Graphene monoxide compositions and electrodes comprising them

Abstract

To provide a novel graphene monoxide material that can be used in many applications such as electrochemical cells and methods of making the same.SOLUTION: Provided are a composition of graphene-based nanomaterials characterized by at least one area of one atomic layer of graphene monoxide, wherein at least a portion of oxygen molecules present in the graphene monoxide are incorporated into specific crystalline structural moieties, methods of making the same, electrodes in electrochemical devices incorporating the same, and compositions of lithium and graphene monoxide, the compositions containing material that result from cycling the electrodes.SELECTED DRAWING: Figure 1-1

Description

[Technical Field]

[0001] Federal Funding Statement This invention was made with government support under Grant No. 1843306 awarded by the National Science Foundation and Grant No. DE-SC0018795 awarded by the U.S. Department of Energy. The government has certain rights in this invention.

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Application No. 62 / 971,074, filed February 6, 2020, the contents of which are incorporated herein by reference. [Background technology]

[0003] Graphene-derived products have recently been commercialized. An important part of this group of materials is oxygenated graphene materials. Oxygenated graphene-based materials contain multiple carbon atoms with randomly distributed oxygen functional groups, such as epoxide, carbonyl, carboxyl, and hydroxyl groups, attached to carbon atoms and arranged with many structural defects in the hexagonal honeycomb carbon framework known as graphene. They can be referred to as graphene oxide, partially reduced graphene oxide, or reduced graphene oxide. These are listed in order of highest to lowest oxygen content, with typical oxygen contents ranging from approximately 0.5:1 atomic oxygen:carbon to approximately 0.05:1 atomic oxygen:carbon ratios. Oxygenated graphene materials have been produced on a large scale for many applications, including sensors, water filters, electrodes in electrochemical cells, anticorrosion coatings, and additives to rubber and plastics. One notable feature of graphene and oxygenated graphene materials is their high surface area.

[0004] The primary method for producing or synthesizing graphene oxide involves treating graphite with acids and oxidizing agents at controlled temperatures (e.g., the Hummer method) to separate individual defective, oxygenated graphene sheets. Graphene oxide powder exhibits a large exotherm at 150-250 °C due to the various oxygen functional groups present in graphene oxide, making its use in applications requiring dry powders difficult. Typically, graphene oxide dispersions are heat-treated to produce partially reduced graphene oxide or reduced graphene oxide.

[0005] Graphene monoxide is a solid form of carbon monoxide and is the only member of the family of oxygenated graphene materials that can have a 1:1 oxygen to carbon atom ratio. Like graphene oxide, the graphene monoxide materials described in this disclosure are platform materials that can be used in many applications, such as electrochemical cells as realized in this disclosure. Summary of the Invention [Problem to be solved by the invention]

[0006] Graphene (G) is a single atomic layer of graphite. While the three-dimensional crystal structure of graphite (Gr) is hexagonal close-packed, a single graphite layer, or graphene, has a hexagonal honeycomb structure composed solely of carbon atoms. The broader graphene family of materials includes several different oxidized forms in descending order of oxygen content: graphene monoxide (GmO), graphene oxide (GO), partially reduced graphene oxide (prGO), and reduced graphene oxide (rGO). The structures in this family of graphene materials offer desirable properties at both the quantum nano- and macroscopic levels. The compositions disclosed herein are based on GmO, which has an average atomic carbon-to-oxygen ratio of 1:1, as well as tailored composites of GmO and G. In some embodiments, these compositions are the product of a process starting with GO.

[0007] When GO is used as the starting material for the G group of materials, most conventional processing methods are designed to remove the four oxygen functional groups that are randomly bonded to the defective graphene crystalline network. These methods aim to produce rGO, which can be labeled and sold as graphene when the atomic percentage of remaining oxygen is low. Some applications of GO require limited reduction of its functional groups to produce prGO, which contains an intermediate amount of oxygen compared to GO and rGO while maintaining the same functional group properties. The oxygen functional groups in GmO are more abundant than those in GO, prGO, and rGO, and are different from those in GO, prGO, and rGO. In some embodiments, the GmO-based composite materials disclosed herein are composed of GmO, G, and a transition metal oxide (TMO) and are designated GmGT materials.

[0008] Ordered crystalline monolayers of GmO have been predicted by density functional theory (DFT) in two publications (Xiang, HJ et al. (2010) “Structural motifs in oxidized graphene: a genetic algorithm study based on density functional theory,” Physical Review B 035416:82(3) and Mattson, EC et al. (2011) “Evidence of nanocrystalline semiconducting graphene monoxide during thermal reduction of graphene oxide in vacuum,” ACS Nano 5:9710-9717) and reported experimentally in one of these references (Mattson, EC et al. (2011)) and in a patent (Chen et al., U.S. Pat. No. 9,236,633). However, this synthetic method is not scalable, producing only a few nanograms of GmO-based material. (This method is carried out in the vacuum of an electron microscope using high-energy electron and X-ray bremsstrahlung showers.) The Chen et al. patent cited above describes the formation of a GmO phase on a metal grid.

[0009] The crystalline GmO produced in this disclosure, and the GmO:G and GmO:TMO ratios, are structurally different from the material of Chen et al., and can be produced on a gram scale. The methods disclosed herein are amenable to further industrial scale-up, and the amount of material produced is sufficient to accomplish the fabrication of electrochemical cells.

[0010] This disclosure reports the generation of compositions by methods to obtain a family of GmGT composite materials and the characterization of these materials. In some embodiments, novel compositions of pure GmO are presented as four distinct crystalline phases and their chemical building block families, linked to perturbations in processing methods. The fabricated materials are incorporated into electrodes and demonstrate superior electrochemical cell performance compared to other carbon-based electrodes in terms of charge rate, gravimetric capacity, low-temperature operation, and minimal lithium (Li) dendrite growth. Testing of GmGT anode materials cycled in batteries through single and multiple lithiation (charge) and delithiation (discharge) cycles demonstrates that the GmO fingerprint remains detectable. The novel compositions predict interactions between Li and GmO, and the theoretical specific capacity of these Li-GmO materials is approximately 957 mAh / g.

[0011] In addition to electrochemical applications, GmO-containing materials in general, and the GmGT family of materials in particular, are platform materials for a wide range of applications. Their properties, distinct from other carbon-oxygen materials, offer beneficial performance in catalytic applications, nuclear fuel packaging, general adsorption and absorption applications, corrosion resistance, electrical sensing applications, membrane and filtration applications, photonics, 3D-printable materials, and composites, improving mechanical, electrical, and thermal performance. The flexible nature of GmO-containing materials allows for flexible and wearable electronics, textiles, flexible membranes, and the incorporation of polymeric materials.

[0012] Thus, disclosed in this disclosure is the following: 1. A composition comprising at least one atomic layer of graphene monoxide, wherein at least a portion of the oxygen molecules present in the graphene monoxide are incorporated into a structure having chemical moieties selected from the group consisting of a 1,3-dioxetane ring, a 1,5-dioxa-cyclooctane ring, a 1,4,7-trioxa-cyclononane ring, a (3,5,8,10)-tetraoxa-(1,6)-cyclodecadiene ring, and a polycarbonyl chain.

[0013] 2. The chemical moiety is atomically ordered in one or more phases of a two-dimensional graphene monoxide crystal structure having a carbon to oxygen atomic ratio of about 1:1; The interatomic lattice spacing of the crystal structure is 0.39 to 0.42 Å -1 and 0.68 to 0.76 Å -1 ;0.39Å -1 and 0.45 Å -1 ;0.33Å -1 and 0.88 Å -1 ; and 0.38 to 0.33 Å -1 and 0.77 to 0.78 Å -1 10. The composition of claim 1, exhibiting a selected area electron diffraction signature selected from the group consisting of:

[0014] 3. The composition of claim 1, further comprising at least one transition metal oxide.

[0015] 4. The composition of claim 3, wherein the transition metal oxide comprises a transition metal selected from the group consisting of Ti, V, Cr, Zr, Nb, Mo, Fe, Co, Ni, Hf, Ta, and W.

[0016] 5. The interatomic lattice spacing of the crystal structure is 0.39 to 0.42 Å -1 and 0.68 to 0.76 Å -1 ;0.39Å -1 and 0.45 Å -1 ;0.33Å -1 and 0.88 Å -1 ; and 0.38 to 0.33 Å-1 and 0.77 to 0.78 Å -1 4. The composition of claim 3, exhibiting a selected area electron diffraction signature selected from the group consisting of:

[0017] 6. The interatomic lattice spacing of the crystal structure is approximately 1,200 cm as measured by infrared spectroscopy. -1 ~1,400cm -1 6. The composition of claim 5, exhibiting carbon-oxygen vibrations with a peak at

[0018] 7. The composition is approximately 116 ppm 13 4. The composition of claim 3, exhibiting a C solid-state NMR chemical shift:

[0019] 8. Approximately 100m 2 4. The composition of claim 3, having a Brunauer-Emmett-Teller (BET) surface area of ​​1 / g or less.

[0020] 9. Approximately 100m 2 / g~about 600m 2 4. The composition of claim 3, having a Brunauer-Emmett-Teller (BET) surface area of ​​1.0 g / g.

[0021] 10. The composition of claim 3, further comprising at least one atomic layer of graphene, wherein the at least one atomic layer of graphene may be randomly stacked or locally ordered as AB or AA stacking in forming a multilayer.

[0022] 11. Graphene monoxide can be crystalline or amorphous; At least a portion of the graphene is crystalline; and 11. The composition of claim 10, wherein the transition metal oxide is amorphous and substantially uniformly distributed throughout the composition or is present in the composition as nanocrystals detectable by electron diffraction and X-ray diffraction.

[0023] 12. The composition of claim 1, further comprising lithium ions or lithium atoms intercalated into or adsorbed onto said atomic layers of graphene monoxide.

[0024] 13. Lithium ions or lithium atoms are transferred to the carbon and oxygen atoms of graphene monoxide from Li2C6O6 to LiC 50 O 50 13. The composition of claim 12, wherein the composition is present in a ratio of up to

[0025] 14. Lithium ions or lithium atoms are substituted for carbon and oxygen atoms of graphene monoxide, such as Li2C2O2, Li2C6O6, Li2C8O8, LiC6O6, LiC8O8, Li2C 18 O 18 , Li2C 32 O 32 , LiC 18 O 18 , LiC 32 O 32 , and LiC 50 O 50 13. The composition of claim 12, wherein the composition is present in a ratio selected from:

[0026] 15. The composition of claim 12, wherein at least a portion of the lithium ions or lithium atoms occupy H sites relative to the graphene monoxide.

[0027] 16. The composition of claim 12, wherein at least a portion of the lithium ions or lithium atoms occupy S sites relative to the graphene monoxide.

[0028] 17. ΔE of lithium ions or lithium atoms in the composition Li is about -0.04 eV (about -6.4 × 10 -21 J) to approximately -0.59 eV (approximately -9.45 × 10 -20 The composition of claim 12, ranging from

[0029] 18. (a) mixing a first solution, suspension, or powder comprising a carbon and oxygen source material with a second solution, suspension, or powder comprising at least one transition metal compound to form a mixture; and (b) heat treating the mixture of step (a) in an environment, for a time, at a temperature, and at a pressure that results in a composition comprising graphene monoxide; wherein at least a portion of the oxygen molecules present in graphene monoxide are incorporated into chemical moieties, the chemical moieties being selected from the group consisting of 1,3-oxetane rings, 1,5-dioxa-cyclooctane rings, 1,4,7-trioxa-cyclononane rings, (3,5,8,10)-tetraoxa-(1,6)-cyclodecadiene rings, and polycarbonyl chains.

[0030] 19. The composition of claim 18, wherein the carbon source material has an atomic oxygen to carbon ratio of about 20% or greater and is selected from the group consisting of graphene oxide, polysaccharides, and phenolic polymers.

[0031] 20. The composition of claim 18, wherein the transition metal oxide comprises a transition metal selected from the group consisting of Ti, V, Cr, Zr, Nb, Mo, Fe, Co, Ni, Hf, Ta, and W.

[0032] 21. The composition of claim 18, wherein in step (a) the atomic ratio of metal atoms to carbon atoms is x, where 0.05≦x≦0.3.

[0033] 22. The composition of claim 18, wherein step (a) further comprises mixing a third solution, suspension, or powder containing an oxidizing agent with the first and second solutions, suspensions, or powders.

[0034] 23. The composition of claim 18, wherein step (a) is carried out at a temperature of less than about 100°C.

[0035] 24. The composition of claim 18, wherein step (b) comprises heating the mixture of step (a) at a temperature less than about 100°C.

[0036] 25. The composition of claim 18, wherein step (b) comprises heating the mixture of step (a) to a temperature of from about 20°C to about 350°C.

[0037] 26. The composition of claim 18, wherein step (b) comprises heating the mixture of step (a) to a temperature of from about 20°C to about 800°C.

[0038] 27. The composition of claim 18, wherein step (b) comprises heating the mixture of step (a) to a temperature of from about 20°C to about 1,000°C.

[0039] 28. The composition of claim 18, further comprising reducing the size of the composition.

[0040] 29. The composition of claim 18, wherein in step (b), the mixture exhibits an exotherm of less than about 300 J / g when heated to 350°C.

[0041] 30. The composition of claim 18, wherein step (b) comprises heating the mixture at a temperature ranging from about 21°C to about 800°C at a constant or variable heating rate.

[0042] 31. The composition of claim 30, wherein in step (b), the mixture exhibits an exotherm of less than 300 J / g when heated to 800°C.

[0043] 32. The interatomic lattice spacing of the structure in the composition is 0.39-0.42 Å -1 and 0.68 to 0.76 Å -1 ;0.39Å -1 and 0.45 Å -1 ;0.33Å -1 and 0.88 Å -1 ; and 0.38 to 0.33 Å -1 and 0.77 to 0.78 Å -1 20. The composition of claim 18, exhibiting a selected area electron diffraction signature selected from the group consisting of:

[0044] 33. The interatomic lattice spacing of the structure in the composition is approximately 1,200 cm by infrared spectroscopy. -1~1,400cm -1 19. The composition of claim 18, exhibiting carbon-oxygen vibrations with a peak at

[0045] 34. The composition is approximately 116 ppm. 13 19. The composition of claim 18, exhibiting a C solid-state NMR chemical shift:

[0046] 35. Approximately 100m 2 19. The composition of claim 18, having a Brunauer-Emmett-Teller (BET) surface area of ​​1 / g or less.

[0047] 36. Approximately 100m 2 / g~about 600m 2 19. The composition of claim 18, having a Brunauer-Emmett-Teller (BET) surface area of ​​1 / g.

[0048] 37. The composition of claim 18, wherein step (b) comprises heat treating the composition at a pressure less than atmospheric pressure.

[0049] 38. Step (b) is about 2 × 10 -6 torr (approx. 2.67 x 10 -4 38. The composition of claim 37, comprising heat treating the composition at a pressure of less than or equal to 100 Pa.

[0050] 39. The composition of claim 18, wherein step (b) comprises heat treating the composition under an inert atmosphere.

[0051] 40. An electrode comprising the composition of claim 1.

[0052] 41. An electrode comprising the composition of claim 3.

[0053] 42. An electrode comprising the composition of claim 18.

[0054] 43. A charge storage device comprising the electrode of claim 40, the charge storage device having a faster charge rate at 1 C or greater than a corresponding charge storage device comprising a graphite-only anode.

[0055] 44. A charge storage device comprising the electrode of claim 41, the charge storage device having a faster charge rate at 1 C or greater than a corresponding charge storage device comprising a graphite-only anode.

[0056] 45. A charge storage device comprising the electrode of claim 42, the charge storage device having a faster charge rate at 1 C or greater than a corresponding charge storage device comprising a graphite-only anode.

[0057] 46. ​​A charge storage device comprising the electrode of claim 40, wherein the charge storage device has a faster charge rate and a higher charge capacity at temperatures between about 0°C and about -20°C than a corresponding charge storage device comprising a graphite-only anode charged at temperatures between about 0°C and about -20°C.

[0058] 47. A charge storage device comprising the electrode of claim 41, wherein the charge storage device has a faster charge rate and a higher charge capacity at temperatures between about 0°C and about -20°C than a corresponding charge storage device comprising a graphite-only anode charged at temperatures between about 0°C and about -20°C.

[0059] 48. A charge storage device comprising the electrode of claim 42, wherein the charge storage device has a faster charge rate and a higher charge capacity at temperatures between about 0°C and about -20°C than a corresponding charge storage device comprising a graphite-only anode charged at temperatures between about 0°C and about -20°C.

[0060] 49. A charge storage device comprising the electrode of claim 40, wherein the energy storage cell exhibits a monotonically decreasing potential versus specific capacity curve.

[0061] 50. A charge storage device comprising the electrode of claim 41, wherein the energy storage cell exhibits a monotonically decreasing potential versus specific capacity curve.

[0062] 51. A charge storage device comprising the electrode of claim 42, wherein the energy storage cell exhibits a monotonically decreasing potential versus specific capacity curve.

[0063] 52. A method of improving the performance of a lithium ion battery, comprising replacing an existing electrode in the lithium ion battery with the electrode of claim 40.

[0064] 53. A method of improving the performance of a lithium ion battery, comprising replacing an existing electrode in the lithium ion battery with the electrode of claim 41.

[0065] 54. A method of improving the performance of a lithium ion battery, comprising replacing an existing electrode in the lithium ion battery with the electrode of claim 42.

[0066] GmGT composition of processed materials There are numerous methods for producing rGO from GO, but fewer for producing prGO [Claudia Backes et al. “Production and processing of graphene and related materials” 2020 2D Mater. 7 022001]. Most are based on a chemical reduction process in liquid solution, yielding a product that is a suspension of solid (p)rGO layers in an aqueous solution. Heating suspensions of GO and (p)rGO is considered safe. However, heating unreduced dry powders of GO involves an exothermic reaction that can lead to a runaway explosion if the powder and heating parameters are not adequately controlled and limited [Y. Qiu, et al. “Explosive thermal reduction of graphene oxide-based materials: Mechanism and safety implications”, CARBON 72 (2014) 215-223].

[0067] In this disclosure, when GO is used as the starting carbon source, the unique final processing goal is to obtain as high an oxygen content as possible and to generate oxygen and carbon moieties in the characteristic functional groups of GmO in a safe material. An additional goal is to produce compositions of GmGT, including the crystalline GmO phase (hereinafter "GmGT-X") and its disordered (amorphous) variants (hereinafter "GmGT-A"), as well as precipitated TMO nanocrystals (hereinafter "GmGT-NC"). A safe processing method has been developed to produce a passivated precursor material (hereinafter "pre-GmGT") that eliminates or minimizes exothermic reactions, enabling GmO-based materials to be produced on a practical scale. The final material is safe for use in applications that may be exposed to high temperatures. Other embodiments of GmO-based materials that do not use GO as the carbon source material are also presented.

[0068] In some embodiments, GmGT materials can be prepared at room temperature starting from a commercially available suspension of GO in water mixed with a base, acid, or oxidizing agent and one or more TM-containing sources. Depending on the TM-containing source, mixing times can range from 5 minutes to several days at temperatures between about 20°C and about 80°C to adjust the number of GmO moieties. As explained below, the atomic ratio "x" of TM to C can be used to fine-tune the final GmGT material.

[0069] In some embodiments, the resulting material is dried at temperatures from about 20°C to less than 100°C to produce sheets of dry material. Optionally, these may be used as films, flakes, or ground into dry powders. Suitable methods include tray drying, spray drying, freeze drying, or drum drying. These methods can be performed in batch, semi-batch, or continuous modes. In some embodiments, the material recovered at this stage provides the pre-GmGT material. In other embodiments, heat treatment under high or low vacuum, or in ambient or inert atmosphere, up to about 300°C, provides the pre-GmGT.

[0070] Further controlled heat treatment to higher temperatures under vacuum or an inert atmosphere as a continuation or separate step yields two main classes of end-product materials: GmGT(I) and GmGT(II), distinguished by the heating rate in the critical temperature region. Within the first class, three distinct compositions emerge with increasing temperature: a) GmGT(I)-A, which contains regions of amorphous GmO, along with crystalline G and molecular TMO, which upon further annealing yields crystalline α-GmO; b) GmGT(I)-X, which contains regions of crystalline α-GmO, along with crystalline G and molecular TMO; and c) GmGT(I)-NC, which contains crystalline GmO, G, and precipitated nanocrystals of TMO. Within the second class, increasing temperature yields only two distinct compositions, GmGT(II)-A and GmGT(II)-NC, similarly described by the crystallinity of the components.

[0071] In one embodiment, when the atomic ratio "x" of TM to C is less than about 0.05, the characterization signature of GmO is not observed upon completion of the particular process defined above. In the intermediate range of x, from about 0.05 to about 0.3, this process method results in the formation of GmO and avoids the precipitation of TMO nanocrystallites ("NCs"), resulting in GmGT-A or GmGT-X materials. When x is greater than about 0.3, nucleation and growth of TMO NCs occurs, with sizes greater than about 10 nm, and the process results in the final GmGT-NC composition.

[0072] Predictive Modeling of Composition The present disclosure discloses oxygenated graphene materials containing oxygen-containing moieties bonded to carbon, where the chemical moieties are selected from the group consisting of 1,3-dioxetane rings, 1,5-dioxa-cyclooctane rings, 1,4,7-trioxa-cyclononane rings, (3,5,8,10)-tetraoxa-(1,6)-cyclodecadiene rings, or oxygen heterocyclic rings consisting of polycarbonyl chains (see Figures 1 and 2 below). These moieties may be bonded in two-dimensional layers called graphene monoxide, which may be ordered in crystalline domains or disordered in amorphous domains. These atomic structures and their arrangement in amorphous or ordered GmO layers are not present in GO, prGO, rGO, or G layers.

[0073] The innovation behind GmO materials and GmO-based composites is that the 2D layered nature of these materials provides solid-phase stability. These GmO layers exhibit unique arrangements of carbon and oxygen atoms, allowing the formation of solid forms of carbon monoxide (CO) that are stable at ambient and elevated temperatures, either as GmO monolayers or as GmO multilayers that can be constructed into nano-, micro-, and macro-scale three-dimensional solids. Furthermore, GmO is stable at high temperatures and low pressures. Unlike the solid nature of GmO, CO is a gas under ambient conditions and can become a 3D solid at very low temperatures (freezing point of −205°C at atmospheric pressure) or very high pressures. Similar to the numerous solid 3D crystalline phases of CO, GmO can also form multiple 2D crystalline phases, including α-, β-, γ-, and δ-GmO crystalline structures and their molecular building blocks described in this disclosure. Compositions containing α-GmO, which has a 1,3-dioxetane ring as the CO building block, are most frequently formed in the synthetic processes described in this disclosure.

[0074] Characterization of source material and product composition signatures Characterization of selected starting carbon sources includes pH measurements on solutions and suspensions, infrared spectroscopy of dry materials and powders for characteristic vibrational absorption lines, optical and transmission electron microscopy for morphology, electron diffraction for crystallinity, energy dispersive spectroscopy for elemental composition, and thermogravimetric analysis and differential scanning calorimetry or differential thermal analysis to determine the mass loss and enthalpy profile of dry powders when heated to the temperatures used in the processes described in this disclosure.

[0075] Characterization of selected TM solutions includes measurement of pH, UV-VIS spectroscopy for optical assessment of color, and inductively coupled plasma mass spectrometry to verify the calculated concentrations of transition metals in solution. Dried solutions and other powders are evaluated by infrared spectroscopy for characteristic vibrational absorption lines, optical and transmission electron microscopy for morphology, electron diffraction for crystallinity, and thermogravimetry and differential scanning calorimetry to determine the mass loss and enthalpy profile of the powders when heated to temperatures used in the processes described in this disclosure.

