Graphene hybrids, methods of making graphene hybrids, batteries and methods of making batteries

Abstract

The present disclosure provides for graphene hybrid materials, methods of making graphene hybrid materials, batteries, methods of making batteries, methods of using batteries, shielding including the graphene hybrid materials, and the like. In an aspect, the graphene hybrid material is a carbon nanotube / graphene hybrid material, where the carbon nanotubes are grown on the surface of the graphene.

Description

[0001] TH 222117-2410 UVA LVG LI4-HYBRID GRAPHENE HYBRIDS, METHODS OF MAKING GRAPHENE HYBRIDS, BATTERIES AND METHODS OF MAKING BATTERIES CROSS-REFERENCE TO RELATED APPLICATION This application claims priority to U.S. provisional application entitled “System and Method for Growing Carbon Nanotubes on Graphene for High-Performance Lithium-Sulfur Batteries” having serial number 63 / 539,777 filed on September 21, 2023, which is entirely incorporated herein by reference. STATEMENT ON FUNDING PROVIDED BY THE U.S. GOVERNMENT This invention was made with government support under Grant No.1728042, awarded by the National Science Foundation. The government has certain rights in the invention. BACKGROUND High-capacity batteries, especially lithium-ion batteries, are in strong demand for electric vehicles (EVs) and stationary storage systems. However, the disposal of end-of-life Li-ion batteries causes severe pollution to the environment and produces waste products that include critical materials. In addition, Li-ion batteries are reaching their theoretical limits, so alternative types of batteries are needed. SUMMARY The present disclosure provides for graphene hybrid materials, methods of making graphene hybrid materials, batteries, methods of making batteries, methods of using batteries, shielding including the graphene hybrid materials, and the like. In an aspect, the present disclosure provides for a material comprising: a carbon nanotube (CNT) / graphene hybrid material, wherein the CNTs are bonded to a surface of the graphene, wherein a ratio of the CNT to graphene is about 1:1 to 3:1. In an aspect, the present disclosure provides for a method for producing carbon nanotube (CNT) / graphene, the method comprising: mixing a graphene solution with a catalyst to form a mixture; freeze drying the mixture to form a powder; placing the powder in a furnace, wherein the powder is adjacent a biomass in the furnace; and producing CNTs on the surface of the graphene to form CNT / graphene powder, wherein producing includes exposing the powder and biomass to a temperature of about 750 to 950 °C in the furnace for 2.5 to 3.5 hours. In an aspect, the present disclosure provides for a lithium battery, comprising: the CNT / graphene hybrid material as described above or herein, wherein the CNT / graphene TH 222117-2410 UVA LVG LI4-HYBRID hybrid material is coated on one or more of a cathode, an anode, or a separator, or wherein the CNT / graphene hybrid material is in an electrolyte mixture. In an aspect, the present disclosure provides for a lithium sulfur battery comprising: a lithium anode, and a hybrid cathode having a coating made of a sulfur impregnated CNT / graphene hybrid material, wherein a plurality of the CNTs comprise sulfur within the CNT, wherein in the CNT / graphene hybrid material is described above or herein, wherein the lithium sulfur battery has a longevity of about 1500 cycles or more, a capacity fading rate of about 0.042% per cycle, and steady Coulombic efficiency of about 97% or more. In an aspect, the present disclosure provides for a method for producing a carbon nanotube (CNT) / graphene material, the method comprising: applying an alkaline wash to a first mixture for about 1 to 3 hours at about 70 to 90 °C to remove a first portion of contaminants comprising aluminum and binders, where after separating the first portion of contaminants a second mixture is formed; applying an acid leaching solution to the second mixture to remove a second portion of contaminants comprising Co and Ni salts, Cu collectors, and a portion of Al collectors, where after separating the second portion of contaminants a third mixture is formed; applying a hydrothermal process to the third mixture to remove a third portion of contaminants comprising binders and the remaining Al to produce purified graphite; subjecting the purified graphite to a shear mixing process contemporaneously combined with a hydrogen passivation process to produce a dispersed graphene solution; mixing the dispersed graphene solution with yeast powder to form a fourth mixture; freeze drying the fourth mixture to form a powder; placing the powder in a furnace, wherein the powder is adjacent a biomass; producing CNTs on the surface of the dispersed graphene to form the CNT / graphene material, wherein producing includes exposing the powder and biomass to a temperature of 750 to 950 °C in the furnace for 2.5 to 3.5 hours; and optionally mixing the CNT / graphene material with sulfur powder and disposed in an autoclave for about 10-14 hours at a temperature of about 150-160 °C and then for about 1.5 to 3 hours at a 190 to 210 °C, wherein a sulfur impregnated carbon nanotube / graphene is formed. In an aspect, the present disclosure provides for a shielding structure comprising the CNT / graphene hybrid material as described above or herein. BRIEF DESCRIPTION OF DRAWINGS Further aspects of the present disclosure will be more readily appreciated upon review of the detailed description of its various embodiments, described below, when taken in conjunction with the accompanying drawings. Fig.1 illustrates schematic for upcycling end-of-life Li-ion battery anode graphite into graphene and growing CNTs on graphene to construct Li-S batteries. TH 222117-2410 UVA LVG LI4-HYBRID Figs.2A to 2H illustrates the characterization and modeling of upcycling graphite into graphene. Fig.2A illustrates a SEM image of recycled graphite (inset: optical image of recycled graphite) before purification. Fig.2B illustrates a SEM image of recycled graphite (inset: optical image of recycled graphite) after purification. Fig.2C illustrates a low- resolution TEM image of an upcycled graphene sheet (inset: corresponding graphene dispersed in DI water). Fig.2D illustrates a XRD spectra of recycled graphite and upcycled graphene. Fig.2A illustrates a carbon EDS map of recycled graphite after purification. Fig. 2F illustrates a high-resolution TEM image of an upcycled graphene sheet (inset: corresponding FFT image). Fig.2G illustrates a DFT calculated H+-induced spacing expansion. Fig.2H illustrates DFT calculated OH--induced spacing expansion. Figs.3A-H illustrate the characterization and modeling of growing CNTs on graphene. Fig.3A illustrates a SEM image of the CNT / graphene hybrid nanostructures (inset: CNT / graphene hybrid powders). Fig.3B illustrates a high-resolution SEM image of the CNT / graphene hybrid nanostructures. Fig.3C illustrates a TEM image of the as-obtained CNTs. Fig.3D illustrates a TEM image of the CNTs on graphene sheets. Fig.3E illustrates a high-resolution TEM image of the CNTs on graphene sheets (inset: high-resolution TEM image of the joint between the CNT and graphene). Fig.3F illustrates point elemental detections of a CNT. Fig.3G illustrates MD simulations showing CNT growth on graphene with P as the catalyst. Fig.3H illustrates number of different carbon rings of the simulated outer CNT wall layer from the MD simulations and experimentally measured carbon rings from a randomly chosen area of a CNT wall. Figs.4A to 4E illustrates the characterization of battery performance. Fig.4A illustrates a charge / discharge cycle of the CNT / graphene battery. Fig.4B illustrates CV curves of the CNT / graphene battery. Fig.4C illustrates EIS patterns of the CNT / graphene battery (inset: equivalent circuit of the patterns). Fig.4D illustrates rate performances of the CNT / graphene battery and the reference batteries. Fig.4E illustrates cycling performance of the CNT / graphene battery. Figs.5A to 5C illustrates TEM images of upcycled graphene. Fig.5A illustrates a low-resolution TEM image of a graphene sheet. Fig.5B illustrates a high-resolution TEM image of the circled area in Fig.5A. Fig.5C illustrates a low-resolution TEM image of another graphene sheet. Fig.6 illustrates a SEM image of CNTs on graphene with the synthesis temperature lower than 850 °C and the time less than 3 hours. Fig.7 illustrates a high-resolution TEM image of a single CNT. Fig.8 illustrates a XRD pattern of the CNT / graphene material. Figs.9A to 9E illustrates EDS maps of CNT buds on yeast / graphene. Fig.9A illustrates a SEM image of the CNT buds. Fig.9B illustrates a carbon map of the CNT buds. TH 222117-2410 UVA LVG LI4-HYBRID Fig.9C illustrates a potassium map of the CNT buds. Fig.9D illustrates an oxygen map of the CNT buds. Fig.9E illustrates a phosphorus map of the CNT buds. Figs.10A to 19H illustrates MD simulations of CNT growth with double-layer graphene as substrate and phosphorus as catalyst (Green: phosphorus, red: original carbon, blue: inserted carbon). Fig.10A illustrates an initial model. Fig.10B illustrates a model with 200 carbon atoms inserted. Fig.10C illustrates a model with 400 carbon atoms inserted. Fig. 10D illustrates a model with 600 carbon atoms inserted. Fig.10E illustrates a model with 800 carbon atoms inserted. Fig.10F illustrates a model with 1000 carbon atoms inserted. Fig. 10G illustrates a model with 1200 carbon atoms inserted. Fig.10H a model with 1400 carbon atoms inserted. Figs.11A to 11C illustrates MD simulations of CNT growth with double-layer graphene as substrate yet without phosphorus (Red: original carbon, blue: inserted carbon). Fig.11A illustrates an initial model. Fig.11B illustrates a model with 100 carbon atoms inserted. Fig.11C illustrates a model with 200 carbon atoms inserted. Figs.12A and 12B illustrates different types of carbon rings on a randomly chosen area of a CNT wall. Fig.12A illustrates an inverse FFT image of a defective CNT wall (inset: FFT image). Fig.12B illustrates a highlighted inverse FFT image of different carbon rings (Blue: C-pentagon, red: C-hexagon, green: C-heptagon). Figs.13A to 13F illustrates CV and EIS curves of reference batteries. Fig.13A illustrates CV curves of the commercial graphite battery at the 0th, 5th, 50th, and 200thcycles. Fig.13B illustrates CV curves of the recycled graphite battery at the 0th, 5th, 50th, and 200thcycles. Fig.13C illustrates CV curves of the upcycled graphene battery at the 0th, 5th, 50th, and 200thcycles. Fig.13D illustrates an EIS plot of the commercial graphite battery at the 0th, 5th, 50th, and 200thcycles. Fig.13E illustrates an EIS plot of the recycled graphite battery at the 0th, 5th, 50th, and 200thcycles. Fig.13F illustrates an EIS plot of the upcycled graphene battery at the 0th, 5th, 50th, and 200thcycles. Fig.14 illustrates a curve fitting patterns of the EIS data of the batteries at the 5th, 50th, and 200thcycles. Red: the commercial graphite battery; Green: the recycled graphite battery; Yellow: the upcycled graphene battery; Blue: the CNT / graphene battery. Figs.15A to 15C illustrates an EIS fitting data of all batteries. Fig.15A illustrates an internal resistance of the batteries with cycle numbers. Fig.15B illustrates a SEI impedance of the batteries with cycle numbers. Fig.15C illustrates a charge-transfer impedance of the batteries with cycle numbers. Figs.16A to 16D illustrates EDS maps of all cathodes. Fig.16A illustrates an EDS map of the sulfur-infiltrated commercial graphite cathode. Fig.16B illustrates an EDS map of the sulfur-infiltrated recycled graphite cathode. Fig.16C illustrates an EDS map of the sulfur- infiltrated upcycled graphene cathode. Fig.16D illustrates an EDS map of the sulfur- TH 222117-2410 UVA LVG LI4-HYBRID infiltrated CNT / graphene cathode. Fig.17A illustrates discharge cycling performances and Coulombic efficiencies of the batteries studied. Fig.17B illustrates the polarization potential of the CNT / graphene battery and the commercial graphite battery. DETAILED DESCRIPTION In general, the present disclosure provides for graphene hybrid materials, methods of making graphene hybrid materials, batteries, methods of making batteries, methods of using batteries, shielding including the graphene hybrid materials, and the like. Additional details are provided herein and in the Examples. This disclosure is not limited to particular embodiments described, and as such may, of course, vary. The terminology used herein serves the purpose of describing particular embodiments only, and is not intended to be limiting, since the scope of the present disclosure will be limited only by the appended claims. Where a range of values is provided, each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limit of that range and any other stated or intervening value in that stated range, is encompassed within the disclosure. