CN108615854A - A kind of silicon substrate lithium ion battery anode active material and its preparation and application - Google Patents
A kind of silicon substrate lithium ion battery anode active material and its preparation and application Download PDFInfo
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- CN108615854A CN108615854A CN201611129229.0A CN201611129229A CN108615854A CN 108615854 A CN108615854 A CN 108615854A CN 201611129229 A CN201611129229 A CN 201611129229A CN 108615854 A CN108615854 A CN 108615854A
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
A kind of silicon substrate lithium ion battery anode active material of present invention offer and its preparation and application, the silicon substrate lithium ion battery anode active material includes porous reduction-oxidation graphite, and the porous silica material for having coated conducting polymer being attached in porous reduction-oxidation graphite hole gap；The aperture of the porous reduction-oxidation graphite is 50nm~2 μm；The thickness of the conducting polymer clad is 50nm~200nm；The aperture of the porous silicon is 100nm~300nm.The conducting polymer is one or more of polyaniline, polypyrrole, polythiophene.Have when the present invention is applied in negative electrode of lithium ion battery and be not pulverized easily, stability is good, and cycle-index waits remarkable advantages more.
Description
Technical field
The invention belongs to technical field of lithium ion, more particularly to a kind of lithium ion battery anode active material and
Preparation method.
Background technology
Lithium ion battery is a kind of rechargeable battery, moves to have come between positive and negative anodes by lithium ion in charge and discharge process
At work.Application of the lithium ion battery in the energy storage fields such as portable electronic device, power vehicle becomes increasingly popular, and develops higher
The lithium ion battery of energy density and power density is also at the important research direction in current energy storage scientific and technical research.And lithium ion
The further development of battery is heavily dependent on the capacity of negative material and substantially proposing for high magnification heavy-current discharge performance
It rises.Currently, commercialization graphite negative electrodes material limits the promotion of battery capacity due to the bottleneck of theoretical capacity (372mA h/g).
On the other hand, graphite cathode can form Li dendrite in charge and discharge process, and then pierce through diaphragm and lead to battery short circuit or even quick-fried
It is fried, cause threat to safe to use.Therefore, develop large capacity, the negative material of high safety becomes Study on Li-ion batteries
Emphasis.The higher alloy material of cathode of the specific discharge capacities such as aluminium, silicon, tin is by larger concern, wherein silicon is held due to its theory
Amount is up to 4200mA h/g (Li22Si5), and relatively low (the 0.2V vs.Li of intercalation potential+/ Li), it is considered as most potential high energy
Measure negative material.
Although silicon based anode material theoretical discharge capacity is higher and intercalation potential is relatively low, itself there are conductivity compared with
Low (10-3) and diffusion coefficient low (10 of the lithium ion in body phase silicon S/cm-14~10-13cm2/ s) the shortcomings that.And it is caused to follow
Ring performance declines main the reason is that silicon volume expansion during embedding lithium is up to 300%, and de- lithium is shunk in the process, in turn
Material dusting, material is lost with collector to be in electrical contact, and the LiPF in the silicon face and electrolyte being exposed6It decomposes and generates
HF react, prevent silicon face from forming stable cabinet dielectric film, constantly consume electrolyte, cause circulating battery steady
Qualitative and cycle performance is deteriorated.In view of the above-mentioned problems, researchers propose various micro-/micro-nano structures and table/interfacial structure to silicon
It is modified, including：1. nano-particle, nucleocapsid etc.；2. porous silicon；3. nano wire, nanotube, nanofiber etc.；4. silicon
Base complex, including silicon/carbon, silicon/polymer, silicon/metal, silicon/intermetallic compound.In recent years, the research of silicon-based anode
Achieve significant progress and great breakthrough：The nanostructure for being inspired and being designed by garnet is recycled with C/2 rate charge-discharges
1000 times, specific capacity and volume capacity respectively reach 1160mA h/g and 1270mA h/cm3；Micropore Si/C materials are in 400mA/g
Charge and discharge cycles 150 times under current density, specific capacity and volume capacity are respectively 1600mA h/g and 1088mA h/cm3；It is low at
Originally, bivalve Si@SiOx@C nucleocapsids recycle 100 specific capacities under 100mA/g and 500mA/g current densities and respectively reach
1450mA h/g and 1230mA h/g.
