CN106654241A - Silicon-carbon negative electrode material structure for power lithium ion battery and preparation method thereof - Google Patents
Silicon-carbon negative electrode material structure for power lithium ion battery and preparation method thereof Download PDFInfo
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- CN106654241A CN106654241A CN201611025046.4A CN201611025046A CN106654241A CN 106654241 A CN106654241 A CN 106654241A CN 201611025046 A CN201611025046 A CN 201611025046A CN 106654241 A CN106654241 A CN 106654241A
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Abstract
The invention provides a silicon-carbon negative electrode material structure for a power lithium ion battery. The silicon-carbon negative electrode material structure comprises double-phase silicon and a carbon shell layer, wherein the double-phase silicon is formed by distributing mono-crystalline silicon nano-crystals into an amorphous silicon phase and is of a kiwi fruit shape, and the weight percent range of the mono-crystalline silicon nano-crystals is 20 percent to 50 percent; the carbon shell layer is a carbon coated layer formed by carrying out condensation polymerization and carbonization on organic matters and is located at the outer part of the double-phase silicon; the weight percent range of the carbon shell layer is 15 percent to 45 percent. The invention further discloses a preparation method of the silicon-carbon negative electrode material structure for the power lithium ion battery. According to the silicon-carbon negative electrode material structure for the power lithium ion battery, provided by the invention, a carbon shell on the outermost layer can obviously improve the conductivity of silicon and outward volume expansion is limited; an elastic softening phenomenon in an amorphous silicon charging process can be used for effectively buffering stress generated by volume change of the silicon and the volume expansion effect of an electrode is greatly alleviated; the mono-crystalline silicon nano-crystals dispersed into the amorphous silicon can intensify the mechanical properties of the amorphous silicon, so that the anti-cracking performance of the amorphous silicon is improved and the circulating stability of an electrode material is improved.
Description
Technical field
The present invention relates to cell art, more particularly to a kind of power lithium-ion battery with silicon-carbon cathode material structure and
Its preparation method.
Background technology
With electric automobile and the development need of portable electronic products technology, lithium rechargeable battery is due to specific energy
Height, operating voltage is high, has extended cycle life, and self discharge is little, pollution-free, lightweight, the advantages of security is good, from nineteen ninety city is put into
It has been rapidly developed since, the market mainstream has been already taken up at present, application is more and more extensive.Presently used high-performance negative pole
Material is mainly carbons material, predominantly Delanium and MCMB.But its theoretical specific capacity is only 372mAh/g, and
And the close lithium metal of intercalation potential platform, quick charge easily occur " analysis lithium " phenomenon cause potential safety hazard.Therefore, high-energy power type
The development of lithium ion battery is in the urgent need to seeking the new negative pole of high power capacity, long-life, fast charging and discharging substituting graphite-like carbon
Negative pole.
In the lithium ion battery negative material having now been found that, Si materials are up to 4200mAh/ due to its theoretical lithium storage content
The advantages such as g, the high and excellent security performance of the content in earth's surface are considered as that most potential high-energy-density lithium battery uses negative
Pole material.Enormousness varying effect, relatively low electrical conductivity and Si surfaces yet with it during electrochemical lithium storage
The problems such as solid electrolyte (SEI) film is unstable, silicon based anode material still needs substantial amounts of effort to be improved further
Work.During discharge and recharge, the rapid large volume of Si sills expands and shrinks, and can not only cause the unstable of SEI films, promotes SEI
Film continuously grows, and also results in the disengagement of electrode material and collector, so as to cause the rapid exhaustion of battery capacity.
To attempt solving this problem, particle nanosizing and structure silicon based composite material are current topmost approach.
At present substantial amounts of nanosizing silicium cathode material has been developed, mainly including silicon nanocrystal, nano wire, nanosphere and nanotube etc..
