CN110391398B - Black phosphorus/reduced graphene oxide composite electrode, preparation method thereof and flexible lithium ion battery comprising composite electrode - Google Patents
Black phosphorus/reduced graphene oxide composite electrode, preparation method thereof and flexible lithium ion battery comprising composite electrode Download PDFInfo
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Abstract
The application provides a method for preparing a black phosphorus/reduced graphene oxide composite electrode, which comprises the following steps: i) Stripping black phosphorus in the solution into a black phosphorus flake dispersion; ii) expanding and oxidizing the bulk graphite into graphene oxide sheets; iii) Mixing the black phosphorus flake dispersion and the graphene oxide flakes to form a uniform dispersion; iv) vacuum-filtering the uniform dispersion to form a black phosphorus/graphene oxide film; and v) chemically reducing, drying and optionally prelithiating the black phosphorus/graphene oxide film to form the flexible black phosphorus/reduced graphene oxide composite electrode. In addition, the application also provides a black phosphorus/reduced graphene oxide composite electrode and a flexible lithium ion battery comprising the composite electrode. The flexible lithium ion battery according to the application has both a high mass energy density and a high volumetric energy density and no significant decay after 100 cycles in the operating bending state.
Description
Cross Reference to Related Applications
The present application claims priority from U.S. provisional patent application No.62/762,114 filed on 4/23 in 2018, the contents of which are incorporated herein by reference.
Technical Field
The application relates to a plurality of layers of black phosphorus/reduced graphene oxide (BP/rGO) composite electrodes (or composite films, composite papers or cathodes) and a preparation method thereof, and BP/rGO cathodes and V cathodes using the same 2 O 5 Flexible Lithium Ion Battery (LIB) assembled with CNT positive electrode and polymer electrolyte.
Background
In order to promote rapid and widespread development of flexible and wearable electronics, it is desirable to develop flexible energy storage devices with high energy densities. Current flexible energy storage devices are mainly aqueous supercapacitors, because the electrodes and electrolytes of supercapacitors can be easily made flexible, but their low energy density severely hampers their widespread use.
Due to the high energy density and mature manufacturing lines, emerging flexible lithium ion batteries are considered the most promising alternatives to flexible supercapacitors. Although the fabrication of flexible lithium ion batteries using conventional electrode materials can be achieved by incorporating highly porous three-dimensional (3D) current collectors or thick polymer electrolytes/separators, they tend to have poor electrochemical performance, especially with very low volumetric energy densities. For example, V.L.PushParaj et al, proc.Natl.Acad.Sci.104 (2007) 13574, disclose the use ofFlexible lithium ion battery with porous carbon nanotube array as electrode, which can only reach 250 Wh.kg -1 And 10 stable cycles. Xu et al, adv. Energy Mater 5 (2015) 1401882 disclose flexible capacitors using carbon nanofibers as electrode substrates, which, although reaching 4000 stable cycles, have an energy density of only 11 Wh.kg -1 。
Therefore, finding a suitable flexible electrode material with high energy density and stable cycling performance would be a key challenge in developing advanced flexible lithium ion batteries.
Disclosure of Invention
The application aims to provide a flexible lithium ion battery with ultra-high energy density based on a layered black phosphorus/reduced graphene oxide composite electrode. The flexible lithium ion battery has both high mass energy density and high volumetric energy density, and the electrochemical performance of the battery does not significantly decay after 100 cycles in an operational bending state.
In order to achieve the above object, the present application developed a BP/rGO composite film as a negative electrode and a method for producing the same comprising BP/rGO negative electrode, vanadium pentoxide/carbon nanotube (V 2 O 5 CNT) positive electrode and polymer electrolyte. Moreover, the present application provides fast ion/electron transport rates and high energy densities by optimizing the ratio of black phosphorus to Graphene Oxide (GO) sheets.
In the present application, the black phosphorus/graphene composite electrode can be prepared simply by vacuum-filtering a black phosphorus and GO mixture dispersion, followed by mild reduction and optionally prelithiation. The BP/rGO mixture is densely stacked into flexible paper that can be used as a conductive substrate and mechanical buffer for efficient storage of lithium in black phosphorus. BP sheets are sandwiched between and uniformly distributed between adjacent rGO layers, thereby ensuring excellent stability of the composite electrode in the repeated lithiation/delithiation process. The independent BP/rGO can be used directly as a negative electrode without a current collector, which ensures flexibility and high energy density of the battery. The flexible battery was assembled by sealing the electrodes and electrolyte using a semi-cured polymer film in an argon atmosphere, and then heat-treating to completely cure the polymer film. The polymer film prevents moisture and oxygen in the air from penetrating into the battery, so that the battery can be used for a long time under ambient conditions.
