Lithium-carbon battery materials produced via plasma pyrolysis

Abstract

Disclosed herein are lithium carbon composite materials and devices including at least one of lithium carbon composite materials. Also disclosed are reactors configured to receive lithium, lithium precursors, carbon, and / or carbon-containing precursors in a solid state, a vapor state, or a combination thereof. The reactors convert material states using a plasma torch as necessary in order to allow impregnation of lithium into pores of a carbon material.

Description

[0001] LITHIUM-CARBON BATTERY MATERIALS PRODUCED VIA PLASMA PYROLYSIS

[0002] BACKGROUND

[0003] Technical Field

[0004] Embodiments of the present disclosure generally relate to lithium-carbon composite materials produced via plasma pyrolysis.

[0005] Description of the Related Art

[0006] Lithium is a potentially useful anode material due to its high specific capacity (3900 mAh / g), low redox potential (-3.04 V), and ability to provide for the entirety of the battery lithium supply, e.g., enable battery chemistries with lithium-free cathode materials. However, the practical application of lithium metal anodes is still prohibited by its low Coulombic efficiency (CE) and growth of lithium dendrites during lithium dissolution / deposition. This propensity for lithium striping and plating degrades battery performance, resulting in limited cycle life and severe safety issues that impede the practical application of batteries with lithium metal in the anode.

[0007] In order to solve these issues, there has been some limited progress in the prior art by attempting to combine lithium with a carbon-based material. For example, it was reported that a lithium-carbon nanotube microsphere composite with a hydrophobic selfassembled monolayer surface passivation layer could provide for a battery wherein the CE increased from the typical value of 0.990 or lower to about 0.993 in the presence of dualsalt electrolyte system of LiPFe and LiNOs ("Stable Lithium-Carbon Composite Enabled by Dual-Salt Additives," L. Zheng et al., Nano-Micro Letters, Volume 13, Article 111, 2021). Such an approach as described in the prior art does not provide sufficient CE to provide for the cycle life requirement for most practical battery applications.

[0008] BRIEF SUMMARY

[0009] Disclosed herein are compositions and manufacturing methods related to lithiumcarbon composite materials, and electrodes and battery including the same, wherein the lithium-carbon composite materials are produced employing plasma pyrolysis. Plasma pyrolysis within a plasma reactor to produce the lithium-carbon composite material provides for distinct advantages, such as extremely rapid heating rates compared to conventional pyrolysis reactors known in the current art. Compared to processes carried out in conventional pyrolysis reactors, plasma pyrolysis in the plasma reactor provides for new routes of molecular dissociation facilitated by highly energetic subatomic particles present in the plasma. Lithium-carbon composite materials have utility as battery materials, for example cathode materials. Accordingly, embodiments of the present disclosure also relate to electrodes comprising lithium-carbon composite materials produced via plasma pyrolysis, and batteries containing the same, and uses thereof.

[0010] Lithium-carbon composite materials may be particulates, for example produced by contacting porous carbon scaffold particles and lithium, wherein the lithium is produced via plasma pyrolysis of a lithium-containing precursor in a plasma reactor, and wherein the temperature in the plasma reactor is above the melting or boiling point of lithium to facilitate the impregnation of lithium into the pores of the porous carbon scaffold particles. In an alternate embodiment, the lithium precursor is lithium metal, and the temperature within the plasma reactor is above the melting or boiling point of lithium to facilitate the impregnation of lithium into the pores of the porous carbon scaffold particles.

[0011] In some embodiments, the lithium-carbon composite particle may include an outer layer comprising carbon, or may include an outer layer comprising inorganic species, or combinations thereof. The outer layer may be created by plasma pyrolysis in a plasma reactor, for example, a carbon layer produced by plasma pyrolysis of a carbon-containing precursor in a plasma reactor. Alternatively, the outer layer may be created by chemical vapor deposition of a carbon containing precursor as known in the art.

[0012] The domain size of the impregnated lithium may vary, for example, the impregnated lithium domain may reflect the size of the pores of the porous carbon scaffold, for example may be in the range of less than 2 nm, or 2 to 50 nm, or greater than 50 nm, or combinations thereof. The porous carbon scaffold can be a particulate porous carbon, and the average particle size can be in the range of 100 nm to 10 cm. The average particle size of the lithium-carbon composite particles can be in the range of 100 nm to 100 pm. In some embodiments, the lithium-carbon composite particles are subjected to diminution after their production in the plasma reactor.

[0013] Without being bound by theory, the degree of heating within the plasma reactor provides for increased diffusion of lithium into the carbon to compared to conventional reactor processing. To this end, the carbon provides nucleation sites for impregnating lithium while dictating maximum particle shape and size. An additional advantage of impregnation of lithium into the pores of the porous carbon scaffold is that the composite particle may retain residual intra-particle void that may provide for further electrochemical benefits for the lithium-carbon composite anode material as disclosed herein. Yet another advantage of confining the growth of lithium in the anode within a nano-porous structure is reduced susceptibility to lithium dendrite formation or plating. Moreover, the lithium-carbon composite structure promotes nano-sized lithium in the anode to retain lithium as an amorphous phase. Such properties provide for improved CE and improved cycle stability in combination with high charge / discharge rates, particularly in combination with lithium’s vicinity within the conductive carbon scaffold. This system provides a high-rate-capable, solid-state lithium diffusion pathway that enables safe battery cycling.

[0014] Such lithium-carbon composite materials as disclosed herein have utility as battery materials, for example as anode active materials for conventional or solid-state lithium-ion batteries, cathode active materials for next-generation battery configurations such as lithium air, silicon batteries, and hybrid anode / cathode active materials for symmetric cell format batteries. Such lithium-carbon composite materials as disclosed herein have utility as battery materials specifically as the key anode material in a lithium carbon battery. Herein a lithium carbon battery is defined as a battery including an anode including a lithium carbon composite.

[0015] BRIEF DESCRIPTION OF THE DRAWINGS

[0016] FIGURE 1 is a partial cutaway view of a plasma reactor formed in accordance with an embodiment of the present invention.

[0017] FIGURE 2 shows an alternate embodiment of components of a plasma reactor.

[0018] FIGURE 3 is a state table of elements introduced into a plasma reactor.

[0019] FIGURE 4 is a partial cutaway view of a plasma reactor in a first configuration.

[0020] FIGURE 5 is a partial cutaway view of a plasma reactor in a second configuration.

[0021] FIGURE 6 is a partial cutaway view of a plasma reactor in a third configuration.

[0022] FIGURE 7 is a partial cutaway view of a plasma reactor in a fourth configuration.

[0023] FIGURE 8 is a partial cutaway view of a plasma reactor in a fifth configuration.

[0024] FIGURE 9 is a partial cutaway view of a plasma reactor in a sixth configuration.

[0025] FIGURE 10 is a partial cutaway view of a plasma reactor in a seventh configuration.

[0026] FIGURE 11 is a partial cutaway view of a plasma reactor in an eighth configuration.

[0027] FIGURE 12 is a partial cutaway view of a plasma reactor in a ninth configuration.

[0028] FIGURE 13 is a partial cutaway view of a plasma reactor in a tenth configuration.

[0029] FIGURE 14 is a partial cutaway view of a plasma reactor in an eleventh configuration.

[0030] FIGURE 15 is a table of schemes performed by one of the reactors of FIGURES 4-14.

[0031] FIGURE 16 is a table of details of a scheme presented in the table of FIGURE 15. FIGURE 17 shows X-ray diffraction (XRD) and Raman spectroscopic analysis for a first lithium precursor example.

[0032] FIGURE 18 shows X-ray diffraction (XRD) and Raman spectroscopic analysis for a second first lithium precursor example.

[0033] FIGURE 19 shows X-ray diffraction (XRD) and Raman spectroscopic analysis for a third lithium precursor example.

[0034] DETAILED DESCRIPTION

[0035] In the following description, certain specific details are set forth to provide a thorough understanding of various embodiments. However, one skilled in the art will understand that the disclosure may be practiced without these details. In other instances, well-known structures have not been shown or described in detail to avoid unnecessarily obscuring descriptions of the embodiments. Unless the context requires otherwise, throughout the specification and claims which follow, the word "include" and variations thereof, such as, "includes" and "including" are to be construed in an open, inclusive sense, that is, as "including, but not limited to." Further, headings provided herein are for convenience only and do not interpret the scope or meaning of the claimed disclosure.

[0036] Reference throughout this specification to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. Also, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the content clearly dictates otherwise. It should also be noted that the term "or" is generally employed in its sense including "and / or" unless the content clearly dictates otherwise.

[0037] Embodiments of the present disclosure generally relate to composite particles including Group 14 elements, e.g., carbon, silicon, and lithium, and electrodes and lithium or silicon carbon battery devices including the same. These materials are produced via novel processes that provide for a lithium or silicon within the pores of porous carbon particles to yield composite particles. Suitable carbon-containing precursors include, but are not limited to, sugars and polyols, organic acids, phenolic compounds, cross-linkers, and amine compounds, and combinations thereof. The lithium impregnated into the carbon porous can be provided as lithium, or alternatively, lithium salts, or other lithium-containing species can serve as the precursor for lithium within the lithium-carbon composite. The silicon impregnated into the carbon porous can be provided as silane or other silicon precursors. Suitable porous scaffolds include, but are not limited to, porous carbon scaffolds, for example carbon having a pore volume including micropores (less than 2 nm), mesopores (2 to 50 nm), and / or macropores (greater than 50 nm).

[0038] A. Porous Scaffold Materials

[0039] For the purposes of embodiments of the current disclosure, a porous scaffold may be used, into which lithium is to be impregnated. In this context, the porous scaffold can include various materials. In some embodiments the porous scaffold material primarily includes carbon, for example hard carbon. Other allotropes of carbon are also envisioned in other embodiments, for example, graphite, amorphous carbon, diamond, C60, carbon nanotubes (e.g., single and / or multi-walled), graphene and / or carbon fibers. The introduction of porosity into the carbon material can be achieved by a variety of means. For instance, the porosity in the carbon material can be achieved by modulation of polymer precursors, and / or processing conditions to create said porous carbon material and described in detail in the subsequent section.

[0040] In other embodiments, the porous scaffold includes a polymer material. To this end, a wide variety of polymers are envisioned in various embodiments to have utility, including, but not limited to, inorganic polymers, organic polymers, and additional polymers. Examples of organic polymers includes, but are not limited to, sulfur-containing polymers such polysulfides and polysulfones, low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), nylon, nylon 6, nylon 6,6, Teflon® ^ (Polytetrafluoroethylene), thermoplastic polyurethanes (TPU), polyureas, poly(lactide), poly(glycolide) and combinations thereof, phenolic resins, polyamides, polyaramids, polyethylene terephthalate, polychloroprene, polyacrylonitrile, polyaniline, polyimide, poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PDOT:PSS), polymerized polydivinylbenzene,, and others known in the arts. The organic polymer can be synthetic or natural in origin. In some embodiments, the polymer is a polysaccharide, such as sucrose, starch, cellulose, cellobiose, amylose, amylopectin, gum Arabic, lignin, and the like. In some embodiments, the polysaccharide is derived from the caramelization of mono- or oligomeric sugars, such as fructose, glucose, sucrose, maltose, raffinose, and the like.

[0041] In certain embodiments, the porous scaffold polymer material includes a coordination polymer. Coordination polymers in this context include, but are not limited to, metal organic frameworks (MOFs). Techniques for production of MOFs, as well as exemplary species of MOFs, are known and described in the art ("The Chemistry and Applications of Metal-Organic Frameworks, Hiroyasu Furukawa et al. Science 341, (2013); DOI: 10.1126 / science.1230444). Examples of MOFs in the context include, but are not limited to, Basolite™ materials and zeolitic imidazolate frameworks (ZIFs).

[0042] Concomitant with the myriad variety of polymers envisioned with the potential to provide a porous substrate, various processing approaches are envisioned in various embodiments to achieve said porosity. In this context, general methods for imparting porosity into various materials are myriad, as known in the art, including, but certainly not limited to, methods involving emulsification, micelle creation, gasification, dissolution followed by solvent removal (for example, lyophilization), axial compaction and sintering, gravity sintering, powder rolling and sintering, isostatic compaction and sintering, metal spraying, metal coating and sintering, metal injection molding and sintering, and the like. Other approaches to create a porous polymeric material, including creation of a porous gel, such as a freeze-dried gel, aerogel, and the like are also envisioned.

[0043] In certain embodiments, the porous scaffold material includes a porous ceramic material. In certain embodiments, the porous scaffold material includes a porous ceramic foam. In this context, general methods for imparting porosity into ceramic materials are varied, as known in the art, including, but certainly not limited to, creation of porous In this context, general methods and materials suitable for including the porous ceramic include, but are not limited to, porous aluminum oxide, porous zirconia toughened alumina, porous partially stabilized zirconia, porous alumina, porous sintered silicon carbide, sintered silicon nitride, porous cordierite, porous zirconium oxide, clay-bound silicon carbide, and the like.

[0044] In certain embodiments, the porous material includes a porous metal. Suitable metals in this regard include, but are not limited to porous aluminum, porous steel, porous nickel, porous Inconcel->, porous Hastelloy->, porous titanium, porous copper, porous brass, porous gold, porous silver, porous germanium, and other metals capable of being formed into porous structures, as known in the art. In some embodiments, the porous scaffold material includes a porous metal foam. The types of metals and methods to manufacture related to the same are known in the art. Such methods include, but are not limited to, casting (including foaming, infiltration, and lost-foam casting), deposition (chemical and physical), gas-eutectic formation, and powder metallurgy techniques (such as powder sintering, compaction in the presence of a foaming agent, and fiber metallurgy techniques).

[0045] B. Porous Carbon Scaffold Materials

[0046] Methods for preparing porous carbon materials from polymer precursors are known in the art. For example, methods for preparation of carbon materials are described in U.S. Patent Nos. 7,723,262, 8,293,818, 8,404,384, 8,654,507, 8,916,296, 9,269,502, 10,590,277, and 11,711,140, the full disclosures of which are hereby incorporated by reference in their entireties for all purposes.

[0047] Accordingly, in one embodiment the present disclosure provides a method for preparing any of the carbon materials or polymer gels described above. The carbon materials may be synthesized through pyrolysis of either a single precursor, for example a saccharide material such as sucrose, fructose, glucose, dextrin, maltodextrin, starch, amylopectin, amylose, lignin, gum Arabic, and other saccharides known in the art, and combinations thereof. Alternatively, the carbon materials may be synthesized through pyrolysis of a complex resin, for instance formed using a sol-gel method using polymer precursors such as phenol, resorcinol, bisphenol A, urea, melamine, and other suitable compounds known in the art, and combinations thereof, in a suitable solvent such as water, ethanol, methanol, and other solvents known in the art, and combinations thereof, with cross-linking agents such as formaldehyde, hexamethylenetetramine, furfural, and other cross-linking agents known in the art, and combinations thereof. The resin may be acid or basic and may contain a catalyst. The catalyst may be volatile or non-volatile. The pyrolysis temperature and dwell time can vary as known in the art.

[0048] In some embodiments, the methods include preparation of a polymer gel by a sol gel process, condensation process or crosslinking process involving monomer precursor(s) and a crosslinking agent, two existing polymers and a crosslinking agent or a single polymer and a crosslinking agent, followed by pyrolysis of the polymer gel. The polymer gel may be dried (e.g., freeze dried) prior to pyrolysis; however drying is not necessarily required.

[0049] The target carbon properties can be derived from a variety of polymer chemistries provided the polymerization reaction produces a resin / polymer with the necessary carbon backbone. Different polymer families include novolacs, resoles, acrylates, styrenes, urethanes, rubbers (neoprenes, styrene-butadienes, etc.), nylons, etc. The preparation of any of these polymer resins can occur via a number of different processes including sol gel, emulsion / suspension, solid state, solution state, melt state, etc. for either polymerization or crosslinking processes.

[0050] In some embodiments the reactant includes phosphorus. In certain other embodiments, the phosphorus is in the form of phosphoric acid. In certain other embodiments, the phosphorus can be in the form of a salt, wherein the anion of the salt includes one or more phosphate, phosphite, phosphide, hydrogen phosphate, dihydrogen phosphate, hexafluorophosphate, hypophosphite, polyphosphate, or pyrophosphate ions, or combinations thereof. In certain other embodiments, the phosphorus can be in the form of a salt, wherein the cation of the salt includes one or more phosphonium ions. The nonphosphate containing anion or cation pair for any of the above embodiments can be chosen for those known and described in the art. In the context, exemplary cations to pair with phosphate-containing anions include, but are not limited to, ammonium, tetraethylammonium, and tetramethylammonium ions. In the context, exemplary anions to pair with phosphate-containing cations include, but are not limited to, carbonate, dicarbonate, and acetate ions.

[0051] In some embodiments, the reactant includes sulfur. In certain other embodiments, the sulfur is in the form of sulfuric acid. In certain other embodiments, the sulfur can be in the form of a salt, wherein the anion of the salt includes one or more sulfate, sulfite, bisulfide, bisulfite, hypothiocyanite, sulfonium, S-methylmethionine, thiocarbonate, thiocyanate, thiophosphate, thiosilicate, or trimethylsulfonium, or combinations thereof.

[0052] In some embodiments, the catalyst includes a basic volatile catalyst. For example, in one embodiment, the basic volatile catalyst includes ammonium carbonate, ammonium bicarbonate, ammonium acetate, ammonium hydroxide, or combinations thereof. In a further embodiment, the basic volatile catalyst is ammonium carbonate. In another further embodiment, the basic volatile catalyst is ammonium acetate.

[0053] In still other embodiments, the method includes admixing an acid. In certain embodiments, the acid is a solid at room temperature and pressure. In some embodiments, the acid is a liquid at room temperature and pressure. In some embodiments, the acid is a liquid at room temperature and pressure that does not provide dissolution of one or more of the other polymer precursors.

[0054] In one embodiment a spherical polydivinylbencene spheres are produced by precipitation polymerization, pyrolyzed, and activated by the methods described herein.

[0055] In one embodiment, a porous carbon can be prepared by pyrolysis of a fluorine containing polymer (e.g., polyvinylidenine fluoride) by heating the material to 600 C under an inert gas such as nitrogen flowing in a horizontal tube furnace. The material was allowed to cool for 30 minutes and subsequently cooled t room departure prior to removing from the furnace. The resulting carbonized material was attrition milled to less than 25-micron particle size distribution and used to prepare electrodes. The porous carbon prepared by this method is rich in fluorine which facilitates formation of lithium fluoride in the initial stage of electrochemical plating of the lithium metal in a lithium-ion battery, thereby increasing the lithiophilicity and reduces detrimental dendrite growth in the battery.

[0056] In certain embodiments, the polymer precursor components are blended together and subsequently held for a time and at a temperature sufficient to achieve polymerization. One or more of the polymer precursor components can have particle size less than about 20 mm in size, for example less than 10 mm, for example less than 7 mm, for example, less than 5 mm, for example less than 2 mm, for example less than 1 mm, for example less than 100 microns, for example less than 10 microns. In some embodiments, the particle size of one or more of the polymer precursor components is reduced during the blending process.

[0057] The blending of one or more polymer precursor components in the absence of solvent can be accomplished by methods described in the art, for example ball milling, jet milling, Fritsch milling, planetary mixing, and other mixing methodologies for mixing or blending solid particles while controlling the process conditions (e.g., temperature). The mixing or blending process can be accomplished before, during, and / or after (or combinations thereof) incubation at the reaction temperature. Reaction parameters include aging the blended mixture at a temperature and for a time sufficient for the one or more polymer precursors to react with each other and form a polymer. In this respect, suitable aging temperature ranges from about room temperature to temperatures at or near the melting point of one or more of the polymer precursors. In some embodiments, suitable aging temperature ranges from about room temperature to temperatures at or near the glass transition temperature of one or more of the polymer precursors. For example, in some embodiments the solvent free mixture is aged at temperatures from about 20°C to about 600°C, for example about 20°C to about 500°C, for example about 20°C to about 400°C, for example about 20°C to about 300°C, for example about 20°C to about 200°C. In certain embodiments, the solvent free mixture is aged at temperatures from about 50 to about 250°C.