Particle nanosizing can mitigate the absolute volume intensity of variation of silicon, while the diffusion length of lithium ion can also be reduced, improve electrification
Learn reaction rate.Although these systems show good lithium battery performance, they yet suffer from variety of problems.Example
Such as, in charge and discharge process, the agglomeration of nano particle strengthens low storehouse caused by problem and high-specific surface area to Si nano-powders
Human relations efficiency.Can avoid particle agglomeration and the body of radial direction can be reduced using CVD growth Si nano wires on the current collector
Product change.But using CVD method complex process, apparatus expensive, process is difficult to control to, and hardly results in the product of uniformity,
When being also difficult to overcome fast charging and discharging simultaneously, nano wire itself fracture caused by local stress institute.On the other hand, also can be by silicon material
Material evenly spreads in other activity or non-active material and forms composite, such as Si-C, Si-Cu-C.Authorization Notice No. is
The Chinese patent " silicon-carbon cathode material of lithium ion battery and preparation method thereof " of 102394288B, discloses silicon-carbon cathode material
Material is made up of Si-C composite material with graphite powder, with higher than gram volume and more general alloy material of cathode has well
Cycle performance；Authorization Notice No. is a kind of Chinese patent " lithium ion cell high-capacity copper silicon/carbon Compound Negative of 101944592B
Pole material and its production technology ", disclosed lithium ion battery negative material capacity is more than 578mAh/g, and 300 times circulation volume is protected
Hold more than 80%.Although above-mentioned silicon based composite material can to a certain extent alleviate the bulk effect of silicon, it is also possible in certain journey
Improve the cycle performance and capacity attenuation of battery on degree, but its mechanism is all that silicon is combined or in crystalline silicon with the physics of other metals
Surface carries out high temperature carbon coating, it is impossible to fundamentally suppress the bulk effect in charge and discharge process, after circulating several times,
Cycle performance starts to be deteriorated, and capacity will start decay again.
Recently, Cubuk et al. (Nano Letter.2014,4065) with McDowell et al. (Nano
Letter.2013,758) reports non-crystalline silicon electrode material and there are two step process of intercalation in charging process, and Li is formed respectivelyη
Si phases and Li3.75Si phases, because two step process of intercalation can cause elastic ruckbildung, can significantly buffer silicon in charge and discharge process
The stress that Volume Changes are produced, so as to significantly reduce electrode volume bulking effect, improves the mechanically stable of amorphous silicon electrode
Property and electrochemical stability.But because this material is in amorphous disordered state, its own electric conductivity is poor, significantly limit amorphous
Application of the silicon as negative material.
The content of the invention
It is an object of the invention to provide a kind of power lithium-ion battery silicon-carbon cathode material structure and preparation method thereof,
It is poor to solve the problems, such as lithium cell cathode material cyclical stability.
In order to solve above-mentioned technical problem, the technical scheme is that：A kind of power lithium-ion battery silicon-carbon is provided
Negative material structure, including：Two-phase silicon, is that monocrystalline silicon nanocrystal is distributed in non-crystalline silicon phase, in Kiwi berry shape, the monocrystalline silicon
Nanocrystalline weight is 20% to 50% than scope；The carbon coating layer that carbon shell is organic matter to be formed Jing after polycondensation, carbonization, position
Outside the two-phase silicon, the weight of the carbon shell is 15% to 45% than scope.
Further, power lithium-ion battery a diameter of 70～150nm of silicon-carbon cathode material structure.
Further, the thickness of the carbon shell is 5～25nm.
Further, the size of the silicon nanocrystal is 4～10nm.
The present invention also provides a kind of preparation method of power lithium-ion battery silicon-carbon cathode material structure, including following step
Suddenly：Under step one, room temperature, non-crystalline silicon is added in deionized water, magnetic agitation 0.5～2 hour, form aaerosol solution, then will
Methyl alcohol, 3- aminopropyl -3- Ethoxysilanes are respectively dropped into, and stir 2～3 hours, form mixed solution, reuse the mode of centrifugation
Collecting reaction product, is washed respectively with ethanol and deionized water, is dried, and obtains the modified non-crystalline silicon in surface；Step 2, by institute
State modified non-crystalline silicon to add in the aqueous solution containing organic pyrolytic carbon raw material, stirring is poured in reactor after 0.5～2 hour,
It is warming up to 160～200 DEG C, 2～8h of insulation terminates to reacting, using centrifugation collecting reaction product, with ethanol and goes respectively
Ion water washing, is dried；Step 3, the product of step 2 is placed in refractory container, under inert atmosphere protection 500 are fired to
～800 DEG C, calcination time is 2～8h, obtains controllable two-phase silico-carbo core shell structure negative material.
