CN110391398A - Black phosphorus/redox graphene combination electrode and preparation method thereof and the flexible lithium ion battery including the combination electrode - Google Patents
Black phosphorus/redox graphene combination electrode and preparation method thereof and the flexible lithium ion battery including the combination electrode Download PDFInfo
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Abstract
Black phosphorus/redox graphene combination electrode method is prepared the present invention provides a kind of, method includes the following steps: i) in the solution removing black phosphorus at black phosphorus piece dispersion liquid；Ii it) expands blocky graphite and is oxidized to graphene oxide sheet；Iii the black phosphorus piece dispersion liquid and the graphene oxide sheet) are mixed to form uniform dispersion；Iv) uniform dispersion is filtered by vacuum to form black phosphorus/graphene oxide membrane；And electronation, drying and optionally prelithiation v) are carried out to the black phosphorus/graphene oxide membrane, to form the flexible black phosphorus/redox graphene combination electrode.In addition, the present invention also provides a kind of black phosphorus/redox graphene combination electrode and including the flexible lithium ion battery of the combination electrode.Flexible lithium ion battery according to the present invention has high quality energy density and high volume energy density simultaneously, and does not decay significantly after 100 circulations under the bending state that works.
Description
Cross reference to related applications
This application claims the U.S. Provisional Patent Application No.62/762 that on April 23rd, 2018 submits, and 114 priority should
The content of application is herein incorporated by reference.
Technical field
It (or is multiple the present invention relates to several layers of black phosphorus/redox graphene (hereinafter referred to as BP/rGO) combination electrode
Close film, extrusion coating paper or cathode) and preparation method thereof and use the BP/rGO cathode, V2O5/ CNT anode and polymer dielectric
Come the flexible lithium ion battery (LIB) assembled.
Background technique
In order to promote the quick and broad development of flexible and wearable electronic device, needing to develop has high-energy density
Flexible energy storage device.Current flexible energy storage device is mainly aqueous super capacitor, because of the electrode and electricity of supercapacitor
Solution matter can be easily made flexibility, but their low energy densities, which seriously hinder it, to be widely applied.
Since with high-energy density and the mature production line for preparing, emerging flexible lithium ion battery is considered flexible
The most promising substitute of supercapacitor.Although can be by mixing using conventional electrode materials manufacture flexible lithium ion battery
Polymer dielectric/the diaphragm for entering highly porous three-dimensional (3D) collector or thickness realizes, but they often have it is poor
Chemical property, especially have low-down volume energy density.For example, V.L.Pushparaj, et al.
It has been delivered in " Proc.Natl.Acad.Sci. " 104 (2007) 13574 using porous carbon nano pipe array as the soft of electrode
Property lithium ion battery, can only achieve 250Whkg-1Energy density and 10 stable circulations.H.Xu, et al.
The flexible capacitor using carbon nano-fiber as electrode basement has been delivered in " Adv.Energy Mater. " 5 (2015) 1401882
Device, although can achieve 4000 stable circulations, its energy density only has 11Whkg-1。
Therefore, find with high-energy density and stablize cycle performance suitable flexibility electrode material will be exploitation it is advanced soft
The key challenge of property lithium ion battery.
Summary of the invention
The purpose of the present invention is to provide a kind of based on stratiform black phosphorus/redox graphene combination electrode superenergy
The flexible lithium ion battery of density.The flexible lithium ion battery has high quality energy density and high volume energy density simultaneously,
And the chemical property of the battery is not decayed significantly after 100 circulations under the bending state that works.
To achieve the goals above, the present invention develop BP/rGO composite membrane as cathode and comprising BP/rGO cathode,
Vanadic anhydride/carbon nanotube (V2O5/ CNT) anode and polymer dielectric flexible lithium ion battery.Moreover, the present invention is logical
The ratio of optimization black phosphorus piece and graphene oxide (GO) piece is crossed, in order to provide quick ion/electron transfer rate and high-energy
Density.
In the present invention, black phosphorus/graphene combination electrode can simply by black phosphorus and GO mixture dispersion liquid into
Row vacuum filtration, is then mildly restored and optionally prepared by prelithiation.BP/rGO mixture is densely stacked into
Flexible paper, which can be used as conductive substrates and mechanical damping agent, for effectively storing lithium in black phosphorus.BP piece is clipped in phase
It is uniformly distributed between adjacent rGO layer and between adjacent rGO layer, to ensure that compound during repeating lithiumation/de- lithium
The excellent stability of electrode.The independent BP/rGO can be directly used as cathode without collector, which ensure that battery is flexible
Property and high-energy density.By assembling flexibility using the polymer film enclosed electrode of semi-solid preparation and electrolyte in argon atmosphere
Then battery is heat-treated so that polymer film is fully cured.Prevent moisture and oxygen in air from seeping by the polymer film
Thoroughly into battery, battery is used for a long time at ambient conditions.
