WO2015175060A2 - Laser induced graphene materials and their use in electronic devices - Google Patents
Laser induced graphene materials and their use in electronic devices Download PDFInfo
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- WO2015175060A2 WO2015175060A2 PCT/US2015/016165 US2015016165W WO2015175060A2 WO 2015175060 A2 WO2015175060 A2 WO 2015175060A2 US 2015016165 W US2015016165 W US 2015016165W WO 2015175060 A2 WO2015175060 A2 WO 2015175060A2
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Classifications
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/66—Current collectors
- H01G11/68—Current collectors characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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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- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/66—Current collectors
- H01G11/70—Current collectors characterised by their structure
-
- 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
Definitions
- the present disclosure pertains to methods of producing a graphene material.
- the methods include exposing a polymer to a laser source.
- the exposing results in formation of a graphene that is derived from the polymer.
- the exposure of the polymer to a laser source also includes a step of tuning one or more parameters of the laser source.
- the one or more parameters include, without limitation, laser wavelength, laser power, laser energy density, laser pulse width, gas environment, gas pressure, gas flow rate, and combinations thereof.
- the laser source includes, without limitation, a solid state laser source, a gas phase laser source, an infrared laser source, a C0 2 laser source, a UV laser source, a visible laser source, a fiber laser source, a near-field scanning optical microscopy laser source, and combinations thereof.
- the laser source is a C0 2 laser source.
- the polymer is in the form of at least one of sheets, films, pellets, powders, coupons, blocks, monolithic blocks, composites, fabricated parts, electronic circuit substrates, and combinations thereof.
- the polymer includes, without limitation, homopolymers, block co-polymers, carbonized polymers, aromatic polymers, vinyl polymers, cyclic polymers, polyimide (PI), polyetherimide (PEI), polyether ether ketone (PEEK), and combinations thereof.
- the polymer includes a doped polymer, such as a boron doped polymer.
- the exposing of a polymer to a laser source includes exposing a surface of a polymer to a laser source. In some embodiments, the exposing results in formation of the graphene on the surface of the polymer. In some embodiments, the exposing includes patterning the surface of the polymer with the graphene. In some embodiments, the graphene becomes embedded with the polymer. In some embodiments, a first surface and a second surface of a polymer are exposed to a laser source to form graphenes on both surfaces of the polymer.
- the exposing of a polymer to a laser source results in conversion of the entire polymer to graphene.
- the formed graphene material consists essentially of the graphene derived from the polymer.
- the methods of the present disclosure also include a step of separating the formed graphene from the polymer to form an isolated graphene.
- the formed graphene includes, without limitation, single-layered graphene, multi-layered graphene, double-layered graphene, triple-layered graphene, doped graphene, porous graphene, unfunctionalized graphene, pristine graphene, functionalized graphene, turbostratic graphene, graphene coated with metal nanoparticles, metal particles coated with graphene, graphene metal carbides, graphene metal oxides, graphene metal chalcogenides, oxidized graphene, graphite, and combinations thereof.
- the formed graphene includes porous graphene.
- the formed graphene includes doped graphene, such as boron-doped graphene.
- the methods of the present disclosure also include a step of incorporating the graphene material or the isolated graphene into an electronic device.
- the electronic device is an energy storage device or an energy generation device, such as a super capacitor or a micro supercapacitor.
- the graphene is utilized as an electrode in the electronic device.
- the graphene is utilized as a current collector in the electronic device.
- the graphene is utilized as an additive in the electronic device.
- the graphene material includes a polymer and a graphene derived from the polymer.
- the graphene is on a surface of the polymer.
- the isolated graphene is derived from a polymer and separated from the polymer.
- the electronic device has a capacitance ranging from about 2 mF/cm 2 to about 1,000 mF/cm 2. In some embodiments, the capacitance of the electronic device retains at least 90% of its original value after more than 10,000 cycles. In some embodiments, the electronic device has power densities ranging from about 5 mW/cm 2 to about 200 mW/cm 2.
- FIGURE 1 provides schemes and illustrations related to graphene materials and isolated graphenes.
- FIG. 1A provides a scheme of methods of making graphene materials and isolated graphenes, and incorporating the products into electronic devices.
- FIG. IB provides an illustration of a formed graphene material 20.
- FIG. 1C provides an illustration of a formed electronic device 30.
- FIG. ID provides an illustration of a formed electronic device 40.
- FIGURE 2 provides data and images relating to laser-induced graphene (LIG) formed from commercial polyimide (PI) films using a C0 2 laser at a power of 3.6 W to write patterns.
- FIG. 2A is a schematic of the synthesis process of LIG from PI.
- FIG. 2B is a scanning electron microscopy (SEM) image of LIG patterned into an owl shape. The scale bar is 1 ⁇ . The bright contrast corresponds to LIG surrounded by the darker-colored insulating PI substrates.
- FIG. 2C is an SEM image of the LIG film circled in FIG. 2B. The scale bar is 10 ⁇ . The inset is the corresponding higher magnification SEM image with a scale bar of 1 ⁇ .
- FIG. 2A is a schematic of the synthesis process of LIG from PI.
- FIG. 2B is a scanning electron microscopy (SEM) image of LIG patterned into an owl shape. The scale bar is 1 ⁇ . The bright contrast correspond
- FIG. 2D provides a cross- sectional SEM image of the LIG film on the PI substrate.
- the scale bar is 20 ⁇ .
- the inset is the SEM image showing the porous morphology of LIG with a scale bar of 1 ⁇ .
- FIG. 2E is a representative Raman spectrum of a LIG film and the starting PI film.
- FIG. 2F is an X- ray diffraction (XRD) of powdered LIG scraped from the PI film.
- XRD X- ray diffraction
- FIGURE 3 provides images of materials and equipment for production of LIG from PI by laser scribing.
- FIG. 3A provides photographs of commercial Kapton PI sheets (left) with a 30 cm ruler, and the laser cutting system (right).
- FIGS. 3B-C provide photographs of an owl and a letter R patterned on PI substrates. The scale bars are 5 mm.
- black contrast is LIG after exposure to the laser, while the lighter background corresponds to PI.
- the laser power used to scribe the images was 3.6 W.
- FIGURE 4 provides Raman spectra of control samples.
- PI sheets were carbonized in a furnace under Ar flow of 300 seem for 3 h with the following annealing temperatures: 800 °C, 1000 °C and 1500 °C. Raman spectra show that these carbonized materials were glassy and amorphous carbon.
- FIGURE 5 provides x-ray photoelectron spectroscopy (XPS) characterization of LIG-3.6 W films (i.e., LIGs formed by exposing PI sheets to lasers powered at 3.6W).
- FIG. 5A provides XPS surveys of LIG and PI. Comparison curves show that the oxygen and nitrogen peaks were significantly suppressed after PI was converted to LIG.
- FIG. 5A provides XPS surveys of LIG and PI. Comparison curves show that the oxygen and nitrogen peaks were significantly suppressed after PI was converted to LIG.
- FIG. 5B provides high resolution Cls XPS spectrum of the LIG film and PI, showing the dominant C— C peak. The
- FIG. 5D provides high resolution Nls XPS spectrum of a LIG-3.6 W film and PI. The intensity of the Nls peak was greatly reduced after laser exposure.
- FIGURE 6 provides Fourier transform infrared (FTIR) spectra of LIG-3.6 W and PI films.
- a broad absorption from 1000 cm “1 to 1700 cm “1 shows that the laser scribing leads to a large variation in the local environment.
- FIGURE 7 provides a transmission electron microscopy (TEM) characterization of LIG- 3.6 W flakes.
- FIG. 7A provides a TEM image of a thin LIG flake atop a carbon grid.
- the scale bar is 200 nm.
- FIG. 7B provides a TEM image of a thick LIG flake showing entangled tree-like ripples.
- the scale bar is 100 nm.
- Inset is the high resolution TEM (HRTEM) image of the yellow-circled region showing the mesoporous structures.
- the scale bar is 5 nm.
- FIGS. 7C-D provide TEM images of LIG in bright and dark field view.
- the scale bar is 10 nm. In dark field view, folded graphene containing several pores between 5 to 10 nm can be seen. These pores indicated in arrows in FIG. 7D result from curvature of the graphene layers induced by abundant pentagon-heptagon pairs.
- FIGURE 8 provides TEM images of LIG obtained with a laser power of 3.6 W.
- FIG. 8A provides an HRTEM image taken at the edge of a LIG flake showing few-layer features and highly wrinkled structures. The scale bar is 10 nm.
- FIG. 8B provides an HRTEM image of
- FIG. 8C provides a Cs-correction scanning TEM (STEM) image taken at the edge of a LIG flake.
- the scale bar is 2 nm.
- the image shows an ultra-polycrystalline nature with grain boundaries.
- FIG. 8D provides a TEM image of selected area indicated as a rectangle in FIG. 8C. It shows a heptagon with two pentagons as well as a hexagon.
- the scale bar is 5 A.
- FIGURE 9 provides a TEM characterization of LIG-3.6 W flakes using filtering techniques.
- FIG. 9A provides a bright-field TEM image of the studied area. The scale bar is 5 nm.
- the outer circle spots are reflections of the type (10,0) or (1.-1,0), corresponding to the basal plane of graphite 00,1.
- the layers are, however, very disordered and produce a rotational pattern with d-spacing of 2.10
- FIG. 9C shows chat the FFT filter uses the inner circle of type (00.2) spots and neglects the outer circle of type (10.0) spots.
- FIG. 9D provides corresponding filtered images from FIG. 9C.
- the scale bar is 5 nm.
- the folded graphene structure was enhanced.
- FIG. 9E shows that the FFT filter uses the outer circle of type (10.0) spots and neglects the inner circle of type (00.2) spots
- FIG. 9F shows a corresponding filtered image from FIG. 9E.
- the scale bar is 5 nm.
- the disordered graphene structure was enhanced.
- FIGURE 10 provides a BET specific surface area of LIG-3.6 W.
- the surface area of this sample was -342 m -g " . Pore sizes are distributed at 2.36 nm, 3.68 nm, 5.37 nm and 8.94 nm.
- FIGURE 11 provides thermogravimetric analysis (TGA) characterizations of LIG-3.6 W, PI and graphene oxide (GO) in argon. Compared to GO, which significantly decomposes at ⁇ 190 °C, LIG is stable at > 900 °C. PI starts to decompose at 550 °C.
- TGA thermogravimetric analysis
- FIGURE 12 provides characterizations of LIG prepared with different laser powers.
- FIG. 12A provides atomic percentages of carbon, oxygen and nitrogen as a function of laser power. These values are obtained from high-resolution XPS. The threshold power is 2.4 W, at which conversion from PI to LIG occurs.
- FIG. 12B provides correlations of the sheet resistance and LIG film thicknesses with laser powers.
- FIG. 12C provides Raman spectra of LIG films obtained with different laser powers.
- FIG. 12D provides statistical analysis of ratios of G and D peak intensities (upper panel), and average domain size along a- axis (L a ) as a function of laser power (x axis) calculated using eq 4.
- FIGURE 13 provides a correlation of threshold laser power to scan rate.
- the threshold power shows a linear dependence on the scan rate. Conditions indicated by the shaded area lead to laser-based graphene-induction.
- FIGURE 14 provides characterizations of backsides of LIG films.
- FIG. 14A provides a scheme of the backsides of LIG films peeled from PI substrates.
- FIGS. 14B-D provide SEM images of backsides of LIG films obtained at laser powers of 2.4 W (FIG. 14B); 3.6 W (FIG. 14C); and 4.8 W (FIG. 14D). All of the scale bars are 10 ⁇ . The images show increased pore size as the laser power was increased.
- FIGURE 15 provides characterization of LIG from different polymers.
- FIG. 15 A provides a photograph of patterns induced by lasers on different polymers (PI, PEI and PET) at a laser power of 3.0 W. The two polymers that blackened were PI and PEI.
- FIG. 15B provides a Raman spectrum of PEI-derived LIG obtained with a laser power of 3.0 W.
- FIGURE 16 provides electrochemical performances of LIG-microsupercapacitor (LIG- MSC) devices from LIG-4.8 W in 1 M H 2 S0 4 with their GB-induced properties.
- FIG. 16A is a digital photograph of LIG-MSCs with 12 interdigital electrodes. The scale bar is 1 mm.
- FIG. 16B provides an SEM image of LIG electrodes. The scale bar is 200 ⁇ .
- FIG. 16C is a schematic diagram of LIG-MSCs device architecture.
- FIGS. 16D-E provide CV curves of LIG- MSCs at scan rates from 20 to 10,000 mV- s "1 .
- FIG. 16F provides specific areal capacitance (CA) calculated from CV curves as a function of scan rates.
- FIG. 16G-H provide CC curves of LIG- MSCs at discharge current densities (ID) varied from 0.2 to 25 mA-cm "2 .
- FIG. 161 provides CA calculated from CC curves vs.
- L FIGS. 16J-K provide charge density distribution of the states within a voltage window (-0.1, 0.1) V for type I and II polycrystalline sheets. The defects at the grain boundaries are shadowed, and numbers show the misorientation angle between the grains.
