CN109192549A - A kind of stabilized lithium powder-carbon nanotube-overlong nanowire combination electrode and preparation method thereof and a kind of supercapacitor - Google Patents
A kind of stabilized lithium powder-carbon nanotube-overlong nanowire combination electrode and preparation method thereof and a kind of supercapacitor Download PDFInfo
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- CN109192549A CN109192549A CN201811020594.7A CN201811020594A CN109192549A CN 109192549 A CN109192549 A CN 109192549A CN 201811020594 A CN201811020594 A CN 201811020594A CN 109192549 A CN109192549 A CN 109192549A
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- overlong nanowire
- carbon nanotube
- lithium powder
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
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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
- Y02E60/13—Energy storage using capacitors
Abstract
The present invention provides a kind of stabilized lithium powder-carbon nanotube-overlong nanowire combination electrodes and preparation method thereof and a kind of supercapacitor.The present invention carries out prelithiation processing to carbon nanotube-hydroxyapatite overlong nanowire pole piece using the stabilized lithium powder of surface cladding lithium fluoride, obtain stabilized lithium powder-carbon nanotube-overlong nanowire combination electrode, the problem of surface coated lithium fluoride of lithium powder can effectively prevent excessive lithium from forming Li dendrite, and surface cladding lithium fluoride lithium powder can be stable be present in air, make prelithiation processing it is more convenient.Combination electrode electrochemical performance provided by the invention, the super capacitor energy density assembled using combination electrode provided by the invention is high, good cycle.
Description
Technical field
The present invention relates to the technical field of supercapacitor, in particular to a kind of stabilized lithium powder-carbon nanotube-overlength is received
Rice noodles combination electrode and preparation method thereof and a kind of supercapacitor.
Background technique
With the rapid development of industry, population is sharply increased, and the consumption of global energy just constantly adds at an amazing speed
Fastly, energy shortage and environmental pollution become current mankind and develop two test faced.Therefore must greatly develop low cost, can
Continue and environmental-friendly novel energy is converted and energy storage device is increasingly prominent to meet present social growth requirement and alleviation
Environmental problem out.In various energy-storage systems, most important is exactly electrochemical energy storage system, including lithium ion battery,
Supercapacitor and fuel cell.In recent years, in the fields such as information technology, electronic product and vehicle used energy new technology it is fast
Speed development, lithium ion super capacitor is big by feat of its specific capacity, charge/discharge speed is fast, the features such as having extended cycle life has attracted and grinds
The great interest for the person of studying carefully.
Carrying out prelithiation processing to the negative electrode material of lithium ion super capacitor can be improved the electrochemistry of supercapacitor
Performance, in existing prelithiation processing method, it is pre- lithium the most simple and effective that metallic lithium powder, which is coated in negative electrode tab surface,
Change mode.But lithium powder additive amount is very few when prelithiation processing is not achieved effect, it is broken that excessive metallic lithium powder easily forms Li dendrite
Bad diaphragm, and can form thick SEI film in negative terminal surface causes resistance to increase, so as to cause the electrochemistry of supercapacitor
Performance decline, and lithium powder is easy to oxidize in air, and stability is poor.
Summary of the invention
In view of this, it is an object of that present invention to provide a kind of stabilized lithium powder-carbon nanotube-overlong nanowire combination electrodes
And preparation method thereof and a kind of supercapacitor, combination electrode provided by the invention using surface fluorination stabilized lithium powder carry out
Prelithiation solves the problems, such as lithium powder readily oxidizable substance, and is not easy to form Li dendrite, is negative using combination electrode provided by the invention
The super capacitor energy density of pole assembling is high, power density is high, good cycle.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
A kind of preparation method of stabilized lithium powder-carbon nanotube-overlong nanowire combination electrode, comprising the following steps:
(1) ultrasonic treatment and sanded treatment are successively carried out after mixing dispersing agent, carbon nanotube and water, obtain carbon nanotube
Dispersion liquid；
(2) it is beaten after mixing hydroxyapatite overlong nanowire and alcohols solvent, obtains hydroxyapatite overlength
Nanowire suspended liquid；
(3) carbon nano tube dispersion liquid and hydroxyapatite overlong nanowire suspension are mixed, by gained mixing slurry
Material is coated in substrate, and carbon nanotube-wet pole piece of hydroxyapatite overlong nanowire is obtained after substrate is removed；By the wet pole
Piece is dry, arrives carbon nanotube-hydroxyapatite overlong nanowire pole piece；
(4) by perfluorinated resin and metallic lithium powder apart under conditions of be heat-treated, obtain stabilized lithium powder；
(5) carbon nanotube-hydroxyapatite overlong nanowire pole piece is carried out at prelithiation using the stabilized lithium powder
Reason, obtains stabilized lithium powder-carbon nanotube-overlong nanowire combination electrode；
The limitation of the not no time sequencing of the step (1), (2) and (4)；
The limitation of the not no time sequencing in the step (3) and (4).