In order to prepare black phosphorus/redox graphene composite negative pole, present invention uses different precursor materials and efficiently,
Economic machined parameters.For example, using graphene oxide to replace graphene as precursor, this is because the graphene oxide can be with
Enhance the mechanical flexibility of final products.Graphene oxide only needs mildly to be restored, this has been saved in turn usually requires height
The energy of temperature reduction.In addition, method used in the present invention needs low energy consumption, such as at 120 DEG C of temperature below
It carries out, and used precursor and solvent can recycle, thus the yield of final products is relatively high.
Detailed description of the invention
It is to the brief description of accompanying drawing, its purpose is that illustrating rather than limiting exemplary implementation disclosed herein below
Scheme.
Fig. 1 be include BP/rGO cathode, V2O5The flexible lithium ion battery of/CNT anode and PVDF-HFP polymer dielectric
Manufacturing method flow chart.
Fig. 2A to 2D is the microphoto of the BP and BP/rGO that are prepared using disclosed synthetic method.Fig. 2A is from top
Scanning electron microscope (SEM) image of the BP/rGO of observation.Fig. 2 B is the cross sectional scanning electron MIcrosope image of BP/rGO.Figure
2C is transmission electron microscope (TEM) image of pure BP.Fig. 2 D is the transmission electron microscope image of BP/rGO.
Fig. 3 shows the electrochemical properties of BP/rGO composite negative pole.Fig. 3 A is in 0.5Ag-1Current density under by each
The cycle performance of the BP/rGO cathode of kind precursor ratio synthesis.Fig. 3 B is times of the BP/rGO cathode synthesized by various precursor ratios
Rate performance.
Fig. 4 A and 4B are prepared V2O5The microphoto of/CNT anode.Fig. 4 A is the SEM image under low magnification.
Fig. 4 B is the SEM image under high-amplification-factor.Fig. 4 C is V2O5The high rate performance of/CNT anode.
Fig. 5 A is the digital photograph of HVDF-HFP polymer dielectric.Fig. 5 B is the SEM figure of identical polymer dielectric
Picture.
Fig. 6 A shows the open-circuit voltage of flexible lithium ion battery.Fig. 6 B illustrates the energy of prototype flexible lithium ion battery
Density.
Fig. 7 is shown first in 0.1Ag-1Current density under activated electrode, then in 0.5Ag-1Current density
The cycle performance of the lower BP/ graphene cathode synthesized according to comparative example 1.
Specific embodiment
Implementation embodiment of the present invention explained below.However, the scope of the present invention is not limited to the embodiment party
Case can carry out various changes to the present invention as long as not damaging purport.
Term " black phosphorus/redox graphene combination electrode " refers to the compound electric comprising black phosphorus and redox graphene
Pole.
Term " V2O5/ CNT combination electrode " refers to the combination electrode comprising vanadic anhydride and carbon nanotube.
Recently new chance will be provided to solve above-mentioned challenge to the extensive exploration of two-dimentional (2D) material.Most of two dimension materials
Material, such as graphene, two-dimensional metallic carbide and two-dimentional black phosphorus, can disperse in a solvent and be assembled into strong with excellent mechanical
The flexible paper of degree.In addition to flexibility, they also have high lithium memory capacity.Particularly, black phosphorus has and with lithium alloyage
Up to 2596mAhg-1Theoretical specific capacity, this is highest in all two-dimensional materials.In addition, between adjacent phosphorus alkene layer
Bulk black phosphorus crystal is easy weak Van der Waals force and high productivity removes into two-dimentional black phosphorus in a liquid, without appointing
What is pre-processed.The black phosphorus sheet body of removing in organic solvent can be with chemical stabilization a couple of days, consequently facilitating manufacturing at room temperature
Electrode comprising two-dimentional black phosphorus.Before all above-mentioned advantages all assign light of the black phosphorus as the advanced electrode material of flexible battery
Scape.
Therefore, in one embodiment, to prepare flexible black phosphorus/redox graphene compound the present invention provides a kind of
The method of electrode, method includes the following steps: i) in the solution removing black phosphorus at black phosphorus piece dispersion liquid；Ii) make blocky stone
Ink expands and is oxidized to graphene oxide sheet；Iii) the black phosphorus piece dispersion liquid and the graphene oxide sheet are mixed to form
Uniform dispersion；Iv the uniform dispersion) is assembled into flexible black phosphorus/graphene oxide membrane by being filtered by vacuum；And v)
Electronation, drying and optionally prelithiation are carried out to the black phosphorus/graphene oxide membrane, to form the flexible black phosphorus/also
Former graphene oxide combination electrode.
