CN103904306B - Silicon negative electrode composite material and preparation method thereof - Google Patents
Silicon negative electrode composite material and preparation method thereof Download PDFInfo
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- CN103904306B CN103904306B CN201410055982.4A CN201410055982A CN103904306B CN 103904306 B CN103904306 B CN 103904306B CN 201410055982 A CN201410055982 A CN 201410055982A CN 103904306 B CN103904306 B CN 103904306B
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a silicon negative electrode composite material. The silicon negative electrode composite material comprises silicon-based nano-particles and a wrapping layer, wherein the wrapping layer is used for wrapping the silicon-based nano-particles; a cavity is formed between the silicon-based nano-particles and the inner wall of the wrapping layer; the wrapping layer comprises oxide. In the silicon negative electrode composite material disclosed by the invention, silicon dioxide and other metal oxygen compounds form core-shell structures on the outer layer of the silicon-based nano-particles, so that the clustering of the silicon-based nano-particles during the cyclic charging and discharging process is effectively inhibited. Meanwhile, a larger space outside the silicon-based nano-particles can be used for expansion, so that extrusion to surrounding space is prevented, and falling of a binding agent and contact with graphite are also prevented, and thus the cycle life of the material can be greatly prolonged. According to the embodiment, the preparation method is simple, easy to operate, good in repeatability, low in cost and little in pollution to the environment, and is suitable for industrial production.
Description
Technical field
The present invention relates to technical field of lithium ion, more particularly, to a kind of silicium cathode composite and preparation method thereof.
Background technology
Lithium ion battery because its energy density height, power density height, good cycle, environmental friendliness, structure diversification and
The excellent specific property such as cheap, has been widely used in various fields.For lithium ion battery negative, the theoretical capacity of silicon materials
Highest, the lithium storage content of monocrystal silicon is 3800mAh/g, and lithium and silicon form alloy LixSi (0<x<4.4), as formation Li4.4Siization
Theoretical lithium storage content during compound is up to 4200mAh/g, much larger than the theoretical lithium storage content (372mAh/g) of graphite.However,
Charge and discharge process, that is, during removal lithium embedded, silicon materials change in volume is larger（Volumetric expansion is up to 400%）, easily cause silicon grain
Rupture efflorescence, makes silicon grain depart from conductive network, internal resistance increases, and leads to reversible capacity to be decayed rapidly, cycle performance is significantly
Decline.For the problems referred to above, researchers try to explore the method improving silicium cathode material circulation performance, such as reduce silicon materials
Grain particle diameter, poromerics, silicon nanowires, thin-film material, composite etc..Wherein relatively effective method is to prepare silicon again
Condensation material pin alleviating the volumetric expansion in battery charge and discharge process, the method oneself through being widely used in lithium ion battery negative material
Study on the modification in.
Carbonaceous negative material change in volume in charge and discharge process is relatively small, and is the good conductor of electronics, therefore by
It is elected to be the dispersible carrier of dispersion silicon grain.In addition silicon is close with the chemical property of carbon, can combine closely.If silicon grain can be in carbon materials
It is in nano-dispersed in material, the space between the structure that material with carbon element itself has and the silicon grain in nano-dispersed can be all lithium ion
Substantial amounts of passage is provided, increases the embedded location of lithium ion.Carbon silicon is combined to reach and improves silicon bulk effect, improves its electrification
Learn the purpose of stability.
CN1761089A discloses a kind of lithium ion battery silicon/carbon graphite composite negative pole material, this composite negative pole material by
Silica flour, graphite mix, and can reduce overall expansion rate to a certain extent in discharge and recharge, improve its cycle performance.
CN180094A discloses a kind of preparation method of silicon/carbon nuclear-shell structured nano-composite material, by by carbon coating in silicon grain
On, to suppress the efflorescence of silicon grain, and to avoid the reunion of possible silicon grain in charge and discharge process.Thus extending it to circulate the longevity
Life.In the patent of Publication No. CA101210112, using the compound method of silicon particle, graphite particle and conducting polymer, will lead
Electric polymer is coated on the surface of graphite particle, and silicon grain is attached on conductive polymer surfaces, thus improving cycle performance.
