CN113620278B - Method for controllably preparing nano-porous graphene flexible electrode based on ion adsorption - Google Patents
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Abstract
The invention discloses a controllable preparation method of a nano porous graphene flexible electrode based on ion adsorption. Ultrasonically dispersing the graphene oxide aqueous solution, placing the graphene oxide aqueous solution in an ice water bath for magnetic stirring, and meanwhile, placing the graphene oxide aqueous solution in the ice water bath for magnetic stirringFeCl is dripped 3 Centrifuging the solution to obtain GO/Fe 3+ A precursor; freeze drying, calcining under inert gas, washing with dilute HCl, and washing with deionized water to neutrality to obtain nano porous graphene; and dispersing in ethanol/water, performing ultrasonic treatment to uniformly disperse, performing suction filtration to obtain a filter cake, drying the filter cake, rolling to obtain a flexible nano porous graphene electrode plate, and using the flexible nano porous graphene electrode plate as a negative electrode to assemble the potassium ion battery. The method is simple and suitable for large-scale preparation of the nano-porous graphene, and the prepared graphene has uniform and controllable pore diameter, excellent charge-discharge specific capacity and good cycling stability.
Description
Technical Field
The invention relates to a preparation method of a flexible electrode, in particular to a controllable preparation method of a nano porous graphene flexible electrode.
Background
Lithium Ion Batteries (LIBs) have been successfully used in commercial rechargeable batteries due to their high efficiency, high energy density, and long cycle life. However, LIBs face serious cost issues in future large-scale energy storage applications due to limited and unevenly distributed lithium resources on earth. Therefore, sodium Ion Batteries (SIBs) and Potassium Ion Batteries (PIBs) have attracted considerable attention due to their low cost and abundance of resources. With Na + K/Na (-2.71V vs standard hydrogen electrode) + The redox potential of/K is lower and is closer to Li + Li (-2.93V and-3.04V vs standard hydrogen electrode). Thus, PIBs have higher open circuit potentials and energy densities than SIBs. In addition, the weaker lewis acidity of K + results in smaller stokes radii of solvated ions in the liquid electrolyte with faster kinetic characteristics. Thus, PIBs are potential candidates for large-scale energy storage devices.
However, suitable electrode materials are sought to accommodate the larger K + (radius:
) It remains a significant challenge. Among the various materials reported so far, graphene has attracted particular attention in the application of PIBs due to its inherent characteristics, such as high energy density, good conductive plane conductivity, excellent tensile modulus and mechanical durability, and the like. However, practical applications of graphene-based materials suggest that pristine graphene is prone to stacking due to strong van der waals forces and pi-pi interactions between its high specific surface area graphite planes. The build-up will result in graphiteThe active surface of the graphene is greatly reduced and hinders ion transport, greatly reducing the charge/discharge capacity of graphene-based electrodes, especially at high charge/discharge rates. Introducing the pores into the basal plane of the graphene will reduce the diffusion distance of ion migration in the charging/discharging process, and can effectively improve the problems of electrode dynamics and mass transfer. In addition, the introduction of the pores can generate more defects on the basal plane of the graphene, so that the graphene can provide more active sites, and the electrochemical performance is greatly improved. Various methods have been developed, such as photocatalytic oxidation, chemical etching (e.g., KOH, H) 2 O 2 、HNO 3 And NaI), metal or metal oxide etching (e.g., ni, fe, cu, and Co), and air oxidation to prepare nanoporous graphene. Among other things, metal oxide etching methods do not involve corrosive/hazardous chemicals (e.g., H) 2 O 2 And KOH), and thus is widely used to prepare nanoporous graphene. However, the reported metal oxide etching process is very prone to form a macroporous structure, which impairs the conductivity, electrochemistry and structural stability of graphene, thereby reducing power density and coulombic efficiency and shortening cycle life. Therefore, the nano porous graphene with simple development process and controllable pore size has important significance for large-scale application of PIBs.
Disclosure of Invention
In order to solve the problems in the background art, an object of the present invention is to provide a low-cost, controllable and effective strategy for preparing porous graphene with nano-pores to reduce the diffusion distance of ion migration during charging/discharging of a rechargeable battery, and to improve electrode kinetics and mass transport problems. Meanwhile, the porous graphene is prepared into a flexible electrode which is directly used for a rechargeable battery to improve the conductivity of the electrode.