Invention content
In view of the problems of the existing technology the present invention, has invented a kind of silicon substrate lithium ion battery anode active material, should
Have when material is applied in negative electrode of lithium ion battery and is not pulverized easily, the advantages that stability is good, and cycle-index is more.The present invention uses
Scheme is realized in detail below：
A kind of silicon substrate lithium ion battery anode active material, including porous reduction-oxidation graphite, and it is attached to porous reduction
The porous silica material for having coated conducting polymer in graphite oxide hole；The aperture of the porous reduction-oxidation graphite is 50nm
~2 μm；The thickness of the conducting polymer clad is 50nm~200nm；The aperture of the porous silicon is 100nm~300nm.
The conducting polymer is one or more of polyaniline, polypyrrole, polythiophene.
The mass ratio of the porous reduction-oxidation graphite and porous silicon is 1:2~2:1；The conducting polymer with it is described more
The mass ratio of hole silicon is 1:10~1:5.
The pore volume of the porous reduction-oxidation graphite is 1~2cm3/g；The pore volume of the porous silicon is 0.5~1cm3/
g。
The preparation method of the silicon substrate lithium ion battery anode active material, includes the following steps,
(1) preparation of porous silica material：Using mesoporous silicon based molecular sieve as raw material, porous silicon is prepared using magnesium reduction；
(2) preparation of the porous silica material of conducting polymer cladding：It is added prepared by step (1) in ethanol water
The dilute hydrochloric acid solution of aniline is added, by institute in porous silicon and surfactant (cetyl trimethylammonium bromide) after mixing
Obtain the aqueous solution progress polymerisation that mixed solution is placed in addition ammonium persulfate under the conditions of -4 to 4 degrees Celsius of ice-water bath, reaction
After washing, dry conducting polymer cladding porous silicon；
(3) preparation of silicon substrate lithium ion battery negative material：Conducting polymer obtained by step (2) is added in deionized water
The porous silicon of cladding and porous reduction-oxidation graphite filter to obtain silicon substrate lithium ion battery negative material after ultrasonic disperse.
It is specially 1 by molar ratio that step (1) described magnesium reduction, which prepares porous silicon,:1~2:1 mesoporous silicon based molecular sieve
With after magnesium powder mixed grinding in volume ratio 5-10：It is roasted in the mixed atmosphere of 95-90 hydrogen and inert gas, at 650~750 DEG C
Postcooling is to room temperature；Gained product of roasting is handled using acid solution, washs, dry to obtain porous silicon.
The inert gas is the gaseous mixture of one or more of argon gas, nitrogen；The acid processing procedure is first
Product of roasting is handled using the dilute hydrochloric acid of a concentration of 1~2mol/L, using a concentration of 5~10wt.% hydrofluoric acid into
Row etching processing；The drying temperature is 60~100 DEG C；The roasting time is 5~7 hours.
The volumetric concentration of ethyl alcohol is 5~10% in step (2) described ethanol water；The matter of porous silicon and surfactant
Amount is than being 1:1~2:1；Whole mass concentration 1~10mg/mL of the porous silicon in ethanol water；The hydrochloric acid solution of the aniline
The mass content of middle aniline is 5~10mg/mL, a concentration of 0.5~2mol/L of hydrochloric acid；Mistake in the aqueous solution of the ammonium persulfate
The mass content of ammonium sulfate is 5~10mg/mL；The quality of the ammonium persulfate and the mass ratio of aniline in the mixed solution are
1:1~3:1；The reaction time is 5~10h, and the condition of the drying process is vacuum drying 12 at 60-80 DEG C~for 24 hours；
The surfactant is one in cetyl trimethylammonium bromide, cetyl dimethyl benzyl ammonium bromide
Kind.
The porous reduction-oxidation graphite synthesis：First Hummer methods is used to synthesize graphite oxide, then is diluted to a concentration of
Then 0.5~1.5mg/mL, ultrasonic disperse 1h or more are freeze-dried 2~4 days, obtain porous oxidation graphite；Then, 1000
H at~1200 DEG C21h or more is restored in atmosphere, obtains porous reduction-oxidation graphite.
The silicon substrate lithium ion battery anode active material is applied in negative electrode of lithium ion battery.
