WO2019079723A2 - Layered lithium-oxygen cathodes - Google Patents

Abstract

Provided herein are "sandwich stacked" lithium-oxygen cathodes and processes of manufacturing and using the same.

Description

LAYERED LITHIUM-OXYGEN CATHODES

CROSS-REFERENCE

[0001] This application claims the benefit of U.S. Provisional Application No. 62/574,460 filed 19 October 2017, which is incorporated herein by reference in its entirety. BACKGROUND OF THE INVENTION

[0002] Batteries comprise one or more electrochemical cell, such cells generally comprising a cathode, an anode and an electrolyte. Lithium ion batteries are high energy density batteries that are fairly commonly used in consumer electronics and electric vehicles. In lithium ion batteries, lithium ions generally move from the negative electrode to the positive electrode during discharge and vice versa when charging. In the as-fabricated and discharged state, lithium ion batteries often comprise a lithium compound (such as a lithium metal oxide) at the cathode (positive electrode) and another material, generally carbon, at the anode (negative electrode).

[0003] Lithium-air or lithium-oxygen batteries (LOB) widely known for its high theoretical energy density stand in the spotlight of world with an expectation that it could promote electric vehicles or high grid energy storages to the next level. Attempts are being made by scientists to overcome the obstacles of LOBs such as low operating rate per unit area, parasitic reactions generating insulative and irreversible byproducts, significant charge overpotential which lowers the roundtrip efficiency, and diffusion limitation with respect to oxygen. Moreover, researchers are looking for ways to expand the system threshold that keeps the LOB from its theoretical specific energy.

SUMMARY OF THE INVENTION

[0004] In some instances, provided herein are materials, such as lithium air or lithium oxygen battery cathode materials, comprise lightweight, highly conductive, highly porous cathode materials, such as carbon nanotubes (CNT), graphene sheets (GS), graphene nanoribbons (GNR), activated carbons (AC), carbon nanofibers (CNF). In certain embodiments herein, layered cathodes are fabricated by successively stacking two different carbons or carbon morphologies (e.g., a two- dimensional carbon component as a first morphology and a one dimensional carbon component as a second carbon component), such graphene or reduced graphene oxides (RGO) (e.g., as a first layer) and carbon nanotubes (CNT), graphene nanoribbons (GNR), or graphene oxide nanoribbons (GONR) (e.g., as a second layer). In some instances, such carbon materials comprise and/or are chosen because they possess two distinct morphologies, e.g., enabling the stacking in layered structures. In some instances, structural variance of the cathodes controlled by different carbons with different morphologies demonstrate synergic effect in terms of improving the overall performance of lithium-oxygen battery (LOB). In some instances, regardless of the amount of carbon loading, the cathodes comprise layered (e.g., "sandwich- stacked" cathodes) that produce the highest value of all capacities in comparison with single layer or mix-type cathodes. Moreover, in certain embodiments, provided herein are processes of operating such batteries in humid environments, such as described herein (e.g., in some instances more humid environments lead to the higher specific capacities in open air systems).

[0005] In some instances, layered or "sandwich-stacked" cathodes composed of alternating two different carbon (e.g., grapheme) components demonstrate the improvement in the electrochemical performance of LOB, such as due to enhanced diffusion process of lithium ion and oxygen and/or to the enlarged three phase interface caused by the change in the surface properties. Moreover, in some instances, configurations provided herein (e.g., using a constant amount of total carbon materials but with a different number of layers) a synergic effect of layered air cathodes is in terms of increasing specific capacity and/or reducing the overpotential.

[0006] Provided in certain embodiments herein are high capacity lithium based (e.g., lithium air or lithium oxygen (used interchangeably herein) batteries, component parts thereof, processes of using the same, processes of manufacturing the same, and the like. In specific embodiments, batteries provided herein comprise a first electrode and a second electrode, the first electrode comprising a multi-layered carbon structure, and the second electrode comprising lithium (e.g., lithium ion, lithium metal alloy, and/or lithium metal).

[0007] In certain embodiments, provided herein (e.g., in a battery, electrode or material provided herein) is a multi-layered carbon structure comprising a first layer, and a second layer, the first layer comprising a first carbon component; and the second layer comprising a second carbon component (e.g., wherein the first and second carbon components are different, such as different chemically (e.g., oxygen content) and/or morphologically (e.g., size, aspect ratio, etc.). In certain embodiments, the carbon components are independently selected from any suitable carbon- containing material, such as carbon allotropes and functionalized (e.g., with oxygen, halide, nitrogen, hydrogen, organic radicals, and/or the like) carbon allotropes. In specific embodiments, the first and/or second carbon component is an oxidized carbon component, such as an oxidized carbon allotrope.

[0008] In specific embodiments, the first carbon component is or comprises a carbon allotrope or an analog thereof, such as an oxide, or the like (e.g., in the form of a particle). For example, in some embodiments, the first carbon component is or comprises a graphene, graphene oxide (GO), a reduced graphene oxide (rGO), or any combination thereof. In certain embodiments, the first carbon component comprises a plurality of particles. In other words, in certain instances, the carbon component comprises a plurality of (e.g., grapheme) particles having a physical morphology, with corresponding physical characteristics. In some embodiments, the plurality of

(e.g., grapheme) particles of the first carbon component have a first dimension (e.g., length, such as longest lateral dimension) of any suitable length. In certain embodiments, the size of the (e.g., graphenic) particles ranges from several hundred nanometers to several micrometers (micron). In specific embodiments, the average first dimension of the plurality of (e.g., graphenic) particles of the first carbon component is about 0.2 micron to about 50 micron, such as about 0.5 micron to about 20 micron. In more specific embodiments, the average first dimension of the plurality of

(e.g., graphenic) particles of the first carbon component is about 2 micron to about 10 micron, such as about 5 micron. In some embodiments, the plurality of (e.g., graphenic) particles of the first carbon component have a second dimension (e.g., width, such as the dimension orthogonal to the longest lateral dimension) of any suitable length. In specific embodiments, the average second dimension of the plurality of (e.g., graphenic) particles of the first carbon component is about 0.2 micron to about 50 micron, such as about 0.5 micron to about 20 micron. In more specific embodiments, the average second dimension of the plurality of (e.g., graphenic) particles of the first carbon component is about 2 micron to about 10 micron, such as about 3 micron.

[0009] In certain embodiments, the (e.g., graphenic) particles of the first carbon component are high surface area and/or low aspect ratio (e.g., the length (e.g., longest lateral dimension) divided by the width (e.g., longest dimension orthogonal to the longest lateral dimension)). In some embodiments, the (e.g., graphenic) particles of the first carbon component have a surface area of at least 300 m²/g, such as at least 400 m²/g (e.g., about 450 m²/g to about 750 m²/g, or about 575 m²/g). In some instances, the (e.g., graphenic) particles of the first carbon component are low aspect ratio or two-dimensional, such as having (e.g., on average) an aspect ratio of about 10 or less (e.g., about 5 or less, about 2 or less, or the like).