In order to prepare the black phosphorus/reduced graphene oxide composite anode, different precursor materials and efficient and economical processing parameters are used in the application. For example, graphene oxide is used as a precursor instead of graphene, because it can enhance the mechanical flexibility of the final product. Graphene oxide only needs to be mildly reduced, which in turn saves energy that would normally require high temperature reduction. In addition, the process used in the present application requires low energy consumption, for example, at a temperature of 120 ℃ or less, and the precursors and solvents used can be recycled, so that the yield of the final product is relatively high.
Drawings
The following is a brief description of the drawings, which are presented for the purposes of illustrating and not limiting the exemplary embodiments disclosed herein.
FIG. 1 is a schematic diagram of a battery including BP/rGO negative electrode, V 2 O 5 Flow chart of a method for manufacturing flexible lithium ion battery of CNT positive electrode and PVDF-HFP polymer electrolyte.
FIGS. 2A to 2D are photomicrographs of BP and BP/rGO prepared using the disclosed synthetic methods. FIG. 2A is a Scanning Electron Microscope (SEM) image of BP/rGO as viewed from the top. FIG. 2B is a sectional scanning electron microscope image of BP/rGO. Fig. 2C is a Transmission Electron Microscope (TEM) image of pure BP. FIG. 2D is a transmission electron microscope image of BP/rGO.
Fig. 3 shows the electrochemical properties of BP/rGO composite anode. FIG. 3A is a graph of 0.5 A.g -1 The cycling performance of BP/rGO cathodes synthesized from various precursor ratios at current densities. Fig. 3B is the rate capability of BP/rGO negative electrodes synthesized from various precursor ratios.
FIGS. 4A and 4B are V produced 2 O 5 Microphotographs of CNT anodes. Fig. 4A is an SEM image at low magnification. Fig. 4B is an SEM image at high magnification. FIG. 4C is V 2 O 5 Rate performance of CNT positive electrode.
Fig. 5A is a digital photograph of an HVDF-HFP polymer electrolyte. Fig. 5B is an SEM image of the same polymer electrolyte.
Fig. 6A shows the open circuit voltage of a flexible lithium ion battery. Fig. 6B shows the energy density of a prototype flexible lithium ion battery.
FIG. 7 shows that at first 0.1 A.g -1 The electrode was activated at a current density of 0.5 A.g -1 The cycling performance of BP/graphene anode synthesized according to comparative example 1.
Detailed Description
Embodiments for carrying out the present application will be described below. However, the scope of the present application is not limited to the embodiments described above, and various modifications may be made thereto without impairing the gist.
The term "black phosphorus/reduced graphene oxide composite electrode" refers to a composite electrode comprising black phosphorus and reduced graphene oxide.
The term "V 2 O 5 The "CNT composite electrode" refers to a composite electrode comprising vanadium pentoxide and carbon nanotubes.
A recent widespread search for two-dimensional (2D) materials would provide new opportunities to address the challenges described above. Most two-dimensional materials, such as graphene, two-dimensional metal carbide, and two-dimensional black phosphorus, can be dispersed in a solvent and assembled into flexible paper with excellent mechanical strength. In addition to flexibility, they have a high lithium storage capacity. In particular, black phosphorus has a value of up to 2596 mAh.g by alloying with lithium -1 Is the highest of all two-dimensional materials. In addition, the weak van der Waals forces between adjacent phospholene layers enable large blocks of black phosphorus crystals to be easily and highly-productively exfoliated into two-dimensional black phosphorus in a liquid without any pretreatment. The exfoliated black phosphorus platelets can be chemically stable in an organic solvent for several days, thereby facilitating the fabrication of electrodes comprising two-dimensional black phosphorus at room temperature. All of the above advantages give the black phosphorus a bright prospect as an advanced electrode material for flexible batteries.
Accordingly, in one embodiment, the present application provides a method of preparing a flexible black phosphorus/reduced graphene oxide composite electrode, the method comprising the steps of: i) Stripping black phosphorus in the solution into a black phosphorus flake dispersion; ii) expanding and oxidizing the bulk graphite into graphene oxide sheets; iii) Mixing the black phosphorus flake dispersion and the graphene oxide flakes to form a uniform dispersion; iv) assembling the uniform dispersion into a flexible black phosphorus/graphene oxide film by vacuum filtration; and v) chemically reducing, drying and optionally prelithiating the black phosphorus/graphene oxide film to form the flexible black phosphorus/reduced graphene oxide composite electrode.