Chen Jun etc.（Ma H,Cheng FY,Chen J,Zhao JZ,Li CS,Tao ZL,Liang J.Nest-like silicon
nanospheres for high-capacity lithium storage.Adv Mater,2007,19:4067–4070）Logical
Cross solvent-thermal method and be prepared for Si nano-hollow ball, find that the nano-silicon of hollow-core construction effectively buffer volumes can change and improve storage lithium
Activity.
Substantial amounts of research shows that silicon-metal alloy, silicon nonmetallic compound all can be effectively reduced in charge and discharge process
The impact that volumetric expansion brings to material electrochemical performance, silicon nonmetallic compound includes Si oxide and other silicon is non-metallic
Compound etc., mainly improves its chemical property by the change of appearance structure, doping and carbon coating etc..
However, due to silicon in discharge and recharge cubical expansivity up to 400%, either by with the mixing of carbon, surface carbon
Cladding, or by adding conducting polymer, all can not solve to lead to battery due to the expansion of silicon to the extruding of surrounding space
The problem that cycle performance declines.
Therefore, those skilled in the art is devoted to developing a kind of lithium ion battery silicon anode material, using this
The lithium ion battery of silicium cathode material is capable of the integrity of holding structure such that it is able to improve during discharge and recharge dilation
Coulombic efficiency, extends circulation, and reduces irreversible capacity.
Content of the invention
It is an object of the invention to, for the weak point of existing lithium ion battery silicon cathode material and preparation method thereof,
Develop a kind of lithium ion battery silicon anode material, this silicium cathode material adopts unique " nucleocapsid " structure, in clad
Be reserved with certain space and between based nanoparticle, thus provide that a kind of specific capacity is high, have extended cycle life, kinetics
Lithium ion battery silicon composite cathode material that can be good and preparation method thereof.
For achieving the above object, on the one hand, the invention provides a kind of silicium cathode composite, including based nanoparticle
And clad, the described clad described based nanoparticle of cladding, wherein, described based nanoparticle is interior with described clad
There is cavity, described clad is the open structure of oxide between wall.
Further, described based nanoparticle be pure nano silicon particles, SiOx granule or they with arbitrary proportion
The mixture of composition.Further, described X=0.5-1.6.
Further, described oxide is selected from SiO2、TiO2、Al2O3、ZrO2One of.
Further, the mean diameter of described silicium cathode composite is 50～1500nm.
Further, the thickness of described clad is 10～500nm.
Further, described clad has hole or crackle.Further, a diameter of the 1 of described hole～
10nm.
Further, the particle diameter of described based nanoparticle is 10～500nm.
On the other hand, the present invention provides a kind of method preparing aforementioned silicium cathode composite, comprises the following steps：
The first step, first based nanoparticle is dispersed in solvent, is subsequently adding silane coupler, continuously stirred
Add ammonia after being uniformly dispersed, loose ground floor coating is coated on based nanoparticle, adds the second shell forerunner
Body, forms sol system after reaction；
Second step, adds HF solution, continuously stirred, centrifugation in the sol system being formed in the first step, will obtain
Product vacuum be dried after, washed with solvent, and be dried again, obtain described silicium cathode composite.
Further, step 1）In solvent selected from methanol used, ethanol, normal propyl alcohol, acetone, at least one in acetonitrile
Or their any mixture.
Further, the matter of the based nanoparticle, silane coupler and the second shell presoma that add in the first step
Measuring ratio is：5:0.05-1:0.05.
Further, step 1）In silane coupler be selected from trimethoxy silicon propyl group ethylenediamine, gamma-amino propyl group trimethoxy
Base silane, γ aminopropyltriethoxy silane, anilinomethyl triethoxysilane, β-(3,4- epoxycyclohexyl) ethyl three
Methoxy silane, γ-(2,3- epoxy the third oxygen) propyl trimethoxy silicane, γ mercaptopropyitrimethoxy silane, γ-sulfydryl
One of propyl-triethoxysilicane or their any mixture.
Further, step 2）In the second shell presoma be esters of silicon acis, titanate esters, Aluminate, in zirconate one
Kind；
Preferably, the molecular formula of described esters of silicon acis is Si (OR)4, wherein R is-CnH2n+ 1, n=1～5；It is highly preferred that institute
State esters of silicon acis be methyl silicate, tetraethyl orthosilicate, positive silicic acid propyl ester, butyl silicate, isopropyl silicate, in silicic acid isobutyl ester
A kind of or their any mixture.
