CN108807008A - A kind of lithium-ion capacitor nano whiskers flexibility lithium titanate/carbon nano tube/graphene composite material and preparation method - Google Patents
A kind of lithium-ion capacitor nano whiskers flexibility lithium titanate/carbon nano tube/graphene composite material and preparation method Download PDFInfo
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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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- 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
- 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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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
- H01G11/46—Metal oxides
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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
- 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
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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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 disclose a kind of lithium-ion capacitor nano whiskers flexibility lithium titanate/carbon nano tube/graphene flexible composite and and preparation method thereof.The present invention prepares nano whiskers lithium titanate using hydro-thermal method first, is then mixed again with carbon nanotube, graphene, and it is evenly dispersed in a solvent, using the approach of vacuum filtration, above-mentioned composite material is prepared.The composite material is woven by one-dimensional nano whiskers lithium titanate, one-dimensional carbon nanotube and two-dimensional graphene by van der waals force intrinsic between nano material, has the characteristics such as flexible, porous, large specific surface area.When being used as lithium-ion capacitor electrode material, without adding binder, conductive agent, in addition, material itself has self-supporting, characteristic flexible, also without collector, is conducive to improve the energy density of lithium-ion capacitor and its application in flexible energy storage field can be expanded.
Description
Technical field
The present invention relates to lithium-ion capacitor electrode material technical fields, and in particular to a kind of lithium-ion capacitor nanometer
Needle-shaped flexibility lithium titanate/carbon nano tube/graphene composite material and preparation method.
Technical background
Embedding lithium battery material lithium titanate (Li in recent years4Ti5O12, LTO) due to advantageous property and increasingly by
The extensive concern of researcher.Spinel type lithium titanate has stable charge and discharge platform (1.55V vs Li/Li+), safety
Can be high, cheap, it is almost nil in the volume change of charge and discharge process lattice, therefore also referred to as " zero strain material ", reason
By upper, the lithium ion battery of assembling not only has fast charging and discharging energy, but also has good cycle life, therefore metatitanic acid
Lithium is a kind of very lithium ion battery electrode material with development potentiality.But lithium titanate native electronic conductivity relatively low (10- 13S/cm), ionic conductivity low (10-6cm2/ s), limit the cycle performance and high rate during charging-discharging of electrode material.Separately
Outside, lithium titanate is as positive electrode, and relatively low relative to lithium current potential, specific capacity, energy density are relatively low；Lithium titanate is as cathode material
Material, then it is more harsh to the selection of positive electrode, therefore the two disadvantages limit the application of lithium titanate.
On the shortcomings that its electric conductivity being concentrated mainly on to the study on the modification of lithium titanate.Metal ion mixing is such as carried out, is passed through
Introducing free electron, either the electronic conductance performance or coated modified carbon of lithium titanate are improved in hole, because carrying out carbon coating,
The problem of lithium titanate structure will not be changed, lithium titanate reunion growth is also prevented while improving lithium titanate ionic conductivity, have
Conducive to the high rate during charging-discharging of raising material；The present invention is based on the electronic conductivity of existing lithium titanate, ionic conductivities
Disadvantage and research and develop.
Invention content
It is an object of the invention to overcome the existing disadvantage of lithium titanate electrical conductance difference, it is woven into graphene/carbon nano-tube
Flexible frame structure overlap lithium titanate nanometer rods, obtain a kind of completely new by lithium titanate, carbon nanotube and graphene three-dimensional
The composite material of self-supporting characteristic.
Lithium titanate/carbon/carbon nano tube/graphene composite material of the present invention, is to first pass around ultrasound by carbon nanotube and graphene
It is blended, is woven into three-dimensional frame structure, then lithium titanate is uniformly adhered in the frame structure.The wherein described carbon nanotube is
One-dimensional multi-walled carbon nanotube, graphene are the redox graphene improved Hummer methods and prepared.