Compared with the graphene serving as a precursor, the graphene oxide serving as the precursor can enhance the mechanical flexibility of the flexible lithium ion battery, form a more uniform layered structure with the black phosphorus sheet, accelerate the transmission of lithium ions and improve the electrochemical performance.
In addition, in order to further increase the high energy density of BP/rGO in flexible cells, the present application also optimizes the ratio of black phosphorus sheets to Graphene Oxide (GO) sheets to optimize the morphology of the electrode, thereby providing fast ion/electron transport rates and high energy density.
In a specific embodiment, in step i), the black phosphorus is exfoliated into black phosphorus flake dispersions in, for example, an N-methylpyrrolidone solvent.
In a specific embodiment, in step ii), the graphite is expanded using, for example, a mixture of sulfuric acid and nitric acid, and then the expanded graphite is oxidized using potassium permanganate and concentrated sulfuric acid. In a specific embodiment, after step ii), the oxidized graphite is washed sequentially with hydrogen peroxide, hydrochloric acid and deionized water.
In particular embodiments, the mass ratio of the black phosphorus flakes to the graphene oxide flakes may be in the range of 1:1 to 1:2.
In a specific embodiment, in step iii), the mixing may be performed using methods conventionally known in the art, preferably by ultrasonic treatment.
In a specific embodiment, in step v), the chemical reduction is performed by hydrogen iodide vapor.
In another embodiment, the present disclosure provides a flexible black phosphorus/reduced graphene oxide composite electrode prepared according to the above-described method.
As described above, the present disclosure describes the synthesis of BP/rGO using a stripped BP dispersion precursor and a vacuum filtration process. After reduction of Graphene Oxide (GO) and removal of residual solvent in the electrode, a density of 1.9 g.cm was successfully prepared -2 To 2.1 g.cm -2 And a film-like black phosphorus/reduced graphene oxide electrode having a thickness of 25 μm to 35 μm. The internal void space of the electrode can be further controlled by adjusting the ratio of precursor BP sheets to precursor GO sheets. BP/rGO electrodes having BP sheet to GO sheet ratios within the scope of the present application are densely packed and have high conductivity and excellent flexibility.
BP/rGO electrode is 0.5 A.g -1 Exhibits 477 mAh.g after 500 cycles at a current density of (2) -1 And the average coulombic efficiency was 99.6% when tested with lithium foil as the counter electrode in a CR2032 coin cell. When the BP/rGO electrode is used as the negative electrode in a flexible lithium ion battery, the full cell can provide 389 Wh.kg -1 And has a high retention of 92.3% after 100 cycles. When the density of the electrode is considered, the volume energy density of the flexible lithium ion battery can reach 498 Wh.L -1 . The above parameters and performance are not limited to the specific examples tested by the present disclosure, but are generic.
In yet another embodiment, the present disclosure provides a flexible lithium ion battery comprising: a negative electrode comprising the flexible black phosphorus/reduced graphene oxide composite electrode described above; a polymer electrolyte; and a positive electrode including a vanadium pentoxide/carbon nanotube composite electrode.
In a specific embodiment, the polymer electrolyte comprises at least one selected from polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyethylene oxide, polymethyl methacrylate, polyacrylonitrile. In a more specific embodiment, the polymer electrolyte comprises polyvinylidene fluoride-hexafluoropropylene.
In particular embodiments, the flexible lithium ion battery is sealed using a polymer film. The polymer film prevents moisture and oxygen in the air from penetrating into the battery, so that the battery can be used for a long time under ambient conditions. In more specific embodiments, polypropylene/polydimethylsiloxane films are used to seal the flexible lithium ion battery.
In particular embodiments, the vanadium pentoxide/carbon nanotube composite electrode is manufactured by a process comprising the steps of:
a) Dispersing vanadium pentoxide powder in a solvent to form a vanadium pentoxide solution;
b) Functionalizing the carbon nanotubes to form functionalized carbon nanotubes;
c) Mixing the vanadium pentoxide solution and the functionalized carbon nanotubes to form a dispersion;
d) Hydrothermally growing the vanadium pentoxide in the dispersion liquid into vanadium pentoxide nanowire by heating;
e) And assembling the dispersion liquid after the hydrothermal growth to form the vanadium pentoxide/carbon nano tube composite electrode.
In a more specific embodiment, the solvent in step a) is H 2 O 2 Hydrogen peroxide in a concentration ranging from 4 to 5 mass%. In a more specific embodiment, the hydrothermal growth in step d) is performed at a temperature of 200 ℃ to 220 ℃ for 72 to 96 hours. In a more specific embodiment, in said step e), vacuum filtration is used for said assembling.