[0010] In various embodiments herein, the particles of the first carbon component comprise any suitable carbon allotrope, such as a graphenic component, e.g., graphene or reduced graphene oxide. Exemplary carbon inclusion materials of the first carbon component include carbon allotropes and analogs or derivatives thereof, such as those modified with hydrogen, oxygen, nitrogen, sulfur, halide, or the like, or combinations thereof. In some embodiments, the graphenic component can also include structural defects, such as opened or modified rings, or the like. In specific embodiments, the graphenic component comprises graphene, graphene oxide, reduced graphene oxide, or a combination thereof. Unless otherwise stated, reference to such materials includes those modified with other elements (e.g., less than 10 wt. %, less than 5 wt. %, less than 3 wt. %, less than 1 wt. %, or the like (e.g., on average)) - for clarity, such amounts don't refer to the oxygen content of graphene oxide or reduced graphene oxide unless otherwise stated herein), such as hydrogen, oxygen, nitrogen, sulfur, halides, or the like, or combinations thereof and are pristine or comprise defects. In specific embodiments, the grapheme components (graphene oxides) comprise (e.g., on average) at least 50 wt. % carbon (e.g., up to about 90 wt. %) and (e.g., on average) about 10 wt. % to about 50 wt. % oxygen (e.g., and less than 5 wt. % other elements, such as described herein). In some embodiments, the grapheme component (e.g., following reductive, such as thermo-reductive treatment) are graphenic components (e.g., reduced graphene oxides) comprising (e.g., on average) at least 85 wt. % carbon (e.g., up to about 99.9 wt. %) and

(e.g., on average) about 0.1 wt. % to about 15 wt. % oxygen (e.g., and less than 5 wt. % other elements, such as described herein). In some embodiments, the graphenic component are graphenic components comprising (e.g., on average) about 70 wt. % to about 99.9 wt. % carbon. In some embodiments, the graphenic component are graphenic components comprising (e.g., on average) about 0.1 wt. % to about 20 wt. % oxygen (e.g., about 4 wt. % to about 6 wt. %). In some embodiments, the graphenic component comprises at least two layers (i.e., at least two stacked graphenic sheets). In specific embodiments, the multi-layered graphene component comprises (e.g., on average) at least 3 layers. In more specific embodiments, the multi -layered graphene component comprises (e.g., on average) at least 5 layers. In some embodiments, the multi-layered graphene component comprises (e.g., on average) about 2 to about 50 layers.

[0011] In specific embodiments, the second carbon component is or comprises a carbon allotrope or an analog thereof, such as an oxide, or the like (e.g., in the form of a particle). For example, in some embodiments, the second carbon component is or comprises a graphene (e.g., graphene nanoribbons), graphene oxide (GO) (e.g., GO nanoribbons), a reduced graphene oxide (rGO) (e.g., rGO nanoribbons), carbon nanotubes (CNT), or any combination thereof. In certain embodiments, the second carbon component comprises a plurality of particles. In other words, in certain instances, the carbon component comprises a plurality of (e.g., graphenic) particles having a physical morphology, with corresponding physical characteristics. In some embodiments, the plurality of (e.g., graphenic) particles of the second carbon component have a first dimension (e.g., length, such as longest lateral dimension) of any suitable length. In certain embodiments, the size of the (e.g., graphenic) particles ranges from several hundred nanometers to sever micrometers (micron). In specific embodiments, the average first dimension of the plurality of (e.g., graphenic) particles of the second carbon component is about 0.2 micron to about 500 micron, such as about 5 micron to about 500 micron. In more specific embodiments, the average first dimension of the plurality of (e.g., graphenic) particles of the second carbon component is about 5 micron to about 100 micron, such as about 50 micron. In some embodiments, the plurality of (e.g., graphenic) particles of the second carbon component have a second dimension (e.g., width, such as the dimension orthogonal to the longest lateral dimension) of any suitable length. In specific embodiments, the average second dimension of the plurality of (e.g., graphenic) particles of the second carbon component is about 0.005 micron to about 25 micron, such as about 0.01 micron to about 10 micron. In more specific embodiments, the average second dimension of the plurality of

(e.g., grapheme) particles of the second carbon component is about 0.01 micron to about 5 micron, such as about 0.1 to about 1 micron (e.g., about 0.2 micron).

[0012] In certain embodiments, the (e.g., grapheme) particles of the second carbon component have lower surface area and/or higher aspect ratio (e.g., relative to the particles of the first carbon component, such as at least 1.1 times, at least 1.2 times, at least 1.5 times, at least 2 times, at least

5 times, at least 10 times, at least 100 times or the like the aspect ratio of the first carbon component). In some embodiments, the (e.g., grapheme) particles of the first carbon component have a surface area of less than 500 m²/g, such as less than 450 m²/g (e.g., about 50 m²/g to about 450 m²/g, about 100 m²/g to about 450 m²/g, about 300 m²/g to about 400 m²/g, or the like). In some instances, the (e.g., grapheme) particles of the second carbon component are high aspect ratio or one dimensional, such as having (e.g., on average) an aspect ratio of about 10 or more (e.g., about 20 or more, about 25 or more, about 50 or more, about 100 or more, or the like).

[0013] In various embodiments herein, the particles of the second carbon component comprise any suitable carbon allotrope, such as a graphene, carbon nanotubes, or an analog thereof. Exemplary carbon inclusion materials of the second carbon component include carbon allotropes and analogs or derivatives thereof, such as those modified with hydrogen, oxygen, nitrogen, sulfur, halide, or the like, or combinations thereof. In some embodiments, a carbon allotrope (e.g., grapheme component) can also include structural defects, such as opened or modified rings, or the like. In specific embodiments, the carbon allotrope (e.g., grapheme component) comprises graphene, graphene oxide, reduced graphene oxide, carbon nanotubes, or a combination thereof. Unless otherwise stated, reference to such materials includes those modified with other elements (e.g., less than 5 wt. %, less than 3 wt. %, less than 1 wt. %, or the like (e.g., on average) - for clarity, such amounts don't refer to the oxygen content of a carbon allotrope, such as graphene oxide or reduced graphene oxide, unless otherwise stated herein), such as hydrogen, oxygen, nitrogen, sulfur, halides, or the like, or combinations thereof and are pristine or comprise defects. In specific embodiments, a grapheme components (graphene oxide) comprises (e.g., on average) at least 50 wt. % carbon (e.g., up to about 90 wt. %) and (e.g., on average) about 10 wt. % to about 50 wt. % oxygen (e.g., and less than 5 wt. % other elements, such as described herein). In some embodiments, the grapheme component (e.g., following reductive, such as thermo-reductive treatment) are grapheme components (e.g., reduced graphene oxides) comprising (e.g., on average) at least 85 wt. % carbon (e.g., up to about 99.9 wt. %) and (e.g., on average) about 0.1 wt. % to about 15 wt. % oxygen (e.g., and less than 5 wt. % other elements, such as described herein). In some embodiments, the grapheme component are grapheme components comprising (e.g., on average) about 70 wt. % to about 99.9 wt. % carbon. In some embodiments, the grapheme component are grapheme components comprising (e.g., on average) about 0.1 wt. % to about 20 wt. % oxygen (e.g., about 4 wt. % to about 6 wt. %). In some embodiments, the grapheme component comprises at least two layers (i.e., at least two stacked grapheme sheets). In specific embodiments, the multi-layered graphene component comprises (e.g., on average) at least 3 layers. In more specific embodiments, the multi-layered graphene component comprises (e.g., on average) at least 5 layers. In some embodiments, the multi-layered graphene component comprises (e.g., on average) about 2 to about 50 layers.