Preferably, the prelithiation in the step (5) is handled the following steps are included: the stabilized lithium powder has been dispersed in
In solvent, by obtained stabilized lithium powder dispersion in the carbon nanotube-hydroxyapatite overlong nanowire pole piece
Then surface carries out hot-forming.
Preferably, the hot-forming temperature be 150~180 DEG C, pressure be 10~12MPa, the time be 5~
10min。
Preferably, in the mixed slurry of the step (3) carbon nanotube and hydroxyapatite overlong nanowire mass ratio
For 3:7~7:3.
Preferably, the mass ratio of perfluorinated resin and metallic lithium powder is 2~5:1 in the step (4).
Preferably, the heat treatment in the step (4) includes the high-temperature heat treatment and Low Temperature Heat Treatment successively carried out；
The temperature of the high-temperature heat treatment is 330~350 DEG C, and the time is 1~2h；
The temperature of the Low Temperature Heat Treatment is 150~180 DEG C, and the time is 10~12h.
The present invention provides stabilized lithium powder-carbon nanotube-overlong nanowires of the preparation of preparation method described in above scheme
Combination electrode, including carbon nanotube-overlong nanowire pole piece and the stabilized lithium powder being supported on the pole piece, the stabilisation
Load capacity of the lithium powder on combination electrode surface is 0.01~0.1g/m2。
The present invention provides a kind of supercapacitor, including anode, diaphragm, cathode and electrolyte, the cathode is above-mentioned
Powder-carbon nanotube-overlong nanowire the combination electrode of stabilized lithium described in scheme.
Preferably, the just extremely active carbon-hydroxyapatite overlong nanowire combination electrode；
The active carbon-hydroxyapatite overlong nanowire combination electrode preparation method the following steps are included:
Decentralized processing is carried out after active carbon and water are mixed, obtains active carbon dispersion liquid；
It is beaten after hydroxyapatite overlong nanowire and alcohols solvent are mixed, obtains hydroxyapatite overlength nanometer
Line suspension；
The active carbon dispersion liquid and hydroxyapatite overlong nanowire suspension are mixed, mixed slurry is coated in base
On bottom, active carbon-wet pole piece of hydroxyapatite overlong nanowire is obtained after substrate is removed；The wet pole piece is dry, to work
Property charcoal-hydroxyapatite overlong nanowire combination electrode.
Preferably, the diaphragm is microporous polypropylene membrane；The electrolyte is LiPF6Electrolyte.
The present invention provides a kind of preparation method of stabilized lithium powder-carbon nanotube-overlong nanowire combination electrode, this hairs
The bright stabilized lithium powder for preparing carbon nanotube-hydroxyapatite overlong nanowire pole piece and surface fluorination first, then using steady
Surely change lithium powder and prelithiation processing is carried out to carbon nanotube-hydroxyapatite overlong nanowire pole piece, obtain stabilized lithium powder-carbon and receive
Mitron-overlong nanowire combination electrode.The present invention carries out prelithiation processing, lithium powder surface cladding to pole piece using stabilized lithium powder
Lithium fluoride the problem of can effectively preventing excessive lithium from forming Li dendrite, thus solve lithium powder additive amount during prelithiation
How many problems, and what the lithium powder of surface cladding lithium fluoride can be stable is present in air, keeps prelithiation processing more square
Just.
