CN103779534B - Independent one-dimensional coaxial nano-structure - Google Patents
Independent one-dimensional coaxial nano-structure Download PDFInfo
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- CN103779534B CN103779534B CN201410027312.1A CN201410027312A CN103779534B CN 103779534 B CN103779534 B CN 103779534B CN 201410027312 A CN201410027312 A CN 201410027312A CN 103779534 B CN103779534 B CN 103779534B
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
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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
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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
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Abstract
The invention discloses an independent one-dimensional coaxial nano-structure. The independent one-dimensional coaxial nano-structure comprises an independent conductive nano-wire and an electrochemical active substance layer, wherein the outer side of the conductive nano-wire is wrapped with the electrochemical active substance layer. The independent conductive nano-wire of the independent one-dimensional coaxial nano-structure provides effective template support and has conductivity, a charge-discharge electronic conductive channel can be provided, a special conductive additive is not needed, and the outer side of the conductive nano-wire is wrapped with the electrochemical active substance layer so as to form the independent one-dimensional coaxial nano-structure.
Description
Technical field
The invention belongs to technical field of lithium ion is and in particular to independent one-dimensional coaxial nanostructured.
Background technology
Lithium ion battery has high-energy-density, high power density, the feature having a safety feature, having extended cycle life, and
Do not contain the polluters such as lead, cadmium, hydrargyrum, be a kind of ideal energy storage device.Need with the high electricity such as current electric automobile
The high speed development of the portable electronics such as the electric tool asked and notebook computer, it proposes more next to the capacity of lithium ion battery
Higher requirement.High-energy-density, the lightweight and long-life is lithium electrician's industry and the important exploitation problem of academia.At present
The lithium ion battery negative material of industrialized production is carbons material, and its theoretical specific capacity is 372mah/g.This material
It is the layer structure using graphite, little lithium ion is intercalation into the centre of graphite laminate structure.However, this reaction pattern six
Carbon atom can only react with a lithium ion, forms lic6.Therefore, limit the raising of capacity.Some materials substituting, such as
Silicon, stannum etc. have advantage on theoretical capacity.For example, silicon materials, theoretical capacity can be up to 4200mah/g and form li4.4si shape
State compound.But it is as the raising of capacity, bring volumetric expansion and may be up to 400% in lithium entrance silicon.In thin film and micron
The silicon materials of the particulate form of magnitude, so big volumetric expansion can lead to the broken, thus losing electrical contact of silicon grain or film
And the overall performance of electrode material.A kind of solution is the concept such as nanometer introducing nanostructured in the design of material
The nanometer concept such as granule, nano wire and nanotube.Nanostructured is often referred to be less than 1 micron at least in unidimensional scale.This is little
Yardstick, can be diameter, thickness of film of thread etc..The unique appearance structure of these materials solves or slow to a certain extent
Solve the broken of the material original shape looks that ion insertion leads to.In research and development in this respect, Stamford material system of U.S. Cui Yi professor exists
Propose within 2009 to be rooted in a nano thread structure of conductive several.(U.S. Patent number: no.12/437,529filed on
May07,2009).In his research, silicon nanowires is grown directly upon on electrode, this is made up of one-dimensional silicon nanowire structure
Active material layer, effectively solve the problems, such as volumetric expansion, and the problems such as electron channel.
Accordingly, it would be desirable to a kind of new one-dimensional coaxial nanostructured is to solve the above problems.
Content of the invention
The present invention is directed to electroactive substance volumetric expansion in prior art and leads to lose chemical property and cannot
There is provided the defect of electron channel, providing a kind of can provide the independent one-dimensional coaxial of conductive channel and electrochemical cycle stability
Nanostructured.
For solving above-mentioned technical problem, the technical scheme that the independent one-dimensional coaxial nanostructured of the present invention is adopted is:
Independent one-dimensional coaxial nanostructured, by depart from substrate constraint conducting nanowires and electroactive substance layer and
The powder of film composition, the outside of described conducting nanowires has wrapped described electroactive substance layer.
Further, a diameter of 10-100nm of described conducting nanowires, the thickness of described electroactive substance layer
For (0nm, 995nm].
Further, it is provided with a tunic, described electroactive substance layer outside described electroactive substance layer
There is and film between gap.This structure can adjust the chemical state of surfacing, is conducive to electrochemical properties.Reserved space
Can reduce due to the stress damage caused by electroactive substance layer discharge and recharge volumetric expansion.Coated on the surface of nano wire
Growth can carve a tunic of decorations.Then the beneficial film such as carbon film of attached one layer of electrochemical reaction, copper film are being wrapped up in outside.This layer
Film can allow electrolyte pass through, and can also form sei film (solid electrolyte interface film) in chemical reaction in bag subordinate list face simultaneously.
In addition, this tunic can also play the effect of restriction to the expansion of active substance.
Further, described conducting nanowires are copper nano-wire, aluminum nano wire, nickel nano wire, cobalt nanowire, carbon nanometer
Line, nickel silicide nano-line, silication cobalt nanowire, silication copper nano-wire, silication nano silver wire, iron silicide nano wires, silication zinc are received
Rice noodle, titanium carbide nano-wires, tin oxide nano-wire, zinc oxide nanowire or indium oxide nano thread.Wherein, conducting nanowires are prepared
Method can adopt gas-solid-liquid method, gas-solid method etc..