The composite material be by lithium titanate precursor, it is compound with carbon nano tube/graphene frame structure.Due to one-dimensional carbon
Nanotube, two-dimensional graphene all have excellent ionic conductivity, thus frame made of being woven via Van der Waals for
There is structure excellent electrical conductance, lithium titanate to be uniformly adhered on the conductive structure effectively improve lithium titanate electrical conductance
The defect of difference so that the high rate performance and cycle performance of composite material can be promoted effectively.In addition, nano bar-shape metatitanic acid
Lithium can increase the contact with electrolyte, improve electrolyte infiltration, improve Ion transfer.The carbon that is attached to of lithium titanate is received simultaneously
Mitron, graphene sheet layer have also obstructed carbon nanotube, graphene tangles due to there are Van der Waals force, stacks reunion.The metatitanic acid
The material of lithium/carbon nano tube/graphene three dimensional composite structure plays mutually modified effect, has given full play to each component material
The advantages of.
Lithium titanate/carbon/carbon nano tube/the graphene composite material itself has self-supporting characteristic, without binder, conductive agent
And collector, the effective rate of utilization of material is improved, the specific capacity and energy density of material are improved.Composite material has itself
Flexibility, flexible for development, portable wearable electronic provides new mentality of designing.
Above-mentioned a kind of lithium titanate/carbon/carbon nano tube/graphene composite material, wherein the lithium titanate：Carbon nanotube：Graphene
Each mass percent be：(0.5~80)：5：(15~95).
The preparation method of above-mentioned lithium titanate/carbon/carbon nano tube/graphene composite material, includes the following steps：
S1. the preparation of lithium titanate nanometer rods：The lithium titanate precursor of nano bar-shape is prepared with hydro-thermal hair, it is spare.
Preferably, by the titanium dioxide (TiO of a certain amount of anatase2) and enough highly basic sodium hydroxide (NaOH
10mol/L), under 150 DEG C of environment, hydro-thermal reaction 72h, the centrifuge washing after persalt (1mol/L) acidleach 8h is prepared
The metatitanic acid of nano bar-shape；Again by itself and a certain amount of lithium hydroxide (LiOH), under 120 DEG C of environment, hydro-thermal is for 24 hours.Then from
The heart washs, and is dried to obtain the lithium titanate precursor of nano bar-shape.
S2. slurrying：In deionized water by ultrasonic disperse by graphene, stable suspension A is formed；By carbon nanotube
In deionized water by ultrasonic disperse, stable suspension B is formed, it is spare；
Specifically, GO prepared by Hummer methods is taken into 200mg, be dispersed in 100ml deionized waters, ultrasonic disperse, formed
Stable suspension A (2mg/ml GO), it is spare；In deionized water by the PVP dispersions of carbon nanotube 200mg and 4mg, ultrasound
Dispersion, forms stable suspension B (2mg/ml CNT), spare.
S3. it mixes for the first time：Suspension A and suspension B are blended according to a certain percentage, ULTRASONIC COMPLEX, are formed stable
Suspension C.
Above-mentioned steps S2-S3 is to prepare carbon nano tube/graphene frame structure to be formed, in case subsequent step uses.
S4. it mixes for second：The lithium titanate precursor of above-mentioned preparation and suspension C are mixed according to certain proportioning, surpassed
Sound is compound, obtains stable suspension D；
S5. it is filtered by vacuum：The above-mentioned suspension D of 10ml are taken, is filtered by vacuum and drying is removed, 80~120 μ m-thicks are prepared
The thin-film material of degree；
S6. it is heat-treated：The thin-film material that will be obtained in S4 is warm under preferably 600 DEG C of argon atmospheres at 500~800 DEG C
2~6h is handled, preferably 2h obtains target product.
The present invention is woven by lithium titanate and graphene with good conductivity, carbon nanotube by molecular force three-dimensional from branch
The shortcomings that electronic conductivity, ionic conductivity of the electrode material of support structure to improve lithium titanate.With such composite film material
As negative electrode of lithium ion battery and lithium-ion capacitor negative material, the shortcomings that significantly improving lithium titanate electrode material.Stone
Black alkene (Grephene) is with sp2The single layer of carbon atom film of the hexagonal crystal plane of hydridization composition.2004, the Nobel Prize
Winner English physicist Geim and Novoselov separate graphene with special adhesive tape from graphite, it was demonstrated that graphene
It can be individually stabilized with single layer structure.Grapheme two-dimension material theoretical specific surface area reaches 2623m2/g.π-π on atomic layer
Conjugated bonds make graphene have the function of good electron-transport, and conductivity is up to 106S/m, electrical conductance is best at room temperature
Material, thus the application field of graphene is very extensive.Exactly because however the presence of the pi-conjugated keys of π-so that graphene sheet layer holds
Easily reunite because of Van der Waals force, stack, so the graphene of pure phase is stored up just with the electric double layer principle on effective ratio area
Can, specific discharge capacity is very limited.Faraday's capacitance material is then that capacity density is larger, but electronic conductivity is low, and internal resistance is larger,
Cyclical stability is poor under high current charge-discharge.Graphene and faraday's capacitance material compound use can be given full play to respective
Advantage improves the chemical property of capacitor.So excellent using graphene two-dimensional layered structure, large specific surface area, electrical conductance
The characteristics of modified lithium titanate, the membrane structure material being combined itself have flexibility.This complex method completely by material from
Molecule force effect between body, preparation process is simple, easy, and environmental pollution is small.