[0076] Processed compositions are uniquely described by a variety of characterization techniques to demonstrate their physical and chemical properties. Predictive calculations for all compositions covered in this disclosure systematically predict signature fingerprints for the techniques used based on the atomic structure of crystalline materials (electron and X-ray diffraction) and molecular vibrations of crystalline and amorphous materials (infrared spectroscopy). With particular attention paid to precursor (pre-GmGT) and final (GmGT) materials, various additional techniques were deployed to identify distinct fingerprints for these classes of materials.

[0077] For example, GmGT samples containing oxygen heterocyclic rings or polycarbonyl chains as novel chemical moieties in oxygenated graphene may possess characteristic vibrations. The molecular vibrations of the 1,3-dioxetane ring moiety, either by itself or in the 1,5-dioxacyclooctane repeat unit of α-GmO crystals, are present in most compositions and have been systematically studied by diffuse reflectance Fourier transform infrared spectroscopy (DR-FTIR), attenuated total reflectance FTIR (ATR-FTIR), and transmission FTIR (T-FTIR) (hereafter referred to as "IR"). These IR techniques are sensitive to the G region and specific TMO vibrations in composites synthesized on a practical scale.

[0078] The crystallinity of GmO and G in GmGT composites is crucial for their composition and related properties and functions. The ordered crystalline domains of the GmO and G layers have been systematically confirmed using their unique 2D diffraction peaks detected by diffraction, such as selected-area electron diffraction (SAED) in a transmission electron microscope (TEM). Interatomic spacings are determined from SAED measurements of diffraction rings and / or spots and compared with calculated spacings predicted by DFT. In GmGT-NC materials, SAED can detect the unique diffraction rings or spots from TMO nanocrystals and identify their structure and stoichiometry. The c-axis spacing of GmGT multilayers has also been measured by TEM-SAED and laboratory-based and synchrotron X-ray diffraction, and is, on average, larger than that of graphite. Disordered GmO and G molecular moieties and crystalline defects, along with molecular or amorphous TMO, which are substantially uniformly distributed throughout the bulk material, contribute to the SAED background. The absence of characteristic GmO diffraction peaks in the TEM-SAED patterns is a conclusive sign that GmO does not form a crystalline phase in the specific treatment.

[0079] The surface morphology of the material itself and as part of the electrode was characterized by scanning electron microscopy (SEM) using secondary and backscattered electrons. Elemental analysis maps from energy dispersive X-ray spectroscopy (EDS) showed a homogeneous distribution of metals in the GmGT composite.

[0080] In some versions of the materials disclosed herein, the TM column of the periodic table can form individual TMOs or combinations of TMOs. In some embodiments, these preferred metal oxides include one or more of Ti, V, Cr, Zr, Nb, and Mo, with other possible members being Ni, Fe, Co, Hf, Ta, and W. Extended X-ray absorption fine structure spectroscopy (EXAFS) shows that there are no chemical bonds between specific examples of TM atoms and carbon atoms. In these versions of GmGT materials, metal atoms are not bonded to carbon, and metal carbonates, metal carbides, or other metal-carbon species are not formed. In this example, the presence of the TM in intimate contact with the GO layer is believed to facilitate chemical transformation of C and O atoms and the formation of oxygen heterocycles consisting of 1,3-dioxetane rings, 1,5-dioxa-cyclooctane rings, 1,4,7-trioxa-cyclononane rings, (3,5,8,10)-tetraoxa-(1,6)-cyclodecadiene rings, or polycarbonyl chains. The chemical transformation may involve catalytic action of TM compounds or their direct chemical reaction with carbon source atoms.

[0081] Characterization of the intermediate GmO-containing material form (pre-GmGT) and the final GmO-containing product (GmGT) materials includes thermogravimetry (TGA) and differential scanning calorimetry (DSC) or differential thermal analysis (TDA) to determine the mass loss and enthalpy profile of the material and evaluate safety enhancements due to additives and processing parameters. Brunauer-Emmett-Teller (BET) surface area measurements are used to characterize the specific surface area and evaluate pore size. Magic angle spinning 13 C solid-state nuclear magnetic resonance (NMR) is used to detect the local chemical environment around the carbon atoms. Proton NMR measurements determine the hydrogen present in some of the oxygen functional groups of GO. This hydrogen is substantially removed by the processing steps used to produce the GmGT material when the starting carbon source material is derived from GO.

[0082] Electrochemical cells fabricated with GmGT materials: Implementation and cell performance characteristics The above GmO-based materials and composites, when produced on a practical scale, can be used to improve the fast charging and low temperature performance of batteries for use in the commercial, leisure, military, and space industries, such as (for example) high power density power tools and automotive transportation, and high energy density consumer electronics.

[0083] Generally, these materials have larger and more easily enlarged interlayer spacing than graphite materials, allowing them to perform better in fuel cells, supercapacitors, solid electrolyte batteries, sodium-ion batteries, lithium-sulfur batteries, and lithium-air batteries.

[0084] The materials disclosed in this disclosure can be used as complete replacements or additives for lithium and sodium ion battery anodes, which may optionally contain additional specific capacity and / or rate capability enhancing particles (e.g., silicon nanoparticles, etc.).

[0085] In lithium-ion battery (LIB) embodiments with anodes comprising GmGT composites, either pure or further composited with graphite crystallites (Gr) and silicon nanoparticles (Si), GmGT improves numerous performance characteristics of the LIB: in addition to fast charging (in the range of 1 C to 10 C) and low-temperature operation (down to -20°C), the mass-specific capacity of GmO is also improved compared to Gr (e.g., α-GmO has a theoretical capacity of 957 mAh / g, 2.6 times better than 372 mAh / g for Gr), and significantly reduced Li metal dendrite growth improves cyclability and safety.

[0086] Lithium interactions with GmGT by SAED of test cells and DFT predictions for the new composition LGm Also disclosed herein are compositions comprising GmO-based materials containing at least one atomic layer region of GmO in combination with lithium atoms, as well as methods for synthesizing these novel lithium and GmO-based compositions (hereinafter "LGm" and "LGmGT") whose crystalline diffraction signatures are detectable by TEM-SAED, in which lithium ions and / or lithium atoms are intercalated or adsorbed into the atomic layers of GmO.

[0087] Density functional theory predicted calculations of lithium atom interactions with a GmO monolayer indicate that the GmO monolayer can retain lithium atoms, which is not the case for a G monolayer, and predict that the maximum theoretical capacity of this novel anode material for Li-ion batteries is 957 mAh / g for the Li2C2O2 composition.

[0088] Lithium ions and / or lithium atoms are transferred to the carbon and oxygen atoms of graphene monoxide from Li2C2O2 to LiC 50 O 50 For example, lithium ions and / or lithium atoms may be present in the LGm composition in ratios up to Li2C2O2, LiC2O2, Li2C6O6, LiC4O4, Li2C8O8, LiC6O6, LiC8O8, Li2C 18 O 18 , Li2C 32 O 32 , LiC 18 O 18 , LiC 32 O 32 and LiC 50 O 50 It is the intent of this invention to recognize all of these forms as novel compositions made possible by this invention.

[0089] In a preferred version of the composition, at least a portion of the lithium ions and / or lithium atoms occupy H sites relative to the graphene monoxide carbon sublattice. In another version of the composition, at least a portion of the lithium ions and / or lithium atoms occupy S sites relative to the graphene monoxide oxygen sublattice. In yet another version of the composition, at least a portion of the lithium ions and / or lithium atoms occupy H and S sites relative to the graphene monoxide. Li transport occurs readily in parallel with the GmO layer, which supports the fast-charging properties of batteries fabricated using the GmGT material.

[0090] The composition may consist of, or consist essentially of, carbon atoms, oxygen atoms, and lithium atoms atomically arranged such that the composition is electrically conductive. [Brief explanation of the drawings]

[0091] [Figure 1-1] Figure 1: Four two-dimensional crystalline phases of solid CO, labeled α-GmO (A) through δ-GmO (D), generated from the building blocks shown in Figure 2. Each structure is represented by a top-view projection, two side-view projections, and one atomic structure perspective. Carbon (oxygen) atoms are depicted as light (dark) gray spheres. [Figure 1-2] This is a continuation of Figure 1-1. [Figure 1-3] This is a continuation of Figure 1-2. [Figure 1-4] This is a continuation of Figure 1-3.

[0092] [Figure 2] Figure 2: Molecular building blocks of the two-dimensional graphene monoxide crystal shown in Figure 1. 1,3-dioxetane (A) is a four-membered heterocycle with two oxygens and two carbons. It is a subblock of 1,5-dioxacyclooctane (B) and 1,4,7-trioxacyclononane. Two further moieties are 3,5,8,10-tetraoxa-1,6-cyclodecadiene (D) and a polycarbonyl chain (E).

[0093] [Figure 3-1] Figure 3: Characterization signature of the pre-GmGT(I) precursor material. (A): SAED intensity profile (black solid line) and graphene peak position (dark gray dashed line). Note the absence of a peak for crystalline α-GmO (light gray solid line). (B): Diffraction peak position (k), lattice spacing (d), and intensity (I) determined from (A). (C): SAED pattern showing randomly stacked multilayer diffraction rings of crystalline G (scale bar = 10 1 / nm). (D): Bright-field TEM image (scale bar = 1 μm). (E): IR absorbance spectrum. (F): SEM image showing the cross-section of a large flake (scale bar = 40 μm). The sheet-like, thicker rGO morphology differs from the thin rGO morphology reported in the literature. (G): TGA curve of mass loss when the material is heated to 300 °C under argon gas flow. (H): DSC curve with a peak at 187.5 °C but no strong exothermic reaction and associated heat flow with a much lower enthalpy than typically seen for GO below 300 °C. [Figure 3-2] This is a continuation of Figure 3-1. [Figure 3-3] This is a continuation of Figure 3-2.

[0094] [Figure 4-1] Figure 4: Characterization signature of the GmGT(I)-A product material. (A): SAED intensity profile (black solid line) and graphene peak position (dark gray dashed line). Note the absence of a peak for crystalline α-GmO (light gray solid line). (B): Diffraction peak position (k), lattice spacing (d), and intensity (I) determined from (A). (C): SAED pattern showing the diffraction rings of G and the absence of α-GmO rings (scale bar = 10 1 / nm). Note that further heating can convert the GmGT(I)-A material to GmGT(I)-X, which may exhibit the diffraction signature of crystalline α-GmO. (D): Bright-field TEM image (scale bar = 1 μm). (F): SEM image (scale bar = 20 μm) showing the thick sheet morphology present in the powdered material, which differs from the thin rGO morphology described in the literature. [Figure 4-2] This is a continuation of Figure 4-1.

[0095] [Figure 5-1] Figure 5: Characterization signature of the GmGT(I)-X product material. (A): SAED intensity profile (black solid line) and peak positions of α-GmO (light gray solid line) and graphene (dark gray dashed line). (B): Diffraction peak positions (k), lattice spacing (d), and intensity (I) determined from (A). (C): SAED pattern showing the diffraction rings of α-GmO and G (scale bar = 10 1 / nm). (D): Bright-field TEM image (scale bar = 1 μm). (E): IR absorbance spectrum. (F): SEM image (scale bar = 100 μm) showing the thick sheet morphology present in the powdered material, which differs from the thin rGO morphology described in the literature. [Figure 5-2] This is a continuation of Figure 5-1.

[0096] [Figure 6-1] Figure 6: Characterization signature of the GmGT(II)-A product material. (A): SAED intensity profile (black solid line) and graphene (dark gray dashed line). Note the absence of a peak for α-GmO (light gray solid line). (B): Diffraction peak position (k), lattice spacing (d), and intensity (I) determined from (A). (C): SAED pattern showing the diffraction rings of G and the absence of α-GmO rings (scale bar = 10 1 / nm). Note that further heating does not produce the diffraction signature of crystalline α-GmO. (D): Bright-field TEM image (scale bar = 1 μm). (E): IR absorbance spectrum. [Figure 6-2] This is a continuation of Figure 6-1.

[0097] [Figure 7-1]Figure 7: Thermal characterization of a blend of GmGT(I)-X and GmGT(II)-A product materials, heated from room temperature to 600 °C at a rate of 10 °C / min, followed by heating at a rate of 3 °C / min from 600 °C to 1100 °C. (A): TGA curve showing the mass loss of the sample as a function of temperature. The fastest loss occurred between 727 °C and 750 °C, with 58.7% mass retained at the highest temperature. (B): DSC curve showing heat flow without the main exothermic peak typically observed for GO. (C): 13C solid-state NMR spectrum showing chemical shifts around the carbon atoms of the starting blend material. [Figure 7-2] This is a continuation of Figure 7-1.

[0098] [Figure 8-1] Figure 8: Characterization signature of partially reduced graphene oxide (prGO) (perturbation of sample 6.6) used as a control material for the GmO-containing sample. (A): SAED intensity profile (black solid line) and graphene (dark gray dashed line). Note the absence of the α-GmO (light gray solid line) peak. (B): Diffraction peak position (k), lattice spacing (d), and intensity (I) determined from (A). (C): SAED pattern showing the diffraction rings of G and the absence of α-GmO rings (scale bar = 10 1 / nm). (D): Bright-field TEM image (scale bar = 1 μm). (E): IR absorbance spectrum. [Figure 8-2] This is a continuation of Figure 8-1.

[0099] [Figure 9-1] Figure 9: Characterization signature of GmGT(I)-X (perturbation of sample 6.2). (A): SAED intensity profile (black solid line) and peak positions of α-GmO (light gray solid line) and graphene (dark gray dashed line). (B): Diffraction peak positions (k), lattice spacing (d), and intensity (I) determined from (A). (C): SAED pattern showing the diffraction rings of α-GmO and G (scale bar = 10 1 / nm). (D): Bright-field TEM image (scale bar = 1 μm). (E): IR absorbance spectrum. [Figure 9-2] This is a continuation of Figure 9-1.

[0100] [Figure 10-1] Figure 10: Characterization signature of GmGT(I)-X (perturbed sample 6.3) produced from a lignin starting carbon source. (A): SAED intensity profile (black solid line) and peak positions of α-GmO (light gray solid line) and graphene (dark gray dashed line). (B): Diffraction peak positions (k), lattice spacing (d), and intensity (I) determined from (A). (C): SAED pattern showing the diffraction rings of α-GmO and G (scale bar = 10 1 / nm). (D): Bright-field TEM image (scale bar = 1 μm). (E): IR absorbance spectrum. [Figure 10-2] This is a continuation of Figure 10-1.

[0101] [Figure 11-1] Figure 11: Characterization signature of GmGT(I)-X (perturbation of sample 6.7) from GO hydrothermally produced from biorenewable resources. (A): SAED intensity profile (black solid line) and peak positions of α-GmO (light gray solid line) and graphene (dark gray dashed line). (B): Diffraction peak positions (k), lattice spacing (d), and intensity (I) determined from (A). (C): SAED pattern showing diffraction rings of α-GmO and G (scale bar = 10 1 / nm). (D): Bright-field TEM image (scale bar = 1 μm). (E): IR absorbance spectrum. [Figure 11-2] This is a continuation of Figure 11-1.

[0102] [Figure 12-1] Figure 12: Characterization signature of GmGT(I)-X (perturbation of sample 6.12) produced using a metal-organic TM source. (A): SAED intensity profile (black solid line) and peak positions of α-GmO (light gray solid line) and graphene (dark gray dashed line). (B): Diffraction peak positions (k), lattice spacing (d), and intensity (I) determined from (A). (C): SAED pattern showing diffraction rings of α-GmO and G (scale bar = 10 1 / nm). (D): Bright-field TEM image (scale bar = 1 μm). (E): IR absorbance spectrum. [Figure 12-2]This is a continuation of Figure 12-1.

[0103] [Figure 13-1] Figure 13: Characterization signature of GmGT(I)-X (perturbation of sample 6.13) produced using peroxide additives. (A): SAED intensity profile (black solid line) and peak positions of α-GmO (light gray solid line) and graphene (dark gray dashed line). (B): Diffraction peak positions (k), lattice spacing (d), and intensity (I) determined from (A). (C): SAED pattern showing diffraction rings of α-GmO and G (scale bar = 10 1 / nm). (D): Bright-field TEM image (scale bar = 1 μm). (E): IR absorbance spectrum. [Figure 13-2] This is a continuation of Figure 13-1.

[0104] [Figure 14-1] Figure 14: Characterization signature of GmGT(I)-X (perturbation of sample 6.14) produced using an acidic additive. (A): SAED intensity profile (black solid line) and peak positions of α-GmO (light gray solid line) and graphene (dark gray dashed line). (B): Diffraction peak positions (k), lattice spacing (d), and intensity (I) determined from (A). (C): SAED pattern showing the diffraction rings of α-GmO and G (scale bar = 10 1 / nm). (D): Bright-field TEM image (scale bar = 1 μm). (E): IR absorbance spectrum. [Figure 14-2] This is a continuation of Figure 14-1.

[0105] [Figure 15] Figure 15: Charge / discharge curves of an anode half-cell in which the anode active material is 100% GrSiGmGT(II)-A. Through half-cell testing, the specific capacity of this batch of GrSiGmGT(II)-A was determined to be 540 mAh / g. The black lines represent two formation cycles at a C / 20 rate. The gray lines represent cycles after formation at a C / 3 rate. The solid lines represent lithiation, and the dashed lines represent delithiation.

[0106] [Figure 16] Figure 16: Charge / discharge curve of a graphite anode half-cell. The specific capacity of this cell was 351 mAh / g at a current of approximately C / 20. The graph shows two formation cycles at C / 20 followed by cycling data at C / 3. This graphite half-cell exhibits a characteristic voltage plateau at approximately 0.2 V. The black line represents lithiation, the gray line represents delithiation, and the cycle numbers are indicated in the figure legend.

[0107] [Figure 17-1] Figure 17: Charge / discharge curves of nickel manganese cobalt oxide (NMC622) and nickel cobalt aluminum oxide (NCA) cathodes paired with GmGT anode materials in pouch full-cell Li-ion batteries. (A): NMC cycled at a 4.3 V upper voltage cutoff exhibited a C / 10 specific capacity of 165 mAh / g and an initial coulombic efficiency of 87%. (B): NMC cycled at a 4.5 V upper voltage cutoff exhibited a C / 10 specific capacity of 187 mAh / g and an initial coulombic efficiency of 85%. (C): NCA cycled at a 4.3 V upper voltage cutoff exhibited a C / 10 specific capacity of 194 mAh / g and an initial coulombic efficiency of 90.4%. (D): NCA cycled at a 4.3 V upper voltage cutoff exhibited a C / 10 specific capacity of 194 mAh / g and an initial coulombic efficiency of 90.4%. The black line represents formation at a C / 10 rate. The gray line represents cycling after formation at a 1C rate. The solid line represents delithiation, and the dashed line represents lithiation. [Figure 17-2] This is a continuation of Figure 17-1.

[0108] [Figure 18-1]Figure 18: (A) is a graph showing the rate capability of pouch cells with a graphite (Gr) anode or a GrSiGmGT(II)-A composite anode (1C = 200 mAh). The gray solid squares represent the charging of the graphite control. The gray open diamonds represent the discharging of the graphite control. The black solid circles represent the charging of 87% graphite / 3% silicon / 10% GmGT(II)-A. The black + symbols represent the discharging of 87% graphite / 3% silicon / 10% GmGT(II)-A. (B) is a graph showing the rate capability shown in Figure 18A 6 normalized based on the capacity at C / 10 for direct comparison of actual rate capabilities. The gray solid squares represent the charging of the graphite control. The gray open diamonds represent the discharging of the graphite control. The solid black circles represent charging of 87% graphite / 3% silicon / 10% GmGT(II)-A. The black + symbols represent discharging of 87% graphite / 3% silicon / 10% GmGT(II)-A. (C) Charge / discharge curves of a pouch cell with a Gr vs. 87% graphite / 3% silicon / 10% GmGT(II)-A anode. The dark solid line represents charging / discharging of the graphite control. The light dotted line represents charging / discharging of 87% graphite / 3% silicon / 10% GmGT(II)-A. [Figure 18-2] This is a continuation of Figure 18-1.

[0109] [Figure 19-1]Figure 19: (A) Graph showing the cycling performance of Test 3(a) (see text) after cycling at 5 °C after one cycle formation at C / 10. The gray solid squares represent the charging of the graphite control. The gray open diamonds represent the discharging of the graphite control. The black solid circles represent the charging of 87% graphite / 3% silicon / 10% GmGT(II)-A. The black + symbols represent the discharging of 87% graphite / 3% silicon / 10% GmGT(II)-A. (B) Graph showing the cycling behavior of Test 3(a) normalized based on reversible capacity. The gray solid triangles represent the charging of 87% graphite / 3% silicon / 10% GmGT(II)-A. The gray X symbols represent the discharging of 87% graphite / 3% silicon / 10% GmGT(II)-A. (C) is a graph showing the capacity of Test 3(b). The solid gray squares represent charging of the graphite control. The open gray diamonds represent discharging of the graphite control. The solid black circles represent charging of 87% graphite / 3% silicon / 10% GmGT(II)-A. The black + symbols represent discharging of 87% graphite / 3% silicon / 10% GmGT(II)-A. (D) is a graph showing the normalized capacity of Test 3(b). The solid gray triangles represent charging of 87% graphite / 3% silicon / 10% GmGT(II)-A. The gray X symbols represent discharging of 87% graphite / 3% silicon / 10% GmGT(II)-A. (E) is a graph showing the charge and discharge capacities of an anode half-cell with 97% graphite / 3% silicon as the active material, but at a lower cycle count. The black dots represent charging and the grey X symbols represent discharging. [Figure 19-2] This is a continuation of Figure 19-1. [Figure 19-3] This is a continuation of Figure 19-2.

[0110] [Figure 20]Figure 20: Graph of capacity (milliamp-hours) versus cycle number for cells made with the target GmGT(II)-A as an additive, after 10 cycles of charging the cell at C / 2 rate and discharging at C / 3 rate at -20°C, followed by 100 charge / discharge cycles at 0°C. (A): Cell with graphite anode. Gray solid circles represent charging of the graphite control. Gray X symbols represent discharging of the graphite control. (B): Cell with GmGT(II)-A anode. Black solid squares represent charging of the 87% graphite / 3% silicon / 10% GmGT(II)-A material. Black + symbols represent discharging of the 87% graphite / 3% silicon / 10% GmGT(II)-A material.

[0111] [Figure 21] Figure 21: Graph showing capacity per gram of active material as a function of charge rate for a series of Li-GmO and Li-Gr composite cells. Each black line represents a half-cell containing a 10% pre-GmGT(II) and GmGT(II)-A blend / 90% graphite anode, and each gray line represents a control cell containing a Gr anode.

[0112] [Figure 22] Figure 22: Low-magnification backscattered electron SEM image showing a uniform distribution of GmGT(II)-A particles (bright features) in a graphite matrix. The relative concentration of these GmO-based particles is consistent with an active anode composition of 10 / 90 GmGT / Gr (scale bar = 100 μm).

[0113] [Figure 23] Figure 23: High-magnification secondary electron SEM image of a GmGT(II)-A particle (large central particle) showing evidence of a two-dimensional flake-like morphology. Neighboring particles (mainly graphite) are well connected to the GmGT(II)-A particle (scale bar = 5 μm).

[0114] [Figure 24]Figure 24: A series of elemental maps of carbon distribution (bright areas in the upper right panel), molybdenum distribution (bright areas in the lower left panel), and oxygen distribution (bright areas in the lower right panel) along with the corresponding BSE image (upper left panel) (the intensity scale between maps is not quantitative). Particles that appear bright in the BSE image (high Z) correspond to molybdenum (Mo)- and oxygen (O)-rich regions in the corresponding elemental map. This is clear evidence that GmGT(II)-A particles are incorporated into the electrode preparation without chemical or mechanical degradation (scale bar = 9 μm).