[0014] In some embodiments, the first and second carbon components are different, such as having particles of different surface areas and/or aspect ratios. In certain embodiments, the first and second carbon components comprise different amounts of oxygen content. For example, in certain embodiments, the wt. % of oxygen of the first carbon component is less than the wt. % of oxygen of the second carbon component.

[0015] In various embodiments, the first and second layers are present in any suitable amount. In some preferred embodiments, the weight ratio of the first layer to the second layer is about 1 :2 to about 20: 1, such as about 1 : 1 to about 10: 1 (e.g., about 1 : 1 to about 9: 1).

[0016] In some instances, the material comprises a third layer, such as wherein the third layer comprises elements as described for the first layer (e.g., wherein the first and third layers may be the same or different, but both have the characteristics described for a first layer described herein). For example, in some instances, a multi-layered material provided herein has a structure of FL- SL-TL, wherein FL is first layer, SL is second layer, and TL is third layer.

[0017] In some embodiments, the first layer (FL) and second layers (SL) repeat to form multiple repeating layers, such as wherein the material comprises a multiple layered structure of FL-SL- FL-SL or FL-SL-FL-SL-FL-SL. In certain instances, each FL is as describe for a first layer herein, but in some instances, layers described as FL may be the same or different (e.g., while maintaining the characteristics herein for first layer(s)). Similarly, in certain instances, each SL is as describe for a second layer herein, but in some instances, layers described as SL may be the same or different (e.g., while maintaining the characteristics herein for second layer(s)). In some instances, the base and top layers have first layer characteristics, such as wherein the multilayered material has the configuration: FL-SL-FL, or FL-SL-FL-SL-FL, or FL-SL-FL-SL-FL-SL-FL, or the like. In various embodiments wherein multilayered structures herein, the overall weight ratio of the first layer to the second layer of the entire material is about 1 :2 to about 20: 1, such as about 1 : 1 to about 10: 1 (e.g., about 1 : 1 to about 9: 1).

[0018] In alternative embodiments, contemplated herein are materials (e.g., first electrodes herein) wherein the carbon components of the first and second layers are intermixed, rather than layered. As illustrated in the examples herein, such materials often give good results, but, in some instances, the best results are observed in the layered or "sandwich" configurations.

[0019] In certain embodiments, batteries and materials provided herein have very good capacities. For example, in some instances, battery materials provided herein have capacities of about 5,000 mAh/g or more. In specific embodiments, the capacities are about 8,000 mAh/g or more, such as about 10,000 mAh/g or more. Such capacities are achieved at any suitable charge rate, such as 1C, C/2, C/5 or the like (e.g., wherein C is the rate necessary to completely charge or discharge the material or cell in one hour time), or a charge and/or discharge rate of about 0.05 mAh/cm².

[0020] In specific embodiments, provided herein is a battery, such as comprising a multi-layered structure as an electrode (e.g., cathode) or electrode (e.g., cathode) component thereof. In specific embodiments, the battery further comprises an electrode (e.g., second electrode) comprising lithium, such as lithium ion, lithium metal, lithium alloy, lithiated metal or metalloid, or the like.

[0021] In certain embodiments, provided herein is a process for preparing a multi-layered material, electrode, or the like provided herein, the process comprising:

a. depositing a first carbon component on a substrate (e.g., current collector), thereby forming a first electrode layer; and

b. depositing a second carbon component on the first electrode layer, thereby forming a second electrode layer.

[0022] In certain embodiments, the first carbon component is as described for the materials described herein. In some embodiment, the second carbon component is as described for the materials provided herein. In certain embodiemtns, the relationship between the first and second carbon components are as described above, such as in exemplary embodiments, wherein (a) the aspect ratio of the second particles is greater than the aspect ratio of the first particles (e.g., on average); and/or (b) the surface area of the second particles is less than the surface area of the first particles (e.g., on average).

[0023] In some embodiments, any one of steps (a) or (b) is repeated in the process, as desired. For example, in specific embodiments, the process further comprises depositing a third carbon component on the second electrode layer, thereby forming a third electrode layer (e.g., wherein the third carbon component is as described for either the first or second carbon component described herein). In specific embodiments, the third component is as described for the first component and/or is identical to the first component of the first layer.

[0024] Any suitable process for depositing the first and/or second (and any subsequent) layers is optionally utilized. In exemplary embodiments, the carbon components are deposited by casting or by electrospraying, such as gas-assisted electrospraying set forth in WO 2017/083462, entitled "Air Controlled Electrospray Manufacturing and Products Thereof," filed on November 10, 2016 and WO 2017/083464, entitled "Alternating Current Electrospray Manufacturing and Products

Thereof," filed November 10, 2016, both of which are incorporated herein by reference in their entities.

[0025] In certain instances, grapheme components are provided and described herein. In general, a grapheme component is a two-dimensional, sheet-like or flake-like carbon form that comprises monolayer graphenes, as well as multi-layer graphenes (e.g., graphenes comprising 1 up to about 40 grapheme layers, such as 1 to about 25 or 1 to about 10 grapheme layers), as opposed to three dimensional carbon structures, such as graphite, and one dimensional structures, such as carbon nanotubes (CNTs), and zero dimensional structures, such as C60 buckyball. A pristine grapheme layer is a single-atom-thick sheet of hexagonally arranged, sp2-bonded carbons atoms occurring within a carbon material structures, regardless of whether that material structure has a 3D order (graphitic) or not. As discussed herein, grapheme components optionally comprise pristine and/or defective or functionalized grapheme layers. For example, defective graphene layers may be optionally functionalized, such as described herein. In some instances, graphene layers are functionalized with oxygen and/or other moieties. For example, graphene oxide is an oxygen functionalized graphene or a chemically modified graphene prepared by oxidation and exfoliation that is accompanied by extensive oxidative modification of the basal plane. Herein, graphene oxide is a single or multi-layered material with high oxygen content, such as characterized by C/O atomic ratios of less than 3.0, such as about 2.0. Reduced graphene oxide (rGO) is graphene oxide that has been reductively processed by chemical, thermal, microwave, photo-chemical, photo-thermal, microbial/bacterial, or other method to reduce the oxygen content. Oxygen content of rGO isn't necessarily zero, but is typically lower than the oxygen content of graphene oxide, such as having a C/O atomic ratio of over 3.0, such as at least 5, at least 10, or the like. In certain instances, graphene layers of rGO are less pristine than that of graphene, such as due to imperfect reduction and assembly of the two-dimensional structure.

[0026] In certain instances, a value "about" an indicated value is a value suitable for achieving a suitable result and/or a result similar as achieved using the identified value. In some instances, a value "about" an indicated value is between ½ and 2 times the indicated value. In certain instances, a value "about" an indicated value is ± 50% the indicated value, ± 25% the indicated value, ± 20% the indicated value, ± 10% the indicated value, ± 5% the indicated value, ± 3% the indicated value, or the like.

