably, the carbon source material is the arene derivative, poly- of alkanes, hydro carbons, alkenes, phenols, 1~3 ring
Any a kind or at least two kinds of of combination in compound, carbohydrate, organic acid, resinae and high polymer material, preferably methane, second
Alkane, ethene, phenol, pitch, epoxy resin, phenolic resin, furfural resin, Lauxite, polyvinyl alcohol, polyvinyl chloride, poly- second
1 kind or at least two kinds of of combination in glycol, PEO, Kynoar, acrylic resin and polyacrylonitrile.
Step (4) the mechanical fusion processing step is：
Negative material presoma is added into fusion machine, regulation rotating speed is 500~3000rpm, and cutter gap width is
0.01~1cm, at least 0.25h is merged, is subsequently placed in reactor, is passed through protective gas, be warming up to 400 DEG C~900 DEG C, protected
Room temperature is cooled to after 0.5~10h of temperature, obtains the step (4) porous silicon-base composite negative pole material；
Preferably, the protective gas is any a kind or at least two kinds of of combination in nitrogen, helium, neon, argon gas；
Preferably, the reactor is vacuum drying oven, batch-type furnace, rotary furnace, roller kilns, pushed bat kiln or tube furnace.
One of the third object of the present invention is to provide a kind of lithium ion battery, for the purpose of the lithium ion battery negative material
Described lithium ion battery porous silicon-base composite negative pole material.
Compared with prior art, the present invention has the advantages that：
(1) the lithium ion battery porous silicon-base composite negative pole material of the invention by designing capsule structure, is being combined
While silicon carbon material advantage, by the way that capsule-core is arranged into noncrystalline, porous silicon so that it has bigger specific surface area and rich
Rich pore passage structure, effectively alleviates volumetric expansion blockage effect of the silicon in charge and discharge process, improves the comprehensive of material
Energy (500 circulation volume conservation rates are more than 93%) and first efficiency (>92%)；And to noncrystalline, porous silicon grain footpath and aperture
Selection also have decided on whether that the reduction of preferable specific capacitance and volumetric expansion blockage effect can be obtained simultaneously；To wall thickness
Setting determine and can obtain firm capsule structure and preferable specific capacitance；
(2) lithium ion battery provided by the invention is high with porous silicon-base composite negative pole material specific capacitance capacity, and expansion is low, pressure
Real density is high, and processing characteristics is good, technique is simple, environment-friendly pollution-free.
Brief description of the drawings
Fig. 1 is SEM (SEM) figure of porous silicon-base composite negative pole material prepared by embodiment 1；
Fig. 2 is the XRD of porous silicon-base composite negative pole material prepared by embodiment 1；
Fig. 3 is the first charge-discharge curve of porous silicon-base composite negative pole material prepared by embodiment 1, as seen from the figure, the material
Expect that first charge-discharge capacity is higher.
Fig. 4 is the cycle performance curve of porous silicon-base composite negative pole material prepared by embodiment 1.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in understanding the present invention, is not construed as the concrete restriction to the present invention.