- FIG. 16L provides a carbon layer fully composed of pentagons and heptagons (pentaheptite).
- FIG. 16N provides calculated quantum capacitance (defined in Example 1) of perfect and polycrystalline/disordered graphene layers.
- FIGURE 17 provides electrochemical characterizations of LIG-MSCs obtained from PI and PEI using different laser powers in 1 M H 2 SO 4 .
- FIG. 17A is a comparison of CV curves of LIG-MSCs obtained from PI at scan rates of 100 mV- s "1 .
- FIG. 17B provides a specific areal capacitances of LIG-MSCs obtained from PI, calculated from CC curves at current densities of 0.2 mA- cm "2 , as a function of the laser power.
- FIG. 17C provides a comparison of CV curves of LIG-MSCs obtained from PEI at scan rates of 1 V- s "1 .
- FIG. 17A is a comparison of CV curves of LIG-MSCs obtained from PI at scan rates of 100 mV- s "1 .
- FIG. 17B provides a specific areal capacitances of LIG-MSCs obtained from PI, calculated from CC curves at current densities of
- 17D provides specific areal capacitances of LIG-MSCs obtained from PEI, calculated from CC curves at a current density of 0.2 mA- cm " , as a function of the laser power. Compared to PEI derived LIG-MSCs, LIG-MSCs obtained from PI have -10 x higher capacitances prepared at the same laser powers.
- FIGURE 18 provides impedance spectroscopy of LIG-MSCs obtained from PI using a laser power of 4.8 W in 1 M H 2 SO 4 .
- Equivalent series resistance is as low as 7 ⁇ obtained at a high frequency range.
- FIGURE 19 provides electrochemical characterizations of LIG-MSCs obtained with a laser power of 4.8 W in BMIM-BF 4 .
- FIGS. 19A-B provide CV curves of LIG-MSCs at scan rates from 20 mV- s " to 5 V- s " .
- FIG. 19C provides specific areal capacitances vs. scan rates.
- FIGS. 19D-E provide CC curves of LIG-MSCs at discharge current densities from 0.1 mA/cm 2 to 7 mA/cm 2 . The voltage drop is shown graphically in FIG. 19E.
- FIG. 19F shows a specific areal capacitances vs. discharge current densities.
- FIGURE 20 provides a comparison of volumetric capacitances that are calculated from CC curves of LIG-MSCs in aqueous electrolyte and ionic liquid (IL).
- FIG. 20A provides specific volumetric capacitances as a function of discharge current densities in 1 M H 2 SO 4 .
- FIG. 20B provides specific volumetric capacitances as a function of discharge current densities in BMIM-BF4.
- FIGURE 21 provides electrochemical performance of LIG-MSCs in series/parallel combinations. Electrolyte for devices in FIGS. 21A-B is 1 M H 2 SO 4 , and for devices in FIG. 21C is BMIM-BF 4 .
- FIG. 21A provides CC curves of two tandem LIG-MSCs connected in series with the same discharge current density of 1 mA/cm . The operation potential window is doubled in serial configuration.
- FIG. 21B provides CC curves of two tandem LIG-MSCs in parallel assembly with the same discharge current density of 1 mA/cm . In this configuration, capacitance is almost doubled.
- FIG. 21A provides CC curves of two tandem LIG-MSCs connected in series with the same discharge current density of 1 mA/cm . In this configuration, capacitance is almost doubled.
- 21C provides CC curves of single LIG-MSCs and 10 parallel LIG-MSCs at discharge current densities of 1 mA/cm 2 and 10 mA/cm 2 , respectively. Current density increases by a factor of 10 with 10 parallel single devices. Inset is a lighted LED powered by 10 parallel LIG-MSCs.
- FIGURE 22 provides a comparison Ragone plots of different energy storage devices.
- FIG. 22A provides a specific volumetric energy and power densities of energy storage devices.
- FIG. 22B provides a specific areal energy and power densities of LIG-MSCs and LSG-MSCs. LSG, battery and Al electrolytic capacitor data were reproduced from the literature for comparison.
- FIGURE 23 provides capacity retention of LIG-MSCs constructed with LIG-4.8 W in 1 M H 2 SO 4 and ionic liquid (BMIM-BF 4 ).
- FIG. 23A shows that capacitance, calculated from CV curves at a scan rate of 100 mV- s " , increases to 114% of the original value after 2750 cycles, and then retains almost the same value after 9000 cycles.
- FIG. 23B shows that capacitance, calculated from CV curves at a scan rate of 100 mV- s "1 , degrades to 95.5% of original value after 1000 cycles, and then stabilizes at 93.5% after 7000 cycles.
- FIGURE 24 provides CV curves of LIG-MSCs obtained with laser power of 4.8 W in 1M H 2 S0 4 (FIG. 24A) and BMIM-BF 4 (FIG. 24B). The curves were obtained at a sweep rate of 100 mV- s "1 after every 1000 cycles.
- FIGURE 25 provides atomic structures of the calculated polycrystalline graphene sheets.
- the arrows indicate the unit cell, and the grain boundary regions are shaded. Numbers show two types of misorientation angles (21.8° and 32.2°) between grains.
- FIGURE 26 provides data and images relating to the formation of boron-doped LIG (B- LIG) and fabrication of MSCs containing the B-LIGs (B-LIG-MSC).
- FIG. 26A provides a synthetic scheme for the preparation of B-LIG and fabrication of the B-LIG-MSC.
- FIG. 26B provides a scheme of the dehydration reaction from PAA to a PI film during a curing process.
- FIG. 26C provides SEM images of 5B-LIG.
- the inset in (FIG. 26C) is the cross sectional SEM image of 5B-LIG on a PI sheet.
- FIG. 26D shows a TEM image of 5B-LIG.
- FIG. 26E shows an HRTEM image of 5B-LIG.
- FIGURE 27 is shows photographs of a PAA solution with 5 wt% of H 3 BO 3 (FIG. 27A) and patterned B-LIG on the PI/H 3 BO 3 sheet after laser induction (FIG. 27B).
- FIGURE 28 shows SEM images of LIG materials with different boron loadings, including OB-LIG (FIG. 28A), IB-LIG (FIG. 28B), 2B-LIG (FIG. 28C), and 8B-LIG (FIG. 28D).
- FIGURE 29 provides TEM and HRTEM images of LIG materials with different boron loadings, including OB-LIG (FIGS. 29A and 29E), IB-LIG (FIGS. 29B and 29F), 2B-LIG
- FIGURE 30 provides data relating to the characterization of 5B-LIG materials.
- FIG. 30A shows the Raman spectrum of 5B-LIG.
- FIG. 30B shows the XRD pattern of 5B-LIG.
- FIG. 30C shows the TGA curve of 5B-LIG and 5B-PI at 5 °C/min under argon.
- FIG. 30D shows the pore size distribution of 5B-LIG.
- FIGURE 31 shows the BET measurement of B-LIG materials.
- the calculated surface area is 191 m /g.
- FIGURE 32 shows XPS survey spectra for 5B-PI (FIG. 32A) and 5B-LIG (FIG. 32B).
- FIGURE 33 shows XPS spectra of 5B-LIG and PI/H 3 BO 3 sheets.
- FIG. 33A shows the Cls spectrum.
- FIG. 33B shows the Ols spectrum.
- FIG. 33C shows the Bis spectrum.
- FIG. 33D shows the Nls spectrum.
- FIGURE 34 provides an electrochemical performance comparison of LIG-MSCs with different H 3 BO 3 loadings.
- FIG. 34A provides a schematic of a B-LIG-MSC device and the digital photograph of a fully-fabricated device under bending.
- FIG. 34B provides CV curves of MSCs from PI derived LIG, PAA derived LIG and PAA/H 3 BO 3 derived LIG at a scan rate of 0.1 V/s.
- FIG. 34C provides CC curves of MSCs from PI derived LIG and PAA/H 3 BO 3 derived LIG at a current density of 1.0 mA/cm 2 .
- FIG. 34A provides a schematic of a B-LIG-MSC device and the digital photograph of a fully-fabricated device under bending.
- FIG. 34B provides CV curves of MSCs from PI derived LIG, PAA derived LIG and PAA/H 3 BO 3 derived LIG at a scan rate of 0.1 V/s.
- FIG. 34D provides CV curves of LIG-MSC and B-LIG-MSC with different H 3 BO 3 loadings. The scan rate is set at 0.1 V/s.
- FIG. 34E provides Galvanostatic CC curves of LIG-MSC and B-LIG-MSC with different H 3 BO 3 loadings. The current density is set at 1 mA/cm 2 .
- FIG. 34F provides a comparison of calculated C A from LIG-MSC and B-LIG- MSC with different H 3 BO 3 loadings. The current density is at 1 mA/cm 2 .
- FIG. 34G provides a chart of LIG-MSC capacitance as a function of current. An expanded schematic of FIG. 34A is also provided.
- FIGURE 35 provides data relating to the electrochemical performance of 5B-LIG-MSC.
- FIG. 35A shows CV curves of 5B-LIG-MSC at scan rates of 10, 20, 50 and 100 mV/s.
- FIG. 35B shows galvanostatic CC curves of 5B-LIG-MSC at current densities of 0.1, 0.2 and 0.5 niA/cm 2 .
- FIG. 35C shows specific C A of 5B-LIG-MSC calculated from CC curves as a function of current density.
- FIG. 35D shows cyclability testing of 5B-LIG-MSC. The charge-discharge cycles are performed at a current density of 1.0 mA/cm 2 .
- FIG. 35A shows CV curves of 5B-LIG-MSC at scan rates of 10, 20, 50 and 100 mV/s.
- FIG. 35B shows galvanostatic CC curves of 5B-LIG-MSC at current densities of 0.1, 0.2 and
- 35E shows a digital photograph of a bent 5B-LIG-MSC at a bending radius of 10 mm.
- FIG. 35F shows capacitance retention of 5B-LIG-MSC at different bending radii.
- FIG. 35G shows bent cyclability testing of flexible 5B- LIG-MSC at a fixed bending radius of -10 mm. The C p is calculated from discharge runtime at a current density of 1.0 mA/cm 2 .
- FIG. 35H shows CV curves of the 5B-LIG-MSC at different bending cycles in (FIG. 35G) at a scan rate of 50 mV/s.
- FIG. 351 shows volumetric Ragone plot of 5B-LIG-MSC and LIG-MSC.
- FIGURE 36 provides additional electrochemical performance of 5B-LIG-MSC.
- FIG. 36A provides CV curves of 5B-LIG-MSC at scan rates of 0.2, 0.5, 1.0 and 2.0 V/s.
- FIG. 36B provides CV curves of 5B-LIG-MSC at scan rates of 5, 10, 15 and 20 V/s.
- FIG. 36C provides galvanostatic CC curves of 5B-LIG-MSC at current densities of 1.0, 2.0 and 5.0 mA/cm 2 .
- FIG. 36D provides galvanostatic CC curves of 5B-LIG-MSC at current densities of 10, 20 and 30 mA/cm .
- FIGURE 37 provides impedance performances of LIG-MSC and 5B-LIG-MSC.
- the testing frequency is ranging from 10 6 Hz to 0.01 Hz.
- This typical Nyquist plot shows a small semicircle for both devices at a high frequency region, corresponding to a fast ionic transport and low external resistance of devices. At the lower frequency region, the Nyquist plot exhibits a linear part resulting from the interface between the electrolyte and the electrode. This interface results in internal resistance of devices. From this Nyquist plot, Applicants can see that 5B-LIG- MSC has both smaller external and internal resistances than LIG-MSC. These results indicate faster ionic transport and better electrode-electrolyte interface in 5B-LIG-MSC.
- FIGURE 38 provides an areal Ragone plot of 5B-LIG-MSC and LIG-MSC.
- FIGURE 39 provides data and illustrations relating to the fabrication and characterization of LIG super capacitors (LIG-SCs).
- FIG. 39A is a schematic illustration showing the fabrication process for assembling a single LIG-SC and stacked LIG-SC.
- FIG. 39B is an optical image of a fully assembled single LIG-SC manually bent.
- FIG. 39C is a cross- sectional SEM image of a PI substrate with both sides laser induced to form graphene.
- FIG. 39D is an SEM image of the LIG films showing a porous 3D network.
- FIG. 39E is a TEM image of a LIG thin film showing nano-sized wrinkles and ripples.
- the inset is a HRTEM image of a LIG nanosheet showing numerous graphene edges
- FIGURE 40 is a photograph of a half-side LIG electrode for LIG-SCs.
- FIGURE 41 is an illustration of the fabrication process of a solid-state LIG-MSC.
- FIGURE 42 provides data relating to an electrochemical performance of a single LIG- SC.
- FIG. 42A provides CV curves of LIG-SCs at scan rates of 5, 10, 20 and 50 mV/s.
- FIG. 42B provides Galvanostatic CC curves of LIG-SCs at current densities of 0.02, 0.05, 0.10 and 0.20 mA/cm 2 .
- FIG. 42C provides specific areal capacitances calculated from CC curves as a function of current density.