Stabilized lithium powder-carbon nanotube-overlong nanowire that the present invention provides the preparation of preparation method described in above scheme is multiple
Composite electrode, including carbon nanotube-overlong nanowire pole piece and the stabilized lithium powder being supported on the pole piece, the stabilized lithium
Load capacity of the powder on combination electrode surface is 0.01~0.1g/m2.In the present invention, hydroxyapatite overlong nanowire and carbon are received
Mitron forms pole piece, and hydroxyapatite overlong nanowire flexibility is good, high temperature resistant, corrosion-resistant, and biological safety is good, carbon nanotube
With good cavernous structure, stabilized lithium powder can be very good to incorporate in pole piece, and by carbon nanotube and hydroxyapatite
The combination electrode of overlong nanowire preparation has good electrolyte wellability, to improve the chemical property of electrode.Implement
Example the result shows that, be the super capacitor energy density height that cathode assembles using combination electrode provided by the invention, good cycle,
Capacitor retention rate after circulation 3500 times can achieve 90% or so.
Detailed description of the invention
Fig. 1 is the power density and energy density relationships of 1# supercapacitor and 2# supercapacitor in the embodiment of the present invention
Curve graph；
Fig. 2 is the cycle performance test chart of 1# supercapacitor and 2# supercapacitor in the embodiment of the present invention.
Specific embodiment
The present invention provides a kind of preparation methods of stabilized lithium powder-carbon nanotube-overlong nanowire combination electrode, including
Following steps:
(1) ultrasonic treatment and sanded treatment are successively carried out after mixing dispersing agent, carbon nanotube and water, obtain carbon nanotube
Dispersion liquid；
(2) it is beaten after mixing hydroxyapatite overlong nanowire and alcohols solvent, obtains hydroxyapatite overlength
Nanowire suspended liquid；
(3) carbon nano tube dispersion liquid and hydroxyapatite overlong nanowire suspension are mixed, mixed slurry is applied
It overlays in substrate, carbon nanotube-wet pole piece of hydroxyapatite overlong nanowire is obtained after substrate is removed；The wet pole piece is done
It is dry, arrive carbon nanotube-hydroxyapatite overlong nanowire pole piece；
(4) by perfluorinated resin and metallic lithium powder apart under conditions of be heat-treated, obtain stabilized lithium powder；
(5) carbon nanotube-hydroxyapatite overlong nanowire pole piece is carried out at prelithiation using the stabilized lithium powder
Reason, obtains stabilized lithium powder-carbon nanotube-overlong nanowire combination electrode；
The limitation of the not no time sequencing of the step (1), (2) and (4)；
The limitation of the not no time sequencing in the step (3) and (4).
The present invention is successively ultrasonically treated after mixing dispersing agent, carbon nanotube and water and sanded treatment, obtains carbon and receives
Mitron dispersion liquid.In the present invention, the dispersing agent is preferably lauryl sodium sulfate (SDS), polyvinylpyrrolidone
(PVP) and one or more of dodecyl sodium sulfate (SDBS)；The dispersing agent and the mass ratio of carbon nanotube are preferably
0.05~0.2:1, more preferably 0.05~0.1:1；The mass concentration of the carbon nano tube dispersion liquid is preferably 3~8%, more
Preferably 4~6%.
In the present invention, the power of the ultrasonic treatment is preferably 50~150KHz, more preferably (80~130) KHz,
The time of the ultrasonic treatment is preferably 20~40min, more preferably 25~35min；The revolving speed of the sanded treatment is preferably
1000~2000r/min, more preferably 1200~1500r/min；The time of the sanded treatment is preferably 15~60min, more
Preferably 20~50min.Present invention preferably uses sand mills to carry out sanded treatment.
The present invention is beaten after mixing hydroxyapatite overlong nanowire and alcohols solvent, and it is super to obtain hydroxyapatite
Long nanowire suspended liquid.In the present invention, the diameter of the hydroxyapatite overlong nanowire is preferably 5~100nm, more preferably
For 30~50nm；The length of the hydroxyapatite overlong nanowire is preferably 30~1200um, more preferably 300~500um.
The present invention does not have particular/special requirement to the source of the hydroxyapatite overlong nanowire, uses source known to those skilled in the art
Hydroxyapatite overlong nanowire, such as commercially available hydroxyapatite overlong nanowire, the hydroxyl that the embodiment of the present invention uses
Base apatite overlong nanowire is bought from Shanghai Silicate Inst., Chinese Academy of Sciences.
In the present invention, the alcohols solvent is preferably ethyl alcohol；The matter of the hydroxyapatite overlong nanowire suspension
Measuring concentration is preferably 3~8%, and more preferably 4~6%；The time of the mashing is preferably 5~10min.The present invention is to described
The specific method of mashing does not have particular/special requirement, can obtain uniform suspension.