Further, the 3- aminopropyls -3- Ethoxysilanes and the mol ratio of the methyl alcohol are 1000：1～5000：1.
Further, the non-crystalline silicon and the mol ratio of the methyl alcohol are 2：1～1：3.
Further, organic pyrolysis carbon raw material be glucose, sucrose, non-crystalline silicon and organic pyrolysis in the aqueous solution
The mass ratio of carbon raw material is 1：3～1：20.
Further, the overall solution volume in step 2 is the 1/2～3/4 of reactor volume.
Further, the inert atmosphere is argon gas or nitrogen.
The power lithium-ion battery silicon-carbon cathode material structure that the present invention is provided, is a kind of nuclear shell structure nano composite wood
Material.Carbon shell is located at outside the two-phase silicon, and two-phase silicon is monocrystalline silicon nanocrystal Dispersed precipitate structure in non-crystalline silicon phase, this
The advantage of structure is：On the one hand, outermost carbon shell can obviously improve the electric conductivity of silicon, and it is swollen to limit its outside volume
It is swollen；On the other hand, the elastic ruckbildung in non-crystalline silicon charging process can effectively buffer the stress of silicon Volume Changes generation, from
And mitigate electrode volume bulking effect significantly；Meanwhile, the monocrystalline silicon nanocrystal being scattered in non-crystalline silicon can strengthen non-crystalline silicon
Mechanical property so as to which break resistance is improved, so as to further improve the cyclical stability of electrode material.
The power lithium-ion battery that the present invention the is provided preparation method process is simple of silicon-carbon cathode material structure, environment friend
It is good, it is easy to accomplish industrialized production.
Description of the drawings
Invention is described further below in conjunction with the accompanying drawings：
Fig. 1 is the step of the preparation method of power lithium-ion battery silicon-carbon cathode material structure provided in an embodiment of the present invention
Rapid schematic flow sheet；
Fig. 2 is the low power TEM electron microscopic picture of the two-phase silico-carbo core shell structure negative material that the embodiment of the present invention one is provided；
Fig. 3 is the high power TEM electron microscopic picture of the two-phase silico-carbo core shell structure negative material that the embodiment of the present invention one is provided；
Fig. 4 is charging and discharging curve figure of first three time of the lithium ion battery of the offer of the embodiment of the present invention one；
Fig. 5 is the capacity versus cycle frequency curve figure of 50 circulations before the lithium ion battery that the embodiment of the present invention one is provided；
The X-ray diffractogram of gained sample under the different calcining heats that Fig. 6 is provided for the present invention.
Specific embodiment
Power lithium-ion battery proposed by the present invention is tied with silicon-carbon cathode material below in conjunction with the drawings and specific embodiments
Structure and preparation method thereof is described in further detail.According to following explanation and claims, advantages and features of the invention will
Become apparent from.It should be noted that, accompanying drawing in the form of simplifying very much and uses non-accurately ratio, only to convenient, bright
The purpose of the embodiment of the present invention is aided in illustrating clearly.
The core concept of the present invention is that the power lithium-ion battery silicon-carbon cathode material structure that the present invention is provided is
A kind of nuclear-shell structured nano-composite material.Carbon shell is located at outside the two-phase silicon, and two-phase silicon is monocrystalline silicon nanocrystal disperse point
Cloth structure in non-crystalline silicon phase, the advantage of this structure is：On the one hand, outermost carbon shell can obviously improve the conduction of silicon
Property, and limit its outside volumetric expansion；On the other hand, the elastic ruckbildung in non-crystalline silicon charging process can effectively be delayed
The stress of silicon Volume Changes generation is rushed, so as to mitigate electrode volume bulking effect significantly；Meanwhile, the monocrystalline being scattered in non-crystalline silicon
Silicon nanocrystal can strengthen the mechanical property of non-crystalline silicon so as to which break resistance is improved, so as to further improve electrode material
Cyclical stability.The power lithium-ion battery that the present invention the is provided preparation method process is simple of silicon-carbon cathode material structure, ring
Border is friendly, it is easy to accomplish industrialized production.
