CN110336003A - A kind of porous silicon-base composite material and preparation method and application - Google Patents
A kind of porous silicon-base composite material and preparation method and application Download PDFInfo
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- CN110336003A CN110336003A CN201910573914.XA CN201910573914A CN110336003A CN 110336003 A CN110336003 A CN 110336003A CN 201910573914 A CN201910573914 A CN 201910573914A CN 110336003 A CN110336003 A CN 110336003A
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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
- H01M4/362—Composites
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 kind of porous silicon-base composite material and its preparations and application.The porous silicon-base composite material is the nano silicon particles and amorphous Si O loaded by porous silicon network skeleton and thereonxNano particle is constituted, and wherein porous silicon network skeleton partial size is 2~50 μm, and aperture is 10~500nm, and nano silicon particles partial size is 1~100nm, SiOxNano particle diameter is 1~100nm, 0 < x≤2.Application the present invention provides the porous silicon-base composite material as lithium ion battery negative material can significantly improve the cyclical stability of silicon-based anode when the porous silicon-base composite material is applied to lithium ion battery negative material.
Description
(1) technical field
The present invention relates to lithium ion battery negative material fields, and in particular to a kind of porous silicon-base composite material and its preparation
Methods and applications.
(2) background technique
The emerging markets such as electric car and plug-in hybrid-power automobile to high-energy density, have extended cycle life and low cost
Lithium ion battery produce huge demand.Graphite is the most common negative electrode material of commercial li-ion battery, since its is lower
Theoretical capacity (372mAh g-1) and be unable to satisfy the performance requirement of high-energy density.Therefore, silicon is because of its high theoretical capacity
(4200mAh g-1) and lower charge and discharge potential (< 0.5Vvs.Li/Li+) and obtain extensive concern, it is considered to be most there is application
One of next-generation lithium ion battery negative material of prospect.However, biggish volume change (> 300%) can lead in process of intercalation
It causes silicon materials rupture, dusting, fall off, eventually lead to capacity attenuation.
In order to overcome the problems, such as that silicon-based anode cyclical stability is poor, porous silica material is normally used for improving its storage lithium
Energy.Because stress caused by silicon volume expansion can be effectively relieved in duct abundant in Porous Silicon structures, so that it is steady to promote circulation
It is qualitative；Moreover, biggish specific surface area, which is also beneficial to electrolyte, preferably infiltrates active material, shorten the diffusion of lithium ion away from
From to obtain excellent high rate performance.As a kind of common porous silicon preparation method, there are many reports for magnesiothermic reduction, but
It is that the magnesium reduction process reported in current document or patent usually has the problems such as low yield, method is cumbersome, and needs to use
The acid solution of the strong corrosives such as hydrofluoric acid has certain risk.CN102259858A discloses a kind of magnesiothermic reduction preparation
The method of porous silicon, this method is with the oxide S iO of siliconx(x=0.5-2) be raw material, by magnesiothermic reduction react generate silicon and
The mixture of magnesia reuses sour selective dissolution and falls magnesia, the final porous silica material for obtaining self-supporting, scanning electricity
Mirror figure shows that product has nano-porous structure, and even aperture distribution；And the XRD diffraction spectrum analysis of material is it is found that this has
The product of nano-porous structure is made of the nano silicon crystal of cubic phase.The preparation method of the porous silicon although reduce costs and
Yield is improved, and preparation process is simple, environmental-friendly, preparation efficiency is high, reproducible, but prepared porous silica material
For lithium ion battery negative material, cyclical stability is still to be improved.
(3) summary of the invention
The first purpose of the invention is to provide a kind of porous silicon-base composite material, the porous silicon-base composite material it is porous
Load has nano silicon particles and unformed SiO on silicon skeletonx(0 < x≤2) nano particle.
A second object of the present invention is to provide a kind of porous silicon-base composite woods environmental-friendly, easy to operate and high yield
The preparation method of material.
Third object of the present invention is to provide the porous silicon-base composite materials as lithium ion battery negative material
Using greatly improving the cyclical stability of silicon-based anode.
For achieving the above object, the present invention adopts the following technical scheme:
It is by porous silicon network skeleton and thereon in a first aspect, the present invention provides a kind of porous silicon-base composite material
The nano silicon particles and amorphous Si O of loadxNano particle is constituted, and wherein porous silicon network skeleton partial size is 2~50 μm, hole
Diameter is 10~500nm, and nano silicon particles partial size is 1~100nm, SiOxNano particle diameter is 1~100nm, 0 < x≤2.