After obtaining carbon nano tube dispersion liquid and hydroxyapatite overlong nanowire suspension, the present invention is by the carbon nanotube
Dispersion liquid and the mixing of hydroxyapatite overlong nanowire suspension, obtain mixed slurry.In the present invention, the carbon nanotube point
Dispersion liquid and the volume ratio of hydroxyapatite overlong nanowire suspension are preferably 1:1~5, more preferably 1:2~4；The present invention is excellent
Choosing carries out the mixing of carbon nano tube dispersion liquid and hydroxyapatite overlong nanowire suspension using microfluidic mixer machine；In the present invention
In, the mass ratio of carbon nanotube and hydroxyapatite overlong nanowire is preferably 3:7~7:3 in the mixed slurry, more preferably
For 4:6~6:4.
After obtaining mixed slurry, the mixed slurry is coated in substrate by the present invention, is obtained carbon after substrate is removed and is received
Mitron-wet the pole piece of hydroxyapatite overlong nanowire.In the present invention, the coating preferably sprays, more preferably using height
Pressure airless sprayer is sprayed；The substrate is preferably paillon；The present invention does not have particular/special requirement to the thickness of the coating,
In specific embodiments of the present invention, coating thickness is preferably determined according to the target thickness of combination electrode.The present invention is to the removing
The method of substrate does not have particular/special requirement, uses stripping means well known to those skilled in the art.
After the completion of removing, the present invention is dry by the wet pole piece of the carbon nanotube-hydroxyapatite overlong nanowire, obtains carbon
Nanotube-hydroxyapatite overlong nanowire pole piece.In the present invention, the temperature of the drying is preferably 30~80 DEG C, more excellent
50~70 DEG C are selected as, the present invention does not have particular/special requirement to the time of the drying, can be completely dried the wet pole piece.
By perfluorinated resin and metallic lithium powder apart under conditions of be heat-treated, obtain stabilized lithium powder.At this
In invention, the mass ratio of the perfluorinated resin and metallic lithium powder is preferably 2~5:1, more preferably 3~4:1；The present invention will be described
Perfluorinated resin and metallic lithium powder are apart from avoiding the problem that subsequent metal lithium powder and resin are not readily separated；In tool of the invention
In body embodiment, it is spaced apart and guarantees that perfluorinated resin and lithium powder do not contact, it is possible to use asbestos board separates perfluorinated resin.
In the present invention, the heat treatment preferably includes the high-temperature heat treatment and Low Temperature Heat Treatment that successively carry out；The height
The temperature of warm processing is preferably 330~350 DEG C, and more preferably 340 DEG C；The time of the high-temperature process is preferably 1~2h, more
Preferably 1.5h；The temperature of the Low Temperature Heat Treatment is preferably 150~180 DEG C, and more preferably 160~170 DEG C, the low temperature
The time of heat treatment is preferably 10~12h, more preferably 11h.In high-temperature heat treatment process, perfluorinated resin is heated to generate fluorine
Gas, in low temperature heat treatment, fluorine gas and lithium powder react, in lithium powder Surface Creation lithium fluoride.
The present invention carries out stabilization processes (surface fluorination processing) to lithium powder, and lithium fluoride is made to be wrapped in lithium powder surface, lithium powder
Surface cladding lithium fluoride can effectively prevent excessive lithium from forming Li dendrite, and it is how many to solve prelithiation process lithium powder additive amount
Problem；And surface cladding lithium fluoride lithium powder can be highly stable be present in air so that prelithiation operation it is more square
Just.
After obtaining stabilized lithium powder, the present invention receives carbon nanotube-hydroxyapatite overlength using the stabilized lithium powder
Rice noodles pole piece carries out prelithiation processing, obtains stabilized lithium powder-carbon nanotube-overlong nanowire combination electrode.In the present invention,
The prelithiation processing preferably includes following steps: in organic solvent by stabilized lithium powder dispersion, the stabilization that will be obtained
Change lithium powder dispersion in the carbon nanotube-hydroxyapatite overlong nanowire pole piece, is then hot pressed into
Type.