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges and are also encompassed within the disclosure, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure. Embodiments of the present disclosure will employ, unless otherwise indicated, techniques of chemistry, material science, electrochemistry and the like, which are within the skill of the art. Such techniques are explained fully in the literature. The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how to perform the methods and use the compositions and compounds disclosed and claimed herein. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in °C, and pressure is at or near atmospheric. Standard temperature and pressure are defined as 20 °C and 1 atmosphere. Before the embodiments of the present disclosure are described in detail, it is to be understood that, unless otherwise indicated, the present disclosure is not limited to particular materials, reagents, reaction materials, manufacturing processes, dimensions, frequency ranges, applications, or the like, as such can vary. It is also to be understood that the terminology used herein is for purposes of describing particular embodiments only, and is TH 222117-2410 UVA LVG LI4-HYBRID not intended to be limiting. It is also possible in the present disclosure that steps can be executed in different sequence, where this is logically possible. It is also possible that the embodiments of the present disclosure can be applied to additional embodiments involving measurements beyond the examples described herein, which are not intended to be limiting. It is furthermore possible that the embodiments of the present disclosure can be combined or integrated with other measurement techniques beyond the examples described herein, which are not intended to be limiting. It should be noted that, as used in the specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a support” includes a plurality of supports. In this specification and in the claims that follow, reference will be made to a number of terms that shall be defined to have the following meanings unless a contrary intention is apparent. Prior to describing the various embodiments, the following definitions are provided and should be used unless otherwise indicated. Definitions “Biomass” can include as-products, by-products, and / or residues of the textile, forestry, and agriculture industries. Biomass includes, but is not limited to, algae, plants, trees, crops, crop residues, grasses, forest and mill residues, saw dust, wood and wood wastes, fast-growing trees, and combinations thereof. In addition, biomass can include waste products from textile production (e.g., materials not used in the end textile product like cuttings, rejected products, excess material that is not going to be used, and the like), textile products (e.g., shirts, pants, undergarments, and the like), and textile products that are intended to be recycled (e.g., shirts, pants, undergarments, and the like that have run their lifespan for a user). In particular, biomass can include cotton materials such as textile products made of cotton (e.g., cotton textile), virgin cotton, processed cotton, cotton straw, cotton waste material produced during the production of the cotton textile product, and cotton textiles that are intended to be recycled (recycled cotton), reclaimed cotton, and the like. Further biomass can include cotton fibers, bamboo fibers, wood fibers, leaf fibers, straw fibers, produced fibers, and fruit peels (e.g., banana peels and citrus peels). In a particular aspect, the biomass comprises cellulose-based fibers (e.g., cellulose fibers). Biomass may include various combinations of all of the specific biomass materials described herein. The term “cotton textile” refers to a textile fabric composed of cotton fibers or other cellulose- based fibers. In various aspects, the present disclosure includes the use of the biomass in the methods of making the CNT / graphene hybrid materials and sulfur impregnated CNT / graphene hybrid materials. The anode of a battery (e.g., lithium-ion battery) can be made of materials such as TH 222117-2410 UVA LVG LI4-HYBRID lithium insertion materials or alloy host materials (e.g., carbon-based materials (e.g., lithium- graphite intercalation compounds), lithium-silicon compounds, lithium-tin alloys, and lithium titanate Li4+xTi5O12^^ZKHUH^^^[^^^^VXFK^DV^Li4Ti5O12(LTO). The cathode of a battery (e.g., lithium-ion battery) can be made of a metal oxides such as: lithium cobalt oxide (LiCoO2) (LCO), lithium manganese oxide (LiMn2O4) (LMO), lithium nickel manganese spinel (LiNi0.5Mn1.5O4) (LMNO), lithium nickel cobalt aluminum oxide (LiNiCoAlO2) (NCA), lithium nickel cobalt manganese oxide (LiNiCoMnO2) (NMC), lithium iron phosphate (LiFePO4) (LFP), and combinations thereof. In various aspects, the present disclosure includes the use of a layer of the CNT / graphene hybrid materials and sulfur impregnated CNT / graphene hybrid materials on the surface of the cathode. The electrolyte of a battery (e.g., lithium-ion battery) can include a solution that can conduct lithium ions between the cathode and anode. A non-aqueous electrolyte solution can be an ether-based electrolyte (that is stabilized with lithium nitrite), a lithium salt dissolved in an organic solvent or a mixture of organic solvents. In an aspect, the lithium salts can include: LiClO4, LiAlCl4, LiI, LiBr, LiB(C2O4)2(LiBOB), LiBF2(C2O4) (LiODFB), LiSCN, LiBF4, LiB(C6H5)4, LiAsF6, LiCF3SO3, LiN(FSO2)2(LIFSI), LiN(CF3SO2)2(LITFSI), LiPF6, LiPF4(C2O4) (LiFOP), LiNO3, and mixtures thereof. In an aspect, the ether-based solvents can include: cyclic ethers (e.g., 1,3-dioxolane, tetrahydrofuran, 2- methyltetrahydrofuran) and chain structure ethers (e.g., 1,2-dimethoxyethane, 1-2- diethoxyethane, ethoxymethoxyethane, tetraethylene glycol dimethyl ether (TEGDME), polyethylene glycol dimethyl ether (PEGDME), and mixtures thereof). In various aspects, the present disclosure includes the use of the CNT / graphene hybrid materials and sulfur impregnated CNT / graphene hybrid materials in the electrolyte. The polymer membrane of a battery can be made of a polyolefin (e.g., polyethylene (PE), polypropylene (PP), a blend of PE and PP), polyethylene terephthalate (PET), polyvinylidene fluoride (PVdF), polyamides (Nylons), polyurethanes, polycarbonates, polyesters, polyetheretherketones (PEEK), polyethersulfones (PES), polyimides (PI), polyamide-imides, polyethers, polyoxymethylene (e.g., acetal), polybutylene terephthalate, polyethylenenaphthenate, polybutene, polyolefin copolymers, acrylonitrile-butadiene styrene copolymers (ABS), polystyrene copolymers, polymethylmethacrylate (PMMA), polyvinyl chloride (PVC), polysiloxane polymers (such as polydimethylsiloxane (PDMS)), polybenzimidazole (PBI), polybenzoxazole (PBO), polyphenylenes, polyarylene ether ketones, polyperfluorocyclobutanes, polytetrafluoroethylene (PTFE), polyvinylidene fluoride copolymers and terpolymers, polyvinylidene chloride, polyvinylfluoride, and liquid crystalline polymers. In various aspects, the present disclosure includes the use of a layer of the CNT / graphene hybrid materials and sulfur impregnated CNT / graphene hybrid materials on the surface of the separator (e.g., polymer membrane or porous polymer membrane). TH 222117-2410 UVA LVG LI4-HYBRID Discussion The present disclosure provides for graphene hybrid materials, methods of making graphene hybrid materials, batteries, methods of making batteries, methods of using batteries, shielding including the graphene hybrid materials, and the like. In an aspect, the graphene hybrid material is a carbon nanotube / graphene hybrid material, where the carbon nanotubes are grown on the surface of the graphene. Unlike other materials that separately combine graphene and carbon nanotubes in a mixture, the present disclosure provides for a material where the carbon nanotubes are grown on and are bonded (e.g., covalently) to the surface of the graphene. In other words, the carbon nanotubes and graphene are part of a single structure. The method of making the carbon nanotube / graphene hybrid material is less expensive than other methods used to independently form graphene and carbon nanotubes (e.g., chemical vapor deposition). In an aspect, the carbon nanotube / graphene hybrid material can be used in batteries (e.g., lithium-ion batteries, lithium sulfur batteries) as coatings for the cathode, the anode, and / or the separator as well as in the electrolyte. In addition, the carbon nanotube / graphene hybrid material can be used in materials for electromagnetic shielding, for example, as a shielding coating in various components (e.g., control panel, junction box, battery holding boxes or cases) for electric vehicles, hybrid electric vehicles, microelectronic devices. Example 1 describes a particular embodiment of the present disclosure in regard to lithium sulfur batteries. As described in Example 1, the present disclosure provides an all-green strategy for growing carbon nanotubes (CNTs) on graphene to form CNT / graphene hybrid material. The graphene was upcycled from end-of-life lithium-ion batteries using an upgraded, low-cost method and the CNTs were then grown directly on the graphene by pyrolyzing a biomass material (e.g., cotton) as the carbon source and yeast powder as the catalyst. Molecular dynamics (MD) simulations unveiled the seamless structure of multi-wall CNT on graphene and validated the true catalytic component in yeast powder (or other catalysts can be used as well). When being used in a Li-S battery cathode, the graphene provided a highly conductive network while the CNTs enabled high sulfur loading and volume buffering, rendering the battery with high capacity, high stability, and long lifespan. The graphene of the CNT / graphene hybrid material provided a highly conductive network while the CNTs enabled high sulfur loading and volume buffering, rendering the battery with high capacity, high stability, and long lifespan. The CNT / graphene hybrid material constructed battery exhibited longevity of over 1,500 cycles with a capacity fading rate of 0.042% per cycle and a steady Coulombic efficiency of over 97%. Such all-green CNT / graphene strategy presents new pathways to upcycling batteries to second life. Additional details are provided in Example 1. TH 222117-2410 UVA LVG LI4-HYBRID While aspects of the present disclosure are directed to batteries, such as lithium sulfur batteries, the scope of the present disclosure is not limited to that discussion and the scope of the present disclosure includes graphene hybrid materials, methods of making graphene hybrid materials, batteries (e.g., as a coating for a cathode, an anode, and / or a separator(s), or use in the electrolyte ), methods of making batteries, methods of using batteries, and in shielding. In general, lithium-ion and lithium sulfur batteries include an anode, a cathode, an electrolyte material, and a separator(s). Conventional rechargeable lithium-ion batteries operate by reversibly passing lithium-ions back and forth between the negative electrode and the positive electrode. A separator and an electrolyte may be disposed between the anode and the cathode. The electrolyte is suitable for conducting lithium-ions and may be in solid (e.g., solid state diffusion) or liquid form. Lithium-ions move from a cathode to an anode during charging of the battery, and in the opposite direction when discharging the battery. With the expanding market for lithium-ion batteries a large quantity of batteries is retired every year, which can cause hazardous waste as well as wasted resources. In an aspect, the present disclosure provides for a solution to extract components that can be used to produce graphene and others that can be recycled (e.g., Cu, Ni, Fe, Mn, Al, and cathode materials). In an aspect, the present disclosure provides for a graphene hybrid material such as a CNT / graphene hybrid material. The CNTs are grown on the surface of the graphene and are each bonded (e.g., covalently) to the surface of the graphene. The ratio of the CNT to graphene is about 1:1 to 3:1. In an aspect, the CNT can be a single walled CNT or a multi- walled CNT (e.g., about 15 to 40 walls or about 20 to 30 walls). The CNT can have an inner diameter of about 10 to 40 nm, and an outer diameter of about 20 to 60 nm, and / or a length of about 1 to 5 microns. In an aspect, the graphene can include single-layer graphene, multi-layer graphene, or both single-layer and multiplayer graphene. A single- layer graphene sheet includes carbon atoms occupying a two-dimensional hexagonal lattice (e.g., honeycomb arrangement) having a thickness of one atom, while multi- layer graphene is a platelet including of more than one graphene plane. The single-layer and multiplayer graphene can have an average edge length of about 0.5 to 2 microns or about 1 micron. In an aspect, the graphene has a (002) orientation. In an aspect, the present discourse provides for methods for producing carbon nanotube (CNT) / graphene hybrid material. The method includes mixing a graphene solution (e.g., a dispersed graphene solution) with a catalyst to form a mixture. The catalyst can include one or more of the following: yeast powder, iron nanoparticles, dipotassium