Second aspect, the present invention provides a kind of preparation methods of porous silicon-base composite material, follow the steps below:
1) by SiOy(0 < y≤2), metal powder reduction agent and fused salt are uniformly mixed according to molar ratio 1:0.1~5:0.1~10
It closes, obtains mixture；The SiOyIn, 0 < y≤2, the metal powder reduction agent is magnesium powder or aluminium powder；
2) mixture for obtaining step 1) is transferred in tube furnace, is warming up to 400~1000 under inert atmosphere protection
DEG C, reaction is cooled to room temperature after 0.2~12 hour, obtains reaction product；
3) reaction product is placed in etching removal byproduct of reaction, the acid in the aqueous solution of the acid of 0.1~10mol/L
For any one or any several arbitrary proportion mixed acid in hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, through centrifugation, washing and
Porous silicon-base composite material is obtained after drying.
In the present invention, the SiOyFor appointing in the Si oxide of silicon monoxide, silica and non-stoichiometric
The mixture for one or more of anticipating.
In the present invention, the fused salt is preferably NaCl, KCl, MgCl2、CaCl2、BaCl2、AlCl3In any one
Or several mixtures mixed with arbitrary proportion.
In the present invention, the SiOy, metal powder reduction agent and fused salt mixing molar ratio be preferably 1:0.5~5:5~
10, most preferably 1:1:10.
In step 2) of the present invention, preferable reaction temperature is 600~800 DEG C, and the reaction time is 2~8 hours；Most preferably react
700 DEG C of temperature, reaction time 5h.
In step 2) of the present invention, the inert atmosphere is preferably argon gas, nitrogen or argon gas and nitrogen arbitrary proportion
Gaseous mixture.
The third aspect, the present invention provides porous silicon-base composite material the answering as lithium ion battery negative material
With.When the porous silicon-base composite material is applied to lithium ion battery negative material, the circulation of silicon-based anode can be significantly improved
Stability.
Compared with prior art, the invention has the benefit that
The preparation method of porous silicon-base composite material of the present invention, unexpectedly load has been gone up silicon and has been received on porous silicon skeleton
Rice grain and amorphous Si OxNano particle not only has higher yield, but also when it is used for lithium ion battery negative material,
The cyclical stability of silicon-based anode can be significantly improved, while there is excellent high rate performance.
Detailed description of the invention
Fig. 1 is the XRD diagram of porous silicon-base composite material in embodiment 1.
Fig. 2 is the TEM figure of porous silicon-base composite material in embodiment 1.
Fig. 3 is the cycle performance of battery figure of porous silicon-base composite material in embodiment 1.
Fig. 4 is the battery high rate performance figure of porous silicon-base composite material in embodiment 1.
Fig. 5 is the cycle performance of battery figure of porous silicon-base composite material in embodiment 2.
Fig. 6 is the cycle performance of battery figure of porous silicon-base composite material in embodiment 3.
Fig. 7 is the cycle performance of battery figure of porous silicon-base composite material in comparative example 1.
Fig. 8 is the SEM figure for the porous silica material being prepared in comparative example 2.
Fig. 9 is the cycle performance of battery figure for the porous silica material being prepared in comparative example 2.
Specific embodiment
With specific embodiment, technical scheme is described further below, but protection scope of the present invention is unlimited
In this:
Embodiment 1:
(1) preparation of porous silicon-base composite material
By SiOy(y ≈ 1) presoma, metal powder Mg and fused salt NaCl are uniformly mixed according to molar ratio 1:1:10；It will mix
It closes object to be transferred in tube furnace, 700 DEG C is warming up under inert atmosphere protection, reaction is cooled to room temperature after 5 hours, is reacted
Product；Reaction product is placed in etching removal byproduct of reaction in the hydrochloric acid solution of 1mol/L, through centrifugation, washing and 80 DEG C of vacuum
Porous silicon-base composite material can be obtained after drying.
(2) preparation of electrode slice
Obtained porous silicon-base composite material, acetylene black, CMC binder are mixed according to weight ratio 7:1.5:1.5, preparation
It at slurry and is applied in copper foil current collector, obtains electrode slice in 60 DEG C of dry 10h under vacuum conditions.It is with metal lithium sheet
To electrode, with the LiPF of 1M6EC/DEC (VEC:VDEC=1:1) solution as electrolyte, is assembled into button cell.It will assemble
Lithium ion battery charge and discharge cycles test is carried out with different current density in 0.01~1.0V voltage range.