Preferably, the molecular formula of described titanate esters is Ti (OR)4, wherein R is-CnH2n+1, n=1～5；It is highly preferred that it is described
Titanate esters be metatitanic acid methyl ester, tetraethyl titanate, titanium propanolate, tetrabutyl titanate, tetra-tert titanate esters, butyl tetra titanate,
One of metatitanic acid tetra isopropyl ester or their any mixture.
Preferably, the molecular formula of described Aluminate is Al (OR)3, wherein R is-CnH2n+1, n=1～5；It is highly preferred that it is described
Aluminate is one of aluminic acid trimethyl, aluminic acid triethyl, aluminic acid three propyl ester or their any mixture.
Preferably, the molecular formula of described zirconate is Zr (OR)4, wherein R is-CnH2n+1, n=1～5；It is highly preferred that it is described
Zirconate is one of zirconic acid methyl ester, zirconic acid ethyl ester, zirconic acid propyl ester, tetrabutyl zirconate or their any mixture.
In the silicium cathode composite of the application, Si oxide and other metal oxide are outside based nanoparticle
Form nucleocapsid structure, effectively inhibit the reunion of nanometer silicon grain in cyclic process.And, in the silicium cathode composite of the application
Using oxide mechanical strength higher, as clad, preferable stability can be kept, carbon can be overcome as clad
It is difficult to keep the defect of cavity structure under the conditions of colding pressing.
The preparation method of the present invention makes the thickness of clad controlled, and all operations all can be carried out, no at room temperature
Need special equipment, can reducing energy consumption, easily operate, reproducible, with low cost, and the pollution to environment is little, is suitable for
In industrialized production.
Technique effect below with reference to design, concrete structure and generation to the present invention for the accompanying drawing is described further, with
It is fully understood from the purpose of the present invention, feature and effect.
Brief description
Fig. 1 is the structural representation of the silicium cathode composite of the present invention.
Fig. 2 is the TEM electron microscopic picture of the silicium cathode composite in embodiments of the invention 1.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than restriction the scope of the present invention.In addition, it is to be understood that after having read the content of present invention instruction, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
The nano silicon particles that 5g particle diameter is 50nm add in 50ml ethanol, stir 0.5 hour, enable nano silicon particles
Dispersed；It is subsequently adding the trimethoxy silicon propyl group ethylenediamine of 0.5g, continuously stirred 1 hour, form uniform dispersion liquid；Then
Add the ammonia of 0.5ml1mol/L, at room temperature, continuously stirred 4 hours, under the catalytic action of ammonia, trimethoxy silicon third
After the hydrolysis of base ethylenediamine, loose organic inorganic hybridization layer is coated on nano silicon particles, composition is R-Si-O, R is 3- ((2- ammonia
Base ethyl) amino) propyl group-, form mixed liquor；Then, add 1g methyl silicate in the mixed liquor being formed, at room temperature,
Continuously stirred 2 hours, one layer of SiO is coated after methyl silicate hydrolysis on organic inorganic hybridization layer2Shell, forms sol
System；The HF solution of 0.05mol/L is added in this sol system, at room temperature, continuously stirred 1 hour, organic inorganic hybridization layer
It is corroded and be removed, SiO2Shell is also corroded out hole or crackle, products therefrom is centrifuged successively, is vacuum dried,
Washing with alcohol three times, then dries, and obtains the nano silicon particles that kernel particle diameter is 50nm, middle is cavity, and clad is SiO2
Silicium cathode composite.
The TEM electron microscopic picture of the silicium cathode composite obtaining in the present embodiment is as shown in Figure 2.