phosphate (K2HPO4), or potassium dihydrogen phosphate (KH2PO4). The mixture can be freeze dried (e.g., the catalyst / graphene dispersion can be frozen at about -20° C for 12 TH 222117-2410 UVA LVG LI4-HYBRID hours and then subjected to freeze-drying for 24 hours) to form a powder. The powder is then placed in a furnace and a biomass (e.g., cotton) is positioned adjacent (e.g., about 1 centimeter to 10s of centimeters away or more) the powder. CNTs can be grown on the surface of the graphene by exposing the powder and biomass to a temperature of about 750 to 950 °C or about 850° C in the furnace for about 2.5 to 3.5 hours. As compared to chemical vapor deposition, the present disclosure provides a method that is less expensive and more efficient. In an aspect, the CNT / graphene hybrid material can be mixed with sulfur powder to form a mixture that is ultimately converted to a sulfur impregnated CNT / graphene hybrid material, where the sulfur is within the CNTs, on the surface of the CNTs, or both within the CNTs and on the surface of the CNTs. The CNT / graphene material and sulfur powder mixture can be disposed in an autoclave for about 10-14 hours at a temperature of about 150-160 °C and then for about 1.5 to 3 hours at a 190 to 210 °C, where after this time the sulfur impregnated carbon nanotube / graphene is formed. The ratio of the CNT / graphene material to the sulfur powder is about 1:1 to 1:2. In an aspect, the method can also include disposing the sulfur impregnated carbon nanotube / graphene onto aluminum foil to form an anode, a cathode, or a separator. In an aspect, the sulfur impregnated carbon nanotube / graphene can be mixed with carbon black and polyvinyl difluoride (90:5:5 ratio) to form a first slurry, where the first slurry is disposed on the aluminum foil, where the first slurry is dried on the aluminum foil for about 10 to 14 hours at about 50 to 70 °C. In an aspect, the ratio of the sulfur impregnated carbon nanotube / graphene to carbon black to polyvinyl difluoride is about 90:5:5. Having described a general method of making CNT / graphene, another method of making CNT / graphene is provided that uses lithium-ion batteries that are at the end of their life span. In an aspect, the method for producing the CNT / graphene hybrid material includes applying an alkaline wash to a first mixture for about 1 to 3 hours at about 70 to 90 °C to remove a first portion of contaminants (e.g., aluminum and binders), where after separating (e.g., aluminum and binders were partially removed, while graphite, and Co and Ni salts were separated from the mixture) the first portion of contaminants a second mixture is formed. In an aspect, the alkaline wash can include NaOH (e.g., about 3 to 5 N NaOH or about 4N NaOH). In an aspect, the first mixture includes one or more materials that comprise carbon. The first mixture can be made by smashing and / or shredding components of a Li-ion battery (e.g., anode, cathode, separator, etc.). Next, an acid leaching solution can be applied to the second mixture to remove a second portion of contaminants (e.g., Co and Ni salts, Cu collectors, manganese, sulfur, and a portion of Al collectors), where after separating (e.g., anode graphite powders were separated for further treatments.) the second portion of contaminants a third mixture is TH 222117-2410 UVA LVG LI4-HYBRID formed. The acid leaching can take 1 to 5 hours. The acid leaching can include use of a sulfuric acid solution (e.g., H2SO4) and a hydrogen peroxide solution (e.g., H2O2solution) (optionally the acid leaching can include heating the solution to 60-90° C). In an embodiment, a mixture solution of 2 molar (M) H2SO4and 37 wt. % H2O2with a volume ratio of 5:1 can be used. In another embodiment, the mixture solution may have a concentration ranging from 2M-4M H2SO4, while the concentration of H2O2can range between 30-40 wt %. For embodiments where a different concentration is utilized, the volume ratio is adjusted accordingly. For example, if a 4M H2SO4and 30 wt. % H2O2solution is used, the volume ratio is adjusted to 2:1 (e.g., instead of 5:1). After the acid leaching process is finished, the leached and expanded graphite (e.g., graphite powder) is washed with de-ionized (DI) water (or any other similar pure water) and is permitted to dry for a number of hours (e.g., overnight). Chemical impurities that are present in the second mixture can be removed by conducting the disclosed acid leaching procedure using the mixture of the sulfuric acid and hydrogen peroxide solutions. For example, chemical impurities such as cobalt, nickel, manganese, aluminum, and other byproducts can be removed from the second mixture utilizing the acid leaching mixture solution. In addition to purifying the second mixture, the acid leaching mixture solution can expand (e.g., extend, separate, and / or swell) the graphene plane layers of the purified graphite material in the third mixture. The purified graphite can have a purity of about 93% or higher (e.g., about 93 to 98%). The purified graphite can have an expansion of about 18% or higher (e.g., about 18 to 30%). Subsequently, a hydrothermal process can be applied to the third mixture to remove a third portion of contaminants (e.g., binders and the remaining Al) to produce purified graphite. The applying the hydrothermal process excludes organic solutions. In an aspect, the purified graphite is devoid (e.g., 98-100% removed) of organic binder material and aluminum after the application of the sodium hydroxide solution. The third mixture (e.g., the purified dry graphite powders (e.g., “expanded graphite”) can be mixed with a NaOH solution and subsequently well sonicated (or ultrasonicated). In an embodiment, the NaOH solution can have a concentration of about 8 M or higher. Once the third mixture is added to the NaOH solution, the resulting mixture is stirred well. In some embodiments, sonication can be used. At this stage, the resulting mixture is subjected to an alkaline hydrothermal process. For example, the mixture may be heated at a temperature of about 160 to 180 or about 180° C for about 4 to 8 hours or about 6 hours in order to eliminate the remaining organic binder material and aluminum impurities present in the graphite material. During the hydrothermal process, the graphene plane layers of the graphite can be further extended, swollen, and / or expanded. Once the hydrothermal stage purification process is completed, the obtained purified graphite is thoroughly washed with deionized TH 222117-2410 UVA LVG LI4-HYBRID water (or any other similar pure water) and permitted to air dry for a number of hours (e.g., any amount of time needed for the quantity of graphite to completely dry). The purified graphite can be subjected to a shear mixing process which can be contemporaneously combined with a hydrogen passivation process to produce a dispersed graphene solution. The purified graphite product can undergo a facile shear mixing procedure (e.g., inserting a shear mixing device into a mixture of deionized water (or any other similar pure water) and the purified graphite material) that is combined or coupled with a hydrogen passivation process. In some embodiments, the purified graphite products may be shear mixed at no less than 3600 rpm for over four hours in deionized water or pure water. Since the graphene plane layers of the graphite material have already been extended and / or expanded during the previous purification processes, the shear mixing method is able to facilitate the conversion of the purified graphite material into a high-quality graphene. More specifically, the shear mixing process effectively exfoliates layers of the graphite in order to produce a high-quality dispersed graphene. Contemporaneously a hydrogen passivation process is added to the shear mixing process, which can improve each of the graphene quality, graphene conversion rate, and graphene production efficiency (as compared to shearing alone). In some embodiments, with the assistance of the hydrogen passivation process, the graphene conversion rate can be improved from 25 wt. % to 35 wt. % or higher (i.e., where the percentage indicates the increased amount of graphite that was converted to graphene by shear mixing). In some embodiments, the hydrogen passivation process entails the application of a hydrogen gas flow to the purified graphite during the shear mixing process. For example, the purified graphite product may be shear mixed at no less than 3600 rpm for four hours in deionized water (or any other similar pure water) that is being subjected to a flow of hydrogen gas (e.g., H2gas), which effectively aerates the deionized water or pure water. In some embodiments, the applied H2gas may be produced by a reaction resulting from a combination of aluminum foil and a 2M hydrochloride acid solution (e.g., HCl solution). Alternatively, the H2gas may be provided directly from a H2gas tank or a similar source. Implementing the hydrogen passivation process in this manner improves the graphene quality by preventing graphene clusters. Further, combining the hydrogen passivation process with the shear mixing process notably produces high quality monolayer graphene. The combining and / or coupling of the shear mixing process with hydrogen passivation enhances the production of high-quality graphene. In particular, the shear mixing process effectively exfoliates the graphite while the H2gas flow further facilitates graphene exfoliation and prevents graphene agglomeration, thereby producing high quality dispersed graphene. The dispersed graphene solution can be mixed with a catalyst (e.g., yeast powder) to TH 222117-2410 UVA LVG LI4-HYBRID form a fourth mixture. The fourth mixture can be freeze dried to form a powder. In a particular embodiment, a yeast / graphene dispersion was frozen at -20 °C for 12 hours and then subjected to freeze-drying for 24 hours) After freeze drying, the freeze-dried powder can be placed in a furnace and a biomass can be placed adjacent (e.g., about 1 centimeter to 100s of centimeters) to the powder in the furnace. CNTs are grown (and bonded to) on the surface of the dispersed graphene to form the CNT / graphene hybrid material. The powder and biomass can be subjected to a temperature of 750 to 950 °C in the furnace for 2.5 to 3.5 hours to form the CNT / graphene hybrid material. In an embodiment, the CNT / graphene hybrid material can be mixed with sulfur powder and disposed in an autoclave for about 10-14 hours at a temperature of about 150- 160 °C and then for about 1.5 to 3 hours at a 190 to 210 °C, where after this time a sulfur impregnated carbon nanotube / graphene is formed. The ratio of the CNT / graphene material to the sulfur powder is about 1:1 to 1:2. In an embodiment, the method can also include disposing the sulfur impregnated carbon nanotube / graphene onto aluminum foil to form an anode, a cathode, or a separator. In an aspect, the sulfur impregnated carbon nanotube / graphene can be mixed with carbon black and polyvinyl difluoride (90:5:5 ratio) to form a first slurry, where the first slurry is disposed on the aluminum foil, wherein first slurry is dried on the aluminum foil for about 10 to 14 hours at about 50 to 70 °C. In an aspect, the ratio of the sulfur impregnated carbon nanotube / graphene to carbon black to polyvinyl difluoride is about 90:5:5. The present disclosure provides for the CNT / graphene hybrid materials and sulfur impregnated CNT / graphene hybrid materials. In an aspect, the CNT / graphene hybrid materials and sulfur impregnated CNT / graphene hybrid materials can be used in batteries such as lithium-ion batteries and lithium sulfur batteries. For example, the hybrid materials can be used as coatings on the anode, the cathode, and the separator(s) as well as in the electrolyte. In an aspect, the coating can be about 500 nm to 500 μm in thickness. In an embodiment, the present disclosure provides for a lithium-ion battery that includes a cathode, an anode, or a separator (e.g., a polymer separator such as a porous polymer separator), where one of more of these components include a layer of the CNT / graphene hybrid material and sulfur impregnated CNT / graphene hybrid material. In another aspect, the lithium-ion battery can include an electrolyte that includes the CNT / graphene hybrid material and sulfur impregnated CNT / graphene hybrid material. In another example, the present disclosure provides for a lithium sulfur battery. The lithium-ion battery includes a lithium anode and a hybrid cathode having a coating made of the sulfur impregnated CNT / graphene hybrid material. The plurality of the CNTs include sulfur within the CNT and / or on the CNT. In an aspect, the lithium sulfur battery has a TH 222117-2410 UVA LVG LI4-HYBRID longevity of about 1500 cycles or more (e.g., 1500 to 2000). In an aspect, the lithium sulfur batter has a capacity fading rate of about 0.040 to 0.044% or about 0.042% per cycle. In an aspect, the lithium sulfur batter has a steady Coulombic efficiency of about 97% or more (e.g., about 97 to 9%). In an aspect, the CNT / graphene hybrid cathode has