The present disclosure provides for the use of BP/rGO cathodes, V 2 O 5 Assembly of flexible lithium ion battery of CNT positive electrode, polymer electrolyte and optionally polymer sealing film. Compared with the existing flexible energy storage device, the flexible lithium ion battery manufactured by the method can fully and stably work under the environment condition, and has greatly improved energy density.
The following is a case where BP/rGO electrode is included as a negative electrode, V 2 O 5 The preparation of flexible lithium ion batteries with CNT electrodes as positive electrode and PVDF-HFP polymer electrolyte as polymer electrolyte is described in more detail. The method has the advantages of mass production and high quality of the obtained flexible lithium ion batteryObvious advantages of different electrochemical properties.
Fig. 1 is a flowchart showing the operation of a procedure for synthesizing key components of a flexible lithium ion battery. Bulk graphite and black phosphorus crystals are commercially available, which are then exfoliated into two-dimensional nanoplatelets dispersed in a solvent. They are then assembled into individual membranes by vacuum filtration. BP/rGO membranes can be obtained by a mild reduction process using hydrogen iodide vapor as the reducing agent. The BP/rGO film needs to be prelithiated before use as the negative electrode for flexible lithium ion batteries. Commercial vanadium pentoxide and carbon nanotube powders are soluble in hydrogen peroxide solution during hydrothermal processes and assembled into individual membranes by vacuum filtration. PVDF-HFP films can be obtained by electrospinning precursor solutions of PVDF-HFP. Uncured PDMS was spin coated onto polypropylene film and then subjected to a mild heat treatment to prepare semi-cured PP/PDMS. All of the above components are stacked layer by layer to manufacture a flexible lithium ion battery. All the above processes are simple, mass-producible and low-cost.
Specifically, the method comprises the following steps:
(1) Preparation of flexible black phosphorus/reduced graphene oxide composite electrode
First, graphite and bulk black phosphorus crystals are exfoliated into their several layers of dispersion (e.g., a dispersion containing 1 to 15 layers of black phosphorus flakes): sulfuric acid and nitric acid were mixed in a volume ratio of 3:1, 200mL of the mixture was intercalated with 5g of graphite, and then thermally expanded at 1050.+ -. 20 ℃ for 15-20 seconds to obtain Expanded Graphite (EG). Then, 0.5g of expanded graphite was taken and oxidized in 100mL of 98% concentrated sulfuric acid at 50℃to 60℃using 3.5g of potassium permanganate for 24.+ -. 1 hour. The oxidized product was washed sequentially with 30% hydrogen peroxide, 0.1 mol/liter hydrochloric acid and deionized water, and the resulting graphene oxide sheet was collected by centrifugation.
Several layers of black phosphorus flake dispersion were obtained by liquid exfoliation of BP crystals under ultrasonic treatment. 0.2g of block-shaped black phosphorus crystals were ground into small particles using a mortar, and then mixed with 200mL of N 2 Bubbling 2-methyl-2-pyrrolidone (99%, supplied by Aldrich) was mixed. The mixture was then sealed in a vial and sonicated for 24±1 hours. The obtained dispersion liquid is mixed with 4500-5500rCentrifugation at pm for 15-20 minutes to remove large precipitates and the dispersion in the upper half was selected as a few layers of black phosphorus flake dispersion.
Then, BP/rGO electrodes were prepared by vacuum filtration and mild reduction: several layers of black phosphorus flake dispersion are mixed with graphene oxide flakes and sonicated for 30-60 minutes to form a uniform dispersion, wherein in the uniform dispersion, the mass ratio of black phosphorus flakes to graphene oxide flakes in the black phosphorus flake dispersion is in the range of 1:1 to 1:2. The black phosphorus/graphene oxide dispersion was then passed through polyvinylidene fluoride (PVDF) filter paper (supplied by Merck Millipore) having a pore size of 0.22-0.4 μm. After evaporating the solvent by vacuum drying, a thin film may be formed on polyvinylidene fluoride filter paper, which is peeled off to obtain an independent black phosphorus/graphene oxide film. The black phosphorus/graphene oxide film was reduced in hydrogen iodide vapor at 90-95 ℃ for 1-2 hours, and then dried in vacuum at 120-130 ℃ for 12-15 hours to obtain an independent BP/rGO electrode.