[0027] These and other objects, features, and characteristics of the batteries, electrodes, materials, compositions and/or processes disclosed herein, will become more apparent upon consideration of the following description and the appended claims with reference to the accompanying drawings and examples, all of which form a part of this specification. It is to be expressly understood, however, that the drawings and examples are for the purpose of illustration and description only and are not intended as a definition of the limits of the invention. As used in the specification and in the claims, the singular form of "a", "an", and "the" include plural referents unless the context clearly dictates otherwise.

BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The novel features of the invention are set forth with particularity in the appended claims. A better understanding of the features and advantages of the present invention will be obtained by reference to the following detailed description that sets forth illustrative embodiments, in which the principles of the invention are utilized, and the accompanying drawings of which:

[0029] FIG. 1 illustrates (a) a schematic illustration of sandwich-stacked cathodes; (b) and (c) cross-sectional FE-SEM images of RGO-GONR sandwich-stacked cathode; (d) a top view FE- SEM image and (e) TEM image of RGO layer; (f) top view FE-SEM image and (g) TEM image of GONR layer.

[0030] FIG. 2 illustrates electrochemical performance and characterization of RGO-GONR cathodes with structural variations, including (a) voltage limit profile (2.4 V-4.8 V) of the 1^st (b) capacity limit profile (1 Ah g^"1), (c) EIS spectra and (d) capillary flow porometry profiles of sandwich- stacked RGO-GONR cathodes with different number of layers but with the same fixed carbon loading of 0.5 mg cm^"2 at a current density of 0.05 mA cm^"2; (e) specific capacity versus carbon loading (0.2 ~ 4.3 mg cm^"2) for single layer RGO/GONR, mixed, sandwich-stacked cathodes; and (f) full discharge capacities for highly loaded sandwich- stacked RGO-GONR cathodes (61 layer) in an open air system with controlled relative humidity.

[0031] FIG. 3 illustrates electrochemical performance and characterization of sandwich-stacked and mixed cathodes with different pairs of carbon: (a) voltage limit profile (2.4 V-4.8 V) of the 1st cycles and (b) capacity limit profile, (c) EIS spectra, (d) capillary flow porometry profile, (e) electrolyte contact angle measurements, and (f) density and electrical conductivity of sandwich- stacked and/or mixed cathodes with different pairs of carbon with different number of layers and with the fixed amount of carbon loading at a current density of 0.05 mA cm^"2.

[0032] FIG. 4 illustrates an X-ray photoelectron spectroscopy (XPS) of exemplary RGO.

[0033] FIG. 5 illustrates N2 isotherm curves of exemplary RGO and its pore size distribution using Barret- Joy ner-Halenda (BJH) method.

[0034] FIG. 6 illustrates an X-ray photoelectron spectroscopy (XPS) of exemplary GONR.

[0035] FIG. 7 illustrates N2 isotherm curves of exemplary GONR and its pore size distribution using Barret- Joy ner-Halenda (BJH) method. [0036] FIG. 8 illustrates (a) gravimetric and (b) areal specific capacities of exemplary single layer and multi-layered cathodes.

DETAILED DESCRIPTION OF THE INVENTION

[0037] Provided in certain embodiments herein are high capacity lithium based (e.g., lithium air or lithium oxygen (used interchangeably herein) batteries, component parts thereof, processes of using the same, processes of manufacturing the same, and the like. In specific embodiments, batteries provided herein comprise a first electrode and a second electrode, the first electrode comprising a multi-layered carbon structure, and the second electrode comprising lithium (e.g., lithium ion, lithium metal alloy, and/or lithium metal).

[0038] In certain embodiments, provided herein (e.g., in a battery, electrode or material provided herein) is a multi-layered carbon structure comprising a first layer, and a second layer, the first layer comprising a first carbon component; and the second layer comprising a second carbon component. In certain embodiments, the carbon components are independently selected from any suitable carbon-containing material, such as carbon allotropes and functionalized (e.g., with oxygen, halide, nitrogen, hydrogen, organic radicals, and/or the like) carbon allotropes. In specific embodiments, the first and/or second carbon component is an oxidized carbon component, such as an oxidized carbon allotrope.

[0039] In some instances, first and second carbon components are chosen such that they possess two distinct morphologies enabling the stacking in layered structures. For example, in certain embodiments, the first and second carbon components are as described herein. In certain embodiments, the relationship between the first and second carbon components are as described above, such as in exemplary embodiments, wherein (a) the aspect ratio of the second particles is greater than the aspect ratio of the first particles (e.g., on average); and/or (b) the surface area of the second particles is less than the surface area of the first particles (e.g., on average).

[0040] FIG. 1 panel (a) illustrates a schematic of high aspect ratio and/or low surface area carbon components, such as carbon nanotubes (CNT), graphene nanoribbons (GNR), and graphene oxide nanoribbons (GONR). While FIG. 1 illustrates GNR and GONR being manufactured from CNTs, is contemplated herein that graphenic nanoribbons are high aspect ratio graphenic components, whether such materials are manufactured from CNTs, graphene, graphene, or other suitable source, such as by direct synthesis. FIG. 1 panel (a) also illustrates a schematic of a multi-layered structure provided herein and a process of manufacturing the same. As illustrated a first composition is deposited on a surface, the first composition comprising a solution or suspension of a first carbon component, such as reduced graphene oxide (e.g., having high surface area and/or low aspect ratio). Following deposition of a first composition, a second composition comprising a solution or suspension of a second carbon component, such as comprising CNT, GNR, GONR, or the like (e.g., having a lower surface area and/or higher aspect ratio) is deposited to form a multi-layered or "sandwich-like" assembly. As illustrated in the figure, deposition can be achieved by drop- casting methods, but other deposition methods are also contemplated herein. In some embodiments, drying (e.g., with heat, air flow, or the like) is performed following deposition of the first and/or second compositions, prior to deposition of a subsequent composition (suspension or solution) / layer. More specifically, as illustrated in FIG. 1 panel (a), in some instances herein, sandwich- stacked cathodes are fabricated by alternating casting method using different pairs of carbon. In some instances, the high aspect ratio of GO R (or other high aspect ratio carbon component) and its entanglement prevent it from getting inside the RGO layer (or other lower aspect ratio carbon component) and prevent the RGO particles from getting inside the GONR layer.

[0041] In some embodiments, a multi-layered material, electrode, or the like herein comprises a multi-layered structure, wherein less than 20% (e.g., wt. %) of the first and second carbon components are mixed. In more specific embodiments, less than 10% of the first and second carbon components are mixed. In still more specific embodiments, less than 5% of the first and second carbon components are mixed. FIG. 1 panel (b) and FIG. 1 panel (c) illustrate field emission scanning electron microscope (FE-SEM) cross-sectional images of the first three layers of a (RGO- GONR) 7-layer cathode at various magnifications. As is illustrated, very little layer or phase intermixing occurs. FIG. 1 panel (d) illustrates a top view FE-SEM image of a RGO layer, panel (e) illustrates a TEM image of the RGO layer, panel (f) illustrates a top view FE-SEM image a GONR layer, and panel (g) illustrates a TEM image of the GONR layer.