[0115] [Figure 25] Figure 25: A series of graphs showing the cycling performance of 200 mAh pouch batteries fabricated using an LCO cathode and a cathode comprising 10% of the inventive materials disclosed herein (pre-GmGT(II) and GmGT(II)-A) and 90% graphite (Gr). (A): Charge / discharge curves of pouch cells with Gr anodes, Gr / pre-GmGT(II) anodes, and Gr / GmGT(II)-A anodes at C / 2 and RT, demonstrating the achievement of the 200 mAh milestone. (B): Cycling performance of these same batteries. The pouch cells were formatted at C / 10 and conditioned for 9 cycles at C / 2 before being charged to 50% state of charge for impedance analysis. (C): Comparison of charge / discharge curves of pouch cells with pure graphite (Gr) anodes, Gr anodes with pre-GmGT(II), and Gr anodes with GmGT(II)-A. The cell was charged at 10C and discharged at C / 3 to mimic potential ultrafast charging and normal driving EV conditions. (D): Corresponding cycle performance for the conditions used in A-C. (E) Charge / discharge profile at -20°C. The cell was charged at 1C and discharged at C / 3, showing a capacity of 33 mAh, which is approximately 20% of the capacity at room temperature. (F) shows the corresponding cycle performance of the cell in E.

[0116] [Figure 26]Figure 26 shows a photograph showing the separator recovered from a cycled 200 mAh graphite-only active anode pouch cell, clearly showing lithium powder deposition (brown areas).

[0117] [Figure 27] Figure 27 shows a photograph of the separator recovered from a cycled 200 mAh Gr / Si / GmGT(II)-A active anode pouch cell, showing significantly less lithium powder deposition compared to Figure 26.

[0118] [Figure 28] Figure 28 is a photographic comparison of lithium deposition on the anode surface for the same pouch cells of Gr / Si / GmGT(II)-A (left) and pure Gr (right) as shown in Figures 26 and 27. The gold / tan color of the Gr anode (right) indicates significant Li plating. The dark brown color of the anode containing the material of the present invention indicates healthy cell performance.

[0119] [Figure 29] Figure 29 shows electron diffraction patterns after the first cycle of lithiation for GmGT(I)-X and GmGT(II)-A materials in the anode of a LIB half cell. (A): SAED patterns from the tested materials show that the α-GmO and G rings are retained, and five additional rings are present in the anode composite after lithiation in a working cell. (B): SAED intensity profiles showing the positions and intensities of the four main GmO and G diffraction peaks (labeled I–IV) and five new diffraction peaks (labeled a–d) upon lithiation. The light gray intensity profile is from the GmGT(I)-X anode, and the dark gray is from the GmGT(II)-A anode.

[0120] [Figure 30]Figure 30 shows electron diffraction data for the anodes of LIB half-cells of GmGT(I)-X and GmGT(II)-A materials after moderate (100) and numerous (800) lithiation cycles. (A): SAED patterns from the test materials show that the distinctive diffraction rings seen after the first lithiation cycle remain. (B): SAED intensity profiles showing the positions and intensities of the four main α-GmO and G diffraction peaks (labeled I–IV) and five new diffraction peaks (labeled a–d) due to the lithiation process. The graphene peaks (I and II) remain at the same positions, the α-GmO peaks (III and IV) shift to slightly smaller scattering angles, and the five additional diffraction rings become more intense. The light gray intensity profile is from the GmGT(I)-X anode, and the dark gray intensity profile is from the GmGT(II)-A anode.

[0121] [Figure 31] Figure 31: Calculated lattice sites favorable for the adsorption of a single Li atom on a GmO monolayer. (A): The lowest energy site is the vacant H site. (B): The second lowest energy site is the S site, i.e., the center of gravity of the triangle formed by three adjacent O atoms. The equivalent α-GmO unit cell is shown in black. In the top view, C atoms are light gray, O atoms are black, and Li atoms are dark gray.

[0122] [Figure 32] Figure 32: Calculated structures of novel compositions formed by Li and α-GmO. (A): The novel Li2C6O6 structure corresponds to the hexal structure of fully lithiated graphite with a maximum theoretical capacity of 372 mAh / g. (B): The novel fully lithiated Li2C2O2 structure based on GmO with a maximum theoretical specific capacity of 957 mAh / g, 2.6 times that of graphite. In the top view (left) and perspective view (right), C atoms are light gray, O atoms are black, and Li atoms are dark gray.

[0123] [Figure 33]Figure 33: Density of states (per GmO formula unit) for a semiconducting, fully relaxed α-GmO monolayer, and for three representative LiC6O6, Li2C6O6, and Li2C2O2 structures that are predicted to be conductive because they have a state at the Fermi energy expressed at 0 eV (0 J). (Pure α-GmO monolayers have no states at the Fermi energy, but have a small band gap.) DETAILED DESCRIPTION OF THE INVENTION

[0124] Abbreviations and definitions: Throughout this specification and the appended claims, singular articles such as "a," "an," and "the," and similar referents, in the context of describing elements (particularly in the context of the claims), should be construed to cover both the singular and the plural unless otherwise stated herein or clearly contradicted by context. Recitations of numerical ranges herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise stated herein, and each separate value is incorporated herein as if it were individually set forth herein. All methods described herein can be performed in any suitable order unless otherwise stated herein or clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "etc.") provided herein, is intended merely to further clarify embodiments and does not limit the scope of the claims unless expressly stated otherwise. No language in this specification should be construed as requiring any non-claimed element.

[0125] As used herein, "about" will be understood by those of ordinary skill in the art and will vary to some extent depending on the context in which it is used. If there are uses of the term that are not clear to persons of ordinary skill in the art, "about" will mean up to ±10% of that particular term, given the context in which it is used.

[0126] In general, a reference to a particular element, such as hydrogen or carbon, includes all isotopes of that element, both natural and man-made. For example, if an R group is defined to include hydrogen, that hydrogen includes deuterium ( 2 H) and tritium ( 3 H) is also included. Therefore, tritium, 14 C. 32 P and 35 Compounds containing radioisotopes such as S are within the scope of the present technology. Procedures for introducing such labels into compounds of the present technology will be readily apparent to those of skill in the art based on the disclosure herein.

[0127] 2D = two-dimensional. 3D = three-dimensional. ATR-FTIR = attenuated total reflectance Fourier transform infrared spectroscopy. BCC = body-centered cubic. BSE-SEM = backscattered electron scanning electron microscopy. DFT = density functional theory. DR-FTIR = diffuse reflectance Fourier transform infrared spectroscopy. EDS = energy dispersive X-ray spectroscopy. EXAFS = extended X-ray absorption fine structure spectroscopy. GmO = a composition containing graphene monoxide, a solid 2D form of CO. α-, β-, γ-, δ-GmO = four crystalline phases of GmO. GmGT(I)-X = a composition containing domains of crystalline graphene monoxide (predominantly α-GmO) with crystalline graphene (G) and molecular transition metal oxide (TMO). GmGT(I)-A = a composition containing domains of amorphous GmO with crystalline G and molecular TMO that upon further annealing produces crystalline α-GmO. GmGT(I)-NC = composition comprising domains of crystalline GmO (predominantly α-GmO) with crystalline G and nanocrystalline TMO. GmGT(II)-A = composition comprising domains of amorphous GmO with crystalline graphene and molecular TMO. GmGT(II)-NC = composition comprising domains of amorphous GmO with crystalline graphene and crystalline TMO. GO = graphene oxide. GrSiGmGT = composition comprising a graphite / silicon / GmGT composite. HDPE = high density polyethylene. LGm = lithium graphene monoxide (Li xCompositions containing methyl methacrylate (MMA). LCO = lithium cobalt oxide (LiCoO2). NCA = lithium nickel cobalt aluminum oxide. NMC = nickel manganese cobalt oxide. NMR = nuclear magnetic resonance. RGA = residual gas analyzer. rGO = reduced graphene oxide. prGO = partially reduced graphene oxide. PTFE = polytetrafluoroethylene. SEM = scanning electron microscopy. TDA = differential thermal analysis. TEM = transmission electron microscopy. TEM-SAED = transmission electron microscopy-selected area electron diffraction. TGA = thermogravimetric analysis. T-FTIR = transmission Fourier transform infrared spectroscopy. TM = transition metal. TMO = transition metal oxide.

[0128] As used herein, "graphene monoxide" or "GmO" refers to a two-dimensional crystalline or amorphous graphene-based nanomaterial containing carbon and oxygen atoms in approximately 1:1 stoichiometry and as specific structural building blocks. The α-phase of crystalline GmO (α-GmO) has a face-centered rectangular lattice crystal structure, with each unit cell containing four oxygen (O) atoms and four carbon (C) atoms. The same lattice can also be described as a quasi-hexagonal basic unit cell with two oxygen atoms and two carbon atoms. The bonds in each C2O2 unit are such that the atoms within a single unit cell form a 1,3-oxetane ring. Each oxygen atom bridges two carbon atoms, forming a single bond with each of the two carbon atoms. Thus, the carbon atoms in α-GmO form a single plane, with oxygen atoms above and below the carbon plane.

[0129] In addition to α-GmO, other crystalline forms of GmO, designated β-GmO, γ-GmO, and δ-GmO, are also described herein, and their unique structural building blocks and crystal lattice unit cells are defined. All phases of crystalline and amorphous GmO can be understood as solid forms of carbon monoxide that are stable over a wide range of temperatures and pressures, including ambient conditions. While GmO also exists at high temperatures and / or low pressures, all known phases of solid, three-dimensional CO crystals exist only at very low temperatures and / or very high pressures.

[0130] α-GmO = Cmmm symmetry and a crystalline phase of GmO with a lattice constant of 0.313 nm (0.295 nm) and an angle of 130° (120°) for relaxed orthorhombic (constrained hexagonal) conditions.

[0131] β-GmO = P6 / mmm symmetry and a crystalline phase of GmO with a hexagonal lattice constant of 0.507 nm and an angle of 120°.

[0132] γ-GmO = a crystalline phase of GmO with C222 symmetry and a lattice constant of 0.313 nm (0.295 nm) and an angle of 130° (120°) in the relaxed orthorhombic (constrained hexagonal) condition. This structure can form superlattices (2x2 and 4x4).

[0133] δ-GmO = Crystalline phase of GmO with Cmma symmetry and an orthorhombic lattice constant of 0.333 nm and an angle of 135°.

[0134] "Graphene" refers to a single layer of graphite (i.e., monolayer graphene), or to graphene layers that are randomly stacked (i.e., few-layer or multi-layer graphene), or locally ordered as AB or AA stacks (i.e., graphite or graphite-like) (hereinafter "G").

[0135] "Transition metal" refers to the elements in groups 3-12 of the periodic table, as well as the lanthanide series (lanthanum through lutetium) and actinide series (actinium through lawrencium) of the periodic table.

[0136] Composition: Overview of the synthesis of GmGT-based materials: The typical process element of the synthesis of GmGT materials involves two stages: I) preparation and mixing of the various ingredients; and II) heat treatment of the mixture under specific conditions of atmosphere, pressure, temperature, and heating rate. Each stage may be performed in multiple steps to achieve the desired result. A preferred example of the synthesis of GmGT-based materials involves three broad steps outlined below: 1) preparing and combining the feed materials; 2) low-temperature heat treatment with controlled, variable heating rates to a temperature T1; and 3) heating to a final temperature T2. f High temperature heat treatment with controlled variable heating rates in an oxygen-controlled environment up to 1000 K. The heat treatment step in this case is separated into two separate heat treatment steps with their own temperature profiles and environmental conditions.

[0137] Step 1 in the preferred route involves mixing an oxygenated carbon material, a transition metal material, and / or an additive material. The carbon source must contain atomic oxygen that is bonded to carbon as part of its structure and distributed throughout the carbon source material. If heating is performed in a substantially oxygen-free environment, the relative atomic ratio of oxygen to carbon should be greater than about 0.15:1, preferably greater than about 0.3:1. A preferred laboratory-scale synthesis method requires that the carbon material be an aqueous suspension of graphene oxide and the TM material be a solute or powder of a TM oxide compound that can be distributed substantially uniformly throughout the carbon source phase. This distribution can be achieved through a mixing process using any suitable method from known state-of-the-art techniques, such as mechanical agitation, stirring, sonication, planetary mixing, or milling (Backes, Claudia, et al. “Production and Processing of Graphene and Related Materials.” 2D Materials, vol. 7, no. 2, 2020, p. 022001., doi:10.1088 / 2053-1583 / ab1e0a.). The effectiveness of transition metal source materials can be attributed to the availability of multiple oxidation states that can support the formation of GmO-based materials. In some embodiments, additives are incorporated to modify the properties of the carbon source, TM source, and / or carbon / TM source mixture. Additives are acids, bases, peroxides, and / or other oxidizing and / or reducing agents used individually, in combination, or sequentially.

[0138] Step 2 of the preferred route involves low-temperature (below T1) heat treatment of the mixture produced in step 1. This may include a distinct drying step to substantially remove moisture from the mixture prior to heat treatment above room temperature if the mixture produced in step 1 has sufficient consistency to allow for pelletizing or granulation methods, or if the mixture from step 1 consists entirely of a powder, or it may be omitted as a distinct step. As a distinct step, drying may be carried out by any suitable conventional method, such as tray drying, spray drying, infrared drying, freeze drying, or drum drying. A preferred method for laboratory synthesis is to dry the resulting mixture in a borosilicate glass tray at temperatures from about 20°C up to 100°C for a period of several hours to several days, depending on the amount of material and the surface area of ​​the tray, to produce a thin film of material on the order of tens of microns in thickness.

[0139] Step 2 may include a distinct sizing step to control the morphology, size, and characteristic dimensions of the material product or to facilitate safe thermal processing above room temperature. Sizing can be performed by any suitable conventional method, such as mechanical chopping, cutting, grinding, milling, granulation, or extrusion / pelletization, depending on the moisture content and / or morphology and characteristic dimensions of the material desired for subsequent processing steps. Preferred methods for laboratory synthesis are mechanical chopping and / or coarse grinding, which yield flake-like material with millimeter-scale lateral dimensions.

[0140] The low-temperature heat treatment in step 2 can be carried out in any furnace / oven type and configuration known in the state of the art suitable for controlled heating to temperature T1. Active heating can be of a convective, conductive, or radiative nature, including microwave or infrared heating. The environment for the material during this heat treatment step can be static or flowing air, inert gas, or a mixture thereof, or a low or high vacuum environment. The heating rate required to produce GmGT-based materials depends on the flow rate of gases evolved during the heat treatment and the rate at which these evolved gases leave the vicinity of the material being processed. Therefore, the heating rate depends on the furnace / oven configuration, the amount and containment vessel of the material being processed, the form factor and characteristic dimensions of the material, and the feedstock used to prepare the material. Preferred methods for laboratory synthesis are a low-vacuum box-type oven equipped with a PID temperature control unit or a high-vacuum chamber equipped with an electrical feedthrough to facilitate resistive heating via a remotely programmed external power source.

[0141] Step 3 involves high temperature (above T1) heat treatment of the material produced in step 2, to a final temperature T f This can be done in any furnace / oven type and configuration known in the state of the art that is suitable for controlled heating to a temperature of 1000 K. Active heating can be convection, conduction, or radiation in nature, including microwave or infrared heating. The environment for the material during this heat treatment process can be static, or it can be a flowing inert or non-reactive gas, or a high-vacuum environment. The heating rate required to produce GmGT-based materials depends on the flow rate of the gases evolved during the heat treatment and the rate at which these evolved gases leave the vicinity of the material being processed. Therefore, the heating rate depends on the furnace / oven configuration, the amount and containment of the material being processed, the form factor and characteristic dimensions of the material, and the feedstock used to prepare the material. The preferred method for laboratory synthesis is a furnace configured for nitrogen or argon gas flow and equipped with a PID temperature control unit, or a high-vacuum chamber equipped with an electrical feedthrough to facilitate resistive heating by a remotely programmed external power source.

[0142] Step 3 may optionally include an explicit sizing step (as described above for Step 2) prior to heat treatment to control the morphology, size, and characteristic dimensions of the material product, or to facilitate efficient or effective high temperature processing. If a sizing step is not desired in Step 3, the desired final temperature T f By appropriately selecting a furnace capable of heating up to 10 ...

[0143] The following description provides additional information and details for synthesizing GmGT-based materials.

[0144] Carbon-containing suspension derived from a graphene oxide source: Table 1 summarizes specific exemplary versions for preparing carbon-based materials derived from commercially available GO sources suitable for the synthesis of GmGT-based materials. The compositions of the carbon-containing suspensions (referred to as Suspensions 1–8 in Table 1) are derived from several commercially available GO sources, including aqueous suspensions of monolayer, bilayer, and few-layer GO at various solid GO concentrations. Low-viscosity GO suspensions are measured using a graduated cylinder, while high-viscosity GO suspensions are measured using a balance. The commercially available GO suspensions are manually stirred or stirred with a glass rod for several minutes before preparing the final suspension. Distilled, deionized water measured using a graduated cylinder is used to dilute the commercially available GO suspension in some embodiments. Additives are incorporated in liquid or powder form in some embodiments, and their amounts are determined according to each embodiment using a graduated cylinder for measuring liquids and a balance for measuring powders. Additives can be acids, bases, peroxides, and / or other oxidizing and / or reducing agents used individually, in combination, or sequentially to control the oxygen functionalities present in the starting GO and influence the specifications of the final composite material. The use of certain additives, such as amino acids, can offer additional benefits due to their endothermic properties at specific temperature windows, enabling the safe synthesis of GmO-containing materials, in addition to their ability to modify the oxygen functionalities of the carbon source material. Specific additives in the examples in Table 1 include ascorbic acid, acetic acid, and hydrogen peroxide. The suspension containing the additive components was covered with paraffin plastic film and mixed for a specified time using a PTFE-coated magnetic stirrer while maintaining a specific temperature. For temperatures above 21 °C, the mixture was maintained at the desired temperature in a water bath. A pH meter was used to measure the pH of the selected suspension.

[0145] In one version, prior to the preparation of individual suspensions, 100 g of a commercially available 42 wt% GO aqueous suspension (The Sixth Element (Changzhou) Materials Technology Co., Ltd., Changzhou, China) was diluted to 10 wt% GO by adding 138 mL of deionized distilled water and mixed with a glass stirrer for approximately 10 minutes to a smooth consistency. The diluted GO solution was stored in a sealable HDPE bottle. To prepare suspension 1.2, the 10 wt% GO was stirred before weighing 500 mg of the suspension into a borosilicate glass beaker. This 500 mg corresponds to 50 mg of solid GO and 0.450 mL of water. 15 mL of deionized distilled water was weighed into a second borosilicate glass beaker, and 500 mg of ascorbic acid powder was added and stirred with a glass rod until dissolved. The ascorbic acid solution was added to the first beaker, a PTFE-coated magnetic stir bar was added to the mixture, and the beaker was covered with paraffin plastic film. The beaker was placed on a magnetic stir plate at room temperature for 96 hours. Table 1 shows several examples of versions starting with graphene oxide (GO). Other carbon-containing solutions and powders are included in the perturbation section below (see Table 5).

[0146] [Table 1]

[0147] Methods for synthesizing TM-containing solutions and powders: Table 2 summarizes specific experimental versions for preparing TM-based materials from commercially available TM-containing sources suitable for the synthesis of GmGT-based materials. Referring to Table 2, the composition of the TM-containing solution includes a solvent measured in a graduated cylinder and a precursor (often a powder) measured on a balance. The solvent and precursor are mixed with a magnetic stirrer, periodically stirred manually, or stirred with a glass rod for a specific time while maintaining a specific temperature, allowing them to equilibrate, and optionally decanted from residual solids using a funnel and filter paper. In some versions, a second precursor is weighed by mass or volume, added to the first solution, and stirred and equilibrated for a specific time while maintaining a specific temperature. In some embodiments, the second solution is also decanted from residual solids using a funnel and filter paper. The final solution contains a range of transition metal concentrations, described as mol-TM / L. In some embodiments, the final solution is dried on a shallow glass tray in a dehydrator at a specific temperature and converted to a powder form. In other embodiments, the specific composition of the TM-containing powder is commercially sourced from materials and chemical suppliers.

[0148] The examples listed in Table 2 are based on molybdenum and chromium. Similar embodiments of TM solutions and powders can be made based on vanadium and niobium, or other related metals. Any combination of these TM-containing solutions and / or powders can also enable the formation of GmGT-based materials.

[0149] In one embodiment for producing Solution 2.1 (see Table 2), the following formulation was followed: 1 L of deionized distilled water (solvent) was mixed with approximately 3 g of molybdenum trioxide (MoO) powder (Precursor 1), then stirred with a magnetic stirrer for 1 minute per day for 6 days while covered and maintained at 21 °C. The solution was decanted through a funnel and filter paper into a second flask to remove any precipitate. Approximately 3 g of molybdenum (Mo) metal powder (Precursor 2) was added to the second flask and stirred for 6 days while covered and maintained at 21 °C. The second solution was decanted through a funnel and filter paper into a final flask to remove any precipitate that may be suspended in the solution, and then stored at room temperature, covered. The solution thus prepared was deep blue in color and had a measured pH of 3.0. In another version, Solution 2.1 was poured into a borosilicate glass beaker and heated in a dehydrator at 52 °C, resulting in Powder 2.2.

[0150] [Table 2]

[0151] [Table 3]

[0152] Method for synthesizing Pre-GmGT(I) and Pre-GmGT(II) materials: Mixing: Specific amounts of carbon source and TM source are combined. Mixing can be accomplished by any known state-of-the-art technique suitable for mixing materials to a uniform, homogeneous state. In the specific example shown in Table 3, the carbon source is manually stirred for several minutes and then weighed into a beaker by mass or volume. The TM source is weighed by mass or volume to achieve the desired C / TM atomic ratio and added to the beaker containing the carbon source. In some versions, the concentration of the TM source is adjusted by omitting water from the source preparation described in Table 2. In other versions, a measured amount of deionized, distilled water is added to the C / TM mixture using a graduated cylinder. The combined mixture is stirred with a magnetic stir bar or sonicated for a specified period of time at room temperature.

[0153] Drying and Recovery: The material suspension from the mixing beaker is carefully poured into a borosilicate glass tray placed in a dehydrator open to the atmosphere. The liquid suspension covers the entire tray area, so the volume of the liquid suspension and the total area of ​​the tray are adjusted to obtain the desired thickness of dried material. The dehydrator is set to a specific temperature and the material is allowed to dry overnight.

[0154] In some versions, the material is not explicitly recovered from the drying tray; rather, the tray of dried material is fed directly to a subsequent low-temperature processing step. This method allows for faster processing because it does not require an explicit material recovery step, for example, by scraping and collecting the material. This tends to produce a compact material with a layered morphology with lateral dimensions the same size as the drying tray. The material produced in this manner is advantageously processed in this large, film-like format or used for further controlled sizing by cutting or grinding. This processing route is advantageous for some applications, reducing the effort required to produce material with large macroscopic lateral dimensions, such as a constant thickness (a few microns to tens of microns or more) and a controlled lateral shape, for example, by cutting.

[0155] In another version, the dried material is scraped off the glass tray with a razor blade, and the loose material is collected on the tray, chopped into coarse flakes, and stored for further processing. The carbon-containing layers dry similarly to one another, resulting in highly uniform flake thickness. Tray drying can also be achieved by any alternative known in the state of the art, such as using a different type of inert tray material, a different drying temperature and time, or providing a controlled environment for the drying process. Similarly, recovery of the dried material from the tray can be achieved by any known state of the art suitable for such processes, including the use of a different scraping tool or mechanism. This drying method produces a highly compact final material suitable for application to battery anodes. This method is scalable and amenable to industrial-scale automated batch processing.