With use graphene as precursor compared with, the present invention using graphene oxide as precursor can be enhanced flexible lithium from
The mechanical flexibility of sub- battery forms layer structure more evenly with black phosphorus piece, accelerates the transmission of lithium ion and improve electrification
Learn performance.
In addition, in order to further increase the high-energy density of BP/rGO in flexible battery, the present invention also optimizes black phosphorus
The ratio of piece and graphene oxide (GO) piece, in the form of optimizing electrode, thus provide quick ion/electron transfer rate and
High-energy density.
In a particular embodiment, in step i), in (for example) N-Methyl pyrrolidone solvent by black phosphorus remove at
Black phosphorus piece dispersion liquid.
In a particular embodiment, in step ii), the mixture using (for example) sulfuric acid and nitric acid makes graphite expansion,
Then make the graphite oxidation after expansion using potassium permanganate and the concentrated sulfuric acid.In a particular embodiment, after step ii), successively
Graphite after washing oxidation with hydrogen peroxide, hydrochloric acid and deionized water.
In a particular embodiment, the mass ratio of the black phosphorus piece and the graphene oxide sheet can be in 1:1 to 1:2's
In range.
In a particular embodiment, in step iii), conventionally known in the art method can be used and carry out described mix
It closes, it is preferable that the mixing is carried out by ultrasonic treatment.
In a particular embodiment, in step v), the electronation is carried out by hydrogen iodide steam.
In another embodiment, present disclose provides the flexible black phosphorus/oxygen reduction fossils prepared according to the above method
Black alkene combination electrode.
As described above, the present disclosure describes the BP dispersion liquid precursors used after removing and vacuum filtration method synthesis BP/
rGO.Graphene oxide (GO) is being restored and removed in electrode after residual solvent, being successfully prepared for density is 1.9gcm-2
To 2.1gcm-2With membranaceous black phosphorus/redox graphene electrode with a thickness of 25 μm to 35 μm.By adjust precursor BP piece with
The ratio of precursor GO piece can further coordination electrode internal void space.The ratio of BP piece and GO piece is within the scope of the present invention
BP/rGO electrode intensively fill, and have high conductivity and excellent flexibility.
BP/rGO electrode is in 0.5Ag-1Current density under by 500 times circulation after 477mAhg is presented-1Stabilization
Capacity, and when in CR2032 button cell with lithium foil be electrode is tested when, average coulombic efficiencies 99.6%.When
When BP/rGO electrode is used as the cathode in flexible lithium ion battery, full battery can provide 389Whkg-1High-energy density, and
And 100 times circulation after with 92.3% high retention rate.When considering the density of electrode, the volume energy of flexible lithium ion battery
Metric density is up to 498WhL-1.The above parameter and performance are not limited to the special case of disclosure test, but have generality.
In another embodiment again, present disclose provides a kind of flexible lithium ion batteries, comprising: cathode comprising
Above-mentioned flexibility black phosphorus/redox graphene combination electrode；Polymer dielectric；And anode comprising vanadic anhydride/carbon
Nanometer tube combination electrode.
In a particular embodiment, the polymer dielectric includes to be selected from Kynoar, Kynoar-hexafluoro third
At least one of alkene, polyethylene glycol oxide, polymethyl methacrylate, polyacrylonitrile.It is described poly- in more specific embodiment
Polymer electrolyte includes Kynoar-hexafluoropropene.
In a particular embodiment, the flexible lithium ion battery is sealed using polymer film.It is anti-by the polymer film
Only the moisture in air and oxygen penetrate into battery, and battery is used for a long time at ambient conditions.More specific
In embodiment, the flexible lithium ion battery is sealed using polypropylene/PDMS membrane.
In a particular embodiment, the vanadic anhydride/carbon nano-tube combination electrode is by method comprising the following steps
Manufacture:
A) disperse vanadium pentoxide powder in a solvent to form vanadic anhydride solution；
B) carbon nanotube is functionalized, to form functionalized carbon nanotube；
C) the vanadic anhydride solution and the functionalized carbon nanotube are mixed, to form dispersion liquid；
D) make the vanadic anhydride hydrothermal growth in the dispersion liquid at vanadium pentoxide nanowires by heating；
E) dispersion liquid after hydrothermal growth is assembled, to form the vanadic anhydride/carbon nano-tube combination electrode.
In more specific embodiment, the solvent in the step a) is H2O2Concentration is in 4 mass % to 5 mass % ranges
Interior hydrogen peroxide.In more specific embodiment, hydrothermal growth in the step d) 200 DEG C to 220 DEG C at a temperature of into
Row 72 to 96 hours.In more specific embodiment, in the step e), the assembling is carried out using vacuum filtration.