The present invention provides a kind of power lithium-ion battery silicon-carbon cathode material structure, including：Two-phase silicon, is that monocrystalline silicon is received
Meter Jing is distributed in non-crystalline silicon phase, and in Kiwi berry shape, the weight of the monocrystalline silicon nanocrystal is 20% to 50% than scope；Carbon shell
Layer, is the carbon coating layer of organic matter formation Jing after polycondensation, carbonization, outside the two-phase silicon, the weight ratio of the carbon shell
Scope is 15% to 45%.
In embodiments of the present invention, power lithium-ion battery a diameter of 70～150nm of silicon-carbon cathode material structure, institute
The thickness for stating carbon shell is 5～25nm, and the size of the silicon nanocrystal is 4～10nm.
Fig. 1 is the step of the preparation method of power lithium-ion battery silicon-carbon cathode material structure provided in an embodiment of the present invention
Rapid schematic flow sheet.With reference to Fig. 1, a kind of power lithium-ion battery that the present invention is provided preparation side of silicon-carbon cathode material structure
Method, comprises the steps：
Under S11, room temperature, non-crystalline silicon is added in deionized water, magnetic agitation 0.5～2 hour, form aaerosol solution, then
Methyl alcohol, 3- aminopropyl -3- Ethoxysilanes are respectively dropped into, are stirred 2～3 hours, form mixed solution, reuse the side of centrifugation
Formula collecting reaction product, is washed respectively with ethanol and deionized water, is dried, and obtains the modified non-crystalline silicon in surface；
S12, the modified non-crystalline silicon is added in the aqueous solution containing organic pyrolytic carbon raw material, stirred 0.5～2 hour
After pour in reactor, be warming up to 160～200 DEG C, 2～8h of insulation terminates to reacting, using centrifugation collecting reaction product,
Washed with ethanol and deionized water respectively, be dried；
S13, the product of S12 is placed in refractory container, 500～800 DEG C, during calcining are fired under inert atmosphere protection
Between be 2～8h, obtain controllable two-phase silico-carbo core shell structure negative material.
In embodiments of the present invention, the 3- aminopropyls -3- Ethoxysilanes and the mol ratio of the methyl alcohol are 1000：1
～5000：1, the non-crystalline silicon is 2 with the mol ratio of the methyl alcohol：1～1：3, organic pyrolysis carbon raw material is glucose, sugarcane
Sugar, non-crystalline silicon and the mass ratio of organic pyrolysis carbon raw material are 1 in the aqueous solution：3～1：20.
Overall solution volume in S12 be reactor volume 1/2～3/4, S13 described in inert atmosphere be argon gas or nitrogen.
Embodiment one
The preparation of negative material：Under room temperature, 100mg non-crystalline silicons are added in deionized water, magnetic agitation 1 hour is formed
Aaerosol solution；Then again by 10ml methyl alcohol, that 80 μ l APTES (3- aminopropyl -3- Ethoxysilanes) are respectively dropped into above-mentioned suspension is molten
In liquid, stir 3 hours, form mixed solution.Then reuse the mode collecting reaction product of centrifugation, respectively with ethanol and go from
Sub- water washing, is dried；The modified non-crystalline silicon in surface is obtained.Add 10ml pure above-mentioned modified 100mg non-crystalline silicons
Stir in water purification, add 400mg glucose, strong stirring 2 hours；Then it is poured in reactor, is warming up to 180 DEG C,
Insulation 4h, reaction terminates；Using centrifugation collecting reaction product, washed with ethanol and deionized water respectively, be dried.By drying
Product afterwards is laid in corundum porcelain boat (can replace corundum porcelain boat with other refractory containers), is fired under inert atmosphere protection
600 DEG C, calcination time is 4h, after cooling, you can obtain two-phase silico-carbo core shell structure negative material.
Fig. 2 is the low power TEM electron microscopic picture of the two-phase silico-carbo core shell structure negative material that the embodiment of the present invention one is provided.
With reference to Fig. 2, gained negative material core shell structure, the complete coated Si core 21 of carbon shell 22, composite construction is a diameter of：70～150nm.Figure
3 is the high power TEM electron microscopic picture of the two-phase silico-carbo core shell structure negative material that the embodiment of the present invention one is provided.With reference to Fig. 3, core
With the presence of monocrystalline silicon, in amorphous silicon, orientation differs its Dispersed precipitate center portion point between monocrystalline silicon crystal grain, a diameter of 4～10nm.