[0156] Alternatively, the material suspension can be spray-dried (e.g., at a rate of 1 kg / h at 70°C as measured in the drying chamber) and collected in powder form from the outlet of the dryer's collection cyclone. The characteristic diameter of the dried particles is controlled by the parameters of the spraying and drying processes, resulting in individual, folded carbon-containing layers. Spray drying is scalable and provides control over the size, shape, and internal morphology of the starting material, allowing for tailoring for specific applications. In some applications, this method does not require further sizing of the material. In addition to producing dry material for batch processing, this method is also suitable as the first step in a continuous spray reactor, where droplets are transported by inert gas through different temperature zones, sequentially producing dried particles of pre-GmGT and final GmGT material, allowing for collection of the final material at the outlet of the continuous reactor.

[0157] Alternatively, the material suspension may be freeze-dried (e.g., evaporation rate of 20 L / hr at 50°C) and then mechanically recovered from trays by conventional methods. This method of drying and recovering the material allows for more rapid drying of starting solutions containing higher amounts of water compared to conventional tray drying methods. Known state-of-the-art alternatives to freeze-drying (e.g., by controlling shelf temperature) can provide a less dense morphology of the dried material or allow for tailoring of the morphology / porosity of the dried material.

[0158] Alternatively, the material suspension can be dried by milling or rolling methods using conventional equipment. In one example, the C / TM mixture is mechanically milled with a mortar and pestle for 1 hour while heated at 50-70°C. This milling-assisted thermal drying method results in a powder that is collected from the mortar. This method is scalable, faster than tray drying, and provides more control over the morphology and size of the dried material.

[0159] Sizing: In some embodiments, control of the characteristic lateral size of the material is necessary to load the material into an appropriate containment vessel for further processing, promote uniform processing, control particle morphology and size, or facilitate control of the exothermic process during low-temperature heat treatment. Conventional equipment for sizing dry materials is used, such as grinding methods using a mortar and pestle, mechanical milling, or chopping. In some examples, the dried material was chopped with a razor blade to produce flakes with a characteristic lateral dimension of approximately 5-10 mm. In other embodiments, the material recovered from the drying process was transferred to an automatic mortar and pestle (Netzsch RM 200 ceramic mortar and pestle) for sizing. In this case, no grinding media was added. Gentle contact pressure was created between the mortar and pestle (downward force set to 0 and lateral pressure set to 6 of a possible 10 rotations). The material was processed for 5 minutes to produce flakes with a characteristic lateral flake size of approximately 1-10 mm. The material was manually fed continuously into the grinding path using a homemade spatula consisting of a small square of celluloid film attached to a bamboo stick. In some embodiments, the material was further processed by increasing the pressure between the mortar and pestle and sieved to produce a 25 μm powder. In some embodiments, no active sizing was performed at this stage of the synthesis.

[0160] Some versions of the synthesis can result in a viscous, paste-like or clay-like consistency of the carbon / TM material mixture, which can be subjected to a granulation or extrusion / pelletization sizing step before drying, or fed directly to a low-temperature heat treatment step. This approach allows for a low-moisture synthesis route, resulting in significantly more cost- and time-efficient large-scale production. When GO material is part of the starting material, practical implementation of this method beyond the laboratory generally requires the inclusion of additives during the preparation of the carbon material feed to chemically passivate the significant exothermicity of GO that occurs during heat treatment above 100 °C. One version of this chemical passivation is shown in Table 1 via Solutions 1.2 and 1.3, where ascorbic acid treatment clearly reduced the subsequent exothermicity of the mixed C / TM material compared to the equivalent mixture without ascorbic acid treatment.

[0161] Low-Temperature Heat Treatment: The material composition dried and sized in the above steps is evaluated for macroscopic uniformity before being used in the heat treatment. The material composition is weighed and placed in a non-reactive material containment vessel, which may be open or covered with a lid. The charge is determined as the average material mass / area, and the form factor of the charged material is recorded as flakes, particles, or film, depending on the characteristic lateral dimensions of the material. Various types of furnaces known in the state of the art can be used to heat the material from room temperature to a final temperature of about 300°C or less, such as low vacuum boxes, high vacuum chambers, inert gas tubes, or muffle air. The maximum mass loss rate T m The temperature is determined by thermogravimetry (TGA) under inert gas and low vacuum conditions and by residual gas analysis (RGA) under high vacuum. The heating rate is T m When approaching and T mThe rate at which the TM component is released must be controlled, but the rate at other temperature intervals is less critical. The final temperature is selected based on the combination of carbon and TM sources used and the desired composite final product material. The material is evaluated throughout the process on both the macroscopic and microscopic scales. If the material appears heterogeneous on the macroscopic scale at any stage up to the low-temperature heat treatment step, the process step or material feed is considered suboptimal and undesirable. Nanoscale crystallinity of the TM is also observed by electron diffraction, and if the process step or material feed results in significant crystallinity of the TM component, the process step or material feed is considered suboptimal and undesirable. The ultimate goal of this process is to avoid runaway thermal reactions (if any) and produce a safe pre-GmGT material (Table 3) that can be heated to high temperatures in large quantities to produce the final GmGT material (Table 4). Two product materials, pre-GmGT (I) or pre-GmGT (II), are considered the desired outcome and form the basis for producing the desired product materials in Table 4. The heating rate required to safely process a material to temperatures beyond its potential exothermic behavior depends on the heating environment (e.g., high vacuum, low vacuum, inert gas, air), the total mass and mass load of the material, the characteristic dimensions including thickness and shape factor of the material, whether the containment vessel is covered or open, and the component starting materials (e.g., GO).

[0162] Sample 3.0 in Table 3 provides a representative example, and additional examples in Table 3 demonstrate the range of processing variables that can produce pre-GmGT(I) materials. This intermediate material is important as a safe precursor for producing crystalline GmGT-based materials. This process (exemplified by Sample 3.0 in Table 3) begins by adding or removing water from the above formulation and mixing 175 mL of a carbon-containing source (Suspension 1.1, Table 1) with 140 mL of a TM-containing source (Solution 2.1, Table 2). Suspension 1.1 is manually stirred for several minutes and then weighed into a beaker. Solution 2.1 is weighed into the same beaker as Suspension 1.1, and the mixture is stirred using a magnetic stir bar. The stirring speed is adjusted to form a shallow vortex in the liquid contents, and the mixture is mixed for 3-4 minutes at room temperature (21 °C).

[0163] Carefully pour the material suspension from the mixing beaker into a clean borosilicate glass tray placed inside the dehydrator. The tray has a measured surface area of ​​approximately 722 cm. 2 The liquid suspension covers the entire tray area. The mixture dries to a uniform film of approximately 25 μm thickness. The dehydrator is set to a drying temperature of 52°C, and the material is allowed to dry overnight (24 hours). The dried material is scraped off the glass tray with a razor blade, and the loose material is stacked on the tray. The stacked material is then scooped with a razor blade and chopped into coarse flakes with characteristic lateral dimensions of approximately 5–10 mm and a thickness of approximately 25 μm. This was controlled during the drying process by selecting the total solids content and tray dimensions. The collected material is placed in an alumina-coated tantalum boat fitted with a tantalum cover and then resistively heated to approximately 300°C in a high vacuum. The temperature of the resistively heated tantalum boat as a function of applied current is calibrated in a separate calibration run. In the calibration run, the quoted temperature comprises the average temperature readings from pyrometers aimed at the center and edges of the boat cover at approximately 5°C increments above 500°C and interpolated to room temperature by a smoothing polynomial of order 2-6. The uncertainty in the quoted temperature reflects the spread in the interpolated polynomial fit and the variation in measured temperatures throughout the containment vessel, which was extrapolated to the quoted temperature. In this embodiment, the temperature at maximum mass loss was 230 ± 45°C, and this critical temperature was approached and departed from with a symmetric, gentle ramp of 0.1°C / min. In this example, the TM species was found to be amorphous. The product of this example process is pre-GmGT(I).

[0164] Using the same starting material and the same drying, collection, and sizing processes as for the pre-GmGT(I) material, the main difference in producing the pre-GmGT(II) material is the heating rate. Sample 3.1 in Table 3 shows the maximum mass loss temperature, T m Again, the temperature is 230±45°C, but in this case, T mapproached five times faster at 0.5 °C / min, compared with the same slower rate of 0.1 °C / min with an asymmetric ramp profile. This intermediate product, pre-GmGT(II), is important as a safe precursor for generating amorphous GmGT-based materials.

[0165] Samples 3.8, 3.9, and 3.10 (Table 3) demonstrate that adding certain TM sources in powder form can result in inhomogeneity in the dried sample, causing the subsequent failure of established processes that yield the desired final composition. Samples 3.3 and 3.4 demonstrate the opposite, positive example, where other specific TM powders may be successful. Sample 3.11 is another negative example, where omitting the TM source fails to produce either pre-GmGT(I) or pre-GmGT(II) material.

[0166] FIG. 3 shows the characterization of representative pre-GmGT(I) materials from Table 3, which is described in detail in the illustrative section of Example 1 below.

[0167] [Table 4]

[0168] [Table 5]

[0169] [Table 6]

[0170] [Table 7]

[0171] [Table 8]

[0172] Methods for synthesizing GmGT(I) and GmGT(II) materials: To produce the GmGT(I) or GmGT(II) materials, starting with the respective pre-GmGT(I) or pre-GmGT(II) materials, they are either maintained in their as-formed form or reduced to smaller, characteristic sizes and subjected to further heat treatment. Any known, state-of-the-art furnace type capable of heating the material to a final temperature of approximately 600-1,000°C or higher in a substantially oxygen-free atmosphere can be used for this process, such as a rotary furnace, a high-temperature spray / atomization tube furnace, a high-vacuum chamber furnace, or an inert gas / vacuum tube furnace. The material is placed in a non-reactive containment vessel, either open or covered, and the average mass per area is determined by dividing the weighed mass of the charged material by the vessel's base area. The material's form factor is recorded as either a film, flake, or powder. The filled vessel is placed in a furnace, heated to the final temperature, and held there for a specified period of time. The specific examples presented in Table 4 are primarily directed to high-vacuum chamber furnace embodiments and inert gas tube furnaces. The heating time is determined by the maximum mass loss rate (T m ) temperature to the final temperature (T f ) reflects the average heating rate up to 1000 kJ / cm. To maintain the desired pressure and mass transfer away from the vicinity of the sample, the heating rate used in each embodiment is based on the amount of material being heated, determined by mass per unit area, whether the material is contained in an open or covered vessel, and the rate at which evolved gases are removed from the furnace. The base pressure of the vacuum furnace is 2×10 -6 torr (2.67 × 10 -4 The gas system of the tube furnace allows for switching between nitrogen and argon, including saturating the feed gas with water vapor to reactively control product formation, allowing for control of gas flow rates. Feed gases containing carbon dioxide or carbon monoxide can also be utilized as effectively inert gases for material systems synthesized by these processes. The material is cooled to room temperature and removed from the furnace, where it can be further sized to meet the specifications for electrode material or other applications. The final product material is characterized in a number of ways, as described below.

[0173] Two broad classes of materials, GmGT(I) and GmGT(II), are obtained based on the heating rate used for their precursor materials, pre-GmGT(I) or pre-GmGT(II), respectively. Within each class are successively generated subclasses. The first series of materials begins when a slow thermal ramp rate is used to generate the pre-GmGT(I) material. The product material GmGT(I) series has three members: GmGT(I)-A: Less than approximately 675°C * Formed at temperatures above 1000°C. Defined as amorphous GmO. These compositions can include graphene and a range of molecular TMOs. GmGT(I)-X: Approx. 675~800℃ * Further annealing at RT leads to the formation of crystalline forms of GmO. These compositions can include a range of graphenes and molecular TMOs. GmGT(I)-NC: When high concentrations of TM are used or the temperature is further increased, GmGT(I)-based materials take on TMO nanocrystals. * The temperature ranges cited here are specific to the source materials and process parameters used in Table 4.

[0174] A second series of materials is obtained when a fast thermal ramp rate is used to generate specific pre-GmGT(II) materials. The GmGT(II) series of product materials has two members: GmGT(II)-A: Less than 600℃ * At temperatures of 600-800°C * These compositions can include a range of graphenes and molecular TMOs. GmGT(II)-NC: With high concentrations of TM or by further increasing the temperature, the amorphous GmGT(II)-based material takes on TMO nanocrystals. * The temperature ranges cited here are specific to the source materials and process parameters used in Table 4.

[0175] It is important to note that the final product GmGT materials listed in Table 4 as a result of a sequential two-stage heating process (e.g., pre-GmGT(I) is produced in one heating system and sent to another heating system to produce GmGT(I)) can also be produced in a one-stage process in the same oven / furnace designed to allow for uninterrupted heat treatment, providing the conditions necessary for continuous heat treatment from the synthesis of pre-GmGT(I) to the synthesis of the final product GmGT(I).

[0176] Sample 4.1 in Table 4 is an illustrative example that allows for the formation of GmGT(I) material. It starts from the pre-GmGT(I) material exemplified by Sample 3.0 in Table 3 and is subjected to further heat treatment in a high vacuum chamber. The material is placed in a non-reactive alumina-lined tantalum boat with a tantalum cover. The material loading is 33 mg / cm. 2 The filled tantalum boat was placed between the electrodes of a vacuum furnace designed for resistance heating, and a base pressure of 2 × 10 -6 torr (2.67 × 10 -4 Pa) and the sample was heated to a final temperature (T f ) and heat to T f The temperature is held at 100°C for 10 minutes. The variable heating rate is adjusted to maintain a nearly constant total pressure in the system. m ) to T f A total time of 15 hours and 17 minutes was used to reach this temperature range (T m ~T f The details of the heating profile in the furnace are chosen to maintain a nearly uniform and continuous mass loss, as determined by residual gas analysis calibration experiments. Upon cooling to room temperature and removal from the vacuum furnace, the material is further sized to meet electrode material specifications. The final product is characterized in a number of ways, as described below.

[0177] Sample 4.2 in Table 4 is an example of a method for producing GmGT(II) material. It starts with the pre-GmGT(II) material exemplified in Sample 3.1 in Table 3 and is subjected to further heat treatment in a high vacuum chamber. The material is placed in a non-reactive alumina-lined tantalum boat with a tantalum cover. The material loading is 33 mg / cm. 2 The filled tantalum boat was placed between the electrodes of a vacuum furnace designed for resistance heating, and a base pressure of 2 × 10 -6 torr (2.67 × 10 -4 Pa, and the sample reached a final temperature (T f ) and heat to T f The temperature is held at 100°C for 10 minutes. The variable heating rate is adjusted to maintain a nearly constant total pressure in the system. m ) to T f A total time of 20 hours and 47 minutes was used to reach this temperature range (T m ~T f The details of the heating profile over the annealing step are chosen to maintain a nearly uniform and continuous mass loss, as determined by residual gas analysis calibration experiments. Upon cooling to room temperature and removal from the vacuum furnace, the material is further sized to meet electrode material specifications. The final product is characterized in a number of ways.

[0178] Figures 4-7 show the characterization of representative GmGT product materials from Table 4. These figures are described in detail in Example 2 in the Examples section below, while Examples 4 and 5 provide more specific details without the figures.

[0179] [Table 9]

[0180] [Table 10]

[0181] [Table 11]

[0182] [Table 12]

[0183] [Table 13]

[0184] Effect of variations in carbon source, additives, TM source, and process conditions on the synthesis of GmGT(I) and GmGT(II) materials: The process overview in this section follows the process descriptions and examples in the above sections set forth in Tables 1-4, with one important difference: it presents results from deliberate, controlled perturbations to the starting sources and, in some embodiments, process parameters that go beyond the range of source compositions and process parameters detailed in the above sections.

[0185] Carbon Sources and Additives: In addition to using commercially available aqueous suspensions of GO as the starting carbon source, as shown in Table 1, suspensions 1.1, 1.2, 1.3, 1.5, 1.6, 1.7, and 1.8 were again used and subjected to further process perturbations, as detailed in Table 5, including several alternative carbon sources as feedstocks to the established process. Some of the alternative carbon sources closely resemble GO, including exploring concentrated graphene oxide aqueous suspensions and powders to shorten drying times, adding acid or base to the established C / TM mixture to alter the pH of the suspension, exploring chemically treated partially reduced GO from commercial sources, and using a hydrothermal method to prepare GO from sugar solutions on a laboratory scale. Commercially available graphite and expanded graphite powders were also explored. Lignin powder was the most divergent source because it does not contain graphene or graphene oxide layers.

[0186] TM Source: Design the desired range of atomic or molar ratios of the components of the final composite, whether or not transition metal oxides are added to the carbon and additive sources, as specified in Table 5. The preparation of the TM-containing solution is described in Table 2 and the accompanying text.

[0187] Blending, Drying, Harvesting, and Sizing: The blending of carbon and TM source, with or without additives, is performed in specific amounts and stirred at a specific temperature for a specific time. Drying is performed on dehydrator trays, by spray drying, by freeze drying, by heat-assisted milling, or by other methods known in the state of the art. Harvesting varies for different drying methods and can be performed according to known state of the art appropriate for the drying method. The material is sized in one or sequential steps to optimize the requirements of the heat treatment process and the final intended use of the product material, and can be performed using any known state of the art method appropriate for sizing dried or substantially dried material.

[0188] Heat Treatment: The material composition dried and sized in the above process is evaluated for macroscopic uniformity before being used in a two-step heat treatment in two different types, or in a single-step heat treatment in the same furnace, but with controlled heating rates at low and high temperatures. Furnace types from the known state of the art can be used as described above. It is important to control the exothermic reaction to avoid runaway controlled perturbations in the low-temperature heat treatment step, and to provide a substantially oxygen-free environment in the high-temperature heat treatment step.

[0189] Figures 8-14 show characterization of specific perturbations associated with the GmGT materials from Table 5. These figures are described in detail in the exemplification sections of Examples 6-11 below.

[0190] [Table 14]

[0191] [Table 15]

[0192] [Table 16]

[0193] [Table 17]

[0194] [Table 18]

[0195] As an illustration of the tabular process description in Table 5, the embodiment of Sample 6.2 is explicitly listed as an example of a process for synthesizing GmGT(I)-X. A 0.5 wt% GO suspension (20 mL) was used as the carbon source and combined with 25 mL of Solution 2.1 as the TM source. Deionized distilled water (330 mL) was added to the mixture and stirred with a glass rod at room temperature for 3-4 minutes. The solution was dried in a borosilicate glass tray at 49 °C for 24 hours, scraped and chopped into pieces with lateral dimensions of approximately 5-10 mm, and loaded in flake form at 10 mg / cm into an alumina-coated tantalum boat with a lid. 2 The covered material charge was placed in a 2 x 10 -6 torr (2.67 × 10 -4 Resistive heating was performed at varying heating rates in different temperature windows in high vacuum at a starting base pressure of 100 Pa. m Approaching T m The heating rate away from the maximum mass loss temperature of 230 ± 45 °C is symmetrically slow at 0.1 °C / min, with a final annealing at temperature T f = 780 ± 20 °C for 4 hours. m From T f The time to reach 0°C was 15 hours and 45 minutes. After cooling to room temperature and removal from the vacuum furnace, the resulting material was characterized and found to be consistent with GmGT(I)-X material.

[0196] Predictive modeling of composition-GmO crystalline phases and their chemical moieties: As disclosed in this disclosure, GmO can be produced on a practical macroscopic scale using the above process as part of a GmO-based composite material termed GmGT. Two groups, GmGT(I) and GmGT(II), are detailed in compositions in which the GmO component can be crystalline (GmGT(I)-X) or amorphous (GmGT(I)-A and GmGT(II)-A). Most of the crystalline GmO-based compositions produced have unique interatomic spacings that result in unique measured diffraction signatures, resulting in desirable properties manifested in electrochemical cells. Some perturbations to processing parameters can result in variations in the observable 2D diffraction and vibrational signatures of the dominant GmO phase (hereafter, α-GmO). Predictive modeling using DFT identifies novel GmO crystal structures and their component chemical moieties.

[0197] Predictive DFT calculations were performed using Quantum ESPRESSO 6.4.1 (Giannozzi, et al. "Advanced capabilities for materials modeling with quantum ESPRESSO," Journal of Physics: Condensed Matter 29:465901 (2017)). Projected augmented wave (PAW) scalar relativistic pseudopotentials with Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation exchange correlation were generated for carbon, oxygen, and lithium atoms from PSlibrary 1.0.0 (AD Corso "Pseudopotentials periodic table: From H to Pu," Computational Materials Science 95:337 (2014)). Wavefunction expansions included 50 Ry (180 eV (2.88 × 10 -17 A plane wave kinetic energy cutoff of 326 Ry (1175 eV (1.883 × 10 J)) was used for the charge density and potential. -16A kinetic energy cutoff of 0.01 J was used. Because Quantum ESPRESSO operates with periodic boundary conditions in all three directions, the approach to modeling a monolayer of GmO was to make the distance between adjacent GmO layers moderately large in the z direction (e.g., 20 Å in these calculations). Figure 1 shows schematics (top view, two side views, and perspective view) of atomic models of the predicted crystalline atomic structures for the four phases of GmO, denoted α, β, γ, and δ, and Figure 2 shows a schematic of the carbon and oxygen building blocks that compose them.

[0198] Crystalline phase of GmO: α-GmO is composed of an eight-membered heterocycle (shown in Figure 2B) containing two bridged 1,3-dioxetanes (shown in Figure 2A) with each ring parallel to each other and aligned in the carbon sublattice armchair direction, as shown in Figure 1A. The symmetry element is #65 D2h-19 Cmmm. The orthorhombic unit cell has a lattice constant of 0.313 nm and an angle of 130° when fully relaxed, with the oxygen distance from the carbon atom plane at ±0.104 nm. When hexagonally constrained, the above parameters are 0.295 nm, 120°, and ±0.108 nm, respectively. This structure can appear in three equivalent domains when the dioxetane pair is in one of three armchair resonance configurations. All carbons in the α-GmO structure are sp 3 It is in a mixed state.

[0199] β-GmO is composed of nine-membered heterocycles (shown in Figure 2C) in which each ring contains three bridged 1,3-dioxetanes (shown in Figure 2A) in an armchair orientation alternating with oxygen-free hexagonal carbon rings, as shown in Figure 1B. The symmetry element is #191 D6h-1 P6 / mmm. The orthorhombic unit cell has a lattice constant of 0.507 nm and an angle of 120°, with oxygen distances from the carbon atom planes of ±0.104 nm. All carbons in the β-GmO structure are sp 3 It is in a mixed state.

[0200] γ-GmO is composed of 10-membered heterocycles (shown in Figure 2D) with bridging oxygens in a planar zigzag orientation, as shown in Figure 1C. The symmetry element is #21 D2-6 C222. The orthorhombic unit cell has a lattice constant of 0.344 nm and an angle of 119° when fully relaxed, with the oxygen distance from the carbon atom plane at ±0.065 nm. When constrained hexagonally, the above parameters are 0.344 nm, 120°, and ±0.066 nm, respectively. This structure can form superlattice arrangements based on the order in which oxygens are arranged above / below the plane of the carbon. The parameters of the 2x2 and 4x4 superlattice structures are shown below. All carbons in the γ-GmO structure are sp 2 It is in a mixed state.

[0201] γ-GmO (2x2): The symmetry element is #53 D2h-7 Pmna. The orthorhombic unit cell has a lattice constant of 0.668 nm and an angle of 114° when fully relaxed with the oxygen distance from the carbon atom plane being ±0.074 nm. When constrained hexagonally, the above parameters are 0.688 nm, 120°, and ±0.076 nm, respectively. All carbons in the γ-GmO structure are sp 2 It is in a mixed state.

[0202] γ-GmO (4x4): The symmetry element is #49 D2h-3 Pccm. The orthorhombic unit cell has a lattice constant of 1.378 nm and an angle of 109° when fully relaxed with the oxygen distance from the carbon atom plane at ±0.060 nm. All carbons in the γ-GmO structure are sp 2 It is in a mixed state.