Further, described electroactive substance layer is active cathode mass or active anode material, described activity
The coated carbon of anode material is crystalline silicon, non-crystalline silicon, stannum, germanium, carbon, silicon oxide, stannum oxide, germanium oxide, carbon are coated silicon, silicon,
The coated stannum of the coated carbon of the coated germanium of the silicon of carbon doping, the carbon of silicon doping, carbon, germanium, the germanium of carbon doping, Ge-doped carbon, carbon,
One or more of carbon of the coated carbon of stannum, the stannum of carbon doping or tin dope, described active cathode mass is licoo2、
lifepo4、limno2、linio2、limn2o4、licopo4、lini1/3co1/3mn1/3o2、linixcoyalzo2、life2(so4)3、
Perfluorocarbon or fef3One or more of.Electroactive substance layer can pass through chemical vapour deposition technique, plating, plasma
The technology such as body chemical vapor phase growing, physical vapour deposition (PVD) are realized.For example, active substance silicon materials can pass through chemical vapor deposition
Prepared by change method.
Further, when described conducting nanowires are nickel silicide nano-line, described conducting nanowires pass through chemical gas
Phase sedimentation prepares；When described conducting nanowires are copper nano-wire or carbon nanocoils, described conducting nanowires pass through quiet
Electrical spinning method prepares；When described conducting nanowires are tin oxide nano-wire, described conducting nanowires pass through laser splash
Physical vapor method prepares；When described conducting nanowires are zinc oxide nanowire, described conducting nanowires are splashed by laser
Penetrate physical vapor method to prepare.
Further, when described electroactive substance layer is non-crystalline silicon or polysilicon, will by thermal chemical vapor method
Non-crystalline silicon or polysilicon wrap on conducting nanowires.
Further, prepared by following steps:
1), one layer of sacrifice layer that can be dissolved is set outside described electroactive substance layer；
2), one tunic is set in the outside of described sacrifice layer, obtains intermediate product a；
3), described intermediate product a is put in the solvent soln that can dissolve described sacrifice layer, described sacrifice layer is dissolved
Obtain described independent one-dimensional coaxial nanostructured afterwards.
Further, when described sacrifice layer is silicon dioxide, described solvent soln is hf solution；When described sacrifice layer
For al2o3When, described solvent soln is naoh solution.
Beneficial effect: the independent conducting nanowires of the independent one-dimensional coaxial nanostructured of the present invention provide effective mould
Plate is supported, has electric conductivity, is provided that charge and discharge electronic conduction passage it is not necessary to special conductive additive, electroactive substance
Bag is attached to outside conducting nanowires, forms independent one-dimensional coaxial nanostructured.Maintain the basic structure feature of axle center nano wire,
Break away from and the direct restriction contacting of substrate simultaneously, widened range of application
Brief description
Fig. 1 is the first structure schematic diagram of the independent one-dimensional coaxial nanostructured of the present invention；
Fig. 2 is the second structural representation of the independent one-dimensional coaxial nanostructured of the present invention；
Fig. 3 is the 3rd structural representation of the independent one-dimensional coaxial nanostructured of the present invention；
Fig. 4 is the scanning electron microscope top view of the nickel silicide nano-line that embodiment 1 prepares；
Fig. 5 is the scanning electron microscope side view of the nickel silicide nano-line that embodiment 1 prepares；
Fig. 6 is the scanning electron microscope top view of the nickel silicide nano-line that embodiment 2 prepares；
Fig. 7 is the scanning electron microscope side view of the nickel silicide nano-line that embodiment 2 prepares；
Fig. 8 is the stereoscan photograph of the nickel silicide nano-line that embodiment 3 prepares；
Fig. 9 is the stereoscan photograph of the nickel silicide nano-line that embodiment 4 prepares；
Figure 10 is the stereoscan photograph of the copper nano-wire that embodiment 5 prepares；
Figure 11 is the stereoscan photograph of the carbon nanocoils that embodiment 6 prepares；
Figure 12 is the stereoscan photograph of the nickel silicide nano-line that the surface that embodiment 9 prepares is wrapped with non-crystalline silicon；
Figure 13 is the transmission electron microscope photo of the nickel silicide nano-line that the surface that embodiment 9 prepares is wrapped with non-crystalline silicon；
Figure 14 is the electron diffraction pattern of the nickel silicide nano-line that the surface that embodiment 9 prepares is wrapped with non-crystalline silicon；
Figure 15 is the stereoscan photograph of the nickel silicide nano-line that the surface that embodiment 12 prepares is wrapped with polysilicon；
Figure 16 is the raman test chart of the nickel silicide nano-line that the surface that embodiment 12 prepares is wrapped with polysilicon；
Figure 17 is the stereoscan photograph of the carbon nanocoils that the surface that embodiment 13 prepares is wrapped with polysilicon；
Figure 18 is that the scanning electron microscope of the nickel silicide nano-line that the surface that embodiment 14 prepares is wrapped with non-crystalline silicon is overlooked
Figure；
Figure 19 is the scanning electron microscope side-looking of the nickel silicide nano-line that the surface that embodiment 14 prepares is wrapped with non-crystalline silicon
Figure；
Figure 20 is the energy of the nickel silicide nano-line that the surface that embodiment 16 prepares is wrapped with amorphous silicon germanium mixture
Scattering spectra (edx), germanium atom accounts for total content atomic percent and is: 2%；
Figure 21 is the energy of the nickel silicide nano-line that the surface that embodiment 16 prepares is wrapped with amorphous silicon germanium mixture
Scattering spectra (edx), germanium atom accounts for total content atomic percent and is: 8%；
Figure 22 is the energy of the nickel silicide nano-line that the surface that embodiment 16 prepares is wrapped with amorphous silicon germanium mixture
Scattering spectra (edx), germanium atom accounts for total content atomic percent and is: 15%；
Figure 23 is first of the independent one-dimensional coaxial nanostructured between electroactive substance layer and film with gap
Structural representation；
Figure 24 is second of the independent one-dimensional coaxial nanostructured between electroactive substance layer and film with gap
Structural representation；
Figure 25 is the 3 of the independent one-dimensional coaxial nanostructured between electroactive substance layer and film with gap
Structural representation.