- FIG. 42D provides cyclability testing of LIG-SCs with a CC current density of 0.8 mA/cm .
- FIGURE 43 provides data relating to the characterization of LIGs.
- FIG. 43A provides a Raman spectrum of LIGs.
- FIG. 43B provides an XRD spectrum of LIGs.
- FIGURE 44 provides a TGA plot of LIG and PI substrates under argon. PI starts to decompose at -550 °C, while LIG remains stable up to 900 °C. The LIG for this analysis was removed from the underlying PI film as described in the Methods.
- FIGURE 45 provides a BET measurement of LIGs.
- FIG. 45A provides nitrogen adsorption/desorption curves of LIGs. The calculated surface area is 330 m 2 /g.
- FIG. 45B provides pore size distributions of LIGs.
- FIGURE 46 provides additional electrochemical performance of a flat, single LIG-SC.
- FIG. 46A provides CV curves of LIG-SCs at scan rates of 0.1, 0.2, 0.5 and 1.0 V/s.
- FIG. 46B provides Galvanostatic CC curves of LIG-SCs at current densities of 0.5, 1.0 and 2.0 mA/cm .
- FIGURE 47 provides electrochemical performance of LIG-SCs under bending.
- FIG. 47A provides CV curves of LIG-SC at varying bending radii. The scan rate was 0.02 V/s.
- FIG. 47B provides capacity retention at different bending radius. Capacitance retention was calculated from CC curves at a current density of 0.05 mA/cm 2 .
- FIG. 47C provides cyclability testing of flexible LIG-SCs. Capacitance retention was calculated from CC curves at a current density of 0.4 mA/cm .
- FIGURE 48 provides electrochemical performances of stacked LIG-SCs in series and parallel circuits.
- FIG. 48A provides an illustration of a stacked series LIG-SC and its corresponding circuit diagram.
- FIG. 48B provides an illustration of a stacked parallel LIG-SC and its corresponding circuit diagram.
- FIG. 48C provides galvanostatic CC curves comparing a single LIG-SC to a stacked series LIG-SC at a current density of 0.5 mA/cm 2 .
- FIG. 48D provides galvanostatic CC curves comparing a single LIG-SC to a stacked parallel LIG-SC at a current density of 0.5 mA/cm 2 .
- FIG. 48A provides an illustration of a stacked series LIG-SC and its corresponding circuit diagram.
- FIG. 48C provides galvanostatic CC curves comparing a single LIG-SC to a stacked series LIG-SC at a current density of 0.5 mA/cm 2 .
- FIG. 48E provides a cyclability testing of a flexible stacked series LIG-SC at a current density of 0.5 mA/cm .
- Inset shows the initial CV curves (black) and the 4000 th CV curve (red) at a scan rate of 0.1 V/s.
- FIG. 48F shows a cyclability testing of a flexible, stacked parallel LIG-SC at a current density of 1.0 mA/cm .
- Inset shows the initial CV curves (black) and the 6000 th CV curve (red) at a scan rate of 0.1 V/s.
- FIGURE 49 provides electrochemical performances of stacked LIG-SCs in series configurations.
- FIG. 49A provides CV curves of series LIG-SCs at scan rates of 5, 10, 20 and 50 mV/s.
- FIG. 49B provides galvanostatic charge-discharge curves of series LIG-SCs at current densities of 0.1, 0.2 and 0.5 mA/cm .
- FIGURE 50 provides electrochemical performance of stacked LIG-SCs in parallel.
- FIG. 50A provides CV curves of parallel LIG-SCs at scan rate of 10, 20, 50 and 100 mV/s.
- FIG. 50B provides galvanostatic charge-discharge curves of parallel LIG-SCs at current densities of 0.1, 0.2, 0.5 and 1.0 mA/cm 2 .
- FIG. 50C provides specific areal capacitance calculated from discharge runtime as a function of current density.
- FIGURE 51 provides electrochemical performances of LIG-MSC devices.
- FIG. 51A provides an illustration of a flexible LIG-MSC. The inset is a photograph of a LIG-MSC fixed at a bending radius of 12 mm.
- FIG. 51B provides CV curves of LIG-MSCs at scan rates of 10, 20, 50 and 100 mV/s.
- FIG. 51C provides Galvanostatic CC curves of LIG-MSCs at current densities of 0.1, 0.2, 0.5 and 1.0 mA/cm 2 .
- FIG. 51D provides specific C A of LIG-MSCs from aqueous 1 M H 2 SO 4 and PVA/H 2 SO 4 calculated from CC curves as a function of the current density.
- FIG. 51A provides an illustration of a flexible LIG-MSC. The inset is a photograph of a LIG-MSC fixed at a bending radius of 12 mm.
- FIG. 51B provides CV curves of LIG-MSC
- FIG. 51E provides capacity retention of LIG-MSC at different bending radii. Capacitance retention was calculated from CC curves at a current density of 0.5 mA/cm 2 .
- FIG. 51F provides cyclability testing of flexible LIG-MSCs. Capacitance retention was calculated from CC curves at a current density of 0.5 mA/cm .
- FIGURE 52 provides additional data relating to the electrochemical performance of flat LIG-MSC devices.
- FIG. 52A provides CV curves of LIG-MSCs at scan rates of 0.2, 0.5, 1.0 and 2.0 V/s.
- FIG. 52B provides CV curves of LIG-MSCs at scan rates of 5.0, 10 and 20 V/s.
- FIG. 52C provides CC curves of LIG-MSCs at current densities of 2, 5, 10 and 20 mA/cm 2 .
- FIGURE 53 provides impedance performances of LIG-MSCs with aqueous 1 M H 2 S0 4 and PVA/H 2 S0 4 electrolyte.
- This typical Nyquist plot shows a small semicircle at a high frequency region that corresponds to the ionic transport which contributes to the external resistance of the device.
- the lower frequency region of the Nyquist plot exhibits linearity due to the interaction between the electrolyte and electrode. This interface results in internal resistance of the device. From this Nyquist plot, Applicants can see that LIG-MSC in PVA/H 2 S0 4 has both a smaller external and internal resistance than those in aqueous H 2 S0 4 .
- FIGURE 54 provides data relating to the cyclability test of LIG-MSCs.
- the CC current density was set at 1.0 mA/cm .
- the capacitance remained >90 after 8000 cycles.
- FIGURE 55 provides electrochemical performance of LIG-MSCs in series or parallel combinations.
- FIG. 55A provides CC curves of two tandem LIG-MSCs connected in series with the same discharge current density. The operation potential window is doubled in series configuration.
- FIG. 55B provides CC curves of two tandem LIG-MSCs in parallel assembly with the same discharge current density. In this configuration capacitance is almost doubled. Both tandem devices and the single device were applied with the same discharge/charge current density.
- FIGURE 56 provides CV curves of the flexible LIG-MSC at different bending radius.
- the scan rate is set at 0.1 V/s.
- FIGURE 57 provides Ragone plots of single LIG-SC, LIG-MSC and commercial energy storage devices.
- FIGURE 58 provides Ragone plots of single LIG-SC and LIG-MSC in specific areal energy and power densities.
- FIGURE 59 provides an absorption spectrum of a polyimide film.
- the four vertical lines represent where a tunable C0 2 laser could specifically address key lines of polymer absorbance to induce graphene formation.
- FIGURE 60 is a drawing showing the use of visible lasers and an option of coupling into a controlled atmosphere chamber with an optical fiber.
- Graphene-based materials have been extensively studied as active electrodes in MSCs due to their unique structure and their extraordinary mechanical and electrical properties. To further improve their performance, many methods have been employed to modulate the electronic band structure of the graphene-derived materials. Among them, doping with heteroatoms (such as boron, nitrogen, phosphorus, and sulfur) has been shown to be an effective way to tailor the electrochemical properties of graphene-derived conductive materials and to enhance their capacitive performances. Particularly, substitutions of carbon with boron in the graphene lattice shifts the Fermi level toward the valance band, thereby enhancing charge storage and transfer within the doped graphene structure.
- heteroatoms such as boron, nitrogen, phosphorus, and sulfur
- the present disclosure pertains to methods of producing a graphene material.
- the methods of the present disclosure include exposing a polymer to a laser source (step 10) to result in the formation of a graphene that is derived from the polymer (step 12).
- the methods of the present disclosure also include a step of incorporating the formed graphene material into an electronic device (step 14).
- the methods of the present dislcosure also include a step of separating the formed graphene from the polymer to form an isolated graphene (step 13), and incorporating the isolated graphene into an electronic device (step 14).
- FIG. IB An example of a graphene material of the present disclosure is shown in FIG. IB.
- graphene material 20 includes polymer 22 with first surface 24.
- Graphene material 20 also includes graphene 26 derived from polymer 22.
- Graphene 26 in this example has an interdigitated pattern on surface 24 of polymer 22.
- the graphene materials and the isolated graphenes of the present disclosure serve as a component of an electronic device.
- the present disclosure pertains to electronic devices that contain the graphene materials and isolated graphenes of the present disclosure.
- FIG. 1C An example of an electronic device of the present dislcosure is shown in FIG. 1C.
- electronic device 30 includes polymer 32 and graphene 36 derived from polymer 32.
- Graphene 36 in this example has an interdigitated pattern and serves as an electrode in electronic device 30.
- electronic device 30 also includes tape 34, paint 37, and electrolyte 38.
- electronic device 30 can serve as an in-plane micro supercapacitor.
- FIG. ID Another example of an electronic device of the present dislcosure is shown in FIG. ID.
- electronic device 40 includes a stack of graphene materials 42, 44 and 46.
- Graphene material 42 includes polymer 50.
- Graphene material 42 also includes graphenes 48 and 52 derived from polymer 50.
- graphenes 48 and 52 are on opposite sides of polymer 50.
- graphene material 44 includes polymer 58 and graphenes 56 and 60 derived from polymer 58.
- Graphenes 56 and 60 are on opposite sides of polymer 58.
- graphene material 46 includes polymer 66 and graphene 64 derived from polymer 66.
- Graphene materials 42 and 44 are separated from one another by solid electrolyte 54.
- graphene materials 44 and 46 are separated from one another by solid electrolyte 62.
- electronic device 40 can serve as a stacked supercapacitor.
- various methods may be utilized to expose various polymers to various laser sources to result in the formation of various types of graphenes.
- Various methods may also be utilized to separate the formed graphenes from the polymers.
- Various methods may also be utilized to incorporate the formed graphene materials and isolated graphenes of the present disclosure into various electronic devices.
- the laser source includes, without limitation, a solid state laser source, a gas phase laser source, an infrared laser source, a C0 2 laser source, a UV laser source, a visible laser source, a fiber laser source, near-field scanning optical microscopy laser source, and combinations thereof.
- the laser source is a UV laser source.
- the laser source is a C0 2 laser source. Additional laser sources can also be envisioned.
- the laser sources of the present disclosure can have various wavelengths.
- the laser source has a wavelength ranging from about 1 nm to about 100 ⁇ .
- the laser source has a wavelength ranging from about 20 nm to about 100 ⁇ .
- the laser source has a wavelength ranging from about 10 nm to about 400 nm.
- the laser source has a wavelength ranging from about 400 nm to about 800 nm.
- the laser source has a wavelength ranging from about 1 ⁇ to about 100 ⁇ .
- the laser source has a wavelength ranging from about 1 ⁇ to about 50 ⁇ .
- the laser source has a wavelength ranging from about 1 ⁇ to about 20 ⁇ . In some embodiments, the laser source has a wavelength ranging from about 5 ⁇ to about 15 ⁇ . In some embodiments, the laser source has a wavelength of about 10 ⁇ . Additional wavelengths can also be envisioned.
- the laser sources of the present disclosure have a wavelength that matches an absorbance band in the absorbance spectrum of a polymer that is being exposed to the laser source. In such embodiments, a more efficient energy transfer from the laser source to the polymer can occur, thereby resulting in conversion of the polymer to graphene in the laser- exposed regions.
- a polymer is chosen such that an absorbance band in the polymer matches the excitation wavelength of the laser source.
- the laser sources of the present disclosure can also have various power ranges.
- the laser source has a power ranging from about 1 W to about 10 W.
- the laser source has a power ranging from about 1 W to about 6 W.
- the laser source has a power ranging from about 2 W to about 5 W.
- the laser source has a power ranging from about 2 W to about 4 W.
- the laser source has a power ranging from about 2 W to about 3 W.
- the laser source has powers ranging from about 2.4 W to about 5.4 W. Additional power ranges can also be envisioned.
- the laser sources of the present disclosure have power ranges that can vary based upon the absorbance of the polymer at a chosen laser wavelength.
- the laser sources of the present disclosure can also have various pulse widths.
- the laser sources of the present disclosure have pulse widths that are in the range of femtoseconds, nanoseconds, or milliseconds.
- the laser sources of the present disclosure have pulse widths that range from about 1 femtosecond to about 1 ms.
- the laser sources of the present disclosure have pulse widths that range from about 1 femtosecond to about 1 ns.
- the laser sources of the present disclosure have pulse widths that range from about 1 ⁇ 8 to about 1 ms.