Embodiment 1
A kind of lithium ion battery preparation method of porous silicon-base composite negative pole material, comprises the following steps：
(1) it is 10 μm of Si-Fe alloy powders and 3mm hardened steel ball by median particle diameter, by ball material mass ratio 100:1 is mixed
After conjunction, it is fitted into the high energy ball mill of 5L stainless cylinder of steel, then passes to argon gas protective gas, under the conditions of rotating speed is 500r/min
High-energy ball milling 100h, obtain Antaciron particle；
(2) Antaciron particle is added slowly in 10wt%HCl solution, persistently stirs 15h, perform etching processing
While, the metal Fe in Antaciron particle is removed, material is formed pore space structure, is then cleaned, filtered and vacuum
Dry；Dried material is added slowly in 10wt%HF solution again afterwards, persistently stirs 10h, at further etching
Reason, meanwhile, the oxide in Antaciron particle is removed, material surface is formed micropore, is then cleaned, filtered and vacuum
Dry, obtain noncrystalline, porous silicon grain；
(3) by phenolic resin in mass ratio 30 that noncrystalline, porous silicon grain and particle diameter are 3 μm:60 are matched, mixing
It is placed in after uniformly in VC mixers, regulating frequency 30Hz, mixes 60min, obtain negative material presoma；
(4) negative material presoma is added into fusion machine, regulation rotating speed is 2000rpm, and cutter gap width is
0.1cm, 2h is merged, is subsequently placed in high temperature box furnace, is passed through nitrogen protective gas, be warming up to 750 DEG C, be cooled to after being incubated 5h
Room temperature, obtain porous silicon-base composite negative pole material；The porous silicon-base composite negative pole material median particle diameter is 12 μm；Capsule-core amorphous
The particle diameter of state porous silicon is 50nm, and aperture 5nm, wall thickness is 5 μm；
Fig. 1 is SEM (SEM) figure of porous silicon-base composite negative pole material prepared by embodiment 1；
Fig. 2 is the XRD of porous silicon-base composite negative pole material prepared by embodiment 1；Can be observed from figure, cracking carbon with
The weaker diffraction maximum of nano-silicon, and peak is wider, it can be determined that it is all amorphous structure that this, which is primarily due to crack carbon and nano-silicon,
The reason for；
Fig. 3 is the first charge-discharge curve of porous silicon-base composite negative pole material prepared by embodiment 1, as seen from the figure, is implemented
The first charge-discharge capacity of porous silicon-base composite negative pole material prepared by example 1 is higher；
Fig. 4 is the cycle performance curve of porous silicon-base composite negative pole material prepared by embodiment 1, as seen from the figure, embodiment 1
The porous silicon-base composite negative pole material of preparation has excellent cycle performance, and it is 93.1% to circulate 500 weeks capability retentions.
Embodiment 2
A kind of lithium ion battery preparation method of porous silicon-base composite negative pole material, comprises the following steps：
(1) be that 30 μm of Si-Ti alloy powders are added in acetone solvent by median particle diameter, afterwards with 0.3mm zirconium ball,
By ball material mass ratio 100:After 1 mixing, load ball milling cavity, then pass to argon gas protective gas, be 2000r/min bars in rotating speed
Under part after ball milling 50h, silicotitanium particle is obtained；
(2) silicotitanium particle is added slowly to 10wt%HNO3In solution, 15h is persistently stirred, performs etching place
While reason, the Titanium in silicotitanium particle is removed, material is formed pore space structure, is then cleaned, filtered and very
Sky is dried；Dried material is added slowly in 10wt%HF solution again afterwards, persistently stirs 10h, further etching
Processing, meanwhile, the oxide in silicotitanium particle is removed, material surface is formed micropore, is then cleaned, filtered and very
Sky is dried, and obtains noncrystalline, porous silicon grain；
(3) by polyvinyl alcohol in mass ratio 5 that noncrystalline, porous silicon grain and particle diameter are 3 μm:95 are matched, Ran Hourong
In ethanol, vacuum drying, negative material presoma is obtained；
(4) negative material presoma being added into fusion machine, regulation rotating speed is 500rpm, and cutter gap width is 1cm,
0.25h is merged, is subsequently placed in batch-type furnace, is passed through nitrogen protective gas, is warming up to 400 DEG C, room temperature is cooled to after being incubated 10h,
Obtain porous silicon-base composite negative pole material；The porous silicon-base composite negative pole material median particle diameter is 30 μm；Capsule-core amorphous state is more
The particle diameter of hole silicon is 10nm, and aperture 0.5nm, wall thickness is 10 μm.