Specific embodiment
Below in conjunction with the accompanying drawings and specific embodiment, it is further elucidated with the present invention it should be understood that these embodiments are merely to illustrate
The present invention rather than restriction the scope of the present invention, after having read the present invention, those skilled in the art are each to the present invention
The modification planting the equivalent form of value all falls within the application claims limited range.
Refer to shown in Fig. 1, Fig. 2 and Fig. 3, the independent one-dimensional coaxial nanostructured of the present invention, including independent conduction
Nano wire and electroactive substance layer, the outside of conducting nanowires has wrapped electroactive substance layer.Wherein, electrical-conductive nanometer
A diameter of 10-100nm of line, the thickness of electroactive substance layer be (0nm, 995nm].The pattern of electroactive substance layer
Cylindric or coniform but or ' sugarcoated haws on a stick shape '.
The masterplate nanometer axial line of the present invention has several functions: 1) provides effective masterplate to support；2) have well
Electric conductivity, is provided that impulse electricity electronic conduction passage；3) provide big specific surface area, be conducive to wrapping up in attached electroactive substance layer
Weight.A lot of materials can be used as this conduction axle center nano wire.
The independent one-dimensional coaxial nanostructured of the present invention, maintains the basic structure feature of axle center nano wire, puts simultaneously
Take off and the direct restriction contacting of substrate, thus having widened range of application.Its benefit may be summarized as follows: in structure: 1) one-dimensional
Coaxial nanometer can form new uniqueness nanostructured as the monomer of building block by technique restructuring.2) independent
One-dimensional coaxial nanometer departing from substrate constraint it is easy to carrying out necessary surface treatment, wrap up in attached etc., such as surface wrapping poly-
Compound etc..In technique: 1) be rooted in conductive base lamella and compare, in technique relatively simple it is not necessary to precise control nucleation and
The concentration of line, easily produces the powder of this structure in a large number；2), can combine with traditional coating process, be blended into tradition coating
In slurry, and the proportioning blending is any according to requirements adjustment.3) it is rooted in conductive substrate layer method often in final step technique
On often wrapped up in attached using high temperature deposition, cause the substantial amounts of residual stress in interface to be easily caused the inefficacy that comes off.Room temperature coating process
Combination, can preferably improve in this regard.
Conducting nanowires can be have the metal nanometer line of electric conductivity for example copper nano-wire, aluminum nano wire, nickel nano wire or
Cobalt nanowire etc.；Can be conductive carbon nanocoils etc.；Metal silicide nano-wire such as nickel silicide nano-line, cobalt silicide nanometer
Line, silication copper nano-wire, silication nano silver wire, iron silicide nano wires, silication zinc nano wire etc.；Metallic carbide nanometer line
As titanium carbide nano-wires etc.；Conductive oxide nano thread such as tin oxide nano-wire, zinc oxide nanowire, indium oxide nano thread
Deng.Wherein, the method preparing conducting nanowires can adopt gas-solid-liquid method, gas-solid method etc..
First, utilize the nickel silicide nano-line of chemical vapour deposition technique preparation
Embodiment 1
Nickeliferous substrate or granule put into chemical vapor deposition reaction chamber, and siliceous reactant gas silane is flowed into reaction
Room.Wherein, the concentration of silane is 5%, and the concentration of silane is adjustable by technique.The temperature control of reative cell at 400 degrees Celsius, air pressure
For 0.1torr, growth time controlled at 1 minute.Lower the temperature after reaction, define the powder of black.Refer to shown in Fig. 4 and Fig. 5,
Fig. 4 and Fig. 5 is top view and the side view of reactant scanning electron microscope.The diameter of nano wire is 20 ran, and length is 2-3
Micron.
Embodiment 2
Nickeliferous substrate or granule put into chemical vapor deposition reaction chamber, and siliceous reactant gas silane is flowed into reaction
Room.Wherein, the concentration of silane is 10%, and the concentration of silane is adjustable by technique.The temperature control of reative cell at 500 degrees Celsius, gas
Press as 300torr, growth time controlled at 1.5 hours.Lower the temperature after reaction, define the film of black.