The present invention utilize hydro-thermal method, nano whiskers lithium titanate precursor is prepared by ion exchange twice, then with
Carbon nano tube/graphene is compound, is prepared and is evenly distributed and has three-dimensional composite material flexible.By certain heat treatment
Obtain target product.Since the composite material has flexible self-supporting characteristic, binder, collection are not necessarily in the manufacturing process of electrode
Fluid, and the electrical conductance of carbon nanotube graphene is excellent, is not necessarily to conductive agent.Lithium-ion capacitor can largely be promoted
Energy density.This provides new method and new approaches to the flexible energy storage device of development.
Description of the drawings
Table after 600 DEG C of heat treatment 2h of the composite material that Fig. 1, lithium titanate/carbon/carbon nano tube/graphene ratio are 70/5/25
See figure；
It is macro after 600 DEG C of heat treatment 2h of the composite material that Fig. 2, lithium titanate/carbon/carbon nano tube/graphene ratio are 70/5/25
See bending figure；
Cuing open after 600 DEG C of heat treatment 2h of the composite material that Fig. 3, lithium titanate/carbon/carbon nano tube/graphene ratio are 70/5/25
Face SEM electron microscopic pictures；
Fig. 4, synthesis nano whiskers lithium titanate powder SEM electron microscopic pictures；
Fig. 5, synthesis nano whiskers lithium titanate powder XRD diagram piece；
Fig. 6, lithium titanate/carbon/carbon nano tube/graphene different proportion composite material and lithium piece assemble half-cell in 0.2C electric currents
Long circulating GCD figures under density；
Fig. 7, lithium titanate/carbon/carbon nano tube/graphene=70/5/25 ratio under different multiplying GCD figure；
Fig. 8, lithium titanate/carbon/carbon nano tube/graphene // activated carbon assembling asymmetric capacitor and activated carbon are assembled into symmetrically
The energy density of capacitor testing-power density curve graph.
Specific implementation mode
Technical scheme of the present invention is described in further detail with reference to specific embodiment, but protection scope of the present invention is simultaneously
It is not limited to as described below.
Embodiment 1
A kind of lithium-ion capacitor nano whiskers flexibility lithium titanate/carbon nano tube/graphene composite material and its preparation
Method
Include the following steps：
S1. the preparation of lithium titanate nanometer rods：Weigh the titanium dioxide (TiO of 2g Detitanium-ore-types2) and enough highly basic hydrogen-oxygens
Change sodium (NaOH 10mol/L), fully dissolves, be transferred in the polytetrafluoroethyllining lining water heating kettle of 100mL, in 150 DEG C of environment
Under, hydro-thermal reaction 72h fully cleans lye, then the centrifuge washing after dilute hydrochloric acid (1mol/L) acidleach 8h, cleans acid solution,
The metatitanic acid of nano bar-shape is prepared；
Nano bar-shape metatitanic acid 0.5g obtained above is weighed, by the lithium hydroxide (LiOH) of itself and 0.4mol/L, at 120 DEG C
Under environment, hydro-thermal is for 24 hours.It is then centrifuged for washing, first alcohol is washed, then is washed, and the lithium titanate precursor of nano bar-shape is dried to obtain.
S2. carbon nano tube/graphene frame structure is prepared：GO prepared by Hummer methods is taken into 200mg, is dispersed in 100ml
In deionized water, ultrasonic disperse forms stable suspension A (2mg/ml GO), spare；By carbon nanotube 200mg and 4mg
PVP disperses in deionized water, and ultrasonic disperse forms stable suspension B (2mg/ml CNT), spare.