The preparation of electrode：By products therefrom and carbon black, polyacrylic acid according to 7：2：1 weight than mixing, then with nitrogen-methyl
Pyrrolidone solution mixes, and with n-methlpyrrolidone slurry viscosity is adjusted, and is then passing through slurry with scraper uniform application
On the Copper Foil of alcohol washes, it is vacuum dried 12 hours at 120 DEG C, then through compressing tablet, cutting is obtained Electrode.
Electrode performance is tested：Performance test is carried out in fastening lithium ionic cell.Battery assembling mode is as follows：With lithium piece work
It is that, to electrode, used as barrier film, electrolyte is using the EC-DEC-EMC (1 containing 1M LiPF6 for Celgard2300：1：1) solution,
LiPF6 is lithium hexafluoro phosphate, and EC is ethylene carbonate, and EMC is methyl ethyl ester.During test, temperature is room temperature, using perseverance
Stream discharge and recharge, current density is 50mA/g, and control reference voltage is 0～1.5V.
Fig. 4 is charging and discharging curve figure of first three time of the lithium ion battery of the offer of the embodiment of the present invention one.With reference to Fig. 4, first three
Secondary charging and discharging curve is followed successively by：For the first time 41, second 42, third time 43, the lithium capacity embedding first of products obtained therefrom is
2187mAh/g, reversible de- lithium capacity is 1388mAh/g, and initial coulomb efficiency is 64%.Fig. 5 is provided for the embodiment of the present invention one
Lithium ion battery before 50 times circulation capacity versus cycle frequency curve figure.With reference to Fig. 5, round dot is represented and charged, and square is represented and put
Electricity.Reversible lithium insertion capacity is 1179mAh/g after 50 circulations.
Embodiment 2
The preparation of negative material：Under room temperature, 200mg non-crystalline silicons are added in deionized water, magnetic agitation 2 hours is formed
Aaerosol solution；Then again by 20ml methyl alcohol, that 80 μ l APTES (3- aminopropyl -3- Ethoxysilanes) are respectively dropped into above-mentioned suspension is molten
In liquid, stir 2 hours, form mixed solution.Then reuse the mode collecting reaction product of centrifugation, respectively with ethanol and go from
Sub- water washing, is dried；The modified non-crystalline silicon in surface is obtained.Add 10ml pure above-mentioned modified 200mg non-crystalline silicons
Stir in water purification, add 400mg sucrose, strong stirring 1 hour；Then it is poured in reactor, is warming up to 180 DEG C, protects
Warm 4h, reaction terminates；Using centrifugation collecting reaction product, washed with ethanol and deionized water respectively, be dried.After being dried
Product be laid in corundum porcelain boat (corundum porcelain boat can be replaced with other refractory containers), be fired under inert atmosphere protection
650 DEG C, calcination time is 4h, after cooling, you can obtain two-phase silico-carbo core shell structure negative material.
Embodiment 3
The preparation of negative material：Under room temperature, 50mg non-crystalline silicons are added in deionized water, magnetic agitation 1 hour, form outstanding
Floating solution；Then again 10ml methyl alcohol, 80 μ l APTES (3- aminopropyl -3- Ethoxysilanes) are respectively dropped into into above-mentioned aaerosol solution
In, stir 2 hours, form mixed solution.The mode collecting reaction product of centrifugation is then reused, respectively with ethanol and deionization
Water washing, is dried；The modified non-crystalline silicon in surface is obtained.Above-mentioned modified 50mg non-crystalline silicons are added into 20ml pure water
Middle stirring, adds 300mg glucose, strong stirring 1 hour；Then it is poured in reactor, is warming up to 200 DEG C, insulation
4h, reaction terminates；Using centrifugation collecting reaction product, washed with ethanol and deionized water respectively, be dried.Will be dried
Product is laid in corundum porcelain boat (can replace corundum porcelain boat with other refractory containers), and under inert atmosphere protection 600 are fired to
DEG C, calcination time is 4h, after cooling, you can obtain two-phase silico-carbo core shell structure negative material.