[0058] The reaction duration is generally sufficient to allow the polymer precursors to react and form a polymer, for example the mixture may be aged anywhere from 1 hour to 48 hours, or more or less depending on the desired result. Typical embodiments include aging for a period of time ranging from about 2 hours to about 48 hours, for example in some embodiments aging includes about 12 hours and in other embodiments aging includes about 4-8 hours (e.g., about 6 hours).

[0059] In certain embodiments, an electrochemical modifier is incorporated during the above-described polymerization process. For example, in some embodiments, an electrochemical modifier in the form of metal particles, metal paste, metal salt, metal oxide or molten metal can be dissolved or suspended into the mixture from which the gel resin is produced.

[0060] Exemplary electrochemical modifiers for producing composite materials may fall into one or more than one of the chemical classifications. In some embodiments, the electrochemical modifier is a lithium salt, for example, but not limited to, lithium fluoride, lithium chloride, lithium carbonate, lithium hydroxide, lithium benzoate, lithium bromide, lithium formate, lithium hexafluorophosphate, lithium iodate, lithium iodide, lithium perchlorate, lithium phosphate, lithium sulfate, lithium tetraborate, lithium tetrafluorob orate, and combinations thereof.

[0061] In certain embodiments, the electrochemical modifier includes a metal, and exemplary species includes, but are not limited to aluminum isopropoxide, manganese acetate, nickel acetate, iron acetate, tin chloride, silicon chloride, and combinations thereof. In certain embodiments, the electrochemical modifier is a phosphate compound, including but not limited to phytic acid, phosphoric acid, ammonium dihydrogen phosphate, and combinations thereof. In certain embodiments, the electrochemical modifier includes silicon, and exemplary species includes, but are not limited to silicon powders, silicon nanotubes, poly crystalline silicon, nanocrystalline silicon, amorphous silicon, porous silicon, nano sized silicon, nano-featured silicon, nano-sized and nano-featured silicon, silicyne, and black silicon, and combinations thereof. Electrochemical modifiers can be combined with a variety of polymer systems through either physical mixing or chemical reactions with latent (or secondary) polymer functionality. Examples of latent polymer functionality include, but are not limited to, epoxide groups, unsaturation (double and triple bonds), acid groups, alcohol groups, amine groups, basic groups. Crosslinking with latent functionality can occur via heteroatoms (e.g. vulcanization with sulfur, acid / base / ring opening reactions with phosphoric acid), reactions with organic acids or bases (described above), coordination to transition metals (including but not limited to Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ag, Au), ring opening or ring closing reactions (rotaxanes, spiro compounds, etc.).

[0062] Electrochemical modifiers can also be added to the polymer system through physical blending. Physical blending can include but is not limited to melt blending of polymers and / or co-polymers, the inclusion of discrete particles, chemical vapor deposition of the electrochemical modifier and co-precipitation of the electrochemical modifier and the main polymer material.

[0063] In some instances, the electrochemical modifier can be added via a metal salt solid, solution, or suspension. The metal salt solid, solution or suspension may include acids and / or alcohols to improve solubility of the metal salt. In yet another variation, the polymer gel (either before or after an optional drying step) is contacted with a paste including the electrochemical modifier. In yet another variation, the polymer gel (either before or after an optional drying step) is contacted with a metal or metal oxide sol including the desired electrochemical modifier.

[0064] In addition to the above exemplified electrochemical modifiers, the composite materials may include one or more additional forms (i.e., allotropes) of carbon. In this regard, it has been found that inclusion of different allotropes of carbon such as graphite, amorphous carbon, conductive carbon, carbon black, diamond, C60, carbon nanotubes (e.g., single and / or multi-walled), graphene and / or carbon fibers into the composite materials is effective to optimize the electrochemical properties of the composite materials. The various allotropes of carbon can be incorporated into the carbon materials during any stage of the preparation process described herein. For example, during the solution phase, during the gelation phase, during the curing phase, during the pyrolysis phase, during the milling phase, or after milling. In some embodiments, the second carbon form is incorporated into the composite material by adding the second carbon form before or during polymerization of the polymer gel as described in more detail herein. The polymerized polymer gel containing the second carbon form is then processed according to the general techniques described herein to obtain a carbon material containing a second allotrope of carbon.

[0065] In some embodiments, the polymer precursor is a polyvinilbenzene spheres produced by precipitation polymerization. In other embodiments, the polymer precursor in the low or essentially solvent free reaction mixture is a urea or an amine containing compound. For example, in some embodiments the polymer precursor is urea, melamine, hexamethylenetetramine (HMT) or combination thereof. Other embodiments include polymer precursors selected from isocyanates or other activated carbonyl compounds such as acid halides and the like.

[0066] Some embodiments of the disclosed methods include preparation of low or solvent- free polymer gels (and carbon materials) including electrochemical modifiers. Such electrochemical modifiers include, but are not limited to nitrogen, silicon, and sulfur. In other embodiments, the electrochemical modifier includes fluorine, iron, tin, silicon, nickel, aluminum, zinc, or manganese. The electrochemical modifier can be included in the preparation procedure at any step. For example, in some the electrochemical modifier is admixed with the mixture, the polymer phase or the continuous phase.

[0067] The porous carbon material can be achieved via pyrolysis of a polymer produced from precursor materials as described above. In some embodiments, the porous carbon material includes an amorphous activated carbon that is produced by pyrolysis, physical or chemical activation, or combination thereof in either a single process step or sequential process steps.

[0068] The temperature and dwell time of pyrolysis can be varied, for example the dwell time can vary from 1 min to 10 min, from 10 min to 30 min, from 30 min to 1 hour, for 1 hour to 2 hours, from 2 hours to 4 hours, from 4 hours to 24 h. The temperature can be varied, for example, the pyrolysis temperature can vary from 200°C to 300°C, from 250°C to 350°C, from 350°C to 450°C, from 450°C to 550°C, from 540°C to 650°C, from 650°C to 750°C, from 750°C to 850°C, from 850°C to 950°C, from 950°C to 1050°C, from 1050°C to 1150°C, from 1150°C to 1250°C. In some embodiments, the pyrolysis temperature varies from 650°C to 1100°C. The pyrolysis can be accomplished in an inert gas, for example nitrogen, or argon.

[0069] In some embodiments, an alternate gas is used to further accomplish carbon activation. In certain embodiments, pyrolysis and activation are combined. Suitable gases for accomplishing carbon activation include, but are not limited to, carbon dioxide, carbon monoxide, water (steam), air, oxygen, and further combinations thereof. The temperature and dwell time of activation can be varied, for example the dwell time can vary from 1 min to 10 min, from 10 min to 30 min, from 30 min to 1 hour, for 1 hour to 2 hours, from 2 hours to 4 hours, from 4 hours to 24 h. The temperature can be varied, for example, the pyrolysis temperature can vary from 200°C to 300°C, from 250°C to 350°C, from 350°C to 450°C, from 450°C to 550°C, from 540°C to 650°C, from 650°C to 750°C, from 750°C to 850°C, from 850°C to 950°C, from 950°C to 1050°C, from 1050°C to 1150°C, from 1150°C to 1250°C. In some embodiments, the temperature for combined pyrolysis and activation varies from 650°C to 1100°C. In some embodiments, combined pyrolysis and activation is carried out to prepare the porous carbon scaffold. In such embodiments, the process gas can remain the same during processing, or the composition of process gas may be varied during processing. In some embodiments, the addition of an activation gas such as CO2, steam, or combination thereof, is added to the process gas following sufficient temperature and time to allow for pyrolysis of the solid carbon-containing precursors.

[0070] Suitable gases for accomplishing carbon activation include, but are not limited to, carbon dioxide, carbon monoxide, water (steam), air, oxygen, and further combinations thereof. The temperature and dwell time of activation can be varied, for example the dwell time can vary from 1 min to 10 min, from 10 min to 30 min, from 30 min to 1 hour, for 1 hour to 2 hours, from 2 hours to 4 hours, from 4 hours to 24 h. The temperature can be varied, for example, the pyrolysis temperature can vary from 200°C to 300°C, from 250°C to 350°C, from 350°C to 450°C, from 450°C to 550°C, from 540°C to 650°C, from 650°C to 750°C, from 750°C to 850°C, from 850°C to 950°C, from 950°C to 1050°C, from 1050°C to 1150°C, from 1150°C to 1250°C. In some embodiments, the activation temperature varies from 650°C to 1100°C.

[0071] Either prior to the pyrolysis, and / or after pyrolysis, and / or after activation, the carbon may be subjected to a particle size reduction. The particle size reduction can be accomplished by a variety of techniques known in the art, for example by jet milling in the presence of various gases including air, nitrogen, argon, helium, supercritical steam, and other gases known in the art. Other particle size reduction methods, such as grinding, ball milling, jet milling, water jet milling, and other approaches known in the art are also envisioned.

[0072] The porous carbon scaffold may be in the form of particles. The particle size and particle size distribution can be measured by a variety of techniques known in the art and can be described based on fractional volume. In this regard, the Dv50 of the carbon scaffold may be between 10 nm and 10 mm, for example between 100 nm and 1 mm, for example between 1 pm and 100 pm, for example between 2 pm and 50 pm, example between 3 pm and 30 pm, example between 4 pm and 20 pm, example between 5 pm and 10 pm. In certain embodiments, the Dv50 is less than 1 mm, for example less than 100 pm, for example less than 50 pm, for example less than 30 pm, for example less than 20 pm, for example less than 10 pm, for example less than 8 pm, for example less than 5 pm, for example less than 3 pm, for example less than 1 pm. In certain embodiments, the DvlOO is less than 1 mm, for example less than 100 pm, for example less than 50 pm, for example less than 30 pm, for example less than 20 pm, for example less than 10 pm, for example less than 8 pm, for example less than 5 pm, for example less than 3 pm, for example less than 1 pm. In certain embodiments, the Dv99 is less than 1 mm, for example less than 100 pm, for example less than 50 pm for example less than 30 pm, for example less than 20 pm, for example less than 10 pm, for example less than 8 pm, for example less than 5 pm, for example less than 3 pm, for example less than 1 pm. In certain embodiments, the Dv90 is less than 1 mm, for example less than 100 pm, for example less than 50 pm, for example less than 30 pm, for example less than 20 pm, for example less than 10 pm, for example less than 8 pm, for example less than 5 pm, for example less than 3 pm, for example less than 1 pm. In certain embodiments, the DvO is greater than 10 nm, for example greater than 100 nm, for example greater than 500 nm, for example greater than 1 pm, for example greater than 2 pm, for example greater than 5 pm, for example greater than 10 pm. In certain embodiments, the Dvl is greater than 10 nm, for example greater than 100 nm, for example greater than 500 nm, for example greater than 1 pm, for example greater than 2 pm, for example greater than 5 pm, for example greater than 10 pm. In certain embodiments, the DvlO is greater than 10 nm, for example greater than 100 nm, for example greater than 500 nm, for example greater than 1 pm, for example greater than 2 pm, for example greater than 5 pm, for example greater than 10 pm.

[0073] In some embodiments, the surface area of the porous carbon scaffold can include a surface area greater than 400 m2 / g, for example greater than 500 m2 / g, for example greater than 750 m2 / g, for example greater than 1000 m2 / g, for example greater than 1250 m2 / g, for example greater than 1500 m2 / g, for example greater than 1750 m2 / g, for example greater than 2000 m2 / g, for example greater than 2500 m2 / g, for example greater than 3000 m2 / g. In other embodiments, the surface area of the porous carbon scaffold can be less than 500 m2 / g. In some embodiments, the surface area of the porous carbon scaffold is between 200 and 500 m2 / g. In some embodiments, the surface area of the porous carbon scaffold is between 100 and 200 m2 / g. In some embodiments, the surface area of the porous carbon scaffold is between 50 and 100 m2 / g. In some embodiments, the surface area of the porous carbon scaffold is between 10 and 50 m2 / g. In some embodiments, the surface area of the porous carbon scaffold can be less than 10 m2 / g.

[0074] In some embodiments, the pore volume of the porous carbon scaffold is greater than 0.4 cm3 / g, for example greater than 0.5 cm3 / g, for example greater than 0.6 cm3 / g, for example greater than 0.7 cm3 / g, for example greater than 0.8 cm3 / g, for example greater than 0.9 cm3 / g, for example greater than 1.0 cm3 / g, for example greater than 1.1 cm3 / g, for example greater than 1.2 cm3 / g, for example greater than 1.4 cm3 / g, for example greater than 1.6 cm3 / g, for example greater than 1.8 cm3 / g, for example greater than 2.0 cm3 / g. In other embodiments, the pore volume of the porous carbon scaffold is less than 0.5 cm3, for example between 0.1 cm3 / g and 0.5 cm3 / g. In certain other embodiments, the pore volume of the porous carbon scaffold is between 0.01 cm3 / g and 0.1 cm3 / g.

[0075] In some other embodiments, the porous carbon scaffold is an amorphous activated carbon with a pore volume between 0.2 and 2.0 cm3 / g. In certain embodiments, the carbon is an amorphous activated carbon with a pore volume between 0.4 and 1.5 cm3 / g. In certain embodiments, the carbon is an amorphous activated carbon with a pore volume between 0.5 and 1.2 cm3 / g. In certain embodiments, the carbon is an amorphous activated carbon with a pore volume between 0.6 and 1.0 cm3 / g.

[0076] In some other embodiments, the porous carbon scaffold includes a tap density of less than 1.0 g / cm3, for example less than 0.8 g / cm3, for example less than 0.6 g / cm3, for example less than 0.5 g / cm3, for example less than 0.4 g / cm3, for example less than 0.3 g / cm3, for example less than 0.2 g / cm3, for example less than 0.1 g / cm3.

[0077] The surface functionality of the porous carbon scaffold can vary. One property which can be predictive of surface functionality is the pH of the porous carbon scaffold. The presently disclosed porous carbon scaffolds include pH values ranging from less than 1 to about 14, for example less than 5, from 5 to 8 or greater than 8. In some embodiments, the pH of the porous carbon is less than 4, less than 3, less than 2 or even less than 1. In other embodiments, the pH of the porous carbon is between about 5 and 6, between about 6 and 7, between about 7 and 8 or between 8 and 9 or between 9 and 10. In still other embodiments, the pH is high and the pH of the porous carbon ranges is greater than 8, greater than 9, greater than 10, greater than 11, greater than 12, or even greater than 13.

[0078] The pore volume distribution of the porous carbon scaffold can vary. For example, the % micropores can include less than 30%, for example less than 20%, for example less than 10%, for example less than 5%, for example less than 4%, for example less than 3%, for example less than 2%, for example less than 1%, for example less than 0.5%, for example less than 0.2%, for example, less than 0.1%. In certain embodiments, there is no detectable micropore volume in the porous carbon scaffold.

[0079] The mesopores including the porous carbon scaffold can vary. For example, the % mesopores can include less than 30%, for example less than 20%, for example less than 10%, for example less than 5%, for example less than 4%, for example less than 3%, for example less than 2%, for example less than 1%, for example less than 0.5%, for example less than 0.2%, for example, less than 0.1%. In certain embodiments, there is no detectable mesopore volume in the porous carbon scaffold.

[0080] In some embodiments, the pore volume distribution of the porous carbon scaffold includes more than 50% macropores, for example more than 60% macropores, for example more than 70% macropores, for example more than 80% macropores, for example more than 90% macropores, for example more than 95% macropores, for example more than 98% macropores, for example more than 99% macropores, for example more than 99.5% macropores, for example more than 99.9% macropores.

[0081] In certain preferred embodiments, the pore volume of the porous carbon scaffold includes a blend of micropores, mesopores, and macropores. Accordingly, in certain embodiments, the porous carbon scaffold includes 0-20% micropores, 30-70% mesopores, and less than 10% macropores. In certain other embodiments, the porous carbon scaffold includes 0-20% micropores, 0-20% mesopores, and 70-95% macropores. In certain other embodiments, the porous carbon scaffold includes 20-50% micropores, 50-80% mesopores, and 0-10% macropores. In certain other embodiments, the porous carbon scaffold includes 40-60% micropores, 40-60% mesopores, and 0-10% macropores. In certain other embodiments, the porous carbon scaffold includes 80-95% micropores, 0- 10% mesopores, and 0-10% macropores. In certain other embodiments, the porous carbon scaffold includes 0-10% micropores, 30-50% mesopores, and 50-70% macropores. In certain other embodiments, the porous carbon scaffold includes 0-10% micropores, 70- 80% mesopores, and 0-20% macropores. In certain other embodiments, the porous carbon scaffold includes 0-20% micropores, 70-95% mesopores, and 0-10% macropores. In certain other embodiments, the porous carbon scaffold includes 0-10% micropores, 70- 95% mesopores, and 0-20% macropores.

[0082] In certain embodiments, the % of pore volume in the porous carbon scaffold representing pores between 100 and 1000 A (10 and 100 nm) includes greater than 30% of the total pore volume, for example greater than 40% of the total pore volume, for example greater than 50% of the total pore volume, for example greater than 60% of the total pore volume, for example greater than 70% of the total pore volume, for example greater than 80% of the total pore volume, for example greater than 90% of the total pore volume, for example greater than 95% of the total pore volume, for example greater than 98% of the total pore volume, for example greater than 99% of the total pore volume, for example greater than 99.5% of the total pore volume, for example greater than 99.9% of the total pore volume.

[0083] In certain embodiments, the pycnometry density of the porous carbon scaffold ranges from about 1 g / cc to about 3 g / cc, for example from about 1.5 g / cc to about 2.3 g / cc. In other embodiments, the skeletal density ranges from about 1.5 cc / g to about 1.6 cc / g, from about 1.6 cc / g to about 1.7 cc / g, from about 1.7 cc / g to about 1.8 cc / g, from about 1.8 cc / g to about 1.9 cc / g, from about 1.9 cc / g to about 2.0 cc / g, from about 2.0 cc / g to about 2.1 cc / g, from about 2.1 cc / g to about 2.2 cc / g or from about 2.2 cc / g to about 2.3 cc / g, from about 2.3 cc to about 2.4 cc / g, for example from about 2.4 cc / g to about 2.5 cc / g.

[0084] In some embodiments, the carbon scaffold pore volume distribution can be described as the number or volume distribution of pores as determined as known in the art based on gas sorption analysis, for example nitrogen gas sorption analysis. In some embodiments the pore size distribution can be expressed in terms of the pore size at which a certain fraction of the total pore volume resides at or below. For example, the pore size at which 10% of the pores reside at or below can be expressed at DPvlO.

[0085] The DPvlO for the porous carbon scaffold can vary, for example DPvlO can be between 0.01 nm and 100 nm, for example between 0.1 nm and 100 nm, for example between 1 nm and 100 nm, for example between 1 nm and 50 nm, for example between 1 nm and 40 nm, for example between 1 nm and 30 nm, for example between 1 nm and 10 nm, for example between 1 nm and 5 nm. The DPv50 for the porous carbon scaffold can vary, for example DPv50 can be between 0.01 nm and 100 nm, for example between 0.1 nm and 100 nm, for example between 1 nm and 100 nm, for example between 1 nm and 50 nm, for example between 1 nm and 40 nm, for example between 1 nm and 30 nm, for example between 1 nm and 10 nm, for example between 1 nm and 5 nm. In other embodiments, the DPv50 is between 2 and 100, for example between 2 and 50, for example between 2 and 30, for example between 2 and 20, for example between 2 and 15, for example between 2 and 10.

[0086] The DPv90 for the porous carbon scaffold can vary, for example DPv90 can be between 0.01 nm and 100 nm, for example between 0.1 nm and 100 nm, for example between 1 nm and 100 nm, for example between 1 nm and 50 nm, for example between 1 nm and 50 nm, for example between 1 nm and 40 nm, for example between 1 nm and 30 nm, for example between 1 nm and 10 nm, for example between 1 nm and 5 nm. In other embodiments, the DPv50 is between 2 nm and 100 nm, for example between 2 nm and 50 nm, for example between 2 nm and 30 nm, for example between 2 nm and 20 nm, for example between 2 nm and 15 nm, for example between 2 nm and 10 nm.