Present disclose provides use BP/rGO cathode, V2O5/ CNT anode, polymer dielectric and optional polymeric seal
The assembling of the flexible lithium ion battery of film.Compared with existing flexible energy storage device, the flexibility lithium ion made of the above method
Battery can substantially stabilized work at ambient conditions, and there is the energy density that greatly improves.
Hereinafter, to including BP/rGO electrode as cathode, V2O5/ CNT electrode is as anode, PVDF-HFP polymer electrolytic
Matter is more specifically described as the preparation method of the flexible lithium ion battery of polymer dielectric.This method has gained
The large-scale production of flexible lithium ion battery and the obvious advantage of excellent electrochemical property.
Fig. 1 is the flow chart for showing the operation of the program of key component of synthesis flexible lithium ion battery.Blocky graphite and
Black phosphorus crystal be it is commercially available, then by they remove at the two-dimensional nano piece being dispersed in solvent.Then they are passed through
Vacuum filtration is assembled into independent film.BP/rGO film can mild reduction process by using hydrogen iodide steam as reducing agent
To obtain.Before the cathode for being used as flexible lithium ion battery, BP/rGO film needs prelithiation.Commercially available vanadic anhydride and carbon
Nanotube powder may be dissolved in hydrogen peroxide solution during hydrothermal process, and be assembled into independent film by vacuum filtration.It is logical
It crosses and the available PVDF-HFP film of electrostatic spinning is carried out to the precursor solution of PVDF-HFP.Uncured PDMS is spin-coated on polypropylene
It on film, is then mildly heat-treated, to prepare the PP/PDMS of semi-solid preparation.All said modules are successively stacked to manufacture flexibility
Lithium ion battery.All above process are all very simple, can volume production and low cost.
Specifically, method includes the following steps:
(1) preparation of flexible black phosphorus/redox graphene combination electrode
Firstly, by graphite and blocky black phosphorus crystal removing at their several layers of dispersion liquid (for example, including 1 to 15 layer of black phosphorus
The dispersion liquid of piece): sulfuric acid and nitric acid are mixed with the volume ratio of 3:1, take 200mL mixture to be embedded in 5g graphite, then 1050
15-20 seconds are thermally expanded at ± 20 DEG C to obtain expanded graphite (EG).Then, take 0.5g expanded graphite at 50 DEG C to 60 DEG C
Expanded graphite is aoxidized 24 ± 1 hours using 3.5g potassium permanganate in 98% concentrated sulfuric acid of 100mL.Successively with 30% hydrogen peroxide,
0.1 mol/L hydrochloric acid and deionized water wash oxidation product, and by the way that resulting graphene oxide sheet is collected by centrifugation.
Pass through the liquid removing several layers of black phosphorus piece dispersion liquid of acquisition of the BP crystal under ultrasonic treatment.Using mortar by 0.2g block
Shape black phosphorus crystal is ground into little particle, then with 200mL, N2Bubbling 2- N-methyl-2-2-pyrrolidone N (99%, mentioned by Aldrich
For) mixing.Then mixture is sealed in the vial and is ultrasonically treated 24 ± 1 hours.By gained dispersion liquid in 4500-
It is centrifuged 15-20 minutes under 5500rpm to remove big sediment, and selects the dispersion liquid of top half as several layers of black phosphorus piece point
Dispersion liquid.
Then, pass through vacuum filtration and mild reduction preparation BP/rGO electrode: by several layers of black phosphorus piece dispersion liquid and oxidation stone
Black alkene piece is mixed and sonicated 30-60 minutes to form uniform dispersion, wherein in the uniform dispersion, the dispersion of black phosphorus piece
The mass ratio of black phosphorus piece and graphene oxide sheet in liquid is in the range of 1:1 to 1:2.Then, make black phosphorus/graphene oxide point
Dispersion liquid is 0.22-0.4 μm polyvinylidene fluoride (PVDF) filter paper (being provided by Merck Millipore) by aperture.Logical
After crossing vacuum drying evaporation solvent, film can be formed on polyvinylidene fluoride filter paper, be removed independent black to obtain
Phosphorus/graphene oxide membrane.Black phosphorus/graphene oxide membrane restores to 1-2 hours in hydrogen iodide steam at 90-95 DEG C, then
12-15 hours are dried in a vacuum at 120-130 DEG C to obtain independent BP/rGO electrode.