[0203] δ-GmO consists of linear carbon monoxide chains (shown in Figure 2E) in a vertical zigzag orientation, as shown in Figure 1D. The symmetry element is #67 D2h-21 Cmma. The orthorhombic unit cell has a lattice constant of 0.333 nm and an angle of 135° when fully relaxed, with the oxygen distance from the carbon atom plane being ±0.121 nm. All carbons in the δ-GmO structure are sp 3 It is in a mixed state.

[0204] Table 6 summarizes the predicted bond lengths and angles of the building blocks, as well as the unit cell dimensions of these two-dimensional GmO crystalline phases. It also lists the predicted diffraction peak positions of the most intense Bragg beams and gives their relative intensities relative to the most intense peaks. Predicted formation energies, all negative, are included, indicating the likelihood of forming these structures under favorable thermodynamic and kinetic conditions. For some structures, NMR isotope shifts were also predicted.

[0205] [Table 19]

[0206] Figure 2 shows a schematic representation of the chemical moieties that are the building blocks of the various crystalline phases of 2D GmO shown in Figure 1. These moieties, or their variants or substructural components, may also be present in amorphous GmO.

[0207] Heterocyclic building blocks containing carbon and oxygen (Figure 1A-D): a) Four-membered heterocycles with two oxygen atoms (Figure 2A): 1,3-dioxetane; b) 8-membered heterocycles containing two bridged dioxetanes (Figure 2B): 1,5-dioxa-cyclooctane with two additional bridging oxygens at the (2,8) and (4,6) positions that make up the dioxetane defined in (Figure 1A); c) 9-membered heterocycle with three bridging dioxetanes (Figure 2C): 1,4,7-trioxa-cyclononane with three bridging oxygens at the (2,9), (3,5) and (6,8) positions constituting the dioxetane defined in (Figure 1A); d) 10-membered heterocycle with four oxygen atoms (FIG. 2D): (3,5,8,10)tetraoxa-(1,6)-cyclodecadiene without additional bridging oxygens and without dioxetane. Carbon- and oxygen-containing chain building blocks (Figure 2E): e) Zigzag chain (Figure 2E): A polycarbonyl in which each C=O bond dipole moment is opposite to the previous C=O bond dipole moment.

[0208] Charge storage devices made using the materials of the present invention: In one embodiment, these materials have improved electrode performance relative to graphite. Generally, cell construction for charge storage devices can be tailored for optimal performance characteristics by, for example, adjusting the anode formulation, cathode selection, electrolyte formulation, electrode loading, and / or combinations thereof. To demonstrate the improved performance of these inventive materials, the anode formulation, cathode selection, loading, and electrolyte formulation are selected to be typical of, and well-suited to, the construction of graphite or graphite / silicon cells. Cell construction options that can further improve the performance of these inventive materials can include different anode formulations, cathode selections, loadings, electrolyte formulations, cell formats, or combinations thereof.

[0209] As a specific example, three active anode compositions were investigated in pouch cells: pure graphite (Gr), graphite containing 3% (by weight) silicon (GrSi), and graphite containing 3% silicon and 10% of the subject GmGT(II)-A material disclosed herein (GrSiGmGT(II)-A). Through half-cell testing, the specific capacity of the pure GmGT(II)-A material was determined to be 540 mAh / g. See Figures 15 and 16.

[0210] Figure 15 shows the charge / discharge curves for an anode half-cell composed of 100% GmGT(II)-A as the anode active material. Two formation cycles at C / 20 yielded a capacity of 540 mAh / g for the GmGT(II)-A material. This value was used in the calculations described below to determine the theoretical capacity of the composite anode used in the pouch cell. A notable feature of this material is its sloped potential profile. This makes it difficult to define the potential relative to lithium. However, the profile shape can be advantageous for predicting the battery's capacity as a function of voltage. In comparison, the graphite anode half-cell (Figure 16) exhibited a capacity of 351 mAh / g at currents approximately C / 20. This graph shows data from two formation cycles at C / 20 followed by cycling at C / 3. The graphite half-cell exhibits a characteristic voltage plateau at approximately 0.2 V.

[0211] Using this result, the specific capacity of the composite material of the present invention, GrSiGmGT(II)-A, was determined to be 445 mAh / g. This value is higher than the specific capacities of graphite and GrSi3, which are 340 mAh / g and 425 mAh / g, respectively. A summary of the materials cycled in the pouch cell is shown in Table 7.

[0212] [Table 20]

[0213] The cathode used in these tests was LiNiCoAlO2 (NCA). The alternative cathode material investigated was Li(Ni), which has been proposed in the literature (Chevrier et al. (19 Sept. 2018) “Design of Positive Electrodes for Li-Ion Full Cells with Silicon,” J. Electrochem. Soc. 165(13): A2968-A2977) as a material that stabilizes the Si alloy in graphite / Si alloy anodes, improving cycle performance and coulombic efficiency. 0.6 Mn 0.2 Co 0.2)O2 (NMC622). NCA was selected after half-cell testing on both NCA and NMC622 cathodes. Testing was performed in the voltage ranges of 2.7-4.3 V and 2.7-4.5 V. Each half-cell underwent two cycles at a C / 10 rate followed by two cycles at a 1C rate. The average capacity loading of the NMC622 electrode was 1.90 mAh / cm. 2 The average capacity loading of the NCA electrode was 1.99 mAh / cm 2 The results of the cycling are shown in Figure 17 (old 5) (A to D).

[0214] Figure 17A shows the charge / discharge curves of NMC622 cycled at an upper voltage cutoff of 4.3 V. The C / 10 specific capacity was 165 mAh / g and the initial coulombic efficiency was 87%. Figure 17B shows the charge / discharge curves of NMC622 cycled at an upper voltage cutoff of 4.5 V. The C / 10 specific capacity was 187 mAh / g and the initial coulombic efficiency was 85%. Figure 17C shows the charge / discharge curves of NCA cycled at an upper voltage cutoff of 4.3 V. The C / 10 specific capacity was 194 mAh / g and the initial coulombic efficiency was 90.4%. Figure 17D shows the charge / discharge curves of NCA cycled at an upper voltage cutoff of 4.3 V. The C / 10 specific capacity was 207 mAh / g and the initial coulombic efficiency was 90.4%.

[0215] The anode slurry contained 94% active material and either pure graphite, a 97:3 mixture of graphite and silicon, or an 87:3:10 mixture of graphite, silicon, and the active material disclosed herein. The inactive materials included in the slurry were 3% carbon black, a standard conductive agent for graphite, and a total of 3% water-based binder (1.5% sodium carboxymethylcellulose, 1.5% styrene butadiene rubber). The anode slurry was cast onto 12 μm Cu foil. For half cells, electrodes were die-cut to the size of a CR2032 coin cell.

[0216] For the 200 mAh pouch cells, the anode under test was paired with a lithium nickel cobalt aluminum oxide (NCA) cathode cast on 20 μm aluminum foil. Active cathode and anode slurries were prepared from binder and carbon black, spread on aluminum foil and copper foil, respectively, and allowed to dry. The cathode thickness was greater than the anode thickness (due to the cathode's lower specific capacity), but the length and width of the cathode were smaller than those of the anode.

[0217] The N:P ratio used was 1.1. This ratio was previously determined by testing in a full coin cell. The capacity of the anode was in excess compared to the capacity of the cathode to prevent lithium deposition on the anode surface. The size was selected based on the theoretical capacity of the NCA and the experimental capacity of the inventive materials disclosed in this disclosure, as determined by half-cell testing.

[0218] After drying the electrodes overnight, they were assembled into pouch cells. At this stage, electrolyte was added and the pouch was sealed. The cells were then cycled at a current rate of C / 20 for two days to form a solid electrolyte interface (SEI) and activate the electrodes. The cells were then evacuated and resealed.

[0219] Overall, 11 full pouch batteries were fabricated: 3 with graphite anodes, 3 with GrSi3 anodes, and 5 with GrSi3GmGT(II)-A anodes. A summary of the cycled cells and their electrodes, including electrode pair information, is shown in Table 8.

[0220] [Table 21]

[0221] Low temperature charge-discharge performance was also tested at 0° C. and −20° C. See Table 9 for a complete list of the various test conditions.

[0222] [Table 22]

[0223] Each pouch cell was conditioned before being subjected to specific testing. The design capacity was approximately 190-200 mAh, but the GrSi capacity loading was approximately 220 mAh, due to the GrSi capacity loading being slightly higher than expected. All anodes were mated with cathodes using a 1:1 N / P ratio. The specific capacity loading was 2.05-2.2 mAh / cm for the cathodes mated with the GrSi. 2 and 2.35mAh / cm 2 The cells were cycled at C / 10 for one cycle, followed by C / 2 for nine cycles. Due to the relatively low initial coulombic efficiency, the GmGT(II)-A cells exhibited a capacity of approximately 175 mAh / g at C / 10 after formation.

[0224] Test 1 was performed to evaluate the rate capability of the material of the present invention compared to pure graphite. The cells were charged at various rates up to 5C and discharged at a C / 3 rate. Cycling continued at the highest rate at which the cell still functioned until failure. The results of Test 1 are shown in Figure 18 (A-C).

[0225] Figure 18A shows the rate capability. Figure 18B shows the rate capability normalized based on the capacity at C / 10 for a direct comparison of the actual rate capability. Figure 18C shows the high-rate charge / discharge curves of pouch cells using graphite (Gr) and graphite / silicon / GmGT(II)-A composite (GrSiGmGT(II)-A) anodes (1C = 200 mAh). The capacity of the graphite pouch cell is close to the designed value (200 mAh), while the capacity of the GrSiGmGT(II)-A pouch cell is 154 mAh. This is due to irreversible capacity loss, which can be improved by pre-lithiation techniques. As shown in Figure 18A, the capacity of the GrSiGmGT(II)-A cell is lower at C / 10 than the Gr cell, but the GrSiGmGT(II)-A cell exhibits higher capacity at a high rate of 5C. More directly, Figure 18B shows that the GrSiGmGT(II)-A cell exhibits superior rate capability to the Gr cell at current rates higher than C / 2. Due to mechanical error in the battery tester, the capacity of two of the three cycles at C / 5 in Figures 18A and 18B was not recorded. Figure 18C compares the charge-discharge curves between the Gr and GrSiGmGT(II)-A pouch cells. The GrSiGmGT(II)-A cell exhibits a significantly lower voltage plateau during charging than the Gr cell. This significantly aids in mitigating potential lithium deposition on the anode.

[0226] Test 2 was conducted to compare the cycle life of cells containing the inventive GmGT(II)-A material disclosed in this disclosure with graphite-only and GrSi cells. The cells were charged and discharged at a C / 2 rate for multiple cycles to evaluate life under typical conditions of use in electronic devices. The results are shown in Figure 19 (A-D).

[0227] Normalized Capacity: Test 3 was used to examine how a composite anode made of GmGT(II)-A material performed under fast-charge conditions compared to pure graphite and graphite-Si combinations. Cells were charged at 5C and discharged multiple times at C / 3 to evaluate fast charging under typical usage and lifetime conditions. This test was performed twice to replicate the results. The results are shown in Figure 19E.

[0228] Figure 19A shows the cycling performance from Test 3a after one cycle of formation at C / 10 and cycling at 5C. Figure 19B shows the cycling behavior from Test 3a normalized based on the reversible capacity. Figures 19C and 19D show the capacity and normalized capacity, respectively, for Test 3b, and Figure 19E shows the same test performed on the GrSi3 cell, albeit with fewer cycles. The design capacity was 200 mAh and the N:P ratio was 1:1. The GrSi3GmGT(II)-A cell initially exhibited low capacity due to irreversible capacity loss during formation. However, during 5C cycling, the GrSi3GmGT(II)-A cell maintained a high percentage of reversible capacity: 42 mAh (28% of reversible capacity) for GrSi3GmGT(II)-A compared to 42 mAh (21% of reversible capacity) for graphite. The 5C capacity of GrSi3 was approximately 110 mAh, but this decreased to approximately 70 mAh (64% of the reversible capacity) by cycle 14. In comparison, GrSi3GmGT(II)-A showed approximately 25% capacity retention at cycle 14.

[0229] Test 4 was performed by charging at a C / 2 rate and discharging at a C / 3 rate at -20°C for 10 cycles, followed by life cycling at 0°C to evaluate low-temperature behavior under typical usage. For graphite, the voltage range was 1.5 V to 4.3 V. For GrSi3GmGT(II)-A, cycling at 0°C was performed over a voltage range of 1.5 V to 4.2 V, again with the upper voltage cutoff changed to 4.3 V. See Figures 20A, 20B, and 21.

[0230] Figures 22-24 are a series of SEM images and elemental maps characterizing the atomic composition and morphology of an electrode fabricated with the GmGT(II)-A material disclosed herein. Figure 22 is a low-magnification backscattered electron (BSE) SEM image showing uniform distribution of the particles (bright features) of the present invention in a graphite matrix. Good particle-matrix bonding and good packing density of the slurry particles are evident. Figure 23 is a high-magnification secondary electron SEM image of a GmGT(II)-A particle (large central particle) showing evidence of a two-dimensional flake-like morphology. Adjacent particles (mainly graphite) are well bonded to the GmGT(II)-A particle. Figure 24 shows the BSE image in the upper left panel and a series of three elemental maps from the same region of the electrode, showing carbon distribution (upper right panel), molybdenum distribution (lower left panel), and oxygen distribution (lower right panel). The intensity scale between the maps shown in Figure 24 is not quantitative. This is clear evidence that the GmGT(II)-A material can be incorporated into the electrode formulation without chemical or mechanical degradation.

[0231] Figure 25 is a series of graphs showing the cycling performance of 200 mAh pouch batteries fabricated using an LCO cathode and a cathode containing 10% of the inventive materials disclosed herein (GmGT(I)-X and GmGT(II)-A) and 90% graphite (Gr). The pouch cells were formatted at C / 10, conditioned for 9 cycles at C / 2, and then charged to a 50% state of charge for impedance analysis. Of particular note in this series of graphs is panel (c) showing a comparison of the charge / discharge curves of pouch cells using anodes of pure graphite (Gr), Gr with GmGT(I)-X, and Gr with GmGT(II)-A. These cells were charged at 10 C and discharged at C / 3 to mimic ultrafast charging and normal driving EV conditions (i.e., commercially desirable performance characteristics for batteries powering electric vehicles). Panel (d) shows the corresponding cycling performance of the batteries charged and discharged under these conditions. It is well known that batteries with graphite anodes cannot be rapidly charged. As expected, under these charging conditions, the pouch cells with graphite anodes were barely charged (only 2 mAh) at 10°C. In contrast, when 10 wt% of the GmGT material disclosed in the present disclosure was used, the pouch cells with GmGT(I)-X / Gr and GmGT(II)-A / Gr were charged to 16 mAh and 21 mAh, respectively, at 10 C. This is approximately 10% of the capacity obtained at C / 10. In summary, batteries incorporating the anode material of the present disclosure exhibit promising ultrafast charging capabilities. The batteries also exhibit excellent performance at low temperatures. Panels (e) and (f) of Figure 25 show the charge / discharge profile and cycling performance at -20°C. Here, the cell was charged at 1 C and discharged at C / 3, demonstrating a capacity of 33 mAh. This is roughly 20% of the capacity when charged / discharged at the same rate, but at room temperature.

[0232] Figures 26, 27, and 28 are a series of photographs of a separator made in accordance with the present disclosure and a conventional graphite separator after cycling, showing the extent of lithium deposition. Figure 26 is a photograph of a conventional graphite separator recovered from a cycled 200 mAh graphite-only active anode pouch cell. The photograph clearly shows lithium powder deposition (brown areas). In contrast, Figure 27 shows a separator made in accordance with the present disclosure and cycled under identical conditions. Figure 27 shows significantly less lithium powder deposition compared to Figure 26. Figure 28 is a side-by-side comparison of a separator of the present invention (left) and a conventional graphite separator (right). The lighter contrast of the conventional anode indicates significant lithium (Li) plating (observed as a gold / tan color upon visual inspection). The dark brown color of the anode containing the material of the present invention indicates healthy battery performance (observed as a dark brown / black color upon visual inspection).

[0233] Predictive modeling of the interaction of Li with GmO: Disclosed herein are compositions containing GmO-based materials in combination with lithium atoms, as well as methods for forming these materials. Using the above synthesis methods, we formed crystalline GmGT(I)-X and amorphous GmGT(II)-A composites containing crystalline graphene and molecular TMOs. These materials were used to form the anodes of single-cell lithium-ion batteries (LIBs). The cells were cycled for various numbers of cycles and tested to analyze the crystalline signatures of the materials upon lithiation (charge) and delithiation (discharge). Specific examples are shown for a single cycle (Figure 29), a moderate number of cycles, and a large number of cycles (Figure 30). Regardless of whether the crystalline or amorphous version was used as the starting material, the crystalline α-GmO and G signatures are present in both cases after cycling. Five additional peaks are observed forming new diffraction signatures.

[0234] Predictive DFT calculations were performed using Quantum ESPRESSO 6.4.1 (Giannozzi, et al. "Advanced capabilities for materials modeling with quantum ESPRESSO," Journal of Physics: Condensed Matter 29:465901 (2017)). Projected augmented wave (PAW) scalar relativistic pseudopotentials with Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation exchange correlation were generated for carbon, oxygen, and lithium atoms from PSlibrary 1.0.0 (AD Corso "Pseudopotentials periodic table: From H to Pu," Computational Materials Science 95:337 (2014)). Wavefunction expansions included 50 Ry (180 eV (2.88 × 10 -17 A plane wave kinetic energy cutoff of 326 Ry (1175 eV (1.883 × 10 J)) was used for the charge density and potential. -16A kinetic energy cutoff of 1 × 1, 2 × 2, 3 × 3, 4 × 4, and 5 × 5 was used. For different concentrations of lithium atoms, 1 × 1, 2 × 2, 3 × 3, 4 × 4, and 5 × 5 periodic supercells were used, carefully selecting k-points that allowed for comparison of energies for different concentrations of lithium atoms. Because Quantum ESPRESSO works with periodic boundary conditions in all three directions, a way to model the interaction of multiple lithium atoms with a monolayer of model α-GmO was to keep the distance between adjacent GmO layers moderately large in the z direction (e.g., 20 Å in these calculations). To avoid long-range electric dipole effects, two layers of α-GmO were used per supercell when the number of lithium atoms above the monolayer was greater (or less) than the number of lithium atoms below the monolayer. Adding a second layer of α-GmO with the number of lithium atoms reversed above and below within the same supercell cancels any long-range electric dipole that may have been introduced by the periodic structure in the z direction. In both cases, the distance between adjacent α-GmO layers was kept at 20 Å. The change in energy of a single lithium atom, ΔE, when it leaves the pure Li structure and adsorbs onto the surface of an α-GmO monolayer. Li is the total energy E of one (super) cell of GmO GmO Calculate E Li =-204.67eV(-3.2792×10 -17 Understanding that J is the total energy of one lithium atom in a pure lithium crystal (body-centered or hexagonal close-packed), E is the total energy of one (super)cell of GmO. GmO+Li , and N as the number of inserted lithium atoms. Li It is calculated by counting

[0235] The goals of the DFT calculations predicting the interaction of lithium atoms with an α-GmO monolayer were: 1) to determine whether a GmO monolayer can hold multiple lithium atoms, and 2) to predict the maximum theoretical capacity of this novel anode material for lithium-ion batteries. The results presented below predict that, unlike graphene monolayers, α-GmO monolayers hold multiple lithium atoms by forming Li-O bonds. Only the α-GmO crystalline monolayer is shown in the tables and figures below. However, calculations predicting other crystalline phases of GmO (β, γ, and δ) also confirm the formation of Li-O bonds. Multiple lithium atoms are adsorbed on the GmO monolayer, either on one or both sides of the monolayer. A wide range of lithium concentrations was examined, from a single lithium atom to complete coverage by multiple lithium atoms, above and below the H-sites of each GmO hexagon.

[0236] A single lithium atom near a GmO monolayer: The first step to understanding the interaction of multiple lithium atoms with multiple GmO monolayers is to explore the preferred site for the adsorption of a single lithium atom on an α-GmO monolayer in the absence of other lithium atoms. The lowest energy configurations start with the following high-symmetry sites: i) O is the site directly above the O atom; ii) T is the top site on the C atom; iii) B site (bridge site) is located above the center of the C-C bridge; iv) H site (cavity site) is located directly above the quasi-hexagonal cavity (Figure 31A), i.e., a vacant site in the carbon sublattice; and v) S site (special site) is located at the center of gravity of the triangle formed by three adjacent O atoms (Figure 31B), i.e., S is a vacant site in the oxygen sublattice.

[0237] [Table 23]

[0238] Table 10 shows the change in energy of a single lithium atom and constant unit cell parameters (α = 130° and α latThe coordinates of the H site on the high-symmetry site of the GmO monolayer constrained to a symmetrical orientation (=3.13 Å) are shown. The H site is the lowest energy site for a single adsorbed lithium atom. ΔE is higher for the S and B sites than for the H site. Li is less negative but is energetically more favorable for lithium atoms than for bulk lithium metal. Therefore, the S and B sites may be occupied during lithium adsorption at higher concentrations.

[0239] To check whether other preferred sites were overlooked, the z-coordinate of a single lithium atom was optimized at multiple points on the GmO monolayer along the corresponding x- and y-components of the lattice constant in small, fixed steps. From this information, the energy and height variations of the lithium atom on the GmO monolayer were mapped to the x- and y-coordinates (not shown). This calculation confirms that the H-site is the most energetically favorable site for a single lithium atom, and that the lithium atom is closest to the GmO monolayer on the S-site. Therefore, if multiple lithium atoms must be densely packed between the GmO layers, the S-site would be preferred for multilayer systems.

[0240] For the lithium atom on the H site, we calculate the change in electron density distribution for the GmO monolayer + single Li system relative to the GmO monolayer and lithium atom alone to determine the gain in electronic charge density for the Li-O bond. The lithium atom leaves the structure and moves to Li + When converted to ions, they release their electrons relatively easily. This behavior is necessary for GmO to function as an anode in lithium-ion batteries. Integrating the electron charge density ρ over the entire area of ​​the supercell yields a linear electron charge density along the z-axis (not shown here), confirming the finding that lithium atoms share their electronic charge with the GmO monolayer. The actual electron charge density distribution around the lithium atoms reveals that the oxygen atoms have the highest density of states. In this sense, the interaction of a single lithium atom with a GmO monolayer is stronger and more advantageous for Li-ion batteries when compared to the interaction with a graphene monolayer.

[0241] Parameters for various concentrations of lithium atoms on one GmO monolayer: Using the term lithium intercalated graphite, the case with the highest capacity for lithium (and therefore the highest capacity for charge) is represented as hexal ordering of LiC6, and the novel Li2C n O n The structure has multiple pairs of lithium atoms above and below the same cavity site, forming LiC n O n The structure has multiple lithium atoms on only one side of the GmO monolayer. An example of a GmO monolayer and lithium structure is Li2C6O6(Li 0.67 The configurations of LiC0 and LiC0 are shown in Figures 32A and 32B. Table 11 shows the average change in lithium atom energy for the fully relaxed structures, indicating that lithium atoms are generally more bound to the GmO monolayer at lower lithium concentrations (corresponding to lower charge capacities). Table 11 also suggests that multiple lithium atoms tend to remain apart from each other rather than forming lithium metal clusters on the monolayer. The repulsive behavior between lithium atoms is important for Li transport in GmO and its potential application in fast-charging batteries.