Embodiment 2
The nano silicon particles that 5g particle diameter is 100nm add in 50ml methanol, stir 0.5 hour, enable nano silicon particles
Enough dispersed；It is subsequently adding the gamma-amino propyl trimethoxy silicane of 0.05g, continuously stirred 1 hour, form uniform point
Dispersion liquid；Then add the ammonia of 0.5ml1mol/L, at room temperature, continuously stirred 4 hours, under the catalytic action of ammonia,
After the hydrolysis of gamma-amino propyl trimethoxy silicane, loose organic inorganic hybridization layer R-Si-O is coated on nano silicon particles, R is
Gamma-amino propyl group, forms mixed liquor；Then, add 1g methyl silicate in the mixed liquor being formed, at room temperature, persistently stir
Mix 2 hours, one layer of SiO is coated after methyl silicate hydrolysis on organic inorganic hybridization layer2Shell, forms sol system；At this
In sol system add 0.05mol/L HF solution, at room temperature, continuously stirred 1 hour, organic inorganic hybridization layer be corroded and
It is removed, SiO2Shell is also corroded out hole or crackle, and products therefrom is centrifuged successively, is vacuum dried, methanol washing
Three times, then dry, obtain the nano silicon particles that kernel particle diameter is 100nm, middle is cavity, and clad is SiO2Silicium cathode
Composite.
Embodiment 3
The nano silicon particles that 5g particle diameter is 500nm add in 50ml methanol, stir 0.5 hour, enable nano silicon particles
Enough dispersed；It is subsequently adding the anilinomethyl triethoxysilane of 1g, continuously stirred 1 hour, form uniform dispersion liquid；So
Add the ammonia of 1ml1mol/L afterwards, at room temperature, continuously stirred 4 hours, under the catalytic action of ammonia, anilinomethyl three
After Ethoxysilane hydrolysis, loose organic inorganic hybridization layer is coated on nano silicon particles, composition is R-Si-O, R is aniline first
Base, forms mixed liquor；Then, add 0.05g butyl titanate in the mixed liquor being formed, at room temperature, continuously stirred 2 is little
When, one layer of TiO is coated after tetrabutyl titanate hydrolysis on organic inorganic hybridization layer2Shell, forms sol system；In this sol
The HF solution of 0.05mol/L is added, at room temperature, continuously stirred 1 hour, organic inorganic hybridization layer was corroded and is gone in system
Remove, products therefrom is centrifuged successively, is vacuum dried, methanol washs three times, then dries, obtaining kernel particle diameter is 500nm
Nano silicon particles, middle is cavity, and clad is TiO2Silicium cathode composite.
Embodiment 4
The nano silicon particles that 5g particle diameter is 200nm add in 50ml methanol, stir 0.5 hour, enable nano silicon particles
Enough dispersed；It is subsequently adding the γ aminopropyltriethoxy silane of 0.5g, continuously stirred 1 hour, form uniform dispersion
Liquid；Then add the ammonia of 1ml1mol/L, at room temperature, continuously stirred 4 hours, under the catalytic action of ammonia, γ-ammonia
After the hydrolysis of base propyl-triethoxysilicane, loose organic inorganic hybridization layer is coated on nano silicon particles, composition is R-Si-O, R
For gamma-amino propyl group, form mixed liquor；Then, the mixed liquor being formed adds 1g aluminic acid trimethyl, at room temperature, continue
Stirring 2 hours, coats one layer of Al on organic inorganic hybridization layer after aluminic acid front three ester hydrolysis2O3Shell, forms sol system；?
The HF solution of 0.05mol/L is added, at room temperature, continuously stirred 1 hour, organic inorganic hybridization layer was corroded in this sol system
And be removed, Al2O3Shell is also corroded out hole or crackle, and products therefrom is centrifuged successively, is vacuum dried, methanol is washed
Wash three times, then dry, obtain the nano silicon particles that kernel particle diameter is 200nm, middle is cavity, and clad is Al2O3Silicon bear
Pole composite.