Refer to shown in Fig. 6 and Fig. 7, Fig. 6 and Fig. 7 is top view and the side view of reactant scanning electron microscope.Nano wire
Diameter is 20 ran, and length is 30-40 micron.
Embodiment 3: chemical gas-phase method prepares nickel silicide nano-line
Nickeliferous nano metal puts into chemical vapor deposition reaction chamber, and siliceous reactant gas silane is flowed into reative cell.
Wherein, the concentration of silane is 5%, and the concentration of silane is adjustable by technique.At 400 degrees Celsius, air pressure is the temperature control of reative cell
0.1torr, growth time controlled at 1 minute.Lower the temperature after reaction, define the powder of black.Refer to shown in Fig. 8, Fig. 8 is anti-
Answer the photo of thing scanning electron microscope.The diameter of nano wire is 20 ran.Length is 2-3 micron.
Embodiment 4: chemical gas-phase method prepares nickel silicide nano-line
Nickeliferous metallic particles puts into chemical vapor deposition reaction chamber, and siliceous reactant gas silane is flowed into reative cell.
Wherein, the concentration of silane is 5%, and the concentration of silane is adjustable by technique.At 450 degrees Celsius, air pressure is the temperature control of reative cell
15torr, growth time controlled at 30 minutes.Lower the temperature after reaction, define the powder of black.Containing the axle prepared by nickel particle
Heart nano wire.
2nd, Nano line of metal copper and carbon nanocoils are prepared by electrostatic spinning technique.
Embodiment 5: electrostatic spinning technique prepares copper nano-wire
Electrostatic spinning technique is to prepare one of most important method of nanofiber at present.The basic device of electrostatic spinning includes
It is made up of high voltage power supply, micro pump, syringe, syringe needle, collection device five part.Its principle is that polymer solution or melt are applied
Plus thousand of to tens of thousands of volt high-pressure electrostatics, when the electric field force in polymer solution or melt overcomes its surface tension, in electric field force
The lower injection of effect forms one stable jet, the drawing-off with jet and division, after final solvent volatilization or melt solidification, high
Polymer fibre sinks and forms the micro nanometer fiber material of similar non-woven fabrics on collecting board.Because it can simply, directly, continuously be made
Standby polymer, metal and its oxide nanofiber, thus become study hotspot both domestic and external.Cuac using nanometer cupric2/
Pva complex method of electrostatic spinning prepares about diameter 200 nanofiber.The fiber collected is being added in 550 degree of in the airs
Heat 2 hours, then in h2It is reduced into copper cash under environment.Refer to shown in Figure 10, Figure 10 is using the preparation of high voltage spraying process
Copper nano-wire stereoscan photograph.
Embodiment 6: electrostatic spinning technique prepares carbon nanocoils
Dissolve in dmf stirred in water bath 4h using polyacrylonitrile (pan) polymer of nanometer carbon containing until forming clear yellow viscous
Shape solution, standby as electrospinning liquid.Prepare about diameter 100 carbon nano-fiber with electrostatic spinning apparatus.By the white collected
Fiber is aoxidizing 1 hour at 300 degree, then rises to 800 DEG C of lower carbonization heating 4 hours in argon.Figure 11 is using this technique
The carbon nanocoils of preparation.
3rd, oxide nano thread is prepared by laser splash physical vapor method.
Embodiment 7:
Grow electric conductive oxidation stannum nanowire using laser splash physical vapor method.Step is as follows:
1), reative cell put into by the substrate by stannum palladium material with containing Au catalyst；It is passed through argon, air pressure in fine vacuum reative cell
Control in 500tor, temperature control is between 400-900 degree.
2), q-switch pulse nd: yag laser is to bombard stannum palladium material under 1w in 10hz frequency power.Bombardment thing is in air-flow
Under be deposited on substrate.
3) lower the temperature after, reacting, obtain the fin oxide condutire nano wire that surface wraps attached a layer.
Embodiment 8:
Using laser splash physical vapor method growth of zinc oxide nano line.Step is as follows:
1), reative cell put into by the substrate by zinc palladium material with containing Au catalyst；It is passed through argon, air pressure in fine vacuum reative cell
Control in 500tor, temperature control is between 400-1000 degree.
2), q-switch pulse nd: yag laser is to bombard zinc palladium material under 1w in 10hz frequency power.Bombardment thing is in air-flow
Under be deposited on substrate.
3) lower the temperature after, reacting, obtain the zinc oxide conducting nanowires that surface wraps attached a layer.
Wherein, electroactive substance layer is active cathode mass or active anode material, and active cathode mass is crystal
The coated carbon of the coated silicon of silicon, non-crystalline silicon, stannum, germanium, silicon oxide, stannum oxide, germanium oxide, carbon, silicon, the silicon of carbon doping, silicon doping
Carbon, the coated carbon of the coated stannum of the coated carbon of the coated germanium of carbon, germanium, the germanium of carbon doping, Ge-doped carbon, carbon, stannum, carbon doping
Stannum or tin dope one or more of carbon；Anode active material is licoo2、lifepo4、limno2、linio2、
limn2o4、licopo4、lini1/3co1/3mn1/3o2、linixcoyalzo2、life2(so4)3, perfluorocarbon or fef3One of or
Multiple.Electroactive substance layer can pass through chemical vapour deposition technique, plating, plasma activated chemical vapour deposition, physics gas
Mutually the technology such as deposition is realized.For example, active substance silicon materials can be prepared by chemical vapor deposition method.