(2) Preparation of vanadium pentoxide/carbon nano tube composite electrode
Synthesis of V by hydrothermal reaction and vacuum filtration 2 O 5 CNT composite film: synthesis of V by growing pure vanadium pentoxide nanowires on carbon nanotubes 2 O 5 CNT positive electrode. 0.36 plus or minus 0.01g of vanadium pentoxide powder is added>98%, provided by Aldrich) was dispersed in 30-32mL deionized water. 5.+ -. 0.1mL of 30% hydrogen peroxide solution was added drop wise to the vanadium pentoxide dispersion to form a brown solution. Carbon nanotubes (supplied by Iljin Nanotech) were purified and functionalized by sonication in 6M nitric acid for 2 hours. 0.09.+ -. 0.001g of functionalized carbon nanotubes was added to the above brown solution to form a black dispersion, and the black dispersion was heated in an autoclave at 200-220 ℃ for 72-96 hours. After the hydrothermal reaction, the product was washed with deionized water and deposited by vacuum filtration on PVDF filter paper with pore size 0.22-0.4 μm. V is obtained by stripping off the deposited film after drying at 60℃for 12-18 hours 2 O 5 CNT electrode.
(3) Preparation of PVDF-HFP Polymer electrolyte
PVDF-HFP polymer electrolyte was prepared by electrospinning:PVDF-HFP polymer precursor (average Mw-455,000, supplied by Aldrich) was dissolved in a mixed solvent consisting of 4mL dimethylformamide and 16mL acetone to form a homogeneous solution having a concentration of 12-13% by weight. High voltage of 17.5kV and 1 mL.h using electrostatic spinning machine (NEU nanofiber electrostatic spinning device, kato) -1 The polymer solution was electrospun onto aluminum foil at a feed rate, the PVDF-HFP nanofiber mat was peeled from the aluminum foil and dried in a vacuum oven at 60-80 ℃ to completely remove the residual solvent. Polymer electrolyte was made by soaking PVDF-HFP pad in a liquid electrolyte consisting of 1M LiPF 6 Ethylene Carbonate (EC): methyl ethyl carbonate (EMC): dimethyl carbonate (DMC) (1:1:1 vol%) solution+1 wt% vinylene carbonate.
(4) Assembly of flexible lithium ion batteries
Using V 2 O 5 Flexible batteries were assembled with CNT positive electrode, BP/rGO negative electrode and PVDF-HFP polymer electrolyte as electrolytes. Will V 2 O 5 the/CNT and BP/rGO papers were cut into pieces of typical 20mm by 20mm transverse dimensions. Prior to assembly of the flexible battery, BP/rGO needs to be prelithiated by shorting BP/rGO with an electrolyte-wetted lithium foil. The cell assemblies were stacked together and sealed between two semi-cured polydimethylsiloxane coated polypropylene polymer films in an argon filled glove box. The cell was subjected to a charge/discharge test to activate the electrodes and release any generated gas. After discharging, the flexible battery was aged in a glove box for 24 to 36 hours to completely cure the polydimethylsiloxane film. Finally, the edges of the polypropylene film were sealed by plastic welding before the flexible battery was taken out of the glove box.
Examples
Example 1
Material
The following reagents and solvents were used without further purification: polyacrylonitrile (PAN, mw=150,000, sigma-Aldrich), N-dimethylformamide (DMF, 99.8%, sigma-Aldrich), hydrochloric acid (37%, fisher), nitric acid (69-72%, fisher), N-methylpyrrolidone (NMP), PVDF-HFP (average Mw-455,000, sigma-Aldrich), sulfuric acid (98%, fisher), hydrogen peroxide (30%, fisher), potassium permanganate (97%, sigma-Aldrich), vanadium pentoxide (> 98%, sigma-Aldrich), polydimethylsiloxane (Sigma-Aldrich), acetone (Fisher).
Characterization of
Morphology was characterized using scanning electron microscopy (SEM, JEOL 7100F) and transmission electron microscopy (TEM, JEOL 2010). Electrochemical performance was measured on a battery test system (Land 2001 CT).
Method of manufacture
In example 1, BP/rGO electrodes were prepared by vacuum filtration and mild reduction of BP/GO dispersion. Synthesis of V by hydrothermal reaction and vacuum filtration 2 O 5 CNT composite film. PVDF-HFP polymer electrolytes were produced by electrospinning.