The suspension B 2.5ml of the suspension A7.5ml and stable dispersion that measure stable dispersion are blended according to a certain percentage,
Add deionized water to 50mL.ULTRASONIC COMPLEX.Form stable suspension C, ULTRASONIC COMPLEX.
S3., the lithium titanate precursor of above-mentioned preparation weighing 80mg is added to the suspension C of aforementioned stable dispersion, ultrasound
Dispersion, obtains stable suspension D；
S4. it is filtered by vacuum：The above-mentioned suspension D of 10ml are taken, is filtered by vacuum and drying is removed, 80~120 μ m-thicks are prepared
Lithium titanate precursor/carbon nanotube/graphene oxide film material of degree；
S5. it is heat-treated：The thin-film material that will be obtained in S4 is heat-treated 2h under 600 DEG C of argon atmospheres, obtains target
Product, i.e. lithium titanate/carbon/carbon nano tube/graphene.
S6. piece is beaten：Thin-film material obtained above is made into the circular electric pole piece of diameter phi=14mm with tablet machine, is done
It is dry, it weighs.Both the negative material of lithium-ion capacitor had been obtained.
S7. half-cell is assembled：It is to electrode assembling half-cell, with CR2032 types with lithium piece by electrode slice obtained above
Button cell model, electrolyte LiClO4(EC/DEC=1, VEC/VDEC), assembled battery order is：Anode shell, metatitanic acid
Lithium composite material, electrolyte, diaphragm (PP diaphragms, Celgard2400), electrolyte, lithium piece, steel disc, spring shim, battery cathode
Shell.Test its high rate performance and cycle performance.Test voltage 1.0~3.0V of range, multiplying power current density：0.2,0.5,1,2,5,
10,20C；Long circulating current density：2C (wherein 1C=0.175A/g).
S8. the preparation of lithium-ion capacitor positive electrode：With commercial activated carbons, Kuraray YP-50F is according to activity
Charcoal：Conductive black：Binder (PVD)=8:1:1 ratio is sized mixing with N-methyl pyrrolidones (NMP) to appropriate viscosity, with scraping
(200 μm) of knife is coated on aluminium foil.It is dry, beat piece.
S9. lithium-ion capacitor is assembled：It is anode, lithium titanate/carbon nanometer with activated carbon electrodes prepared by above-mentioned smear method
Pipe/graphene is cathode, and assembling lithium-ion capacitor is matched by certain mass.With CR2032 type button cell models, electrolyte
For LiClO4(EC/DEC=1, VEC/VDEC), sequence is：Anode shell, absorbent charcoal material (anode), diaphragm (PP every
Film, Celgard2400), electrolyte, lithium titanate/carbon/carbon nano tube/graphene (cathode), steel disc, spring shim, battery cathode shell.
Test its high rate performance and cycle performance.Test voltage 1.0~3.0V of range, multiplying power current density：0.2,0.5,1,2,5,10,
20C；Long circulating current density：2C (wherein 1C=0.175A/g).
Embodiment 2
A kind of lithium-ion capacitor nano whiskers flexibility lithium titanate/carbon nano tube/graphene composite material and its preparation
Method
Include the following steps：
S1. the preparation of lithium titanate nanometer rods：Weigh the titanium dioxide (TiO of 2g Detitanium-ore-types2) and enough highly basic hydrogen-oxygens
Change sodium (NaOH 10mol/L), fully dissolves, be transferred in the polytetrafluoroethyllining lining water heating kettle of 100ml, in 150 DEG C of environment
Under, hydro-thermal reaction 72h fully cleans lye, then the centrifuge washing after dilute hydrochloric acid (1moL/L) acidleach 8h, cleans acid solution,
The metatitanic acid of nano bar-shape is prepared；
Nano bar-shape metatitanic acid 0.5g produced above is weighed, by the lithium hydroxide (LiOH) of itself and 0.4mol/L, at 120 DEG C
Under environment, hydro-thermal is for 24 hours.It is then centrifuged for washing, first alcohol is washed, then is washed, and the lithium titanate precursor of nano bar-shape is dried to obtain.
S2. carbon nano tube/graphene frame structure is prepared：GO prepared by Hummer methods is taken into 200mg, is dispersed in 100ml
In deionized water, ultrasonic disperse forms stable suspension A (2mg/ml GO), spare；By carbon nanotube 200mg and 4mg
PVP disperses in deionized water, and ultrasonic disperse forms stable suspension B (2mg/ml CNT), spare.