In order to solve the above technical problem, as shown in fig. 8, the present invention adopts the following technical solutions:
s1, ultrasonically dispersing a Graphene Oxide (GO) aqueous solution, placing the solution in an ice water bath for magnetic stirring, and simultaneously dropwise adding FeCl according to a certain molar ratio 3 Solution, centrifugally separating the solution after the dropwise addition, washing the obtained precipitate with deionized water, and vacuum coolingFreeze drying to obtain GO/Fe 3+ A precursor;
s2, freeze-drying GO/Fe 3+ Calcining the precursor under the protection of inert gas, washing with a dilute HCl solution, washing with deionized water to neutrality, performing centrifugal separation, and performing vacuum freeze drying to obtain nano porous graphene;
s3, dispersing the nano porous graphene in a mixed solution of ethanol and water, performing suction filtration after ultrasonic dispersion to obtain a filter cake, drying the filter cake, and rolling to obtain the flexible porous graphene electrode plate.
The S1 specifically comprises the following steps: ultrasonically dispersing a graphene oxide aqueous solution with the concentration of 0.5mg/mL, then placing the graphene oxide aqueous solution into an ice water bath for magnetic stirring, and simultaneously carrying out magnetic stirring according to the graphene oxide and FeCl 3 FeCl is added dropwise according to the molar ratio of 1 3 Solutions, feCl 3 The concentration of the solution is 0.05-0.1 mol/L, the solution obtained after the dropwise addition is carried out is subjected to centrifugal separation treatment, the precipitate obtained by centrifugation is washed by deionized water and is subjected to vacuum freeze drying for 24-72 h, and GO/Fe is obtained 3+ And (3) precursor.
The S2 specifically comprises the following steps: freeze drying GO/Fe 3+ Calcining the precursor under the protection of inert gas atmosphere, keeping the temperature rise rate at 5-20 ℃/min to reach the calcining temperature of 500-800 ℃, then keeping the calcining temperature for 0-120 min, finally washing the calcined product by using 1-3 mol/L diluted HCl solution, then repeatedly washing the calcined product by using deionized water to be neutral, carrying out centrifugal separation, and carrying out vacuum freeze drying on the obtained precipitate to obtain the nano porous graphene.
The method regulates and controls the pore size of the flexible porous graphene electrode plate by controlling the calcination temperature and the calcination time, and the pore size distribution range is 0.5-20 nm.
The controllable preparation of the nano porous graphene flexible electrode based on ion adsorption is directly used as a negative pole piece of a rechargeable battery.
The product of the invention can be used as a negative electrode material for rechargeable batteries.
The method is simple, is suitable for large-scale preparation of the nano-porous graphene, and the prepared graphene has uniform and controllable pore diameter and wide use value and popularization significance. Meanwhile, when the flexible electrode is directly applied to rechargeable batteries, the flexible electrode has excellent charge-discharge specific capacity and good cycling stability, and when the flexible electrode is applied to negative electrode materials of PIBs, the charge-discharge specific capacity and cycling stability of the PIBs can be effectively improved.
The invention has the beneficial effects that:
according to the method, metal oxide nanoparticles generated in situ based on single ion adsorption are used as a mild etchant to prepare the porous graphene with the nano holes, and the prepared nano porous graphene is subjected to suction filtration and rolling to obtain the flexible nano porous graphene sheet.
The prepared nano-pores on the flexible nano-porous graphene can form an interpenetrating network, so that the diffusion and permeation of electrolyte can be effectively promoted, the transmission path of ions and electrons can be shortened, and the electrode dynamics and the mass transmission of the rechargeable battery can be greatly improved. Meanwhile, the edge of the introduced hole can provide more ion insertion/emigration sites, and the charge-discharge specific capacity of the rechargeable battery is effectively improved.
When the nano porous graphene flexible electrode is used as a negative electrode material and applied to PIBs (cathode materials), the nano porous graphene flexible electrode shows excellent charge-discharge specific capacity, good rate performance and lasting cycle stability.