Embodiment 4
The preparation of negative material：Under room temperature, 300mg non-crystalline silicons are added in deionized water, magnetic agitation 2 hours is formed
Aaerosol solution；Then again 10ml methyl alcohol, 160 μ l APTES (3- aminopropyl -3- Ethoxysilanes) are respectively dropped into into above-mentioned suspension
In solution, stir 2 hours, form mixed solution.The mode collecting reaction product of centrifugation is then reused, respectively with ethanol and going
Ion water washing, is dried；The modified non-crystalline silicon in surface is obtained.Above-mentioned modified 250mg non-crystalline silicons are added into 15ml
Stir in pure water, add 600mg sucrose, strong stirring 1 hour；Then it is poured in reactor, is warming up to 160 DEG C,
Insulation 8h, reaction terminates；Using centrifugation collecting reaction product, washed with ethanol and deionized water respectively, be dried.By drying
Product afterwards is laid in corundum porcelain boat (can replace corundum porcelain boat with other refractory containers), is fired under inert atmosphere protection
800 DEG C, calcination time is 6h, after cooling, you can obtain two-phase silico-carbo core shell structure negative material.
Embodiment 5
The preparation of negative material：Under room temperature, 400mg non-crystalline silicons are added in deionized water, magnetic agitation 2 hours is formed
Aaerosol solution；Then again 40ml methyl alcohol, 200 μ l APTES (3- aminopropyl -3- Ethoxysilanes) are respectively dropped into into above-mentioned suspension
In solution, stir 3 hours, form mixed solution.The mode collecting reaction product of centrifugation is then reused, respectively with ethanol and going
Ion water washing, is dried；The modified non-crystalline silicon in surface is obtained.Above-mentioned modified 400mg non-crystalline silicons are added into 30ml
Stir in pure water, add 500mg glucose, strong stirring 1 hour；Then it is poured in reactor, is warming up to 200
DEG C, 8h is incubated, reaction terminates；Using centrifugation collecting reaction product, washed with ethanol and deionized water respectively, be dried.Will
Dried product is laid in corundum porcelain boat (can replace corundum porcelain boat with other refractory containers), is forged under inert atmosphere protection
Burn to 550 DEG C, calcination time is 8h, after cooling, you can obtain two-phase silico-carbo core shell structure negative material.
The X-ray diffractogram of gained sample under the different calcining heats that Fig. 6 is provided for the present invention.With reference to Fig. 6, amorphous silicon
Particle is raised with temperature, and diffraction peak type narrows, and intensity increases, and illustrates to there occurs crystallization conversion, generates nano silicon crystal.With
Temperature is raised, and highest peak (111) crystal face is moved to left, and interplanar distance increase, crystal formation is more stable.Knowable to XRD results, by adjusting
Calcining heat, it is possible to achieve monocrystalline silicon is controllable with amorphous silicon components in two-phase silicon structure.
Obviously, those skilled in the art can carry out various changes to the present invention and deform the essence without deviating from the present invention
God and scope.So, if these modifications of the present invention and modification belong to the scope of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to comprising these changes and modification.
Claims (10)
1. a kind of power lithium-ion battery silicon-carbon cathode material structure, it is characterised in that include：
Two-phase silicon, is that monocrystalline silicon nanocrystal is distributed in non-crystalline silicon phase, in Kiwi berry shape, the weight ratio of the monocrystalline silicon nanocrystal
Scope is 20% to 50%；
Carbon shell, is the carbon coating layer of organic matter formation Jing after polycondensation, carbonization, outside the two-phase silicon, the carbon shell
Weight than scope be 15% to 45%.
2. power lithium-ion battery as claimed in claim 1 silicon-carbon cathode material structure, it is characterised in that its a diameter of 70
～150nm.
3. power lithium-ion battery as claimed in claim 1 silicon-carbon cathode material structure, it is characterised in that the carbon shell
Thickness be 5～25nm.
4. power lithium-ion battery as claimed in claim 1 silicon-carbon cathode material structure, it is characterised in that the silicon nanometer
Brilliant size is 4～10nm.