a sulfur loading of about 60 to 70 weight percent or about 65 weight percent. In another aspect, the present disclosure provides for a shielding structure comprising the CNT / graphene hybrid material or the sulfur impregnated CNT / graphene hybrid material. For example, the shielding structure includes a layer of the CNT / graphene hybrid material, where the layer can be about 100 nanometers to millimeters or on the order of centimeters depending upon the application. The shielding structure can find use in electric vehicles, hybrid electric vehicles, and microelectronic devices. In an aspect, the CNT / graphene hybrid material can be applied to the structure that houses electronic motor parts that may be susceptible to electromagnetic interference. For example, the CNT / graphene hybrid material can be applied (e.g., sprayed, painted, poured, and the like or disposed on a material as a layer or coating (e.g., textile, aluminum foil, and the like) and the material is disposed on the housing) to the housing for electronic motor parts such as control panels, junction boxes, power converters, electric motors, batteries, traction batteries, battery interconnectors, battery enclosures, cables, transmission, sensors. The CNT / graphene hybrid material can be applied to the housing and / or in other areas to reduce EMI, where the CNT / graphene hybrid material can be applied as a coating. Now having described various features of the present disclosure, the following provides various embodiments of the present disclosure. Aspect. A material comprising: a carbon nanotube (CNT) / graphene hybrid material, wherein the CNTs are bonded to a surface of the graphene, wherein a ratio of the CNT to graphene is about 1:1 to 3:1. Aspect. The material of any of the aspects, wherein the CNT is a multi-walled CNT. Aspect. The material of any of the aspects, wherein the CNT have a diameter of about 10 to 60 nm, a length of about 1 to 5 microns, and about 20 to 30 walls. Aspect. The material of any of the aspects, wherein the graphene comprises both single-layer and multiplayer graphene with an average edge length of about 0.5 to 2 microns or about 1 micron. Aspect. The material of any of the aspects, wherein the graphene has a (002) orientation. Aspect. A method for producing carbon nanotube (CNT) / graphene, the method comprising: mixing a graphene solution with a catalyst to form a mixture; freeze drying the mixture to form a powder; TH 222117-2410 UVA LVG LI4-HYBRID placing the powder in a furnace, wherein the powder is adjacent a biomass in the furnace; and producing CNTs on the surface of the graphene to form CNT / graphene powder, wherein producing includes exposing the powder and biomass to a temperature of about 750 to 950 °C in the furnace for 2.5 to 3.5 hours. Aspect. The method of any of the aspects, wherein the catalyst is selected from the group consisting of: yeast, iron nanoparticles, dipotassium phosphate (K2HPO4), potassium dihydrogen phosphate (KH2PO4), and iron carbide. Aspect. The method of any of the aspects, wherein the biomass is selected from the group consisting of: algae, plants, trees, crops, crop residues, grasses, forest and mill residues, saw dust, wood and wood wastes, and fast-growing trees. Aspect. The method of any of the aspects, wherein the biomass material is a cotton material. Aspect. The method of any of the aspects, wherein the cotton material is virgin cotton, processed cotton, cotton straw, waste cotton, recycled cotton, reclaimed cotton, or a combination of these. Aspect. The method of any of the aspects, wherein the CNT is a multi-walled CNT. Aspect. The method of any of the aspects, wherein the CNT have an outer diameter of about 20 to 60 nm, a length of about 1 to 5 microns, and about 20 to 30 walls. Aspect. The method of any of the aspects, wherein the graphene comprises both single-layer and multiplayer graphene with an average edge length of about 1 micron. Aspect. The method of any of the aspects, wherein the graphene has a (002) orientation. Aspect. The method of any of the aspects, further providing: mixing the CNT / graphene material with sulfur powder and disposed in an autoclave for about 10-14 hours at a temperature of about 150-160 °C and then for about 1.5 to 3 hours at a 190 to 210 °C, wherein a sulfur impregnated carbon nanotube / graphene is formed. Aspect. A lithium battery, comprising: the CNT / graphene hybrid material of any of the aspects, wherein the CNT / graphene hybrid material is coated on one or more of a cathode, an anode, or a separator, or wherein the CNT / graphene hybrid material is in an electrolyte mixture. Aspect. The lithium battery of any of the aspects, wherein the CNT / graphene hybrid material is coated on two of: the cathode, the anode, or the separator. Aspect. The lithium battery of any of the aspects, wherein the CNT / graphene hybrid material is coated on the cathode. Aspect. The lithium battery of any of the aspects, wherein the CNT / graphene hybrid TH 222117-2410 UVA LVG LI4-HYBRID material is coated on the cathode. Aspect. The lithium battery of any of the aspects, wherein the CNT / graphene hybrid material is coated on the separator. Aspect. The lithium battery of any of the aspects, wherein the separator is selected from the group consisting of: a polymer membrane, a non-woven membrane, and an inorganic composite membrane. Aspect. The lithium battery of any of the aspects, wherein the CNT / graphene hybrid material is in the electrolyte mixture. Aspect. A lithium sulfur battery comprising: a lithium anode, and a hybrid cathode having a coating made of a sulfur impregnated CNT / graphene hybrid material, wherein a plurality of the CNTs comprise sulfur within the CNT, wherein in the CNT / graphene hybrid material is described of any of the aspects, wherein the lithium sulfur battery has a longevity of about 1500 cycles or more, a capacity fading rate of about 0.042% per cycle, and steady Coulombic efficiency of about 97% or more. Aspect. The lithium sulfur battery of any of the aspects, wherein the CNT / graphene hybrid cathode has a sulfur loading of about 60 to 70 weight percent. Aspect. The lithium sulfur battery of any of the aspects, wherein the CNT / graphene hybrid cathode has a concentration of about 15% to 34% of CNTs. Aspect. A method for producing a carbon nanotube (CNT) / graphene material, the method comprising: applying an alkaline wash to a first mixture for about 1 to 3 hours at about 70 to 90 °C to remove a first portion of contaminants comprising aluminum and binders, where after separating the first portion of contaminants a second mixture is formed; applying an acid leaching solution to the second mixture to remove a second portion of contaminants comprising Co and Ni salts, Cu collectors, and a portion of Al collectors, where after separating the second portion of contaminants a third mixture is formed; applying a hydrothermal process to the third mixture to remove a third portion of contaminants comprising binders and the remaining Al to produce purified graphite; subjecting the purified graphite to a shear mixing process contemporaneously combined with a hydrogen passivation process to produce a dispersed graphene solution; mixing the dispersed graphene solution with yeast powder to form a fourth mixture; freeze drying the fourth mixture to form a powder; placing the powder in a furnace, wherein the powder is adjacent a biomass; producing CNTs on the surface of the dispersed graphene to form the CNT / graphene material, wherein producing includes exposing the powder and biomass to a temperature of TH 222117-2410 UVA LVG LI4-HYBRID 750 to 950 °C in the furnace for 2.5 to 3.5 hours; and optionally mixing the CNT / graphene material with sulfur powder and disposed in an autoclave for about 10-14 hours at a temperature of about 150-160 °C and then for about 1.5 to 3 hours at a 190 to 210 °C, wherein a sulfur impregnated carbon nanotube / graphene is formed. Aspect. The method of any of the aspects, wherein the first mixture includes one or more materials that comprise carbon. Aspect. The method of any of the aspects, further comprising: smashing components of a Li-ion battery, where the components include a cathode, an anode, and separators to form the first mixture. Aspect. The method of any of the aspects, wherein the alkaline wash comprises NaOH. Aspect. The method of any of the aspects, wherein the NaOH is about 4N NaOH. Aspect. The method of any of the aspects, wherein the acid leaching solution includes a hydrogen peroxide solution and a sulfuric acid solution. Aspect. The method of any of the aspects, wherein the purified graphite has a purity of about 93% or higher., Aspect. The method of any of the aspects, wherein the purified graphite has an expansion of about 18% or higher. Aspect. The method of any of the aspects, wherein applying the hydrothermal process excludes organic solutions. Aspect. The method of any of the aspects, wherein a ratio of the CNT / graphene material to the sulfur powder is about 1:2. Aspect. The method of any of the aspects, further comprising disposing the sulfur impregnated carbon nanotube / graphene onto aluminum foil to form an cathode. Aspect. The method of any of the aspects, wherein the sulfur impregnated carbon nanotube / graphene is mixed with carbon black and polyvinyl difluoride to form a first slurry, where the first slurry is disposed on the aluminum foil, wherein first slurry is dried on the aluminum foil for about 10 to 14 hours at about 50 to 70 °C. Aspect. The method of any of the aspects, wherein a ratio of the sulfur impregnated carbon nanotube / graphene to carbon black to polyvinyl difluoride is about 90:5:5. Aspect. The method of any of the aspects, wherein the first portion of contaminants include one or more of binders and aluminum. Aspect. The method of any of the aspects, wherein the second portion of contaminants include one or more of cobalt, nickel, manganese, copper, sulfur, and aluminum. Aspect. The method of any of the aspects, wherein the third portion of contaminants TH 222117-2410 UVA LVG LI4-HYBRID include one or more of binders and aluminum. Aspect. The method of any of the aspects, wherein the purified graphite is devoid of organic binder material and aluminum after the application of the sodium hydroxide solution. Aspect. The method of any of the aspects, wherein the shear mixing process exfoliates the purified graphite. Aspect. The method of any of the aspects, wherein the hydrogen passivation process is combined with the shear mixing process by applying a hydrogen gas flow to the purified graphite during the shear mixing process. Aspect. The method of any of the aspects, wherein the biomass material is a cotton material. Aspect. The method of any of the aspects, wherein the cotton material is waste cotton, recycled cotton, cotton straw, or a combination of these. Aspect. A shielding structure comprising the CNT / graphene hybrid material of any of the aspects. Aspect. The shielding structure of any of the aspects, wherein the CNT / graphene hybrid material is a coating the shielding structure. Aspect. The shielding structure of any of the aspects, wherein the shielding structure in an electronic motor part. Aspect. The shielding structure of any of the aspects, wherein the electronic motor part is in an electronic vehicle, hybrid electronic vehicle, or microelectronic device. Aspect. The shielding structure of any of the aspects, wherein the electronic motor part is a control panel, a junction box, a cable, or a transmission. Aspect. The shielding structure of any of the aspects, wherein the shielding structure is a battery housing structure in an electronic vehicle. While embodiments of the present disclosure are described in connection with the Examples and the corresponding text and figures, there is no intent to limit the disclosure to the embodiments in these descriptions. On the contrary, the intent is to cover all alternatives, modifications, and equivalents included within the spirit and scope of embodiments of the present disclosure. EXAMPLE 1 Batteries are critical energy storage devices to decarbonizing our societies [1-3]. High-capacity batteries, especially lithium-ion batteries, are in strong demand for electric vehicles (EVs) and stationary storage systems [4-6]. However, the disposal of end-of-life Li- ion batteries not only causes severe pollution to the environment, but also throws away TH 222117-2410 UVA LVG LI4-HYBRID critical materials. Therefore, it is vital to recycle and reintegrate end-of-life batteries into the battery supply chain to meet climate change and circular economy goals and to ensure good stewardship of critical materials [7,8]. On the other hand, Li-ion batteries are reaching their theoretical limits. Lithium-sulfur (Li-S) battery is one of the most promising "post-Li-ion" energy storage systems due to its high theoretical capacity (1,672 mAh / g) and energy density (2,600 Wh / kg) [9-13]. Nevertheless, the sulfur in Li-S battery cathodes suffers from an extremely low electrical conductivity and a large volume expansion (78%) upon lithiation