Experiment 1
Preparation of BP/rGO negative electrode, V 2 O 5 CNT positive electrode and PVDF-HFP electrolyte: sulfuric acid and nitric acid were mixed in a volume ratio of 3:1, 200mL of the mixture was intercalated with 5g of graphite (commercially available as Natural graphite, supplied by Asbury), and the graphite was then thermally expanded at 1050℃for 15 seconds to obtain expanded graphite. 0.5g of expanded graphite was taken and oxidized at 50℃for 24 hours using 3.5g of potassium permanganate and 100mL of 98% concentrated sulfuric acid. The oxidized product was washed sequentially with 30% hydrogen peroxide, 0.1 mol/liter hydrochloric acid and deionized water, and the resulting graphene oxide sheet was collected by centrifugation. Several layers of Black Phosphorus flake dispersion were obtained by liquid stripping of BP crystals (trade name Black Phosphorus, supplied by Aldrich) under sonication. 0.2g of the bulk black phosphorus crystals were ground into small particles using a mortar and then mixed with 200mL of nitrogen sparged N-methylpyrrolidone solvent (99%, supplied by Aldrich). The mixture was then sealed in a vial and sonicated for 24 hours. The resulting dispersion was centrifuged at 5000rpm for 15 minutes to remove large precipitates, and the upper half of the dispersion was selected as a few layers of black phosphorus flake dispersion. Several layers of black phosphorus flake dispersion were mixed with graphene oxide flakes and sonicated for 30 minutes toA uniform dispersion was formed in which the mass ratio of black phosphorus flakes to graphene oxide flakes in the black phosphorus flake dispersion was 2:3, and then the uniform dispersion was passed through PVDF filter paper (supplied by Merck Millipore) having a pore size of 0.22 μm. After evaporation of the solvent by vacuum drying, a film was formed on PVDF filter paper, which was peeled off to give an independent BP/GO film. The BP/GO membrane was reduced in hydrogen iodide vapor at 95 ℃ for 1 hour, then annealed in vacuum at 120 ℃ for 12 hours to obtain an independent BP/rGO electrode.
Synthesis of V by growing pure vanadium pentoxide nanowires on carbon nanotubes 2 O 5 CNT positive electrode. 0.36g of vanadium pentoxide powder was added>98%, provided by Aldrich) was dispersed in 30mL deionized water. 5mL of a 30% hydrogen peroxide solution was added dropwise to the vanadium pentoxide dispersion to form a brown solution. Carbon nanotubes (supplied by Iljin Nanotech) were purified and functionalized by sonication in 6M nitric acid for 2 hours. 0.09g of functionalized carbon nanotubes was added to the brown solution to form a black dispersion, which was heated in an autoclave at 200 ℃ for 96 hours. After the hydrothermal reaction, the product was washed with deionized water and deposited by vacuum filtration on PVDF filter paper with a pore size of 0.22 μm. V was obtained by stripping the deposited film after drying at 60℃for 12 hours 2 O 5 CNT electrode.
PVDF-HFP polymer precursor (average Mw-455,000, supplied by Aldrich) was dissolved in a mixed solvent consisting of 4mL of N, N-dimethylformamide and 16mL of acetone to form a uniform solution having a polymer precursor concentration of 12% by weight. High voltage of 17.5kV and 1 mL.h using electrospinning device (NEU nanofiber electrospinning apparatus, kato) -1 The polymer solution was electrospun onto aluminum foil at the feed rate of (2). The PVDF-HFP nanofiber mat was peeled from the aluminum foil and dried in a vacuum oven at 80 ℃ to remove residual solvent. The polymer electrolyte was made by immersing PVDF-HFP mat in a liquid electrolyte consisting of 1M lithium hexafluorophosphate carbonate: methyl ethyl carbonate: dimethyl carbonate (1:1:1 by volume%) solution+1 mass% vinylene carbonate.
Experiment 2
Characterization of electrodes and electrolytes: characterization of BP/rGO, V by SEM and TEM 2 O 5 Morphology of/CNT and PVDF-HFP.
Fig. 2A shows a continuous graphene oxide region with wrinkles caused by cross-linking of adjacent graphene oxide sheets. The low magnification SEM image also shows black flakes sandwiched between graphene oxide layers. Fig. 2B is a cross-sectional SEM image of densely packed and aligned GO and BP layers in a BP/rGO film. The BP/rGO membrane with high density ensures high volumetric capacity of the flexible lithium ion battery. Fig. 2C is a TEM image of a prepared black phosphorus flake having a lateral dimension of several hundred nanometers to several micrometers. Fig. 2D is a TEM image of a BP/rGO composite, wherein the black flakes are uniformly distributed on the graphene oxide layer. FIGS. 4A-B are prepared V 2 O 5 Microphotographs of CNT films. Fig. 4A shows a low magnification SEM image of entangled vanadium pentoxide nanowires. The nanowires have an ultra-high aspect ratio with a typical length of more than 100 μm, which ensures V 2 O 5 High mechanical strength of CNT films. Fig. 4B is a high magnification SEM image of the same sample. The carbon nanotubes are uniformly distributed in the entangled vanadium pentoxide nanowire, which is V 2 O 5 Electron transport during the lithiation/delithiation cycle of the CNT positive electrode provides a conductive network. The diameter of the vanadium pentoxide nanowire is about 100nm, so that the diffusion of lithium ions is facilitated and the rate performance is improved. Fig. 5 is a micrograph of the PVDF-HFP polymer electrolyte prepared. As shown in fig. 5A, after the liquid electrolyte is added to the electrospun PVDF-HFP mat, the electrolyte is transparent and flexible. Fig. 5B is an SEM image of PVDF-HFP nanofibers showing the porous structure required for uptake of liquid electrolyte.