- the laser sources of the present disclosure have pulse widths that range from about 1 ⁇ 8 to about 100 ⁇ 8.
- the laser sources of the present disclosure have pulse widths that range from about 10 ⁇ 8 to about 50 ⁇ 8. In some embodiments, the laser sources of the present disclosure have pulse widths of about 15 ⁇ 8. Additional pulse widths can also be envisioned.
- the laser source is a C0 2 laser source with a wavelength of about 10.6 ⁇ .
- C0 2 laser sources to polymer surfaces (e.g., polyimides) at wavelengths of about 10.6 ⁇ provides porous graphenes with optimal electrical properties.
- the polymers of the present disclosure may be exposed to a single laser source.
- the polymers of the present disclosure may be exposed to two or more laser sources.
- the polymers of the present disclosure may be simultaneously exposed to two or more laser sources.
- the two or more laser sources may have the same or different wavelengths, power ranges, and pulse widths.
- Various methods may be utilized to expose polymers to a laser source.
- the exposure occurs manually.
- the exposure occurs automatically.
- the exposure occurs automatically through computer-controlled mechanisms.
- the exposure occurs automatically through a computer patterning system.
- the exposure occurs automatically through automated processing lines.
- the exposure occurs automatically through automated processing lines with multiple laser sources.
- the multiple laser sources could vary in wavelength or power to cause different degrees of graphene formation over different regions of the polymer.
- the exposure of polymers to a laser source includes pulsed laser irradiation. In some embodiments, the exposure of polymers to a laser source includes continuous laser irradiation. In some embodiments, the exposure of polymers to a laser source includes patterning a surface of the polymer with the formed graphene. For instance, in some embodiments, the surface of the polymer is patterned into interdigitated shapes.
- the exposure of a polymer to a laser source includes a step of tuning one or more parameters of the laser source.
- the one or more tunable parameters of the laser source include, without limitation, laser wavelength, laser power, laser energy density, laser pulse widths, gas environment, gas pressure, gas flow rate, and combinations thereof.
- the one or more parameters of a laser source are tuned according to one or more attributes of the exposed polymer.
- the one or more attributes of the exposed polymer include, without limitation, polymer type, polymer thickness, polymer morphology, polymer structure, polymer absorbance spectrum, a substrate upon which a polymer may be affixed, and combinations thereof.
- the one or more parameters of a laser source are tuned in order to maximize the absorption of the laser wavelength by the polymer.
- the laser wavelength of the laser source is tuned to match an absorbance band of a polymer.
- such tuning optimizes laser light absorbance by the polymer and results in optimal graphene formation upon laser-polymer interaction.
- the absorbance band of the polymer corresponds to the wavelength of the laser source.
- the one or more parameters of a laser source are tuned in order to control the penetration depth of the laser wavelength by the polymer.
- the penetration depth (or absorption depth) of a laser source is maximized by tuning the wavelength of the laser source.
- a strongly absorbed wavelength can be focused on a polymer surface to create a desired form of graphene.
- the availability to choose from many wavelengths can allow for selection of a wide range of penetration depths into a polymer or type of polymer by changing the wavelength of the laser source. This in turn allows for controlling the depth of the formed graphene and the type of polymer from which graphene can be formed.
- the laser source can be tuned to create a narrow and shallow line of graphene on a surface of a polymer by using a well-focused laser at lower power ranges.
- the exposure of a polymer to a laser source includes a step of tuning one or more parameters of the polymer.
- a polymer's absorbance band can be tuned to match the excitation wavelength of a laser source.
- the tuning occurs by modifying the structure of the polymer.
- the modification can ensure optimal graphene formation upon laser-polymer interaction.
- the absorbance band of a polymer can be modified to match the excitation wavelength of the laser source by adding a compound to the polymer that absorbs well at the excitation wavelength of the laser source.
- the exposure of a polymer to a laser source can include the utilization of optical microscopic techniques.
- the microscopic techniques can be used to provide nanometer- scaled patterns of graphene on the polymer surface.
- NOM near-field scanning optical microscopy
- the nanometer- scaled patterns of graphene on the polymer surface can have resolutions of about 20 nm.
- the laser sources of the present disclosure may be applied to various types of polymers.
- the polymers of the present disclosure include, without limitation, vinyl polymers, homopolymers, block co-polymers, carbonized polymers, aromatic polymers, cyclic polymers, polyimide (PI), polyetherimide (PEI), polyether ether ketone (PEEK), and combinations thereof.
- the polymers of the present disclosure include polyimides.
- the polymers of the present disclosure may be chosen based on the chosen laser source. For instance, in some embodiments, a polymer with an absorbance wavelength may be exposed to a laser source with a matching laser excitation wavelength.
- the polymers of the present disclosure lack graphite oxides. In some embodiments, the polymers of the present disclosure lack graphene oxides. In some embodiments, the polymers of the present disclosure include aromatic monomers. The use of additional polymers can also be envisioned.
- the polymers of the present disclosure may also be modified in various manners.
- the polymers of the present disclosure may include doped polymers.
- the doped polymers of the present disclosure may be doped with one or more dopants.
- the one or more dopants include, without limitation, heteroatoms, metals, metal oxides, metal chalcogenides, metal nanoparticles, metal salts, organic additives, inorganic additives, metal organic compounds, and combinations thereof.
- the one or more dopants include, without limitation, molybdenum, tungsten, iron, cobalt, manganese, magnesium, copper, gold, palladium, nickel, platinum, ruthenium, metal chalcogenides, metal halides, metal acetates, metal acetoacetonates, related salts thereof, and combinations thereof.
- the polymers of the present disclosure may be doped with one or more metal salts.
- the metal salts include, without limitation, iron acetylacetonate, cobalt acetylacetonate, molyddenyl acetylacetonate, nickel acetylacetonate, iron chloride, cobalt chloride, and combinations thereof.
- the doped polymers of the present disclosure include heteroatom- doped polymers.
- the heteroatom-doped polymers of the present disclosure include, without limitation, boron-doped polymers, nitrogen-doped polymers, phosphorus-doped polymers, sulfur-doped polymers, and combinations thereof.
- the heteroatom-doped polymers of the present disclosure include boron-doped polymers.
- the doped polymers of the present disclosure are in the form of polymer composites.
- the dopants that are associated with the doped polymers of the present disclosure can have various shapes.
- the dopants can be in the form of nanostructures.
- the nanostructures can include, without limitation, nanoparticles, nanowires, nanotubes, and combinations thereof. Additional dopant structures can also be envisioned.
- the polymers of the present disclosure include carbonized polymers.
- the carbonized polymers include glassy or amorphous carbons.
- the polymers of the present disclosure are carbonized by annealing at high temperatures (e.g., temperatures ranging from about 500 °C to about 2,000 °C).
- the polymers of the present disclosure include chemically treated polymers.
- the polymers of the present disclosure are chemically treated in order to enhance their surface areas.
- the polymers of the present disclosure are thermally treated with a base, such as potassium hydroxide.
- the polymers of the present disclosure can have various shapes.
- the polymers of the present disclosure are in the form of a sheet or a film, such as a flat sheet or film.
- the polymers of the present disclosure include commercially available polyimide (PI) films.
- the polymers of the present disclosure are in the form of a powder.
- the polymers of the present disclosure are in the form of pellets.
- the polymers of the present disclosure are in the form of a coupon.
- the polymers of the present disclosure are in the form of a block.
- the polymers of the present disclosure are in the form of a fabricated part, such an an aircraft wing.
- the polymers of the present disclosure are in the form of an electronics circuit substrate. In some embodiments, the polymers of the present disclosure are in the form of a monolithic block. In some embodiments, the polymers of the present disclosure are in the form of a composite.
- the polymers of the present disclosure are in the form of squares, circles, rectangles, triangles, trapezoids, spheres, pellets, and other similar shapes. In some embodiments, the polymers of the present disclosure are in the form of rectangles. In some embodiments, the polymers of the present disclosure are in the form of films. In some embodiments, the polymers of the present disclosure are in the form of rolls of films.
- the polymers of the present disclosure can also have various sizes. For instance, in some embodiments, the polymers of the present disclosure have lengths or widths that range from about 100 m to about 1 mm. In some embodiments, the polymers of the present disclosure have lengths or widths that range from about 100 cm to about 10 mm. In some embodiments, the polymers of the present disclosure have lengths or widths that range from about 10 cm to about 1 cm. In some embodiments, the polymers of the present disclosure are in the form of rolls of films that are 100 m long and 1 m wide.
- the polymers of the present disclosure can also have various thicknesses. For instance, in some embodiments, the polymers of the present disclosure have thicknesses that range from about 10 cm to about 1 ⁇ . In some embodiments, the polymers of the present disclosure have thicknesses that range from about 1 cm to about 1 mm. In some embodiments, the polymers of the present disclosure have thicknesses that range from about 0.3 nm to about 1 cm. In some embodiments, the polymers of the present disclosure have thicknesses that range from about 10 mm to about 1 mm.
- the polymers of the present disclosure can also have various properties. For instance, in some embodiments, the polymers of the present disclosure are optically transparent. In some embodiments, the polymers of the present disclosure are rigid. In some embodiments, the polymers of the present disclosure are flexible. In some embodiments, the polymers of the present disclosure are thermally stable (over 500 °C).
- Graphenes may form from various polymers in various manners.
- the exposing of a polymer to a laser source includes exposing a surface of a polymer to a laser source.
- the exposing results in formation of the graphene on the surface of the polymer.
- Graphene can form on surfaces of polymers in various manners. For instance, in some embodiments, the graphenes form a pattern on a surface of the polymer. In some embodiments, the graphene becomes embedded with the polymer. In some embodiments, the graphene forms on an outside surface of the polymer. [00124] In some embodiments, the polymer includes a first surface and a second surface. In some embodiments, the first surface is exposed to the laser source. As a result, the graphene forms on the first surface of the polymer. In some embodiments, the first surface and the second surface of the polymer are exposed to the laser source. As a result, the graphene forms on the first surface and the second surface of the polymer. In some embodiments, the first surface and the second surface are on opposite sides of the polymer. As a result, the graphene can form on opposite sides of the polymer in some embodiments.
- the exposing of a polymer to a laser source results in conversion of the entire polymer to graphene (e.g., embodiments where the polymer is in powder form).
- the formed graphene material consists essentially of the graphene derived from the polymer.
- the graphene forms in a three-dimensional pattern from a polymer.
- the methods of the present disclosure can be utilized for the three-dimensional printing of graphene.
- graphene can form from polymers by various mechanisms. For instance, in some embodiments, graphene forms by conversion of sp 3 -carbon atoms of polymers to sp 2 -carbon atoms. In some embodiments, graphene forms by photothermal conversion. In some embodiments, graphene is formed by photochemical conversion. In some embodiments, graphene is formed by both photochemical and photothermal conversion.
- graphene forms by extrusion of one or more elements.
- the one or more elements can include, without limitation, hydrogen, oxygen, nitrogen, sulfur, and combinations thereof.
- the methods of the present disclosure also include a step of separating the formed graphenes from the polymer.
- the separated graphenes are referred to herein as isolated graphenes.
- separating occurs chemically, such as by dissolving the polymer. In some embodiments, separating occurs mechanically, such as by mechanically stripping the graphene from the polymer. In some embodiments, separating occurs by scraping the formed graphene from a surface of a polymer. Additional methods by which to separate formed graphenes from polymers can also be envisioned.
- the methods of the present disclosure may be utilized to form various types of graphenes.
- the formed graphenes may be associated with or separated from polymers.
- the graphenes of the present disclosures include, without limitation, single-layered graphene, multi-layered graphene, double-layered graphene, triple- layered graphene, doped graphene, porous graphene, unfunctionalized graphene, pristine graphene, functionalized graphene, turbostratic graphene, oxidized graphene, graphite, graphene coated with metal nanoparticles, metal particles coated with graphene, graphene metal carbides, graphene metal oxides, graphene metal chalcogenides, and combinations thereof.
- the graphenes of the present disclosure lack graphene oxides.
- the graphenes of the present disclosure includes porous graphene.
- the porous graphenes include mesoporous graphenes, microporous graphenes, and combinations thereof.
- the pores in the porous graphenes include diameters between about 1 nanometer to about 5 micrometers.
- the pores include mesopores with diameters of less than about 50 nm.
- the pores include mesopores with diameters of less than about 9 nm.
- the pores include mesopores with diameters between about 1 ⁇ and about 500 ⁇ .
- the pores include mesopores with diameters between about 5 nm and about 10 nm. In some embodiments, the pores include mesopores with diameters between about 1 ⁇ and about 500 ⁇ . In some embodiments, the pores include micropores with diameters of less than about 2 nm. In some embodiments, the pores include micropores with diameters that range from about 1 nm to about 1 ⁇ . Additional pore diameters can also be envisioned.
- the graphenes of the present disclosure include doped graphene.
- the doped graphenes are doped with one or more dopants.
- the dopants include, without limitation, heteroatoms, metals, metal oxides, metal chalcogenides, metal nanoparticles, metal salts, organic additives, inorganic additives, metal organic compounds, and combinations thereof.