Drawings
FIG. 1 is GO/Fe prepared in example 3+ Scanning electron micrographs of the precursor (a) electron energy spectrograms (b-d are C, O and Fe spectra, respectively);
FIG. 2 is GO/Fe prepared in example 3+ Spherical aberration electron microscope picture of the precursor;
FIG. 3 is a transmission electron microscope image (a-d) of the nanoporous graphene prepared in examples 1, 2, 3, 4;
fig. 4 shows the flexible nano-porous graphene electrode prepared in example 2 (a) and after bending (b);
fig. 5 shows short cycle performance of the nano-porous graphene flexible electrodes prepared in examples 1, 2, 3 and 4 applied to PIBs;
fig. 6 is a rate capability of the nano-porous graphene flexible electrodes prepared in examples 1, 2, 3, and 4 applied to PIBs;
fig. 7 shows the long-cycle performance of the nano-porous graphene flexible electrode prepared in example 1 applied to PIBs.
FIG. 8 is a schematic view of the process of the method of the present invention.
Detailed Description
Specific embodiments of the present invention will be further described with reference to the accompanying drawings.
The examples of the invention are as follows:
example 1
(1)GO/Fe 3+ Preparing a precursor: and (3) carrying out ultrasonic treatment on the Graphene Oxide (GO) aqueous solution with the concentration of 0.5mg/mL for 60min to form a uniform and stable solution. Placing the mixture in an ice water bath for magnetic stirring for 30min, and simultaneously adding FeCl dropwise according to the molar ratio of 1 3 Solutions, feCl 3 The concentration of the solution is 0.05mol/L, the obtained solution is centrifugally separated after the dropwise addition is finished, the rotating speed of a centrifugal machine is 10000r/min, and the obtained precipitate is washed by deionized water to obtain GO/Fe 3+ The precursor is subjected to vacuum freeze-drying at-60 ℃, the freeze-drying time is 48h, and Fe can be seen from an electronic energy spectrogram and a spherical aberration electron microscope image 3+ The GO is uniformly distributed on the surface of the GO and shows a monodisperse state;
(2) Preparing nano porous graphene: freeze drying GO/Fe 3+ And putting the precursor into a tubular furnace, calcining under the protection of inert gas atmosphere, wherein the heating rate is 10 ℃/min, the calcining time is 0min, the calcining temperature is 600 ℃, finally, washing the calcined product by using 1mol/L HCl, repeatedly washing the product by using deionized water to be neutral, performing centrifugal separation, and performing vacuum freeze drying on the obtained precipitate at the temperature of-60 ℃ to obtain the nano porous graphene, wherein the aperture of the nano porous graphene is about 0.5-1 nm.
(3) Preparing a nano porous graphene flexible electrode: and (3) redispersing the nano-porous graphene in ethanol/water, performing ultrasonic treatment to fully disperse the nano-porous graphene, and performing suction filtration to obtain a nano-porous graphene filter cake. And drying the filter cake, and then rolling, wherein the temperature of the oven is 40 ℃, and the rolling thickness is 0.2mm, so as to obtain the flexible nano porous graphene electrode plate.
Dissolving a flexible nano-porous graphene electrode plate serving as a negative electrode, metal potassium serving as a positive electrode and Whatman GF/D glass fiber serving as a diaphragm in 0.8M KPF 6 Ethylene carbonate/diethyl carbonate (volume ratio 1 2 O<0.1ppm and O 2 <0.1 ppm) of assembled PIBs having a specific discharge capacity of about 390mAh/g at a current density of 0.1A/g. Under the high current density of 1A/g, after 1500 cycles, the discharge specific capacity of the material is still kept at about 250mAh/g, and the material has excellent rate capability and cycling stability.
Example 2
(1)GO/Fe 3+ Preparing a precursor: and (3) carrying out ultrasonic treatment on the Graphene Oxide (GO) aqueous solution with the concentration of 0.5mg/mL for 60min to form a uniform and stable solution. Placing the mixture in an ice water bath, magnetically stirring the mixture for 30min, and simultaneously dropwise adding FeCl according to the molar ratio of 1 3 Solutions, feCl 3 The concentration of the solution is 0.05mol/L, the obtained solution is centrifugally separated after the dropwise addition is finished, the rotating speed of a centrifugal machine is 10000r/min, and the obtained precipitate is washed by deionized water to obtain GO/Fe 3+ Performing vacuum freeze drying on the precursor at-60 ℃, wherein the freeze drying time is 48h;
(2) Preparing nano porous graphene: freeze drying GO/Fe 3+ And placing the precursor in a tubular furnace, calcining under the protection of inert gas atmosphere, wherein the heating rate is 10 ℃/min, the calcining time is 0min, the calcining temperature is 700 ℃, finally washing the calcined product by using 1mol/L HCl, then repeatedly washing the product to be neutral by using deionized water, centrifugally separating, and carrying out vacuum freeze drying on the obtained precipitate at the temperature of-60 ℃ to obtain the nano porous graphene, wherein the aperture of the nano porous graphene is about 1-2 nm.