[0014] . Hence, an effective framework that synergistically provides high electrical conductivity and excellent volume buffering capability is required to solve these challenges in Li-S batteries. Today’s Li-ion batteries include of lithium metal oxide cathodes, carbon (graphite) anodes, liquid electrolytes, polymer separators, and metal current collectors

[0015] . Many efforts have been focused on recovery of lithium, cobalt, and nickel from end-of-life Li-ion battery cathodes [16-18]. Compared to the cathode recycling, anode recycling has been largely overlooked. Graphite is commonly used as the anode material in Li-ion batteries and the anode graphite is considered a non-renewable resource

[0019] . Recently we upcycled anode graphite into graphene

[0020] . Graphene, a two-dimensional material made up of sheets of carbon atoms with exceptional electrical, mechanical, and thermal properties, has the potential to revolutionize industries ranging from healthcare to energy storage devices such as batteries [21,22]. However, graphene alone in Li-S batteries cannot encapsulate sulfur to increase sulfur loading and buffer volume expansion

[0023] . Carbon nanotubes (CNTs) can load more sulfur because of their tubular structure [24-26]. CNT / graphene hybrid nanostructures are anticipated to render the CNT / graphene / sulfur cathode with high conductivity and provide extra storage to load more sulfur and accommodate volume expansion. However, most of recent studies regarding CNT / graphene composites simply mixed the two materials with relatively weak connections, which limited the electrical conductivity and mechanical properties. Seamlessly growing CNTs on graphene can generate much stronger connections and natural interfaces, allowing electrons to be more freely conducted and accommodating more severe deformations such as large volume expansions. Both advantages can improve the performance of Li-S batteries. Yet, growing CNTs on graphene has been challenging and costly

[0027] . Chemical vapor deposition (CVD) is one of the most commonly adopted methods to grow CNTs on graphene, however, the cost-effectiveness of using CVD is debatable and the carbon sources are usually non-green

[0028] . Utilizing low-cost “green” feedstocks is favorable for lowering carbon emission and sustaining supply chain. Herein, we report an all-green strategy for growing carbon nanotubes (CNTs) on graphene. The graphene was upcycled from end-of-life lithium-ion batteries using an TH 222117-2410 UVA LVG LI4-HYBRID upgraded, low-cost method and the CNTs were then grown directly on the graphene by pyrolyzing cotton as the carbon source and yeast as the catalyst (Fig.1). Molecular dynamics (MD) simulations unveiled the seamless structure of multi-wall CNT on graphene and validated the true catalytic component in yeast for the first time. When being used in a Li-S battery cathode, the graphene provided a highly conductive network while the CNTs enabled high sulfur loading and volume buffering, rendering the battery with high capacity, high stability, and long lifespan. Such all-green CNT / graphene strategy presents new pathways to upcycling batteries to second life. Material and Methods End-of-Life Battery Pre-treatment End-of-life batteries were manually disassembled. The cathodes (LiCoO2, etc.) and anodes (graphite), together with separators, were collected and smashed into smaller parts. The mixture was briefly washed twice with diluted H2SO4and H2O2acids and sieved. The liquid was collected for Co and Ni recycling and the solid remnant (mixture of graphite with impurities and separators) was collected for further processing. Upcycling Graphite to Graphene End-of-life Li-ion battery anode graphite contains a large number of impurities including Cu and Al current collector scraps, remnant Co and Ni salts from cathodes, F-containing binders, and leftover S. Such graphite powders were first alkaline washed for 2 hours at 80 °C using 4N NaOH solutions to partially remove Al and binders and break remaining graphite chunks. After filtration and washing with DI water, the powders were acid leached for 2 hours at 80 °C using 4N H2SO4solution mixed with 35% H2O2solution at a volume ratio of 5:1 to remove other impurities such as Co and Ni salts, Cu collectors, and most Al collectors. Thereafter, a newly introduced alkaline hydrothermal process was conducted using 8N NaOH solutions at 160 °C for 6 hours to further remove stubborn binders and Al residuals. This step has not been reported elsewhere and can be added to existed battery recycling routines. After filtrated and dried at 80 °C for 12 hours, the powders in DI water were shear mixed at 3,600 rpm for 5 hours to produce graphene. The graphene concentration was measured to be 1 mg / mL. Growing CNTs on Graphene The graphene solution was mixed with yeast with a mass ratio of 1:15 by ultrasonication at room temperature for 20 minutes. The obtained graphene / yeast solution was then frozen for 12 hours and freeze-dried for 12 hours. The freeze-dried powders were transported to a homemade steel box and placed at one end of the box, together with a roll of 0.35 g cotton cloth at the other end (Fig.1). The steel box was transferred into a quartz tube furnace, thermally heated to and maintained at 850 °C for 3 hours with Ar flow, and then cooled down to room temperature. TH 222117-2410 UVA LVG LI4-HYBRID Battery Assembling The obtained CNT / graphene powders were mixed with sulfur powders at a mass ratio of 1:2 and transferred to an autoclave which was then thermally treated at 155 °C for 12 hours and at 200 °C for 2 hours to impregnate sulfur into the CNT / graphene powders to form CNT / graphene / S composite powders. The as-obtained powders, carbon black, and polyvinyl difluoride (PVDF) were mixed with a mass ratio of 90:5:5 in N-methyl-2-pyrrolidone (NMP) solution to produce a homogeneous slurry. The slurry was coated onto a piece of Al foil and dried at 60 °C for 12 hours. Afterward, the CNT / graphene / S coated Al foil was punched into circular disks to be used as cathodes. The reference materials including commercial graphite (Sigma-Aldrich), recycled end-of-life anode graphite, and graphene from the end-of-life anode graphite (upcycled graphene) were treated using the same procedures with the same mass ratio of sulfur to make the reference cathodes for comparison. The Li-S coin cells were assembled using the aforementioned cathodes, lithium metal anodes, and polypropylene separators (Cellgard 2400). The electrolyte was produced by dissolving 1 mol / L lithium bis(trifluoromethanesulfony)imide and 0.4 mol / L LiNO3in an organic solvent of dimethoxyethane + 1,3-dioxolane at a 1:1 vol ratio. The amount of electrolyte for each cell ZDV^^^^^ / ^ Density Functional Theory and Molecular Dynamics Calculations The QUANTUMESPRESSO software package was used to perform the density functional theory (DFT) calculations with a norm-conserving pseudopotential and with the SCAN meta-GGA exchange-correlation functional [29,30]. A gamma k-point mesh was used, and the kinetic energy cutoffs for the wave function and charge density were 30 and 300 Ry, respectively. The models were relaxed using the Broyden-Fletcher-Goldfarb-Shanno quasi- Newton algorithm

[0031] . MD calculations were conducted using the Largescale Atomic / Molecular Massively Parallel Simulator (LAMMPS)

[0032] . Models of double-layer graphene with twelve doped atoms (potassium, phosphorous, or carbon) in the center were constructed to simulate the CNT growth on graphene. The calculations were performed using the canonical ensemble (N, V, T), where the absolute temperature was raised to 1,123 K (850 °C) in 1.05 ps before successively adding carbon atoms every 5 ps. The interatomic interactions were described by the reactive force field (ReaxFF)