[0087] In some embodiments, the DPv90 is less than 100 nm, for example less than 50 nm, for example less than 40 nm, for example less than 30 nm, for example less than 20 nm, for example less than 15 nm, for example less than 10 nm. In some embodiments, the carbon scaffold includes a pore volume with greater than 70% micropores (and DPv90 less than 100 nm, for example DPv90 less than 50 nm, for example DPv90 less than 40 nm, for example DPv90 less than 30 nm, for example DPv90 less than 20 nm, for example DPv90 less than 15 nm, for example DPv90 less than 10 nm, for example DPv90 less than 5 nm, for example DPv90 less than 4 nm, for example DPv90 less than 3 nm. In other embodiments, the carbon scaffold includes a pore volume with greater than 80% micropores and DPv90 less than 100 nm, for example DPv90 less than 50 nm, for example DPv90 less than 40 nm, for example DPv90 less than 30 nm, for example DPv90 less than 20 nm, for example DPv90 less than 15 nm, for example DPv90 less than 10 nm, for example DPv90 less than 5 nm, for example DPv90 less than 4 nm, for example DPv90 less than 3 nm.

[0088] The DPv99 for the porous carbon scaffold can vary, for example DPv99 can be between 0.01 nm and 1000 nm, for example between 0.1 nm and 1000 nm, for example between 1 nm and 500 nm, for example between 1 nm and 200 nm, for example between 1 nm and 150 nm, for example between 1 nm and 100 nm, for example between 1 nm and 50 nm, for example between 1 nm and 20 nm. In other embodiments, the DPv99 is between 2 nm and 500 nm, for example between 2 nm and 200 nm, for example between 2 nm and 150 nm, for example between 2 nm and 100 nm, for example between 2 nm and 50 nm, for example between 2 nm and 20 nm, for example between 2 nm and 15 nm, for example between 2 nm and 10 nm.

[0089] In certain embodiments, the carbon scaffold is modified prior to impregnation of lithium. For example, in certain embodiments, the surface of the carbon pores is functionalized for the purpose of creating a more lithiophilic surface, i.e., surface that interacts preferentially with lithium or lithium containing precursor materials, wherein said preferential interaction can manifest as preferential diffusion, deposition, adsorption of the like.

[0090] In some embodiments metal oxides are used to functionalize the porous carbon and improve lithiophilicity and thereby improve SEI stability of a lithium metal anode. In this embodiment, a porous carbon scaffold is modified with zinc oxide via a hydrothermal solgel synthesis reaction. Zinc acetate dihydrate is dissolved in water and stirred with micronized porous carbon powder. A strong oxidizing agent such as NaOH is then added dropwise into the reaction solution and allowed to react for up to 2 hours, before being separated by filtration and allowed to dry. In some embodiments the metal oxide may be aluminum oxide, nickel oxide, manganese oxide, cobalt oxide, tin oxide, or titanium oxide.

[0091] In still further embodiments the metal oxide is deposited via atomic layer deposition, physical vapor deposition onto the porous carbon surface and then subsequently converted to a metal oxide via chemical or thermal oxidation reactions. In still further embodiments, the porous carbon may be coated with a polymer containing lithium.

[0092] C. Impregnation of Lithium in Carbon Via Chemical Vapor Infiltration (CVI) of

[0093] Plasma-Liquified, Plasma-Vaporized, or Plasma-Pyrolyzed Lithium orLithium- Containing Precursor

[0094] Chemical vapor deposition (CVD) is a process wherein a substrate provides a solid surface including the first component of the composite, and the gas thermally decomposes on this solid surface to provide the second component of the composite. Such a CVD approach can be employed, for instance, to create Li-C composite materials wherein the lithium is coating on the outside surface of carbon particles. Alternatively, chemical vapor infiltration (CVI) is a process wherein a substrate provides a porous scaffold including the first component of the composite, and the gas, for example a gaseous lithium-containing precursor, thermally decomposes (i.e., plasma-pyrolysis) within the porosity (into the pores) of the porous scaffold material to provide the second component of composite (i.e., plasma pyrolyzed lithium). In an alternate embodiment, the species entering the pores of the porous scaffold can be plasma-liquified or plasma-vaporized lithium, which further impregnates into the pores of the porous carbon scaffold, thereby incorporating with the carbon scaffold to yield the lithium-carbon composite.

[0095] In an embodiment, lithium is created within the pores of the porous carbon scaffold by subjecting the porous carbon particles to a lithium containing precursor at elevated temperature such that the lithium containing precursor exists in a gaseous state. In certain embodiments, the porous scaffold is a porous pyrolyzed carbon material, and the resulting lithium-pyrolyzed carbon composite created by CVI is subject to processing to activate the carbon material according to activation methods generally described herein. In other embodiments, the porous scaffold is a porous polymer material, and the resulting lithiumpolymer composite created by CV1 is subject to processing to accomplish polymer pyrolysis according to pyrolysis methods generally described herein. In related embodiments, the porous scaffold is a porous polymer material, and the resulting lithium-polymer composite created by CV1 is subject to processing to accomplish polymer pyrolysis and activation according to pyrolysis and activation methods generally described herein.

[0096] The gasified lithium containing precursor can be mixed with other inert gases, for example, nitrogen, argon, and combinations thereof. The temperature and time of processing can be varied, for example the temperature can be between 200°C and 1700°C, for example between 200°C and 300°C, for example between 300°C and 400°C, for example between 400°C and 500°C, for example between 500°C and 600°C, for example between 600°C and 700°C, for example between 700°C and 800°C, for example between 800°C and 900°C, for example between 900°C and 1000°C, for example between 1000°C and 1100°C, for example between 1100°C and 1200°C, for example between 1200°C and 1400°C, for example between 1300°C and 1400°C for example between 1400°C and 1700°C.

[0097] In one embodiment, lithium is heated to achieve plasma pyrolysis at or above its boiling point (1330°C). In other embodiments, the lithium-containing precursor is heated at or above its boiling point to achieve plasma pyrolysis. Exemplary lithium-containing precursors in this regard include, but are not limited to, lithium acetylsalicylate (boiling point = 350°C], lithium amide (boiling point = 430°C], lithium bromide (boiling point = 1265°C], lithium tetrab orohydride (boiling point = 380°C], lithium chloride (boiling point = 1383°C], lithium hydride (boiling point = 950°C], and lithium hydroxide (boiling point = 1626°C], lithium carbonate (melting point = 723 °C), lithium acetate (melting point = 286 °C), lithium fluoride (melting point = 846 °C), lithium hydrogen sulfate (melting point = 171 °C), lithium dihydrogen phosphate (melting point = 100 °C), lithium nitrate (melting point = 261 °C), lithium phosphate (melting point = 837 °C), lithium sulfate (melting point = 860 °C), lithium sulfide (melting point = 950 °C), lithium disulfide (melting point = 370 °C), lithium sulfite (melting point = 455 °C). Additional exemplary of lithium containing precursors include lithium metal alloys including lithium aluminum alloy (melting point = 718 °C), lithium aluminum copper alloys (melting point in range of 600 °C to 655 °C), lithium tin alloys (melting point in range of 344 °C to 488 °C), and lithium silicon alloys (melting point = 700 °C).

[0098] The temperature inside the plasma reactor to accomplish plasma pyrolysis of the lithium.

[0099] The pressure for the CV1 process can be varied. In some embodiments, the pressure is atmospheric pressure. In some embodiments, the pressure is below atmospheric pressure. In some embodiments, the pressure is above atmospheric pressure. D. Description of Various Plasma Reactor Designs and Reaction Schemes

[0100] In various embodiments, FIGURE 1 illustrates a plasma reactor 50 configured for the production of lithium carbon composite materials. The plasma reactor 50 includes a direct current (DC) torch (e.g., non-transferred arc) 56 located within a first chamber 52. In various embodiments, the torch 56 is directed tangentially into the reactor interior, especially at an upper end of the essentially cylindrical first chamber 52. When the lithium, lithium-containing precursors, carbon, and / or carbon-containing precursors and a carrier gas (e.g., argon, hydrogen, nitrogen, or a combination thereof) are introduced at high velocities ionization occurs within the first chamber 52. This results in a rotary turbulent motion within the reactor 50, which results in efficient mixing of a plasma produced by a plasma torch 56, of the lithium compound, and of formed lithium vapors. The plasma torch 56 may be placed at other locations in the reactor 50, such as, without limitation, at the top of the reactor 50 in parallel with an entry direction or location of other precursors.

[0101] In one embodiment, the hot gas from the plasma torch (Ar, Eh, N2, or a combination thereof) is mixed with the lithium, lithium precursors, carbon and / or carbon-containing precursors and carrier gas in the chamber 52. Here a first evaporation and / or decomposition reaction can proceed or start. In a similar embodiment, the mixture of the gases happens afterwards in a second chamber 58, where the first chamber 52 serves to redirect the stream of hot plasma gas from a single jet to a flow enclosing the nozzle 54 and enclosing the gas flow resigning from the nozzle 54 symmetrically. In some embodiments, ionization mainly occurs inside the plasma torch 56. In other embodiments ionization occurs both inside the plasma torch 56 and the reactor 50.

[0102] In other embodiments, the plasma source includes In various embodiments, the plasma torch 56 is an alternating current (AC) arc torch (e.g., 3 -phase AC torch), a liquid- stabilized arc torch, a radio frequency-inductively coupled plasma source (RF-ICP), a microwave plasma source, or a combination of two of the named plasma sustaining principles like a hybrid torch consisting of a DC arc and an additional ICP stage. The plasma torch 56 may produce an arc with a core that can exhibit temperatures of 8000°C, 10000°C or even more dependent on the amperage of the arc, the plasma gases used, their pressures and other parameters. At an exit of the plasma torch 56, plasma is ejected with temperatures between 2000°C and 5000°C depending upon power and gas flow.

[0103] Lithium, lithium precursors, carbon, and / or carbon-containing precursors are added to the reactor 50 via a nozzle 54 or at other locations. In one embodiment, the nozzle 54 outputs lithium below or at the bottom of the first chamber 52 or at or near a top of a smaller diameter second chamber 58. The arrows indicate flow of heated gas produced by the plasma from the plasma torch 56. At a lower portion of the second chamber 58, the heated or activated lithium or lithium-containing precursor is combined with a created or introduced porous carbon material. The reactor 50 includes a heat-resistant interior into which a mixture of lithium or lithium precursor and carbon or a carbon-containing precursor is introduced with a carrier gas heated to a predefined temperature. In preferred embodiments, the temperatures within the reactor 50 are at or above 1330°C to maintain lithium in the vapor phase, i.e., in excess of the boiling point of lithium, such that lithium does not condense into liquid phase within the reactor 50. For example, the temperature within the reactor 50 may by between 1300° to 1400°C, or 1400°C to 1600°C, or 1600°C to 2000°C or 2000°C to 5000°C. In further preferred embodiments, the temperatures within the reactor 50 are in excess of 180.5 C to maintain lithium in the liquid phase, i.e., in excess of the melting point of lithium, such that the lithium does not solidify in solid phase within the reactor 50.

[0104] In some embodiments, the walls of the reactor 50 are at a temperature above the melting point of lithium such that no solid lithium deposits can form. In further embodiments, the walls of the reactor 50 have a temperature above the boiling point of lithium such that no liquid lithium deposits can form. The reactor 50 may also include suitable insulation to prevent excessive heat loss.

[0105] In various embodiments, FIGURE 2 illustrates an alternative configuration for a nozzle 64 into a reactor. The nozzle 64 is positioned adjacent the plasma torch 56 thus allowing flow of materials directly into the plasma produced by the plasma torch 56. The particles of a solid precursor come in contact with a noticeable hotter part of the plasma jet and thus possibly stays in contact with the hot plasma gas longer, therefore heating up to higher temperatures.

[0106] It is envisioned that various schemes 60 can be employed for production of the lithium-caron composite material in a plasma reactor. Theses scheme can be categorized according to the physical state of the carbon or carbon-containing precursor material and the physical state of the lithium or lithium precursor charged into the plasma reactor (FIGURE 3). Other schemes are illustrated below with regard to FIGURES 15 and 16.

[0107] The carbon can be introduced into the plasma reactor in the form of a solid carbon material, or the carbon can be produced in the plasma reactor as a result of plasma pyrolysis of a carbon-containing precursor material, for example a carbon-containing gas. The lithium can be introduced into the plasma reactor as plasma-liquified lithium, or plasma-vaporized lithium, or lithium gas formed as a result of plasma pyrolysis of a lithium precursor material.

[0108] The plasma reactor can comprise a single stage reactor, or a 2-stage reactor, or a 3- stage reactor. In certain embodiment, the plasma reactor can include 4 or more stages.

[0109] In various embodiments, additional streams of carrier gases may be used at different entry points of the reactor 50 for temperature control purposes. 1. Vapor (Li)-Solid (C)

[0110] In various embodiments, referring to FIGURE 4, a reactor 50-1 (similar to the reactor 50) is configured to introduce a lithium-containing precursor (e.g., LiH, LiCO3) via a nozzle 54-1. At a lower portion of a first chamber 52-1 plasma heated lithium-containing precursor is decomposed to form a vaporized lithium (i.e., a vapor (fog / mist)) in the second chamber 58-1 before contacting a bed of carbon 68 located in a second chamber 58- 1.

[0111] In various embodiments, referring to FIGURE 5, a solid Li-containing precursor and solid carbon particles are introduced together through a nozzle 54-2 of a reactor 50-2. Plasma from a plasma torch 56-2 causes the lithium precursor to decompose into a vapor then forming a fog / mist at a second chamber 58-2 of the reactor 50-2. The lithium fog / mist impregnates within / reacts with the solid carbon particles in the second chamber 58-2.

[0112] In various embodiments, referring to FIGURE 6, a porous fixed bed 57 for the carbon (fairly large particle size) to sit on allows the flow of molten L12C2 through to a collection point while the solid carbon material would not be able to pass with the Li gas stream applying pressure from above. Liquid lithium carbide material melts through a porous separator 59 to produce condensed Li2C 2 droplets. The separator 59 is non-interacting and is able to handle high temperatures.

[0113] In various embodiments, referring to FIGURE 7, hot vaporous (or liquid) Li is blown against a tilted C-surface like a graphite tube 62 located in a lower chamber 58-4. This allows product to flow down the surface of the graphite tube 62 and collect below the reaction zone thus avoiding clogging issues.

[0114] In various embodiments, referring to FIGURE 8, a reactor 70 includes a plasma torch chamber 72 that includes a plasma torch 76 and a nozzle 78 for introducing a lithium precursor into plasma 75 produced by the plasma torch 76. The high temperature of the plasma 75 causes the lithium precursor to vaporize. The lithium vapor is introduced into a second chamber 74 via a lower entry port. In the second chamber 74 the lithium vapor is introduced to a fluidized bed 77 of carbon particles. The arrows represent additional carrier gas flow to fluidize the porous carbon particles. At the top a mixture of carrier gas and plasma gas is leaving the reactor.

[0115] 2. Solid (Li) - Solid (C)

[0116] In various embodiments, FIGURE 9 illustrates a crucible system 80 that includes a crucible 86 positioned below a plasma 83 produced by a plasma torch 82 within a chamber 84. The crucible 86 includes an aerodynamic cover with port directed at the plasma 83. Premixed carbon and lithium are received within the crucible 86. The heat generated within the crucible 86 causes the lithium to vaporize and impregnate within the carbon. In various embodiments, FIGURE 10 illustrates a reactor 90 having a mixed / fixed bed 92 located within a chamber 94 below a plasma 93 produced by a plasma torch 96. Premixed solid carbon and lithium are placed on the bed 92. The plasma 93 causes the lithium to vaporize and impregnate within the carbon.

[0117] In various embodiments, FIGURE 11 illustrates a reactor 50-5 that receives pelletized solid precursors at a nozzle 54-5. The pelletized solid precursors may be preagglomerated carbon and lithium. Plasma 53 produced by a plasma torch 56-5 in a first chamber 52-5 causes pelletized lithium to vaporize.

[0118] 3. Solid (Li) - Vapor (C)

[0119] Referring to FIGURE 12, a reactor 50-6 receives a solid nano lithium stream (Li- containing precursor) via a nozzle 54-6. The Li-containing precursor evaporates and is passed to a second chamber 58-6. A thermocouple 55 is located within the second chamber 58-6 to measure gas temperature. A hydrocarbon-containing precursor gas is inserted in the second chamber 58-6. The reactor 50-6 may include a location in the second chamber 58-6 before the introduction of hydrocarbon-containing precursor gas whereby cold inert quench gas is inserted. In response to the measured gas temperature, the amount of quench gas, the kind of quench gas, and / or temperature of the quench gas, can be adjusted for controlling the gas temperature inside the reactor 50-6 to an optimal value. The quench gas can be used to control the temperature inside the reactor. The quench gas can be used to stop reactions following the injection of precursors or even triggering reactions. In particular, the temperature could be tuned to enable vaporous Li to condense.

[0120] After injection of the hydrocarbon-containing precursor gas, a cloud of condensed lithium nanodroplets are formed. After introduction of the hydrocarbon-containing precursor gas, a cloud of condensed Li nanodroplets is formed, thus allowing Li to impregnate porous carbon particles. The temperature in the lower part of the second chamber 58-4 is high enough to decompose the carbon-containing precursor gas injected there. Carbon is then deposited onto the Li particles / droplets (similarly to CVI, where one substance is deposited in the pores of another substance).

[0121] Referring to FIGURE 13, a reactor 50-7 is a 2-stage reactor. Solid lithium precursors are received into the reactor 50-7 via a nozzle 54-7. A second chamber 58-7 has a first stage section and a second stage section. In the first stage section evaporation, melting and / or condensation of received lithium occurs. In the second stage section carbon gas (hydrocarbon) is added whereby the carbon reacts with the melted or condensed lithium. The reactor 50-7 may include a location in the second chamber 58-7 before the introduction of hydrocarbon-containing precursor gas whereby a cold inert quench gas is inserted.

[0122] 4. Vapor - Vapor Referring to FIGURE 14, a reactor 50-8 receives a nano-lithium vapor stream mixed with a hydrocarbon-containing precursor gas at a nozzle 54-8. In a first chamber 52-8, the nano-lithium vapor stream becomes superheated. At a second chamber 58-8, evaporation of Li precursor and decomposition of the hydrocarbon-containing precursor gas occurs, thus producing a cloud of condensed LiC-containing nano- or micro-sized droplets. Before the formation of the LiC-containing nano- or micro-sized droplets, cold inert quench gas may be injected to cool or solidify them. Lithium vapor, the lithium may condense to form a mist or fog containing nanometer- or micrometer-sized lithium-droplets or particles.

[0123] In various embodiments, other methods of polymerization may be used with the reactors described above. For example, pressure-induced polymerization, chemical, ultraviolet, electron beams, or a combination of any of these methods may be used.

[0124] In various embodiments, silicon or silicon-containing precursors may be substituted for lithium or lithium-containing precursors in the embodiments described above to allow for infiltration, impregnation, condensation, or deposition of silicon within a porous carbon material, thereby producing a Si-C compound for use in an anode of an electrical storage device.

[0125] In various embodiments, the reactors described above may receive electrochemical modifiers. The processes described above may cause doping of the electrochemical modifiers within the to-be-formed LiC compound. Other types of doping or dopants are described in more detail below.

[0126] As shown in FIGURES 15 and 16, various reaction schemes for producing the lithium-carbon composite in a plasma reactor are described in more detail below.

[0127] E. Specific Reaction Schemes for Producing Lithium-Carbon Composite Materials in a Plasma Reactor

[0128] E.l Scheme I: Pre-Mixed Solid Carbon and Solid Lithium Charged into the Plasma Reactor.