(2) vanadic anhydride/carbon nano-tube combination electrode preparation
Pass through hydro-thermal reaction and vacuum filtration synthesis V2O5/ CNT composite membrane: by growing pure five oxidation on the carbon nanotubes
Two vanadium nano wires synthesize V2O5/ CNT anode.By 0.36 ± 0.01g vanadium pentoxide powder (> 98%, provided by Aldrich)
It is dispersed in 30-32mL deionized water.30% hydrogen peroxide solution of 5 ± 0.1mL is added dropwise to vanadic anhydride dispersion liquid
In to form brown solution.Make within 2 hours carbon nanotube (being provided by Iljin Nanotech) by being ultrasonically treated in 6M nitric acid
Purifying and functionalization.0.09 ± 0.001g functionalized carbon nanotubes are added in above-mentioned brown solution to form black dispersion liquid,
The black dispersion liquid is heated 72-96 hours in autoclave at 200-220 DEG C.After hydro-thermal reaction, by product spend from
Sub- water washing is simultaneously deposited on the PVDF filter paper that aperture is 0.22-0.4 μm by vacuum filtration.Pass through 12- dry at 60 DEG C
The film of deposition is removed after 18 hours to obtain V2O5/ CNT electrode.
(3) preparation of PVDF-HFP polymer dielectric
Pass through electrostatic spinning and prepare PVDF-HFP polymer dielectric: by PVDF-HFP polymer precursor (average Mw~
455,000, provided by Aldrich) in the mixed solvent being made of 4mL dimethylformamide and 16mL acetone is dissolved in be formed
Concentration is the homogeneous solution of 12-13 weight %.Use electrostatic spinning device (NEU nano fiber electrostatic spinning device, Kato) In
The high voltage and 1mLh of 17.5kV-1Feed rate under by polymer solution Electrospun to aluminium foil, by PVDF-HFP nanometers
Fiber mat is dried from removing on aluminium foil and in vacuum drying oven at 60-80 DEG C to completely remove remaining solvent.Passing through will
PVDF-HFP pad, which is immersed in following liquid electrolyte, manufactures polymer dielectric, and the liquid electrolyte is by 1M LiPF6Carbon
Sour ethyl (EC): methyl ethyl carbonate (EMC): the carbonic acid of+1 weight % of dimethyl carbonate (DMC) (1:1:1 volume %) solution is sub-
Vinyl acetate composition.
(4) assembling of flexible lithium ion battery
Use V2O5/ CNT anode, BP/rGO cathode and PVDF-HFP polymer dielectric assemble flexibility as electrolyte
Battery.By V2O5/ CNT and BP/rGO paper is cut into piece of the typical transverse having a size of 20mm × 20mm.Before assembling flexible battery,
It needs to make BP/rGO short circuit by the lithium foil soaked with electrolyte to make BP/rGO prelithiation.It will in the glove box of argon gas filling
Battery component is stacked and is sealed between the polyacrylic polymer film of dimethyl silicone polymer coating of two semi-solid preparations.
Charge/discharge test is carried out with active electrode to battery and discharges the gas of any generation.After electric discharge, flexible battery is existed
Aging 24-36 hours in glove box, so that PDMS membrane is fully cured.Finally, flexible being taken out from glove box
Before battery, the edge of polypropylene screen is sealed by plastic welding.
Embodiment
Embodiment 1
Material
Using following reagent and solvent without being further purified: polyacrylonitrile (PAN, Mw=150,000, Sigma-
Aldrich), n,N-Dimethylformamide (DMF, 99.8%, Sigma-Aldrich), hydrochloric acid (37%, Fisher), nitric acid
(69-72%, Fisher), N-Methyl pyrrolidone (NMP), PVDF-HFP (average Mw~455,000, Sigma-Aldrich),
Sulfuric acid (98%, Fisher), hydrogen peroxide (30%, Fisher), potassium permanganate (97%, Sigma-Aldrich), five oxidations two
Vanadium (> 98%, Sigma-Aldrich), dimethyl silicone polymer (Sigma-Aldrich), acetone (Fisher).
Characterization
Shape is characterized using scanning electron microscope (SEM, JEOL7100F) and transmission electron microscope (TEM, JEOL2010)
Looks.Chemical property is measured on battery test system (Land 2001CT).
Manufacturing method
In embodiment 1, pass through the vacuum filtration of BP/GO dispersion liquid and mild also original preparation BP/rGO electrode.Pass through
Hydro-thermal reaction and vacuum filtration are to synthesize V2O5/ CNT composite membrane.PVDF-HFP polymer dielectric is produced by electrostatic spinning.