- the doped graphenes include, without limitation, heteroatom- doped graphenes.
- the heteroatom-doped graphenes of the present disclosure include, without limitation, boron-doped graphenes, nitrogen-doped graphenes, phosphorus-doped graphenes, sulfur-doped graphenes, silicon-doped graphenes, and combinations thereof.
- the heteroatom-doped graphenes of the present disclosure include boron-doped graphenes.
- the heteroatom-doped graphenes of the present disclosure include boron-doped porous graphenes.
- the dopants that are associated with doped graphenes of the present disclosure are in the form of heteroatom carbides.
- the heteroatom carbides include, without limitation, boron carbides, boron-nitrogen carbides, silicon-carbides, and combinations thereof.
- the dopants of the doped graphenes of the present disclosure are in the form of nanoparticles.
- the nanoparticles are coated on the graphene.
- the nanoparticles include, without limitation, metal oxides, metal carbides, metal chalcogenides, and transition metal dichalcogenides.
- the metal oxides include, without limitation, iron oxides, cobalt oxides, nickel oxides, molybdenum oxides, and copper oxides.
- the metal carbides include, without limitation, iron carbides, tungsten carbides, nickel carbides, manganese carbides, cobalt carbides, and molybdenum carbides.
- the transition metal dichalcogenides include, without limitation, tungsten disulfide, molybdenum disulfide, and molybdenum diselenide.
- the graphenes of the present disclosure can have various surface areas. For instance, in some embodiments, the graphenes of the present disclosure have surface areas ranging from about 100 m 2 /g to about 3,000 m 2 /g. In some embodiments, the graphenes of the present disclosure have surface areas ranging from about 500 m 2 /g to about 2800 m 2 /g. In some embodiments, the graphenes of the present disclosure have surface areas ranging from about 100 m 2 /g to about 400 m 2 /g. In some embodiments, the graphenes of the present disclosure have surface areas ranging from about 150 m 2 /g to about 350 m 2 /g.
- the graphenes (e.g., porous graphene layers) of the present disclosure can have various thicknesses. For instance, in some embodiments, the graphenes of the present disclosure have thicknesses that range from about 0.3 nm to about 1 cm. In some embodiments, the graphenes of the present disclosure have thicknesses that range from about 0.3 nm to about 50 ⁇ . In some embodiments, the graphenes of the present disclosure have a thickness of about 25 ⁇ .
- the graphenes of the present disclosure can also have various shapes. For instance, in some embodiments, the graphenes of the present disclosure are in the form of flakes. In some embodiments, the graphenes of the present disclosure are highly wrinkled. In some embodiments, the graphenes of the present disclosure have ripple-like wrinkled structures. [00143] In some embodiments, the graphenes of the present disclosure have a three-dimensional network. For instance, in some embodiments, the graphenes of the present disclosure are in the shape of a foam with porous structures.
- the graphenes of the present disclosure have an ordered porous morphology. In some embodiments, the graphenes of the present disclosure are in polycrystalline form. In some embodiments, the graphenes of the present disclosure are in ultra- polycrystalline form. In some embodiments, the graphenes of the present disclosure contain grain boundaries. In some embodiments, the graphenes of the present disclosure include a polycrystalline lattice. In some embodiments, the polycrystalline lattice may include ring structures. In some embodiments, the ring structures include, without limitation, hexagons, heptagons, pentagons, and combinations thereof. In some embodiments, the graphenes of the present disclosure have a hexagonal crystal structure. In some embodiments, the graphenes of the present disclosure have heptagon-pentagon pairs that comprise 20% to 80% of the surface structure.
- the graphenes of the present disclosure include pristine graphene. In some embodiments, the graphenes of the present disclosure include unfunctionalized graphene. In some embodiments, the graphenes of the present disclosure include functionalized graphene that has been functionalized with one or more functional groups. In some embodiments, the functional groups include, without limitation, oxygen groups, hydroxyl groups, esters, carboxyl groups, ketones, amine groups, nitrogen groups, and combinations thereof.
- the graphenes of the present disclosure can have various carbon, nitrogen and oxygen contents.
- the graphenes of the present disclosure have a carbon content ranging from about 70 wt% to about 98 wt%.
- the graphenes of the present disclosure have an oxygen content ranging from about 0 wt% to about 25 wt .
- the graphenes of the present disclosure have a nitrogen content ranging from about 0 wt to about 7.5 wt .
- the methods of the present disclosure may occur under various reaction conditions.
- the methods of the present disclosure can occur under ambient conditions.
- the ambient conditions include, without limitation, room temperature, ambient pressure, and presence of air.
- the methods of the present disclosure occur at room temperature in the presence of air.
- the methods of the present disclosure can occur in the presence of one or more gases.
- the one or more gases include, without limitation, hydrogen, ammonia, argon nitrogen, oxygen, carbon dioxide, methane, ethane, ethene, chlorine, fluorine, acetylene, natural gas, and combinations thereof.
- the methods of the present disclosure can occur in an environment that includes ambient air.
- the environment includes, without limitation, hydrogen, argon, methane, and combinations thereof. Additional reaction conditions can also be envisioned.
- the methods of the present disclosure can be utilized to form various types of graphene materials.
- the present disclosure pertains to the graphene materials that are formed by the methods of the present disclosure.
- the graphene materials of the present disclosure include a polymer and a graphene derived from the polymer. In some embodiments, the graphene is on a surface of the polymer. In some embodiments, the graphene materials of the present disclosure consist essentially of graphenes. [00154] Suitable graphenes, polymers and polymer surfaces were described previously. Suitable arrangements of graphenes on polymer surfaces were also described previously (e.g., FIG. IB). For instance, in some embodiments, the graphene includes a pattern on a surface of the polymer. In some embodiments, the graphene is embedded with the polymer. In some embodiments, the graphene is on an outside surface of the polymer.
- the graphene is on a first surface of the polymer. In some embodiments, the graphene is on a first surface and a second surface of the polymer. In some embodiments, the first surface and the second surface are on opposite sides of the polymer.
- the methods of the present disclosure can also be utilized to form various types of isolated graphenes.
- the present disclosure pertains to the isolated graphenes that are formed by the methods of the present disclosure.
- the isolated graphene is derived from a polymer and separated from the polymer. Suitable graphenes, polymers and polymer surfaces were described previously.
- the methods of the present disclosure also include a step of incorporating the graphene materials and isolated graphenes of the present disclosure into an electronic device.
- the graphene materials and isolated graphenes of the present disclosure serve as a component of the electronic device.
- the present disclosure pertains to methods of forming an electronic device by forming a graphene material or an isolated graphene of the present disclosure and incorporating the graphene material or the isolated graphene into the electronic device.
- the present disclosure pertains to electronic devices that contain the graphene materials or isolated graphenes of the present disclosure.
- the graphene materials and isolated graphenes of the present disclosure can be incorporated into various electronic devices in various manners. Furthermore, the graphene materials and isolated graphenes of the present disclosure can serve as various electronic device components.
- the incorporation includes stacking a plurality of graphene materials into the electronic device.
- the graphene materials are stacked in a series configuration.
- the graphene materials are stacked in a parallel configuration.
- the electronic device is an energy storage device or an energy generation device.
- the electronic device includes, without limitation, supercapacitors, micro supercapacitors, pseudo capacitors, batteries, micro batteries, lithium-ion batteries, sodium-ion batteries, magnesium-ion batteries, electrodes (e.g., conductive electrodes), sensors (e.g., gas, humidity and chemical sensors), photovoltaic devices, electronic circuits, fuel cell devices, thermal management devices, biomedical devices, and combinations thereof.
- the graphene materials and isolated graphenes of the present disclosure may be utilized in the electronic devices as components of hydrogen evolution reaction catalysts, oxygen reduction reaction catalysts, oxygen evolution reaction catalysts, hydrogen oxidation reaction catalysts, and combinations thereof.
- the incorporation of graphene materials and isolated graphenes of the present disclosure into electronic devices may result in the formation of various structures.
- the electronic devices of the present disclosure may be in the form of at least one of vertically stacked electronic devices, in-plane electronic devices, symmetric electronic devices, asymmetric electronic devices, and combinations thereof.
- the electronic devices of the present disclosure include an in-plane electronic device.
- the electronic devices of the present disclosure include a flexible electronic device.
- the electronic devices of the present disclosure include a super capacitor (SC), such as a flexible, solid-state supercapacitor.
- SC super capacitor
- the electronic device is a microsupercapacitor (MSC), such as a flexible microsupercapacitor or a flexible in-plane microsupercapacitor (MSC) (e.g., FIG. 1C).
- MSC microsupercapacitor
- the electronic devices of the present disclosure include vertically stacked electronic devices, such as vertically stacked supercapacitors (e.g., FIG. ID).
- the electronic devices of the present disclosure may also be associated with an electrolyte.
- the graphene materials and isolated graphenes of the present disclosure may be associated with an electrolyte.
- the electrolyte may be placed between two graphene materials in an electronic device.
- the electrolyte includes, without limitation, solid state electrolytes, liquid electrolytes, aqueous electrolytes, organic salt electrolytes, ion liquid electrolytes, and combinations thereof.
- the electrolyte is a solid state electrolyte.
- the solid state electrolyte is made from inorganic compounds.
- the solid state electrolyte includes polymeric electrolytes.
- the solid-state electrolyte is made from poly(vinyl alcohol) (PVA) and sulfuric acid (H 2 S0 4 ).
- the graphenes associated with the graphene materials and isolated graphenes of the present disclosure can be utilized as various electronic device components.
- the graphenes of the present disclosure may be utilized as an electrode in an electronic device.
- the graphenes of the present disclosure may be utilized as a positive electrode, a negative electrode, and combinations thereof.
- the graphenes of the present disclosure may be utilized as interdigitated electrodes.
- the graphenes of the present disclosure may be utilized as conductive fillers in an electronic device. In some embodiments, the graphenes of the present disclosure may be utilized as conductive wires in an electronic device. [00169] In some embodiments, the graphenes of the present disclosure may be utilized as a current collector in an electronic device. In some embodiments, the graphenes of the present disclosure may be utilized as a current collector and an electrode in an electronic device.
- the graphenes of the present disclosure may be utilized as additives in an electronic device.
- the isolated graphenes of the present disclosure may be utilized as additives in an electronic device, such as an energy storage device.
- the graphenes of the present disclosure are used in energy storage devices. In some embodiments, the graphenes of the present disclosure are used as part of a battery anode. In some embodiments, the graphenes of the present disclosure are used as part of a battery cathode. In some embodiments the graphenes of the present disclosure may be used in batteries as conductive fillers, such as anodes or as cathodes. In some embodiments, the graphenes of the present disclosure are utilized as additives in the electronic device.
- the methods of the present disclosure provide a one-step and scalable approach for making various types of graphene materials and isolated graphenes.
- the methods of the present disclosure may employ roll-to-roll manufacturing processes for more efficient manufacturing of the graphene materials and isolated graphenes.
- the methods of the present disclosure may be utilized to form graphene materials and isolated graphenes without the utilization of any metals, such as metal surfaces or metal catalysts.
- the graphenes of the graphene materials and isolated graphenes of the present disclosure can have various advantageous properties. For instance, in some embodiments, the electrochemical performance of the graphenes is enhanced with three times larger areal capacitance and 5 to 10 times larger volumetric energy density at various power densities. In some embodiments, the graphenes have decomposition temperatures of more than about 900 °C. In some embodiments, the graphenes are stable at temperatures up to about 2,000 °C. In some embodiments, the graphene has high electrical conductivity.
- the electronic devices of the present disclosure have a capacitance ranging from about 2 mF/cm 2 to about 1000 mF/cm 2. In some embodiments, the electronic devices of the present disclosure have a capacitance ranging from about 10 mF/cm 2 to about 20 mF/cm 2. In some embodiments, the electronic devices of the present disclosure have a capacitance of more than about 4 mF/cm . In some embodiments, the electronic devices of the present disclosure have a capacitance of more than about 9 mF/cm . In some embodiments, the electronic devices of the present disclosure have a capacitance of about 16.5 mF/cm .
- the electronic devices of the present disclosure retain at least 90% of their capacitance value after more than 10,000 cycles. For instance, in some embodiments, the electronic devices of the present disclosure retain at least 95% of their capacitance value after more than 10,000 cycles. In some embodiments, the electronic devices of the present disclosure retain at least 90% of their capacitance value after more than 7,000 cycles. In some embodiments, the electronic devices of the present disclosure retain at least 90% of their capacitance value after more than 9,000 cycles.
- the capacitance of the electronic devices of the present disclosure increase by at least 110% of their original value after more than 10,000 cycles. For instance, in some embodiments, the capacitance of the electronic devices of the present disclosure increase by at least 110% of their original value after more than 2,500 cycles.
- the electronic devices of the present disclosure have power densities that range from about 5 mW/cm 2 to about 200 mW/cm 2. In some embodiments, the electronic devices of the present disclosure have power densities of about 9 mW/cm .