[0129] According to reaction Scheme I, the raw materials fed into the plasma reactor are solid carbon and solid lithium, and they are present in the plasma reactor as a pre-mixture, denoting the carbon and lithium are either mixed before being charged into the reactor, are mixed during the process of charging into the reactor, or are charged into the reactor as separate streams and subsequently mixed in the plasma reactor while heating the plasma reactor to the target process temperature. In all these embodiments, the solid carbon and solid lithium-containing precursor are mixed before being subject to heating the plasma reactor, this configuration is denoted as pre-mixing or a pre-mix.

[0130] In a solid lithium - solid carbon state section of the table of FIGURE 3, a fixed bed, an agitated bed with an introduced plasma heated inert gas, and / or pelletized precursors may be used. According to some embodiments for Scheme I, the solid carbon and solid lithium are introduced into the plasma as a pre-mixture, i.e., are pre-mixed prior to charging into the plasma reactor. In other embodiments, the solid carbon and solid lithium are mixed within the plasma reactor. The solid carbon and solid lithium can be charged into the plasma reactor as a pre-mixture and can be further mixed in the plasma reactor. In some embodiments, the solid carbon, the solid lithium, or the pre-mixture of solid lithium and solid carbon are subjected to diminution prior to charging, or during charging into to charging in the plasma reactor. The solid carbon and solid lithium pre-mixture can be held within in the plasma reactor in various form factors as known in that art, for example the pre-mixture can be present as a static bed, or can be an agitated bed, such as a fluid bed, vibratory bed, and the like. The process can be run as a batch process or as a continuous process.

[0131] In certain embodiment, the carbon is non-porous. In such embodiments, the non- porous carbon has a surface area less than 500 m2 / g, for example less than 400 m2 / g, or less than 300 m2 / g, or less than 200 m2 / g, or less than 100 m2 / g, or less than 50 m2 / g, or less than 30 m2 / g, or less than20 m2 / g, or less than 10 m2 / g, or less than 5 m2 / g, or less than 2 m2 / g, or less than 1 m2 / g.

[0132] The temperature within the plasma reactor can be between the melting point and boiling point of lithium, i.e., between 180.5 °C and 1330°C, such that the solid lithium is converted to a plasma-liquified form. Without being bound by theory, the plasma-liquified lithium may comprise lithium gas, lithium ions, lithium radicals, or combinations thereof. The solid carbon can be non-porous and the solid lithium is converted to a liquid form that incorporates into the solid carbon material to form the lithium carbon composite material. In a further specific embodiment, the lithium carbon composite material comprises lithium carbide. Accordingly, the lithium-carbon composite is produced in the plasma reactor involving the following steps (Scheme 1.1a): a) Providing a pre-mixture of non-porous solid carbon material and solid lithium material in the plasma reactor; b) heating the pre-mixture of non-porous solid carbon material and solid lithium material to a temperature between 180.5°C and 1330°C to provide a mixture of non-porous solid carbon and plasma-liquified lithium; and c) holding the mixture of non-porous solid carbon and plasma-liquified lithium at 180.5°C and 1330°C for sufficient time to incorporate liquid lithium into the solid carbon material to yield the lithium-carbon composite material.

[0133] In an alternate embodiment, the temperature within the plasma reactor is between 180.5 and 1330 C, the solid carbon is porous, and the solid lithium is converted to a liquid form that impregnates into the pores of the porous solid carbon material to form the lithium carbon composite material. In a further specific embodiment, the lithium carbon composite material comprises lithium carbide. Accordingly, the lithium-carbon composite is produced in the plasma reactor involving the following steps (Scheme 1.1b): a) Providing a pre-mixture of porous solid carbon material and solid lithium material in the plasma reactor; b) heating the pre-mixture of porous solid carbon material and solid lithium material to a temperature between 180.5°C and 1330°C to provide a mixture of porous solid carbon and liquid lithium; and c) holding the mixture of porous solid carbon and plasma-liquified liquid lithium at 180.5°C and 1330°C for sufficient time to impregnate liquid lithium into the pores of the solid carbon material to yield the lithium-carbon composite material.

[0134] The temperature within the plasma reactor can be above the boiling point of lithium, i.e., greater than 1330°C, such that the solid lithium is plasma-vaporized. Without being bound by theory, the resulting species in the plasma-vaporized lithium comprises lithium gas, lithium ions, lithium radicals, or combinations thereof. The solid carbon can be non-porous and the plasma-heated lithium incorporates into the solid carbon material to form the lithium carbon composite material. In a further specific embodiment, the lithium carbon composite material comprises lithium carbide. Accordingly, the lithium-carbon composite is produced in the plasma reactor involving the following steps (Scheme 1.2a): a) Providing a pre-mixture of non-porous solid carbon material and solid lithium material in the plasma reactor; b) heating the pre-mixture of solid carbon material and solid lithium material to a temperature greater than 1330°C to provide a mixture of non-porous solid carbon and plasma-vaporized lithium; and c) holding the mixture of non-porous solid carbon and plasma-vaporized lithium at greater than 1330°C for sufficient time to incorporate the plasma- heated lithium into the solid carbon material to yield the lithium-carbon composite material.

[0135] In an alternate embodiment, the temperature within the plasma reactor is above the boiling point of lithium, i.e., greater than 1330°C, the solid carbon is porous, and the plasma-vaporized lithium impregnates into the pores of the solid carbon material to form the lithium carbon composite material. Without being bound by theory, the plasma- vaporized lithium comprises lithium gas, lithium ions, lithium radicals, or combinations thereof. In a further specific embodiment, the lithium carbon composite material comprises lithium carbide. Accordingly, the lithium-carbon composite is produced in the plasma reactor involving the following steps (Scheme 1.2b): a] Providing a pre-mixture of porous solid carbon material and solid lithium material in the plasma reactor; b] heating the pre-mixture of porous solid carbon material and solid lithium material to a temperature greater than 1330°C to provide a mixture of non- porous solid carbon and plasm-vaporized lithium; and c] impregnating of plasma-vaporized lithium into the pores of the solid carbon material to yield the lithium-carbon composite material.

[0136] The source of solid lithium can be solid lithium metal and the form factor for the lithium can be provided as known in the art, for example lithium foil, lithium particles, stabilized lithium particles, and the like. The temperature in the plasma reactor is at or exceeding the melting point of lithium, and in another embodiment the temperature in the plasma reactor is at or exceeding the boiling point of lithium.

[0137] The solid carbon can be introduced into the plasma reactor in various form factors known in the art, such as monolithic, pellets, or particulate. In some embodiments, the carbon may be introduced into the plasma reactor as different allotropes, as discussed elsewhere in this disclosure. In some embodiments the carbon can be introduced into the plasma reactor as a combination of different carbon materials, which can vary in their allotrope and form factor as discussed elsewhere in this disclosure.

[0138] In some preferred embodiments, the carbon is porous, and comprises micropores, mesopore, and macropores. In other preferred embodiments, the carbon is porous, and comprises micropores and mesopores. According to the se embodiments, the micropore content as a fraction of the total pore volume can vary, for example from 0-10% or 10% to 20%, or 20% to 50%, or 50% to 70%, or 70% to 80% or 80% to 90% or greater than 90%. In further embodiments, the mesopore content as a fraction of the total pore volume can vary, for example from 0-10% or 10% to 20%, or 20% to 50%, or 50% to 70%, or 70% to 80% or 80% to 90% or greater than 90%. In further embodiments, the macropore content as a fraction of the total pore volume can vary, for example from 0-10% or 10% to 20%, or 20% to 50%, or 50% to 70%, or 70% to 80% or 80% to 90% or greater than 90%. It is also envisioned that the carbon porosity can be combination of fractional contents of micropores, mesopores, and macropores as elucidated above.

[0139] According to reaction Scheme 1, the raw materials fed into the plasma reactor are solid carbon and solid lithium, and they are present in the plasma reactor as a co-mixture that converts into the lithium-carbon composite product. According to some embodiments for Scheme 1, the solid carbon and solid lithium are introduced into the plasma as a mixture, i.e., are premixed prior to charging into the plasma reactor. In other embodiments, the solid carbon and solid lithium are mixed within the plasma reactor. The solid carbon and solid lithium can be held in the plasma reactor in various solid particle configurations as known in that art, for example the mixture can be present as a static bed, and can be an agitated bed, such as a fluid bed, vibratory bed, and the like.

[0140] E.2 Scheme 11: Separate Solid Carbon and Plasma-Liquified or Plasma- Vaporized Lithium Mixed in the Plasma Reactor

[0141] According to reaction Scheme 11, solid carbon is fed into the plasma reactor, and solid lithium is charged into the plasma reactor as a separate stream that is converted to either liquid lithium and / or lithium gas depending on the temperature, and the converted lithium combines with the solid carbon in the plasma reactor to yield the lithium-carbon composite material. The raw materials’ feed properties (solid carbon and solid lithium), the solid particles’ configurations (static, agitated, and the like) and process mode (batch or continuous) can vary as described for Scheme 1.

[0142] Plasma-melted lithium or plasma-vaporized lithium is introduced to a static bed of carbon. In another embodiment, vaporized lithium is introduced into an agitated bed of carbon, such as flowing particulate carbon in a gas stream, i.e., a flow parallel with solid particulate carbon, such as a fluid bed, or other configurations for agitating particles within the reactor, such as a vibratory reactor. In one embodiment, the particulate carbon is suspended in a gas stream including a gaseous lithium and / or Li-containing precursor and possibly other inert gases. The temperature of this gas mixture is hot enough to evaporate the Li or to decompose the Li precursor but not hot enough to evaporate the carbon.

[0143] The source of solid lithium can be solid lithium metal, and the form factor for the lithium can be provided as known in the art, for example lithium foil, lithium particles, stabilized lithium particles, and the like. The solid carbon can be introduced into the plasma reactor in various form factors known in the art, such as monolithic, pellets, or particulate. In some embodiments, the carbon may be introduced into the plasma reactor as different allotropes, as discussed elsewhere in this disclosure. In some embodiments the carbon can be introduced into the plasma reactor as a combination of different carbon materials, which can vary in their allotrope and form factor as discussed elsewhere in this disclosure.

[0144] In various embodiments, the carbon is porous, and comprises micropores, mesopore, and macropores. In other preferred embodiments, the carbon is porous, and comprises micropores and mesopores. According to the se embodiments, the micropore content as a fraction of the total pore volume can vary, for example from 0-10% or 10% to 20%, or 20% to 50%, or 50% to 70%, or 70% to 80% or 80% to 90% or greater than 90%. In further embodiments, the mesopore content as a fraction of the total pore volume can vary, for example from 0-10% or 10% to 20%, or 20% to 50%, or 50% to 70%, or 70% to 80% or 80% to 90% or greater than 90%. In further embodiments, the macropore content as a fraction of the total pore volume can vary, for example from 0-10% or 10% to 20%, or 20% to 50%, or 50% to 70%, or 70% to 80% or 80% to 90% or greater than 90%. It is also envisioned that the carbon porosity can be combination of fractional contents of micropores, mesopores, and macropores as elucidated above.

[0145] In various embodiments, surface area, pore volume, and % micro / meso / macro pore size fractions are determined via nitrogen gas adsorption on a Micromeritics® Tristar 11+ porosimeter at 77K using the density functional theory (DFT) model with carbon slit pore assumption from a relative partial pressure range of 0.01 - 0.99. In particular, the specific surface area (m2 / g) is calculated using the Brunauer-Emmett-Teller (BET) method from the relative partial pressure range of 0.01 - 0.1. The pore volume is determined from the single point adsorption of gas ata partial pressure of 0.97. The % micro / meso / macro pore size fractions is determined from the tabular plot of pore widths versus cumulative pore volume (cm3 / g) wherein the % microporosity is the fraction of cumulative pore volume contributed from the 0 - 2 nm pore width, the % mesopore fraction is the cumulative pore volume between 2 - 50 nm pore widths, and % macropore fraction is the cumulative pore volume greater than 50 nm.

[0146] Solid lithium can be charged into the plasma reactor at a temperature between the melting point and boiling point of lithium, i.e., between 180.5 °C and 1330°C, such that the solid lithium is converted to a liquid form, i.e., plasma-liquified lithium. Without being bound by theory, the plasma-liquified lithium may comprise lithium gas, lithium ions, lithium radicals, or combinations thereof. Separately, the solid non-porous carbon is charged into the plasma reactor. The plasma-liquefied lithium contacts the non-porous solid carbon in the plasma reactor, and subsequently the plasma-liquified lithium incorporates into the solid carbon material to form the lithium carbon composite material. In a further specific embodiment, the lithium carbon composite material comprises lithium carbide. Accordingly, the lithium-carbon composite is produced in the plasma reactor involving the following steps (Scheme 11.1a): a) Providing non-porous solid carbon material in the plasma reactor and heating the non-porous solid-carbon material in the plasma reactor to a temperature between 180.5°C and 1330°C; b) providing solid lithium in the plasma reactor at a temperature between 180.5°C and 1330°C to convert the solid lithium material to plasma-liquified lithium; c) contacting the plasma-liquified lithium and non-porous solid carbon in the plasma reactor to provide a mixture of non-porous solid carbon and plasma- liquified lithium; and d) holding the mixture of non-porous solid carbon and plasma-liquified lithium at 180.5°C and 1330°C for sufficient time to incorporate liquid lithium into the solid carbon material to yield the lithium-carbon composite material. In an alternate embodiment analogous to the above embodiment, the solid carbon is porous, the solid lithium is charged into the plasma reactor at a temperature between 180.5°C and 1330°C to convert the solid lithium material to plasma-liquified lithium, and subsequently the porous solid carbon material and the plasma-liquified lithium are contacted in the plasma reactor maintaining 180.5°C and 1330°C temperature such that the liquified lithium impregnates into the pores of the porous solid carbon material to form the lithium carbon composite material. Without being bound by theory, the plasma-liquified lithium may comprise lithium gas, lithium ions, lithium radicals, or combinations thereof. In a further specific embodiment, the lithium carbon composite material comprises lithium carbide. Accordingly, the lithium-carbon composite is produced in the plasma reactor involving the following steps (Scheme 11.1b): a) Providing porous solid carbon material in the plasma reactor and heating the porous solid-carbon material in the plasma reactor to a temperature between 180.5°C and 1330°C b) providing solid lithium in the plasma reactor at a temperature between 180.5°C and 1330°C to convert the solid lithium material to plasma-liquified lithium; c) contacting the plasma-liquified lithium and porous carbon in the plasma reactor to provide a mixture of porous solid carbon and plasma-liquified lithium; and d) holding the mixture of porous solid carbon and plasma-liquified lithium at 180.5°C and 1330°C for sufficient time for the plasma-liquified lithium to impregnate into the pores of the solid carbon material to yield the lithiumcarbon composite material.

[0147] The temperature within the plasma reactor can be above the boiling point of lithium, i.e., greater than 1330°C, such that the solid lithium is converted to plasma- vaporized lithium. Without being bound by theory, the plasma-vaporized lithium may comprise lithium gas, lithium ions, lithium radicals, or combinations thereof. The solid carbon can be non-porous and the solid lithium is converted to a gas form that incorporates into the non-porous solid carbon material to form the lithium carbon composite material. In a further specific embodiment, the lithium carbon composite material comprises lithium carbide. Accordingly, the lithium-carbon composite is produced in the plasma reactor involving the following steps (Scheme 11.2a): a) Providing non-porous solid carbon material in the plasma reactor and heating the non-porous solid-carbon material in the plasma reactor to a temperature above 1330°C; b) providing solid lithium in the plasma reactor at a temperature above 1330°C to convert the solid lithium material to plasma-vaporized lithium; c) contacting the plasma-vaporized lithium and non-porous solid carbon in the plasma reactor to provide a mixture of non-porous solid carbon and plasma- vaporized lithium; and d) holding the mixture of non-porous solid carbon and plasma-vaporized lithium at greater than 1330°C for sufficient time to incorporate plasma- vaporized lithium into the solid carbon material to yield the lithium-carbon composite material.

[0148] The temperature within the plasma reactor can be above the boiling point of lithium, i.e., greater than 1330°C, such that the solid lithium is converted to plasma- vaporized lithium. The solid carbon can be porous and the solid lithium is converted to a plasma-vaporized form that impregnates into the pores of the porous solid carbon material to form the lithium carbon composite material. Without being bound by theory, the plasma-vaporized lithium may comprise lithium gas, lithium ions, lithium radicals, or combinations thereof. In a further specific embodiment, the lithium carbon composite material comprises lithium carbide. Accordingly, the lithium-carbon composite is produced in the plasma reactor involving the following steps (Scheme 11.2b): a) Providing porous solid carbon material in the plasma reactor and heating the porous solid-carbon material in the plasma reactor to a temperature above 1330°C; b) providing solid lithium in the plasma reactor and heating the solid lithium in the plasma reactor to a temperature above 1330°C to convert the solid lithium material to plasma-vaporized lithium; c) contacting the plasma-vaporized lithium and porous solid carbon in the plasma reactor to provide a mixture of porous solid carbon and plasma- vaporized lithium; and d) holding the mixture of porous solid carbon and plasma-vaporized lithium at greater than 1330°C for sufficient time to impregnate plasma-vaporized lithium into the pores of the porous solid carbon material to yield the lithium-carbon composite material.

[0149] E.3 Scheme 111: Pre-Mixed Solid Carbon and Solid Lithium-Containing Precursor Charged into the Plasma Reactor (Reaction of Solid Carbon and Plasma-Pyrolyzed Lithium)

[0150] According to reaction Scheme 111, the raw materials fed into the plasma reactor are solid carbon and solid lithium-containing precursor, and they are present in the plasma reactor as a pre-mixture, denoting the carbon and lithium-containing precursor are either mixed before being charged into the reactor, or are mixed during the process of charging into the reactor, or are charged into the reactor as separate streams and subsequently mixed in the plasma reactor while heating the plasma reactor to the target process temperature. In all these embodiments, the solid carbon and solid lithium-containing precursor are mixed before being subject to heating in the plasma reactor, this configuration is denoted as pre-mixing or a pre-mix. The raw materials’ feed properties (solid carbon and solid lithium precursor), the solid particles’ configurations (static, agitated, and the like) and process mode (batch or continuous) can vary as described for Scheme 1.

[0151] In a solid lithium-containing precursor - solid carbon state section of the table 70, a fixed bed, an agitated bed with an introduced plasma heated inert gas, and / or pelletized precursors may be used.

[0152] According to some embodiments for Scheme 111, the solid carbon and solid lithium- containing precursor are introduced into the plasma as a pre-mixture, i.e., are pre-mixed prior to charging into the plasma reactor. In other embodiments, the solid carbon and solid lithium-containing precursor are mixed within the plasma reactor. The solid carbon and solid lithium can be charged into the plasma reactor as a pre-mixture and can be further mixed in the plasma reactor. In some embodiments, the solid carbon, the solid lithium- containing precursor, or the pre-mixture of solid lithium-containing precursor and solid carbon are subjected to diminution prior to charging, or during charging into to charging in the plasma reactor. The solid carbon and solid lithium-containing precursor pre-mixture can be held within in the plasma reactor in various form factors as known in that art, for example the pre-mixture can be present as a static bed, or can be an agitated bed, such as a fluid bed, vibratory bed, and the like. The process can be run as a batch process or as a continuous process.

[0153] The temperature within the plasma reactor can be between the melting point and boiling point of lithium, i.e., between 180.5 °C and 1330°C, such that the solid lithium- containing precursor is converted to plasma-pyrolyzed lithium-containing precursor, i.e., plasma-pyrolyzed lithium. Without being bound by theory, the plasma-pyrolyzed lithium may comprise liquid lithium, lithium ions, lithium radicals, or combinations thereof. The solid carbon can be non-porous and the plasma-pyrolyzed lithium incorporates into the solid carbon material to form the lithium carbon composite material. In a further specific embodiment, the lithium carbon composite material comprises lithium carbide. Accordingly, the lithium-carbon composite is produced in the plasma reactor involving the following steps (Scheme 111.1a): a) Providing a pre-mixture of non-porous solid carbon material and solid lithium-containing precursor material in the plasma reactor; b) heating the pre-mixture of non-porous solid carbon material and solid lithium material to a temperature between 180.5°C and 1330°C to provide a mixture of non-porous solid carbon and plasma-pyrolyzed lithium; and c) holding the mixture of non-porous solid carbon and plasma-pyrolyzed lithium at 180.5°C and 1330°C for sufficient time to incorporate plasma- pyrolyzed lithium into the solid carbon material to yield the lithium-carbon composite material.