Embodiment 3
A kind of lithium ion battery preparation method of porous silicon-base composite negative pole material, comprises the following steps：
(1) be that 80 μm of Si-Cu-Fe alloy powders are added in alcohol solvent by median particle diameter, afterwards with 0.01mm zirconiums
Ball, by ball material mass ratio 200:After 1 mixing, load ball milling cavity, then pass to argon gas protective gas, be 3000r/ in rotating speed
Under the conditions of min after ball milling 1h, copper silicon ferroalloy particles are obtained；
(2) copper silicon ferroalloy particles are added slowly in 10wt%HCl solution, persistently stir 15h, perform etching place
While reason, metal Fe and Ni metal in precursor one are removed, material is formed pore space structure, is then cleaned, filtered
And vacuum drying；Dried material is added slowly in 10wt%HF solution again afterwards, persistently stirs 10h, further
Etching processing, meanwhile, the oxide in copper silicon ferroalloy particles is removed, material surface is formed micropore, is then cleaned, taken out
Filter and vacuum drying, obtain noncrystalline, porous silicon grain；
(3) by pitch in mass ratio 5 that noncrystalline, porous silicon grain and particle diameter are 20 μm:100 are matched, and are well mixed
After be placed in VC mixers, regulating frequency 10Hz, mix 120min, obtain negative material presoma；
(4) negative material presoma is added into fusion machine, regulation rotating speed is 3000rpm, and cutter gap width is
0.01cm, 1h is merged, is subsequently placed in batch-type furnace, is passed through nitrogen protective gas, be warming up to 900 DEG C, be cooled to after being incubated 0.5h
Room temperature, obtain porous silicon-base composite negative pole material；The porous silicon-base composite negative pole material median particle diameter is 20 μm；Capsule-core amorphous
The particle diameter of state porous silicon is 300nm, and aperture 100nm, wall thickness is 8 μm.
Embodiment 4
A kind of lithium ion battery preparation method of porous silicon-base composite negative pole material, comprises the following steps：
(1) it is 1 μm of Si-Al alloy powders and 0.1mm hardened steel ball by median particle diameter, by ball material mass ratio 100:1
It is fitted into after mixing in high energy ball mill, then passes to argon gas protective gas, the high-energy ball milling under the conditions of rotating speed is 3000r/min
60h, obtain silico-aluminum particle；
(2) silico-aluminum particle is added slowly in 10wt%HCl solution, persistently stirs 15h, perform etching processing
While, the metallic aluminium in silico-aluminum particle is removed, material is formed pore space structure, is then cleaned, filtered and vacuum
Dry；Dried material is added slowly in 10wt%HF solution afterwards, persistently stirs 10h, further etching processing,
Meanwhile the oxide in silico-aluminum particle is removed, material surface is formed micropore, then cleaned, filtered and vacuum is done
It is dry, obtain noncrystalline, porous silicon grain；
(3) it is 1 μm of citric acid in mass ratio 20 by noncrystalline, porous silicon grain and particle diameter:80 are matched, and are distributed to third
In alcoholic solvent, dry, obtain negative material presoma；
(4) negative material presoma is added into fusion machine, regulation rotating speed is 2000rpm, and cutter gap width is
0.5cm, 2h is merged, is subsequently placed in high temperature box furnace, is passed through nitrogen protective gas, be warming up to 600 DEG C, be cooled to after being incubated 2h
Room temperature, obtain porous silicon-base composite negative pole material；The porous silicon-base composite negative pole material median particle diameter is 1 μm；Capsule-core amorphous
The particle diameter of state porous silicon is 30nm, and aperture 0.5nm, wall thickness is 0.5 μm.
Comparative example 1
Difference with embodiment 1 is without step (2).
Comparative example 2
Difference with embodiment 1 is that the time of step (1) high-energy ball milling is 20h, and step (3) silicon is 3 μm with particle diameter
Phenolic resin in mass ratio 30:90 are matched.Porous silicon-base composite negative pole material median particle diameter prepared by comparative example is 15 μm；
The particle diameter of capsule-core noncrystalline, porous silicon is 350nm, and aperture 7nm, wall thickness is 12 μm；
Performance test：
The negative material that embodiment and comparative example provide is prepared into battery, concretely comprised the following steps：
By negative material, conductive agent and binding agent in mass ratio 94:1:In a solvent, control solid content exists 5 mixed dissolutions
50%, coated in copper foil current collector, vacuum drying, cathode pole piece is made；Then the ternary prepared by traditional maturation process is just
LiPF6/EC+DMC+EMC (the v/v=1 of pole pole piece, 1mol/L:1:1) electrolyte, Celgard2400 barrier films, shell are using normal
Advise production technology and assemble 18650 cylinder cells；
On Wuhan Jin Nuo Electronics Co., Ltd.s LAND battery test systems, the charge and discharge for testing the cylindrical battery of preparation is electrical
Can, test condition is：Normal temperature, 0.2C constant current charge-discharges, charging/discharging voltage are limited in 2.75~4.2V.