Embodiment 5
The nano silicon particles that 5g particle diameter is 100nm add in 50ml methanol, stir 0.5 hour, enable nano silicon particles
Enough dispersed；It is subsequently adding the γ aminopropyltriethoxy silane of 1g, continuously stirred 1 hour, form uniform dispersion
Liquid；Then add the ammonia of 1ml1mol/L, at room temperature, continuously stirred 4 hours, under the catalytic action of ammonia, γ-ammonia
After the hydrolysis of base propyl-triethoxysilicane, loose organic inorganic hybridization layer is coated on nano silicon particles, composition is R-Si-O, R
For gamma-amino propyl group, form mixed liquor；Then, the mixed liquor being formed adds 0.5g zirconic acid methyl ester, at room temperature, continue
Stirring 2 hours, coats one layer of ZrO on organic inorganic hybridization layer after the hydrolysis of zirconic acid methyl ester2Shell, forms sol system；At this
In sol system add 0.05mol/L HF solution, at room temperature, continuously stirred 1 hour, organic inorganic hybridization layer be corroded and
It is removed, products therefrom is centrifuged successively, is vacuum dried, methanol washs three times, then dries, obtaining kernel particle diameter is
The nano silicon particles of 100nm, middle is cavity, and clad is ZrO2Silicium cathode composite.
Embodiment 6
5g particle diameter is the SiOx of 100nm（X=0.5-1.6）Nano-particle adds in 50ml ethanol, stirs 0.5 hour, makes
Nano silicon particles can be dispersed；It is subsequently adding the trimethoxy silicon propyl group ethylenediamine of 1g, continuously stirred 1 hour, formed uniformly
Dispersion liquid；Then add the ammonia of 0.5ml1mol/L, at room temperature, continuously stirred 4 hours, in the catalytic action of ammonia
Under, after the hydrolysis of trimethoxy silicon propyl group ethylenediamine, loose organic inorganic hybridization layer is coated on nano silicon particles, composition is R-Si-
O, R are 3- ((2- amino-ethyl) amino) propyl group, form mixed liquor；Then, the mixed liquor being formed adds 1g positive silicic acid first
Ester, at room temperature, continuously stirred 2 hours, coats one layer of SiO on organic inorganic hybridization layer after methyl silicate hydrolysis2Shell,
Form sol system；The HF solution of 0.05mol/L is added in this sol system, at room temperature, continuously stirred 1 hour, organic
Inorganic hybrid layer is corroded and is removed, SiO2Shell is also corroded out hole or crackle, products therefrom is centrifuged successively,
Vacuum drying, washing with alcohol three times, then dry, and obtain the SiOx nano-particle that kernel particle diameter is 100nm, middle is cavity,
Clad is SiO2Silicium cathode composite.
Embodiment 7
5g particle diameter is 100nm containing Si and SiOx（X=0.5-1.6）Nano-particle（Si：SiOx=2：1 (weight ratio)）Plus
Enter in 50ml ethanol, stir 0.5 hour, enable nano silicon particles dispersed；It is subsequently adding the trimethoxy silicon propyl group second of 1g
Diamidogen, continuously stirred 1 hour, forms uniform dispersion liquid；Then add the ammonia of 0.5ml1mol/L, at room temperature, continue
Stirring 4 hours, under the catalytic action of ammonia, coats loose on nano silicon particles after the hydrolysis of trimethoxy silicon propyl group ethylenediamine
Organic inorganic hybridization layer, composition is R-Si-O, and R is 3- ((2- amino-ethyl) amino) propyl group, forms mixed liquor；Then, in shape
1g methyl silicate is added in the mixed liquor becoming, at room temperature, continuously stirred 2 hours, in organic nothing after methyl silicate hydrolysis
One layer of SiO is coated on machine hybrid layer2Shell, forms sol system；The HF solution of 0.05mol/L is added in this sol system,
At room temperature, continuously stirred 1 hour, organic inorganic hybridization layer was corroded and is removed, SiO2Shell be also corroded out hole or
Crackle, products therefrom is centrifuged successively, is vacuum dried, washing with alcohol three times, then dries, obtaining kernel particle diameter is
The nano-particle having Si and SiOx of 100nm, middle is cavity, and clad is SiO2Silicium cathode composite.
Comparative example 1
It is silicium cathode material using the nano silicon particles not doing any process.
Comparative example 2
Operational approach is similar to Example 1, as different from Example 1 not using HF process after cladding, directly from
The heart separates, and after the granule of gained is vacuum dried, is washed with methanol three times, obtains the nano silicon particles that kernel is 100nm, middle
For organic inorganic hybridization layer, shell is SiO2Silicium cathode composite.