Experiment 3
Assembling a flexible battery: v used as positive electrode 2 O 5 CNT, BP/rGO as negative electrode and gel polymer electrolyte as electrolyte and separator assembled flexible battery. All of the above components were synthesized in experiment 1. Will V 2 O 5 the/CNT and BP/rGO sheets were cut into sheets having typical dimensions of 20mm by 20 mm. In the group ofThe BP/rGO anode was prelithiated by shorting the BP/rGO with an electrolyte-wetted lithium foil for at least 12 hours prior to loading the flexible battery. The prepared cell assemblies were stacked one after the other in an argon filled glove box and sealed between two semi-cured polydimethylsiloxane coated polypropylene polymer films. The two polydimethylsiloxane films will merge together creating a compressive force on the electrode and electrolyte, thereby ensuring good electrical contact of the cell. The cell is then discharged for one cycle to activate the electrodes and release any generated gas. After the discharge process, the assembled flexible battery was placed in a glove box at room temperature for 24 hours to completely cure the polydimethylsiloxane. Finally, the edges of the polypropylene film were completely sealed by plastic welding before the flexible battery was taken out of the glove box.
Experiment 4
BP/rGO negative electrode, V 2 O 5 Electrochemical characterization of CNT positive and flexible cell: assembly of button cell to measure BP/rGO and V 2 O 5 Electrochemical performance of CNT electrode to lithium foil. BP/rGO electrode circulates between 0 and 3V, while V 2 O 5 the/CNT electrode was cycled between 1.5V and 4V on a LAND 2001CT battery tester. The energy density of the flexible cell was 0.2 A.g at a voltage of 1 to 4V on a CHI660c electrochemical workstation -1 Is measured at a current density of (c). The weight of the battery is based on the total mass of the positive and negative electrodes. The energy density is calculated based on the numerical integration of the constant current charge-discharge curve.
Fig. 3 shows the electrochemical performance of BP/rGO cathodes with various BP/GO precursor ratios measured on lithium foil using CR2032 coin cells. FIG. 3A shows that the concentration of the catalyst is 0.5A.g -1 BP/rGO at current density. FIG. 3B shows the measurement of 0.1 A.g -1 To 3 A.g -1 The ratio capacity of BP/rGO at the current density of (C). BP/GO ratio was 2:3, an optimized electrochemical performance at 0.2 A.g -1 Provides 737 mAh.g at a current density of (3) -1 Is a reversible capacity of (a). BP/GO ratio was 2:3 maintains 477 mAh.g after 500 cycles -1 And an average coulombic efficiency of 99.6%. FIG. 4C showsAt 0.1 A.g -1 To 3 A.g -1 V for lithium foil test using CR2032 coin cell at current density of (c) 2 O 5 Rate capability of CNT positive electrode. V (V) 2 O 5 CNT positive electrode 0.1 A.g -1 The lower part has 332 mAh.g -1 The capacity retention after 100 stable cycles was 94.1% and the coulombic efficiency was close to 100%. Fig. 6B shows the cyclic energy density of a flexible battery tested in either flat or curved conditions. Typical energy density of flexible lithium ion battery can reach 389 Wh.kg -1 And also has a high retention of 92.3% after 100 cycles of stabilization. When the densities of the positive and negative electrodes are considered, it is estimated that the flexible lithium ion battery has 498wh·l -1 Is a volume energy density of (c). Namely, the flexible lithium ion battery of the present application combines both high energy density and excellent cycle performance.
Example 2
A flexible lithium ion battery was prepared in a similar manner as in example 1, except that: the amount of the black phosphorus sheet dispersion liquid and the graphene oxide sheets was changed so that the mass ratio of the black phosphorus sheets to the graphene oxide sheets in the black phosphorus sheet dispersion liquid was 1:1. The cycle performance of the prepared BP/graphene anode was then tested in a similar manner to example 1.
Example 3
A flexible lithium ion battery was prepared in a similar manner as in example 1, except that: the amount of black phosphorus flake dispersion and graphene oxide flakes was varied such that the mass ratio of black phosphorus flakes to graphene oxide flakes in the black phosphorus flake dispersion was 1:2. The prepared BP/graphene anode was then tested for circularity in a similar manner to example 1.