(3) Preparing a nano porous graphene flexible electrode: and (3) redispersing the nano-porous graphene in ethanol/water, performing ultrasonic treatment to fully disperse the nano-porous graphene, and performing suction filtration to obtain a nano-porous graphene filter cake. And drying the filter cake, and then rolling, wherein the temperature of an oven is 40 ℃, and the rolling thickness is 0.2mm, so as to obtain the flexible nano porous graphene electrode plate.
Taking a flexible nano porous graphene electrode plate as a negative electrodePotassium metal as positive electrode, whatman GF/D glass fiber as diaphragm, dissolved in 0.8M KPF 6 Ethylene carbonate/diethyl carbonate (volume ratio 1 2 O<0.1ppm and O 2 <0.1 ppm) of assembled PIBs, having a specific discharge capacity of about 350mAh/g at a current density of 0.1A/g and a specific discharge capacity of about 190mAh/g at a current density of 2A/g.
Example 3
(1)GO/Fe 3+ Preparing a precursor: and (3) carrying out ultrasonic treatment on the Graphene Oxide (GO) aqueous solution with the concentration of 0.5mg/mL for 60min to form a uniform and stable solution. Placing the mixture in an ice water bath, magnetically stirring the mixture for 30min, and simultaneously dropwise adding FeCl according to the molar ratio of 1 3 Solutions, feCl 3 The concentration of the solution is 0.05mol/L, the obtained solution is centrifugally separated after the dropwise addition is finished, the rotating speed of a centrifugal machine is 10000r/min, and the obtained precipitate is washed by deionized water to obtain GO/Fe 3+ Performing vacuum freeze drying on the precursor at-60 ℃, wherein the freeze drying time is 48h;
(2) Preparing nano porous graphene: freeze drying GO/Fe 3+ And placing the precursor in a tubular furnace, calcining under the protection of inert gas atmosphere, wherein the heating rate is 10 ℃/min, the calcining time is 0min, the calcining temperature is 800 ℃, finally washing the calcined product by using 1mol/L HCl, repeatedly washing the product to be neutral by using deionized water, centrifugally separating, and carrying out vacuum freeze drying on the obtained precipitate at the temperature of-60 ℃ to obtain the nano porous graphene, wherein the aperture of the nano porous graphene is 3-5 nm.
(3) Preparing a nano porous graphene flexible electrode: and (3) redispersing the nano-porous graphene in ethanol/water, performing ultrasonic treatment to fully disperse the nano-porous graphene, and performing suction filtration to obtain a nano-porous graphene filter cake. And drying the filter cake, and then rolling, wherein the temperature of the oven is 40 ℃, and the rolling thickness is 0.2mm, so as to obtain the flexible nano porous graphene electrode plate.
Dissolving a flexible nano-porous graphene electrode plate serving as a negative electrode, metal potassium serving as a positive electrode and Whatman GF/D glass fiber serving as a diaphragm in 0.8M KPF 6 Ethylene carbonate/diethyl carbonate in solutionVolume ratio 1 2 O<0.1ppm and O 2 <0.1 ppm) of assembled PIBs, the specific discharge capacity of the assembled PIBs is about 380mAh/g at a current density of 0.1A/g, the specific discharge capacity of the assembled PIBs is about 380mAh/g at a current density of 2A/g, and the specific discharge capacity of the assembled PIBs is about 120mAh/g at a current density of 2A/g.