- Example 1 Laser-induced Porous Graphene Films from Commercial Polymers
- Example 1.1 Laser scribing
- FIGS. 2A and 3A irradiation of a commercial polyimide (PI) film by a C0 2 infrared laser under ambient conditions converts the film into porous graphene (also referred to as laser-induced graphene (LIG)).
- LIG laser-induced graphene
- SEM scanning electron microscopy
- Example 1.2 Analytical characterization
- LIG films obtained with a laser power of 3.6 W were further characterized with SEM, Raman spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared (FTIR) spectroscopy.
- FIG. 2C shows that LIG films exhibit the appearance of a foam with porous structures resulting from the rapid liberation of gaseous products.
- Cross-sectional SEM images of LIG reveal ordered porous morphology (FIG. 2D). These porous structures render enhanced accessible surface areas and facilitate electrolyte penetration into the active materials.
- the pattern indicates the high degree of graphene formation.
- the asymmetry of the (002) peak, with tailing at smaller 2 ⁇ angles, also points to an increased I c .
- the expanded I c can be attributed to regions where defects are distributed on hexagonal graphene layers.
- the crystalline size along the c-axis (L c ) and a-axis (L a ) are calculated to be -17 nm and -32 nm, respectively.
- FIG. 7A shows thin LIG flakes with few-layer features as further indicated from the edges of the flake in FIG. 8A. Moreover, ripple-like wrinkled structures can be observed from the surface of the flakes. These structures in graphene have been shown to improve the electrochemical performance of devices. Thicker flakes exhibit mesoporous structures (FIG. 7B). High-resolution TEM (HRTEM) images in FIG. 8B reveals that the nano- shaped ripples are exposed edges of graphene layers. The formation of these ripples could be attributed to thermal expansion caused by laser irradiation. The average lattice space of -3.4 A shown in FIG.
- FIG. 8B corresponds to the distance between two neighboring (002) planes in graphitic materials, and it agrees well with the XRD results.
- the aberration-corrected scanning transmission electron microscopy (Cs-STEM) image (FIG. 8C) shows the unusual ultra- polycrystalline feature of LIG flakes with disordered grain boundaries. This observation is further depicted in FIG. 8D, where a hexagon lattice and a heptagon with two pentagons is shown. These abundant pentagon-heptagon pairs can account for the curvature of the graphene layers leading to the porous structure (FIGS. 7C-D and 9). Theoretical calculations suggest that the aforementioned defects could enhance electrochemical capacity (as discussed in detail herein).
- LIG has a surface area of -340 m 2 -g - " 1 by BET, with pore sizes of less than 9 nm (FIG. 10).
- Thermogravimetric analysis (TGA) measurement under argon (FIG. 11) shows that the decomposition temperature of PI is -550 °C and LIG is > 900 °C, while that of the often used graphene precursor, graphene oxide (GO), is - 190 °C.
- Table 1 provides a summary of atomic percentage of elements in raw material (PI) and LIG derived from different laser powers. All of the data were obtained by high-resolution XPS scans.
- the threshold power shows a linear dependence on the scan rate (FIG. 13). If the scan rate increases, higher threshold power needs to be applied in order to initiate the graphitization. Meanwhile, the sheet resistance (R s ) of LIG-2.4 W is reduced to ⁇ 35 ⁇ a "1 (Fig. 12B). Below the threshold of 2.4 W, PI is an insulator with R s » 90 ⁇ a "1 (instrument limit).
- FIG. 12B shows two distinct slopes of Rs vs. laser power.
- the slope when the laser power was ⁇ 4.2 W is larger than the one when it was > 4.2 W. This suggests that when the laser power is ⁇ 4.2 W, the thermal power dominates the quality of the films. Therefore, increased laser power leads to higher graphene formation. As the thermal power rises above 4.2 W, oxidation starts to play an increasingly deleterious role in the quality of the films. Therefore the slope lessens.
- FIG. 12C shows representative Raman spectra of LIG films attained with laser powers from 2.4 to 5.4 W. The statistical analysis of I G I D VS. laser powers is plotted in the upper panel of FIG. 12D.
- the L a values calculated from the average IQ I D ratio using eq 4 and the methods described in this Example is shown in the lower panel of FIG. 12D, showing increased L a up to -40 nm as the laser power rises to 4.8 W. This increase can be attributed to increased surface temperatures. Further increase in power degrades the quality of the LIG with L a of -17 nm in LIG-5.4 W, which is attributable to the partial oxidation of LIG in air. This can be further verified from profound defect-correlated D' peaks centered at -1620 cm "1 in LIG-5.4 W (FIG. 12C).
- the reason for other step growth polymers being inactive is not conclusively known, but suggested by the fact that at 10.6 ⁇ , the C0 2 laser wavelength has a strong absorbance in the polyimide film (FIG. 59).
- use of lasers that have other wavelengths can be used to target polymers that have absorbances at the laser wavelength line.
- Table 2 provides a summary of polymers, their chemical repeat units and their LIG-forming capability. Out of 15 polymers, only PI and PEI were successfully converted to LIG in this example. Nonaromatic hydrocarbons undergo almost complete degradation without graphene formation. Formation of LIG from poly- or heterocyclic structures such as the imide group in PI and PEI polymers favor LIG formation. PAN films are not commercially available and were thus prepared in-house. Though PAN is a precursor to carbon fiber, it does not form graphene well unless heated slowly to permit cyclization and N-extrusion.
- Example 1.5 Fabrication of LIG-MSCs
- LIG- MSCs in-plane interdigitated LIG microsupercapacitors
- Well- defined LIG-MSC electrodes are directly written on PI sheets with a neighboring distance of -300 ⁇ (FIGS. 16A-B). This distance can be further decreased by using a smaller laser aperture.
- silver paint was applied on common positive and negative electrodes, and then Kapton tape was employed to define the active electrodes.
- FIG. 16C depicts the device architecture of the fabricated LIG-MSCs. Cyclic voltammetry (CV) and galvanostatic charge-discharge (CC) measurements were performed to investigate the electrochemical performance of the fabricated LIG-MSCs. All CV curves of LIG- MSCs made with LIG electrodes at various laser powers are pseudo-rectangular in shape, which indicates good double-layer capacitive behaviors (FIG. 17). LIG-MSCs constructed with LIG- 4.8 W electrodes generally exhibit the highest specific areal capacitance (CA) (FIG. 17B). The C A of LIG-MSCs made from PEI is -10% of those from PI (FIGS. 17C-D), possibly associated with the lower nitrogen content.
- CA areal capacitance
- FIGS. 16D-E are the CV curves at scan rates ranging from 20 to 10,000 mV- s "1 . Although there exist certain levels of oxygen or nitrogen contents in LIG, the devices do not exhibit pseudo-capacitive behavior, as suggested from CV curves at a small rate of 20 mV- s "1 , which shows no anodic and cathodic peaks. Even at a high rate of 10,000 mV- s "1 , the CV curve maintains its pseudo-rectangular shape, and this is suggestive of high power performance.
- the CA as a function of scan rate is shown in FIG. 16F.
- the CA is >4 mF- cm " , which is comparable to or higher than the values obtained in recently reported GO-derived supercapacitors.
- FIG. 19 shows CV and CC curves of LIG-MSCs in l-butyl-3- methylimidazolium tetrafluoroborate (BMIM-BF 4 ), which suggest optimal capacitive behaviors.
- BMIM-BF 4 l-butyl-3- methylimidazolium tetrafluoroborate
- I D discharge volumetric current densities
- LIG-MSCs When compared with recently demonstrated reduced GO-film (called MPG films) MSCs (MPG-MSCs) and laser-scribed graphene MSCs (LSG-MSCs), LIG-MSCs can deliver comparable Ey, although power performance needs to be enhanced. Using specific areal energies (E A ) and power (P A ) densities, one can obtain reasonable values for comparing performance of in-plane MSCs intended for commercial applications.
- FIG. 22B shows that LIG-MSCs exhibit ⁇ 100x higher E A and ⁇ 4x P A than MPG-MSCs. Furthermore, LIG-MSCs offer slightly better E A than LSG-MSCs with comparable power performance.
- cycling performance shows that there is negligible capacitance degrading after 9000 cycles in aqueous electrolytes and 7000 cycles in ionic liquid electrolytes (FIG. 23).
- CV curves at every 1000 cycles show no involved pseudo-capacitive peaks (FIG. 24).
- the high capacitance of the LIG- MSC can be attributed to the 3D network of highly conductive graphene showing high surface area and abundant wrinkles, which provide easy access for the electrolyte to form a Helmholtz layer.
- density function theory (DFT) calculations suggest that the ultra-polycrystalline nature of LIG-MSC can also improve the capacitance.
- the total capacitance (C) is contributed by the quantum capacitance (C q ), and the liquid electrolyte (Ci) consisting of Helmholtz and diffusion regions:
- C 1 C q l + Cf 1 .
- C ⁇ is mostly controlled by surface area.
- C q represents the intrinsic property of the electrode material and can be calculated from its electronic structure in eq 1:
- Equation 1 S is the surface area, V is the applied voltage, D is the density of states, 8F is the Fermi level, and e is the electron charge.
- FIGS. 8C-D as well as FIG. 12D indicate the abundance of grain boundaries (GBs), which are composed of pentagon and heptagon pairs. These defects are more 'metallic' than regular hexagons, and therefore can be expected to enhance the charge storage performance. Calculations are performed by using DFT.
- the GB effect is modeled by a planar polycrystalline graphene sheet (FIG. 25). Two types of GBs are considered as representatives (FIGS. 16J-K).
- FIG. 16L also referred to as a "pentaheptite.”
- the calculated C q is shown in FIG. 16N.
- a polycrystalline sheet has a much higher C q than perfect graphene, as a result of a higher density of states near the Fermi level due to the presence of GBs.
- the type II GB enhances the storage more than in type I, as it has a higher defect density along the GBs.
- the highest q is found in pentaheptite due to its highest disorders and metallicity.
- Kapton polyimide (PI, Cat. No. 2271K3, thickness: 0.005") and other polymers sheets used in this Example were all purchased from McMaster-Carr unless stated otherwise. The polymers were used as received unless noted otherwise.
- Laser scribing on polymer sheets were conducted with a carbon dioxide (C0 2 ) laser cutter system (Universal X-660 laser cutter platform): 10.6 ⁇ wavelength of laser with pulse duration of -14 ⁇ 8. The beam size is ⁇ 120 ⁇ .
- Laser power was varied from 2.4 W to 5.4 W with increments of 0.6 W.
- the laser system offers an option of controlling the scan rates from 0.7 to 23.1 inches per second.
- the laser system also provides an option of setting pulses per inch (ppi) with a range from 10 to 1000 ppi.
- ppi pulses per inch
- Example 1.8 Device Fabrication
- LIG electrodes were directly written using the computer-controlled C0 2 laser.
- the LIG serves as both the active electrodes and current collectors.
- silver paint was applied on the common areas of the positive and negative electrodes.
- the electrodes were extended with conductive copper tapes and then connected to electrochemical workstation.
- Kapton polyimide tape was employed to define the interdigitated area (FIG. 16C).
- SEM images were taken on a FEI Quanta 400 high resolution field emission instrument.
- the TEM and HRTEM were performed using a 21 OOF field emission gun.
- Aberration-corrected scanning transmission electron microscopy (Cs-STEM) images were taken using an 80 KeV JEOL ARM200F equipped with a spherical aberration corrector.
- the LIG films were peeled off and sonicated in chloroform before being transferred onto a C-flat TEM grid.
- X-ray photoelectron spectroscopy (XPS) was performed using a PHI Quantera SXM Scanning X-ray Microprobe with a base pressure of 5 x 10 ⁇ 9 Torr.
- the surface area of LIG was measured with a Quantachrome autosorb-3b BET surface analyzer. TGA (Q50, TA Instruments) thermograms were carried out between 100 °C to 900 °C at 5 °C-min _1 under argon; the water content was calculated from the weight loss between room temperature and 100 °C. The sheet resistances were measured using a Keithley four-point probe meter (model: 195 A, detection limit: 20 ⁇ ). The LIG samples for XRD, BET and TGA experiments were powder scratched from LIG films. Other characterizations were conducted directly on LIG films.
- S is the total surface area of active electrodes (in cm 2 ) with 0.6 cm 2 for the devices configuration used in this work; v is the voltage sweep rate (in V- s "1 ); V/ and Vi are the potential limits of CV curves; and I(V) is the voltammetric current (in amperes).
- I ⁇ V)dV is the integrated area from CV curves.
- the total surface area of the device including the spacing between electrodes was ⁇ 0.86 cm , which is used for calculating the power and energy density in the Ragone plot shown in FIG. 22.
- the specific areal (CA, in mF-cm “2 ) and volumetric capacitance (CV, in F- m "3 ) were calculated from charge-discharge (CC) curves by eq 6 and 7:
- / is the discharge current (in amperes) and dV/dt is the slope of galvanostatic discharge curves.
- S is the total area of the active positive and negative electrodes and d is the thickness of active materials.
- d was ⁇ 25 ⁇ .