The suspension B 2.5mL of the suspension A12.5mL and stable dispersion that measure stable dispersion are blended according to a certain percentage,
Add deionized water to 50mL, ULTRASONIC COMPLEX.Form stable suspension C, ULTRASONIC COMPLEX.
S3., the lithium titanate precursor of above-mentioned preparation weighing 70mg is added to the suspension C of aforementioned stable dispersion, ultrasound
Dispersion, obtains stable suspension D；
S4. it is filtered by vacuum：The above-mentioned suspension D of 10ml are taken, is filtered by vacuum and drying is removed, 80~120 μ m-thicks are prepared
Lithium titanate precursor/carbon nanotube/graphene oxide film material of degree；
S5. it is heat-treated：The thin-film material that will be obtained in S4 is heat-treated 2h under 600 DEG C of argon atmospheres, obtains target
Product, i.e. lithium titanate/carbon/carbon nano tube/redox graphene.
S6. piece is beaten：Thin-film material obtained above is made into the circular electric pole piece of diameter phi=14mm with tablet machine, is done
It is dry, it weighs.Both the negative material of lithium-ion capacitor had been obtained.
S7. half-cell is assembled：It is to electrode assembling half-cell, with CR2032 types with lithium piece by electrode slice obtained above
Button cell model, electrolyte LiClO4(EC/DEC=1, VEC/VDEC), assembled battery order is：Anode shell, metatitanic acid
Lithium composite material, electrolyte, diaphragm (PP diaphragms, Celgard2400), electrolyte, lithium piece, steel disc, spring shim, battery cathode
Shell.Test its cycle performance.Test voltage 1.0~3.0V of range, long circulating current density：2C (wherein 1C=0.175A/g).
S8. the preparation of lithium-ion capacitor positive electrode：With commercial activated carbons, Kuraray YP-50F is according to activity
Charcoal：Conductive black：Binder (PVD)=8:1:1 ratio is sized mixing with N-methyl pyrrolidones (NMP) to appropriate viscosity, with scraping
(200 μm) of knife is coated on aluminium foil.It is dry, beat piece.
S9. lithium-ion capacitor is assembled：It is anode, lithium titanate/carbon nanometer with activated carbon electrodes prepared by above-mentioned smear method
Pipe/graphene is cathode, and assembling lithium-ion capacitor is matched by certain mass.With CR2032 type button cell models, electrolyte
For LiClO4(EC/DEC=1, VEC/VDEC), sequence is：Anode shell, absorbent charcoal material (anode), diaphragm (PP every
Film, Celgard2400), electrolyte, lithium titanate/carbon/carbon nano tube/graphene (cathode), steel disc, spring shim, battery cathode
Shell.Test its high rate performance and cycle performance.Test voltage 1.0~3.0V of range, multiplying power current density：0.2,0.5,1,2,5,
10,20C；Long circulating current density：2C (wherein 1C=0.175A/g).
Embodiment 3
A kind of lithium-ion capacitor nano whiskers flexibility lithium titanate/carbon nano tube/graphene composite material and its preparation
Method
Include the following steps：
S1. the preparation of lithium titanate nanometer rods：Weigh the titanium dioxide (TiO of 2g Detitanium-ore-types2) and enough highly basic hydrogen-oxygens
Change sodium (NaOH 10mol/L), fully dissolves, be transferred in the polytetrafluoroethyllining lining water heating kettle of 100mL, in 150 DEG C of environment
Under, hydro-thermal reaction 72h fully cleans lye, then the centrifuge washing after dilute hydrochloric acid (1mol/L) acidleach 8h, cleans acid solution,
The metatitanic acid of nano bar-shape is prepared；
Nano bar-shape metatitanic acid 0.5g produced above is weighed, by the lithium hydroxide (LiOH) of itself and 0.4mol/L, at 120 DEG C
Under environment, hydro-thermal is for 24 hours.It is then centrifuged for washing, first alcohol is washed, then is washed, and the lithium titanate precursor of nano bar-shape is dried to obtain.