, as negative electrode active material, cobalt acid lithium is as positive pole for the silicium cathode composite being respectively adopted embodiment 1 to 7 offer
Active substance, is assembled into lithium ion battery, and numbering respectively is S1-S7.As a comparison, will be coated using not doing in comparative example 1
As the lithium ion battery of negative electrode active material (positive active material is also cobalt acid lithium), to number be D1 to nano silicon particles, using right
The silicium cathode composite of ratio 2 is that lithium ion battery as negative electrode active material numbers is D2.
To numbering be S1-S7 and D1, D2 battery carry out efficiency test first：First 3.4V is charged to 0.02C, then
3.85V is charged to 0.1C, then 4.3V is charged to 0.2C, with 4.3V constant voltage to 0.05C, be then discharged to 0.5C
3.0V, with discharge capacity divided by charging capacity, that is, obtains efficiency first, acquired results are shown in Table 1.It is S1-S7 and D1, D2 to numbering
Battery be circulated test：For the battery after chemical conversion, 4.3V, 4.3V constant voltage to 0.05C are charged to 0.7C, stands 5 points
After clock, 3.0V is discharged to 0.5C, sees its capability retention after so circulation 50cycle, acquired results are shown in Table 1.
Table 1：Numbering is S1-S7 and D1, the efficiency first of the battery of D2 and circulation 50cycle after capability retention.
As can be seen from Table 1：After nano silicon particles are coated, efficiency is improved significantly first, and circulates
Capability retention afterwards is also greatly improved, and the presence due to there being shell is described, the stability of silicon materials can be greatly improved.Pass through
Contrast with comparative example 1,2 and find, the presence of cavity has a great impact to the stability of this material, when not having cavity, even if having
Cladding, will not bring larger improvement to its performance, only in the presence of cavity, efficiency first just can be promoted to improve.This be because
In the presence of cavity, it is reserved with certain space, can be unlikely to viscous in charge and discharge process volumetric expansion or contraction for silicon
Knot agent, the contact of conductive agent impact, and therefore, the presence of this cavity is greatly improved capacity when efficiency and circulation first
Conservation rate.
The preferred embodiment of the present invention described in detail above.It should be appreciated that the ordinary skill of this area need not be created
The property made work just can make many modifications and variations according to the design of the present invention.Therefore, all technical staff in the art
Pass through the available technology of logical analysis, reasoning, or a limited experiment under this invention's idea on the basis of existing technology
Scheme, all should be in the protection domain being defined in the patent claims.
Claims (11)
1. a kind of method preparing silicium cathode composite, described silicium cathode composite, including based nanoparticle and cladding
Layer, described clad coats described based nanoparticle, free between the inwall of described based nanoparticle and described clad
Chamber, described clad is the loose structure of oxide；Wherein, described oxide is SiO2、TiO2、Al2O3、ZrO2One of；
Described clad has hole and the crackle of HF corrosion；A diameter of 1～10nm of described hole；It is characterized in that, including
Following steps：
The first step, first based nanoparticle is dispersed in solvent, is subsequently adding silane coupler, continuously stirred dispersion
Uniformly add ammonia afterwards, be stirred at room temperature, loose ground floor coating coated on nano silicon particles, adds second shell
Layer presoma, forms sol system after reaction；
Second step, adds HF solution in the sol system being formed in the first step, is continuously stirred at room temperature, centrifugation, will
After the product vacuum obtaining is dried, is washed with solvent, and be dried again, obtain described silicium cathode composite；
In the first step, the mass ratio of the based nanoparticle, silane coupler and the second shell presoma of addition is：5:0.05-
1:0.05；In the first step, solvent used is one of methanol, ethanol, normal propyl alcohol, acetone, acetonitrile or their any mixing
Thing.
2. method according to claim 1 is it is characterised in that step 1) in silane coupler be trimethoxy silicon propyl group second
Diamidogen, gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, anilinomethyl triethoxysilane, β-
(3,4- epoxycyclohexyl) ethyl trimethoxy silane, γ-(2,3- epoxy the third oxygen) propyl trimethoxy silicane, γ-sulfydryl third
One of base trimethoxy silane, γ-Mercaptopropyltriethoxysilane or their any mixture.
3. method according to claim 1 is it is characterised in that step 1) in the second shell presoma be esters of silicon acis, titanium
One of acid esters, Aluminate, zirconate.