Embodiment 9:
Thermal chemical vapor method prepares the nickel silicide nano-line that attached one layer of non-crystalline silicon is wrapped on surface
When electroactive substance layer is non-crystalline silicon, non-crystalline silicon is wrapped and comprises the following steps on nickel silicide nano-line:
1), nickel silicide nano-line is put into chemical vapor deposition reaction chamber, reative cell is warming up to 490 degree under argon gas；
2), silane is flowed into chemical vapor deposition reaction chamber, wherein, the concentration of silane is 5%；
3), by the temperature control of chemical vapor deposition reaction chamber at 490 degrees Celsius, air pressure is 100tor, and growth time is
60 minutes；
4) lower the temperature after, reacting, obtain the nickel silicide nano-line that attached one layer of non-crystalline silicon is wrapped on surface.
Refer to shown in Figure 12,13 and 14, figure is the stereoscan photograph wrapping up in attached gleanings, transmission electron microscope and electronics
Diffraction spectra.The attached one layer of non-crystalline silicon of uniform bag can be seen on the nickel silicide nano-line of 20nm.Wrap up in the straight of attached nano wire
Footpath is about 300nm.
Embodiment 10:
Thermal chemical vapor method prepares the nickel silicide nano-line that attached one layer of non-crystalline silicon is wrapped on surface
When electroactive substance layer is non-crystalline silicon, non-crystalline silicon is wrapped and comprises the following steps on nickel silicide nano-line:
1), conducting nanowires are put into chemical vapor deposition reaction chamber；
2), silane is flowed into chemical vapor deposition reaction chamber, wherein, the concentration of silane is 10%；
3), by the temperature control of chemical vapor deposition reaction chamber at 520 degrees Celsius, air pressure is 25tor, and growth time is 60
Minute；
4) lower the temperature after, reacting, obtain the nickel silicide nano-line that attached one layer of non-crystalline silicon is wrapped on surface.
Embodiment 11:
Thermal chemical vapor method prepares the nickel silicide nano-line that attached one layer of polysilicon is wrapped on surface
When electroactive substance layer is non-crystalline silicon, non-crystalline silicon is wrapped and comprises the following steps on nickel silicide nano-line:
1), nickel silicide nano-line is put into chemical vapor deposition reaction chamber；Reative cell is warming up to 535 degree under argon gas.
2), silane is flowed into chemical vapor deposition reaction chamber, wherein, the concentration of silane is 100%；
3), by the temperature control of chemical vapor deposition reaction chamber at 535 degrees Celsius, air pressure is 0.8tor, and growth time is
120 minutes；
4) lower the temperature after, reacting, obtain the nickel silicide nano-line that attached one layer of non-crystalline silicon is wrapped on surface.
Embodiment 12:
Thermal chemical vapor method prepares the nickel silicide nano-line that attached one layer of polysilicon is wrapped on surface
When electroactive substance layer is non-crystalline silicon, non-crystalline silicon is wrapped and comprises the following steps on nickel silicide nano-line:
1), nickel silicide nano-line is put into chemical vapor deposition reaction chamber；Reative cell is warming up to 550 degree under argon gas.
2), silane is flowed into chemical vapor deposition reaction chamber, wherein, the concentration of silane is 10%；
3), by the temperature control of chemical vapor deposition reaction chamber at 550 degrees Celsius, air pressure is 25tor, and growth time is 30
Minute；
4) lower the temperature after, reacting, obtain the nickel silicide nano-line that attached one layer of polysilicon is wrapped on surface.
Figure 15 and Figure 16 is stereoscan photograph and the raman test chart wrapping up in attached gleanings.Can observe on raman figure
Jointly exist to crystalline state and amorphous state.Can obtain under the conditions of this case process by calculating, the degree of order of silicon is about 14%.
Embodiment 13:
Thermal chemical vapor method prepares the carbon nanocoils that attached one layer of polysilicon is wrapped on surface
When electroactive substance layer is polysilicon, polysilicon is wrapped and comprises the following steps on carbon nanocoils:
1), carbon nanocoils are put into chemical vapor deposition reaction chamber；Reative cell is warming up to 600 degree under argon gas.
2), silane is flowed into chemical vapor deposition reaction chamber, wherein, the concentration of silane is 5%；
3), by the temperature control of chemical vapor deposition reaction chamber at 600 degrees Celsius, air pressure is 25tor, and growth time is 30
Minute；
4) lower the temperature after, reacting, obtain the carbon nanocoils that attached one layer of polysilicon is wrapped on surface.
Figure below is the stereoscan photograph wrapping up in attached gleanings.
Figure 17 is the stereoscan photograph wrapping up in attached gleanings.
Embodiment 14:
Both Plasma Chemical Vapor method prepares the nickel silicide nano-line that attached one layer of non-crystalline silicon is wrapped on surface
When electroactive substance layer is non-crystalline silicon, non-crystalline silicon is wrapped and comprises the following steps on nickel silicide nano-line:
1), nickel silicide nano-line is put into PCVD reative cell；Reative cell is warming up to 350 under argon gas
Degree, air pressure controls in 2tor.