The present invention disperses stabilized lithium powder in organic solvent, to obtain stabilized lithium powder dispersion liquid.In the present invention, institute
Stating organic solvent is preferably nonpolar solvent or weak polar solvent, more preferably benzene and/or toluene；The matter of the stabilized lithium powder
Amount and the volume ratio of organic solvent are preferably 0.5~1g:100~200mL, more preferably 0.5~0.75g:100~150ml.This
Invention does not have particular/special requirement to the specific method of the dispersion, using dispersing method well known to those skilled in the art, can incite somebody to action
Stabilized lithium powder is evenly dispersed in organic solvent.
After obtaining stabilized lithium powder dispersion liquid, the stabilized lithium powder is divided dispersion in carbon nanotube-by the present invention
Hydroxyapatite overlong nanowire pole piece.The present invention does not have particular/special requirement to the specific method of the coating, uses ability
Coating method known to field technique personnel.The present invention does not have particular/special requirement to the thickness of the coating, preferably according to lithium powder
Targeted loads amount and the concentration of stabilized lithium powder dispersion liquid determine coating thickness.
In the present invention, the hot-forming temperature is preferably 150~180 DEG C, and more preferably 160~170 DEG C, when
Between preferably 5~10min, more preferably 6~8min, pressure is preferably 10~12MPa, more preferably 11MPa.The present invention is preferred
It is carried out using vulcanizing press hot-forming.
The present invention provides stabilized lithium powder-carbon nanotube-overlong nanowires of the preparation of preparation method described in above scheme
Combination electrode, including carbon nanotube-overlong nanowire pole piece and the stabilized lithium powder being supported on the pole piece.In the present invention
In, load capacity of the stabilized lithium powder on combination electrode surface is preferably 0.01~0.1g/cm2, more preferably 0.05~
0.08g/cm2.In the present invention, hydroxyapatite overlong nanowire and carbon nanotube form pole piece, and hydroxyapatite overlength is received
Rice noodles flexibility is good, high temperature resistant, corrosion-resistant, and biological safety is good, and carbon nanotube has good cavernous structure, stabilized lithium powder
It can be very good to incorporate in pole piece, to improve the chemical property of electrode.
The present invention provides a kind of supercapacitors, including anode, diaphragm, cathode and electrolyte.In the present invention, described
Cathode is stabilized lithium powder-carbon nanotube-overlong nanowire combination electrode described in above scheme, and details are not described herein.
In the present invention, the anode is preferably active carbon-hydroxyapatite overlong nanowire combination electrode, the activity
Charcoal-hydroxyapatite overlong nanowire combination electrode preparation method preferably includes following steps:
Disperse after active carbon and water are mixed, obtains active carbon dispersion liquid；
It is beaten after hydroxyapatite overlong nanowire and alcohols solvent are mixed, obtains hydroxyapatite overlength nanometer
Line suspension；
The active carbon dispersion liquid and hydroxyapatite overlong nanowire suspension are mixed, mixed slurry is coated in base
On bottom, active carbon-wet pole piece of hydroxyapatite overlong nanowire is obtained after substrate is removed；The wet pole piece is dry, to work
Property charcoal-hydroxyapatite overlong nanowire combination electrode.
The present invention disperses after mixing active carbon and water, obtains active carbon dispersion liquid.In the present invention, the dispersion
Dispersion preferably includes the ultrasonic disperse successively carried out and shearing dispersion, and the time of the ultrasonic disperse is preferably 20~40min, institute
The time for stating shearing dispersion is preferably 15~60min；The present invention does not have particular/special requirement to the specific method of the shearing dispersion, makes
With shearing dispersing method well known to those skilled in the art, such as stir；The present invention to the power of the ultrasonic disperse and
The dynamics of shearing dispersion does not have particular/special requirement, can be evenly dispersed by active carbon.In the present invention, the active carbon dispersion
The mass concentration of active carbon is preferably 3~8% in liquid, and more preferably 4~6%.
In the present invention, the preparation method, the type of alcohols solvent of the hydroxyapatite overlong nanowire suspension with
And the concentration of suspension is consistent with above scheme, details are not described herein.
In the present invention, the mixing of the active carbon dispersion liquid and hydroxyapatite overlong nanowire suspension, is mixed
Close slurry.In the present invention, the volume ratio of the active carbon dispersion liquid and hydroxyapatite overlong nanowire suspension is preferably 1
~3:1, more preferably 2:1.