5. a kind of power lithium-ion battery as claimed in claim 1 preparation method of silicon-carbon cathode material structure, its feature
It is to comprise the steps：
Under step one, room temperature, non-crystalline silicon is added in deionized water, magnetic agitation 0.5～2 hour, form aaerosol solution, then will
Methyl alcohol, 3- aminopropyl -3- Ethoxysilanes are respectively dropped into, and stir 2～3 hours, form mixed solution, reuse the mode of centrifugation
Collecting reaction product, is washed respectively with ethanol and deionized water, is dried, and obtains the modified non-crystalline silicon in surface；
Step 2, the modified non-crystalline silicon is added in the aqueous solution containing organic pyrolytic carbon raw material, stirred 0.5～2 hour
After pour in reactor, be warming up to 160～200 DEG C, 2～8h of insulation terminates to reacting, using centrifugation collecting reaction product,
Washed with ethanol and deionized water respectively, be dried；
Step 3, the product of step 2 is placed in refractory container, 500～800 DEG C is fired under inert atmosphere protection, calcining
Time is 2～8h, obtains controllable two-phase silico-carbo core shell structure negative material.
6. the power lithium-ion battery as claimed in claim 5 preparation method of silicon-carbon cathode material structure, it is characterised in that
3- aminopropyls -3- the Ethoxysilanes are 1000 with the mol ratio of the methyl alcohol：1～5000：1.
7. the power lithium-ion battery as claimed in claim 5 preparation method of silicon-carbon cathode material structure, it is characterised in that
The non-crystalline silicon is 2 with the mol ratio of the methyl alcohol：1～1：3.
8. the power lithium-ion battery as claimed in claim 5 preparation method of silicon-carbon cathode material structure, it is characterised in that
Organic pyrolysis carbon raw material is glucose, sucrose, and non-crystalline silicon is with the mass ratio of organic pyrolysis carbon raw material in the aqueous solution
1：3～1：20.
9. the power lithium-ion battery as claimed in claim 5 preparation method of silicon-carbon cathode material structure, it is characterised in that
Overall solution volume in step 2 is the 1/2～3/4 of reactor volume.
10. the power lithium-ion battery as claimed in claim 5 preparation method of silicon-carbon cathode material structure, its feature exists
In the inert atmosphere is argon gas or nitrogen.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102376944A (en) * | 2011-11-24 | 2012-03-14 | 深圳市贝特瑞新能源材料股份有限公司 | Method for preparing silicon carbide alloy negative electrode material for lithium ion battery |
| CN102709531A (en) * | 2012-01-09 | 2012-10-03 | 宁德新能源科技有限公司 | Lithium ion battery and cathode thereof |
| CN103904307A (en) * | 2012-12-24 | 2014-07-02 | 宁波杉杉新材料科技有限公司 | Silicon-carbon composite material, preparation method and application thereof |
| CN105489855A (en) * | 2015-11-25 | 2016-04-13 | 天津师范大学 | Core-shell silicon carbon composite negative electrode material for high-capacity type lithium ion battery and preparation method therefor |
| CN105895873A (en) * | 2016-04-15 | 2016-08-24 | 华南师范大学 | Silicon/carbon compound anode material for lithium ion battery as well as preparation method and application thereof |
-
2016
- 2016-11-17 CN CN201611025046.4A patent/CN106654241A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102376944A (en) * | 2011-11-24 | 2012-03-14 | 深圳市贝特瑞新能源材料股份有限公司 | Method for preparing silicon carbide alloy negative electrode material for lithium ion battery |
| CN102709531A (en) * | 2012-01-09 | 2012-10-03 | 宁德新能源科技有限公司 | Lithium ion battery and cathode thereof |
| CN103904307A (en) * | 2012-12-24 | 2014-07-02 | 宁波杉杉新材料科技有限公司 | Silicon-carbon composite material, preparation method and application thereof |
| CN105489855A (en) * | 2015-11-25 | 2016-04-13 | 天津师范大学 | Core-shell silicon carbon composite negative electrode material for high-capacity type lithium ion battery and preparation method therefor |
| CN105895873A (en) * | 2016-04-15 | 2016-08-24 | 华南师范大学 | Silicon/carbon compound anode material for lithium ion battery as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 曲喜新等: "《电子薄膜材料》", 31 October 1996 * |
| 王阳元等: "《多晶硅薄膜及其在集成电路中的应用》", 31 August 1988 * |
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