[0154] In an alternate embodiment, the temperature within the plasma reactor is between 180.5 and 1330 C, the solid carbon is porous, and the solid lithium-containing precursor is plasma pyrolyzed resulting in conversion to liquid lithium that impregnates into the pores of the porous solid carbon material to form the lithium carbon composite material. In a further specific embodiment, the lithium carbon composite material comprises lithium carbide. Accordingly, the lithium-carbon composite is produced in the plasma reactor involving the following steps (Scheme 111.1b): a) Providing a pre-mixture of porous solid carbon material and solid lithium- containing precursor material in the plasma reactor; b) heating the pre-mixture of porous solid carbon material and solid lithium- containing precursor material to a temperature between 180.5°C and 1330°C to provide a mixture of porous solid carbon and plasma-pyrolyzed lithium; and c) holding the mixture of porous solid carbon and plasma-pyrolyzed lithium- containing precursor at 180.5°C and 1330°C for sufficient time to impregnate plasma-pyrolyzed lithium into the pores of the solid carbon material to yield the lithium-carbon composite material.

[0155] The temperature within the plasma reactor can be above the boiling point of lithium, i.e., greater than 1330°C, such that the solid lithium-containing precursor is plasma pyrolyzed. Without being bound by theory, the products of plasma pyrolysis may include lithium gas, lithium ions, lithium radicals, or combinations thereof. The solid carbon can be non-porous and the plasma-pyrolyzed lithium incorporates into the solid carbon material to form the lithium carbon composite material. In a further specific embodiment, the lithium carbon composite material comprises lithium carbide. Accordingly, the lithiumcarbon composite is produced in the plasma reactor involving the following steps (Scheme 111.2a): a) Providing a pre-mixture of non-porous solid carbon material and solid lithium-containing precursor material in the plasma reactor; b) heating the pre-mixture of solid carbon material and solid lithium material to a temperature greater than 1330°C to provide a mixture of non-porous solid carbon and the plasma-pyrolyzed lithium; and c) holding the mixture of non-porous solid carbon and plasma-pyrolyzed lithium-containing precursor at greater than 1330°C for sufficient time to impregnate the plasma-pyrolyzed lithium into the solid carbon material to yield the lithium-carbon composite material.

[0156] In an alternate embodiment, the temperature within the plasma reactor is above the boiling point of lithium, i.e., greater than 1330°C, the solid carbon is porous, and the solid lithium-containing precursor is plasma pyrolyzed. Without being bound by theory, the products of plasma pyrolysis may include lithium gas, lithium ions, lithium radicals, or combinations thereof. In a further specific embodiment, the lithium carbon composite material comprises lithium carbide. Accordingly, the lithium-carbon composite is produced in the plasma reactor involving the following steps (Scheme 111.2b) : a) Providing a pre-mixture of porous solid carbon material and solid lithium- containing material in the plasma reactor; b) heating the pre-mixture of porous solid carbon material and solid lithium- containing precursor material to a temperature greater than 1330°C to provide a mixture of porous solid carbon and plasma-pyrolyzed lithium; and c) holding the mixture of non-porous solid carbon and plasma-pyrolyzed lithium at greater than 1330°C for sufficient time to impregnate the plasma- pyrolyzed lithium into the pores of the porous carbon material to yield the lithium-carbon composite material.

[0157] E.4 Scheme IV: Separate Solid Carbon and Plasma-Pyrolyzed Lithium Mixed in the Plasma Reactor

[0158] According to reaction Scheme IV, solid carbon is fed into the plasma reactor, and solid lithium-containing precursor is charged into the plasma reactor as a separate stream that is plasma pyrolyzed and mixed with the solid carbon in the plasma reactor to yield the lithium-carbon composite material. The raw materials’ feed properties (solid carbon and solid lithium), the solid particles’ configurations (static, agitated, and the like) and process mode (batch or continuous) can vary as described for Scheme 1.

[0159] The plasma-pyrolyzed lithium-containing precursor is introduced to a static bed of carbon. In another embodiment, plasma-pyrolyzed lithium-containing precursor is introduced into an agitated bed of carbon, such as flowing particulate carbon in a gas stream, i.e., a flow parallel with solid particulate carbon, such as a fluid bed, or other configurations for agitating particles within the reactor, such as a vibratory reactor. In one embodiment, the particulate carbon is suspended in a gas stream including a gaseous lithium and / or lithium-containing precursor and possibly other inert gases. The temperature of this mixture is hot enough to plasma-pyrolyze the lithium-containing precursor but not hot enough to evaporate the carbon. Other aspects of plasma processing per Scheme IV include embodiments for the species and form factor of the lithium-containing precursor, properties of the carbon, properties of the plasma reactor, and so on, are described elsewhere within this disclosure.

[0160] Solid lithium-containing precursor is charged into the plasma reactor at a temperature between the melting point and boiling point of lithium, i.e., between 180.5 °C and 1330°C, such that the solid lithium-containing precursor materials is plasma pyrolyzed. Without being bound by theory, the plasma-liquified lithium may comprise liquid lithium, lithium ions, lithium radicals, or combinations thereof. Separately, the solid non-porous carbon is charged into the plasma reactor. The plasma-pyrolyzed lithium contacts the non- porous solid carbon in the plasma reactor, and subsequently the plasma-pyrolyzed lithium incorporates into the solid carbon material to form the lithium carbon composite material. In a further specific embodiment, the lithium carbon composite material comprises lithium carbide. Accordingly, the lithium-carbon composite is produced in the plasma reactor involving the following steps (Scheme IV. la): a) Providing non-porous solid carbon material in the plasma reactor and heating the non-porous solid-carbon material in the plasma reactor to a temperature between 180.5°C and 1330°C; b) providing solid lithium-containing precursor in the plasma reactor at a temperature between 180.5°C and 1330°C to provide for plasma-pyrolyzed lithium; c) contacting the plasma-pyrolyzed lithium and non-porous solid carbon in the plasma reactor to provide a mixture of non-porous solid carbon and plasma- pyrolyzed lithium; and d) holding the mixture of non-porous solid carbon and plasma-pyrolyzed lithium at 180.5°C and 1330°C for sufficient time to incorporate plasma- pyrolyzed lithium into the solid carbon material to yield the lithium-carbon composite material.

[0161] In an alternate embodiment, the temperature within the plasma reactor is between 180.5 and 1330 C, the solid carbon is porous, and in a separate stream entering the plasma reactor the solid lithium-containing precursor is plasma pyrolyzed and mixed with the porous carbon material such that the plasma-pyrolyzed lithium impregnates into the pores of the porous solid carbon material to form the lithium carbon composite material. In a further specific embodiment, the lithium carbon composite material comprises lithium carbide. Accordingly, the lithium-carbon composite is produced in the plasma reactor involving the following steps (Scheme IV. lb): a) Providing porous solid carbon material in the plasma reactor and heating the porous solid-carbon material in the plasma reactor to a temperature between 180.5°C and 1330°C; b] providing solid lithium-containing precursor in the plasma reactor at a temperature between 180.5°C and 1330°C to provide for plasma-pyrolyzed lithium; c] contacting the plasma-pyrolyzed lithium and porous solid carbon in the plasma reactor to provide a mixture of non-porous solid carbon and plasma- pyrolyzed lithium; and d] holding the mixture of non-porous solid carbon and plasma-pyrolyzed lithium at 180.5°C and 1330°C for sufficient time for impregnation of plasma- pyrolyzed lithium into the solid carbon material to yield the lithium-carbon composite material.

[0162] In an alternate embodiment, the temperature within the plasma reactor is greater than 1330°C, the solid carbon is non-porous, the solid lithium-containing precursor is plasma pyrolyzed, and the resulting plasma-pyrolyzed lithium is mixed with the porous carbon in the plasma reactor, and the plasma-pyrolyzed lithium incorporates into the non- porous carbon to yield the lithium-carbon composite as follows. In a further specific embodiment, the lithium carbon composite material comprises lithium carbide. Accordingly, the lithium-carbon composite is produced in the plasma reactor involving the following steps (Scheme lV.2a): a] Providing non-porous solid carbon material in the plasma reactor and heating the non-porous solid-carbon material in the plasma reactor to a temperature above 1330°C; b] providing solid lithium-containing precursor in the plasma reactor at a temperature between above 1330°C to provide for plasma-pyrolyzed lithium; c] contacting the plasma-pyrolyzed lithium and non-porous solid carbon in the plasma reactor to provide a mixture of non-porous solid carbon and plasma- pyrolyzed lithium; and d] holding the mixture of non-porous solid carbon and plasma-pyrolyzed lithium above 1330°C for sufficient time to incorporate plasma-pyrolyzed lithium into the solid carbon material to yield the lithium-carbon composite material.

[0163] In an alternate embodiment, the temperature within the plasma reactor is between above 1330 C, the solid carbon is porous, and in a separate stream entering the plasma reactor the solid lithium-containing precursor is plasma pyrolyzed and mixed with the porous carbon material such that the plasma-pyrolyzed lithium impregnates into the pores of the porous solid carbon material to form the lithium carbon composite material. In a further specific embodiment, the lithium carbon composite material comprises lithium carbide. Accordingly, the lithium-carbon composite is produced in the plasma reactor involving the following steps (Scheme lV.2b): a] Providing porous solid carbon material in the plasma reactor and heating the porous solid-carbon material in the plasma reactor to a temperature above 1330°C; b] providing solid lithium-containing precursor in the plasma reactor at a temperature above 1330°C to provide for plasma-pyrolyzed lithium; c] contacting the plasma-pyrolyzed lithium and porous solid carbon in the plasma reactor to provide a mixture of non-porous solid carbon and plasma- pyrolyzed lithium; and d] holding the mixture of non-porous solid carbon and plasma-pyrolyzed lithium above 1330°C for sufficient time for impregnation of plasma- pyrolyzed lithium into the solid carbon material to yield the lithium-carbon composite material.

[0164] E.5 Scheme V: Gaseous Carbon-Containing Precursor and Solid Lithium in the Plasma Reactor

[0165] According to reaction Scheme V, a gaseous carbon-containing precursor is fed into the plasma reactor, at a temperature sufficient to accomplish plasma pyrolysis of the gaseous carbon-containing precursor. Exemplary gaseous carbon-containing precursors include, but are not limited to, methane, propane, butane, cyclohexane, ethane, propylene, ethylene and acetylene. The temperature in the plasma reactor can be varied, for example the temperature in the plasma reactor can be between 100°C and 500°C, or 500°C to 1000°C, or 1000°C to 2000°C, or 2000°C to 3000°C, or greater than 3000°C, in order to provide plasma-pyrolyzed carbon. Solid lithium is introduced in the plasma reactor at a temperature between the melting point and boiling point of lithium, i.e., between 180.5 °C and 1330°C, to provide plasma-liquified lithium. The plasma-liquified lithium can be mixed with the plasma-pyrolyzed carbon in the plasma reactor in order to yield the lithiumcarbon composite material. The temperature of the mixture in the plasma reactor can be varied, for example the temperature in the plasma reactor can be between 100°C and 500°C, or 500°C to 1000°C, or 1000°C to 2000°C, or 2000°C to 3000°C, or greater than 3000°C, in order to provide lithium-carbon composite material. Accordingly, the lithiumcarbon composite is produced in the plasma reactor involving the following steps (Scheme V.la): a) Providing solid lithium in the plasma reactor at a temperature between 180.5°C and 1330°C to yield plasma-liquified lithium; b] providing gaseous carbon-containing precursor in the plasma reactor at a temperature suitable to yield plasma-pyrolyzed carbon; c) mixing the plasma-liquified lithium with the plasma-pyrolyzed carbon; and d) holding the mixture of plasma-liquified lithium and plasma-pyrolyzed carbon material in the plasma reactor at a temperature between 180.5°C and 1330°C to yield the lithium-carbon composite material.

[0166] In a similar embodiment, the lithium is heated in the plasma reactor at a temperature greater than 1330°C to yield plasma-vaporized lithium (Scheme V.lb). Accordingly, the lithium-carbon composite is produced in the plasma reactor involving the following steps (Scheme V.lb): a) Providing solid lithium in the plasma reactor at a temperature greater than 1330°C to yield plasma-vaporized lithium; b) providing gaseous carbon-containing precursor in the plasma reactor at a temperature suitable to yield plasma-pyrolyzed carbon; c) mixing the plasma-vaporized lithium with the plasma-pyrolyzed carbon; and d) holding the mixture of plasma-vaporized lithium and plasma-pyrolyzed carbon material in the plasma reactor at a temperature greater than 1330°C to yield the lithium-carbon composite material.

[0167] E.6 Scheme VI: Plasma-co-Pyrolysis of Gaseous Carbon-Containing Precursor and Lithium-Containing Precursor in the Plasma Reactor

[0168] According to reaction Scheme VI, a solid lithium-containing precursor is fed into the plasma reactor at a temperature sufficient to accomplish plasma-liquification, i.e., the solid lithium-containing precursor is heated in the plasma reactor to a temperature above the melting point of the lithium-containing precursor. Exemplary lithium-containing precursors and their melting points are described elsewhere in this disclosure. The plasma-liquified lithium-containing precursor and the gaseous carbon-containing precursor are mixed in the plasma reactor at a temperature sufficient to accomplish copyrolysis of the plasma-liquified lithium-containing precursor and the gaseous carbon- containing precursor to yield the lithium-carbon composite material. The temperature of the mixture in the plasma reactor can be varied, for example the temperature in the plasma reactor can be between 100°C and 500°C, or 500°C to 1000°C, or 1000°C to 2000°C, or 2000°C to 3000°C, or greater than 3000°C, in order to provide lithium-carbon composite material. Accordingly, the lithium-carbon composite is produced in the plasma reactor involving the following steps (Scheme VI. la): a) Providing solid lithium-containing precursor in the plasma reactor at a temperature above the melting point of the lithium-containing precursor to yield plasma-liquified lithium-containing precursor; b) mixing the plasma-liquified lithium-containing precursor with a gaseous carbon-containing precursor; and c) holding the mixture of plasma-liquified lithium-containing precursor and gaseous carbon-containing precursor in the plasma reactor at a temperature sufficient to accomplish co-plasma-pyrolysis of the mixture to yield the lithium-carbon composite material.

[0169] In a related embodiment, a solid lithium-containing precursor is fed into the plasma reactor at a temperature sufficient to accomplish plasma-vaporization, i.e., the solid lithium-containing precursor is heated in the plasma reactor to a temperature above the boiling point of the lithium-containing precursor. Exemplary lithium-containing precursors and their boiling points are described elsewhere in this disclosure. The plasma- vaporized lithium-containing precursor and the gaseous carbon-containing precursor are mixed in the plasma reactor at a temperature sufficient to accomplish co-pyrolysis of the plasma-vaporized lithium-containing precursor and the gaseous carbon-containing precursor to yield the lithium-carbon composite material. The temperature of the mixture in the plasma reactor can be varied, for example the temperature in the plasma reactor can be between 100°C and 500°C, or 500°C to 1000°C, or 1000°C to 2000°C, or 2000°C to 3000°C, or greater than 3000°C, in order to provide lithium-carbon composite material. Accordingly, the lithium-carbon composite is produced in the plasma reactor involving the following steps (Scheme VI. lb): a) Providing solid lithium-containing precursor in the plasma reactor at a temperature above the boiling point of the lithium-containing precursor to yield plasma-vaporized lithium-containing precursor; b) mixing the plasma-vaporized lithium-containing precursor with a gaseous carbon-containing precursor; and c) holding the mixture of plasma-vaporized lithium-containing precursor and gaseous carbon-containing precursor in the plasma reactor at a temperature sufficient to accomplish co-plasma-pyrolysis of the mixture to yield the lithium-carbon composite material.

[0170] F. Coatings Applied to Lithium-Carbon Composite

[0171] In certain embodiments, the lithium carbon composite particles include a terminal particle coating. Without being bound by theory, this coating can impart benefits such as enhanced electrochemical performance and increased safety for materials handling, battery construction and battery operation.

[0172] In certain embodiments, the surface layer can include a carbon layer. The surface layer is envisioned to provide for a suitable SEI layer. In this context, the surface carbon layer needs to be a good ionic conductor to shuttle Li-ions. Alternatively, the carbon layer can include an artificial SEI layer, for example the carbon layer can include poly(3,4- ethylenedioxythiophene)- co -poly (ethylene glycol) copolymer. The coating may include nitrogen and / or oxygen functionality to further improve the layer with respect to promoting a stable SEI layer. The coating needs to provide sufficient electrical conductivity, adhesion, and cohesion between particles. The surface should provide a stable SEI layer, the latter is typically included of species such as LiF, L12CO3, and Li2O. Inorganic material with relatively low bulk modulus may provide a more stable SEI layer, for example a more amorphous vs. crystalline layer is preferred, for instance Li2COs vs. LiF.

[0173] To this end, a layer of carbon can be applied to the lithium carbon composite particle. Without being bound by theory, this carbon layer should provide low surface area to provide a more stable SEI layer, higher first cycle efficiency, and greater cycle stability in a lithium-ion battery. Various carbon allotropes can be envisioned in the context of providing a surface layer to the silicon-impregnated porous carbon materials, including graphite, graphene, hard or soft carbons, for example pyrolytic carbon.

[0174] In alternative embodiments, the aforementioned coating can be achieved with a precursor solution as known in the art, followed by a carbonization process. For example, particles can be coated by a wurster process or related spray drying process known in the art to apply a thin layer of precursor material on the particles. The precursor coating can then be pyrolyzed, for example by further fluidization of the wurster-coated particles in the presence of elevated temperature and an inert gas as consistent with descriptions disclosed elsewhere herein.

[0175] In alternative embodiments, the particles can be covered in a carbonaceous layer accomplished by chemical vapor deposition (CVD). Without wishing to be bound by theory, it is believed that CVD methods to deposit carbon layers (e.g., from a hydrocarbon gas) result in a carbon that is graphitizable (also referred to as "soft" carbon in the art). Methodologies for CVD generally described in the art can be applied to the composite materials disclosed herein. CVD is generally accomplished by subjecting the composite particulate material for a period of time at elevated temperature in the presence of a suitable deposition gas containing carbon atoms. Suitable gases in this context include, but are not limited to methane, propane, butane, cyclohexane, ethane, propylene, ethylene and acetylene. The temperature can be varied, for example between 350 to 1050°C, for example between 350 and 450°C, for example between 450 and 550°C, for example between 550 and 650°C, for example between 650 and 750°C, for example between 750 and 850°C, for example between 850 and 950°C, for example between 950 and 1050°C. In certain embodiments, the deposition gas is methane and the deposition temperature is greater than or equal to 950°C. In certain embodiments, the deposition gas is propane and the deposition temperature is less than or equal to 750°C. In certain embodiments, the deposition gas is cyclohexane and the deposition temperature is greater than or equal to 800°C. In certain embodiments, the deposition gas is acetylene and the deposition temperature is greater than or equal to 400°C. In certain embodiments, the deposition gas is ethylene and the deposition temperature is greater than or equal to 500°C. In certain embodiments, the deposition gas is propylene and the deposition temperature is greater than or equal to 400°C.

[0176] In certain embodiments, the reactor to accomplish the coating can be agitated, in order to agitate the lithium carbon composite particles. In other exemplary modes, the particles can be fluidized, for example the impregnation with silicon-containing reactant can be carried out in a fluidized bed reactor. A variety of different reactor designs can be employed in this context as known in the art, including, but not limited to, elevator kiln, roller hearth kiln, rotary kiln, box kiln, and modified fluidized bed designs.