Fig. 3 shows the results of the cycle and rate performance tests according to examples 2 and 3, which show that: BP/rGO cathodes with BP/GO ratio of 1:1 and 1:2 can provide better cycle performance and specific capacity, namely BP/rGO cathode with BP/GO ratio of 1:2 keeps the specific capacity of 477mAh.g-1 after 500 cycles, and average coulombic efficiency is 99.6%; and BP/rGO cathode with BP/GO ratio of 1:2 can ensure specific capacity of 329 mAh.g-1 after 500 cycles, and average coulomb efficiency is 99.6%.
Comparative example 1
A flexible lithium ion battery was prepared in a similar manner as in example 1, except that: graphene is directly used as a precursor.
Fig. 7 shows the results of testing the cycle performance of the prepared BP/graphene anode in a similar manner to example 1, using graphene directly as a precursor. The results indicate that the prepared electrode can only be cycled 50 times with significant capacity fade using graphene directly as a precursor.
Conclusion(s)
While the present application has been shown and described herein with respect to materials, electrospinning parameters, hydrothermal temperatures, reduction levels, black phosphorus content, and component placement that have been described and illustrated herein to explain the nature of the present application, it should be understood that many other variations may be made by those skilled in the art within the principles and scope of the present disclosure as expressed in the appended claims.
Claims (12)
1. A method of preparing a flexible black phosphorus/reduced graphene oxide composite electrode, the method comprising the steps of:
i) Stripping black phosphorus in the solution into a black phosphorus flake dispersion;
ii) expanding and oxidizing the bulk graphite into graphene oxide sheets;
iii) Mixing the black phosphorus flake dispersion and the graphene oxide flakes to form a uniform dispersion, wherein the mass ratio of the black phosphorus flakes to the graphene oxide flakes is in the range of 1:1 to 1:2, and performing the mixing by ultrasonic treatment;
iv) vacuum-filtering the uniform dispersion to form a black phosphorus/graphene oxide film; and
v) chemically reducing and drying the black phosphorus/graphene oxide film to form the flexible black phosphorus/reduced graphene oxide composite electrode.
2. The method of claim 1, wherein in step v) the black phosphorus/graphene oxide film is chemically reduced, dried and prelithiated to form the flexible black phosphorus/reduced graphene oxide composite electrode.
3. The method according to claim 1, wherein in step v) the chemical reduction is performed by hydrogen iodide vapour.
4. A flexible black phosphorus/reduced graphene oxide composite electrode produced by the method according to any one of claims 1 to 3.
5. A flexible lithium ion battery comprising:
a negative electrode comprising the flexible black phosphorus/reduced graphene oxide composite electrode according to claim 4;
a polymer electrolyte; and
and the positive electrode comprises a vanadium pentoxide/carbon nano tube composite electrode.
6. The flexible lithium ion battery of claim 5 wherein the polymer electrolyte comprises at least one selected from the group consisting of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyethylene oxide, polymethyl methacrylate, polyacrylonitrile.
7. The flexible lithium ion battery of claim 5, further comprising sealing the flexible lithium ion battery with a polymer film.
8. The flexible lithium ion battery of claim 5 wherein the vanadium pentoxide/carbon nanotube composite electrode is manufactured by a process comprising the steps of:
a) Dispersing vanadium pentoxide powder in a solvent to form a vanadium pentoxide solution;
b) Functionalizing the carbon nanotubes to form functionalized carbon nanotubes;
c) Mixing the vanadium pentoxide solution and the functionalized carbon nanotubes to form a dispersion;
d) Hydrothermally growing the vanadium pentoxide in the dispersion liquid into vanadium pentoxide nanowire by heating;
e) And assembling the dispersion liquid after the hydrothermal growth by adopting vacuum suction filtration to form the vanadium pentoxide/carbon nano tube composite electrode.
9. The flexible lithium ion battery of claim 8 wherein the solvent in step a) is H 2 O 2 Hydrogen peroxide in a concentration ranging from 4 to 5 mass%.
10. The flexible lithium ion battery of claim 8 wherein the hydrothermal growth in step d) is performed at a temperature of 200 ℃ to 220 ℃ for 72 to 96 hours.
11. The flexible lithium ion battery of any one of claims 5-10, wherein the negative electrode has a density of 1.9 g-cm -3 To 2.1 g.cm -3 And the negative electrode has a thickness of 25 μm to 35 μm.
12. The flexible lithium ion battery of any of claims 5-10, wherein the flexible lithium ion battery has a mass energy density of up to 389 Wh-kg after 100 stabilization cycles -1 And a volumetric energy density of up to 498 Wh.kg -1 。
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