2), silane and argon are flowed into chemical vapor deposition reaction chamber, wherein, the flow-rate ratio of silane and argon is 15:
100；
3), r.f. power density is 0.15w/cm2；
4), pole piece is spaced about 12 millimeters；
5) lower the temperature after, reacting, obtain the nickel silicide nano-line that attached one layer of non-crystalline silicon is wrapped on surface.
Figure 18 and Figure 19 is scanning electron microscope top view photograph and the side-looking photo wrapping up in attached gleanings.It is observed that nano wire
Shape wraps up in attached heavy formation.
Embodiment 15:
Both Plasma Chemical Vapor method prepares the nickel silicide nano-line that attached one layer of non-crystalline silicon is wrapped on surface
When electroactive substance layer is non-crystalline silicon, non-crystalline silicon is wrapped and comprises the following steps on nickel silicide nano-line:
1), nickel silicide nano-line is put into PCVD reative cell；Reative cell is warming up to 450 under argon gas
Degree, air pressure controls in 10tor.
2), silane and argon are flowed into chemical vapor deposition reaction chamber, wherein, the flow-rate ratio of silane and argon is 10:
100；
3), r.f. power density is 0.15w/cm2；Wherein, r.f. represents radio frequency (radio frequency)；
4), pole piece is spaced about 12 millimeters；
5) lower the temperature after, reacting, obtain the nickel silicide nano-line that attached one layer of non-crystalline silicon is wrapped on surface.
Embodiment 16:
Thermal chemical vapor method prepares the nickel silicide nano-line that attached one layer of amorphous silicon germanium mixture is wrapped on surface
When electroactive substance layer is amorphous silicon germanium mixture, case step:
1), nickel silicide nano-line is put into chemical vapor deposition reaction chamber；Reative cell is warming up to 520 degree under argon gas；
2), silane germane is flowed into chemical vapor deposition reaction chamber, wherein, the concentration ratio of germane silane ratio is 3:97；
3), by the temperature control of chemical vapor deposition reaction chamber at 520 degrees Celsius, air pressure is 25tor, and growth time is 60
Minute；
4) lower the temperature after, reacting, obtain the nickel silicide nano-line that attached one layer of amorphous silicon germanium mixture is wrapped on surface.
Figure 20,21 and 22 are that amorphous silicon germanium mixture energy dispersive composes (edx): germanium atom accounts for total content atomic percent
For: 2%, 8% and 15%.
Embodiment 17:
Thermal chemical vapor method prepares the nickel silicide nano-line that attached one layer of amorphous silicon germanium mixture is wrapped on surface
When electroactive substance layer is amorphous silicon germanium mixture, comprise the following steps:
1), nickel silicide nano-line is put into chemical vapor deposition reaction chamber；Reative cell is warming up to 520 degree under argon gas；
2), silane and germane are flowed into chemical vapor deposition reaction chamber, wherein, the concentration ratio of germane and silane is 20:80；
3), by the temperature control of chemical vapor deposition reaction chamber at 520 degrees Celsius, air pressure is 25tor, and growth time is 60
Minute；
4) lower the temperature after, reacting, obtain the conducting nanowires that attached one layer of amorphous silicon germanium is wrapped on surface.
Embodiment 18:
Prepare the carbon nanocoils that surface is wrapped with cobalt acid lithium using magnetron sputtering method
Wrap up in attached cobalt acid lithium using magnetron sputtering method on carbon nanocoils surface.Comprise the following steps:
1), carbon nanocoils powder is put into magnetron sputtering chamber；It is passed through argon in fine vacuum reative cell, air pressure controls
5mtor；
2), sputtering power electric current density: 20ma/cm, power density: 30w/cm.
3) lower the temperature after, reacting, obtain the carbon nanocoils that attached one layer of cobalt acid lithium is wrapped on surface.
4), high annealing.
Embodiment 19:
Prepare the carbon nanocoils that surface is wrapped with cobalt acid lithium using magnetron sputtering method
Cobalt acid lithium bag is attached on carbon nanocoils and comprises the following steps:
1), carbon nanocoils are put into magnetron sputtering chamber；It is passed through argon in fine vacuum reative cell, air pressure controls in 5mtor.
2), sputtering power electric current density: 40ma/cm, power density: 60w/cm.
3) lower the temperature after, reacting, obtain the carbon nanocoils that attached one layer of cobalt acid lithium is wrapped on surface.
4), high annealing.
Embodiment 20:
Prepare the carbon nanocoils that surface is wrapped with cobalt acid lithium using magnetron sputtering method
Cobalt acid lithium bag is attached on carbon nanocoils conducting nanowires and comprises the following steps:
1), cobalt acid lithium palladium material and carbon nanocoils conducting nanowires powder are put into reative cell；Logical in fine vacuum reative cell
Enter argon, air pressure controls in 500tor.
2), q-switch pulse nd: yag laser is to bombard cobalt acid lithium target under 1w in 10hz frequency power.Bombardment thing exists
It is deposited on carbon nanocoils under air-flow.