S2. carbon nano tube/graphene frame structure is prepared：GO prepared by Hummer methods is taken into 200mg, is dispersed in 100ml
In deionized water, ultrasonic disperse forms stable suspension A (2mg/mL GO), spare；By carbon nanotube 200mg and 4mg
PVP disperses in deionized water, and ultrasonic disperse forms stable suspension B (2mg/mL CNT), spare.
The suspension B 2.5mL of the suspension A17.5mL and stable dispersion that measure stable dispersion are blended according to a certain percentage,
Add deionized water to 50ml, ULTRASONIC COMPLEX.Form stable suspension C, ULTRASONIC COMPLEX.
S3., the lithium titanate precursor of above-mentioned preparation weighing 60mg is added to the suspension C of aforementioned stable dispersion, ultrasound
Dispersion, obtains stable suspension D；
S4. it is filtered by vacuum：The above-mentioned suspension D of 10ml are taken, is filtered by vacuum and drying is removed, 80~120 μ m-thicks are prepared
Lithium titanate precursor/carbon nanotube/graphene oxide film material of degree；
S5. it is heat-treated：The thin-film material that will be obtained in S4 is heat-treated 2h under 600 DEG C of argon atmospheres, obtains target
Product, i.e. lithium titanate/carbon/carbon nano tube/redox graphene.
S6. piece is beaten：Thin-film material obtained above is made into the circular electric pole piece of diameter phi=14mm with tablet machine, is done
It is dry, it weighs.Both the negative material of lithium-ion capacitor had been obtained.
S7. half-cell is assembled：It is to electrode assembling half-cell, with CR2032 types with lithium piece by electrode slice obtained above
Button cell model, electrolyte LiClO4(EC/DEC=1, VEC/VDEC), assembled battery order is：Anode shell, metatitanic acid
Lithium composite material, electrolyte, diaphragm (PP diaphragms, Celgard2400), electrolyte, lithium piece, steel disc, spring shim, battery cathode
Shell.Test its cycle performance.Test voltage 1.0~3.0V of range, long circulating current density：2C；(wherein 1C=0.175A/
g)。
S8. the preparation of lithium-ion capacitor positive electrode：With commercial activated carbons, Kuraray YP-50F is according to activity
Charcoal：Conductive black：Binder (PVD)=8:1:1 ratio is sized mixing with N-methyl pyrrolidones (NMP) to appropriate viscosity, with scraping
(200 μm) of knife is coated on aluminium foil.It is dry, beat piece.
S9. lithium-ion capacitor is assembled：It is anode, lithium titanate/carbon nanometer with activated carbon electrodes prepared by above-mentioned smear method
Pipe/graphene is cathode, and assembling lithium-ion capacitor is matched by certain mass.With CR2032 type button cell models, electrolyte
For LiClO4(EC/DEC=1, VEC/VDEC), sequence is：Anode shell, absorbent charcoal material (anode), diaphragm (PP every
Film, Celgard2400), electrolyte, lithium titanate/carbon/carbon nano tube/graphene (cathode), steel disc, spring shim, battery cathode shell.
Test its high rate performance and cycle performance.Test voltage 1.0~3.0V of range, multiplying power current density：0.2,0.5,1,2,5,10,
20C；Long circulating current density：2C；(wherein 1C=0.175A/g).
Comparative example 1
It is compared, is included the following steps with lithium titanate nanometer rods smear method：
S1. the preparation of lithium titanate nanometer rods：Weigh the titanium dioxide (TiO of 2g Detitanium-ore-types2) and enough highly basic hydrogen-oxygens
Change sodium (NaOH 10mol/L), fully dissolves, be transferred in the polytetrafluoroethyllining lining water heating kettle of 100ml, in 150 DEG C of environment
Under, hydro-thermal reaction 72h fully cleans lye, then the centrifuge washing after dilute hydrochloric acid (1mol/L) acidleach 8h, cleans acid solution.
The metatitanic acid of nano bar-shape is prepared；
Nano bar-shape metatitanic acid 0.5g produced above is weighed, by the lithium hydroxide (LiOH) of itself and 0.4mol/L, at 120 DEG C
Under environment, hydro-thermal is for 24 hours.It is then centrifuged for washing, first alcohol is washed, then is washed, and the lithium titanate precursor of nano bar-shape is dried to obtain.
S2. above-mentioned lithium titanate precursor is taken and is placed in corundum crucible in right amount, is heat-treated in tube furnace.Heat treatment condition
For：600 DEG C, 2h, argon atmosphere.