[0242] Theoretical capacities were calculated for all compositions sampled in Table 11. When lithium atoms are arranged above and below each cavity site in the GmO monolayer, a maximum theoretical capacity of 957 mAh / g is predicted for the Li2C2O2 configuration. This capacity is 2.6 times the theoretical capacity of graphite (372 mAh / g for LiC6). When each cavity site holds a lithium atom on only one side of the GmO monolayer, it has 1.3 times the capacity of graphite. All other configurations have lower capacities than graphite. The gradual increase in capacity from bottom to top in Table 11 equates to the increasing capacity of graphite as more lithium is inserted until the final hexal ordering of LiC6 is reached.

[0243] [Table 24]

[0244] The maximum capacity Li2C2O2 and LiC2O2 structures in Table 11 all have ΔE Li >0 eV (and therefore attracts lithium atoms less than bulk lithium metal), these energies are much closer to 0 eV than their equivalents in graphene. For example, the predicted energy for the hexal structure (Li2C6) corresponding to lithium atoms on both sides of graphene is +0.60 eV (9.61 × 10 -20 J), but the ΔE of the same structure in GmO(Li2C6O6) Li is -0.04 eV (-6.4 × 10 -21 Furthermore, previous experience with graphene and graphite indicates that these structures are feasible for multilayers of GmO used in lithium-ion battery anodes, as shown above for batteries made with GmO-based anode materials.

[0245] Therefore, for multiple lithium atoms, lower concentrations are energetically more stable than higher concentrations. Lithium atoms tend to move away from each other. This repulsive behavior can significantly contribute to the fast charging observed in lithium-ion batteries using GmO-containing electrodes. The maximum lithium concentration investigated, with the Li2C2O2 configuration, has an excellent charge capacity of 957 mAh / g, 2.6 times that of graphite. It is noteworthy that reported ab initio studies show that the Li2C6O6 configuration is energetically stable, whereas the equivalent configuration in graphene (Li2C6) is unfavorable.

[0246] The lithiated GmO material can be produced by methods other than incorporating GmGT material into fabricated LIB cells that are then cycled. The LGm material can be produced, for example, by electrochemical intercalation. Alternatively, the pre-GmGT material can be suspended in an aqueous solution of Li2CO3, dried, and heat-treated at a high enough temperature to produce the GmO-based material. Alternatively, the final GmGT material can be suspended in an aqueous solution of Li2CO3 and dried by the method described above. This modified GmGT powder can then be used directly in LIB electrode formation, as described above, to facilitate conventional formation cycling and reduce irreversible lithium loss.

[0247] Band structure, density of states and electronic conductivity: Lithium (Li x Comparing the energy bands of the LiC2O2 and unlithiated (α-GmO) compositions confirmed that the pure α-GmO monolayer is a semiconductor [references: Mattson et al. (2011). “Evidence of nanocrystalline semiconducting graphene monoxide during thermal reduction of graphene oxide in vacuum,” ACS Nano 5:9710 and Pu et al. (2013) “Strain-induced band-gap engineering of graphene monoxide and its effect on graphene, Phys. Rev. B 87:085417]. 32 O 32We have demonstrated that even at low concentrations of lithium atoms, such as , the composition is a conductor. The highest concentration of lithium investigated in Li2C2O2 (Figure 32B) has the most metallic properties, indicating that the addition of Li closes the energy band gap of the semiconducting GmO monolayer, turning this novel composition into a conductor. The densities of states for the fully relaxed GmO monolayer, LiC6O6, Li2C6O6, and Li2C2O2 structures are shown in Figure 33. The lithiated structures have more states around the Fermi energy, are conductive, and are consistent with the band structure, making them desirable for battery anodes.

[0248] Therefore, by analyzing the band structure and density of states, Li2C 32 O 32 The conductive properties of the composition were confirmed even at such low concentrations. By integrating the density of states for various structures around the Fermi energy and analyzing the redistribution of charge density, it was found that lithium atoms readily donate electrons to Li while leaving GmO. + It has been demonstrated that GmO can become ions, making it a suitable battery anode material for lithium-ion batteries.

[0249] Li migration near a GmO monolayer: The energy plot of lithium transport near the α-GmO monolayer was obtained using the nudged elastic band (NEB) method implemented in Quantum ESPRESSO [Henkelman and Jonsson (2000) “A climbing image nudged elastic band method for finding saddle points and minimum energy paths,” J. Chem. Phys. 113: 9901–9904]. ... -19 Although the transfer of lithium atoms through the GmO cavities is difficult due to an energy barrier of 0.34 eV (5.45 × 10 J) (not shown here), lithium migration at the surface of the GmO monolayer proceeds easily from one H site to the next through the S site, B site, and S site. The highest energy barrier is 0.34 eV (5.45 × 10 J) at the B site. -20J), which indicates that lithium can move at high speed parallel to the GmO layer.

[0250] Therefore, the lithium atom migration considered in the nudged elastic band method excludes lithium migration through cavities in the GmO lattice due to the high energy barrier. At the surface of GmO, lithium migration occurs rapidly between adjacent H sites via S, B, and S sites. This result confirms measurements on electrochemical cells fabricated with GmO-based materials, which show much faster charging than comparably constructed graphite anodes. [Example]

[0251] The following examples are intended to illustrate the above invention and should not be construed to narrow its scope. Those skilled in the art will readily recognize that the examples may suggest other ways in which the present invention can be practiced. It should be understood that various modifications and variations can be made while remaining within the scope of the present invention.

[0252] Example 1. Synthesis and characterization of pre-GmGT materials: Sample 3.18 in Table 3 is representative of a synthetic process for producing pre-GmGT(I) material. In this example, suspension 1.1 was combined with solution 2.1 in a typical ratio, followed by a typical low-temperature treatment in a low-vacuum oven. Sample 3.18 was found to yield GmGT(I)-X upon further high-temperature treatment, listed in Table 4 as sample 4.13. Figure 3 summarizes the identification fingerprint of the pre-GmGT(I) material from several characterizations.

[0253] Figures 3A-3D show TEM data collected from a Hitachi H-9000NAR 300 keV transmission electron microscope (TEM) for the pre-GmGT(I) material, followed by subsequent data analysis. The rings observed in the SAED pattern shown in Figure 3C are characteristic of the G component of the pre-GmGT(I) material. This indicates that the G component of the pre-GmGT(I) composite is essentially crystalline, possessing several distinct orientation domains within the region of the sample selected by the 1.5 μm diameter TEM aperture (indicated by the ring spots), and that numerous smaller orientation domains of crystalline G are also present, as indicated by the smoothness of the diffraction rings between different diffraction spots. There are no detectable diffraction features that could be associated with regions of crystalline TM compound. Figure 3D is a bright-field TEM image of the area corresponding to the SAED data, revealing the compact, flake-like nature of the material. Furthermore, there is no indication of nanocrystals or aggregates of TM-containing nanoparticles. Figure 3A was obtained from the SAED pattern by centering the diffraction pattern, rotationally averaging the intensity distribution, subtracting a piecewise linear background suppressed everywhere below the raw data intensity, and plotting the results as a function of calibrated spatial frequency. Measurement of the peak positions corresponding to the rings present in the SAED pattern (Figure 3B) confirms the spatial frequencies and atomic spacings corresponding to the in-plane spacing of graphite or graphene. There is no evidence of crystalline TM particles in this region of the sample, which is characteristic of pre-GmGT material.

[0254] Figure 3E shows representative IR data collected from pre-GmGT(I) material using diffuse reflectance (DIFFIR from PIKE instruments) with a commercially available FTIR (Bruker Vertex) infrared spectrometer. Approximately 1-5% by mass of the ground sample was weighed, added to 5 mg of potassium bromide powder, and placed in a cup for reflectance measurement. A background measurement of 5 mg of potassium bromide powder was measured as before and subtracted from the previous measurement to obtain the reflected / scattered infrared intensity of the sample. This data is analogous to an infrared absorption spectrum in arbitrary units and provides a vibrational fingerprint signature of the sample. The spectrum exhibits typical fingerprint features unique to pre-GmGT material: 1) a 1,000 cm peak typical of Mo-O vibrations in the MoO bond form; -1 2) a relatively sharp absorption line just below the -1 and 3) a broad feature at 1700 cm suggesting a defect sp2 CC vibration. -1 Nearby derivative-like features.

[0255] Figure 3F, for example, shows representative SEM data collected from pre-GmGT(I) material using a Hitachi S-4800 FE-SEM operating at 15 keV. This particular experimental sample was obtained using the same process as sample 3.18, without the sizing step to produce a powder-like material. Typical SEM images of pre-GmGT(I) material (e.g., Figure 3F) show large flakes with a compact, layered, sheet-like morphology that differs from the thin GO or rGO morphologies described in the literature.

[0256] Figures 3G and 3H show TGA and DSC data, respectively, for pre-GmGT(I) material, prepared in a similar manner as described for the SEM sample material in Figure 3F. The TGA / DSC data were collected using, for example, a TA Instruments Discovery SDT 650 simultaneous TGA / DSC instrument. The material sample was heated from room temperature to 300 °C at a rate of 10 °C / min under a 100 mL / min flow of argon gas. This sample did not exhibit the exothermic peak below 300 °C typically observed with graphene oxide. The enthalpy calculated by integrating the heat flow curve over the temperature range of 122 to 266 °C, without baseline subtraction, was 149.7 J / g. A heat flow peak of 2.243 W / g occurred at 187.5 °C. The maximum mass loss rate occurred at the end of the heating profile. These features represent a characteristic fingerprint of the pre-GmGT material; that is, exothermicity is virtually absent for this material. At the end of heating to 300° C., the sample retained 86.6% of its starting mass and the fingerprint of the pre-GmGT material.

[0257] For example, in BET measurements of the pre-GmGT(I) material (sample 3.18), a complete nitrogen adsorption isotherm was obtained using a Micromiritics ASAP 2020 BET surface area / pore size analyzer. Degassing was performed by evacuation from 50 mmHg / s to 10 μmHg at 90°C for 90 minutes, followed by heating at a rate of 10°C / min, and then holding at 240°C for 240 minutes at a holding pressure of 100 mmHg. For the pre-GmGT(I) material, the BET surface area was 6.5 m in this example. 2 The fingerprint of the pre-GmGT material is the measured BET surface area, which indicates a compact material with a graphite-like specific surface area, clearly different from that of virgin graphite, graphene, or typical rGO materials.

[0258] In this example, the pre-GmGT material is typified as a compact, layered material (confirmed by SEM and TEM) with a low specific surface area (similar to graphite) as determined by BET surface area measurements and virtually no exotherm when heated to approximately 300°C as determined by TGA / DSC measurements. The Gm component of the pre-GmGT material contains functional groups related to C-O-C moieties as determined by FTIR measurements, further indicating that the T component of pre-GmGT is at least partially fully oxidized TMO. While the G component of pre-GmGT is substantially crystalline, the T component is substantially amorphous and uniformly distributed throughout the material as determined by SAED measurements and imaging.

[0259] Example 2. Synthesis and characterization of GmGT(I) and GmGT(II) materials: Using the example of GmGT(I) and GmGT(II) materials, fingerprints from standard measurements are shown. Selected examples, produced by the processes outlined in Tables 3 and 4, are described in the detailed description above. Sample characterization is now described.

[0260] Figure 4 shows data collected for GmGT(I)-A according to sample 4.1 in Table 4, but at a final temperature of approximately 625 °C. The rings observed in the SAED pattern shown in Figure 4C are characteristic of the G component of the GmGT(I) material. This indicates that the G component of the GmGT(I) composite is essentially crystalline, possessing several distinct orientation domains within the region of the sample selected by the 1.5 μm diameter aperture of the TEM (indicated by the ring spots). Numerous smaller orientation domains of crystalline G are also present, as indicated by the smoothness of the diffraction rings between different diffraction spots. There are no detectable diffraction features that could be associated with regions of crystalline TM compound or crystalline GmO compound. Figure 4D is the corresponding bright-field TEM image, revealing the compact, flake-like nature of the material. The small dark spots are likely small fragments of larger flakes, as they do not exhibit crystalline diffraction features. The dark features may represent aggregates of TM-containing nanoparticles. Figure 4A is a rotational average of the SAED intensity line profile (see Example 1 above), and Figure 4B, derived from the line profile, confirms the spatial frequencies and atomic spacing corresponding to the in-plane spacing of graphite or graphene. There is no evidence of crystalline TM particles in this region of the sample, which is characteristic of GmGT(I)-A material.

[0261] Figure 4E shows representative IR data with typical fingerprint features unique to GmGT(I)-A material: 1) 1250 cm typical of C-O-C type vibrations -1 and 2) a broad feature at 1700 cm suggesting a defect sp2 CC vibration. -1 The characteristic Mo-O features present in the pre-GmGT material are significantly reduced and broadened significantly in this material, which is processed at a much higher temperature.

[0262] Figure 4F shows representative SEM data collected from the GmGT(I)-A material. The representative SEM image of the GmGT(I)-A material shows large flakes with a compact, layered, sheet-like morphology distinct from the thin G or rGO morphologies.

[0263] Figure 5 shows data collected for GmGT(I)-X according to sample 4.1 in Table 4. The spots / rings and faint rings observed in the SAED pattern shown in Figure 5C are characteristic of the G and GmO components of the GmGT(I)-X material, respectively. These spots indicate that the G component of the GmGT(I)-X composite is essentially crystalline, possessing primarily one orientation domain within the region of the sample selected by the 1.5 μm diameter aperture of the TEM (indicated by the spots), while the GmO component of the composite is essentially crystalline, possessing several orientation domains within the region of the sample, as well as numerous smaller orientation domains of crystalline GmO, as indicated by the smoothness of the diffraction rings. There are no detectable diffraction features that could be associated with regions of crystalline TM compound. Figure 5D is the corresponding bright-field TEM image, demonstrating the compact, flake-like nature of the material. There is little or no indication of nanocrystals or aggregates of TM-containing nanoparticles. FIG. 5A is a SAED line scan, and FIG. 5B confirms the measured spatial frequency and atomic spacing, which corresponds to the in-plane spacing of graphite or graphene.

[0264] Figure 5E shows representative IR data with typical fingerprint features unique to GmGT(I)-X materials: 1) 1250 cm typical of C-O-C type vibrations; -1 and 2) a broad feature at 1700 cm suggesting a defect sp2 CC vibration. -1 The characteristic Mo-O features present in the GmGT(I)-X material were significantly reduced and broadened, similar to the GmGT(I)-A material described above.

[0265] Figure 5F shows representative SEM data collected from the GmGT(I)-X material. Typical SEM images of the GmGT(I)-X material show large flakes with a compact, layered, sheet-like morphology distinct from the thin G or rGO morphologies.

[0266] The synthesis of GmGT(I)-NCs follows a process similar to that of sample 4.1 in Table 4, but with a final temperature above 800 °C. The rings observed in the SAED pattern (not shown) are characteristic of the G component of the GmGT(I) material, with additional rings matching the diffraction signature of MoO nanocrystals. The characteristic α-GmO rings are located close to some of the MoO rings and are observed in samples with a low number of nanocrystals, but may become less apparent as the ratio of TM:C atoms increases and the number and size of nanocrystals increase.

[0267] IR data (not shown here) show fingerprint features specific to the GmGT(I)-NC material similar to those observed for GmGT(I)-X: 1) a 1250 cm vibration typical of C-O-C type vibrations; -1 2) a broad feature in the region of 1700 cm, suggesting a defect sp2 CC vibration -1 and 3) the absence of Mo-O vibrations due to MoO3 seen in the starting material with unreduced MoO3. The Mo-O vibrations due to MoO2 are too weak to be detected in the spectrum due to the weak dipole.

[0268] Figure 6 shows data collected on GmGT(II)-A according to sample 4.2 in Table 4. The rings observed in the SAED pattern shown in Figure 6C are characteristic of the G component of the GmGT(II)-A material. This indicates that the G component of the GmGT(II) composite is essentially crystalline, possessing several orientation domains within the region of the sample selected by the 1.5 μm diameter aperture of the TEM, as indicated by the smoothness of the diffraction rings (as indicated by the intensity variation along the rings), along with numerous smaller orientation domains. There are no detectable diffraction features that could be associated with regions of crystalline TM compounds or well-ordered crystallographic GmO compounds. Figure 6D is the corresponding bright-field TEM image, showing the compact, flake-like state of the material on the perforated carbon grid. Figure 6A is an SAED line scan, and Figure 6B confirms the spatial frequencies and atomic spacing corresponding to the in-plane spacing of graphite or graphene. There is no evidence of significant crystalline TM particles in this region of the sample, which is characteristic of GmGT(II)-A material.

[0269] Figure 6E shows representative IR data with typical fingerprint features specific to GmGT(II)-A material: 1) 1250 cm typical of COC-type vibrations -1 and 2) a broad feature at 1700 cm suggesting a defect sp2 CC vibration. -1 Nearby derivative-like features.

[0270] As described in Example 1, BET measurements revealed that the BET surface area of ​​the GmGT(I)-X material was 8.4 m 2 For the blend of GmGT(I)-X and GmGT(II)-A materials, the BET surface area was 8.5 m 2 The fingerprint of the GmGT material, measured by BET surface area, indicates a compact material with a graphite-like specific surface area, clearly different from that of virgin graphite, graphene, or typical rGO materials.

[0271] Figures 7A and 7B show TGA and DSC data for blends of GmGT(I)-X and GmGT(II)-A materials, respectively. TGA / DSC data were collected using, for example, a TA Instruments Discovery SDT 650 simultaneous TGA / DSC instrument. The sample material was heated from room temperature to 600°C at a rate of 10°C / min, and then continued to heat from 600°C to 1100°C at a rate of 3°C / min. The sample did not exhibit the exothermic peak below 300°C typically seen with graphene oxide. When the heat flow curve was integrated from 122 to 266°C, the enthalpy was 263.7 J / g without baseline subtraction. A heat flow peak of 3.307 W / g occurred at 191.94°C. These features (room temperature to 300°C) represent the characteristic fingerprint of the GmGT material; that is, the exothermicity of this material is virtually nonexistent. At the end of heating in this example, the sample retained 58.7% of its starting mass. Mass loss occurred at the maximum rate between 727 and 750 °C, which is a characteristic fingerprint of GmGT materials.

[0272] Figure 7C shows the results for a blend of GmGT(I)-X and GmGT(II)-A materials. 13 C solid-state NMR data are shown. The material powder was packed into a 3.2 mm rotor, for example, and 128 scans were acquired on a Bruker Avance III HD 600 MHz instrument at 20 kHz with a 0.5 second recycle delay. Previous carbon and hydrogen NMR experiments showed that the GmGT material has a small amount of hydrogen, making it conductive and eliminating the need for high-power decoupling. The short recycle delay is a fingerprint of the GmGT material, as are the peaks at chemical shifts of approximately 117 ppm and approximately 160 ppm. The peaks in Figure 7C marked with an asterisk are adequately interpreted as sidebands of the 117 ppm and 160 ppm peaks.

[0273] Example 3. Determination of the relative proportions of components of composite GmGT product materials from EDS measurements of atomic percentages:

[0274] [Table 25]

[0275] Table 12 shows quantitative measurements of the atomic percentages of carbon, oxygen, and molybdenum in the final and intermediate composites, as well as the derived relative molecular percentages of the GmGT-based materials, including the GmO-like component (calculated as CO), the G-like component (calculated as C), and the TMO component (calculated as MoO). The measured atomic percentages of C, O, and Mo obtained by EDS are normalized so that the relative percentages of the individual atomic species sum to 1. Impurities are ignored in this estimation. The relative oxygen content is then divided into two distinct types of oxygen species: one is assumed to be associated with the Mo atoms as MoO, and the remaining oxygen content is assumed to be the species associated with the GmO-like material as CO. This oxygen species designation similarly divides carbon into two species: one species is assumed to be associated with the aforementioned GmO-like material as CO, and the remaining carbon content is assumed to be the species associated with the graphene-like material as C. By artificially separating the oxygen and carbon atoms as two distinct species and assigning the molecules in this manner, it is possible to roughly characterize the relative molecular percentages of the G, GmO-like, and TMO components in the final or intermediate composites, providing semiquantitative access to material composition as a function of the feedstock and synthesis process. Importantly, the molar concentrations of the GmO-like components in these product-material composites are generally substantial. For the 10:1 Mo:C blend sample, significant amounts of TMO precipitate as determined by TEM / SAED characterization (not shown), resulting in MoO nanocrystals (as determined by SAED measurements) measuring tens of microns in size distributed throughout the material flake.

[0276] Example 4. Synthesis of GmGT-X product material using an inert gas environment: Sample 4.4 in Table 4 provides a second example of producing GmGT(I) material in a tube furnace under flowing nitrogen gas. The starting material was Sample 3.17 in Table 3, with a powder form factor of 16 mg / cm. 2The mass used was placed in an open quartz crucible and placed in the central temperature zone of a tube furnace before establishing a flow rate of 3.1 L / min of ultra-high purity nitrogen gas. f ) was maintained for 10 minutes. m From T f The time to reach 0°C was 1 hour and 32 minutes, significantly shorter than vacuum annealing and selected as the fastest temperature ramping recommended by the furnace manufacturer. Due, at least in part, to the uncovered containment vessel (quartz crucible) and subsequent ability to flow gas, the faster heating rate allows for rapid transport of evolved gases away from the sample region. Upon cooling to room temperature and removal from the tube furnace, the material is already in the desired size and morphology for incorporation into the formation of battery electrode materials. The final product is characterized in many ways similar to the above examples to demonstrate that it possesses the properties of a GmGT(I) material.

[0277] Example 5. Synthesis of rGO using the process to produce GmGT material: Sample 4.8 in Table 4 was prepared starting from the precursor material (sample 3.11 in Table 3) and heated to the highest temperature (T f The sample was left at 4°C for 4 hours and all other vacuum furnace heat treatment parameters were essentially the same as for Sample 4.1: the same non-reactive tantalum boat with cover, 31 mg / cm 2 material usage, flake shape factor, 2 × 10 -6 torr (2.67 × 10 -4 Base pressure (Pa), final temperature (T f ), T m From T f The ramp time was 15 hours and 45 minutes to reach the desired temperature. The final product did not exhibit the characterization fingerprint of the GmGT material. The failure to produce the GmGT material indicates that the synthesis process requires a usable TM component.

[0278] Example 6. Use of Commercial GO Powder and prGO Powder as Alternative Carbon Sources: (Sample 6.6 in Table 5): Commercially available partially reduced graphene oxide (prGO) was procured from Graphenea (Cambridge, Massachusetts, USA) and used as a carbon source to generate prGO containing 13–17% oxygen in the material using a chemical method. 400 mg of prGO was mixed with 80 mL of solution 2.1 as the TM source and stirred for 3–4 minutes at room temperature using a magnetic stirrer. The solution was dried in a borosilicate glass tray at 52 °C for 24 hours, scraped, and transferred to an alumina-coated tantalum boat with a lid in powder form at 40 mg / cm. 2 The covered material charge was placed in a 2 x 10 -6 torr (2.67 × 10 -4 The resistive heating was carried out in high vacuum at a starting base pressure of 1000 kJ / cm² (200 kPa) and at variable heating rates in different temperature windows. m Approaching T m The heating rate away from the maximum mass loss temperature of 230 ± 45 °C is symmetrically slow at 0.1 °C / min, with a final annealing at temperature T f = 780 ± 20 °C for 4 hours. m From T f The time to reach 0°C was 15 hours and 45 minutes. After cooling to room temperature and removal from the vacuum furnace, the resulting material was characterized. The characterization of this material is included in Figure 8.

[0279] The rings observed in the SAED pattern shown in Figure 8C are characteristic of prGO-like materials, where the G-like component of the composite is essentially crystalline, with numerous smaller oriented domains, as indicated by the smoothness of the diffraction rings between distinct spots. There are limited diffraction features associated with regions of crystalline TMO, visible as scattered spots in Figure 8C. Figure 8D is the corresponding bright-field TEM image, showing the thin state of the material and evident few TMO nanocrystals, characteristic of prGO materials. Figure 8A is an SAED line scan, and Figure 8B confirms the measured spatial frequency and atomic spacing, which correspond to the in-plane spacing of prGO.