Test result is shown in Table 1：
The performance test results of the embodiment of table 1 and comparative example
From table 1, the porous silicon-base composite negative pole material that is prepared using herein described method, specific surface area it is low (2~
4m2/ g), compacted density height (1.6~1.8g/cm3) discharge capacity is more than 1000mAh/g, initial coulomb efficiency is more than 92%, follows
500 weeks capability retentions of ring are more than 93%；And comparative example 1 and without porous silicon pores hole forming step, obtained material
Discharge capacity and first charge-discharge efficiency it is low, efficiency only has 79.5% first, and 500 weeks capability retentions of circulation only reach
84.3%；And comparative example 2 have adjusted the size of lithium ion battery porous silicon-base composite negative pole material porous silicon capsule-core and cyst wall,
It was found that its 500 circulation volume conservation rates are decreased obviously, coulombic efficiency also shows without the negative material that the application provides first
It is good.
Applicant states that the present invention illustrates the detailed process equipment of the present invention and technological process by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, selection of concrete mode etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (45)
- A kind of 1. lithium ion battery porous silicon-base composite negative pole material, it is characterised in that the negative material is capsule structure, Capsule-core is noncrystalline, porous silicon, and cyst wall is conductive carbon material；The particle diameter of the noncrystalline, porous silicon is 10~300nm, and the aperture of noncrystalline, porous silicon is 0.5~100nm；The thickness of the cyst wall is 0.5~10 μm；Noncrystalline, porous silicon containing 5~60wt%, 40~95wt% conductive carbon material in the negative material.
- 2. lithium ion battery as claimed in claim 1 porous silicon-base composite negative pole material, it is characterised in that the negative pole material The median particle diameter of material is 1~30 μm.
- 3. lithium ion battery porous silicon-base composite negative pole material as claimed in claim 2, it is characterised in that the negative pole material The median particle diameter of material is 2~20 μm.
- 4. lithium ion battery as claimed in claim 3 porous silicon-base composite negative pole material, it is characterised in that the negative pole material The median particle diameter of material is 4~15 μm.
- 5. lithium ion battery as claimed in claim 1 porous silicon-base composite negative pole material, it is characterised in that the negative material Specific surface area be 1~20m2/g。
- 6. lithium ion battery as claimed in claim 5 porous silicon-base composite negative pole material, it is characterised in that the negative pole material The specific surface area of material is 2~10m2/g。
- 7. lithium ion battery as claimed in claim 1 porous silicon-base composite negative pole material, it is characterised in that the negative pole material The powder body compacted density of material is 0.5~2.5g/cm3。
- 8. lithium ion battery as claimed in claim 7 porous silicon-base composite negative pole material, it is characterised in that the negative pole material The powder body compacted density of material is 0.8~2g/cm3。
- 9. a kind of preparation method of the lithium ion battery porous silicon-base composite negative pole material as described in claim any one of 1-8, Characterized in that, methods described comprises the following steps：(1) silicon alloy raw material Si-M is taken, extra-fine grinding is carried out, obtains silicon alloy particle, the median particle diameter of the silicon alloy particle For 0.1~100 μm；(2) silicon alloy particle is etched, metallic element therein is removed, obtains noncrystalline, porous silicon grain；(3) it is noncrystalline, porous silicon is homogeneously compound with carbon source material, obtain negative material presoma；(4) negative material presoma is subjected to mechanical fusion, after sintered, obtains porous silicon-base composite negative pole material.
- 10. method as claimed in claim 9, it is characterised in that step (1) the silicon alloy raw material Si-M is crystalline state silicon alloy Any a kind or at least two kinds of of combination in Si-M or amorphous silicon alloy Si-M, the metallic element M in the silicon alloy raw material Any a kind in aluminium, titanium, nickel, tin, tungsten, iron, copper, manganese, cobalt, germanium, zinc, magnesium, gallium metal simple substance or at least two kinds of combinations.
- 11. method as claimed in claim 9, it is characterised in that the extra-fine grinding is in dry ball milling or wet ball grinding Any a kind.