[0033] . Materials and Structural Characterization Scanning electron microscopy (SEM) (FEI Quanta 650 with energy-dispersive X-ray spectroscopy (EDS) detector), X-ray diffraction (XRD) (Empyrean Multipurpose X-ray GLIIUDFWRPHWHU^HTXLSSHG^ZLWK^&X^.Į^UDGLDWLRQ^^^^ ^^^^^^^^^QP^^^^DQG^WUDQVPLVVLRQ^HOHFWURQ^ microscopy (TEM) (FEI Titan Transmission Electron Microscope) were used to characterize the as-prepared CNT / graphene hybrid nanostructures, reference materials, and cathodes. Electrochemical Characterization TH 222117-2410 UVA LVG LI4-HYBRID A LAND CT2003A battery test instrument was used to conduct galvanostatic charge / discharge measurements, including cyclic performance, rate performance, and polarization potential. The polarization voltage was calculated using the following equation in the test station where is the polarization voltage,^is the terminal voltage, ^ is the current, ^^is the ohmic resistance, and^^^is the open-circuit voltage, which were measured by the test station. A CHI 660E electrochemical workstation was employed to conduct the electrochemical impedance spectroscopy (EIS) tests in the frequency range from 100 kHz through 0.01 Hz with an alternating current (AC) perturbation of 5 mV, as well as the cyclic voltammetry (CV) test from 1.5 V to 2.8 V with a scan rate of 0.0001 V / s. Zview software was applied to perform the curve-fitting on the EIS test data. Results and Discussion Upcycling Anode Graphite into Graphene Anode graphite often has impurities consisting of Co, S, Mn, Ni, F, Al, and Si (Table S1, supporting information). The alkaline and acid leaching treatments removed most impurities of Co, S, Mn, Ni, and Si. Follow-up, novel alkaline hydrothermal treatment with concentrated NaOH further eliminated stubborn aluminum and binders without using expensive organic solutions, which highly increases the cost, or high-temperature treatment

[0034] , which makes exfoliation harder by compressing graphite structure, enabling the graphite with a purity of more than 94% and swollen structure (Fig.2). This novel step has not been reported elsewhere and can be added to existed recycling process to achieve high-purity graphite and certain applications (eg. high-quality graphene production). With the assistance of both hydrogen ions and hydroxide ions, the carbon layer spacing in the treated graphite expanded from 0.336 nm to 0.402 nm (19.64% expansion) (Fig.5, supporting information), which facilitated the shear mixing exfoliation of the graphite into graphene (Fig.2c). The same carbon layer spacing has also been found by Zhang et al., where an expansion of 14.7% was experimentally observed

[0020] . The as-obtained graphene consists of both single- layer and multilayer graphene with an average edge length of 1 micron. XRD inspection (Fig. 2d) revealed graphite (002) peaks from both recycled graphite and the graphene derived from it (upcycled graphene), indicating the high purity of the obtained graphene. High- resolution TEM imaging (Fig.2f and Fig.5C, supporting information) reveals the high-quality upcycled graphene with (002) orientation

[0035] . The Li-ion intercalation and deintercalation in battery cycling expanded the carbon layers of the anode graphite, and the acid / alkaline leaching of recycled graphite further expanded the layers

[0020] . The expanded layers enable more efficient exfoliations to harvest TH 222117-2410 UVA LVG LI4-HYBRID graphene. To study the phenomenon, a set models consisting of H+, OH-, and graphene layers were established for the density functional theory (DFT) study. The H+and OH- ions are able to insert into the space between two carbon layers, leading to 14.78% spacing expansion (from 4.343 Å to 4.985 Å) due to the H+insertion (Fig.2g) and 25.67% expansion (from 4.343 Å to 5.458 Å) from the OH- insertion (Fig.2h). This explains the experimentally observed 19.64% expansion resulting from the acid / alkaline leaching and alkaline hydrothermal treatments. Greenly Growing CNTs on Graphene Pyrolysis was employed to grow CNTs on the upcycled graphene (Fig.1). Graphene / yeast powders were obtained by adding yeast into graphene solution and freeze- drying the solution. The powders were placed into a homemade steel box together with a roll of cotton cloth (or other biomass materials) to provide gaseous carbon during pyrolysis. Such eco-friendly approach to growing CNTs on graphene produced less carbon emission than other CNT growth methods (Table S2, supporting information). SEM inspection (Fig.3a and 3b) revealed that graphene sheets were fully covered with CNTs. It is worth noting that without yeast or without the cotton cloth, no CNTs were observed on the graphene after pyrolysis under the same conditions, suggesting that yeast is essential for CNT growth as catalyst instead of carbon sources. In addition, if pyrolysis temperature was below 850 °C and / or pyrolysis time was less than 3 hours, CNTs were not fully developed (Fig.6, supporting information). Tubular CNTs (Fig.3c) provide storage room for sulfur loading. HRTEM inspection unveiled that the CNTs have diameters of 20 – 60 nm and lengths of several microns with 20 – 30 wall layers (Fig.7, supporting information). XRD inspection (Fig.8, supporting information) revealed that the CNT / graphene hybrid nanostructures are of high purity without preferred orientation. TEM imaging (Fig.3d and 3e) revealed that the CNTs grew seamlessly on the graphene with the base of concentric carbon rings which were validated by MD simulations (Fig.3h). This CNT / graphene hybrid nanostructures provide unobstructed paths for electron and ion transportation, enabling superlative electrical conductivity. The CNT growth started with carbon buds where K and P were detected (Fig.9, supporting information). K was thought as the main catalytic element in yeast, whereas P was suspected to be irrelevant in the catalytic process since it was homogeneously distributed

[0036] . To explore the function of P, point elemental detections were conducted along individual CNTs (Fig.3f). Clearly, both K and P are proportional to the distance from the tips of the CNTs, indicating that not only K but also P could have provided catalytic functions to the CNT growth. Moreover, the concentrations of K and P have a constant atomic ratio of around 1.5:1, and no other element was detected except for C and O. Therefore, it is rational to believe that the true catalyst in yeast is a mixture of K2HPO4and TH 222117-2410 UVA LVG LI4-HYBRID KH2PO4with K to P atomic ratio of 1.5:1, which are commonly used in yeast production

[0037] . Since K2HPO4and KH2PO4both have low melting points, during the catalytic process, they melted on the graphene sheet surface to provide beds for carbon atoms to deposit and precipitate out into tubular CNTs. A study

[0038] suggests that tubular CNTs are usually synthesized when catalysts are in the liquid form whereas bamboo-like CNTs are formed when catalysts are in the solid form. The obtained CNTs (Fig.3c) exhibited tubular structure, suggesting that the catalysts were in liquid form when the reaction happened, which explained why solid catalyst particles were not found in the obtained CNTs. MD simulations (Fig.10, supporting information) unveiled that only P was able to stimulate CNT growth, suggesting that P probably provided the catalytic function whereas K could serve other functions. This conclusion is reported for the first time and different from the previous study, where K was considered the catalyst

[0036] . It is worth noticing that the catalytic function of P only happens when P is doped in the graphene matrix. The P doping can be evidenced by the X-ray photoelectron spectroscopy (XPS) data published elsewhere, where a peak between the C-O peak (286.2 eV) and the C-C peak (284.7 eV) was neglected by the author, which related to the C-P bond

[0039] . Therefore, the CNT growth can be grouped into four stages: 1) P-containing salts from yeast were deposited on graphene, 2) P- containing salts melted when temperature rose up, 3) P doped into the graphene matrix after melting, and 4) doped P atoms captured carbon atoms from the carrier gas to form CNTs. When only carbon atoms were used in the model (a control model), no CNT formed, suggesting that only P-doped graphene can stimulate CNT growth (Fig.11, supporting information). As an example, the twelve P atoms in graphene matrix yielded a multilayer CNT (Fig.3g). Most P atoms remained at the bottom of the CNT as experimentally observed (Fig.3f). Sectional views (Fig.3g) showed a series of similar concentric rings, which were also experimentally seen under TEM (Fig.3e). The CNT walls consist mostly of C-hexagons (126) with a small number of C-pentagons (47) and C-heptagons (26) (Fig.3h). An inverse FFT (IFFT) image of the as-grown CNT (Fig.12 supporting information) exhibited a similar structure that contained 239 C-hexagons and 33 C-pentagons and 27 C-heptagons (Fig.3h), which are in consistent with the simulation results. Electrochemical Characterization and Discussion The CNT / graphene hybrid nanostructures loaded with sulfur was used to construct the Li-S battery cathode with a piece of polypropylene separator and a piece of Li metal anode. For comparison, commercial graphite, recycled graphite, and upcycled graphene were also loaded with sulfur to construct reference Li-S battery cathodes. The CNT / graphene battery showed a typical charge / discharge cycle with obvious double stages during discharge at a current rate of 0.5 C (Fig.4a). During discharging, four stages were observed denoting I through IV to describe the transformation of solid sulfur to S82-(stage I), S82-to S62-and S42- TH 222117-2410 UVA LVG LI4-HYBRID (stage II), S42-to Li2S2(stage III), and Li2S2to Li2S (stage IV). For charging, three stages appear to occur denoting V, VI, and VII to exposit the conversion of Li2S to low-order polysulfides (stage V), low-order to high-order polysulfides (stage VI), and high-order polysulfides to solid sulfur (stage VII). These stages can be corresponded to the peaks in the CV curves of the CNT / graphene battery (Fig.4b). The CV tests were carried out on the CNT / graphene battery (Fig.4b) and the reference batteries (Fig.13A, B, and C supporting information) before cycling, at the 5thcycle, 50thcycle, and 200thcycle. All CV curves possess two peaks in the cathodic curve and one peak in the anodic curve without any abnormal peaks, indicating common Li-S battery cycling behaviors without side reactions. The peaks (1) and (2) in the cathodic curve correspond respectively to the second plateau (stage III) and the first plateau (stage I) in the typical charge / discharge cycle. The peaks (3) in the anodic curve correspond to stages V and VI in the typical charge / discharge cycle. The peak intensities of the CNT / graphene battery first drastically decrease and then increase, which matches the battery cycling performance (Fig. 4e). Comparing the peak positions and intensities of all the batteries, the CNT / graphene battery is comparable with the commercial graphite battery, and better than the recycled graphite battery and the upcycled graphene battery. This is probably because the structure of the CNT / graphene hybrid was restored during the high-temperature treatment, which enabled better stability than the recycled graphite and upcycled graphene. EIS testing was conducted on the CNT / graphene battery (Fig.4c) and the reference batteries (Fig.13D, E, and F supporting information) to further study the functionality of CNT / graphene hybrid in its Li-S battery. All EIS tests were performed when the batteries were fully charged. For each battery, the impedance data before cycling, at the 5thcycle, 50thcycle, and 200thcycle were studied. Most EIS patterns, including the test on batteries before cycling, exhibited two semicircles at the high-frequency regime and intermediate-frequency regime and a straight line at the low-frequency regime. All newly assembled batteries were stood for 6 hours before testing, during which solid electrolyte interface (SEI) started to form. This was the reason for several fresh batteries showing the two-semicircle pattern. The intercept between the first semicircle and the x-axis can be denoted as Rint, which is the internal resistance contributed by the electrodes, the electrolyte, and the interfaces between them. The first semicircle at the high-frequency regime can be noted as a resistor and a capacitor, where the resistor can be written as RSEI, which is the resistance of Li ions passing through the SEI. The second semicircle at the intermediate-frequency regime can also be identified as a resistor and a capacitor, of which the resistor is known as Rct, which is the charge-transfer resistance. Both resistances can be obtained by calculating the diameters of the semicircles. The straight line at the low-frequency regime is the Warburg impedance, which corresponds to the ion diffusion-limited condition. All batteries exhibited TH 222117-2410 UVA LVG LI4-HYBRID big semicircles before cycling, indicating the existence of passivation layers on some of the Li metal anodes blocking Li-ions and electrons. After cycling, the semicircles largely diminished, illustrating the removal of these passivation layers. Overall, the CNT / graphene battery exhibited the surprisingly low and stable RSEIcomparing with the rest of the batteries, meaning that the formation of SEI on CNT / graphene cathode was efficient and of high quality. The comparable Rintand RCTof the CNT / graphene battery with the commercial graphite battery also illustrated the good electrochemical quality of the CNT / graphene material. Table 1. Curve fit data of EIS tests. To quantify impedance changes, curve fitting was performed to the EIS data at the 5thcycle, 50thcycle, and 200thcycle (Fig.14, supporting information), and the results are summarized in Table 1. All Rintvalues (Fig.15A, supporting information) are stable and similar, indicating that the CNT / graphene would not increase the internal resistance. The RSEIvalues (Fig.15B, supporting information) were calculated following