[0177] The thickness of the carbon coating can vary, for example 1-2 nm, 2-5 nm, 5-10 nm, 10-20 nm, 20-50 nm, or 50-100 nm. The mass percentage of the carbon coating on the lithium carbon composite particles as a fraction of the total particle mass can vary, for example 0.01-0.1%, 0.1-0.5%, 0.5-1%, 1-2%, 2-5%, or greater than 5%. In alternative embodiments, the terminal carbon coating can be 0.1% to 5 %.

[0178] The composite material including lithium and carbon can also include a terminal coating that does not include carbon. In some embodiments, such a non-carbonaceous coating can be accomplished by atomic layer deposition (ALD) as known in the art. The thickness of the ALD coating can vary, for example 1-2 nm, 2-5 nm, 5-10 nm, 10-20 nm, 20- 50 nm, or 50-100 nm. The mass percentage of the ceramic coating on the lithium carbon composite particles as a fraction of the total particle mass can vary, for example 0.01-0.1%, 0.1-0.5%, 0.5-1%, 1-2%, 2-5%, or greater than 5%. Exemplary non-carbonaceous coatings in this regard include, but are not limited to, oxides including aluminum, oxides including zirconium, and oxides including titanium. In alternative embodiments, the terminal ALD coating can be 0.1% to 5 %.

[0179] The lithium carbon composite material can also be terminally carbon coated via a hydrothermal carbonization wherein the particles are processed by various modes according to the art. Hydrothermal carbonization can be accomplished in an aqueous environment at elevated temperature and pressure. Examples of temperature to accomplish the hydrothermal carbonization vary, for example between 150°C and 300°C, for example, between 170°C and 270°C, for example between 180°C and 260°C, for example, between 200 and 250°C. Alternatively, the hydrothermal carbonization can be carried out at higher temperatures, for example, between 200 and 1000°C, for example, between 300 and 400°C, for example between 400 and 600°C, for example between 600 and 750°C, for example between 750 and 1000°C. In some embodiments, the hydrothermal carbonization can be carried out at a temperature and pressure to achieve graphitic structures. The range of pressures suitable for conducting the hydrothermal carbonization are known in the art, and the pressure can vary, for example, increase, over the course of the reaction. The pressure for hydrothermal carbonization can vary from 0.1 MPa to 200 MPA. In certain embodiments the pressure of hydrothermal carbonization is between 0.5 MPa and 5 MPa. In other embodiments, the pressure of hydrothermal carbonization is between 1 MPa and 10 MPa, or between 5 and 20 MPa. In yet other embodiments, the pressure of hydrothermal carbonization is between 10 MPa and 50 MPa. In yet other embodiments, the pressure of hydrothermal carbonization is between 50 MPa and 150 MPa. In yet other embodiments, the pressure of hydrothermal carbonization is between 100 MPa and 200 MPa. Feedstock suitable as a carbon source for hydrothermal carbonization are also known in the art. Such feedstocks for hydrothermal carbonization typically include carbon and oxygen, these include, but are not limited to, sugars, oils, biowastes, polymers, and polymer precursors described elsewhere within this disclosure. In further embodiments, the hydrocarbon gas may be methane, propane, ethane, butane, butylene, benzene, toluene, styrene, propylene, or acetylene.

[0180] G. Doping with Electrochemical Modifiers

[0181] In certain embodiments, the lithium carbon composite material can be doped with species that accomplish modification of electrochemical properties. Such electrochemical modifiers can provide enhanced electrochemical properties including, but not limited to, increased capacity, reduced resistance, increased storage stability, lithium metal dendrite suppression, and increased cycle stability.

[0182] In some embodiments, the electrochemical modifier serves to suppress lithium dendrite formation. Lithium dendrite growth as a result of continuous (and often high rate) lithium plating / stripping can lead to battery failure (sometimes catastrophic) as a result of shorting the electrodes together. Porous carbon particles and / or electrodes thereof decorated with nano-metal seeds e.g., Sn, Ni, In, Ag, Zn, Al, etc.) can alloy and / or form eutectics with lithium prior to reaching plating voltages. This can act to suppress dendrite formation by mitigating high localized current regions and lowering the overpotential (and thus resistance) for lithium plating. In certain related embodiments, the electrochemical modifier is a metal oxide, for example an oxide of Sn, Ni, In, Ag, Zn, Al, etc., or combinations thereof. In certain related embodiments, the electrochemical modifier includes a phosphate, for example transition metal phosphate, alkali metal phosphate, or rare weather metal phosphates.

[0183] In certain embodiments, the electrochemical modifier can be as a non-metal dopant, for example, oxygen, nitrogen, fluorine, chlorine, phosphorus, silicon, transition metal, and the like. Without bound by theory, the non-metal dopant serves as an electronegative site to attract and grow lithium.

[0184] H. Physico- and Electrochemical Properties of Lithium-Carbon Composite

[0185] In certain embodiments, the lithium particles embedded within the composite include nano-sized features. The nano-sized features can have a characteristic length scale, for example less than 2 nm, 2 nm to 50 nm, or greater than 50 nm.

[0186] The dispensation of the lithium within the carbon composite can vary, for example the lithium can be impregnated into the pores of the porous carbon, where the fractional filling of the carbon internal void volume can vary. For example, the percent filling of the lithium within the total carbon pore volume can be 1 to 90%, for example, 1% to 10%, 10% to 20%, 20% to 30%, 30% to 40%, 40% to 50%, 50% to 60%, 60% to 70%, 70% to 80%, or 80% to 90%, Alternatively, the percent filling of the lithium within the total carbon pore volume can be 15 to 85%, for example, 20% to 80%, 30% to 70%, or 40% to 60%.

[0187] The lithium domains can be interspersed into the carbon skeletal structure, and / or the lithium domains can be completely surrounded by carbon. The geometry of the lithium domains within the carbon can vary, for example can be spherical, cylindrical, or tortuous structures. In some embodiments, the lithium exists as a layer coating the inside of pores within the porous carbon scaffold.

[0188] The size of the impregnated lithium can vary, for example less than 2 nm, 2 nm to 5 nm, 5 nm to 10 nm, 5 nm to 20 nm, 5 nm to 30 nm, 2 nm to 50 nm, 2 nm to 30 nm, 5 nm to 50 nm, 10 nm to 100 nm, 10 to 150 nm, 50 nm to 150 nm, 300 nm to 1000 nm, or 2 nm to 1000 nm.

[0189] Certain physicochemical and electrochemical properties of the lithium carbon composite can vary. Certain such properties are exemplified in Table 1.

[0190] Table 1. Embodiments for lithium carbon composite properties.

[0191] According to Table 1, the lithium carbon composite may include combinations of various properties. For example, the lithium carbon composite may include surface area less than 100 m2 / g, a first cycle efficiency greater than 80%, and a reversible capacity of at least 1300 mAh / g; or may include surface area less than 100 m2 / g, a first cycle efficiency greater than 80%, and a reversible capacity of at least 1600 mAh / g; or may include surface area less than 20 m2 / g, a first cycle efficiency greater than 85%, and a reversible capacity of at least 1600 mAh / g; or may include, surface area less than 10 m2 / g, a first cycle efficiency greater than 85%, and a reversible capacity of at least 1600 mAh / g; or may include surface area less than 10 m2 / g, a first cycle efficiency greater than 90%, and a reversible capacity of at least 1600 mAh / g; or may include surface area less than 10 m2 / g, a first cycle efficiency greater than 90%, and a reversible capacity of at least 1800 mAh / g. The lithium carbon composite can include a combination of the aforementioned properties, in addition to also including a carbon scaffold including properties also described herein. Accordingly, Table 2 provides a description of certain embodiments for combination of properties for the lithium carbon composite. Table 2. Embodiments for lithium carbon composite properties.

[0192] As used in herein, the percentage "microporosity," "mesoporosity" and "macroporosity" refers to the percent of micropores, mesopores and macropores, respectively, as a percent of total pore volume. For example, a carbon scaffold having 90% microporosity is a carbon scaffold where 90% of the total pore volume of the carbon scaffold is formed by micropores.

[0193] According to Table 2, the lithium carbon composite may include combinations of various properties. For example, the lithium carbon composite may include surface area less than 100 m2 / g, a first cycle efficiency greater than 80%, a reversible capacity of at least 1600 mAh / g, a lithium content of 15%-85%, a carbon scaffold total pore volume of 0.2- 1.2 cm3 / g wherein the scaffold pore volume includes >80% micropores, <20% mesopores, and <10% macropores. For example, the lithium carbon composite may include surface area less than 20 m2 / g, a first cycle efficiency greater than 85%, and a reversible capacity of at least 1600 mAh / g, a lithium content of 15%-85%, a carbon scaffold total pore volume of 0.2-1.2 cm3 / g wherein the scaffold pore volume includes >80% micropores, <20% mesopores, and <10% macropores. For example, the lithium carbon composite may include surface area less than 10 m2 / g, a first cycle efficiency greater than 85%, and a reversible capacity of at least 1600 mAh / g, a lithium content of 15%-85%, a carbon scaffold total pore volume of 0.2- 1.2 cm3 / g wherein the scaffold pore volume includes >80% micropores, <20% mesopores, and <10% macropores. For example, the lithium carbon composite may include surface area less than 10 m2 / g, a first cycle efficiency greater than 90%, and a reversible capacity of at least 1600 mAh / g, a lithium content of 15%-85%, a carbon scaffold total pore volume of 0.2- 1.2 cm3 / g wherein the scaffold pore volume includes >80% micropores, <20% mesopores, and <10% macropores. For example, the lithium carbon composite may include area less than 10 m2 / g, a first cycle efficiency greater than 90%, and a reversible capacity of at least 1800 mAh / g, a lithium content of 15%-85%, a carbon scaffold total pore volume of 0.2-1.2 cm3 / g wherein the scaffold pore volume includes >80% micropores, <20% mesopores, and <10% macropores.

[0194] Also, according to Table 2, the lithium carbon composite may include a carbon scaffold with >80% micropores, lithium content of 30-60%, and average Coulombic efficiency of >0.9969. For example, the lithium carbon composite may include a carbon scaffold with >80% micropores, lithium content of 30-60%, average Coulombic efficiency of >0.9970, and Z<10. For example, the lithium carbon composite may include a carbon scaffold with >80% micropores, lithium content of 30-60%, and average Coulombic efficiency of >0.9975. For example, the lithium carbon composite may include a carbon scaffold with >80% micropores, lithium content of 30-60%, and average Coulombic efficiency of >0.9980. For example, the lithium carbon composite may include a carbon scaffold with >80% micropores, lithium content of 30-60%, and average Coulombic efficiency of >0.9985. For example, the lithium carbon composite may include a carbon scaffold with >80% micropores, lithium content of 30-60%, and average Coulombic efficiency of >0.9990. For example, the lithium carbon composite may include a carbon scaffold with >80% micropores, lithium content of 30-60%, and average Coulombic efficiency of >0.9995. For example, the lithium carbon composite may include a carbon scaffold with >80% micropores, lithium content of 30-60%, and average Coulombic efficiency of >0.9970. For example, the lithium carbon composite may include a carbon scaffold with >80% micropores, lithium content of 30-60%, and average Coulombic efficiency of >0.9999.

[0195] Without being bound by theory, the filling of lithium within the pores of the porous carbon traps porosity within the porous carbon scaffold particle, resulting in inaccessible volume, for example volume that is inaccessible to nitrogen gas. Accordingly, the lithium carbon composite material may exhibit a pycnometry density of less than 2.1 g / cm3, for example less than 2.0 g / cm3, for example less than 1.9 g / cm3, for example less than 1.8 g / cm3, for example less than 1.7 g / cm3, for example less than 1.6 g / cm3, for example less than 1.4 g / cm3, for example less than 1.2 g / cm3, for example less than 1.0 g / cm3.

[0196] In some embodiments, the lithium carbon composite material may exhibit a pycnometry density between 1.7 g / cm3and 2.1 g / cm3, for example between 1.7 g.cm3 and 1.8 g / cm3, between 1.8 g.cm3 and 1.9 g / cm3, for example between 1.9 g.cm3 and 2.0 g / cm3, for example between 2.0 g.cm3 and 2.1 g / cm3. In some embodiments, the lithium carbon composite material may exhibit a pycnometry density between 1.8 g / cm3and 2.1 g / cm3. In some embodiments, the lithium carbon composite material may exhibit a pycnometry density between 1.8 g.cm3 and 2.0 g / cm3. In some embodiments, the lithium carbon composite material may exhibit a pycnometry density between 1.9 g / cm3and 2.1 g / cm3.

[0197] The pore volume of the composite material exhibiting extremely durable intercalation of lithium can range between 0.01 cm3 / g and 0.2 cm3 / g. In certain embodiments, the pore volume of the composite material can range between 0.01 cm3 / g and 0.15 cm3 / g, for example between 0.01 cm3 / g and 0.1 cm3 / g, for example between 0.01 cm3 / g and 0.05 cm3 / g.

[0198] The particle size distribution of the composite material exhibiting extremely durable intercalation of lithium is important to both determine power performance as well as volumetric capacity. As the packing improves, the volumetric capacity may increase. In one embodiment the distributions are either Gaussian with a single peak in shape, bimodal, or polymodal (>2 distinct peaks, for example trimodal). The properties of particle size of the composite can be described by the DO (smallest particle in the distribution), Dv50 (average particle size) and DvlOO (maximum size of the largest particle). The optimal combination of particle packing and performance will be some combination of the size ranges below. The particle size reduction in such embodiments can be carried out as known in the art, for example by jet milling in the presence of various gases including air, nitrogen, argon, helium, supercritical steam, and other gases known in the art.

[0199] In one embodiment the DvO of the composite material can range from 1 nm to 5 microns. In another embodiment the DvO of the composite ranges from 5 nm to 1 micron, for example 5-500 nm, for example 5-100 nm, for example 10-50 nm. In another embodiment the DvO of the composite ranges from 500 nm to 2 microns, or 750 nm to 1 pm, or 1-2 pm to 2 microns. In other embodiments, the DvO of the composite ranges from 2-5 pm, or > 5 pm.

[0200] In some embodiments the Dv50 of the composite material ranges from 5 nm to 20 pm. In other embodiments the Dv50 of the composite ranges from 5 nm to 1 pm, for example 5-500 nm, for example 5-100 nm, for example 10-50 nm. In another embodiment the Dv50 of the composite ranges from 500 nm to 2 pm, 750 nm to 1 pm, 1-2 pm. In still other embodiments, the Dv50 of the composite ranges from 1 to 1000 pm, for example from 1-100 pm, for example from 1-10 pm, for example 2-20 pm, for example 3-15 pm, for example 4-8 pm. In certain embodiments, the Dv50 is >20 pm, for example >50 pm, for example >100 pm.

[0201] The span [Dv90-Dvl0] / (Dv50], wherein DvlO, Dv50 and Dv90 represent the particle size at 10%, 50%, and 90% of the volume distribution, can be varied from example from 100 to 10, from 10 to 5, from 5 to 2, from 2 to 1; in some embodiments the span can be less than 1. In certain embodiments, the composite including carbon and porous lithium material particle size distribution is unimodal. In certain embodiments, the composite including carbon and porous lithium material particle size distribution has a right-hand skew. In certain embodiments, the composite including carbon and porous lithium material particle size distribution has a left-hand skew. In certain embodiments, the composite including carbon and porous lithium material particle size distribution can be multimodal, for example, bimodal, or trimodal.

[0202] The surface functionality of the presently disclosed composite material exhibiting extremely durable intercalation of lithium may be altered to obtain the desired electrochemical properties. One property which can be predictive of surface functionality is the pH of the composite materials. The presently disclosed composite materials include pH values ranging from less than 1 to about 14, for example less than 5, from 5 to 8 or greater than 8. In some embodiments, the pH of the composite materials is less than 4, less than 3, less than 2 or even less than 1. In other embodiments, the pH of the composite materials is between about 5 and 6, between about 6 and 7, between about 7 and 8 or between 8 and 9 or between 9 and 10. In still other embodiments, the pH is high and the pH of the composite materials ranges is greater than 8, greater than 9, greater than 10, greater than 11, greater than 12, or even greater than 13. The lithium carbon composite material may include varying amounts of carbon, oxygen, hydrogen, and nitrogen as measured by gas chromatography CHNO analysis. In one embodiment, the carbon content of the composite is greater than 98 wt% or even greater than 99.9 wt% as measured by CHNO analysis. In another embodiment, the carbon content of the lithium-carbon composite ranges from about 10-90%, for example 20-80%, for example 30-70%, for example 40-60%.

[0203] In some embodiments, lithium carbon composite material includes a nitrogen content ranging from 0-90%, for example 0.1-1%, for example 1-3%, for example 1-5%, for example 1-10%, for example 10-20%, for example 20-30%, for example 30-90%.

[0204] In some embodiments, the oxygen content ranges from 0-90%, for example 0.1-1%, for example 1-3%, for example 1-5%, for example 1-10%, for example 10-20%, for example 20-30%, for example 30-90%.

[0205] The morphology of the carbon scaffold particles can vary. For example, the carbon scaffold particles are spherical in shape. In certain embodiments, the morphology of the lithium carbon particles are spherical in shape the surface morphology of the The lithium carbon composite material may also incorporate an electrochemical modifier selected to optimize the electrochemical performance of the non-modified composite. The electrochemical modifier may be incorporated within the pore structure and / or on the surface of the porous carbon scaffold, within the embedded lithium, or within the final layer of carbon, or conductive polymer, coating, or incorporated in any number of other ways. For example, in some embodiments, the composite materials include a coating of the electrochemical modifier (e.g., lithium or AI2O3) on the surface of the carbon materials. In some embodiments, the composite materials include greater than about 100 ppm of an electrochemical modifier. In certain embodiments, the electrochemical modifier is selected from iron, tin, silicon, nickel, aluminum and manganese.

[0206] In certain embodiments the electrochemical modifier includes an element with the ability to lithiate from 3 to 0 V versus lithium metal {e.g., silicon, tin, sulfur). In other embodiments, the electrochemical modifier includes metal oxides with the ability to lithiate from 3 to 0 V versus lithium metal e.g., iron oxide, molybdenum oxide, titanium oxide). In still other embodiments, the electrochemical modifier includes elements which do not lithiate from 3 to 0 V versus lithium metal {e.g., aluminum, manganese, nickel, metal- phosphates). In yet other embodiments, the electrochemical modifier includes a non-metal element {e.g., fluorine, nitrogen, hydrogen). In still other embodiments, the electrochemical modifier includes any of the foregoing electrochemical modifiers or any combination thereof {e.g., tin-silicon, nickel-titanium oxide).

[0207] The electrochemical modifier may be provided in any number of forms. For example, in some embodiments the electrochemical modifier includes a salt. In other embodiments, the electrochemical modifier includes one or more elements in elemental form, for example elemental iron, tin, silicon, nickel, or manganese. In other embodiments, the electrochemical modifier includes one or more elements in oxidized form, for example iron oxides, tin oxides, silicon oxides, nickel oxides, aluminum oxides or manganese oxides.

[0208] In certain embodiments, an oxidized porous carbon is prepared by heating a porous carbon as free flowing powder of monolith to between 300°C and 1000°C, or more preferably 400-500°C, under ambident air gas flow in a horizontal tube furnace and allowed to dwell from 0-12 hour, or more preferably 0.25-1 hour. The air flow may contain a concentration of oxygen between 1-100 mol%. The material is subsequently cooled to room temperature and removed from the furnace. The resulting oxidized porous carbon material is attrition milled to less than 25-micron particle size distribution for preparation of electrodes. This porous carbon is rich in oxygen surface functionality which facilitates formation of lithium oxides in the initial stage of electrochemical plating of lithium metal in a lithium-ion battery, thereby increasing the lithiophiolicity and reduction of detrimental dendrite growth.

[0209] The electrochemical properties of the composite material can be modified, at least in part, by the amount of the electrochemical modifier in the material, wherein the electrochemical modifier is an alloying material such as silicon, tin, indium, aluminum, germanium, gallium. Accordingly, in some embodiments, the composite material includes at least 0.10%, at least 0.25%, at least 0.50%, at least 1.0%, at least 5.0%, at least 10%, at least 25%, at least 50%, at least 75%, at least 90%, at least 95%, at least 99% or at least 99.5% of the electrochemical modifier.