- AV -V drop is the discharge potential range ( V max is the maximum voltage, 1 V for H 2 SO 4 , 3.5 V for BMIM-BF 4 ), V drop is voltage drop indicated from the difference of the first two data points in the discharge curves.
- PA specific areal
- At is, discharge time (in s).
- Microsupercapacitors [00231] In this Example, Applicants demonstrate that boron-doped porous graphene can be prepared in ambient air using a facile laser induction process from boric acid containing polyimide sheets. At the same time, active electrodes can be patterned for flexible microsupercapacitors. As a result of boron doping, the highest areal capacitance of as-prepared devices reaches 16.5 mF/cm , three times higher than non-doped devices, with concomitant energy density increases of 5 to 10 times at various power densities. The superb cyclability and mechanical flexibility of the device is also well-maintained.
- B-LIG boron-doped LIG
- the synthesis starts by dissolving H 3 BO 3 into poly(pyromellitic dianhydride-co-4,4'-oxydianiline amic acid) (or poly(amic acid), PAA) solution as a boron precursor, followed by condensation of the PAA to produce boric acid containing PI sheet.
- Subsequent laser induction using a commercial CO 2 laser writes patterns on the as-prepared PI sheet under ambient conditions.
- the surface of the PI sheet, with its H 3 BO 3 transforms into B-LIG.
- the B-LIG on the PI film can be patterned into interdigitated shapes for flexible MSCs.
- the resulting B-LIG has significantly improved electrochemical performance over the non-doped structures, with three times higher capacitance and 5 to 10 times higher energy density than Applicants achieved in pristine boron-free samples (e.g. , Example 1).
- the transformation of PAA to PI is preferred for the successful formation of LIG with high electrochemical properties. Meanwhile, the cyclability and flexibility of as-prepared devices are well-maintained, demonstrating the potential of B-LIG materials for future low-cost energy storage devices.
- FIG. 26A shows a scheme for the synthesis and patterning process of B-LIG materials for MSCs.
- H 3 BO 3 various weight percentages of H 3 BO 3 (0, 1, 2, 5 and 8 wt relative to PAA) were added and mixed under bath-sonication for 30 minutes to form a uniform precursor solution.
- the solution was poured into an aluminum dish and the solvent removed in a vacuum oven at 60 °C for 3 days, resulting in a solid PAA/H 3 BO 3 sheet.
- the PAA/H 3 BO 3 sheet was then placed in a hydraulic press (Carver press) and heated to 200 °C for 30 min under a pressure of -0.3 MPa to dehydrate the PAA/H 3 BO 3 sheet and form the PI/H 3 BO 3 film. During this step, PAA and H 3 BO 3 will dehydrate and transform into PI and BO x as shown in FIG. 26B.
- the dehydration from PAA to PI is preferred for successful formation of LIG and will be discussed in detail herein.
- H 3 BO 3 the incorporation of H 3 BO 3 into the PAA was preferable. Attempts to incorporate boron from sources other than H 3 BO 3 , including ammonia borane and m-carborane, resulted in little or no boron doping of the LIG. Without being bound by theory, Applicants envision that this is because boric acid dehydrates and polymerizes on heating while the other two evaporate or sublime, causing the failure of boron doping.
- the major advantage of this synthetic process is that B-LIG can be fabricated and patterned at the same time during laser induction, making it an ideal material for future roll-to-roll processing.
- FIG. 26C shows an SEM image of the as-prepared 5B-LIG that exhibits a porous structure due to the rapid formation of gaseous products during laser induction.
- the inset in FIG. 26C reveals that the thickness of 5B- LIG on the PI sheet surface is ⁇ 25 ⁇ .
- FIG. 26D shows the TEM image of 5B-LIG at low magnification containing few-layer graphene structures with nanoscale ridges and wrinkles, which would be beneficial for higher accessible surface area and therefore enhanced electrochemical performance.
- HRTEM High-resolution TEM
- 26E further confirms the graphitic nature of the 5B-LIG nanosheet. Numerous graphene edges were found on the surface of the 5B-LIG nanosheet, again indicating a highly accessible surface area.
- LIG materials with different loadings of H 3 BO 3 (0B-LIG, 1B-LIG, 2B-LIG, and 8B-LIG) were also prepared and imaged with SEM and TEM (FIGS. 28-29). No significant difference was found among these samples, indicating that the loading of H B0 3 has little effect on the morphology of the resulting LIG.
- the Raman spectrum of 5B-LIG in FIG. 30A shows three characteristic peaks for graphene derived material: the D peak at -1350 cm "1 induced by defects or disordered bent sites, the G peak at -1590 cm - " 1 showing graphitic sp 2 carbon, and the 2D peak at -2700 cm "1 originating from second order zone boundary phonons.
- the large D peak observed here could arise from numerous graphene edges, consistent with TEM observations (FIG. 26E), boron doping into the LIG sheets, or the bending of the graphene layers in the porous structure.
- the high degree of graphitization of 5B-LIG is also verified by thermogravimetric analysis (TGA) measurement under argon (FIG. 30C).
- TGA thermogravimetric analysis
- FIG. 30C thermogravimetric analysis
- the PI/H 3 B0 3 substrate begins to decompose at 550 °C, whereas 5B-LIG remains stable over 900 °C. From BET analysis (FIG. 31), the surface area of 5B-LIG is 191 m 2 /g.
- FIG. 30D shows the pore size distribution of 5B-LIG, which are all ⁇ 10 nm (26 A, 41 A and 73 A).
- X-ray photoelectron spectroscopy was performed on a H 3 B0 3 -loaded sample before and after laser induction, as shown in FIG. 32 for survey spectra and FIG. 33 for elemental spectra.
- the Bis peak (FIG. 33C) shifted from 192.5 eV in B-PI down to 191.9 eV in 5B-LIG after laser induction, showing that boron in the LIG sheet was in the oxidized form (BC0 2 ).
- the position of Nls changed little after laser treatment (FIG. 33D), but its atomic percentage dropped from 7.6% to 2.0%, again indicating that the imide group is the main reacting site during laser induction process.
- PAA sheets with or without H 3 BO 3 were directly laser induced and fabricated into MSC to first compare their electrochemical performance. Cyclic voltammetry (CV) and charge-discharge (CC) measurements of corresponding MSC devices are exhibited and compared in FIGS. 34B-C. Both PAA-derived LIG-MSC and boron-doped PAA-derived LIG-MSC showed smaller and tilted CV curves compared to boron-free Pi-derived LIG-MSC in FIG. 34B, representing a lower capacitance and a higher resistance. The large voltage drop observed at the initial stage of discharge run in PAA-derived LIG-MSC from FIG.
- FIG. 34E shows the influence of boron content on C A , which increases from 0 to 5% reaching a maximum ⁇ 4 times greater than undoped-LIG, and then decreasing slightly at higher loadings.
- the boron doping level is low, increasing boron dopants into LIG will increase the hole charge density thus enhancing the electrons charge storage.
- H 3 B0 3 is needed to maximize the device performance.
- FIG. 35A show CV curves of a 5B-LIG-MSC at scan rates of 0.01, 0.02, 0.05 and 0.10 V/s. The maintained pseudo-rectangular shape of CV curves over different scan rates represents good EDL formation of the devices.
- FIG. 35B shows the galvanostatic CC curves at different current densities (0.1, 0.2 and 0.5 mA/cm ), all of which are nearly triangular, further confirming their optimal capacitive behaviors. Additional CV curves at higher scan rates and CC curves at higher current densities are shown in FIG. 36 to demonstrate that 5B-LIG-MSC can operate over a wide range of scan rates and current densities.
- the C A determined from these CC curves shows little decrease over current densities covering two orders of magnitude, with a maximum of 16.5 mF/cm at a current density of 0.05 mA/cm , which is four times larger than that of the non-doped LIG made from the same process without H 3 BO 3 incorporated. Furthermore, C A of 5B-LIG-MSC remains over 3 mF/cm even when operated at a high current density of 40 mA/cm , indicating optimal power performance.
- Electrochemical impedance measurements shown in FIG. 37 further demonstrate that both external and internal resistances of 5B-LIG-MSC are lower than that of LIG-MSC. These results indicate faster ionic transport and better electrode-electrolyte interface when the LIG material is doped with boron.
- the cyclability of 5B-LIG-MSCs was also tested over 12000 CC cycles at a current density of 1.0 mA/cm 2 with over 90% of the capacitance retained (FIG. 35D), proving high stability of performance from the B-LIG-MSC.
- the assembled MSC from 5B-LIG also shows optimal durability under mechanical stress.
- the calculated C A from discharge runtime remained essentially constant, as shown in FIG. 35F.
- the C A of the device was unchanged (FIG. 35G), and CV curves during different bending cycles as shown in FIG. 35H are identical to each other, suggesting that bending had little effect on the electrochemical performance of 5B-LIG-MSC.
- Example 2.1 Materials synthesis and device fabrication
- PAA poly(pyromellitic dianhydride-co-4,4'-oxydianiline amic acid)
- PAA poly(pyromellitic dianhydride-co-4,4'-oxydianiline amic acid)
- H 3 BO 3 B0394, Aldrich
- 10 mg for 1 wt , 20 mg for 2 wt , 50 mg for 5 wt , and 80 mg for 8wt were added to the PAA solution with bath sonication for 30 minutes, and then poured into an aluminum dish and placed in a vacuum oven at 60 °C and a pressure of ⁇ 120 mm Hg for 3 days to evaporate the solvent.
- the filming process was done in a hydraulic press (Carver, No. 3912) with an applied load of 3xl0 5 Pa at 200 °C for 30 minutes to dehydrate the PAA/H 3 BO 3 and form the PI/H 3 BO 3 sheet.
- Laser induction was then conducted on the PI/H 3 BO 3 substrate with a 10.6 ⁇ carbon dioxide (CO 2 ) laser cutter system (Universal X-660 laser cutter platform at a pulse duration of -14 ⁇ 8).
- the laser power was fixed at 4.8 W during laser induction. All experiments were performed under ambient conditions.
- LIG was patterned into 12 interdigitated electrodes with a length of 5 mm, a width of 1 mm, and a spacing of -300 ⁇ between two neighboring microelectrodes (FIG. 27B).
- Pellco ® colloidal silver paint No. 16034, Ted Pella
- the electrodes were then extended with conductive copper tape which were connected to an electrochemical workstation (CHI608D, CHI Instruments) for testing.
- a Kapton polyimide tape was employed to protect the common areas of the electrodes from electrolyte.
- MSC device -0.25 mL of electrolyte was dropped onto the active B-LIG area on PI substrate, followed by placing the device overnight in a desiccator that was connected to a house vacuum (-120 mm Hg) to remove excess water.
- Example 2.2 Material characterization
- SEM images were obtained on a FEI Quanta 400 high resolution field emission SEM.
- TEM and HRTEM images were obtained using a JEOL 21 OOF field emission gun transmission electron microscope.
- TEM samples were prepared by peeling off 5B-LIG from a PI substrate, followed by sonicating them in chloroform, and dropping them onto a lacey carbon copper grid.
- Raman spectra were recorded on a Renishaw Raman microscope using a 514-nm laser with a power of 5 mW.
- the surface area of 5B-LIG was measured with a Quantachrome Autosorb-3b BET surface analyzer. TGA (Q50, TA instrument) was carried out from room temperature to 900 °C at 5 °C/min under argon flow. XPS was performed using a PHI Quantera SXM Scanning X-ray Microprobe with a base pressure of 5 x 10 ⁇ 9 Torr. Survey spectra were recorded in 0.5 eV step size with a pass energy of 140 eV. Elemental spectra were recorded in 0.1 eV step sizes with a pass energy of 26 eV. All the spectra were corrected using Cls peaks (284.5 eV) as references. CV and galvanostatic CC measurements were performed using a CHI 608D workstation (USA). All of measurements were conducted under ambient conditions.
- Example 2.3 Calculation of parameters as indications for electrochemical performance of LIG derived devices
- CA specific areal capacitances (CA, in mF/cm 2 ) and volumetric capacitances (CV, in F/m ) from galvanostatic charge-discharge (CC) curves
- CC galvanostatic charge-discharge
- / is the discharge current (in amperes); dV/dt is the slope of galvanostatic discharge curves; and S is total area of active positive and negative electrodes. Considering the dimensions of 12 such electrodes (5 mm in length and 1 mm in width), S is calculated as 0.6 cm 2 , d is the thickness of active materials with 25 ⁇ , as revealed in FIG. 26C inset.
- At discharge time (in seconds).
- Example 3 Flexible and Stackable Laser Induced Graphene Supercapacitors
- Applicants demonstrate that laser induction can be utilized to transform commercial polyimide films into porous graphene for the fabrication of flexible, solid-state supercapacitors.
- Two different solid-state electrolyte supercapacitors are described, namely vertically stacked graphene supercapacitors and in-plane graphene microsupercapacitors, each with enhanced electrochemical performance, cyclability, and flexibility.
- Devices with a solid- state polymeric electrolyte exhibit areal capacitance of >9 mF/cm at a current density of 0.02 mA/cm , over twice that of conventional aqueous electrolytes.