Compared with prior art, the present invention having the advantage that：The conduction that this patent is supported with porous reduction-oxidation graphite
Polymer overmold porous silicon forms flexible clad in porous silicon surface, and porous reduction-oxidation graphite provides skeleton, increases conductive
Volume expansion of the silicon in charge and discharge process can be accommodated while property.Porous silicon restores sial type molecule by magnesium at high temperature
Prepared by sieve, molecular sieve is made to still maintain its pore passage structure after being reduced.Then use chemical oxidative polymerization in porous silicon surface
Coat flexible conductive polymer.Have when the present invention is applied in negative electrode of lithium ion battery and be not pulverized easily, stability is good, cycle time
Number waits remarkable advantages.
Description of the drawings
Fig. 1 is the SEM figures of porous silicon prepared by SBA15 reduction；
Fig. 2 is the XRD diagram of porous silicon prepared by SBA15 reduction.
Specific implementation mode
Embodiment 1
The aperture of porous silicon obtained by the above method is 100nm~300nm, and pore volume is 0.5~1cm3/ g, conduction are poly-
The thickness for closing object clad is 50nm~200nm, and the aperture of porous reduction-oxidation graphite is 50nm~2 μm, pore volume is 1~
2cm3/g。
Embodiment 2
Above-mentioned final product is assembled into lithium ion battery as negative electrode active material, in 0.01~1.5V voltage ranges
The discharge capacity for the first time of charge and discharge under interior, 200mA/g current densities, battery reaches 2000~3000mAh/g, recycles it 200 times
Capacity retention ratio is up to 85~90% afterwards.
Claims (10)
1. a kind of silicon substrate lithium ion battery anode active material, it is characterised in that：Including porous reduction-oxidation graphite, and it is attached to
The porous silica material for having coated conducting polymer in porous reduction-oxidation graphite hole gap；The hole of the porous reduction-oxidation graphite
Diameter is 50nm~2 μm；The thickness of the conducting polymer clad is 50nm~200nm；The aperture of the porous silicon is 100nm
~300nm.
2. silicon substrate lithium ion battery anode active material as described in claim 1, it is characterised in that：The conducting polymer is poly-
One or more of aniline, polypyrrole, polythiophene.
3. silicon substrate lithium ion battery anode active material as described in claim 1, it is characterised in that：The porous oxygen reduction fossil
The mass ratio of ink and porous silicon is 1:2~2:1；The mass ratio of the conducting polymer and the porous silicon is 1:10~1:5.
4. silicon substrate lithium ion battery anode active material as described in claim 1, it is characterised in that：The porous oxygen reduction fossil
The pore volume of ink is 1~2cm3/g；The pore volume of the porous silicon is 0.5~1cm3/g。
5. a kind of preparation method of any silicon substrate lithium ion battery anode active materials of claim 1-4, it is characterised in that：
Include the following steps,
(1) preparation of porous silica material：Using mesoporous silicon based molecular sieve as raw material, porous silicon is prepared using magnesium reduction；
(2) preparation of the porous silica material of conducting polymer cladding：It is added in ethanol water porous prepared by step (1)
Silicon and surfactant (cetyl trimethylammonium bromide) are added the dilute hydrochloric acid solution of aniline, gained are mixed after mixing
The aqueous solution progress polymerisation that solution is placed in addition ammonium persulfate under the conditions of -4 to 4 degrees Celsius of ice-water bath is closed, reaction terminates
Afterwards washing, dry conducting polymer cladding porous silicon；
(3) preparation of silicon substrate lithium ion battery negative material：Conducting polymer cladding obtained by step (2) is added in deionized water
Porous silicon and porous reduction-oxidation graphite, filter to obtain silicon substrate lithium ion battery negative material after ultrasonic disperse.
6. the preparation method of silicon substrate lithium ion battery negative material as claimed in claim 5, it is characterised in that：Step (1) is described
It is specially 1 by molar ratio that magnesium reduction, which prepares porous silicon,:1~2:1 mesoporous silicon based molecular sieve with after magnesium powder mixed grinding in
Volume ratio 5-10：Postcooling is roasted in the mixed atmosphere of 95-90 hydrogen and inert gas, at 650~750 DEG C to room temperature；Using
Acid solution handles gained product of roasting, washs, dries to obtain porous silicon.