- 12. method as claimed in claim 11, it is characterised in that the ball-grinding machine is selected from high-speed stirred mill, planetary ball Any a kind in grinding machine, tube mill, type taper grinder, rod mill and sand mill.
- 13. method as claimed in claim 12, it is characterised in that the ball-grinding machine is selected from planetary ball mill.
- 14. method as claimed in claim 11, it is characterised in that the material of the ball milling pearl in described mechanical milling process is selected from not Become rusty steel, agate, ceramics, zirconium oxide, aluminum oxide, any a kind in hard alloy.
- 15. method as claimed in claim 9, it is characterised in that the median particle diameter of the silicon alloy particle is 0.1~100 μm.
- 16. method as claimed in claim 15, it is characterised in that the median particle diameter of the silicon alloy particle is 0.5~50 μm.
- 17. method as claimed in claim 16, it is characterised in that the median particle diameter of the silicon alloy particle is 1~15 μm.
- 18. method as claimed in claim 11, it is characterised in that a diameter of 0.1~20mm of ball milling pearl of the dry ball milling, Ratio of grinding media to material is (10~200):1；Rotational speed of ball-mill is 100~3000rpm, and Ball-milling Time is 1~100h.
- 19. method as claimed in claim 11, it is characterised in that the ball milling pearl a diameter of 0.01 of the wet ball grinding~ 20mm, ratio of grinding media to material are (10~200):1, rotating speed is 100~3000rpm, and Ball-milling Time is 1~50h.
- 20. method as claimed in claim 11, it is characterised in that the wet ball grinding solvent for use be organic solvent and/or Water.
- 21. method as claimed in claim 20, it is characterised in that the organic solvent is in tetrahydrofuran, acid amides, alcohol and ketone Any a kind or at least two kinds of of combination.
- 22. method as claimed in claim 21, it is characterised in that the organic solvent be tetrahydrofuran, dimethyl acetamide, Any a kind or at least two kinds of of combination in C1-C6 alcohol and C3-C8 ketone.
- 23. method as claimed in claim 22, it is characterised in that the C1-C6 alcohol be methanol, ethanol, ethylene glycol, propyl alcohol, Isopropanol, 1,2- propane diols, 1,3- propane diols, glycerine, n-butanol, 1,2- butanediols, 1,3 butylene glycol, 1,4- butanediols, Any a kind or at least two kinds of of combination in n-amyl alcohol and 2- hexanols.
- 24. method as claimed in claim 22, it is characterised in that the C3-C8 ketone is acetone, methyl ethyl ketone, methyl-prop Base ketone, 1-METHYLPYRROLIDONE, ethyl propyl ketone, methyl butyl ketone, ethyl n-butyl ketone, methyl amyl ketone and first Any a kind or at least two kinds of of combination in base hexyl ketone.
- 25. method as claimed in claim 9, it is characterised in that step (2) etching is acid etch, is specially：Silicon is closed Gold grain is immersed in the first etching acid solution, stirring, etching metallic element M；The second etching acid solution is transferred them to afterwards In, stirring, etch metal oxide.
- 26. method as claimed in claim 25, it is characterised in that the first etching acid is selected from and can reacted with metallic element M More active acid.
- 27. method as claimed in claim 26, it is characterised in that it is described first etching acid selected from hydrochloric acid, nitric acid, nitrous acid, Any a kind in sulfuric acid, sulfurous acid, carbonic acid, boric acid, phosphoric acid, hydrofluoric acid, hydrogen cyanide, perchloric acid, acetic acid, benzoic acid, selenic acid or At least two kinds of combinations.
- 28. method as claimed in claim 25, it is characterised in that the second etching acid is can be with reactive metal oxide More active acid.
- 29. method as claimed in claim 28, it is characterised in that the second etching acid is hydrochloric acid, nitric acid, nitrous acid, sulphur Any a kind in acid, sulfurous acid, carbonic acid, boric acid, phosphoric acid, hydrofluoric acid, hydrogen cyanide, perchloric acid, acetic acid, benzoic acid, selenic acid or extremely Few 2 kinds combination.