- laser induction on both sides of polyimide sheets enables the fabrication of vertically stacked supercapacitors to multiply its electrochemical performance while preserving device flexibility.
- LIG-SCs flexible laser induced graphene based super capacitors
- PVA poly(vinyl alcohol)
- FIG. 39A schematically illustrates the process in fabricating flexible, solid-state LIG- SCs.
- the process begins by first transforming the surface of a PI sheet into porous graphene under laser induction using a commercially available, computer controlled CO 2 laser cutting system, and then assembling either a single LIG-SC or stacked LIG-SC.
- FIGS. 40 and 39B show the photograph of a half- side LIG electrode and a typical single LIG-SC device manually bent to demonstrate its intrinsic flexibility.
- An advantage of this fabrication method is that LIG can be easily produced under ambient conditions on both sides of the PI sheet with a remaining central insulating PI layer to separate them (FIG.
- FIG. 39C shows a cross sectional scanning electron microscope (SEM) image, where a thick LIG layer (-25 ⁇ ) is clearly formed on both sides of the PI substrate after laser induction and is separated by an unexposed middle PI layer that serves to electrically isolate the top and bottom LIG layers from each other.
- SEM image in FIG. 39D shows the porous structure of LIG
- TEM image in FIG. 39E shows the nanoscale ripples and wrinkles in the LIG films.
- HRTEM high-resolution TEM
- the Raman spectrum of LIG in FIG. 43A clearly shows three characteristic peaks of graphene derived material, specifically, a D peak at -1350 cm “1 induced by defects, folding or symmetry-broken carbon, G peak at -1590 cm “1 generated by graphitic carbon, and a 2D peak at -2700 cm “1 originating from second-order zone boundary phonons.
- a D peak at -1350 cm “1 induced by defects, folding or symmetry-broken carbon G peak at -1590 cm “1 generated by graphitic carbon
- 2D peak at -2700 cm "1 originating from second-order zone boundary phonons.
- the D peak could arise from numerous graphene edges existing in LIG flakes, which are also observed in the above TEM images.
- the high degree of graphitization of LIG is further supported by thermogravimetric analysis (TGA) under argon (FIG. 44), since PI decomposes at -550 °C, whereas LIG remains stable at >900 °C.
- TGA thermogravimetric analysis
- FIG. 44 shows that the surface area of LIG is -330 m 2 /g with a pore size distribution between 2-10 nm (FIG. 45B).
- LIG was first fabricated into a flexible, single LIG-SC by sandwiching a solid, polymeric electrolyte (PVA and H 2 S0 4 ) between two single-sided LIG-PI sheets which functioned both as the working electrode and current collector
- PVA and H 2 S0 4 polymeric electrolyte
- the cyclic voltammetry (CV) curves shown in FIG. 42A were pseudo -rectangular over varying scan rates (5, 10, 20, and 50 mV/s), which is indicative of good EDL stability.
- FIG. 42A were pseudo -rectangular over varying scan rates (5, 10, 20, and 50 mV/s), which is indicative of good EDL stability.
- FIG. 47A compares the CV curves of a flexible single LIG-SC over different bending radii (12 mm to 24 mm) and remarkably shows that the bent device exhibits nearly identical behavior to the flat LIG-SC. Also, FIG. 47B shows that the calculated C A under different bending radii remained almost constant. From FIG. 47C, the C A was well-maintained after 7000 bending cycles at a radius of 14 mm, indicating that repeated bending has little effect on its electrochemical performance.
- FIGS. 48A-B are illustrations of a series and parallel LIG-SC assembled from stacked solid-state LIG-SCs, where double-sided LIG sheets are layered with alternating deposits of polymeric electrolyte and capped with single-sided LIG-PI sheets.
- FIGS. 48C-D show the CC curves of a 3-stack solid-state series and parallel LIG-SC, respectively.
- the stacked series LIG-SC has a 2x higher working voltage window, while the stacked parallel LIG-SC shows a 2x longer discharge time when operated at the same current density, resulting in a 2x higher capacitance.
- the CC curves present nearly triangular shapes with miniscule voltage drop indicating negligible internal and contact resistances.
- FIGS. 49-50 Additional CV and CC curves at various scan rates and current densities for the stacked series and parallel LIG-SCs are shown in FIGS. 49-50 to demonstrate their remarkable durability over a wide range of scan rates and current densities. Even though the SCs are stacked, the assembled stacked LIG-SCs still show high flexibility.
- FIGS. 48E-F show that the capacitance of the stacked LIG-SC circuits are nearly 100% of their initial value, even after being subjected to several thousand bending cycles at a bending radius of 17 mm. Additionally, the CV curves at different bending cycles are nearly overlapped (insets of FIGS. 48E-F), indicating well maintained flexibility.
- FIG. 51A is an illustration of a flexible LIG-MSC fabricated on a PI sheet that uses PVA/H 2 SO 4 as solid-state electrolyte.
- FIG. 51B shows CV curves of the LIG-MSC device at different scan rates (0.01, 0.02, 0.05 and 0.1 V/s) with stable pseudo-rectangular shape due to good EDL formation.
- FIG. 51A is an illustration of a flexible LIG-MSC fabricated on a PI sheet that uses PVA/H 2 SO 4 as solid-state electrolyte.
- FIG. 51B shows CV curves of the LIG-MSC device at different scan rates (0.01, 0.02, 0.05 and 0.1 V/s) with stable pseudo-rectangular shape due to good EDL formation.
- FIG. 51C shows the galvanostatic CC curves of LIG-MSCs at different current densities (0.1, 0.2, 0.5 and 1.0 mA/cm ), all of which are nearly triangular due to their optimal capacitive behaviors.
- FIG. 52 shows additional CV curves at higher scan rates and CC curves at higher current densities. The calculated C A from CC curves at different current densities are plotted in FIG. 51D, where the devices strikingly exhibit a capacitance of greater than 9 mF/cm 2 at a current density of 0.02 mA/cm .
- FIG. 51E shows that the in-plane LIG-MSCs made from LIG exhibits nearly 100% of its calculated capacitance regardless of bending radii. Similar to the single LIG-SC, CV curves of LIG-MSC over different bending radii are almost identical to the ones in the flat devices (FIG. 56). After 7000 bending cycles, the capacitance remained at its initial value (FIG. 51F), further supporting the universality of this laser induction method in producing energy storage units.
- FIG. 57 is a Ragone plot comparing single LIG-SCs and LIG-MSCs in either aqueous or solid-state polymeric electrolytes to commercially available electrolytic capacitors and Li thin film batteries.
- aluminum (Al) electrolytic capacitors deliver ultrahigh power, their energy density is two orders of magnitude lower than LIG-derived devices.
- lithium ion thin-film batteries can provide high energy density, their power performance is three orders of magnitude lower than either single LIG-SCs or LIG-MSCs.
- LIG- MSC with a solid-state polymer electrolyte stores ⁇ 2x more energy.
- Example 3.1 Materials production and LIG supercapacitor fabrication
- Kapton polyimide (PI, Cat. No. 2271K3, thickness: 0.005") was purchased from McMaster-Carr and used as received unless noted otherwise.
- Laser induction of graphene was conducted with a 10.6 ⁇ C0 2 laser system (Universal X-660 laser cutter platform) at a pulse duration of -14 ⁇ 8. All experiments were conducted under ambient conditions using 4.8 W of laser power.
- Two types of LIG based SCs were fabricated: single or stacked LIG-SCs and in- plane LIG-MSCs.
- LIG was produced either on one side or both sides of the PI sheet with an active area of 2 cmx3 cm, whereas for MSCs, LIG was patterned into interdigitated electrodes with a length of 5 mm, a width of 1 mm, and a spacing of -300 ⁇ between two neighboring microelectrodes.
- Solid-state LIG-SCs were fabricated by dropping - 1 mL of PVA-H 2 S0 4 onto a LIG-PI substrate and then sandwiching it with a second LIG-PI substrate. Finally, the device was placed in a desiccator that was connected to house vacuum (- 10 mmHg) to remove excess water overnight.
- -0.25 mL of PVA-H 2 S0 4 was dropped onto the active LIG area on the PI substrate, followed by placing the device overnight in a desiccator that was connected to house vacuum to remove excess water.
- the MSCs with aqueous electrolyte were also fabricated by dropping -0.2 mL 1 M H 2 S0 4 onto the active LIG on PI sheets.
- SEM images were taken on a FEI Quanta 400 high resolution field emission SEM.
- the TEM and HRTEM images were taken using a JEOL 21 OOF field emission gun transmission electron microscope.
- TEM samples were prepared by peeling off LIG from the PI substrate, followed by sonicating them in chloroform, and dropping them onto a lacey carbon copper grid.
- Raman spectra were recorded on a Renishaw Raman microscope using 514-nm laser with a power of 5 mW.
- the surface area of LIG was measured with a Quantachrome Autosorb-3b BET surface analyzer. TGA (Q50, TA instrument) was carried out at room temperature to 900 "C at 5 "C/min under argon. CV and constant current CC measurements were conducted under ambient conditions using a CHI 608D workstation (USA).
- Example 3.3 Calculation of parameters as indications for the electrochemical performance of LIG based devices
- / is the discharge current (in amperes)
- dV/dt is the slope of the galvanostatic discharge curve immediately following the voltage drop
- S is the total area of the active positive and negative electrodes.
- d is the thickness of active materials with 25 ⁇ as indicated in the FIG. 39C inset.
- EA in ⁇ ⁇ / ⁇
- volumetric energy densities Ey, in Wh/m
- Ai discharge time (in s).
- Rapid heating of polyimides by absorption of a focused C0 2 laser beam is an exemplary process by which a polymer is converted into a graphene material.
- the C0 2 laser overlaps with a vibrational absorption band of the polyimide, which is preferred for the conversion of the laser beam into heat.
- the energy density depends on both the spot size and the penetration depth of the beam into the material. Assuming equal spot sizes, when the beam is strongly absorbed, the energy is deposited in a thinner layer, leading to more rapid heating. On the other hand, weak absorption will lead to a larger volume absorbing the light, slower heating and less efficient conversion to graphene.
- the laser intensity may be increased either by focusing more tightly or increasing the laser power to produce the necessary energy density.
- the penetration depth, or absorption depth is controlled by the wavelength of the laser.
- a wavelength-tunable laser is important for controlling the depth of the graphene formation, and thereby introduces the capability for making 3-dimensional structures in the LIG films.
- FIG. 59 provides an absorption spectrum of a polyimide film.
- the spectrum shows a strong absorption band in the 9 to 11 micrometer range.
- the four solid lines represent center wavelength of the of two rotational-vibrational branches for two vibrational bands of the tunable C0 2 laser.
- the center frequency of each band is 9.3, 9.5, 10.3 and 10.6 micrometers.
- Each of these four bands consists of a number of rotational lines, which are individually selectable. This is represented by the dotted lines on either side of the solid line on the spectrum in FIG. 59.
- the 9.3 micrometer band has a tuning range of—0.15 micrometers, and the other three bands have tuning ranges of -0.2 micrometers.
- the availability to choose from many wavelengths allows selection of a wide range of penetration depths into a polymer film by changing the wavelength of the laser (e.g., C0 2 laser).
- This also provides a mechanism to make vertical 3D structures into a polymer film.
- a strongly absorbed wavelength is focused on the surface to create a narrow and shallow line of LIG. Then the focus is shifted to below the surface, and the laser wavelength is changed to allow greater penetration.
- the partially attenuated converging beam now coming to a focus below the LIG line already made.
- the porous LIG material allows the gases to escape as more LIG is generated below the surface layer. The process can be repeated with an even deeper focus and the laser tuned further off-resonance for greater penetration.
- One way to optimize the generation of such 3D structures is that the incoming beam is divided into two parts, which straddle the first shallow line and pass on either side as they converge to the subsurface focal point.
- the focal point may be shifted off the axis of the initial graphene line on the surface to provide subsurface "tunneling", as long as there is a channel of porous graphene for the gases to escape.
- An alternative way to construct 3D structures is to add a new layer of polymer film or liquid precursor by spraying or flooding the surface. Then the focal point is moved up to generate a new LIG line on top of the existing LIG material below. Since the added liquid or sprayed-on material may have a different absorption strength than the LIG material already formed, then the wavelength is optimized to form LIG in the newly deposited material.
- FIG. 60 is a drawing showing the use of visible lasers and an option of coupling into a controlled atmosphere chamber with an optical fiber. This permits the careful control of the environment in the chamber for termination of the graphene edges with specific gases, and for the use of multiple laser sources.
- the optical fiber coupling could also be used with an NSOM (not illustrated).
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CN106232520B (en) | 2020-12-11 |
CA2940050A1 (en) | 2015-11-19 |
EP3107864A4 (en) | 2018-02-28 |
US20170062821A1 (en) | 2017-03-02 |
JP2017514783A (en) | 2017-06-08 |
US20200112026A1 (en) | 2020-04-09 |
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MX2016010718A (en) | 2016-11-07 |
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CA2940050C (en) | 2023-10-31 |
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US10505193B2 (en) | 2019-12-10 |
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