[0280] Figure 8E shows the 1250 cm vibration typical of the C-O-C type vibrations remaining in the prGO material. -1A broad feature in the region of 1700 cm suggests a defect sp2 CC vibration present in prGO. -1 Representative IR data are shown, with nearby derivative-like features and relatively distinct Mo-O vibrations characteristic of MoO3 remaining in the material as heterogeneously incorporated TMO. Some of these IR features are shared with the GmGT material, but when combined with TEM / SAED or BET surface area measurements (not shown), the consensus fingerprint criteria for the GmGT material are not met.

[0281] This example is important because it demonstrates that commercially available prGO cannot be used to produce the desired composition: the relative atomic ratio of oxygen to carbon for the starting carbon material in this case is approximately 0.15:1, which presents a lower limit necessary for synthesizing GmO-based materials when processed in vacuum.

[0282] Figure 9 shows data collected on GmGT(I)-X produced according to sample 6.8 in Table 5, using GO powder as the starting carbon source. The rings observed in the SAED pattern shown in Figure 9C are characteristic of the G and α-GmO components of the GmGT(I)-X material. This indicates that the G and GmO components of the GmGT(I)-X composite are crystalline in nature, possessing numerous small, oriented domains, as indicated by the smoothness of the diffraction rings. There are no detectable diffraction features that can be associated with regions of crystalline TM compounds. Figure 9D is the corresponding bright-field TEM image, showing the compact, flake-like nature of the material. Figure 9A is an SAED line scan, and Figure 9B confirms the measured spatial frequencies and atomic spacings corresponding to α-GmO and the in-plane spacing of graphite or graphene. There is no evidence of crystalline TM particles in this region of the sample, which is characteristic of GmGT(I)-X material.

[0283] Figure 9E shows representative IR data with typical fingerprint features unique to GmGT(I)-X materials: 1) 1250 cm typical of C-O-C type vibrations -1 2) a broad feature in the region of 1700 cm, suggesting a defect sp2 CC vibration -1 and 3) derivative-like features near 1000 cm indicative of MoO. -1 There is a broad Mo-O feature less than 1000 cm, which indicates MoO3. -1 There is no broad Mo-O feature below this.

[0284] This example demonstrates the feasibility of using GO powder as the starting carbon source, enabling a faster and more economical low-water synthesis route than the dilute aqueous GO route.

[0285] Example 7. Use of lignin as a bio-renewable carbon source to produce GmGT(I)-X materials: Table 5 uses an embodiment of Sample 6.3, which used lignin as the starting carbon source to produce GmGT(I)-X material. Lignin powder (26 mg) was used as the carbon source and combined with 5.2 mL of Solution 2.1 as the TM source and stirred with a glass rod for 2 minutes at room temperature. The solution was dried in a silicon tray at room temperature for 24 hours, scraped, and poured into an alumina-coated tantalum boat with a lid in powder form at 2.2 mg / cm. 2 The covered material charge was placed in a 2 x 10 -6 torr (2.67 × 10 -4 The resistive heating was carried out in high vacuum at a starting base pressure of 1000 kJ / cm² (200 kPa) and at variable heating rates in different temperature windows. m Approaching T m The heating rate away from the maximum mass loss temperature of 230 ± 45 °C is symmetrically slow at 0.05 °C / min, with a final annealing at temperature T f= 705 ± 20 °C for 10 min. The heat treatment parameters in this case were chosen to match the thermal profile known to produce GmGT(I)-X materials when using GO-based carbon sources as starting materials. m The value does not necessarily correspond directly to the temperature of maximum mass loss rate. m From T f The time to reach 0°C was 16 hours and 45 minutes. After cooling to room temperature and removal from the vacuum furnace, the resulting material was characterized and found to be consistent with GmGT(I)-X material.

[0286] Figure 10 shows data collected on GmGT(I)-X produced from lignin. The rings observed in the SAED pattern shown in Figure 10C are characteristic of the G and α-GmO components of the GmGT(II)-X material. This indicates that the G and GmO components of the GmGT(I)-X composite are essentially crystalline, possessing numerous very small oriented domains, as indicated by the smoothness and broadening of the diffraction rings. There are no detectable diffraction features that can be associated with regions of crystalline TM compound. Figure 10D is the corresponding bright-field TEM image, showing an aggregated collection of small, particle-like structures that appear to be overlapping in the thinnest region of the sample. Figure 10A is an SAED line scan, and Figure 10B confirms the measurements of spatial frequencies and atomic spacings corresponding to the in-plane spacing of α-GmO and graphite or graphene. There is no evidence of crystalline TM particles in this region of the sample, which is characteristic of GmGT(I)-X material.

[0287] Figure 10E shows representative IR data with typical fingerprint features specific to lignin and GmO. IR measurements are macroscopic measurements of a few milligrams of material, while microscopic TEM can detect microscopic crystallinity. The IR spectrum shows a 1250 cm vibration typical of C-O-C type vibrations. -1 and broad features in the region of 1700 cm suggesting defect sp2 CC type vibrations. -1In addition to the characteristic features of GmO, such as nearby derivative-like features, it contains some additional features of lignin.

[0288] Figures 10A-D show the characteristic signature of α-GmO crystalline layers coexisting with graphene crystalline layers, obtained by transmission electron microscopy and analysis. Molecular MoO2 is uniformly distributed and detectable by EDS (not shown), but there is no evidence of crystalline TM components from SAED. IR data (Figure 10E) show the same characteristic absorption features of GmGT material synthesized from a GO-derived starting carbon source. This example is important because it paves the way to economical starting materials. Alternative carbon sources from the same or similar material group as lignin can also be used as feedstocks for this synthesis route.

[0289] Example 8. Hydrothermally produced GO from bio-renewable carbon sources to produce GmGT materials: (Sample 6.7 in Table 5): GO layers were synthesized using hydrothermal processing of sugar in the laboratory, and the surface tension of the liquid was used to separate them from other products. The GO was collected and resuspended in water, and 10 mL of this suspension was combined with 40 mL of TM-containing solution 2.1. Magnetic stirring was used at room temperature for 3-4 minutes, and the solution was dried in a borosilicate glass tray at 49 °C for 24 hours. The dried material was scraped off and deposited in flake form at 2.5 mg / cm in an alumina-coated tantalum boat with a lid. 2 The covered material charge was placed in a 2 x 10 -6 torr (2.67 × 10 -4 Resistive heating was performed in high vacuum at varying heating rates in different temperature windows with a starting base pressure of 1000 Pa. m Approaching T m The heating rate away from the maximum mass loss temperature of 230 ± 45 °C is symmetrically slow at 0.1 °C / min, with a final annealing at temperature T f = 780 ± 20 °C for 4 hours. m From T f The time to reach the destination was 15 hours and 45 minutes.

[0290] Figure 11 shows data collected on GmGT(I)-X synthesized according to sample 6.7 in Table 5. The spots and faint rings observed in the SAED pattern shown in Figure 11C are characteristic of the G and GmO components of the GmGT(I)-X material, respectively. The spots indicate that the G component of the GmGT(I)-X composite is essentially crystalline (indicated by the ring spots) in a single orientation domain within the region of the sample selected by the 1 μm diameter aperture of the TEM, and that the GmO component of the composite is essentially crystalline, with several orientation domains within this region of the sample, as indicated by the smoothness of the diffraction rings. The SAED data shown in the figure was obtained from a featureless region of the flake (see Figure 11D), and as a result, there are no detectable diffraction features that can be associated with crystalline TM compound. SAED data (not shown) collected from a neighboring region on the flake that appears to be agglomerates of particles confirmed these features to be MoO nanoparticles. Figure 11D is the corresponding bright-field TEM image, showing a few layered flakes of the sample, with dark regions representing aggregated TMO nanoparticles. Figure 11A is the SAED line scan, and Figure 11B confirms the measured spatial frequency and atomic spacing, which correspond to the in-plane spacing of graphite or graphene and α-GmO.

[0291] Figure 11E shows representative IR data with features unique to glucose and GmO-based materials. IR measurements are macroscopic measurements of a few milligrams of material, while microscopic TEM can detect microscopic fingerprints. In addition to the characteristic features of heterogeneously incorporated TMO and GmO, the IR spectrum contains several additional signatures of glucose: 1) a 1,000 cm vibration typical of Mo-O vibrations in the MoO bond form; -1 2) a relatively sharp absorption line just below the -1 and 3) a broad feature at 1700 cm suggesting a defect sp2 CC vibration.-1 Nearby derivative-like features.

[0292] This example is important because it demonstrates that renewable biogenic carbon sources in the form of sugars can be used as cheaper and more environmentally friendly feedstocks to produce desired compositions.

[0293] Example 9. Organometallic TM powders as an alternative for producing GmGT materials: Metalorganic powder was used as the TM source to generate GmGT(I)-X (sample 6.12 in Table 5): GO suspension 1.1 (25 mL) from Table 1 was mixed with 128 mg of dried C 10 H 14 The usefulness of the organometallic Mo TM source was demonstrated by combining MoO powder (powder 2.6 in Table 2) with 375 mL of water. Magnetic stirring was used for 3-4 minutes at room temperature, and the solution was dried in a borosilicate glass tray at 52 °C for 24 hours. The dried material was scraped off, chopped into 5-10 mm size flakes, and deposited in a lidded alumina-coated tantalum boat at 5.8 mg / cm. 2 The covered material charge was placed in a 2 x 10 -6 torr (2.67 × 10 -4 Resistive heating was performed at varying heating rates in different temperature windows in high vacuum at a starting base pressure of 100 Pa. m Approaching T m The heating rate away from the maximum mass loss temperature of 230 ± 45 °C is symmetrically slow at 0.1 °C / min, with a final annealing at temperature T f = 780 ± 20 °C for 4 hours. m From T f The time to reach the destination was 15 hours and 45 minutes.

[0294] Figure 12 shows data collected on GmGT(I)-X prepared according to sample 6.12 in Table 5. The rings observed in the SAED pattern shown in Figure 12C are characteristic of the G and GmO components of the GmGT(I)-X material. This indicates that the G and GmO components of the GmGT(I)-X composite are crystalline in nature, with numerous smaller oriented domains, as indicated by the smoothness of the diffraction rings. There are no detectable diffraction features that can be associated with regions of crystalline TM compound. Figure 12D is the corresponding bright-field TEM image, showing the compact, flake-like nature of the material. Figure 12A is a TEM line scan, and Figure 12B confirms the measured spatial frequencies and atomic spacings corresponding to α-GmO and the in-plane spacing of graphite or graphene. There is no evidence of crystalline TM particles in this region of the sample, which is characteristic of GmGT(I)-X material.

[0295] FIG. 12E shows representative IR data with typical fingerprint features specific to GmGT(I)-X materials: 1) 1250 cm typical of COC-type vibrations -1 and 2) a broad feature at 1700 cm suggesting a defect sp2 CC vibration. -1 Nearby derivative-like features.

[0296] This example is important because it demonstrates that an organometallic TM source combined with a carbon-containing solution is an alternative route to producing GmGT(I)-X, as evidenced by the fingerprints observed in the TEM and IR data.

[0297] Example 10. Use of hydrogen peroxide as an additive to GO carbon source: (Sample 6.13, Table 5): Suspension 1.8 (336 mL) from Table 1 contained commercially available GO and H2O2. This suspension was combined with 50 mL of solution 2.1 from Table 2 and 50 mL of deionized distilled water. Magnetic stirring was used for 3-4 minutes at room temperature, and the solution was dried in a borosilicate glass tray at 52 °C for 24 hours. The dried material was scraped off, chopped into 5-10 mm size flakes, and placed in a lidded alumina-coated tantalum boat at a concentration of 13 mg / cm2. 2 The covered material charge was placed in a 2 x 10 -6 torr (2.67 × 10 -4 The resistive heating was carried out in high vacuum at a starting base pressure of 1000 kJ / cm² (200 kPa) and at variable heating rates in different temperature windows. m Approaching T m The heating rate away from the maximum mass loss temperature of 230 ± 45 °C is symmetrically slow at 0.1 °C / min, with a final annealing at temperature T f = 705 ± 20°C for 10 minutes. m From T f The time to reach the destination was 20 hours and 50 minutes.

[0298] Figure 13 shows data collected on GmGT(I)-X prepared according to sample 6.13 in Table 5. The rings observed in the SAED pattern shown in Figure 13C are characteristic of the G and GmO components of the GmGT(I)-X material. This indicates that the G and GmO components of the GmGT(I)-X composite are crystalline in nature, with numerous smaller oriented domains, as indicated by the smoothness of the diffraction rings. There are no detectable diffraction features that can be associated with regions of crystalline TM compound. Figure 13D is the corresponding bright-field TEM image, showing the compact, flake-like nature of the material. Some areas of dark spots in the image may be evidence of minor precipitation of TMO particles. Figure 13A is an SAED line scan, and Figure 13B confirms the measured spatial frequencies and atomic spacings corresponding to α-GmO and the in-plane spacing of graphite or graphene. There is no evidence of crystalline TM particles in this region of the sample, which is characteristic of GmGT(I)-X material.

[0299] FIG. 13E shows representative IR data with typical fingerprint features specific to GmGT(I)-X materials: 1) 1250 cm typical of COC-type vibrations -1 and 2) a broad feature at 1700 cm suggesting a defect sp2 CC vibration. -1 This example is significant because it demonstrates that the oxidizing agent added to certain standard processes described above is an alternative route to producing GmGT(I)-X, as evidenced by the fingerprints observed in TEM and IR data, and can be used with a reducing agent in a two-step process involving chemical passivation (reducing agent) followed by an oxidation step that endows GO with the necessary oxygen or tailored oxygen functional groups to enable GmGT production.

[0300] Example 11. Acetic acid after M2 / C2 mixing: Characterization of the material listed in Table 5, sample 6.14, is included in Figure 14, which shows data collected for GmGT(I)-X. The rings observed in the SAED pattern shown in Figure 14C are characteristic of the G and GmO components of the GmGT(I)-X material. This indicates that the G and GmO components of the GmGT(I)-X composite are crystalline in nature, possessing numerous smaller oriented domains, as indicated by the smoothness of the diffraction rings. There are a few diffraction features associated with regions of nanocrystalline MoO (isolated spots at spatial frequencies not corresponding to the G or α-GmO interplanar spacing). Figure 14C is the corresponding bright-field TEM image, showing the compact flake-like nature of the material, with a few isolated small crystals observable. Figure 14A is an SAED line scan, and Figure 14B confirms the measured spatial frequencies and atomic spacings corresponding to the α-GmO and in-plane spacings of graphite or graphene.

[0301] FIG. 14E shows representative IR data with typical fingerprint features unique to GmGT(I)-X materials: 1) 1250 cm typical of COC-type vibrations -1and 2) a broad feature in the region of 1700 cm suggesting a defect sp2 CC vibration. -1 Nearby derivative-like features.

[0302] This example is important because it demonstrates that adding acid to the starting carbon / TM material mixture in the particular standard process described above (essentially adjusting the pH with an acid additive) is another path to producing GmGT(I)-X, as evidenced by the fingerprints observed in the TEM and IR data. Similar results are obtained when the pH is adjusted to the basic side of neutral by the addition of ammonium hydroxide.

[0303] Example 12. Use of GmGT(II)-A as an additive active anode material in pouch lithium-ion battery cells: In a specific example, the material is an anode slurry containing 94% active material and either a 97:3 (by weight) mixture of graphite and silicon in the case of the control cell, or a 90:10 mixture of graphite and GmGT(II)-A material, or an 87:3:10 mixture of graphite, silicon, and GmGT(II)-A material. The inactive materials in the slurry were 3% carbon black, a standard conductive agent for graphite, and a total of 3% water-based binder (1.5% sodium carboxymethylcellulose, 1.5% styrene butadiene rubber). The slurry was mixed using an ultrasonic mixer. The anode slurry was cast onto 12 μm Cu foil and allowed to dry. The electrode foil was calendered and cut to size for coin and pouch cell construction. For half cells, the material was die-cut to the size of a CR2032 coin cell. For the 200 mAh pouch battery, the anode under test was paired with a lithium nickel cobalt aluminum oxide (NCA) cathode cast onto 20 μm aluminum foil. Active cathode and anode slurries were prepared from the binder and carbon black, spread onto aluminum foil and copper foil (respectively), and allowed to dry. The cathode thickness was thicker than the anode thickness (due to the cathode's lower specific capacity), but the length and width of the cathode were generally smaller than those of the anode. The N:P ratio used was 1.1, and the anode capacity was in excess compared to the cathode capacity to prevent lithium deposition on the anode surface. The size was selected based on the theoretical capacity of the NCA and the empirical capacity of the GmGT(II)-A material (determined by half-cell testing). After drying the electrodes overnight, they were transferred to a dry lab and assembled into pouch cells. At this stage, electrolyte was added and the pouch was sealed.

[0304] Example 13. GmGT material as active anode material in lithium metal half-cells: Electrodes can be fabricated using mixing and coating techniques with the specific examples listed in Table 13. For example, a FlackTek planetary centrifugal mixer was used to create a slurry dispersion with a solids content of approximately 50% and a viscosity of approximately 6450 mPa. The resulting dispersion is easily coated onto a suitable electrode substrate material using conventional methods (e.g., drop coating, dip coating, spray coating, etc.). The resulting electrodes exhibit good electronic behavior and uniform physical properties, including limited numbers of large particles and few or no pinholes, making them a drop-in replacement for graphite in current commercial processes.

[0305] In one embodiment, these GmO-based materials have improved performance when compared to expanded graphite with TMO nanoparticles, prGO with TMO nanoparticles, expanded graphite, and prGO as electrodes opposite a Li metal electrode. In general, cell construction for charge storage devices can be tailored to obtain optimal performance characteristics by, for example, adjusting the anode formulation, cathode selection, electrolyte formulation, electrode loading, and / or combinations thereof.

[0306] To demonstrate the improved performance of these inventive materials, various electrode formulations using GmGT materials with standard electrolyte and Li metal were compared to half-cells assembled with electrodes formulated with various carbon-based or carbon-TMO combination materials. These electrodes exhibit desirable performance when incorporated into electrochemical cells (see Table 13).

[0307] [Table 26]

[0308] [Table 27]

[0309] [Table 28]

[0310] Anode half-cells were tested to evaluate how perturbations in material synthesis affect battery performance and compared it to commercially available and laboratory-made controls. Materials were tested in CR2032 coin cells. The active anode materials were varied (Table 13), the counter electrode was lithium metal, the separator was Celgard, and the electrolyte was 1.0 M LiPF6 in 2:4:4 EC:DEC:DMC.

[0311] The formation and cycling procedures were kept constant throughout the set. Cell performance is summarized in Table 13, where the first-cycle lithiation capacity and reversible lithiation capacity define how much lithium was consumed during the formation of the first lithiation and second delithiation, respectively. The first- and second-cycle coulombic efficiencies report the percentage of lithiation capacity retained during delithiation during the first and second formation cycles, respectively. Similarly, the specific capacity and coulombic efficiencies are reported for each material at different points during cycle life and under various charge / discharge rates.

[0312] The materials tested included the GmGT material; commercial controls of Gr, prGO, and expanded graphite (EG); control materials prepared in the laboratory by adding TMO to commercial prGO and commercial EG and processing them in the same way as the GmGT material; and other controls, including pre-GmGT (I), synthesized in the laboratory, and in-house thermally synthesized rGO. Each of these controls demonstrates the necessity of specific steps in the specific process described above, demonstrating that all steps are necessary to achieve GmGT performance in a battery, and that the commercial controls behave differently from GmGT in half-cells.

[0313] The results of half-cells using commercially available prGO+TMO and EG+TMO indicated that the process requires a starting GO with a high oxygen content rather than rGO or Gr, even with the addition of TMO. A TM source is a necessary component of the material synthesis, as half-cells containing thermally synthesized rGO in the laboratory without TMO showed that the heating profile alone resulted in battery performance inferior to that of GmGT. Pre-GmGT (I), which was only heated in an oven to approximately 245 °C, also resulted in inferior battery performance compared to GmGT. This indicates that a final high-temperature annealing step in the specific process described above is necessary to achieve GmGT battery performance.

[0314] Two types of GmGT were tested as additives to graphite in anode half-cells containing 10% active material and the remaining 90% graphite. Both GmGT(II)-X and GmGT(I)-A showed clear performance enhancement over pure graphite when used as a 10% additive.

[0315] Perturbations in material processing at various steps in the synthesis process affected battery performance. When GmGT(I)-X was produced using renewable feedstocks, all performance measurements were lower than those of the baseline material blend. When intermediate materials were spray-dried during the process to produce GmGT(I)-X, GmGT(I)-X was comparable to that produced in a temperature-controlled environment. When GmGT(I)-X was annealed in an inert environment, the performance of half cells deviated from that of the standard blend in preliminary tests. In particular, this material did not function at 10°C. Alternatives: After formation, two perturbations significantly increased the ICE while maintaining the specific capacity of the material at various rates: GmGT(I)-X produced using a powdered catalyst and GmGT(I)-X produced using a high concentration of starting GO source.

[0316] Example 14. Synthesis of GmO-based materials substantially free of TM components: To synthesize metal-free or substantially metal-free GmO-based materials, starting with GmGT(I)-X material obtained via any of the appropriate synthetic routes detailed in Table 4 or Table 5, the material can be further processed to remove TM components from the product material. For example, the GmGT material can be treated under a partial pressure of flowing nitrogen gas containing chlorine gas, as known in the art, or other reactive gases such as hydrogen, while heating at a temperature of approximately 800°C. Alternatively, the solid GmGT(I)-X material can be suspended in a solvent that dissolves the TM species present therein. Possible solvents include water and alcohols (e.g., methanol, ethanol, propanol, isopropanol, etc.). Adjusting the pH of the aqueous solvent can also be used to increase the solubility of the transition metal and alter the oxidation state of the transition metal to preferably dissolve it in solution. Further oxidation of the transition metal oxides by mild heating in any combination of oxidizing (e.g., oxygen or air) or reducing (e.g., H2, N2H4) atmospheres can also be used as a means to enhance the solubility of the TM components prior to removal by standard washing.

[0317] Example 15. Synthesis of GmGT(I)-X materials in the presence of Sn: Suspension 1.7 from Table 1 was mixed with solution 2.1 from Table 2 in volume proportions of 100 mL and 80 mL, respectively. The mixture was processed according to a known process for producing GmGT(I)-X materials, with typical examples detailed in the columns corresponding to samples 3.0 and 4.1 in Tables 3 and 4, respectively. The significant difference was that the material mixture was dried in a Sn-cured silicone tray at room temperature for 6 days. The final product material thus synthesized was a GmGT(I)-X material with a stronger α-GmO component (as observed by SAED, not shown) than in the typical process without drying in a Sn-cured silicone tray. EDS measurements showed significant Sn "impurity" that was later confirmed to leach into the mixture as it dried. This is an example of how a reactive tray can provide beneficial metal oxides for the formation of the product material.

[0318] As disclosed above, the TM component of the GmGT material synthesis provides polyvalent metal cations that coordinate oxygen interaction with the carbon material, which is believed to be a key feature for obtaining the desired material from the described process. Because multiple oxidation states are a characteristic of TMO materials, TMO materials naturally exhibit this characteristic. Sn in this example, either by itself or in conjunction with a Mo-based TMO intentionally provided in the synthesis route, may have played a similar role as a metal oxide with multiple oxidation states. Therefore, as a general feature, this example demonstrates that other non-TM material sources can be used in place of or in addition to the TM sources disclosed elsewhere in this disclosure. Potential candidates other than transition metals include, but are not limited to, Al, Si, or Sn. It should be noted that metal oxide components may be precipitated to improve battery performance by providing high specific capacity.