Example 4
(1)GO/Fe 3+ Preparing a precursor: and (3) carrying out ultrasonic treatment on the Graphene Oxide (GO) aqueous solution with the concentration of 0.5mg/mL for 60min to form a uniform and stable solution. Placing the mixture in an ice water bath, magnetically stirring the mixture for 30min, and simultaneously dropwise adding FeCl according to the molar ratio of 1 3 Solutions, feCl 3 The concentration of the solution is 0.05mol/L, the obtained solution is centrifugally separated after the dropwise addition is finished, the rotating speed of a centrifugal machine is 10000r/min, and the obtained precipitate is washed by deionized water to obtain GO/Fe 3+ Performing vacuum freeze drying on the precursor at-60 ℃, wherein the freeze drying time is 48h;
(2) Preparing nano porous graphene: freeze drying GO/Fe 3+ And putting the precursor into a tubular furnace, calcining under the protection of inert gas atmosphere, wherein the heating rate is 10 ℃/min, the calcining time is 1h, the calcining temperature is 800 ℃, finally, washing the calcined product by using 1mol/L HCl, repeatedly washing the product by using deionized water to be neutral, carrying out centrifugal separation, and carrying out vacuum freeze drying on the obtained precipitate at the temperature of-60 ℃ to obtain the nano porous graphene, wherein the aperture of the nano porous graphene is about 20nm.
(3) Preparing a nano porous graphene flexible electrode: and (3) redispersing the nano-porous graphene in ethanol/water, performing ultrasonic treatment to fully disperse the nano-porous graphene, and performing suction filtration to obtain a nano-porous graphene filter cake. And drying the filter cake, and then rolling, wherein the temperature of an oven is 40 ℃, and the rolling thickness is 0.2mm, so as to obtain the flexible nano porous graphene electrode plate. Dissolving a flexible nano-porous graphene electrode plate serving as a negative electrode, metal potassium serving as a positive electrode and Whatman GF/D glass fiber serving as a diaphragm in 0.8M KPF 6 Ethylene carbonate/diethyl carbonate (volume ratio 1 2 O<0.1ppm and O 2 <0.1 ppm) assembling PIBs atThe specific discharge capacity of the lithium ion battery is about 300mAh/g under the current density of 0.1A/g, and about 50mAh/g under the current density of 2A/g.
Example 5
(1)GO/Fe 3+ Preparing a precursor: and (3) carrying out ultrasonic treatment on the Graphene Oxide (GO) aqueous solution with the concentration of 0.5mg/mL for 80min to form a uniform and stable solution. Placing the mixture in an ice water bath, magnetically stirring the mixture for 45min, and simultaneously dropwise adding FeCl according to the molar ratio of 1 3 Solutions, feCl 3 The concentration of the solution is 0.08mol/L, the obtained solution is centrifugally separated after the dropwise addition is finished, the rotating speed of a centrifugal machine is 8000r/min, and the obtained precipitate is washed by deionized water to obtain GO/Fe 3+ Performing vacuum freeze drying on the precursor at-60 ℃, wherein the freeze drying time is 48h;
(2) Preparing nano porous graphene: freeze drying GO/Fe 3+ And placing the precursor in a tubular furnace, calcining under the protection of inert gas atmosphere, wherein the heating rate is 5 ℃/min, the calcining time is 30min, the calcining temperature is 600 ℃, finally washing the calcined product by using 2mol/L HCl, repeatedly washing the product to be neutral by using deionized water, centrifugally separating, and carrying out vacuum freeze drying on the obtained precipitate at-60 ℃ to obtain the nano porous graphene.
(3) Preparing a nano porous graphene flexible electrode: and (3) redispersing the nano-porous graphene in ethanol/water, wherein the ratio of the ethanol to the water is 2. And drying the filter cake and then rolling to obtain the flexible nano porous graphene electrode plate. And (3) re-dispersing the nano porous graphene in ethanol/water, performing ultrasonic treatment to fully disperse the nano porous graphene, and performing suction filtration to obtain a nano porous graphene filter cake. And drying the filter cake, and then rolling, wherein the temperature of the oven is 60 ℃, and the rolling thickness is 0.3mm, so as to obtain the flexible nano porous graphene electrode plate.