Experiment 1
Prepare BP/rGO cathode, V2O5/ CNT anode and PVDF-HFP electrolyte: by sulfuric acid and nitric acid with the volume ratio of 3:1
Mixing takes 200mL mixture to be embedded in 5g graphite (trade name Natural graphite, provided by Asbury), then exists
Graphite is set to thermally expand 15 seconds to obtain expanded graphite at 1050 DEG C.Take 0.5g expanded graphite, using 3.5g potassium permanganate and
100mL, 98% concentrated sulfuric acid aoxidize expanded graphite 24 hours at 50 DEG C.Successively with 30% hydrogen peroxide, 0.1 mol/L hydrochloric acid
Oxidation product is washed with deionized water, and by the way that resulting graphene oxide sheet is collected by centrifugation.By making BP under ultrasonic treatment
Crystal (trade name Black Phosphorus, provided by Aldrich) liquid is removed to obtain several layers of black phosphorus piece dispersion liquid.Make
0.2g bulk black phosphorus crystal is ground into little particle with mortar, the N-Methyl pyrrolidone solvent being then bubbled with 200mL nitrogen
(99%, provided by Aldrich) it mixes.Then mixture is sealed in the vial and is ultrasonically treated 24 hours.Gained is dispersed
Liquid is centrifuged 15 minutes at 5000rpm to remove big sediment, and selects the dispersion liquid of top half as several layers of black phosphorus piece
Dispersion liquid.Several layers of black phosphorus piece dispersion liquid and graphene oxide sheet are mixed and sonicated 30 minutes to form uniform dispersion,
Wherein in the uniform dispersion, the mass ratio of black phosphorus piece and graphene oxide sheet in black phosphorus piece dispersion liquid is 2:3, is then made
The uniform dispersion is 0.22 μm of PVDF filter paper (being provided by Merck Millipore) by aperture.It is steamed by vacuum drying
After sending out solvent, film is formed on PVDF filter paper, is removed to obtain independent BP/GO film.95 in hydrogen iodide steam
BP/GO film is restored 1 hour at DEG C, anneals 12 hours in a vacuum at 120 DEG C then to obtain independent BP/rGO electrode.
V is synthesized by growing pure vanadium pentoxide nanowires on the carbon nanotubes2O5/ CNT anode.0.36g five is aoxidized
Two vanadium powders (> 98%, provided by Aldrich) are dispersed in 30mL deionized water.30% hydrogen peroxide solution of 5mL is added dropwise
It is added in vanadic anhydride dispersion liquid to form brown solution.In 6M nitric acid by be ultrasonically treated make within 2 hours carbon nanotube (by
Iljin Nanotech is provided) it purifies and is functionalized.0.09g functionalized carbon nanotubes are added in above-mentioned brown solution with shape
At black dispersion liquid, it is heated 96 hours at 200 DEG C in autoclave.After hydro-thermal reaction, by product deionized water
It washs and passes through vacuum filtration and be deposited on the PVDF filter paper that aperture is 0.22 μm.By being removed after being dried 12 hours at 60 DEG C
The film of deposition obtains V2O5/ CNT electrode.
PVDF-HFP polymer precursor (average Mw~455,000, provided by Aldrich) is dissolved in by 4mL N, N- bis-
The in the mixed solvent of methylformamide and 16mL acetone composition is the uniform molten of 12 weight % to form polymer precursor concentration
Liquid.Using Electrospun device (NEU nano fiber electrostatic spinning device, Kato) in the high voltage and 1mLh of 17.5kV-1Feeding
It will be on polymer solution Electrospun to aluminium foil under rate.PVDF-HFP nanofiber mat is removed from aluminium foil and in vacuum drying oven
In at 80 DEG C dry to remove remaining solvent.By by PVDF-HFP pad be immersed in following liquid electrolyte manufacture it is poly-
Polymer electrolyte, the liquid electrolyte by 1M lithium hexafluoro phosphate ethylene carbonate: methyl ethyl carbonate: dimethyl carbonate (be 1:
1:1 is counted with volume %) solution+1 the vinylene carbonate of quality % form.
Experiment 2
The characterization of electrode and electrolyte: BP/rGO, V are characterized by SEM and TEM2O5The form of/CNT and PVDF-HFP.
Fig. 2A shows the continuous oxidation graphene region with the wrinkle as caused by the crosslinking of adjacent graphene oxide sheet.
Low magnification SEM image also shows the black phosphorus piece being clipped between graphene oxide layer.Fig. 2 B is intensively filled out in BP/rGO film
GO and BP layers of the cross-sectional SEM image for filling and arranging.The height of flexible lithium ion battery is ensured with highdensity BP/rGO film
Volume capacity.Fig. 2 C is the TEM image of prepared black phosphorus piece, and the lateral dimension of the black phosphorus piece is several hundred nanometers to several microns.
Fig. 2 D is the TEM image of BP/rGO composite material, and wherein black phosphorus piece is evenly distributed in graphene oxide layer.Fig. 4 A-B is made
Standby V2O5The microphoto of/CNT film.Fig. 4 A shows the low magnification SEM image of the vanadium pentoxide nanowires of entanglement.