[0210] The particle size of the composite material may expand upon full lithiation as compared to the non-lithiated composite state. For example, the expansion factor, defined as ratio of the average particle size of particles of composite material upon lithiation divided by the average particle size under non-lithiated conditions. As described in the art, this expansion factor can be relatively large for previously known, non-optimal silicon- containing materials, for example about 4X (corresponding to a 400% volume expansion upon lithiation). The current inventors have discovered composite materials including a lithium composite material that can exhibit a lower extent of expansion, for example, the expansion factor can vary from 3.5 to 4, from 3.0 to 3.5, from 2.5 to 3.0, from 2.0 to 2.5, from 1.5 to 2.0, from 1.0 to 1.5.

[0211] It is envisioned that composite materials in certain embodiments will include a fraction of trapped pore volume, namely, void volume non-accessible to nitrogen gas as probed by nitrogen gas sorption measurement. Without being bound by theory, this trapped pore volume is important in that it provides volume into which silicon can expand upon lithiation. The internal void volume can be determined by various methods, such from pycnometry density and / or press density. In certain embodiments, the ratio of trapped void volume to the lithium volume including the composite particle is between 0.1:1 and 10:1. For example, the ratio of trapped void volume to the silicon volume including the composite particle is between 1:1 and 5:1, or 5:1 to 10:1. In embodiments, the ratio of ratio of trapped void volume to the lithium volume including the composite particle is between 2:1 and 5:1, or about 3:1.

[0212] In certain embodiments, the electrochemical performance of the composite disclosed herein is tested in a half-cell; alternatively, the performance of the composite is tested in a full cell, for example a full cell coin cell, a full cell pouch cell, a prismatic cell, or other battery configurations known in the art. The anode composition including the composite can further include various species, as known in the art. Additional formulation components include, but are not limited to, conductive additives, such as conductive carbons such as Super C45, Super P, Ketjenblack carbons, and the like, conductive polymers and the like, binders such as styrene-butadiene rubber sodium carboxymethylcellulose (SBR-Na-CMC), polyvinylidene difluoride (PVDF), polyimide (PI), polyacrylic acid (PAA) and the like, and combinations thereof. In certain embodiments, the binder can include a lithium ion as a counterion (e.g., lithium polyacrylic acid (LiPAA), lithium carboxymethylcellulose (Li-CMC), etc.).

[0213] Other species including the electrode are known in the art. The % of active material in the electrode by weight can vary, for example between 1 and 5 %, for example between 5 and 15%, for example between 15 and 25%, for example between 25 and 35%, for example between 35 and 45%, for example between 45 and 55%, for example between 55 and 65%, for example between 65 and 75%, for example between 75 and 85%, for example between 85 and 95%. In some embodiments, the active material includes between 80 and 95% of the electrode. In certain embodiments, the amount of conductive additive in the electrode can vary, for example between 1 and 5%, between 5 and 15%, for example between 15 and 25%, for example between 25 and 35%. In some embodiments, the amount of conductive additive in the electrode is between 5 and 25%. In certain embodiments, the amount of binder can vary, for example between 1 and 5%, between 5 and 15%, for example between 15 and 25%, for example between 25 and 35%. In certain embodiments, the amount of conductive additive in the electrode is between 5 and 25%.

[0214] The anode including the lithium carbon composite material can be paired with various cathode materials to result in a full cell lithium-ion battery. Examples of suitable cathode materials are known in the art. Examples of such cathode materials include, but are not limited to LiCot (LCO), LiNi0.8Co0.15Al0.05O2 (NCA), LiNii / sCoi / sMm / sOz (NMC), LiNio.5Mm.5O4 (LNMO), LiMmO4 and variants (LMO), LiFeP04 (LFP), FeF2, CuF2, and S.

[0215] For the full cell lithium carbon battery including a lithium carbon composite, the pairing of cathode to anode can be varied. For example, the ratio of cathode-to-anode capacity can vary from 0.7 to 1.3. In certain embodiments, the ratio of cathode-to-anode capacity can vary from 0.7 to 1.0, for example from 0.8 to 1.0, for example from 0.85 to 1.0, for example from 0.9 to 1.0, for example from 0.95 to 1.0. In other embodiments, the ratio of cathode-to-anode capacity can vary from 1.0 to 1.3, for example from 1.0 to 1.2, for example from 1.0 to 1.15, for example from 1.0 to 1.1, for example from 1.0 to 1.05. In yet other embodiments, the ratio of cathode-to-anode capacity can vary from 0.8 to 1.2, for example from 0.9 to 1.1, for example from 0.95 to 1.05.

[0216] For the full cell lithium carbon battery including the lithium carbon composite, the voltage window for charging and discharging can be varied. In this regard, the voltage window can be varied as known in the art. For instance, the choice of cathode plays a role in the voltage window chosen, as known in the art. Examples of voltage windows vary, for example, in terms of potential versus Li / Li+, from 2.0 V to 5.0 V, for example from 2.5 V to 4.5V, for example from 2.5V to 4.2V. In such embodiments, the plating voltage of the lithium carbon composite anode (charging of the battery) occurs between 0 and -100 mV, for example between 0 and -50 mV, for example between 0 and -40 mV, for example between 0 and -30 m, for example between 0 and -20 mV, for example between 0 and -10 mV, for example between 0 and -5 mV, for example between 0 and -1 mV.

[0217] To assess the ability of the lithium carbon anode to suppress lithium dendrite formation upon constant current charge / discharge cycling, one can assess the performance of a half cell with lithium metal foil as the counter electrode and the lithium carbon composite as the active material included within the working electrode. Specifically, the electrochemical test of the half-cell includes constant current charge / discharge cycling, with the desired result to minimize or eliminate short circuiting due to lithium dendrite formation.

[0218] For the full cell lithium carbon battery including the lithium carbon composite, the strategy for conditioning the cell can be varied as known in the art. For example, the conditioning can be accomplished by one or more charge and discharge cycles at various rate(s), for example at rates slower than the desired cycling rate. As known in the art, the conditioning process may also include a step to unseal the lithium-ion battery, evacuate any gases generated during the conditioning process, followed by resealing the lithium-ion battery.

[0219] For the lithium carbon battery including the lithium carbon composite, the cycling rate can be varied as known in the art, for example, the rate can between C / 20 and 20C, for example between CIO to 10C, for example between C / 5 and 5C. In certain embodiments, the cycling rate is C / 10. In certain embodiments, the cycling rate is C / 5. In certain embodiments, the cycling rate is C / 2. In certain embodiments, the cycling rate is 1C. In certain embodiments, the cycling rate is 1C, with periodic reductions in the rate to a slower rate, for example cycling at 1C with a C / 10 rate employed every 20thcycle. In certain embodiments, the cycling rate is 2C. In certain embodiments, the cycling rate is 4C. In certain embodiments, the cycling rate is 5C. In certain embodiments, the cycling rate is 10C. In certain embodiments, the cycling rate is 20C. The lithium carbon exhibits a first cycle efficiency (FCE), as measured in a half or full cell as described above. In preferred embodiments, the FCE is greater or equal to 70%, for example 80%, for example 85%, for example 90%, for example 95%, for example 96%, for example 98%, for example 99%.

[0220] In certain embodiments, the electrolyte can include various additives known to provide improved performance, such as fluoroethylene carbonate (FEC) or other related fluorinated carbonate compounds, or ester co-solvents such as methyl butyrate, vinylene carbonate, and other electrolyte additives known to improve electrochemical performance.

[0221] Coulombic efficiency can be averaged, for example averaged over cycles 2 or later to cycle 20 or later when tested in a half cell. In certain embodiments, the average efficiency of the composite with extremely durable intercalation of lithium is greater than 0.9, or 90%. In certain embodiments, the average efficiency is greater than 0.95, or 95%. In certain other embodiments, the average efficiency is 0.99 or greater, for example 0.991 or greater, for example 0.992 or greater, for example 0.993 or greater, for example 0.994 or greater, for example 0.995 or greater, for example 0.996 or greater, for example 0.997 or greater, for example 0.998 or greater, for example 0.999 or greater, for example 0.9991 or greater, for example 0.9992 or greater, for example 0.9993 or greater, for example 0.9994 or greater, for example 0.9995 or greater, for example 0.9996 or greater, for example 0.9997 or greater, for example 0.9998 or greater, for example 0.9999 or greater.

[0222] The lithium carbon composite materials disclosed herein have utility as the key battery active material for lithium carbon batteries. For example, an anode-free electrochemical cell in which a freestanding lithium carbon composite acts as both the current collector and lithium host, rather than a conventional copper current collector. For example, an electrochemical cell in which the lithium carbon composite acts as the lithium source rather than a conventional intercalation-type cathode. For example, in a Li-ion capacitor application in which the lithium carbon composite acts as the Li-bearing anode paired with an activated carbon cathode.

[0223] EXAMPLES

[0224] Example 1. Properties of various carbon scaffold materials. The properties of various carbon scaffold materials are presented in Table 3. The exemplary carbon materials vary in properties such as total pore volume (for example varying from 0.5 to greater than 2 cm3 / g, and also varying percentages of micro-, meso- and macropores.

[0225] Example 2. Melt infusion method of synthesis for lithium carbon composite (LCC). In a typical but preferred embodiment a portion of micronized porous carbon powder is placed in a metal or ceramic crucible and physically mixed with a portion of lithium metal in the form of foil or powder. The Li: C weight ratio is adjusted so as to partially fill the available pore volume of the carbon allowing for some residual void {e.g., 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1 w / w Li:C). The mixture is then heated under in an inert atmosphere {e.g., argon, nitrogen, helium, or vacuum) to at least the melting point of the lithium metal (e.g., 180°C, 190°C, 200°C, 220°C, 250°C, 300°C, 400°C, etc.). The mixture dwells at peak temperature for a period of time {e.g., O.lhr, Ihr, 2hr, 5hr, lOhr, 24hr, etc.) to allow molten lithium to permeate the carbon pore structure via capillary forces. The LCC is formed at this time then subsequently cooled to ambient temperature and removed for processing.

[0226] In another embodiment the lithium metal and porous carbon powder are kept separated in the same heated reactor environment and the temperature is heated much hotter to increase the vapor pressure of the molten lithium (e.g., 900°C, 1000°C, 1100°C, 1200°C, 1300°C, 1350°C, etc.). This would facilitate vapor phase deposition of lithium metal within the pore structure of the carbon via capillary condensation. The Li: C ratio would therefore be controlled by the dwell time at peak temperature e.g., O.lhr, Ihr, 2hr, 5hr, lOhr, 24hr, etc.).

[0227] In yet another embodiment the lithium metal source is in the form of an electrode / target for a plasma physical vapor deposition apparatus and the porous carbon is acting as the counter electrode. The synthesis of the LCC is performed by applying a voltage bias between the electrodes under a partial pressure of argon gas. This facilitates evaporation of the lithium metal via ion bombardment resulting in lithium metal deposition taking place on the porous carbon. The rate of deposition can be controlled by the applied voltage bias and current. The Li: C ratio can be controlled by dwell time similar to the above embodiments.

[0228] Example 3. Melt infusion method of synthesis for lithium carbon composites (LCC). In a typical but preferred embodiment a portion of micronized porous carbon powder is placed in a metal or ceramic crucible and physically mixed with a portion of lithium metal in the form of foil or powder. The Li: C weight ratio is adjusted so as to partially fill the available pore volume of the carbon allowing for some residual void {e.g., 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1 w / w Li:C). The mixture is then heated under in an inert atmosphere {e.g., argon, nitrogen, helium, or vacuum) to at least the melting point of the lithium metal (e.g., 180°C, 190°C, 200°C, 220°C, 250°C, 300°C, 400°C, etc.). The mixture dwells at peak temperature for a period of time {e.g., O.lhr, Ihr, 2hr, 5hr, lOhr, 24hr, etc.) to allow molten lithium to permeate the carbon pore structure via capillary forces. The LCC is formed at this time then subsequently cooled to ambient temperature and removed for processing.

[0229] In another embodiment the lithium metal and porous carbon powder are kept separated in the same heated reactor environment and the temperature is heated much hotter to increase the vapor pressure of the molten lithium e.g., 900°C, 1000°C, 1100°C, 1200°C, 1300°C, 1350°C, etc.). This would facilitate vapor phase deposition of lithium metal within the pore structure of the carbon via capillary condensation. The Li: C ratio would therefore be controlled by the dwell time at peak temperature {e.g., O.lhr, Ihr, 2hr, 5hr, lOhr, 24hr, etc.).

[0230] In yet another embodiment the lithium metal source is in the form of an electrode / target for a plasma physical vapor deposition apparatus and the porous carbon is acting as the counter electrode. The synthesis of the LCC is performed by applying a voltage bias between the electrodes under a partial pressure of argon gas. This facilitates evaporation of the lithium metal via ion bombardment resulting in lithium metal deposition taking place on the porous carbon. The rate of deposition can be controlled by the applied voltage bias and current. The Li: C ratio can be controlled by dwell time similar to the above embodiments.

[0231] Example 4. Liquid phase methods of synthesis for lithium carbon composites. In a typical embodiment a solution of naphthalene in an anhydrous aprotic ethereal solvent {e.g., tetrahydrofuran, dimethoxyethane, diethyl ether etc.) is prepared in an inert gas environment {e.g., argon, nitrogen, helium, etc.). While stirring or sonicating a portion of lithium metal (1:1 molar ratio to naphthalene) is added to the solution in the form of foil, pellets, or powder. The lithium metal is allowed to completely dissolve to a transparent green solution. Porous carbon is then added to the solution in a desired LLC ratio as indicated in Example 1. Subsequently the solvent and naphthalene are then removed from the mixture via either solvent exchange with a non-ethereal aprotic solvent {e.g., toluene, acetonitrile, etc.) followed by evaporation to yield the dry LCC material which can then be removed for processing.

[0232] In another perhaps preferred embodiment, the same synthesis procedure as in Example 1 is conducted but the mixture is then heated to a temperature so as to facilitate evaporation of both the naphthalene and solvent species (e.g., >220°C). Leaving behind only the LCC material and foregoes the use of additional solvents.

[0233] Example 5. Vapor phase methods of synthesis for lithium carbon composites. An embodiment wherein lithium is created within the pores of the porous carbon scaffold by subjecting the porous carbon particles to a lithium containing precursor gas via chemical vapor infiltration (CV1) at elevated temperature and the presence of a lithium- containing gas, preferably lithium bis(trimethylsilyl)amide, in order to decompose said gas into lithium. In some embodiments, the lithium containing gas may be composed of organic derivatives (such as methyl lithium, phenyl lithium, and the like) or mixtures thereof. The lithium containing precursor gas can be mixed with other inert gas(es), for example, nitrogen gas, or hydrogen gas, or argon gas, or helium gas, or combinations thereof. The temperature and time of processing can be varied, for example the temperature can be between 100°C and 900°C, for example between 100°C and 250°C, for example between 250°C and 300°C, for example between 300°C and 350°C, for example between 300°C and 400°C, for example between 350°C and 450°C, for example between 350°C and 400°C, for example between 400°C and 500°C, for example between 500°C and 600°C, for example between 600°C and 700°C, for example between 700°C and 800°C, for example between 800°C and 900°C, for example between 600°C and 1100°C. The mixture of gas can include between 0.1 and 1 % gaseous lithium precursor and remainder inert gas. Alternatively, the mixture of gas can include between 1% and 10% lithium precursor and remainder inert gas. Alternatively, the mixture of gas can include between 10% and 20% lithium precursor and remainder inert gas. Alternatively, the mixture of gas can include between 20% and 50% lithium precursor and remainder inert gas. Alternatively, the mixture of gas can include above 50% lithium precursor and the remaining inert gas. Alternatively, the gas can essentially be 100% lithium precursor gas. The pressure for the CV1 process can be varied. In some embodiments, the pressure is atmospheric pressure. In some embodiments, the pressure is below atmospheric pressure. In some embodiments, the pressure is above atmospheric pressure.

[0234] Example 6. Addition of alloying species for synthesis of lithium carbon composites. As is known in the art, lithium metal can be alloyed with other elements in some cases forming lower melting point (<180°C) eutectic mixtures. These eutectic mixtures can be exploited to more easily direct formation / precipitation of lithium metal within the porous carbon structure. In one such embodiment, the porous carbon scaffold is first loaded with an alloying agent {e.g., silver) in the form of a solution containing the alloy precursor e.g., 0.1M silver nitrate in water). The solution is added to the dry porous carbon powder via a technique known in the art as incipient wetness at a low relative concentration (e.g., 0.1%, 1%, 2%, 5%, or 10% w / w Ag:C). The water solvent is subsequently removed via evaporation and the alloy precursor is decomposed / reduced to its metal neutral oxidation state (i.e., silver metal) throughout the pore structure of the carbon in the form of discrete nanoparticles {e.g., 1-50 nm in diameter). This Ag / C composite can then be used as the host material for lithium metal formation as described in the above synthesis Examples. In the case of Example 1, the melt infusion step of lithium metal within the carbon pores would preferentially occur where there is a silver nanoparticle since the eutectic melting point of ~0.1 w / w Li / Ag alloy occurs at a lower temperature than lithium metal itself (i.e., 143°C versus 180°C for pure lithium). As the eutectic Li / Ag alloy reaches a lithium saturation point it will precipitate solid lithium from the eutectic melt thus directing the bulk of lithium metal formation in the carbon pore structure where the silver nanoparticles originally resided. In another embodiment as in the case of Example 3, the silver nanoparticles within the carbon pore structure can act as a catalytic seed particle for deposition and subsequent alloying of lithium metal from the lithium precursor gas during CV1.

[0235] Example 7. Reduction of lithium salts for synthesis of lithium carbon composites. An embodiment wherein lithium is created within the pores of the porous carbon scaffold by mixing the porous carbon particles with lithium salt e.g., LiF, LiCl, LiNOs, Li2CO3, Lil, LiBr, LiAlF , LiOH, Li2O, LiO2, Li3N, etc.) at elevated temperature with or without the presence of a reducing agent {e.g., H2, NaBF , oxalic acid, glucose, carbon, etc.) in order to decompose said salt into lithium metal. The lithium salt can be pre-dissolved in solvents {e.g., tetrahydrofuran, propylene carbonate, acetone, etc.) so as to more easily flow / absorb into the nano-pores of the porous carbon scaffold. The reduction temperature and time of processing can be varied, for example the temperature can be between 0°C and 900°C, for example between 0°C and 250°C, for example between 250°C and 300°C, for example between 300°C and 350°C, for example between 300°C and 400°C, for example between 350°C and 450°C, for example between 350°C and 400°C, for example between 400°C and 500°C, for example between 500°C and 600°C, for example between 600°C and 700°C, for example between 700°C and 800°C, for example between 800°C and 900°C, for example between 600°C and 1100°C. The solvent / salt mixture can include between 0.1 and 1 % lithium salt and remainder liquid solvent. Alternatively, the mixture of solvent / salt can include between 1% and 10% lithium salt and remaining liquid solvent. Alternatively, the mixture of solvent / salt can include between 10% and 20% lithium salt and remaining liquid solvent. Alternatively, the mixture of solvent / salt can include between 20% and 50% lithium salt and remainder liquid solvent. Alternatively, the mixture of solvent / salt can include above 50% lithium salt and remaining liquid solvent. Alternatively, the solvent / salt can essentially be 100% lithium salt. The pressure for the reduction process can be varied. In some embodiments, the pressure is atmospheric pressure. In some embodiments, the pressure is below atmospheric pressure. In some embodiments, the pressure is above atmospheric pressure.

[0236] Example 8. Electrochemical methods of forming lithium carbon composites.