Example 6
(1)GO/Fe 3+ Preparing a precursor: and (3) carrying out ultrasonic treatment on a Graphene Oxide (GO) aqueous solution with the concentration of 0.5mg/mL for 120min to form a uniform and stable solution. Placing in ice water bath, magnetically stirring for 60minFeCl is added dropwise according to the molar ratio of 1 3 Solutions, feCl 3 The concentration of the solution is 0.1mol/L, the obtained solution is centrifugally separated after the dropwise addition is finished, the rotating speed of a centrifugal machine is 9000r/min, and the obtained precipitate is washed by deionized water to obtain GO/Fe 3+ Performing vacuum freeze drying on the precursor at-60 ℃, wherein the freeze drying time is 48h;
(2) Preparing nano porous graphene: freeze drying GO/Fe 3+ And putting the precursor into a tubular furnace, calcining under the protection of inert gas atmosphere, wherein the heating rate is 5 ℃/min, the calcining time is 120min, the calcining temperature is 800 ℃, finally washing the calcined product by using 3mol/L HCl, then repeatedly washing the product by using deionized water to be neutral, centrifugally separating, and carrying out vacuum freeze drying on the obtained precipitate at the temperature of-60 ℃ to obtain the nano porous graphene.
(3) Preparing a nano porous graphene flexible electrode: and (3) redispersing the nano-porous graphene in ethanol/water, wherein the ratio of ethanol/water is 3. And drying the filter cake and then rolling to obtain the flexible nano porous graphene electrode plate. And (3) redispersing the nano-porous graphene in ethanol/water, performing ultrasonic treatment to fully disperse the nano-porous graphene, and performing suction filtration to obtain a nano-porous graphene filter cake. And drying the filter cake, and then rolling, wherein the temperature of the oven is 80 ℃, and the rolling thickness is 0.3mm, so as to obtain the flexible nano porous graphene electrode plate.
The protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and adaptations to those skilled in the art without departing from the principles of the present invention should also be considered as within the scope of the present invention.
Claims (3)
1. A method for preparing a nano-porous graphene flexible electrode based on ion adsorption control is characterized by comprising the following steps:
s1, carrying out ultrasonic dispersion on Graphene Oxide (GO) aqueous solution, and placing the Graphene Oxide (GO) aqueous solution in ice waterMagnetically stirring in bath while adding FeCl dropwise according to a certain molar ratio 3 Solution is added dropwise, the obtained solution is subjected to centrifugal separation, the obtained precipitate is washed by deionized water and is subjected to vacuum freeze drying, and GO/Fe is obtained 3+ A precursor;
s2, freeze-drying GO/Fe 3+ Calcining the precursor under the protection of inert gas, washing with a dilute HCl solution, washing with deionized water to neutrality, performing centrifugal separation, and performing vacuum freeze drying to obtain nano porous graphene;
s3, dispersing the nano porous graphene in a mixed solution of ethanol and water, performing suction filtration after ultrasonic dispersion to obtain a filter cake, drying the filter cake, and rolling to obtain a flexible porous graphene electrode plate;
the S1 specifically comprises the following steps:
ultrasonically dispersing a graphene oxide aqueous solution with the concentration of 0.5mg/mL, placing the graphene oxide aqueous solution in an ice-water bath for magnetic stirring, and simultaneously carrying out magnetic stirring according to graphene oxide and FeCl 3 FeCl is added dropwise at a molar ratio of 1 3 And (3) performing centrifugal separation treatment on the solution after the dropwise addition is finished, washing the precipitate obtained by centrifugation with deionized water, and performing vacuum freeze drying for 24-72 h to obtain GO/Fe 3+ A precursor;
the S2 specifically comprises the following steps:
freeze drying GO/Fe 3+ Calcining the precursor under the protection of an inert gas atmosphere, keeping the temperature of the precursor to be 500-800 ℃ at the heating rate of 5-20 ℃/min, keeping the calcination temperature for 0-120 min, washing the calcined product with 1-3 mol/L dilute HCl solution, repeatedly washing the product with deionized water to be neutral, centrifuging, and carrying out vacuum freeze drying on the obtained precipitate to obtain the nano porous graphene.
2. The utility model provides a controllable preparation nanometer porous graphite alkene flexible electrode based on ion absorption which characterized in that: prepared by the method of claim 1.
3. The application of the ion adsorption-based controllable preparation of the nano-porous graphene flexible electrode according to claim 2 is characterized in that: the controllable preparation of the nano porous graphene flexible electrode based on ion adsorption is directly used as a negative pole piece of a rechargeable battery.
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| US20140178759A1 (en) * | 2012-12-21 | 2014-06-26 | Lawrence Livermore National Security, Llc | Graphene-supported metal oxide monolith |
| WO2015114668A2 (en) * | 2014-01-31 | 2015-08-06 | Council Of Scientific & Industrial Research | A one pot, self-assembled process for producing individual and dispersible graphene nano-spheres |
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