[0040] , where ^ is the conductivity of the SEI layer, ^ is the thickness, and ^ is the surface area. All batteries had similar SEI conductivities and thicknesses since they all used the same electrolyte and active materials, indicating that the RSEIis inversely proportional to the surface area. Compared with graphene-based batteries, the commercial graphite battery and recycled graphite battery exhibited higher RSEIbecause graphite has smaller surface area than graphene. Between the graphene-based batteries, the upcycled graphene battery has higher RSEIthan the CNT / graphene battery because the CNTs contributed extra surface areas. The recycled graphite battery and upcycled graphene battery exhibited significant RSEILQVWDELOLW\^^^^^^^^ȍ^WR^^^^^^^ȍ^WR^^^^^^^ȍ^^DQG^^^^^^^^ȍ^WR^^^^^^^ȍ^WR^^^^^^ȍ^^^ respectively, which could be ascribed to that both recycled graphite and upcycled graphene were structurally damaged due to previous battery operations and recycling / upcycling process. Therefore, the SEI layers formed on the recycled graphite and upcycled graphene were unstable, leading to the observed variations. The high-temperature treatments were able to heal the damaged structure as seen in the CNT / graphene battery which did not show such variation. These conclusions can also be used to explain the Coulombic efficiency of TH 222117-2410 UVA LVG LI4-HYBRID the batteries, which will be discussed in the cycling performance section. The Rctvalues (Fig. 15C, supporting information) were calculated following

[0041] , where ^ is the molar gas constant, ^ is the absolute temperature, ^ is the Faraday constant, ^ is the total electroactive surface area, ^^is the standard exchange rate constant, and ^ is the intercalation level. As all the batteries were in fully charged status, they had similar ^ (approaching 0) and ^values. Therefore, the only changeable term is the total electroactive surface area ^, which is related to the passivation layer thickness and potential difference. In most observed cases, the Rctvalues slightly decreased and then slightly increased because the passivation layers on the electrodes were thinner (higher ^) in the initial stabilization stage and then became thicker (lower ^) in the accumulation stage. However, the upcycled graphene battery and the CNT / graphene battery showed an initial increase and then decrease in Rct, which was probably ascribed to the uneven distribution of the passivation layers, resulting in an abnormally low value. The uneven distribution of the passivation layers in turn led to large polarizations in these two batteries, which were seen in their CV patterns. Rate abilities of all the batteries were tested after running 100 cycles for stabilization. Current rates of 0.2 C, 0.4 C, 0.8 C, and 1.6 C were used in this study (Fig.4d). Among all batteries, the recycled graphite battery exhibited the highest retention rate (64.54% from 649.836 mAh g-1to 419.418 mAh g-1) when the current rate was octupled from 0.2 C to 1.6 C because the layers that were previously expanded before recycling were able to tolerate large sulfur volume expansion even at a high current rate

[0042] . The upcycled graphenebattery showed the lowest retention rate (36.12% from 701.185 mAh g-1 to 253.271 mAh g-1)when the same current rate increment was applied. This was because graphene could not buffer sulfur volume change [23,43]. The CNT / graphene battery revealed a retention rate of 57.33% from 737.88 mAh g-1to 423 mAh g-1, which is higher than the commercial graphite battery (53.14% from 539.64 mAh g-1to 286.752 mAh g-1). This indicates that CNTs on graphene were able to accommodate sulfur volume expansion more effectively than pure graphite [44,45]. Additionally, the CNT / graphene battery exhibited higher specific capacities than other batteries since the CNTs were capable of loading more sulfur. The specific capacities of all the batteries were fully recovered when the operation rate returned to 0.8 C. The CNT / graphene battery with a sulfur loading of 2.18 mg cm-2(64.9 wt%) exhibited an initial discharge capacity of 1,151.2 mAh g-1with a lifespan over 1,500 times at a current rate of 0.5 C (Fig.4e). For comparison, the commercial graphite battery, recycled graphite battery, and upcycled graphene battery with respective sulfur loading of 1.84 mg cm-2(44.6 wt%), 1.87 mg cm-2(43.2 wt%), and 2.13 mg cm-2(47.7 wt%) were also tested (Fig.16, TH 222117-2410 UVA LVG LI4-HYBRID supporting information). The initial capacities were found to be proportional to the sulfur contents in the electrodes (Fig.17A, supporting information). It is worth noting that all the carbon-based cathode materials were mixed with the same amount of sulfur with a carbon / sulfur mass ratio of 1:2, yet only the CNT / graphene hybrid could achieve 64.9 wt% sulfur loading whereas others could only hold no more than 48 wt% sulfur. This indicates that the CNTs on graphene provided extra room to load more sulfur. As the result, the commercial graphite battery failed at the 926thcycle, which is much longer than the recycled graphite battery’s 405 cycles and the upcycled graphene battery’s 519 cycles, yet shorter than the CNT / graphene’s 1,500 cycles. Upon growing CNTs on graphene, the graphene’s defects were healed and the CNTs were able to accommodate sulfur volume change, jointly rendering the battery with a much longer lifespan. Comparing with other CNT / graphene Li-S batteries, our 1,500-cycle lifespan is still the longest (Table S3, supporting information). The commercial graphite battery and CNT / graphene battery were found to be more stable than the recycled graphite battery and the upcycled graphene battery. The CNT / graphene battery exhibited a capacity fading rate of only 0.042% per cycle, which is lower than the commercial graphite battery (0.047% per cycle), the recycled graphite battery (0.188% per cycle), and the upcycled graphene battery (0.090% per cycle). This result is also better than most of the CNT / graphene Li-S batteries (Table S3, supporting information). The Coulombic efficiency revealed intriguing findings. The Coulombic efficiency is largely related to the distribution of Li ions during operation, which are one of the necessary ions to form SEI layers

[0046] . Owing to the damaged structures of the cathodes in the recycled graphite battery and the upcycled graphene battery, the SEI layers on the cathodes were also unstable, leading to lower and more fluctuated Coulombic efficiencies than the commercial graphite battery and CNT / graphene battery, in consistent with the RSEIresults from the EIS section, where the RSEIvalues of the recycled graphite battery and upcycled graphene battery were varied with cycle number. Additionally, because the CNT / graphene battery has the lowest RSEI, its Coulombic efficiency was the highest and maintained above 97% during its entire lifespan. Polarization potentials of the CNT / graphene battery and the commercial graphite battery were collected to evaluate the level of polarization within these batteries (Fig. S13b, supporting information). A large polarization of 0.64 V was detected at the first cycle of the commercial graphite battery, which is much larger than that of the CNT / graphene battery’s 0.34 V. During the entire lifetime of the commercial graphite battery, the polarization was also stronger than the CNT / graphene battery, which indicated that the reaction rate and the ion diffusion rate in the electrolyte of the CNT / graphene battery were much higher than the commercial graphite battery. This evidenced that the CNT / graphene composite possessed better interfaces to facilitate sulfur reactions and connect the sulfur and the electrolyte, agreeing well with the expected functionality of the CNT / graphene hybrid. TH 222117-2410 UVA LVG LI4-HYBRID Conclusion End-of-life Li-ion battery anode graphite found its second life in Li-S battery cathodes by upcycling the anode graphite into graphene which was then used as the substrate to grow CNTs by pyrolyzing cotton as the carbon source and yeast as the catalyst to form CNT / graphene nanostructures. In the sulfur infiltrated CNT / graphene cathodes, the graphene provided a highly conductive network while the CNTs enabled high sulfur loading and volume buffering, rendering the battery with high capacity, high stability, and long lifespan. Additionally, the CNT / graphene nanostructures should find applications in an extensive range of fields such as reinforcements in composites. The all-green CNT / graphene hybrids present new pathways to circular economy. Reference [1] D. D. Lecce, R. Verrelli, and J. Hassoun, Lithium-Ion Batteries for Sustainable Energy Storage: Recent Advances towards New Cell Configurations, Green Chem.19 (2017) 3442-3467. [2] C. Friebe, A. Lex-Balducci, and U. S. Schubert, Sustainable Energy Storage: Recent Trends and Developments toward Fully Organic Batteries, ChemSusChem 12 (2019) 4093-4115. https: / / doi.org / 10.1002 / cssc.201901545 [3] A. R. Dehghani-Sanij, E. Tharumalingam, M. B. Dusseault, and R. Fraser, Study of Energy Storage Systems and Environmental Challenges of Batteries, Renew. Sust. Energ. Rev.109 (2019) 192-208. https: / / doi.org / 10.1016 / j.rser.2019.01.023 [4] F. H. Gandoman, J. Jaguemont, S. Goutam, R. Gopalakrishnan, Y. Firouz, T. Kalogiannis, N. Omar, and J. V. Mierlo, Concept of Reliability and Safety Assessment of Lithium-Ion Batteries in Electric Vehicles: Basics, Progress, and Challenges, Appl. Energy 251 (2019) 113343. https: / / doi.org / 10.1016 / j.apenergy.2019.113343 [5] A. Eftekhari, Lithium Batteries for Electric Vehicles: from Economy to Research Strategy, ACS Sustain. Chem. Eng.7 (2019) 5602-5613. https: / / doi.org / 10.1021 / acssuschemeng.8b01494 [6] X. Zeng, M. Li, D. A. El-Hady, W. Alshitari, A. S. Al-Bogami, J. Lu, and K. Amine, Commercialization of Lithium Battery Technologies for Electric Vehicles, Adv. Energy Mater.9 (2019) 1900161. https: / / doi.org / 10.1002 / aenm.201900161 [7] G. Harper, R. Sommerville, E. Kendrick, L. Driscoll, P. Slater, R. Stolkin, A. Walton, P. Christensen, O. Heidrich, S. Lambert, A. Abbott, K. Ryder, L. Gaines, and P. Anderson, Recycling Lithium-Ion Batteries from Electric Vehicles, Nature 575 (2019) 75-86. [8] E. Fan, L. Li, Z. Wang, J. Lin, Y. Huang, Y. Yao, R. Chen, and F. Wu, Sustainable Recycling Technology for Li-Ion Batteries and Beyond: Challenges and Future TH 222117-2410 UVA LVG LI4-HYBRID Prospects, Chem. Rev.120 (2020) 7020-7063. https: / / doi.org / 10.1021 / acs.chemrev.9b00535 [9] Y. Song, W. Cai, L. Kong, J. Cai, Q. Zhang, and J. Sun, Rationalizing Electrocatalysis of Li–S Chemistry by Mediator Design: Progress and Prospects, Adv. Energy Mater.10 (2020) 1901075. https: / / doi.org / 10.1002 / aenm.201901075