7. the preparation method of silicon substrate lithium ion battery negative material as claimed in claim 6, it is characterised in that：The inert gas
For the gaseous mixture of one or more of argon gas, nitrogen；The acid processing procedure is first to use a concentration of 1~2mol/L's
Dilute hydrochloric acid handles product of roasting, and processing is performed etching using the hydrofluoric acid of a concentration of 5~10wt.%；The dry temperature
Degree is 60~100 DEG C；The roasting time is 5~7 hours.
8. the preparation method of silicon substrate lithium ion battery negative material as claimed in claim 5, it is characterised in that：Step (2) is described
The volumetric concentration of ethyl alcohol is 5~10% in ethanol water；The mass ratio of porous silicon and surfactant is 1:1~2:1；It is porous
Whole mass concentration 1~10mg/mL of the silicon in ethanol water；The mass content of aniline is 5 in the hydrochloric acid solution of the aniline
~10mg/mL, a concentration of 0.5~2mol/L of hydrochloric acid；The mass content of ammonium persulfate is 5 in the aqueous solution of the ammonium persulfate
~10mg/mL；The mass ratio of the quality of the ammonium persulfate and aniline in the mixed solution is 1:1~3:1；When the reaction
Between be 5~10h, the condition of the drying process is vacuum drying 12 at 60-80 DEG C~for 24 hours；
The surfactant is one kind in cetyl trimethylammonium bromide, cetyl dimethyl benzyl ammonium bromide.
9. the preparation method of silicon substrate lithium ion battery negative material as claimed in claim 5, it is characterised in that：The porous reduction
Graphite oxide synthesizes：First Hummer methods is used to synthesize graphite oxide, then is diluted to a concentration of 0.5~1.5mg/mL, ultrasound point
1h or more is dissipated, is then freeze-dried 2~4 days, obtains porous oxidation graphite；Then, the H at 1000~1200 DEG C2In atmosphere also
Former 1h or more obtains porous reduction-oxidation graphite.
10. a kind of application of any silicon substrate lithium ion battery anode active materials of claim 1-4, it is characterised in that described
Material is applied in negative electrode of lithium ion battery.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109616623A (en) * | 2018-10-31 | 2019-04-12 | 深圳市德方纳米科技股份有限公司 | A kind of silicon-based anode material and preparation method thereof |
| CN109755506A (en) * | 2018-12-18 | 2019-05-14 | 宁波革鑫新能源科技有限公司 | A kind of Si-C composite material and preparation method thereof |
| CN110010861A (en) * | 2019-03-07 | 2019-07-12 | 南方科技大学 | Silicon based composite material and preparation method thereof, lithium ion battery |
| CN111029537A (en) * | 2018-10-10 | 2020-04-17 | 湖南晋烨高科股份有限公司 | Lithium battery negative electrode material, preparation method thereof and lithium battery negative electrode |
| CN111933922A (en) * | 2020-08-06 | 2020-11-13 | 中科(马鞍山)新材料科创园有限公司 | Negative pole piece with coating layer, preparation method and application thereof |
| US11059724B2 (en) | 2019-06-18 | 2021-07-13 | Ningde Amperex Technology Limited | Porous material and preparation methods thereof, and anodes and devices including the same |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111029537A (en) * | 2018-10-10 | 2020-04-17 | 湖南晋烨高科股份有限公司 | Lithium battery negative electrode material, preparation method thereof and lithium battery negative electrode |
| CN111029537B (en) * | 2018-10-10 | 2023-05-26 | 湖南晋烨高科有限公司 | Lithium battery negative electrode material, preparation method thereof and lithium battery negative electrode |
| CN109616623A (en) * | 2018-10-31 | 2019-04-12 | 深圳市德方纳米科技股份有限公司 | A kind of silicon-based anode material and preparation method thereof |
| CN109755506A (en) * | 2018-12-18 | 2019-05-14 | 宁波革鑫新能源科技有限公司 | A kind of Si-C composite material and preparation method thereof |
| CN110010861A (en) * | 2019-03-07 | 2019-07-12 | 南方科技大学 | Silicon based composite material and preparation method thereof, lithium ion battery |
| US11059724B2 (en) | 2019-06-18 | 2021-07-13 | Ningde Amperex Technology Limited | Porous material and preparation methods thereof, and anodes and devices including the same |
| CN111933922A (en) * | 2020-08-06 | 2020-11-13 | 中科(马鞍山)新材料科创园有限公司 | Negative pole piece with coating layer, preparation method and application thereof |
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