3) lower the temperature after, reacting, obtain the carbon nanocoils that attached one layer of cobalt acid lithium is wrapped on surface.
Laser splash oxide refer to this article: advanced materials, volume 15, issue 20,
pages 1754–1757,october,2003；nano letters 4,1241-1245(2004)；nano letters 4,
2151-2155(2004).
Refer to shown in Figure 23, Figure 24 and Figure 25, outside electroactive substance layer, be provided with a tunic, electro-chemical activity
There is between material layer and film gap.This structure can adjust the chemical state of surfacing, is conducive to electrochemical properties.Reserved
Space can reduce due to the stress damage caused by electroactive substance layer discharge and recharge volumetric expansion.
The independent one-dimensional coaxial nanostructured of above-mentioned band one tunic is prepared by following steps:
1), in electroactive substance layer 2 one layer of sacrifice layer that can be dissolved of outside setting；
2), one tunic 3 is set in the outside of sacrifice layer, obtains intermediate product a；
3), intermediate product a is put in the solvent soln that can dissolve sacrifice layer, sacrifice layer obtains independent after being dissolved
One-dimensional coaxial nanostructured.
Wherein, film 3 can be carbon film, al2o3Film, tio2Film, cds film or fe2o3Film.When sacrifice layer is for silicon dioxide,
Solvent soln is hf solution；When sacrifice layer is al2o3When, solvent soln is naoh solution.
The surface of nano wire coated can grow one layer of film that can carve decorations, is then wrapping up in attached one layer to electrochemistry outside
React beneficial film, such as copper film.This tunic can allow electrolyte pass through, simultaneously can also bag subordinate list face shape in chemical reaction
Become sei.In addition, this tunic can also play the effect of restriction to the expansion of active substance.
The conducting nanowires of the independent one-dimensional coaxial nanostructured of the present invention provide effective template to support, have conduction
Property, it is provided that charge and discharge electronic conduction passage, electroactive substance layer bag is attached to outside conducting nanowires, formed independent one-dimensional common
Axle nanostructured.
The one-dimensional coaxial silicon/nickel SiClx nanometer material structure being rooted in conductive substrate has been invented by peace Jim Press company of the U.S..
(U.S. Patent number: ghyrn e loveness, william s delhagen, rainer fasching, song han,
zuqin liu:template electrode structures for depositing active
Materials.amprius june 2011:us20110159365-a1) this be rooted in one-dimensional coaxial nanowire provide following
Benefit: 1) axle center nano wire provides the path of electric transmission；2) center nano wire provides the carrier film version of electrochemistry active ingredient；
3) space between nano wire provides expansion headspace；4) nano wire directly links substrate and provides the passage of electric transmission,
Do not need special conductive additive, etc..However, such structure is more difficult in the precise control of nano wire concentration.Separately
Outward, interlink between nano wire formation three-dimensional space network structure, when cumulative stress to a certain extent, nano wire layer and substrate
Abutting edge easily causes fatigue phenomenon to form interface and come off with stress during repeated charge, leads to the moment of battery to be lost
Effect.
The independent one-dimensional coaxial nanostructured of the present invention, maintains the basic structure feature of axle center nano wire, puts simultaneously
Take off and the direct restriction contacting of substrate, thus having widened range of application.Its benefit may be summarized as follows: in structure: 1) one-dimensional
Coaxial nanometer can form new uniqueness nanostructured as the monomer of building block by technique restructuring.2) independent
One-dimensional coaxial nanometer departing from substrate constraint it is easy to carry out necessary surface treatment, wrap up in attached etc..Such as surface wraps polymerization
Thing etc..In technique: 1) be rooted in conductive base lamella and compare, in technique relatively simple it is not necessary to precise control nucleation and line
Concentration, easily produce in a large number the powder of this structure；2), can combine with traditional coating process, be blended into tradition coating slurry
In material, and the proportioning blending is any according to requirements adjustment.3) it is rooted in conductive substrate layer method often in final step technique
Often wrapped up in using high temperature deposition attached, cause the substantial amounts of residual stress in interface to be easily caused the inefficacy that comes off.Room temperature coating process
In conjunction with can preferably improve in this regard.
Claims (7)
1. a kind of independent one-dimensional coaxial nanostructured it is characterised in that: by depart from substrate constraint conducting nanowires (1) and electricity
The powder that chemically reactive substance layer (2) and film (3) form, the outside of described conducting nanowires (1) has wrapped described electrochemistry and has lived
Property material layer (2), a diameter of 10-100nm of described conducting nanowires (1), the thickness of described electroactive substance layer (2) is
(0nm, 995nm]；It is provided with a tunic (3), described electroactive substance layer outside described electroactive substance layer (2)
(2) and film (3) between, there is gap, this film (3) is carbon film, al2o3Film, tio2Film, cds film or fe2o3Film.
2. as claimed in claim 1 a kind of independent one-dimensional coaxial nanostructured it is characterised in that: described conducting nanowires
(1) be copper nano-wire, aluminum nano wire, nickel nano wire, cobalt nanowire, carbon nanocoils, nickel silicide nano-line, silication cobalt nanowire,
Silication copper nano-wire, silication nano silver wire, iron silicide nano wires, silication zinc nano wire, titanium carbide nano-wires, tin oxide nano
Line, zinc oxide nanowire or indium oxide nano thread.