[0319] Example 16. Synthesis of GmGT(I)-X materials in the presence of δ-GmO constrained structures: Synthesis according to sample 4.7 in Table 4 yielded a 0.38 Å -1 , 0.66 Å -1 and 0.77 Å -1 The δ-GmO crystal exhibits a clear SAED (not shown) diffraction signature consistent with a constrained δ-GmO structure, with measured peaks at 1000 s. These peak positions are consistent with the theoretically predicted positions in Table 6. This example demonstrates that additional GmO crystal structures and their associated chemical moieties can be tailored by combining and selecting carbon and TM sources. Some of the embodiments of the invention related to the present invention are shown below. [Aspect 1] 1. A composition comprising at least one atomic layer of graphene monoxide, wherein at least a portion of the oxygen molecules present in the graphene monoxide are incorporated into a structure having a chemical moiety selected from the group consisting of a 1,3-dioxetane ring, a 1,5-dioxa-cyclooctane ring, a 1,4,7-trioxa-cyclononane ring, a (3,5,8,10)-tetraoxa-(1,6)-cyclodecadiene ring, and a polycarbonyl chain. [Aspect 2] the chemical moieties are atomically ordered in one or more phases of a two-dimensional graphene monoxide crystalline structure having a carbon to oxygen atomic ratio of about 1:1; The interatomic lattice spacing of the crystal structure is 0.39 to 0.42 Å -1 and 0.68 to 0.76 Å -1 ;0.39Å -1 and 0.45 Å -1 ;0.33Å -1 and 0.88 Å -1 ; and 0.38 to 0.33 Å -1 and 0.77 to 0.78 Å -1 2. The composition of embodiment 1, wherein the composition exhibits a selected area electron diffraction signature selected from the group consisting of: [Aspect 3] The composition of embodiment 1, further comprising at least one transition metal oxide. [Aspect 4] 4. The composition of embodiment 3, wherein the transition metal oxide comprises a transition metal selected from the group consisting of Ti, V, Cr, Zr, Nb, Mo, Fe, Co, Ni, Hf, Ta, and W. [Aspect 5] The interatomic lattice spacing of the crystal structure is 0.39 to 0.42 Å -1 and 0.68 to 0.76 Å -1 ;0.39Å -1 and 0.45 Å -1 ;0.33Å -1 and 0.88 Å -1 ; and 0.38 to 0.33 Å -1 and 0.77 to 0.78 Å -1 4. The composition of embodiment 3, wherein the composition exhibits a selected area electron diffraction signature selected from the group consisting of: [Aspect 6] The interatomic lattice spacing of the crystal structure is approximately 1,200 cm by infrared spectroscopy. -1 ~1,400cm -1 6. The composition of embodiment 5, wherein the composition exhibits carbon-oxygen vibrations with a peak at [Aspect 7] The composition is at about 116 ppm 13 4. The composition of embodiment 3, exhibiting a C solid-state NMR chemical shift. [Aspect 8] Approximately 100m 2 4. The composition of embodiment 3, having a Brunauer-Emmett-Teller (BET) surface area of ​​less than or equal to 1 / g. [Aspect 9] Approximately 100m 2 / g~about 600m 2 / g of Brunauer-Emmett-Teller (BET) surface area. [Aspect 10]

[0023] Aspect 4. The composition of aspect 3, further comprising at least one atomic layer of graphene, wherein the at least one atomic layer of graphene can be randomly stacked or locally ordered as an AB or AA stack in forming a multilayer. [Aspect 11] The graphene monoxide is crystalline or amorphous; At least a portion of the graphene is crystalline; and 11. The composition of embodiment 10, wherein the transition metal oxide is amorphous and substantially uniformly distributed throughout the composition, or is present in the composition as nanocrystals detectable by electron diffraction and X-ray diffraction. [Aspect 12] 10. The composition of embodiment 1, further comprising lithium ions or lithium atoms intercalated in or adsorbed on said atomic layers of graphene monoxide. [Aspect 13] The lithium ions or lithium atoms are bonded to the carbon and oxygen atoms of the graphene monoxide in a range of from Li2C6O6 to LiC 50 O 50 13. The composition of embodiment 12, wherein the composition is present in a ratio of up to [Aspect 14] The lithium ions or lithium atoms are preferably Li2C2O2, Li2C6O6, Li2C8O8, LiC6O6, LiC8O8, Li2C 18 O 18 , Li2C 32 O 32 , LiC 18 O 18 , LiC 32 O32 and LiC 50 O 50 13. The composition of embodiment 12, wherein the composition is present in a ratio selected from: [Aspect 15] 13. The composition of embodiment 12, wherein at least a portion of the lithium ions or lithium atoms occupy H sites relative to the graphene monoxide. [Aspect 16] 13. The composition of embodiment 12, wherein at least a portion of the lithium ions or lithium atoms occupy S sites relative to the graphene monoxide. [Aspect 17] ΔE of the lithium ions or lithium atoms in the composition Li ranges from about −0.04 eV to about −0.59 eV. [Aspect 18] (a) mixing a first solution, suspension, or powder comprising a carbon and oxygen source material with a second solution, suspension, or powder comprising at least one transition metal compound to form a mixture; and (b) heat treating the mixture of step (a) in an environment, for a time, at a temperature, and at a pressure that results in a composition comprising graphene monoxide; wherein at least a portion of the oxygen molecules present in the graphene monoxide are incorporated into chemical moieties selected from the group consisting of a 1,3-dioxetane ring, a 1,5-dioxa-cyclooctane ring, a 1,4,7-trioxa-cyclononane ring, a (3,5,8,10)-tetraoxa-(1,6)-cyclodecadiene ring, and a polycarbonyl chain. [Aspect 19] 20. The composition of embodiment 18, wherein the carbon source material has an atomic oxygen to carbon ratio of about 20% or greater and is selected from the group consisting of graphene oxide, polysaccharides, and phenolic polymers. [Aspect 20] 19. The composition of embodiment 18, wherein the transition metal oxide comprises a transition metal selected from the group consisting of Ti, V, Cr, Zr, Nb, Mo, Fe, Co, Ni, Hf, Ta, and W. [Aspect 21] 20. The composition of embodiment 18, wherein in step (a) the composition has an atomic ratio "x" of metal atoms to carbon atoms, wherein 0.05≦"x"≦0.3. [Aspect 22] Aspect 19. The composition of aspect 18, wherein step (a) further comprises mixing a third solution, suspension, or powder comprising an oxidizing agent with the first and second solutions, suspensions, or powders. [Aspect 23] 20. The composition of embodiment 18, wherein step (a) is carried out at a temperature of less than about 100°C. [Aspect 24] 20. The composition of embodiment 18, wherein step (b) comprises heating the mixture of step (a) at a temperature less than about 100°C. [Aspect 25] 20. The composition of embodiment 18, wherein step (b) comprises heating the mixture of step (a) to a temperature of from about 20°C to about 350°C. [Aspect 26] 20. The composition of embodiment 18, wherein step (b) comprises heating the mixture of step (a) to a temperature of from about 20°C to about 800°C. [Aspect 27] 20. The composition of embodiment 18, wherein step (b) comprises heating the mixture of step (a) to a temperature of from about 20°C to about 1,000°C. [Aspect 28] 20. The composition of embodiment 18, further comprising reducing the size of the composition. [Aspect 29] 20. The composition of embodiment 18, wherein in step (b), the mixture, when heated to 350° C., exhibits an exotherm of less than about 300 J / g. [Aspect 30] 20. The composition of embodiment 18, wherein step (b) comprises heating the mixture at a temperature ranging from about 21° C. to about 800° C. at a constant or variable heating rate. [Aspect 31] 31. The composition of embodiment 30, wherein in step (b), the mixture, when heated to 800° C., exhibits an exotherm of less than 300 J / g. [Aspect 32] The interatomic lattice spacing of the structure in the composition is 0.39 to 0.42 Å -1and 0.68 to 0.76 Å -1 ;0.39Å -1 and 0.45 Å -1 ;0.33Å -1 and 0.88 Å -1 ; and 0.38 to 0.33 Å -1 and 0.77 to 0.78 Å -1 20. The composition of embodiment 18, wherein the composition exhibits a selected area electron diffraction signature selected from the group consisting of: [Aspect 33] The interatomic lattice spacing of the structure in the composition is about 1,200 cm by infrared spectroscopy. -1 ~1,400cm -1 20. The composition of embodiment 18, wherein the composition exhibits carbon-oxygen vibrations with a peak at [Aspect 34] The composition is at about 116 ppm 13 20. The composition of embodiment 18, exhibiting a C solid-state NMR chemical shift. [Aspect 35] Approximately 100m 2 20. The composition of embodiment 18, having a Brunauer-Emmett-Teller (BET) surface area of ​​1 / g or less. [Aspect 36] Approximately 100m 2 / g~about 600m 2 19. The composition of embodiment 18, having a Brunauer-Emmett-Teller (BET) surface area of ​​1 / g. [Aspect 37] 20. The composition of embodiment 18, wherein step (b) comprises heat treating the composition at a pressure less than atmospheric pressure. [Aspect 38] Step (b) is about 2 × 10 -6 torr (2.67 × 10 -4 38. The composition of embodiment 37, comprising heat treating the composition at a pressure of less than or equal to 100 Pa. [Aspect 39] 20. The composition of embodiment 18, wherein step (b) comprises heat-treating the composition under an inert atmosphere. [Aspect 40] An electrode comprising the composition of embodiment 1. [Aspect 41] An electrode comprising the composition of embodiment 3. [Aspect 42] 20. An electrode comprising the composition of embodiment 18. [Aspect 43] A charge storage device comprising the electrode of embodiment 40, wherein the charge storage device has a faster charge rate at 1 C or greater than a corresponding charge storage device comprising a graphite-only anode. [Aspect 44] A charge storage device comprising the electrode of embodiment 41, wherein the charge storage device has a faster charge rate at 1 C or greater than a corresponding charge storage device comprising a graphite-only anode. [Aspect 45] A charge storage device comprising the electrode of embodiment 42, wherein the charge storage device has a faster charge rate at 1 C or greater than a corresponding charge storage device comprising a graphite-only anode. [Aspect 46] 41. A charge storage device comprising the electrode of embodiment 40, wherein the charge storage device has a faster charge rate and a higher charge capacity at temperatures between about 0° C. and about −20° C. than a corresponding charge storage device comprising a graphite-only anode charged at temperatures between about 0° C. and about −20° C. [Aspect 47] 42. A charge storage device comprising the electrode of embodiment 41, wherein the charge storage device has a faster charge rate and a higher charge capacity at temperatures between about 0° C. and about −20° C. than a corresponding charge storage device comprising a graphite-only anode charged at temperatures between about 0° C. and about −20° C. [Aspect 48] 43. A charge storage device comprising the electrode of embodiment 42, wherein the charge storage device has a faster charge rate and a higher charge capacity at temperatures between about 0° C. and about −20° C. than a corresponding charge storage device comprising a graphite-only anode charged at temperatures between about 0° C. and about −20° C. [Aspect 49] 41. A charge storage device comprising the electrode of embodiment 40, wherein the energy storage cell exhibits a monotonically decreasing potential versus specific capacity curve. [Aspect 50] 42. A charge storage device comprising the electrode of embodiment 41, wherein the energy storage cell exhibits a monotonically decreasing potential versus specific capacity curve. [Aspect 51] 43. A charge storage device comprising the electrode of embodiment 42, wherein the energy storage cell exhibits a monotonically decreasing potential versus specific capacity curve. [Aspect 52] 41. A method of improving the performance of a lithium ion battery, comprising replacing an existing electrode in the lithium ion battery with the electrode of embodiment 40. [Aspect 53] 42. A method of improving the performance of a lithium ion battery, comprising replacing an existing electrode in the lithium ion battery with the electrode of embodiment 41. [Aspect 54] 43. A method of improving the performance of a lithium ion battery, comprising replacing an existing electrode in the lithium ion battery with the electrode of embodiment 42.

Claims

1. 1. A composition comprising at least one atomic layer of graphene monoxide, wherein at least a portion of the oxygen molecules present in the graphene monoxide are incorporated into a structure having chemical moieties, the chemical moieties comprising chemical moieties in a crystallographically amorphous phase, and further wherein the chemical moieties are selected from the group consisting of a 1,3-dioxetane ring, a 1,5-dioxa-cyclooctane ring, a 1,4,7-trioxa-cyclononane ring, a (3,5,8,10)-tetraoxa-(1,6)-cyclodecadiene ring, and a polycarbonyl chain.

2. the chemical moieties further comprise chemical moieties atomically ordered in one or more crystalline phases of a two-dimensional graphene monoxide crystal structure having a carbon to oxygen atomic ratio of about 1:1; The interatomic lattice spacing of the crystal structure is 0.39 to 0.42 Å －１ and 0.68 to 0.76 Å －１ 0.39 Å －１ and 0.45 Å －１ 0.33 Å －１ and 0.88 Å －１ and 0.33 to 0.38 Å －１ and 0.77 to 0.78 Å －１ 10. The composition of claim 1, exhibiting a selected area electron diffraction signature selected from the group consisting of:

3. The composition of claim 1 further comprising at least one transition metal oxide.

4. 4. The composition of claim 3, wherein the transition metal oxide comprises a transition metal selected from the group consisting of Ti, V, Cr, Zr, Nb, Mo, Fe, Co, Ni, Hf, Ta, and W.

5. the chemical moieties further comprise chemical moieties atomically ordered in one or more crystalline phases of a two-dimensional graphene monoxide crystal structure having a carbon to oxygen atomic ratio of about 1:1; The interatomic lattice spacing of the two-dimensional graphene oxide crystal structure is 0.39 to 0.42 Å. －１ and 0.68 to 0.76 Å －１ 0.39 Å －１ and 0.45 Å －１ 0.33 Å －１ and 0.88 Å －１ and 0.33 to 0.38 Å －１ and 0.77 to 0.78 Å －１ 4. The composition of claim 3, exhibiting a selected area electron diffraction signature selected from the group consisting of:

6. The interatomic lattice spacing of the two-dimensional graphene oxide crystal structure is about 1,200 cm by infrared spectroscopy. －１ ~1,400cm －１ The composition of claim 5, which exhibits a carbon-oxygen vibration peak at

7. The composition is at about 116 ppm １３ 4. The composition of claim 3, exhibiting a C solid state NMR chemical shift of

8. Approximately 100m ２ 4. The composition of claim 3, having a Brunauer-Emmett-Teller (BET) surface area of ​​0.1g or less.

9. Approximately 100m ２ / g ~ approx. 600m ２ 4. The composition of claim 3, having a Brunauer-Emmett-Teller (BET) surface area of ​​1.0g / g.

10. 4. The composition of claim 3, further comprising at least one atomic layer of graphene, wherein the at least one atomic layer of graphene may be randomly stacked or locally ordered as an AB or AA stack in forming a multilayer.

11. At least a portion of the graphene is crystalline; and 11. The composition of claim 10, wherein the transition metal oxide is amorphous and substantially uniformly distributed throughout the composition or is present in the composition as nanocrystals detectable by electron diffraction and X-ray diffraction.

12. 10. The composition of claim 1, further comprising lithium ions or lithium atoms intercalated in or adsorbed onto said atomic layers of graphene monoxide.

13. The lithium ions or lithium atoms are Li with respect to the carbon atoms and oxygen atoms of the graphene monoxide. ２ C ６ O ６ From LiC ５０ O ５０ The composition of claim 12, wherein the composition is present in a ratio of up to

14. The lithium ions or lithium atoms are Li with respect to the carbon atoms and oxygen atoms of the graphene monoxide. ２ C ２ O ２ , Li ２ C ６ O ６ , Li ２ C ８ O ８ , LiC ６ O ６ , LiC ８ O ８ , Li ２ C １８ O １８ , Li ２ C ３２ O ３２ , LiC １８ O １８ , LiC ３２ O ３２ and LiC ５０ O ５０ 13. The composition of claim 12, wherein the composition is present in a ratio selected from:

15. 13. The composition of claim 12, wherein at least a portion of the lithium ions or lithium atoms occupy H sites relative to the graphene monoxide.

16. 13. The composition of claim 12, wherein at least a portion of the lithium ions or lithium atoms occupy S sites relative to the graphene monoxide.

17. ΔE of the lithium ions or lithium atoms in the composition Ｌｉ The composition of claim 12, wherein the .lambda.

18. (a) mixing a first solution, suspension, or powder comprising a carbon and oxygen source material with a second solution, suspension, or powder comprising at least one transition metal compound to form a mixture; and (b) heat treating the mixture of step (a) in an environment, for a time, at a temperature, and at a pressure that results in a composition comprising at least one atomic layer of graphene monoxide; wherein at least a portion of the oxygen molecules present in the graphene monoxide are incorporated into a structure having chemical moieties, the chemical moieties comprising chemical moieties in a crystallographically amorphous phase, and further wherein the chemical moieties are selected from the group consisting of a 1,3-dioxetane ring, a 1,5-dioxa-cyclooctane ring, a 1,4,7-trioxa-cyclononane ring, a (3,5,8,10)-tetraoxa-(1,6)-cyclodecadiene ring, and a polycarbonyl chain.

19. 20. The method of claim 18, wherein the carbon and oxygen source material has an atomic oxygen to carbon ratio of about 20% or greater and is selected from the group consisting of graphene oxide, polysaccharides, and phenolic polymers.

20. 20. The method of claim 18, wherein the transition metal compound comprises a transition metal selected from the group consisting of Ti, V, Cr, Zr, Nb, Mo, Fe, Co, Ni, Hf, Ta, and W.

21. 20. The method of claim 18, having an atomic ratio "x" of metal atoms to carbon atoms in step (a), where 0.05≦"x"≦0.

3.

22. 20. The method of claim 18, wherein step (a) further comprises mixing a third solution, suspension, or powder comprising an oxidizing agent with the first and second solutions, suspensions, or powders.

23. 20. The method of claim 18, wherein step (a) is carried out at a temperature of less than about 100°C.

24. 20. The method of claim 18, wherein step (b) comprises heating the mixture of step (a) at a temperature less than about 100°C.

25. 20. The method of claim 18, wherein step (b) comprises heating the mixture of step (a) to a temperature of from about 20°C to about 350°C.

26. 20. The method of claim 18, wherein step (b) comprises heating the mixture of step (a) to a temperature of from about 20°C to about 800°C.

27. 20. The method of claim 18, wherein step (b) comprises heating the mixture of step (a) to a temperature of from about 20°C to about 1,000°C.

28. 20. The method of claim 18, further comprising reducing the size of the composition.

29. 20. The method of claim 18, wherein in step (b), the mixture exhibits an exotherm of less than about 300 J / g when heated to 350°C.

30. 20. The method of claim 18, wherein step (b) comprises heating the mixture at a temperature range of about 21°C to about 800°C at a constant or variable heating rate.

31. 31. The method of claim 30, wherein in step (b), the mixture exhibits an exotherm of less than 300 J / g when heated to 800°C.

32. The chemical moieties further comprise chemical moieties atomically ordered in one or more phases of a two-dimensional graphene monoxide crystalline structure, wherein the crystalline structure within the composition has an interatomic lattice spacing of 0.39 to 0.42 Å. －１ and 0.68 to 0.76 Å －１ 0.39 Å －１ and 0.45 Å －１ 0.33 Å －１ and 0.88 Å －１ and 0.33 to 0.38 Å －１ and 0.77 to 0.78 Å －１ 20. The method of claim 18, wherein the selected area electron diffraction signature is selected from the group consisting of:

33. The chemical moieties further include chemical moieties atomically ordered in one or more phases of a two-dimensional graphene monoxide crystalline structure, wherein the crystalline structure within the composition has an interatomic lattice spacing of about 1,200 cm by infrared spectroscopy. －１ ~1,400cm －１ The method of claim 18, wherein the carbon-oxygen vibration peak is

34. The composition is at about 116 ppm １３ 20. The method of claim 18, wherein the C solid state NMR chemical shifts are shown.

35. Approximately 100m ２ 19. The method of claim 18, wherein the carbon nanotube has a Brunauer-Emmett-Teller (BET) surface area of ​​1 / g or less.

36. Approximately 100m ２ / g ~ approx. 600m ２ 19. The method of claim 18, wherein the surface has a Brunauer-Emmett-Teller (BET) surface area of ​​1.0-1.0 g / g.

37. 20. The method of claim 18, wherein step (b) comprises heat treating the composition at a pressure less than atmospheric pressure.

38. Step (b) is about 2 × 10 －６ torr (2.67 x 10 －４ 38. The method of claim 37, comprising heat treating the composition at a pressure of less than or equal to 1000 Pa.

39. 20. The method of claim 18, wherein step (b) comprises heat treating the composition under an inert atmosphere.

40. 1. An electrode comprising a composition comprising at least one atomic layer of graphene monoxide, wherein at least a portion of the oxygen molecules present in the graphene monoxide are incorporated into a structure having chemical moieties, the chemical moieties comprising chemical moieties in a crystallographically amorphous phase, and further wherein the chemical moieties are selected from the group consisting of a 1,3-dioxetane ring, a 1,5-dioxa-cyclooctane ring, a 1,4,7-trioxa-cyclononane ring, a (3,5,8,10)-tetraoxa-(1,6)-cyclodecadiene ring, and a polycarbonyl chain.

41. 41. The electrode of claim 40, wherein the composition further comprises at least one transition metal oxide.

42. 41. The electrode of claim 40, wherein the composition further comprises graphite, silicon, a binder, or a combination thereof.

43. 1. A charge storage device comprising: an electrode comprising a composition comprising at least one atomic layer of graphene monoxide, wherein at least a portion of the oxygen molecules present in said graphene monoxide are incorporated into a structure having chemical moieties, said chemical moieties comprising chemical moieties in a crystallographically amorphous phase, and further wherein said chemical moieties are selected from the group consisting of a 1,3-dioxetane ring, a 1,5-dioxa-cyclooctane ring, a 1,4,7-trioxa-cyclononane ring, a (3,5,8,10)-tetraoxa-(1,6)-cyclodecadiene ring, and a polycarbonyl chain.

44. 44. The charge storage device of claim 43, wherein the charge storage device has a faster charge rate at 1 C or greater than a corresponding charge storage device including a graphite-only anode.

45. 45. The charge storage device of claim 44, wherein the electrode further comprises at least one transition metal oxide.

46. 44. The charge storage device of claim 43, wherein the charge storage device has a faster charge rate and a higher charge capacity at temperatures between about 0°C and about -20°C than a corresponding charge storage device including a graphite-only anode charged at temperatures between about 0°C and about -20°C.

47. 47. The charge storage device of claim 46 comprising an electrode, said electrode further comprising at least one transition metal oxide.

48. 44. The charge storage device of claim 43, wherein the charge storage device exhibits a monotonically decreasing potential versus specific capacitance curve.

49. 49. The charge storage device of claim 48, wherein the electrode further comprises at least one transition metal oxide.

50. 44. The charge storage device of claim 43, wherein the charge storage device is a lithium ion battery.

51. 51. The charge storage device of claim 50, wherein the composition further comprises at least one transition metal oxide.

52. 1. A composition comprising at least two phases selected from crystalline α, β, γ, and δ phases of two-dimensional graphene monoxide and an amorphous phase, wherein each of the at least two phases comprises at least one atomic layer of graphene monoxide, and at least a portion of the oxygen molecules present in the graphene monoxide are incorporated into a structure having a chemical moiety selected from the group consisting of a 1,3-dioxetane ring, a 1,5-dioxa-cyclooctane ring, a 1,4,7-trioxa-cyclononane ring, a (3,5,8,10)-tetraoxa-(1,6)-cyclodecadiene ring, and a polycarbonyl chain.

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