- 30. method as claimed in claim 25, it is characterised in that in the first etching acid solution and the second etching acid solution Solvent independently selected from for water and/or organic solvent.
- 31. method as claimed in claim 30, it is characterised in that the organic solvent is in tetrahydrofuran, acid amides, alcohol and ketone Any a kind or at least two kinds of of combination.
- 32. power require 30 as described in method, it is characterised in that the organic solvent be tetrahydrofuran, dimethyl acetamide, 1 kind or at least two kinds of of combination in C1-C6 alcohol and C3-C8 ketone.
- 33. method as claimed in claim 32, it is characterised in that the C1-C6 alcohol be methanol, ethanol, ethylene glycol, propyl alcohol, Isopropanol, 1,2- propane diols, 1,3- propane diols, glycerine, n-butanol, 1,2- butanediols, 1,3 butylene glycol, 1,4- butanediols, Any a kind or at least two kinds of of combination in n-amyl alcohol and 2- hexanols.
- 34. method as claimed in claim 32, it is characterised in that the C3-C8 ketone is acetone, methyl ethyl ketone, methyl-prop Base ketone, 1-METHYLPYRROLIDONE, ethyl propyl ketone, methyl butyl ketone, ethyl n-butyl ketone, methyl amyl ketone and first 1 kind or at least two kinds of of combination in base hexyl ketone.
- 35. method as claimed in claim 9, it is characterised in that step (3) the homogeneous composite amorphous state porous silicon and carbon source The mass ratio of material is 1:2~1:20.
- 36. method as claimed in claim 9, it is characterised in that described homogeneous to be complex as that solid phase is compound or liquid phase is compound.
- 37. method as claimed in claim 36, it is characterised in that the compound processing step of the solid phase is：By the amorphous Porous silicon grain mixes with the carbon source that particle diameter is 5~20 μm, and mixing quality ratio is 1:2~1:20, it is subsequently placed in VC mixers, 5~50Hz of regulating frequency, at least 30min is mixed, obtains noncrystalline, porous silicon grain.
- 38. method as claimed in claim 36, it is characterised in that the compound processing step of the liquid phase is：By the amorphous Porous silicon grain mixes with the carbon source that particle diameter is 5~20 μm, and mixing quality ratio is 1:2~1:20, it is dispersed in water or organic solvent In, dry, obtain noncrystalline, porous silicon grain.
- 39. the method as described in claim 37 or 38, it is characterised in that the carbon source material is alkanes, hydro carbons, alkenes, phenol Any a kind in class, the arene derivative of 1~3 ring, polymer, carbohydrate, organic acid, resinae and high polymer material Or at least two kinds of combination.
- 40. method as claimed in claim 39, it is characterised in that the carbon source be methane, ethane, ethene, phenol, pitch, It is epoxy resin, phenolic resin, furfural resin, Lauxite, polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, PEO, poly- 1 kind or at least two kinds of of combination in vinylidene, acrylic resin and polyacrylonitrile.
- 41. method as claimed in claim 9, it is characterised in that step (4) the mechanical fusion processing step is：Negative material presoma is added into fusion machine, regulation rotating speed is 500~3000rpm, and cutter gap width is 0.01 ~1cm, at least 0.25h is merged, is subsequently placed in reactor, is passed through protective gas, be warming up to 400 DEG C~900 DEG C, insulation Room temperature is cooled to after 0.5~10h, obtains the step (4) porous silicon-base composite negative pole material.
- 42. method as claimed in claim 41, it is characterised in that the protective gas is nitrogen, helium, neon, argon gas In any a kind or at least two kinds of of combination.
- 43. method as claimed in claim 41, it is characterised in that the reactor is vacuum drying oven, batch-type furnace, rotary furnace, roller Road kiln, pushed bat kiln or tube furnace.
- 44. a kind of lithium ion battery, it is characterised in that the lithium ion battery negative material is any one of claim 1-8 institutes The lithium ion battery stated porous silicon-base composite negative pole material.
- 45. a kind of lithium ion battery, it is characterised in that the lithium ion battery negative material is any one of claim 9-43 The lithium ion battery that described method is prepared porous silicon-base composite negative pole material.
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