S3. smear：By the lithium titanate powder after above-mentioned heat treatment：Conductive black：Binder (PVDF)=8：1：1 ratio
Example is sized mixing with N-methyl pyrrolidones (NMP) to appropriate viscosity, is coated on aluminium foil for (50 μm) with scraper, dry.
S4. piece is beaten：Electrode material obtained above is made into the circular electric pole piece of diameter phi=14mm with tablet machine, is done
It is dry, it weighs.Button weight, pure aluminum foil φ=14mm mass 6.45mg.Active material quality=(mElectrode- 6.45) * 80%.
S5. half-cell is assembled：It is to electrode assembling half-cell, with CR2032 types with lithium piece by electrode slice obtained above
Button cell model, assembled battery order are：Anode shell, lithium titanate composite material, electrolyte, diaphragm (PP diaphragms,
Celgard2400), electrolyte, lithium piece, steel disc, spring shim, battery cathode shell.Test its high rate performance and cycle performance.It surveys
Try 1.0~3.0V of voltage range, long circulating current density： 2C；(wherein 1C=0.175A/g).
Comparative example 2
It is assembled into symmetrical double layer capacitor, comparison/activated carbon (anode) // lithium titanate/carbon/carbon nano tube/stone with activated carbon
Black alkene (cathode).
Include the following steps：
S1. by business activated carbon (model:Kuraray YP-50F)：Conductive black (CB)：Binder (PVDF)=
8：1：1 ratio mixing, is sized mixing with N-methyl pyrrolidones, until appropriate viscosity, then uses (200 μm) of scraper to be coated in aluminium foil
On, it is dry；
S2. above-mentioned activated carbon is made into a diameter ofCircular electric pole piece, weigh, button weight, pure aluminum foil φ=
14mm mass 6.45mg.Active material quality=(mElectrode- 6.45) * 80%.
S3. choose that two panels is identical in quality or similar activated carbon electrodes piece is assembled into button symmetric capacitor battery.In group
When dress asymmetry capacitor, positive and negative anodes quality is matched according to electrode reserve of electricity equal principle, with CR2032 type button cell moulds
Type, assembled battery order are：Anode shell, absorbent charcoal material, electrolyte, diaphragm (PP diaphragms, Celgard2400), electrolysis
Liquid, absorbent charcoal material, steel disc, spring shim, battery cathode shell.Test its high rate performance and cycle performance.Test voltage range
0.01~3.0V, long circulating current density：0.35A/g.
Referring to figs. 1 to Fig. 8, the experimental results showed that, successfully prepare nano whiskers lithium titanate by two one-step hydrothermals.By its
It is attached in self supporting structure made of graphene/carbon nano-tube braiding, the defect of lithium titanate electrical conductance difference can be obviously improved.
The three-dimensional conductive structure that graphene/carbon nano-tube is woven into itself has self-supporting characteristic, is not necessarily to binder, conductive additive,
Material has flexibility, is not necessarily to collector, this is significant to the development wearable energy storage device of flexible portable.This kind of composite wood
Material is its high rate performance and cycle performance to be tested, the results show that composite material to button cell made of electrode assembling with lithium piece
In with the increase of metatitanic acid lithium content, its specific capacity is increased, after wherein LTO contents reach 80%, cyclical stability compared with
Difference illustrates lithium titanate in the lithium titanate composite material of content 80% because of the graphene/carbon nanometer of reunion growth and low amounts
Pipe conductive structure etc. factors affect its cyclical stability.LTO/CNT/G=70/5/25 composite materials are tested in 20C (1C=
175mA g-1) current density under still have 101mAh g-1Specific capacity；It is recycled by 1000 times under the current density of 2C,
Its capacity retention ratio can be up to 80%.Energy density, the power density of the lithium-ion capacitor assembled have obtained significantly
It is promoted.
Claims (6)
1. a kind of lithium-ion capacitor nano whiskers flexibility lithium titanate/carbon nano tube/graphene composite material, feature exist
In the composite material is woven by nano whiskers lithium titanate, carbon nanotube and graphene by nano material, described needle-shaped
The mass percent of lithium titanate, carbon nanotube, graphene is：(0.5~80)：5；(95~15).