The superelevation length-width ratio that there is nano wire typical length to be greater than 100 μm, which ensure that V2O5The high mechanical strength of/CNT film.Fig. 4 B is
The high-amplification-factor SEM image of same sample.Carbon nanotube is evenly distributed in the vanadium pentoxide nanowires of entanglement, this is
V2O5Electron-transport during the lithiumation of/CNT anode/de- lithium circulation provides conductive network.The diameter of vanadium pentoxide nanowires is
About 100nm spreads to be conducive to lithium ion and improves high rate performance.Fig. 5 is prepared PVDF-HFP polymer dielectric
Microphoto.As shown in Figure 5A, liquid electrolyte is added to electrospinning PVDF-HFP pad in after, electrolyte be it is transparent and
Flexible.Fig. 5 B is the SEM image of PVDF-HFP nanofiber, and which show porous structures needed for intake liquid electrolyte.
Experiment 3
The assembling of flexible battery: the V used as anode2O5/ CNT, as cathode BP/rGO and as electrolyte and every
The gel polymer electrolyte of film assembles flexible battery.All said modules synthesize in experiment 1.By V2O5/ CNT and BP/rGO
Piece is cut into the piece of the typical sizes with 20mm × 20mm.Before assembling flexible battery, pass through the lithium foil soaked with electrolyte
Make BP/rGO short circuit at least 12 hours to make BP/rGO cathode prelithiation.The heap one by one in the glove box of argon gas filling
Folded prepared battery component, and be sealed in two semi-solid preparations dimethyl silicone polymer coating polyacrylic polymer film it
Between.Two PDMS membranes will merge, and generate compressing force on electrode and electrolyte, so that it is guaranteed that battery
Excellent electric contact.Then battery discharge one is recycled, with active electrode and discharges the gas of any generation.Discharge process it
Afterwards, the flexible battery assembled is placed in glove box 24 hours so that dimethyl silicone polymer is fully cured at room temperature.
Finally, the edge of polypropylene screen is fully sealed by plastic welding before taking out flexible battery in glove box.
Experiment 4
BP/rGO cathode, V2O5The electrochemical Characterization of/CNT anode and flexible battery: assembling button cell is to measure BP/rGO
And V2O5Chemical property of/CNT the electrode to lithium foil.BP/rGO electrode recycles between 0 and 3V, and V2O5/ CNT electrode exists
It is recycled between 1.5V to 4V on LAND 2001CT cell tester.The energy density of flexible battery is in CHI660c electrochemistry work
In 0.2Ag under 1 to 4V voltage on standing-1Current density under measure.The weight of battery is based on positive and cathode total
Quality.Numerical integration based on constant current charge-discharge curve calculates energy density.
Fig. 3 shows the BP/rGO with various BP/GO precursor ratios measured using CR2032 button cell lithium foil
The chemical property of cathode.Fig. 3 A is indicated in 0.5Ag-1Current density under BP/rGO circulation volume.Fig. 3 B is shown
0.1A·g-1To 3Ag-1Current density under BP/rGO rate capability.BP/GO ratio realizes the electricity of optimization when being 2:3
Chemical property, in 0.2Ag-1Current density under 737mAhg is provided-1Reversible capacity.BP/GO ratio is the excellent of 2:3
Change BP/rGO electrode and keeps 477mAhg after 500 circulations-1Specific capacity, and average coulombic efficiencies be 99.6%.Fig. 4 C
It indicates in 0.1Ag-1To 3Ag-1Current density under the V that lithium foil is tested using CR2032 button cell2O5/ CNT anode
Rate capability.V2O5/ CNT anode is in 0.1Ag-1There is down 332mAhg-1Excellent specific capacity, 100 times stablize circulation
Capacity retention ratio afterwards is 94.1%, and coulombic efficiency is close to 100%.Fig. 6 B expression is tested under flat or bending condition
The circulating energy density of flexible battery.The exemplary energy density of flexible lithium ion battery can achieve 389Whkg-1, and
Stablize the high retention rate that can also have 92.3% after circulation 100 is enclosed.When considering the density of anode and cathode, flexible lithium is estimated
Ion battery has 498WhL-1Volume energy density.That is, flexible lithium ion battery of the invention combines high-energy simultaneously
Density and excellent cycle performance.
Embodiment 2
Flexible lithium ion battery is prepared according to mode similar to Example 1, the difference is that: change the dispersion of black phosphorus piece
The amount of liquid and graphene oxide sheet makes the mass ratio of black phosphorus piece and graphene oxide sheet in black phosphorus piece dispersion liquid be 1:1.So
Afterwards according to mode similar to Example 1, the cycle performance of prepared BP/ graphene cathode is tested.
Embodiment 3
Flexible lithium ion battery is prepared according to mode similar to Example 1, the difference is that: change the dispersion of black phosphorus piece
The amount of liquid and graphene oxide sheet makes the mass ratio of black phosphorus piece and graphene oxide sheet in black phosphorus piece dispersion liquid be 1:2.So
Afterwards according to mode similar to Example 1, the cyclicity of prepared BP/ graphene cathode is tested.