After obtaining mixed slurry, mixed slurry will be coated in substrate by the present invention, obtain active carbon-after substrate is removed
The wet pole piece of hydroxyapatite overlong nanowire；The wet pole piece is dry, it is compound to active carbon-hydroxyapatite overlong nanowire
Electrode.In the present invention, carbon nanometer described in the drying process and above scheme of the coating, the removing of substrate and wet pole piece
Pipe-hydroxyapatite overlong nanowire preparation process is consistent, and details are not described herein.
In the present invention, the diaphragm of the supercapacitor is preferably microporous polypropylene membrane, and electrolyte is preferably LiPF6Electricity
Solve liquid.
In the present invention, it is also preferable to include anode covers and negative electrode casing for the supercapacitor, and the present invention is to the anode cover
There is no particular/special requirement with negative electrode casing, using well known to those skilled in the art.
The present invention does not have particular/special requirement to the assemble method of the supercapacitor, and use is well known to those skilled in the art
Method is assembled.
Below with reference to embodiment to a kind of stabilized lithium powder-carbon nanotube-overlong nanowire compound electric provided by the invention
Pole and preparation method thereof and a kind of supercapacitor are described in detail, but they cannot be interpreted as protecting the present invention
The restriction of range.
Embodiment 1
(1) 0.5g carbon nanotube, 0.05g SDS and water are placed in a beaker, by ultrasonic disperse 30min, sand mill sand
30min is ground, carbon nanotube aqueous liquid dispersion is obtained.
(2) hydroxyapatite overlong nanowire is beaten 5min with beater in alcohol, obtains hydroxyapatite overlength
Nanowire suspended liquid.
(3) obtained carbon nano tube dispersion liquid and hydroxyapatite overlong nanowire suspension are passed through into airflow counter-collision machine
After evenly mixing, by high pressure airless spray equipment, by mixed slurry, (carbon nanotube and hydroxyapatite overlength are received in mixed slurry
The mass ratio of rice noodles is 3:7) it sprays in foil substrate, it after removing paillon, is dried in 60 DEG C of drying boxes, carbon nanotube-is made
Hydroxyapatite overlong nanowire pole piece.
(4) it takes 3g perfluorinated resin to be placed in quartz curette, adds 1g metallic lithium powder, metallic lithium powder is separated with perfluorinated resin and put
It sets, then quartz curette is put into tube furnace and is heated to 350 DEG C of heat preservation 2h, then be cooled to 150 DEG C of heat preservation 12h, obtain stabilized lithium
Powder.
(5) stabilized lithium powder is dissolved in benzene and is dispersed, stabilized lithium powder homogeneous dispersion is applied to and is prepared
Carbon nanotube-hydroxyapatite overlong nanowire pole piece on, by vulcanizing press temperature be 150 DEG C, pressure 10Mpa
Under, hot pressing 10min is cut into the pole piece of φ 14mm, stabilized lithium powder-carbon nanotube-overlong nanowire combination electrode is made, wherein
The load capacity of stabilized lithium powder is 0.05g/cm2。
Embodiment 2
(1) 1g carbon nanotube, 0.06g SDS and water are placed in a beaker, by ultrasonic disperse 30min, sand mill is sanded
30min obtains carbon nanotube aqueous liquid dispersion.
(2) hydroxyapatite overlong nanowire is beaten 5min with beater in alcohol, obtains hydroxyapatite overlength
Nanowire suspended liquid.
(3) obtained carbon nano tube dispersion liquid and hydroxyapatite overlong nanowire suspension are passed through into airflow counter-collision machine
After evenly mixing, by high pressure airless spray equipment, by mixed slurry, (carbon nanotube and hydroxyapatite overlength are received in mixed slurry
The mass ratio of rice noodles is 4:6) it sprays in foil substrate, it after removing paillon, is dried in 60 DEG C of drying boxes, carbon nanotube-is made
Hydroxyapatite overlong nanowire pole piece.
(4) it takes 5g perfluorinated resin to be placed in quartz curette, adds 1g metallic lithium powder, metallic lithium powder is separated with perfluorinated resin and put
It sets, then quartz curette is put into tube furnace and is heated to 330 DEG C of heat preservation 1h, then be cooled to 180 DEG C of heat preservation 10h, form stabilized lithium
Powder.