2. a kind of lithium-ion capacitor preparation method of nano whiskers flexibility lithium titanate/carbon nano tube/graphene composite material,
It is characterized in that, comprising the steps of：
S1. the preparation of lithium titanate nanometer rods：The lithium titanate precursor of nano bar-shape is prepared with hydro-thermal hair, it is spare；
S2. slurrying：In deionized water by ultrasonic disperse by graphene, stable suspension A is formed；Carbon nanotube is passed through
Ultrasonic disperse in deionized water, forms stable suspension B, spare；
S3. it mixes for the first time：Suspension A and suspension B are mixed according to corresponding proportion, ultrasound forms and stablizes suspension C；
Second of mixing of S4：The nano whiskers lithium titanate precursor for taking certain mass, is added in suspension C, ultrasonic disperse, shape
At stable, evenly dispersed suspension D；
S5. it is filtered by vacuum：The suspension D of a certain amount of stable dispersion is taken, is filtered by vacuum, before nano whiskers lithium titanate is prepared
Body/carbon nano tube/graphene composite material；
S6. it is heat-treated：Nano whiskers lithium titanate precursor/carbon nano tube/graphene composite material that S5 is obtained, 500~
800 DEG C, it is heat-treated 2~6h under argon atmosphere, obtains nano whiskers lithium titanate/carbon/carbon nano tube/graphene composite material.
3. preparation method according to claim 2, which is characterized in that in the preparation process of suspension B described in S2 steps
The surfactant used is PVP K30.
4. preparation method according to claim 3, which is characterized in that the nano whiskers lithium titanate of middle addition described in S4 steps
Presoma, diameter 50-100nm, 2-3 μm of length.
5. preparation method according to claim 4, which is characterized in that in step S2 carbon nanotube be multi wall, diameter 60nm,
3-5 μm of length；Graphene is redox graphene, and the number of plies 5~7, size is more than 5 μm.
6. preparation method according to claim 4, it is characterised in that treatment temperature described in S6 steps is 600 DEG C, is heat-treated
Time is 4h.
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| CN110783526A (en) * | 2019-11-12 | 2020-02-11 | 浙江锋锂新能源科技有限公司 | Self-supporting electrode, preparation method thereof and mixed solid-liquid electrolyte lithium storage battery with self-supporting electrode |
| CN111525137A (en) * | 2020-06-03 | 2020-08-11 | 湖北亿纬动力有限公司 | Positive electrode slurry and application thereof in battery |
| CN111564620A (en) * | 2020-05-23 | 2020-08-21 | 江西理工大学 | Method for rapidly preparing flexible battery by using carbon nanotube continuum |
| CN112670447A (en) * | 2020-12-25 | 2021-04-16 | 中博龙辉装备集团股份有限公司 | Lithium titanate electrode with quick charging performance and preparation method thereof |
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| CN110164712A (en) * | 2019-06-20 | 2019-08-23 | 上海大学(浙江·嘉兴)新兴产业研究院 | A kind of lithium-ion capacitor electrode material and preparation method thereof |
| CN110164712B (en) * | 2019-06-20 | 2021-06-01 | 上海大学(浙江·嘉兴)新兴产业研究院 | Lithium ion capacitor electrode material and preparation method thereof |
| CN110783526A (en) * | 2019-11-12 | 2020-02-11 | 浙江锋锂新能源科技有限公司 | Self-supporting electrode, preparation method thereof and mixed solid-liquid electrolyte lithium storage battery with self-supporting electrode |
| CN110783526B (en) * | 2019-11-12 | 2022-07-08 | 浙江锋锂新能源科技有限公司 | Self-supporting electrode, preparation method thereof and mixed solid-liquid electrolyte lithium storage battery with self-supporting electrode |
| CN111564620A (en) * | 2020-05-23 | 2020-08-21 | 江西理工大学 | Method for rapidly preparing flexible battery by using carbon nanotube continuum |
| CN111564620B (en) * | 2020-05-23 | 2024-02-02 | 江西理工大学 | Method for rapidly preparing flexible battery by using carbon nano tube continuum |
| CN111525137A (en) * | 2020-06-03 | 2020-08-11 | 湖北亿纬动力有限公司 | Positive electrode slurry and application thereof in battery |
| CN112670447A (en) * | 2020-12-25 | 2021-04-16 | 中博龙辉装备集团股份有限公司 | Lithium titanate electrode with quick charging performance and preparation method thereof |
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