[0042] In some embodiments, carbon components provided herein have any suitable amount of carbon and/or other atoms, such as oxygen, halogen, hydrogen, nitrogen, sulfur, and/or the like. In certain embodiments, the carbon-to-oxygen (C:0) atomic percentage ratio of a carbon component is about 1 : 1 to about 20: 1, such as about 6:4 to about 12: 1, or about 7:3 to about 9: 1. For example, in some instances, lower oxygen content carbon components, such as RGO, CNT, or GNR have a C:0 atomic percentage ratio of about 9: 1 whereas higher oxygen content carbon components, such as GO or GONR, have a C:0 atomic percentage ratio of about 7:3.

[0043] In various embodiments, the weight ratio of a first carbon component (and/or first layer) to a second carbon component (and/or second layer) is any suitable ratio. In exemplary embodiments, the weight ratio of first carbon component (and/or first layer) to a second carbon component (and/or second layer) is about 1 :2 to about 10: 1. In specific embodiments, the weight ratio is about 1 : 1 to about 5: 1, such as about 7:3. In some preferred embodiments, the weight ratio is the overall weight ratio of a multi-layered material provided herein. In some embodiments, wherein multiple layers comprising the first and/or second carbon components are present, the amount of first and/or second carbon components are distributed in the respective layers in any suitable amount, such as equally (e.g., ±10%, ±5%, or the like) between the layers. For example, in specific embodiments, such as wherein the multi-layered structure has an FL-SL-FL structure, about 50% of the first component is in the first FL and about 50% of the first carbon component is in the second FL, while 100% of the second component is in the SL. In further examples, such as wherein the multi-layered structure has an FL-SL-FL- SL-FL structure, about 1/3 of the first carbon component is in the first FL, about 1/3 of the first carbon component is in the second FL, and about 1/3 of the first carbon component is in the third FL, while about 50% of the second carbon component is in the first SL, and about 50% of the second carbon component is in the second SL.

[0044] FIG. 2 illustrates the electrochemical performance and characterization of exemplary RGO-GO R cathodes with different number of layers at a current density of 0.05 mA cm^"2. Among all the pairs, the sandwich-stacked RGO-GONR (7-layer) cathode produced the highest specific capacity, and the specific capacities of the sandwich-stacked cathode with different number of layers varied from 1,745 mAh g^"1 (3 -layer) to 13,458 mAh g^"1 (7-layer) (FIG. 2 (panel a)), which is almost one order of magnitude difference with the same types and the same amount of total carbon loaded. FIG. 2 (panel e) shows the change in capacities of RGO-GONR cathodes with increasing amount of carbon loading, and regardless of the amount, the sandwich-type RGO- GONR cathode achieved the best capacities, with the mixed materials better than the either component individually.

[0045] In certain embodiments, batteries or battery cells provided herein are operated at high humidities, such as at least 40% relative humidity (RH). In some embodiments, the humidity is at least 50% RH, at least 60% RH, at least 70% RH, at least 80% RH, or the like. In some instances, oxygen diffusion is limited in the liquid phase electrolyte when higher carbon amount are utilized. In certain instances, such limitations lead to lower gravimetric specific capacities and eventually arrives at the total capacity threshold in the non-aqueous LOB system. In certain instances, this systematic limitation is overcome by utilizing a controlled humidity environment. In some instances, higher relative humidity leads to a higher specific capacities of the sandwich-type RGO- GONR (e.g., 61 layers) cathode, such as illustrated in FIG. 2 (panel f).

[0046] FIG. 3 illustrates electrochemical performance of a variety of sandwich-stacked and mixed cathodes with three different pairs of carbon (RGO-GONR, RGO-GNR, RGO-CNT). As illustrated, single layer cathode of RGO had greater specific capacity (3,564 mAh g^"1) than the single layer cathode of the GONR, GNR, or CNT, and both mixed and sandwich-stacked (7-layer) cathodes produced higher specific capacities than the single layer RGO cathode as shown in FIG. 3 (panel a). In terms of rechargeability with capacity limited to 1,000 mAh g^"1, the sandwich- stacked RGO-GNR (7-layer) cathode produced the longest cycle life (FIG. 3 (panel b)) which outnumbers that of the single layer RGO cathode in (FIG. 2 (panel b)). EXAMPLES

Example 1 - Cathode Fabrication (GNR/RGO)

[0047] GNR was made by unzipping multi-walled CNTs (Hodogaya Chemical Corp.) with hexadecyl-functionalization and oxidation. Carbon and polytetrafluoroethylene (PTFE) binder were dispersed in isopropyl alcohol (5 mL) in a weight ratio of 80:20. The slurries were ultra- sonicated, stirred overnight and casted onto a gas diffusion substrate (Toray). The fabricated cathodes were dried overnight and transferred to the glove box for cell assembly. The total amount of carbon loaded on the substrate is 1 ± 0.05 mg, and the weight ratio of RGO and GNR is 70:30. The size of RGO is 5 μιη in length, 3 μιη in width. GNR has much higher aspect ratio with the dimension of 0.2 μιη in diameter and 50 μιη in average length.

[0048] Deposition of RGO layer is followed by deposition of the GNR layer. Generally, a third RGO layer is deposited to form a three-layered cathode structure. Five layer and Seven layered structures are also manufactured by depositing additional, alternating, RGO and GNR layers. The weight ratio of RGO and GNR is kept at 70:30 for all cases, and each layer for each cathode is equally distributed in weight within the total amount of each material. For sandwich-type cathodes, different odd number of layers (1 to 9) were coated with fixed amount of total loading (1 mg), having the first and the last layers always RGO. As the total number of layers increases, each layer for each cathode contain less amount of materials so it could match the total amount of carbon. For example, in the case of 7-layer cathode, there are four layers of RGO and three layers of GNR, alternating by one after another, and each layer of RGO weighs approximately 0.18 mg and GNR 0.1 mg, whereas in the case of 3-layer cathode, the numbers are 0.35 mg and 0.3 mg, respectively. The weight of cathode was carefully measured every time each layer was casted.

[0049] FIG. 4 illustrates an X-ray photoelectron spectroscopy (XPS) full spectrum of the RGO utilized herein, indicating a 5.7% oxygen content and a 94.3% carbon content. FIG. 5 illustrates N2 isotherm curves of RGO and its pore size distribution using Barret- Joy ner-Halenda (BJH) method.