4. method according to claim 3 is it is characterised in that the molecular formula of described esters of silicon acis is Si (OR)4, wherein R be-
CnH2n+ 1, n=1～5.
5. method according to claim 3 is it is characterised in that the molecular formula of described titanate esters is Ti (OR)4, wherein R be-
CnH2n+1, n=1～5.
6. method according to claim 3 is it is characterised in that the molecular formula of described Aluminate is Al (OR)3, wherein R be-
CnH2n+1, n=1～5.
7. method according to claim 3 is it is characterised in that the molecular formula of described zirconate is Zr (OR)4, wherein R be-
CnH2n+1, n=1～5.
8. method according to claim 4 is it is characterised in that described esters of silicon acis is methyl silicate, tetraethyl orthosilicate, just
One of silicic acid propyl ester, butyl silicate, isopropyl silicate, silicic acid isobutyl ester or their any mixture.
9. method according to claim 5 is it is characterised in that described titanate esters are metatitanic acid methyl ester, tetraethyl titanate, metatitanic acid third
One of ester, tetrabutyl titanate, tetra-tert titanate esters, butyl tetra titanate, metatitanic acid tetra isopropyl ester or they appoint
Meaning mixture.
10. method according to claim 6 it is characterised in that described Aluminate be aluminic acid trimethyl, aluminic acid triethyl,
One of aluminic acid three propyl ester or their any mixture.
11. methods according to claim 7 are it is characterised in that described zirconate is zirconic acid methyl ester, zirconic acid ethyl ester, zirconic acid
One of propyl ester, tetrabutyl zirconate or their any mixture.
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| CN201410055982.4A CN103904306B (en) | 2014-02-19 | 2014-02-19 | Silicon negative electrode composite material and preparation method thereof |
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| CN103904306B true CN103904306B (en) | 2017-02-08 |
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| CN108206268A (en) * | 2016-12-19 | 2018-06-26 | 华为技术有限公司 | Negative material and preparation method thereof, cathode pole piece and lithium ion battery |
| CN106935817B (en) * | 2017-03-07 | 2019-05-31 | 浙江工业大学 | A kind of preparation method of secondary cluster structure Silicon Based Anode Materials for Lithium-Ion Batteries |
| CN106848276A (en) * | 2017-04-19 | 2017-06-13 | 合肥工业大学 | A kind of titanium dioxide of core-shell structure cladding silicon lithium ion battery cathode material and preparation method thereof |
| CN107195887A (en) * | 2017-06-12 | 2017-09-22 | 上海大学 | A kind of preparation method of the nanometer anode material of organic inorganic hybridization modification |
| CN110085852A (en) * | 2019-05-28 | 2019-08-02 | 中国科学院重庆绿色智能技术研究院 | Conductive structure and electrode |
| CN113285063B (en) * | 2020-02-20 | 2023-08-08 | 北京小米移动软件有限公司 | Negative electrode material, negative electrode sheet, preparation method of negative electrode sheet, battery and electronic equipment |
| CN111477858A (en) * | 2020-05-08 | 2020-07-31 | 广西师范大学 | Si @ TiO2Preparation method of hollow core-shell composite material |
| CN112366306B (en) * | 2021-01-12 | 2021-04-09 | 拓米(成都)应用技术研究院有限公司 | Nano silicon composite negative electrode material and manufacturing method thereof |
| CN113113579A (en) * | 2021-03-10 | 2021-07-13 | 欣旺达电动汽车电池有限公司 | Negative electrode active material, preparation method thereof and lithium ion battery |
| CN114068901A (en) * | 2021-11-15 | 2022-02-18 | 陕西煤业化工技术研究院有限责任公司 | Silicon-carbon composite negative electrode material, preparation method and application |
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| CN103474636A (en) * | 2013-09-18 | 2013-12-25 | 上海交通大学 | Silicon-based lithium ion battery negative electrode material and preparation method thereof |
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| CN102122708A (en) * | 2010-01-08 | 2011-07-13 | 中国科学院物理研究所 | Negative pole material for lithium-ion secondary battery, negative pole containing negative pole material, preparation method of negative pole and battery containing negative pole |
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