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[0020] J. He, Y. Chen, P. Li, F. Fu, Z. Wang, and W. Zhang, Three-dimensional CNT / graphene–sulfur hybrid sponges with high sulfur loading as superior-capacity cathodes for lithium–sulfur batteries, J. Mater. Chem. A 36 (2015) 18605-18610. https: / / doi.org / 10.1039 / C5TA04445F It should be noted that ratios, concentrations, amounts, and other numerical data may be expressed herein in a range format. It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate, a concentration range of “about 0.1 percent to about 5 percent” should be interpreted to include not only the explicitly recited concentration of about 0.1 weight percent to about 5 weight percent but also include individual concentrations (e.g., 1 percent, 2 percent, 3 percent, and 4 percent) and the sub-ranges (e.g., 0.5 percent, 1.1 percent, 2.2 percent, 3.3 percent, and 4.4 percent) TH 222117-2410 UVA LVG LI4-HYBRID within the indicated range. The term “about” can include traditional rounding according to significant figures of the numerical value. In addition, the phrase “about ‘x’ to ‘y’” includes “about ‘x’ to about ‘y’”. Many variations and modifications may be made to the above-described aspects. All such modifications and variations are intended to be included herein within the scope of this disclosure and protected by the following claims.

Claims

TH 222117-2410 UVA LVG LI4-HYBRID CLAIMS What is claimed:

1. A material comprising: a carbon nanotube (CNT) / graphene hybrid material, wherein the CNTs are bonded to a surface of the graphene, wherein a ratio of the CNT to graphene is about 1:1 to 3:

1.

2. The material of claim 1, wherein the CNT is a multi-walled CNT.

3. The material of claims 1 or 2, wherein the CNT have a diameter of about 10 to 60 nm, a length of about 1 to 5 microns, and about 20 to 30 walls.

4. The material of claims 1 or 2, wherein the graphene comprises both single-layer and multiplayer graphene with an average edge length of about 0.5 to 2 microns or about 1 micron.

5. The material of claim 1, wherein the graphene has a (002) orientation.

6. A method for producing carbon nanotube (CNT) / graphene, the method comprising: mixing a graphene solution with a catalyst to form a mixture; freeze drying the mixture to form a powder; placing the powder in a furnace, wherein the powder is adjacent a biomass in the furnace; and producing CNTs on the surface of the graphene to form CNT / graphene powder, wherein producing includes exposing the powder and biomass to a temperature of about 750 to 950 °C in the furnace for 2.5 to 3.5 hours.

7. The method of claim 6, wherein the catalyst is selected from the group consisting of: yeast, iron nanoparticles, dipotassium phosphate (K2HPO4), potassium dihydrogen phosphate (KH2PO4), and iron carbide.

8. The method of claim 6, wherein the biomass is selected from the group consisting of: algae, plants, trees, crops, crop residues, grasses, forest and mill residues, saw dust, wood and wood wastes, and fast-growing trees.

9. The method of claim 6, wherein the biomass material is a cotton material.TH 222117-2410 UVA LVG LI4-HYBRID 10. The method of claim 9, wherein the cotton material is virgin cotton, processed cotton, cotton straw, waste cotton, recycled cotton, reclaimed cotton, or a combination of these.

11. The method of claim 6, wherein the CNT is a multi-walled CNT.

12. The method of claim 11, wherein the CNT have an outer diameter of about 20 to 60 nm, a length of about 1 to 5 microns, and about 20 to 30 walls.

13. The method of claim 12, wherein the graphene comprises both single-layer and multiplayer graphene with an average edge length of about 1 micron.

14. The method of claim 13, wherein the graphene has a (002) orientation.

15. The method of claim 6, further providing: mixing the CNT / graphene material with sulfur powder and disposed in an autoclave for about 10-14 hours at a temperature of about 150-160 °C and then for about 1.5 to 3 hours at a 190 to 210 °C, wherein a sulfur impregnated carbon nanotube / graphene is formed. 16 A lithium battery, comprising: the CNT / graphene hybrid material of anyone of claims 1 to 5, wherein the CNT / graphene hybrid material is coated on one or more of a cathode, an anode, or a separator, or wherein the CNT / graphene hybrid material is in an electrolyte mixture.

17. The lithium battery of claim 16, wherein the CNT / graphene hybrid material is coated on two of: the cathode, the anode, or the separator.

18. The lithium battery of claim 17, wherein the CNT / graphene hybrid material is coated on the cathode.

19. The lithium battery of claim 18, wherein the CNT / graphene hybrid material is coated on the separator.

20. The lithium battery of claim 17, wherein the CNT / graphene hybrid material is coated on the separator.

21. The lithium battery of claim 20, wherein the separator is selected from the groupTH 222117-2410 UVA LVG LI4-HYBRID consisting of: a polymer membrane, a non-woven membrane, and an inorganic composite membrane.

22. The lithium battery of claim 17, wherein the CNT / graphene hybrid material is in the electrolyte mixture.

23. A lithium sulfur battery comprising: a lithium anode, and a hybrid cathode having a coating made of a sulfur impregnated CNT / graphene hybrid material, wherein a plurality of the CNTs comprise sulfur within the CNT, wherein in the CNT / graphene hybrid material is described in any of claims 1 to 5, wherein the lithium sulfur battery has a longevity of about 1500 cycles or more, a capacity fading rate of about 0.042% per cycle, and steady Coulombic efficiency of about 97% or more.

24. The lithium sulfur battery of claim 23, wherein the CNT / graphene hybrid cathode has a sulfur loading of about 60 to 70 weight percent.

25. The lithium sulfur battery of claim 23, wherein the CNT / graphene hybrid cathode has a concentration of about 15% to 34% of CNTs.

26. A method for producing a carbon nanotube (CNT) / graphene material, the method comprising: applying an alkaline wash to a first mixture for about 1 to 3 hours at about 70 to 90 °C to remove a first portion of contaminants comprising aluminum and binders, where after separating the first portion of contaminants a second mixture is formed; applying an acid leaching solution to the second mixture to remove a second portion of contaminants comprising Co and Ni salts, Cu collectors, and a portion of Al collectors, where after separating the second portion of contaminants a third mixture is formed; applying a hydrothermal process to the third mixture to remove a third portion of contaminants comprising binders and the remaining Al to produce purified graphite; subjecting the purified graphite to a shear mixing process contemporaneously combined with a hydrogen passivation process to produce a dispersed graphene solution; mixing the dispersed graphene solution with yeast powder to form a fourth mixture; freeze drying the fourth mixture to form a powder; placing the powder in a furnace, wherein the powder is adjacent a biomass; producing CNTs on the surface of the dispersed graphene to form the CNT / graphene material, wherein producing includes exposing the powder and biomass to a temperature ofTH 222117-2410 UVA LVG LI4-HYBRID 750 to 950 °C in the furnace for 2.5 to 3.5 hours; and optionally mixing the CNT / graphene material with sulfur powder and disposed in an autoclave for about 10-14 hours at a temperature of about 150-160 °C and then for about 1.5 to 3 hours at a 190 to 210 °C, wherein a sulfur impregnated carbon nanotube / graphene is formed.

27. The method of claim 26, wherein the first mixture includes one or more materials that comprise carbon.

28. The method of claim 26, further comprising: smashing components of a Li-ion battery, where the components include a cathode, an anode, and separators to form the first mixture.

29. The method of claim 26, wherein the alkaline wash comprises NaOH.

30. The method of claim 26, wherein the NaOH is about 4N NaOH.

31. The method of claim 26, wherein the acid leaching solution includes a hydrogen peroxide solution and a sulfuric acid solution.

32. The method of claim 26, wherein the purified graphite has a purity of about 93% or higher., 33. The method of claim 26, wherein the purified graphite has an expansion of about 18% or higher.

34. The method of claim 26, wherein applying the hydrothermal process excludes organic solutions.

35. The method of claim 26, wherein a ratio of the CNT / graphene material to the sulfur powder is about 1:

2.

36. The method of claim 26, further comprising disposing the sulfur impregnated carbon nanotube / graphene onto aluminum foil to form a cathode.

37. The method of claim 36, wherein the sulfur impregnated carbon nanotube / graphene is mixed with carbon black and polyvinyl difluoride to form a first slurry, where the first slurryTH 222117-2410 UVA LVG LI4-HYBRID is disposed on the aluminum foil, wherein first slurry is dried on the aluminum foil for about 10 to 14 hours at about 50 to 70 °C.

38. The method of claim 37, wherein a ratio of the sulfur impregnated carbon nanotube / graphene to carbon black to polyvinyl difluoride is about 90:5:

5.

39. The method of claim 36, wherein the first portion of contaminants include one or more of binders and aluminum.

40. The method of claim 39, wherein the second portion of contaminants include one or more of cobalt, nickel, manganese, copper, sulfur, and aluminum.

41. The method of claim 40, wherein the third portion of contaminants include one or more of binders and aluminum.

42. The method of claim 36, wherein the purified graphite is devoid of organic binder material and aluminum after the application of the sodium hydroxide solution.

43. The method of claim 36, wherein the shear mixing process exfoliates the purified graphite.

44. The method of claim 36, wherein the hydrogen passivation process is combined with the shear mixing process by applying a hydrogen gas flow to the purified graphite during the shear mixing process.

45. The method of claim 36, wherein the biomass material is a cotton material.

46. The method of claim 45, wherein the cotton material is waste cotton, recycled cotton, cotton straw, or a combination of these.

47. A shielding structure comprising the CNT / graphene hybrid material of claims 1 to 5.

48. The shielding structure of claim 47, wherein the CNT / graphene hybrid material is a coating the shielding structure.

49. The shielding structure of claim 47, wherein the shielding structure in an electronic motor part.TH 222117-2410 UVA LVG LI4-HYBRID 50. The shielding structure of claim 49, wherein the electronic motor part is in an electronic vehicle, hybrid electronic vehicle, or microelectronic device.

51. The shielding structure of claim 50, wherein the electronic motor part is a control panel, a junction box, a cable, or a transmission.

52. The shielding structure of claim 50, wherein the shielding structure is a battery housing structure in an electronic vehicle.

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