Example 2 - Cathode Fabrication (GONR/RGO)

[0050] GONR was made by unzipping multi-walled CNTs (Hodogaya Chemical Corp.) with hexadecyl-functionalization and oxidation. Carbon and polytetrafluoroethylene (PTFE) binder were dispersed in isopropyl alcohol (5 mL) in a weight ratio of 80:20. The slurries were ultra- sonicated, stirred overnight and casted onto a gas diffusion substrate (Toray). The fabricated cathodes were dried overnight and transferred to the glove box for cell assembly. The total amount of carbon loaded on the substrate is 1 ± 0.05 mg, and the weight ratio of RGO and CNT/GNR/GONR is 70:30. The size of RGO is 5 μιη in length, 3 μιη in width. GONR has much higher aspect ratio with the dimension of 0.2 μπι in diameter and 50 μπι in average length. [0051] Deposition of RGO layer is followed by deposition of the GONR layer. Generally, a third RGO layer is deposited to form a three-layered cathode structure. Five layer and seven layered structures are also manufactured by depositing additional, alternating, RGO and GONR layers. The weight ratio of RGO and GONR is kept at 70:30 for all cases, and each layer for each cathode is equally distributed in weight within the total amount of each material. For sandwich-type cathodes, different odd number of layers (1 to 9) were coated with fixed amount of total loading (1 mg), having the first and the last layers always RGO. As the total number of layers increases, each layer for each cathode contain less amount of materials so it could match the total amount of carbon. For example, in the case of 7-layer cathode, there are four layers of RGO and three layers of GONR, alternating by one after another, and each layer of RGO weighs approximately 0.18 mg and GONR 0.1 mg, whereas in the case of 3-layer cathode, the numbers are 0.35 mg and 0.3 mg, respectively. The weight of cathode was carefully measured every time each layer was casted.

[0052] FIG. 1 panel (a) illustrates a schematic of sandwich-stacked materials fabricated by alternating casting RGO and GONR. FIG. 1 panel (b) and FIG. 1 panel (c) illustrate field emission scanning electron microscope (FE-SEM) cross-sectional images of the first three layers of a (RGO- GONR) 7-layer cathode at various magnifications. As is illustrated, very little layer or phase intermixing occurs. FIG. 1 panel (d) illustrates a top view FE-SEM image of a RGO layer, panel (e) illustrates a TEM image of the RGO layer, panel (f) illustrates a top view FE-SEM image a GONR layer, and panel (g) illustrates a TEM image of the GONR layer.

[0053] FIG. 6 illustrates an X-ray photoelectron spectroscopy (XPS) full spectrum of the GONR utilized herein, indicating a 29.2% oxygen content and a 70.8% carbon content. FIG. 7 illustrates N2 isotherm curves of GONR and its pore size distribution using Barret- Joy ner-Halenda (BJH) method.

[0054] Additional carbon loadings are performed, such as wherein loadings of 0.46, 1.0, 2.14, 5.22, and 8.58 mg are utilized, which correspond to 3, 7, 15, 37, and 61 alternating layers of RGO and GONR in the sandwich-stacked cathodes, and each layer weighs the same with that of the 7- layer cathodes.

Example 3 - Cathode Fabrication (CNT/RGO)

[0055] Carbon and polytetrafluoroethylene (PTFE) binder were dispersed in isopropyl alcohol (5 mL) in a weight ratio of 80:20. The slurries were ultra-sonicated, stirred overnight and casted onto a gas diffusion substrate (Toray). The fabricated cathodes were dried overnight and transferred to the glove box for cell assembly. The total amount of carbon loaded on the substrate is 1 ± 0.05 mg, and the weight ratio of RGO and CNT is 70:30. The size of RGO is 5 μπι in length, 3 μπι in width. CNT has much higher aspect ratio with the dimension of 0.2 μπι in diameter and 50 μπι in average length. [0056] Deposition of RGO layer is followed by deposition of the CNT layer. Generally, a third RGO layer is deposited to form a three-layered cathode structure. Five layer and Seven layered structures are also manufactured by depositing additional, alternating, RGO and CNT layers. The weight ratio of RGO and CNT is kept at 70:30 for all cases, and each layer for each cathode is equally distributed in weight within the total amount of each material. For sandwich-type cathodes, different odd number of layers (1 to 9) were coated with fixed amount of total loading (1 mg), having the first and the last layers always RGO. As the total number of layers increases, each layer for each cathode contain less amount of materials so it could match the total amount of carbon. For example, in the case of 7-layer cathode, there are four layers of RGO and three layers of CNT, alternating by one after another, and each layer of RGO weighs approximately 0.18 mg and CNT 0.1 mg, whereas in the case of 3-layer cathode, the numbers are 0.35 mg and 0.3 mg, respectively. The weight of cathode was carefully measured every time each layer was casted.

Example 4 - Cell Fabrication (GNR/RGO)

[0057] Lithium metal disc (MTI Corp.) was used as anode and the cathode of Example 1 is used as the cathode. 1 M lithium trifluoromethanesulfonate (L1CF3SO3) / 1, 2-dimethoxy ethane (DME) were used as an electrolyte which impregnated a glass fiber separator (GF/D, Whatman).

[0058] Cell assembly begins with placing a lithium disc foil followed by a glass fiber soaked by electrolyte and the cathode. All of the assembly process was done in the argon filled glove box. (< 0.1 ppm. 02 and H20) The LOB cell was then taken out from the glove box and purged with ultrahigh purity oxygen for 5 min to replace the inside argon.

[0059] EIS was evaluated at the electrochemical workstation (Princeton Applied Research, PARSTAT 4000) within a frequency range of 50,000 to 0.01 Hz using 5 mV input voltage amplitude. Galvanostatic tests were done under a cut-off voltage (2.4 V to 4.8 V versus Li/Li⁺) at 0.05 mA cm^"2. The microstructured morphologies of the cathode materials were observed by TEM (FEI F20 Tecnai) and FE-SEM (Tescan Mira3). Electrolyte contact angle measurement was performed on a contact angle goniometer (Rame-Hart 500) with automated dispensing system. The surface properties were further investigated by XPS spectroscopy (Surface Science Instruments, SSX-100) at ~ 2 x 10^"9 Torr operating pressure, and monochromatic Al K-alpha X-rays (1486.6 eV) were used with beam diameter of 1 mm. Pore size distributions of cathodes in micro-scale (> 0.1 μπι) were obtained by the capillary flow porometer (Porous Materials, Inc., CFP-1100- AEHXL). Thickness was measured five times for each cathode by the digital thickness gauge with high accuracy up to 0.001 mm (Mitutoyo), averaged out and confirmed by the FE-SEM cross- sectional images. Conductivity measurements of the sandwich-stacked cathodes were performed by using a 4-point probe set up (Cascade CP06) with a Keithley 2400 as a sourcemeter. The source current was 0.2 A, and measurement range was 100 mV. Example 5 - Cell Fabrication (GONR/RGO)

[0060] Lithium metal disc (MTI Corp.) was used as anode and the cathode of Example 2 is used as the cathode. 1 M lithium trifluoromethanesulfonate (L1CF3SO3) / 1, 2-dimethoxy ethane (DME) were used as an electrolyte which impregnated a glass fiber separator (GF/D, Whatman).

[0061] Cell assembly begins with placing a lithium disc foil followed by a glass fiber soaked by electrolyte and the cathode. All of the assembly process was done in the argon filled glove box. (< 0.1 ppm. 02 and H20) The LOB cell was then taken out from the glove box and purged with ultrahigh purity oxygen for 5 min to replace the inside argon.