Fig. 1 is the XRD spectra of the obtained porous silicon-base composite material in the present embodiment, as can be seen from the figure broad peak
Corresponding to unbodied SiOx, the peak of crystalline silicon is then corresponding with silicon standard card.Fig. 2 is obtained porous in the present embodiment
The TEM of silicon based composite material schemes, and can be observed to have loaded many nano particles on the network skeleton of porous silicon, wherein in nano-silicon
In crystal grain it is observed thatInterplanar distance, and amorphous Si OxNano particle does not observe lattice fringe then.Fig. 3 and
Fig. 4 is the battery performance figure of the obtained porous silicon-base composite material in the present embodiment, shows excellent cyclical stability
And high rate performance, in 4Ag-1Current density under at the 500th week be still able to maintain 958mAh g-1Reversible capacity.
Embodiment 2:
By SiOy(y ≈ 2) presoma, metal powder Al and fused salt AlCl3It is uniformly mixed according to molar ratio 1:5:8；It will mixing
Object is transferred in tube furnace, and 650 DEG C are warming up under inert atmosphere protection, and reaction is cooled to room temperature after 3 hours, is obtained reaction and is produced
Object；Reaction product is placed in etching removal byproduct of reaction in the sulfuric acid solution of 0.1mol/L, it is true through centrifugation, washing and 100 DEG C
Porous silicon-base composite material can be obtained after sky is dry.
Electrode, assembled battery are prepared by the method in embodiment 1, and carries out charge and discharge cycles test.
Embodiment 3:
By SiOy(y ≈ 1.5) presoma, metal powder Mg and fused salt KCl are uniformly mixed according to molar ratio 1:2:7；It will mix
It closes object to be transferred in tube furnace, 500 DEG C is warming up under inert atmosphere protection, reaction is cooled to room temperature after 3 hours, is reacted
Product；Reaction product is placed in etching removal byproduct of reaction in the nitric acid solution of 2mol/L, through centrifugation, washing and 90 DEG C of vacuum
Porous silicon-base composite material can be obtained after drying.
Electrode, assembled battery are prepared by the method in embodiment 1, and carries out charge and discharge cycles test.
Comparative example 1:
By SiOy(y ≈ 0.7) presoma, metal powder Mg are uniformly mixed according to molar ratio 1:0.1；Mixture is transferred to
In tube furnace, 800 DEG C are warming up under inert atmosphere protection, reaction is cooled to room temperature after 0.2 hour, obtains reaction product；It will
Reaction product is placed in etching removal byproduct of reaction in the acetum of 10mol/L, after centrifugation, washing and 90 DEG C of vacuum drying
Porous silicon-base composite material can be obtained.
Electrode, assembled battery are prepared by the method in embodiment 1, and carries out charge and discharge cycles test.
Comparative example 2
Porous silicon is prepared according to the method for CN102259858A embodiment 1:
(1) by SiO powder and magnesium powder, 1:1 is placed in tubular type atmosphere after evenly mixing under protection of argon gas in molar ratio at room temperature
In furnace, 500 DEG C, and isothermal reaction 6 hours are heated in argon gas stream, then cooled to room temperature；
(2) products therefrom is placed in the hydrochloric acid that concentration is 0.1mol/L and is sufficiently impregnated 24 hours, remove magnesia, filtering
After obtain solid product, then first sufficiently cleaned through deionized water, then sufficiently cleaned through dehydrated alcohol, obtain porous silicon after dry
Powder.
Electrode, assembled battery are prepared by the method in embodiment 1, and carries out charge and discharge cycles test.
Fig. 8 is the SEM figure for the porous silica material being prepared in this comparative example, it can be found that sample is porous silicon network bone
Frame, surface have no nano particle load.Fig. 9 is the battery performance figure for the porous silica material being prepared in this comparative example, can
To find that its capacity attenuation is very fast.
The above content is the preferable embodiments of combination to illustrate to what the contents of the present invention were done, but it cannot be assumed that this hair
Bright specific implementation is only defined in the embodiment.To understanding for those skilled in the art in the invention, this is not being departed from
In the case where the Research Thinking of invention, several differentiation and replacement can be also carried out, these are deduced and replacement is all contained in the present invention
In claim limited range.