(5) stabilized lithium powder is dissolved in benzene and is dispersed, stabilized lithium powder homogeneous dispersion is applied to and is prepared
Carbon nanotube-hydroxyapatite overlong nanowire pole piece on, by vulcanizing press temperature be 180 DEG C, pressure 12Mpa
Under, hot pressing 5min is cut into the pole piece of φ 14mm, stabilized lithium powder-carbon nanotube-overlong nanowire combination electrode is made, wherein
The load capacity of stabilized lithium powder is 0.1g/cm2。
Embodiment 3
It weighs 0.5g active carbon to be placed in a beaker, obtains active carbon water by ultrasonic disperse 30min, shearing dispersion 30min
Property dispersion liquid.
Hydroxyapatite overlong nanowire is beaten 10min with beater in alcohol, hydroxyapatite overlength is obtained and receives
Rice noodles suspension.
Obtained active carbon dispersion liquid and hydroxyapatite overlong nanowire suspension is uniform by airflow counter-collision machine
After mixing, mixed slurry is sprayed in foil substrate by high pressure airless spray equipment, after removing paillon, is dried in 60 DEG C of drying boxes
It is dry, it is cut into the pole piece of φ 14mm, active carbon-hydroxyapatite overlong nanowire combination electrode is made.
Stabilized lithium powder-carbon nanotube-overlong nanowire the combination electrode prepared using embodiment 1 is cathode, with active carbon-
Hydroxyapatite overlong nanowire combination electrode is anode, with LiPF6For electrolyte, porous polypropylene film is diaphragm, true
Electrolyte is added to be assembled into lithium ion super according to the sequence of negative electrode casing, negative electrode tab, diaphragm, positive plate, anode cover in empty-handed casing
Capacitor is denoted as 1# supercapacitor.
It the use of the carbon nanotube in 1 step of embodiment (3)-hydroxyapatite overlong nanowire pole piece is cathode, according to phase
Same method assembles supercapacitor, is denoted as 2# supercapacitor.
The power density and energy density of 1# supercapacitor and 2# supercapacitor are tested, test condition are as follows:
The current density of constant current charge-discharge is 100mA/g~7000mA/g, and the voltage window of charge and discharge is 2~4V.Acquired results such as Fig. 1
Shown, Fig. 1 is the power density of supercapacitor and the relation curve of energy density.According to Fig. 1 as can be seen that 1# super capacitor
Device is compared with 2# capacitor, and with the increase of power density, energy density reduces amplitude and is obviously reduced.
The cycle performance of 1# supercapacitor and 2# supercapacitor is tested, test condition is that charging and discharging currents are close
Degree is 400mA/g, and the voltage window of charge and discharge is 2~4V, and as indicated with 2, Fig. 2 is the cycle performance of supercapacitor to test result
Test chart.According to fig. 2 as can be seen that after circulation 3500 times, the capacitor retention rate of 1# supercapacitor can achieve 90% left side
The right side, and the capacitor retention rate of 2# capacitor is below 70%.
According to the above results as can be seen that stabilized lithium provided by the invention powder-carbon nanotube-overlong nanowire compound electric
It is great to have superior chemical property, using the super capacitor energy density height that the combination electrode is assembled as cathode, cyclicity
It can be good.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of stabilized lithium powder-carbon nanotube-overlong nanowire combination electrode, comprising the following steps:
(1) ultrasonic treatment and sanded treatment are successively carried out after mixing dispersing agent, carbon nanotube and water, obtain carbon nanotube dispersion
Liquid；
(2) it is beaten after mixing hydroxyapatite overlong nanowire and alcohols solvent, obtains hydroxyapatite overlength nanometer
Line suspension；
(3) carbon nano tube dispersion liquid and hydroxyapatite overlong nanowire suspension are mixed, gained mixed slurry is applied
It overlays in substrate, carbon nanotube-wet pole piece of hydroxyapatite overlong nanowire is obtained after substrate is removed；The wet pole piece is done
It is dry, arrive carbon nanotube-hydroxyapatite overlong nanowire pole piece；
(4) by perfluorinated resin and metallic lithium powder apart under conditions of be heat-treated, obtain stabilized lithium powder；
(5) prelithiation processing is carried out to carbon nanotube-hydroxyapatite overlong nanowire pole piece using the stabilized lithium powder, obtained
To stabilized lithium powder-carbon nanotube-overlong nanowire combination electrode；
The limitation of the not no time sequencing of the step (1), (2) and (4)；
The limitation of the not no time sequencing in the step (3) and (4).