Example 6 - Cell Fabrication (CNT/RGO)

[0062] Lithium metal disc (MTI Corp.) was used as anode and the cathode of Example 3 is used as the cathode. 1 M lithium trifluoromethanesulfonate (L1CF3SO3) / 1, 2-dimethoxy ethane (DME) were used as an electrolyte which impregnated a glass fiber separator (GF/D, Whatman).

[0063] Cell assembly begins with placing a lithium disc foil followed by a glass fiber soaked by electrolyte and the cathode. All of the assembly process was done in the argon filled glove box. (< 0.1 ppm. 02 and H20) The LOB cell was then taken out from the glove box and purged with ultrahigh purity oxygen for 5 min to replace the inside argon.

[0064] FIG. 2 illustrates the electrochemical performance and characterization of the RGO- GO R cathodes with different number of layers at a current density of 0.05 raA cm^"2. Among all the pairs, the sandwich- stacked RGO-GO R (7-layer) cathode produced the highest specific capacity, and the specific capacities of the sandwich-stacked cathode with different number of layers varied from 1,745 mAh g^"1 (3-layer) to 13,458 mAh g^"1 (7-layer) (FIG. 2 (panel a)), which is almost one order of magnitude difference with the same types and the same amount of total carbon loaded. FIG. 2 (panel e) shows the change in capacities of RGO-GONR cathodes with increasing amount of carbon loading, and regardless of the amount, the sandwich-type RGO- GONR cathode achieved the highest capacities of all.

[0065] Higher relative humidity was observed to lead to the higher specific capacities of the sandwich-type RGO-GONR (61 layers) cathode as shown in FIG. 2 (panel f). FIG. 2 (panel b) demonstrates cyclability with capacities limited to 1,000 mAh g^"1. Electrochemical impedance spectroscopy (EIS) data were obtained on the LOB cells with sandwich-type RGO-GONR cathodes with different number of layers. The greater width of the semicircle of the Nyquist plots indicates the higher polarization resistance, and therefore the slower charge-transfer kinetics. The single layer GONR cathode has the greatest width of the semicircle whereas the smallest width belongs to the single layer RGO cathode as shown in FIG. 2 (panel c). Capillary flow porometry profiles in FIG. 2 (panel d) show the pore distribution with the average pore size of the sandwich- type RGO-GO R cathodes with different number of layers and that more alternating layers give larger pores inside the cathode structure.

[0066] The comparisons of sandwich-stacked and mixed cathodes with three different pairs of carbon (RGO-GONR, RGO-GNR, RGO-CNT) in electrochemical performance and characterization are presented in FIG. 3. Single layer cathode of RGO had greater specific capacity (3,564 mAh g^"1) than the single layer cathode of the GONR, GNR, or CNT, and both mixed and sandwich- stacked (7-layer) cathodes produced higher specific capacities than the single layer RGO cathode as shown in FIG. 3 (panel a). In terms of rechargeability with capacity limited to 1,000 mAh g^"1, the sandwich-stacked RGO-GNR (7-layer) cathode produced the longest cycle life (FIG. 3 (panel b)) which outnumbers that of the single layer RGO cathode in FIG. 2 (panel b). In the comparison of mix and sandwich-stacked cathodes in EIS spectra in FIG. 3 (panel c), the tilt angles of the tails of the Nyquist plot have subtle difference, while the widths of the semicircles stay similar, which indicates that the mix and sandwich-stacked cathodes have different diffusion mechanism of lithium ions and oxygen in the active materials. FIG. 3 (panel d) shows the capillary flow porometry data of both mixed and sandwich-stacked cathodes with different pairs of carbon. Although the average pore size of the sandwich-stacked RGO-CNT cathode, unlike the other pairs of RGO-GONR and RGO-GNR, is not greater than the mixed cathode. Electrolyte contact angle measurements show the difference in the surface properties of all cathodes. Electrical conductivities and volumetric mass densities of all cathodes were measured and plotted in FIG. 3 (panel f). It is noteworthy that RGO-GONR cathodes, regardless of the type of coating, are more densely packed due to the highly dispersive nature of GONR in the slurry solution, and RGO-GNR cathodes are denser than RGO-CNT cathodes.

[0067] As illustrated in FIG. 8, the total capacity threshold and its rate of increase at a constant current with respect to the amount of carbon loading are dependent on the type of active materials used for the LOB cathodes, and our layered cathodes with different amount of carbon loadings performed greater than the single layer cathodes of RGO and GONR in terms of gravimetric and areal specific capacities.

Claims

CLAIMS What is Claimed is:

1. A battery comprising a first electrode and a second electrode, the first electrode comprising a multi-layered carbon structure, and the second electrode comprising lithium (e.g., lithium ion, lithium metal alloy, and/or lithium metal).

2. The battery of claim 1, wherein the multi-layered carbon structure comprises a first layer, and a second layer,

the first layer comprising a first carbon component (e.g., a grapheme component); and the second layer comprising a second carbon component (e.g., a one dimensional carbon component, such as a grapheme ribbon or a carbon nanotube).

3. The battery of any one of the preceding claims, wherein the first carbon component is a first carbon allotrope, or an oxide thereof.

4. The battery of claim 3, wherein first carbon component is a graphene, a graphene oxide (GO) or a reduced graphene oxide (rGO).

5. The battery of any one of the preceding, wherein the first layer comprises first particles comprising the first carbon component.

6. The battery of claim 5, wherein the first particles have a first dimension (e.g., length) of about 0.5 micron to about 20 micron (e.g., about 5 micron) (e.g., on average) and a second dimension (e.g., width) of about 0.5 micron to about 20 micron (e.g., about 3 micron) (e.g., on average).

7. The battery of either one of claims 5 or 6, wherein the first particles have a surface area of about 450 m²/g to about 750 m²/g (e.g., about 575 m²/g).

8. The battery of any one of claims 5-7, wherein the first particles have a low aspect ratio (e.g., about 10 or less) (e.g., wherein aspect ratio = longer of the first or second dimension / shorter of the first or second dimension).

9. The battery of any one of the preceding claims, wherein the first carbon component comprises about 0.1 wt. % to about 20 wt. % oxygen (e.g., about 4 wt. % to about 6 wt. %).

10. The battery of any one of the preceding claims, wherein the first carbon component thereof comprises about 70 wt. % to about 99.9 wt. % carbon.

11. The battery of any one of the preceding claims, wherein the first and second carbon components are different.

12. The battery of any one of the preceding claims, wherein the second carbon component is a second carbon allotrope, or an oxide thereof.

13. The battery of either one of claims 11 or 12, wherein t the second carbon component is a graphene oxide (GO) (or nanoribbons thereof), a reduced graphene oxide (rGO) (e.g., nanoribbons thereof) or CNT.

14. The battery of any one of the preceding, wherein the second layer comprises second particles comprising the second carbon component.

15. The battery of claim 14, wherein the second particles having a third dimension (e.g., width) of about 0.01 micron to about 5 micron (e.g., about 0.2 micron) (e.g., on average) and a fourth dimension (e.g., length) of about 5 micron to about 500 micron (e.g., about 50 micron) (e.g., on average).