Claims (10)
1. a kind of porous silicon-base composite material, it is characterised in that: the porous silicon-base composite material is by porous silicon network skeleton
And the nano silicon particles and amorphous Si O loaded thereonxNano particle is constituted, and wherein porous silicon network skeleton partial size is 2
~50 μm, aperture is 10~500nm, and nano silicon particles partial size is 1~100nm, SiOxNano particle diameter be 1~100nm, 0 <
x≤2。
2. a kind of preparation method of porous silicon-base composite material as described in claim 1, follows the steps below:
1) by SiOy, metal powder reduction agent and fused salt uniformly mixed according to molar ratio 1:0.1~5:0.1~10, mixed
Object；The SiOyIn, 0 < y≤2, the metal powder reduction agent is magnesium powder or aluminium powder；
2) mixture for obtaining step 1) is transferred in tube furnace, 400~1000 DEG C is warming up under inert atmosphere protection, instead
It is cooled to room temperature after answering 0.2~12 hour, obtains reaction product；
3) it is salt that reaction product is placed in etching removal byproduct of reaction, the acid in the aqueous solution of the acid of 0.1~10mol/L
Acid, sulfuric acid, nitric acid, acetic acid, any one or any several arbitrary proportion mixed acid in oxalic acid, through centrifugation, washing and drying
Porous silicon-base composite material is obtained afterwards.
3. preparation method as claimed in claim 2, it is characterised in that: the SiOyFor silicon monoxide, silica and non-ization
Learn any one or a few the mixture in the Si oxide of metering ratio.
4. preparation method as claimed in claim 2, it is characterised in that: the fused salt is NaCl, KCl, MgCl2、CaCl2、
BaCl2、AlCl3In any one or a few with arbitrary proportion mix mixture.
5. the preparation method as described in one of claim 2-4, it is characterised in that: the SiOy, metal powder reduction agent and fused salt
Mixing molar ratio be 1:0.5~5:5~10.
6. preparation method as claimed in claim 5, it is characterised in that: the SiOy, metal powder reduction agent and fused salt mixing
Molar ratio is 1:1:10.
7. the preparation method as described in one of claim 2-4, it is characterised in that: in step 2), reaction temperature is 600~800
DEG C, the reaction time is 2~8 hours.
8. preparation method as claimed in claim 7, it is characterised in that: in step 2), 700 DEG C of reaction temperature, the reaction time is
5h。
9. the preparation method as described in one of claim 2-4, it is characterised in that: in step 2), the inert atmosphere is argon
The gaseous mixture of gas, nitrogen or argon gas and nitrogen arbitrary proportion.
10. application of the porous silicon-base composite material as described in claim 1 as lithium ion battery negative material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111082000A (en) * | 2019-11-29 | 2020-04-28 | 湖北万润新能源科技发展有限公司 | Preparation method for optimizing SiOx @ C performance by using pore-forming agent |
| CN112366294A (en) * | 2020-07-31 | 2021-02-12 | 万向一二三股份公司 | Graphite/silicon/carbon composite negative electrode material and preparation method thereof |
| CN113793929A (en) * | 2021-09-16 | 2021-12-14 | 金川集团股份有限公司 | Porous Si/SiOxPreparation and application of composite material |
| CN113800523A (en) * | 2021-09-09 | 2021-12-17 | 哈尔滨工业大学 | Layered porous silicon material and preparation method and application thereof |
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| CN108336342A (en) * | 2018-02-28 | 2018-07-27 | 宁波富理电池材料科技有限公司 | Si/SiOx/C composite negative pole materials, preparation method and lithium ion battery |
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| CN112366294A (en) * | 2020-07-31 | 2021-02-12 | 万向一二三股份公司 | Graphite/silicon/carbon composite negative electrode material and preparation method thereof |
| CN112366294B (en) * | 2020-07-31 | 2022-02-15 | 万向一二三股份公司 | Graphite/silicon/carbon composite negative electrode material and preparation method thereof |
| CN113800523A (en) * | 2021-09-09 | 2021-12-17 | 哈尔滨工业大学 | Layered porous silicon material and preparation method and application thereof |
| CN113793929A (en) * | 2021-09-16 | 2021-12-14 | 金川集团股份有限公司 | Porous Si/SiOxPreparation and application of composite material |
| CN113793929B (en) * | 2021-09-16 | 2024-03-01 | 金川集团股份有限公司 | Porous Si/SiO x Preparation and application of composite material |
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