2. preparation method according to claim 1, which is characterized in that the processing of prelithiation in the step (5) include with
Lower step: in organic solvent by stabilized lithium powder dispersion, by obtained stabilized lithium powder dispersion in the carbon
Nanotube-hydroxyapatite overlong nanowire pole piece, then carries out hot-forming.
3. preparation method according to claim 2, which is characterized in that the hot-forming temperature is 150~180 DEG C,
Pressure is 10~12MPa, and the time is 5~10min.
4. preparation method according to claim 1, which is characterized in that carbon nanotube in the mixed slurry of the step (3)
Mass ratio with hydroxyapatite overlong nanowire is 3:7~7:3.
5. preparation method according to claim 1, which is characterized in that perfluorinated resin and metallic lithium powder in the step (4)
Mass ratio be 2~5:1.
6. preparation method according to claim 1, which is characterized in that heat treatment in the step (4) include successively into
Capable high-temperature heat treatment and Low Temperature Heat Treatment；
The temperature of the high-temperature heat treatment is 330~350 DEG C, and the time is 1~2h；
The temperature of the Low Temperature Heat Treatment is 150~180 DEG C, and the time is 10~12h.
7. stabilized lithium powder-carbon nanotube-overlong nanowire of the preparation of preparation method described in claim 1~6 any one is multiple
Composite electrode, including carbon nanotube-overlong nanowire pole piece and the stabilized lithium powder being supported on the pole piece, the stabilized lithium
Load capacity of the powder on combination electrode surface is 0.01~0.1g/m2。
8. a kind of supercapacitor, including anode, diaphragm, cathode and electrolyte, which is characterized in that the cathode is claim
Powder-carbon nanotube-overlong nanowire the combination electrode of stabilized lithium described in 7.
9. supercapacitor according to claim 8, which is characterized in that described just extremely active carbon-hydroxyapatite is super
Long nano wire combination electrode；
The active carbon-hydroxyapatite overlong nanowire combination electrode preparation method the following steps are included:
Decentralized processing is carried out after active carbon and water are mixed, obtains active carbon dispersion liquid；
It is beaten after hydroxyapatite overlong nanowire and alcohols solvent are mixed, it is outstanding to obtain hydroxyapatite overlong nanowire
Supernatant liquid；
The active carbon dispersion liquid and hydroxyapatite overlong nanowire suspension are mixed, mixed slurry is coated in substrate
On, active carbon-wet pole piece of hydroxyapatite overlong nanowire is obtained after substrate is removed；The wet pole piece is dry, to activity
Charcoal-hydroxyapatite overlong nanowire combination electrode.
10. supercapacitor according to claim 8 or claim 9, which is characterized in that the diaphragm is microporous polypropylene membrane；Institute
Stating electrolyte is LiPF6Electrolyte.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012057031A1 (en) * | 2010-10-27 | 2012-05-03 | 協立化学産業株式会社 | Conductive undercoating agent composition |
| WO2014119663A1 (en) * | 2013-02-01 | 2014-08-07 | 株式会社日本触媒 | Electrode precursor, electrode, and battery |
| CN106654215A (en) * | 2016-12-30 | 2017-05-10 | 温州大学 | Small biological molecule and graphene composite material functional film and preparation method thereof |
| CN107565081A (en) * | 2017-07-11 | 2018-01-09 | 中国科学院上海硅酸盐研究所 | A kind of hydroxyapatite overlong nanowire based high-temp-resistant battery diaphragm and its application |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012057031A1 (en) * | 2010-10-27 | 2012-05-03 | 協立化学産業株式会社 | Conductive undercoating agent composition |
| WO2014119663A1 (en) * | 2013-02-01 | 2014-08-07 | 株式会社日本触媒 | Electrode precursor, electrode, and battery |
| CN106654215A (en) * | 2016-12-30 | 2017-05-10 | 温州大学 | Small biological molecule and graphene composite material functional film and preparation method thereof |
| CN107565081A (en) * | 2017-07-11 | 2018-01-09 | 中国科学院上海硅酸盐研究所 | A kind of hydroxyapatite overlong nanowire based high-temp-resistant battery diaphragm and its application |
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