3. as claimed in claim 1 a kind of independent one-dimensional coaxial nanostructured it is characterised in that: described electro-chemical activity thing
Matter layer (2) be active cathode mass or active anode material, described active anode material be crystalline silicon, non-crystalline silicon, stannum, germanium, carbon,
The coated germanium of the coated carbon of the coated silicon of silicon oxide, stannum oxide, germanium oxide, carbon, silicon, the silicon of carbon doping, the carbon of silicon doping, carbon,
The carbon of the coated stannum of the coated carbon of germanium, the germanium of carbon doping, Ge-doped carbon, carbon, stannum coated carbon, the stannum of carbon doping or tin dope
One or more of, described active cathode mass is licoo2、lifepo4、limno2、linio2、limn2o4、licopo4、
lini1/3co1/3mn1/3o2、linixcoyalzo2、life2(so4)3, perfluorocarbon or fef3One or more of.
4. as claimed in claim 2 a kind of independent one-dimensional coaxial nanostructured it is characterised in that: when described conducting nanowires
During for nickel silicide nano-line, described conducting nanowires are prepared by chemical vapour deposition technique；When described conducting nanowires are
When copper nano-wire or carbon nanocoils, described conducting nanowires are prepared by method of electrostatic spinning；When described conducting nanowires are
During tin oxide nano-wire, described conducting nanowires are prepared by laser splash physical vapor method；When described conducting nanowires
During for zinc oxide nanowire, described conducting nanowires are prepared by laser splash physical vapor method.
5. as claimed in claim 3 a kind of independent one-dimensional coaxial nanostructured it is characterised in that: described electro-chemical activity thing
When matter layer (2) is non-crystalline silicon or polysilicon, by thermal chemical vapor method, non-crystalline silicon or polysilicon are wrapped in conducting nanowires (1)
On.
6. as claimed in claim 1 a kind of independent one-dimensional coaxial nanostructured it is characterised in that: prepared by following steps
Obtain:
1), one layer of sacrifice layer that can be dissolved is set outside described electroactive substance layer (2)；
2), one tunic (3) is set in the outside of described sacrifice layer, obtains intermediate product a；
3), described intermediate product a is put in the solvent soln that can dissolve described sacrifice layer, described sacrifice layer obtains after being dissolved
To a kind of described independent one-dimensional coaxial nanostructured.
7. as claimed in claim 6 a kind of independent one-dimensional coaxial nanostructured it is characterised in that: when described sacrifice layer be two
During silicon oxide, described solvent soln is hf solution；When described sacrifice layer is al2o3When, described solvent soln is naoh solution.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102576857A (en) * | 2009-05-27 | 2012-07-11 | 安普雷斯股份有限公司 | Core-shell high capacity nanowires for battery electrodes |
| CN102800851A (en) * | 2012-08-17 | 2012-11-28 | 奇瑞汽车股份有限公司 | Silicon carbon composite material and preparation method thereof, lithium ion battery containing same |
| CN103031610A (en) * | 2012-12-07 | 2013-04-10 | 北京航空航天大学 | Method for preparing single ultra-long Cu nanowire and measuring electrical properties of the nanowire |
| CN103107317A (en) * | 2013-01-17 | 2013-05-15 | 奇瑞汽车股份有限公司 | Si-C composite material and preparation method thereof and lithium ion battery containing same |
| CN103210530A (en) * | 2010-08-27 | 2013-07-17 | 纽约州立大学研究基金会 | Branched nanostructures for battery electrodes |
| CN103238238A (en) * | 2010-10-22 | 2013-08-07 | 安普雷斯股份有限公司 | Composite structures containing high capacity porous active materials constrained in shells |
| CN103325998A (en) * | 2013-05-15 | 2013-09-25 | 同济大学 | Flexible nano SnO2/Si composite lithium ion battery negative-electrode material and preparation method thereof |
-
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102576857A (en) * | 2009-05-27 | 2012-07-11 | 安普雷斯股份有限公司 | Core-shell high capacity nanowires for battery electrodes |
| CN103210530A (en) * | 2010-08-27 | 2013-07-17 | 纽约州立大学研究基金会 | Branched nanostructures for battery electrodes |
| CN103238238A (en) * | 2010-10-22 | 2013-08-07 | 安普雷斯股份有限公司 | Composite structures containing high capacity porous active materials constrained in shells |
| CN102800851A (en) * | 2012-08-17 | 2012-11-28 | 奇瑞汽车股份有限公司 | Silicon carbon composite material and preparation method thereof, lithium ion battery containing same |
| CN103031610A (en) * | 2012-12-07 | 2013-04-10 | 北京航空航天大学 | Method for preparing single ultra-long Cu nanowire and measuring electrical properties of the nanowire |
| CN103107317A (en) * | 2013-01-17 | 2013-05-15 | 奇瑞汽车股份有限公司 | Si-C composite material and preparation method thereof and lithium ion battery containing same |
| CN103325998A (en) * | 2013-05-15 | 2013-09-25 | 同济大学 | Flexible nano SnO2/Si composite lithium ion battery negative-electrode material and preparation method thereof |
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