Fig. 3 gives the circulation and high rate performance test result according to embodiment 2 and 3, the results showed that BP/GO ratio is
The BP/rGO cathode of 1:1 and 1:2 can provide preferable cycle performance and specific capacity, that is, BP/GO ratio is the BP/rGO of 1:2
Cathode keeps the specific capacity of 477mAhg-1 after 500 circulations, and average coulombic efficiencies are 99.6%；And BP/GO ratio
The BP/rGO cathode that example is 1:2 protects the specific capacity of 329mAhg-1 after 500 circulations, and average coulombic efficiencies are
99.6%.
Comparative example 1
Flexible lithium ion battery is prepared according to mode similar to Example 1, the difference is that: directly use graphene
As precursor.
Fig. 7 expression directly uses graphene as precursor, then according to mode similar to Example 1, to prepared
The result that the cycle performance of BP/ graphene cathode is tested.The result shows that directly use graphene as precursor, it is prepared
Electrode can only recycle 50 circles, and with apparent capacity attenuation.
Conclusion
Although the present invention provides only exemplary implementation scheme, it will be appreciated that, it is being described herein and is saying
Bright material, electrospinning parameters, hydrothermal temperature, reducing degree, black phosphorus content and component layout to explain essence of the invention
Aspect, make in the principle and range of the disclosure that those skilled in the art can express in such as appended claims it is many its
He changes.
Claims (14)
1. a kind of prepare flexible black phosphorus/redox graphene combination electrode method, method includes the following steps:
I) black phosphorus is removed into black phosphorus piece dispersion liquid in the solution；
Ii it) expands blocky graphite and is oxidized to graphene oxide sheet；
Iii the black phosphorus piece dispersion liquid and the graphene oxide sheet) are mixed to form uniform dispersion；
Iv) uniform dispersion is filtered by vacuum to form black phosphorus/graphene oxide membrane；And
V) electronation, drying and optionally prelithiation are carried out to the black phosphorus/graphene oxide membrane, it is black to form the flexibility
Phosphorus/redox graphene combination electrode.
2. according to the method described in claim 1, wherein the mass ratio of the black phosphorus piece and the graphene oxide sheet 1:1 extremely
In the range of 1:2.
3. according to the method described in claim 1, carrying out the mixing by ultrasonic treatment wherein in step iii).
4. according to the method described in claim 1, carrying out the electronation by hydrogen iodide steam wherein in step v).
5. a kind of flexibility black phosphorus/redox graphene combination electrode, is by according to claim 1 to any one of 4 institutes
Made from the method stated.
6. a kind of flexible lithium ion battery, comprising:
Cathode comprising flexibility black phosphorus/redox graphene combination electrode according to claim 5；
Polymer dielectric；And
Anode comprising vanadic anhydride/carbon nano-tube combination electrode.
7. flexible lithium ion battery according to claim 6, wherein the polymer dielectric includes to be selected from polyvinylidene fluoride
At least one of alkene, Kynoar-hexafluoropropene, polyethylene glycol oxide, polymethyl methacrylate, polyacrylonitrile.
8. flexible lithium ion battery according to claim 6 further includes sealing the flexible lithium ion using polymer film
Battery.
9. flexible lithium ion battery according to claim 6 the, wherein vanadic anhydride/carbon nano-tube combination electrode is
By method comprising the following steps manufacture:
A) disperse vanadium pentoxide powder in a solvent to form vanadic anhydride solution；
B) carbon nanotube is functionalized, to form functionalized carbon nanotube；
C) the vanadic anhydride solution and the functionalized carbon nanotube are mixed, to form dispersion liquid；
D) make the vanadic anhydride hydrothermal growth in the dispersion liquid at vanadium pentoxide nanowires by heating；
E) dispersion liquid after hydrothermal growth is assembled, to form the vanadic anhydride/carbon nano-tube combination electrode.
10. flexible lithium ion battery according to claim 9, wherein the solvent in the step a) is H2O2Concentration is in 4 matter
Measure the hydrogen peroxide within the scope of % to 5 mass %.
11. flexible lithium ion battery according to claim 9, wherein the hydrothermal growth in step d) is at 200 DEG C to 220 DEG C
At a temperature of carry out 72 to 96 hours.
12. flexible lithium ion battery according to claim 9, wherein in the step e), using vacuum filtration come into
The row assembling.
13. the flexible lithium ion battery according to any one of claim 6 to 12, wherein the density of the cathode is
1.9g·cm-3To 2.1gcm-3, and the cathode with a thickness of 25 μm to 35 μm.
14. the flexible lithium ion battery according to any one of claim 6 to 12, wherein the flexible lithium ion battery passes through
It crosses the mass energy density that 100 are stablized after recycling and is up to 389Whkg-1, and volume energy density is up to 498Whkg-1。
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