16. The battery of either one of claims 14 or 15, wherein the second particles have a surface area of about 100 m²/g to about 450 m²/g (e.g., about 375 m²/g).

17. The battery of any one of claims 14-16, wherein the second particles have a high aspect ratio (e.g., about 20 or more).

18. The battery of any one of claims 14-17, wherein (a) the aspect ratio of the second particles is greater than the aspect ratio of the first particles (e.g., on average); and/or (b) the surface area of the second particles is less than the surface area of the first particles (e.g., on average).

19. The battery of any one of the preceding claims, wherein the second carbon component comprises about 10 wt. % to about 50 wt. % oxygen (e.g., about 25 wt. % to about 35 wt. %).

20. The battery of any one of the preceding claims, wherein the second carbon component comprises about 50 wt. % to about 90 wt. % carbon.

21. The battery of any one of the preceding claims, wherein the wt. % of oxygen of the first oxide of a carbon allotrope is less than the wt. % of oxygen of the second oxide of a carbon allotrope.

22. The battery of any one of the preceding claims, wherein the weight ratio of the first layer to the second layer is about 1 : 1 to about 9: 1.

23. The battery of any one of the preceding claims, wherein the first electrode further comprises a third layer, the third layer comprising a third carbon component, the second layer being positioned between the first and third layers.

24. The battery of claim 23, wherein the third carbon allotrope or analog thereof is as characterized by any one or more of claims 3-10.

25. The battery of either one of claims 23 or 24, wherein the first electrode further comprises a fourth and fifth layer, the fourth layer comprising a fourth carbon component, the fifth layer comprising a fifth carbon component, the fourth layer being positioned between the third and fifth layers.

26. The battery of claim 25, wherein the fourth carbon component is as characterized by any one or more of claims 12-20, and the fifth carbon component is as characterized by any one or more of claims 3-10.

27. The battery of either one of claims 25 or 26, wherein the first electrode further comprises a sixth and seventh layer, the sixth layer comprising a sixth carbon component, the seventh layer comprising a seventh carbon component the sixth layer being positioned between the fifth and seventh layers.

28. The battery of claim 27, wherein the sixth carbon component is as characterized by any one or more of claims 12-20, and the seventh carbon component is as characterized by any one or more of claims 3-10.

29. The battery of either one of claims 27 or 28, wherein the first, third, fifth, and seventh carbon components are the same; the second, fourth, and sixth carbon components are the same.

30. The battery of any one of the preceding claims, wherein the specific capacity of the first electrode is about 5,000 mAh/g or more (e.g., about 8,000 mAh/g or more, or about 10,000 mAh/g or more) (e.g., on charge and/or discharge, such as at a current density of 0.05 mA/cm²).

31. A battery comprising a first electrode and a second electrode, the first electrode comprising a first carbon component and a second carbon component, the first carbon component, and the second electrode comprising lithium (e.g., lithium ion and/or metal).

32. The battery of claim 31, wherein the first and second carbon components for an alternating layered structure, a first layer comprising the first carbon component, a second layer comprising the second carbon component, and any subsequent layers alternatingly comprising the first carbon component and the second carbon component.

33. The battery of claim 32, wherein the alternating layered structure comprises at least 5 layers.

34. The battery of claim 33, wherein the alternating layered structure comprises 7 layers.

35. The battery of any one of claims 31-34, wherein the first carbon component is as characterized in any one or more of claims 3-10.

36. The battery of any one of claims 31-35, wherein the second carbon component is as characterized in any one or more of claims 12-20.

37. The battery of any one of the preceding claims, wherein each layer has a thickness of about 50 micron or less (e.g., about 25 micron or less) (e.g., on average).

38. An electrode as describe for the first electrode in any one of claims 1-37.

39. A process for preparing an electrode, the process comprising: a. depositing a first carbon component on a substrate (e.g., current collector), thereby forming a first electrode layer; b. depositing a second carbon component on the first electrode layer, thereby forming a second electrode layer.

40. The process of claim 39, wherein the process further comprises depositing a third carbon component on the second electrode layer, thereby forming a third electrode layer.

41. The process of claim 40, wherein the first carbon component and third carbon component are the same.

42. The process of any one of claims 39-41, wherein the first carbon component is a carbon allotrope or analog thereof.

43. The process of any one of claims 39-42, wherein the first carbon component is a first carbon allotrope, or oxide thereof.

44. The process of claim 43, wherein the first carbon component is a graphene, a graphene oxide (GO) or a reduced graphene oxide (rGO).

45. The process of any one of claims 39-44, wherein first particles comprise the first carbon component.

46. The process of claim 45, wherein the first particles having a first dimension (e.g., length) of about 0.5 micron to about 20 micron (e.g., about 5 micron) (e.g., on average) and a second dimension (e.g., width) of about 0.5 micron to about 20 micron (e.g., about 3 micron) (e.g., on average).

47. The process of either one of claims 45 or 46, wherein the first particles have a surface area of about 450 m²/g to about 750 m²/g (e.g., about 575 m²/g).

48. The process of any one of claims 45-47, wherein the first particles have a low aspect ratio (e.g., about 10 or less) (e.g., wherein aspect ratio = longer of the first or second dimension / shorter of the first or second dimension).

49. The process of any one of claims 39-48, wherein the first carbon component comprises about 0.1 wt. % to about 20 wt. % oxygen (e.g., about 4 wt. % to about 6 wt. %).

50. The process of any one of claims 39-49, wherein the first carbon component comprises about 70 wt. % to about 99.9 wt. % carbon.

51. The process of any one of the preceding claims, wherein the second carbon component is a carbon allotrope or analog thereof.

52. The process of any one of the preceding claims, wherein the second carbon component is a second oxide of a carbon allotrope.

53. The process of either one of claims 51 or 52, wherein the second oxide of a carbon allotrope is a graphene oxide (GO) or a reduced graphene oxide (rGO) (e.g., nanoribbons thereof).

54. The process of any one of the preceding, wherein second particles comprise the second carbon component.

55. The process of claim 44, wherein the second particles having a third dimension (e.g., width) of about 0.01 micron to about 5 micron (e.g., about 0.2 micron) (e.g., on average) and a fourth dimension (e.g., length) of about 5 micron to about 500 micron (e.g., about 50 micron) (e.g., on average).

56. The process of either one of claims 54 or 55, wherein the second particles have a surface area of about 100 m²/g to about 450 m²/g (e.g., about 375 m²/g).

57. The process of any one of claims 54-56, wherein the second particles have a high aspect ratio (e.g., about 20 or more).

58. The process of any one of claims 54-57, wherein (a) the aspect ratio of the second particles is greater than the aspect ratio of the first particles (e.g., on average); and/or (b) the surface area of the second particles is less than the surface area of the first particles (e.g., on average).

59. The process of any one of the preceding claims, wherein the second carbon component comprises about 10 wt. % to about 50 wt. % oxygen (e.g., about 25 wt. % to about 35 wt. %).

60. The process of any one of the preceding claims, wherein the second carbon component comprises about 50 wt. % to about 90 wt. % carbon.

61. The process of any one of the preceding claims, wherein the carbon components are deposited by casting or by electrospraying.