[0237] In one embodiment, the lithium carbon composite can be synthesized via an electroplating mechanism wherein an electrolytic cell is assembled with a porous carbon working electrode (prepared via slurry casting on a copper foil or nickel sheet current collector) and lithium metal counter electrode separated from each other in an liquid electrolyte containing a lithium salt (e.g., LiPFe, LiFSI, LiTFSI, LiCl, LiBr, Lil, LiNOs, etc.) and anhydrous organic solvent (e.g., propylene carbonate, ethylene carbonate, 1,3-dioxolane, 1,2- dimethoxyethane, tetrahydrofuran, acetonitrile, etc.). A negative voltage bias (e.g., -IV, -2V, -3V, -4V, -5V, -6V, etc.) is applied to facilitate Li+ reduction in the porous carbon electrode. The amount of charge (Ah) transferred is used to track Li metal loading and subsequently the applied voltage is stopped once a desired Li loading is achieved. The lithium-carbon electrode can then be transferred to and used as the anode in a Li-ion battery.

[0238] An embodiment similar to above wherein the porous carbon electrode is prepared on a roll-to-roll coater that is subsequently conveyed into an electrolyte bath (described above) housed in an inert atmosphere where a negative voltage bias is applied as described in the above embodiment and lithium plating takes place while the electrode is continuously in motion on the rollers. Therefore, the extent of the lithium metal loading is dictated by the conveyance speed of the roll-to-roll apparatus. Furthermore, the electrolyte bath may contain a dissolved polymer (e.g., polyacrylonitrile, polyvinylidene fluoride, polydopamine, etc.) such that when the electrode leaves the bath and subsequently dries the polymer film is left on the electrode surface acting as a barrier to the atmosphere thus minimizing oxidation of the lithium metal formed in the porous carbon.

[0239] In an alternative more preferred embodiment the lithium electroplating can be performed in-situ in an as-assembled Li-ion battery wherein the porous carbon electrode (described above) is the anode and a conventional Li-bearing transition metal oxide as known in the art (e.g., LiFePCk, LiCot , NCA, NMC111, NMC532, NMC622, etc.) acts as the cathode. Lithium electroplating takes place as the battery is charged to its 100% state of charge operating voltage (e.g., 4.2V). In this "anode-free" configuration the Li+ source is the cathode. The process is reversed (Li+ stripping from the porous carbon electrode) when the battery is discharged. This embodiment is preferred because it does not require reactive lithium metal to be handled in an environment outside the battery and furthermore the energy density of the battery can be improved since the cathode acts as the sole source of Li+ in the system.

[0240] Example 9. Terminal coating methods for lithium carbon composites. Owing to the highly reactive nature of lithium metal in atmospheric conditions (e.g., oxidative reaction with water, oxygen, and carbon dioxide) it may be necessary to coat / protect the surface of the lithium utilizing terminal coating methods described herein. In one embodiment following synthesis of the LCC as described in Examples 1-6 the composite is subsequently heated to temperature (e.g., 400-1000°C) so as to facilitate decomposition of a hydrocarbon gas {e.g., acetylene, propylene, ethylene, methane, propane, propadiene / propyne, etc.). At peak temperature the hydrocarbon gas is introduced into the heated chamber containing the LCC material and allowed to undergo a chemical vapor deposition reaction depositing carbon on the surface of the LCC material according to the reaction equation CxHy -> C + H2. The thickness of the coating can be controlled by the dwell time in which the hydrocarbon gas is present e.g., O.lhr - 6hr). The application of the carbon coating will subsequently protect the silicon from oxidation in atmospheric conditions. In another embodiment the LCC material can be coated with a polymer {e.g., polydopamine, polyacrylonitrile, polyaniline, polypyrrole, etc.) to allow for lower temperature {e.g., <200°C) processing.

[0241] Example 10. Surface functionality methods and metrics. The surface functionality of the presently disclosed composite material included of carbon and lithium may be altered to obtain the desired electrochemical properties. One such property for particulate composite materials is the concentration of atomic species at the surface of the composite material relative to the interior of the composite material. Such a difference in concentration of atomic species of the surface vs. interior of the particulate composite material can be determined as known in the art, for example by x-ray photoelectron spectroscopy (XPS). For example, the concentration of Li:C at the surface (defined as the terminal 5 nm of the particulate surface) may be determined by this method. In some embodiments the ratio of Li:C at the surface ranges from about 0.1:1 to 10:1. In certain other embodiments, the ratio of Li:C at the surface is about 0:1. In other embodiments, the ratio of Li: C at the surface is about 1:0. In another example, the Li:O ratio at the surface ranges from about 0:1 to 1:0.

[0242] Another property which can be predictive of surface functionality is the pH of the LCC composite materials. The presently disclosed composite materials include pH values ranging from less than 1 to about 14, for example less than 5, from 5 to 8 or greater than 8. In some embodiments, the pH of the composite materials is less than 4, less than 3, less than 2 or even less than 1. In other embodiments, the pH of the composite materials is between about 5 and 6, between about 6 and 7, between about 7 and 8 or between 8 and 9 or between 9 and 10. In still other embodiments, the pH is high and the pH of the composite materials ranges is greater than 8, greater than 9, greater than 10, greater than 11, greater than 12, or even greater than 13.

[0243] Other methods and metrics for determination of carbon structure include X-ray diffraction (XRD) and Raman spectroscopic analysis. With regards to XRD, the graphitic nature of carbon materials can be assessed by monitoring peak intensity at various 2q corresponding to various Miller indices. Without being bound by theory, diffraction lines of graphite are classified into various groups, such as 001, hkO, and hkl indices, mainly because of the strong anisotropy in structure. One such species is 002, corresponding to basal planes of graphite, which is located at 20 ~ 26°; this peak is prominent in highly graphitic carbon materials. Carbon material with lesser extent of graphite nature and small crystallite sizes may be characterized by very broad 001 lines (e.g., 002) and shifting {e.g., 20 ~ 23°), due to the lesser extent of stacked layers, and by unsymmetrical hk lines e.g., 10 corresponding to 20 ~ 43°). Furthermore, the Scherrer formula may be used to calculate crystallite size (Lc) from the 002 line and crystallite size (La) from the 100 line.

[0244] With regards to Raman spectroscopy, this method can also be employed to assess graphite nature of carbon as reported in the art The position, shape, and magnitude of the Raman D- and G bands is known to the art for calculation of the La value from the Tuinstra Koenig (TK) model for >2nm grain size or the Ferrari (FR) model (Ferrari, A. C., & Robertson, J. (1970); Tuinstra, F., & Koening, J. L. (1970). Raman spectrum of graphite. The Journal of Chemical Physics, 53(3), 1126-1130). Interpretation of Raman spectra of disordered and amorphous carbon. Physical Review B, 61(20), 14095-14107) when TK model calculates <2nm grain size. These models provide a measure of the disorder in carbon materials and represent the length of the graphene crystallite sheets in carbon materials.

[0245] Yet another analysis method is determination of oxygen, nitrogen and hydrogen employing an inert gas fusion instrument. The lithium-carbon composite material may include varying amounts of carbon, oxygen, hydrogen, and nitrogen as measured by an inert gas fusion instrument known in the art (LECO ONH 836). The lithium-carbon composite sample is flash heated in a graphite arc furnace to ~3000°C under flowing helium gas. The oxygen in the sample is carbo-thermally reduced to CO2 and / or CO which is entrained in the helium gas stream and quantified downstream using an 1R spectrometer. Hydrogen is evolved from the sample in the form of H2 which is converted catalytically to H2O in the gas phase and quantified also using an 1R spectrometer. Lastly, the nitrogen is evolved from the sample in the form of N2 and quantified using a thermal conductivity detector.

[0246] In some embodiments, lithium-carbon composite material includes a nitrogen content ranging from 0-90%, for example 0.1-1%, for example 1-3%, for example 1-5%, for example 1-10%, for example 10-20%, for example 20-30%, for example 30-90%. In some embodiments, the oxygen content ranges from 0-90%, for example 0.1-1%, for example 1- 3%, for example 1-5%, for example 1-10%, for example 10-20%, for example 20-30%, for example 30-90%.

[0247] Example 11. Stability of lithium carbon composite under ambient conditions. The instability of lithium metal under ambient conditions is well known in the art. The current disclosure provides for a lithium that is protected within a porous carbon scaffold, with optional terminal coating applied to the composite particle. This protection can be described in terms of the confinement of lithium within the carbon scaffold and is manifested as decreased or eliminated reactivity in air (oxygen), stability in contact with other battery components (chemical), stability in operation (electrochemical), and suppression of dendrites upon battery cycling. For example, a metric such as onset time or severity for reaction with organic solvent can be measured by H2 evolution and / or total quantity. Alternatively, one can measure onset time or severity of tarnishing / color change / oxidation of lithium-carbon in air. Alternatively, stability can be assessed by TGA / DSC by measuring mass uptake due to oxidation of the lithium within the composite. In addition, DSC also is known to provide information about lithium melting point, whose alteration yields information about the stability and / or disposition of lithium within the carbon scaffold porosity. Alternatively, stability can be measured in a half cell vs. lithium metal to determine the number of galvanostatic cycles until dendrite failure, i.e., short circuit of the half cell. Alternatively, stability can be assessed by small angle X-ray scattering (SAXS) or neutron scattering to determine the distribution and size of lithium in the pore of the porous carbon.

[0248] Example 12. Loading and capacity of lithium carbon composite. Without being bound by theory, the limit for impregnating lithium into the pores of the porous carbon is related to the carbon total pore volume.

[0249] Example 13. Synthesis of lithium carbide using convective plasma heating.

[0250] Description of chemical reaction and process conditions:

[0251] In another embodiment, the lithium carbide material is synthesized from unreactive precursors that include lithium carbonate and nano-porous amorphous carbon. Thermodynamically, the reaction of Li2COs + 4C = L12C2 + 3CO(g) proceeds spontaneously (with a negative Gibbs free energy, positive enthalpy (endothermic), and positive entropy) at temperatures exceeding approximately 1300°C. A reactor similar to those shown above are configured with a DC non-transferred arc plasma torch as a high temperature heat source is positioned vertically towards a tungsten crucible containing consolidated, well blended ratios of lithium carbonate and nano-porous amorphous carbon powders. The sample chamber is evacuated and purged with inert gas (e.g., argon) and the plasma torch is ignited using a flow of 1:1 v / v argon / hydrogen at 517 SLPM and 61 kW of electrical power. After the temperature has been reached, the plasma heating is maintained for five minutes then shutoff, quenched with an inert purge gas, and reactor and sample contents allowed to cool to room temperature. The chamber is opened and the sample is collected under inert gas conditions.

[0252] Description of analysis conditions:

[0253] Analysis of the plasma-produced lithium carbide material is performed first qualitatively by adding a small amount of water to the sample to confirm reactivity (via bubbling and basic pH measurement of the liquid) according to the reaction Li2 C2 + 2H2O = 2LiOH + C2H2(g). The powder was also characterized using x-ray diffraction (XRD) analysis under inert (argon) atmosphere. XRD parameters were as follows, a copper K-alpha 40 kV, 50 mA x-ray source, in ID scan mode, at a scan speed of 0.2° / min, step width of 0.01°, and 0 / 20 scan axis.

[0254] As can be seen in Figure 17, the plasma-produced sample contains a mixture of compounds most predominately of which are lithium carbide (reflections at ~24°, 29°, and 46°), graphite (26° and 44°), and aluminum (38°) from the sample holder.

[0255] In yet another embodiment, the sample temperature is increased even further to ~1500°C and held for a longer dwell time of ~10 minutes in order to facilitate more complete conversion to lithium carbide. Figure 18 shows the XRD spectra of this sample with the prominent phases consisting of lithium carbide (reflections at ~24°, 29°, and 46°) and lithium oxide (reflections at ~34°, 56°, and 67°).

[0256] Example 14. Synthesis of lithium carbide using convective plasma heating.

[0257] Description of chemical reaction and process conditions:

[0258] In yet another embodiment, the route to produce lithium carbide using lithium hydride and amorphous carbon has been repeated using the plasma reactor and a stationary crucible that is heated by the hot gas flow (pure argon) that has been heated by the plasma to ~900°C according to the reaction 2LiH + 2C = 11202 + Ehfg) which proceeds spontaneously with a negative Gibbs free energy, positive enthalpy (exothermic), and positive entropy at temperatures exceeding ~600°C.

[0259] As shown in Figure 19, the XRD spectra shows the sample obtained using this approach along with corresponding reference spectra for lithium carbide, lithium oxide, and lithium hydride. The primary phase present is lithium carbide with essentially no residual lithium hydride present indicating a complete reaction.

[0260] EXPRESSED EMBODIMENTS

[0261] Embodiment 1. A reactor comprising a housing, a plasma torch configured to produce plasma within the housing, and one or more nozzles configured to introduce silicon, a silicon-containing precursor, lithium, a lithium-containing precursor, carbon, or a carbon-containing precursor in a solid state, a vapor state, a liquid state, or a combination thereof into the housing resulting in lithium or silicon infiltrating into pores of a carbon material, depositing on the carbon material, or reacting with the carbon material.

[0262] Embodiment 2. The reactor of Embodiment 1, wherein the housing comprises a first chamber receiving the plasma and a second chamber being cooler than the first chamber. Embodiment 3. The reactor of Embodiment 2, wherein one of the nozzles includes an output port adjacent to a transition point between the first chamber and the second chamber.

[0263] Embodiment 4. The reactor of Embodiment 3, further comprising an input port disposed at the second chamber, the input port configured to inject one of a carbon-based gas or a lower temperature inert quenching gas.

[0264] Embodiment 5. The reactor of Embodiment 4, further comprising a second input port disposed at the second chamber, the second input port configured to inject a dopant material.

[0265] Embodiment 6. The reactor of Embodiment 2, wherein the second chamber comprises a first stage section configured to evaporate, melt, and / or condensate lithium and a second stage section configured to receive a carbon-based gas and cause reaction of the carbon-based gas with melted or condensed lithium.

[0266] Embodiment 7. The reactor of any of the previous Embodiments, wherein the housing comprises a crucible disposed proximate to the plasma.

[0267] Embodiment 8. The reactor of any of the previous Embodiments, further comprising a fixed bed or a fluidized bed configured to receive a porous carbon material.

[0268] Embodiment 9. The reactor of any of the previous Embodiments, wherein the one or more nozzles comprises a nozzle configured to direct material directly into the plasma.

[0269] Embodiment 10. The reactor of any of the previous Embodiments, wherein the plasma is directed tangentially into the first chamber for generating a flow of gases.

[0270] Embodiment 11. The reactor of any of the previous Embodiments, further comprising a graphite tube configured to receive a hot vapor or liquid.

[0271] Embodiment 12. The reactor of any of the previous Embodiments, further comprising a porous separator configured to allow condensation to occur thereby forming droplets.

[0272] Embodiment 13. The reactor of Embodiment 12, wherein the droplets comprise L12C2 droplets.

[0273] Embodiment 14. A method of preparing a lithium-carbon composite material, the method comprising providing a pre-mixture of non-porous solid carbon material and solid lithium material in the plasma reactor, heating the pre-mixture of non-porous solid carbon material and solid lithium material to a temperature between 180.5°C and 1330°C to provide a mixture of non-porous solid carbon and plasma-liquified lithium, and holding the mixture of non-porous solid carbon and plasma-liquified lithium at 180.5°C and 1330°C for sufficient time to incorporate liquid lithium into the solid carbon material to yield the lithium-carbon composite material.

[0274] Embodiment 15. A method of preparing a lithium-carbon composite material, the method comprising providing a pre-mixture of porous solid carbon material and solid lithium material in the plasma reactor, heating the pre-mixture of porous solid carbon material and solid lithium material to a temperature between 180.5°C and 1330°C to provide a mixture of porous solid carbon and liquid lithium, and holding the mixture of porous solid carbon and plasma-liquified liquid lithium at 180.5°C and 1330°C for sufficient time to impregnate liquid lithium into the pores of the solid carbon material to yield the lithium-carbon composite material.

[0275] Embodiment 16. A method of preparing a lithium-carbon composite material, the method comprising providing a pre-mixture of non-porous solid carbon material and solid lithium material in the plasma reactor, heating the pre-mixture of non-porous solid carbon material and solid lithium material to a temperature greater than 1330°C to provide a mixture of non-porous solid carbon and plasma-vaporized lithium, and holding the mixture of non-porous solid carbon and plasma-vaporized lithium at greater than 1330°C for sufficient time to incorporate the plasma-heated lithium into the solid carbon material to yield the lithium-carbon composite material.

[0276] Embodiment 17. A method of preparing a lithium-carbon composite material, the method comprising providing a pre-mixture of porous solid carbon material and solid lithium material in the plasma reactor, heating the pre-mixture of porous solid carbon material and solid lithium material to a temperature greater than 1330°C to provide a mixture of non-porous solid carbon and plasma-vaporized lithium, and impregnating of plasma-vaporized lithium into the pores of the solid carbon material to yield the lithiumcarbon composite material.

[0277] Embodiment 18. A method of preparing a lithium-carbon composite material, the method comprising providing non-porous solid carbon material in the plasma reactor and heating the non-porous solid-carbon material in the plasma reactor to a temperature between 180.5°C and 1330°C, providing solid lithium in the plasma reactor at a temperature between 180.5°C and 1330°C to convert the solid lithium material to plasma- liquified lithium, contacting the plasma-liquified lithium and non-porous solid carbon in the plasma reactor to provide a mixture of non-porous solid carbon and plasma-liquified lithium, and holding the mixture of non-porous solid carbon and plasma-liquified lithium at 180.5°C and 1330°C for sufficient time to incorporate liquid lithium into the solid carbon material to yield the lithium-carbon composite material. Embodiment 19. A method of preparing a lithium-carbon composite material, the method comprising providing porous solid carbon material in the plasma reactor and heating the porous solid-carbon material in the plasma reactor to a temperature between 180.5°C and 1330°C, providing solid lithium in the plasma reactor at a temperature between 180.5°C and 1330°C to convert the solid lithium material to plasma-liquified lithium, contacting the plasma-liquified lithium and porous carbon in the plasma reactor to provide a mixture of porous solid carbon and plasma-liquified lithium, and holding the mixture of porous solid carbon and plasma-liquified lithium at 180.5°C and 1330°C for sufficient time for the plasma-liquified lithium to impregnate into the pores of the solid carbon material to yield the lithium-carbon composite material.

[0278] Embodiment 20. A method of preparing a lithium-carbon composite material, the method comprising providing non-porous solid carbon material in the plasma reactor and heating the non-porous solid-carbon material in the plasma reactor to a temperature above 1330°C, providing solid lithium in the plasma reactor at a temperature above 1330°C to convert the solid lithium material to plasma-vaporized lithium, contacting the plasma- vaporized lithium and non-porous solid carbon in the plasma reactor to provide a mixture of non-porous solid carbon and plasma-vaporized lithium, and holding the mixture of non- porous solid carbon and plasma-vaporized lithium at greater than 1330°C for sufficient time to incorporate plasma-vaporized lithium into the solid carbon material to yield the lithium-carbon composite material.

[0279] Embodiment 21. A method of preparing a lithium-carbon composite material, the method comprising providing porous solid carbon material in the plasma reactor and heating the porous solid-carbon material in the plasma reactor to a temperature above 1330°C, providing solid lithium in the plasma reactor and heating the solid lithium in the plasma reactor to a temperature above 1330°C to convert the solid lithium material to plasma-vaporized lithium, contacting the plasma-vaporized lithium and porous solid carbon in the plasma reactor to provide a mixture of porous solid carbon and plasma- vaporized lithium, and holding the mixture of porous solid carbon and plasma-vaporized lithium at greater than 1330°C for sufficient time to impregnate plasma-vaporized lithium into the pores of the porous solid carbon material to yield the lithium-carbon composite material.

[0280] Embodiment 22. A method of preparing a lithium-carbon composite material, the method comprising providing a pre-mixture of non-porous solid carbon material and solid lithium-containing precursor material in the plasma reactor, heating the pre-mixture of non-porous solid carbon material and solid lithium material to a temperature between 180.5°C and 1330°C to provide a mixture of non-porous solid carbon and plasma-pyrolyzed lithium, and holding the mixture of non-porous solid carbon and plasma-pyrolyzed lithium at 180.5°C and 1330°C for sufficient time to incorporate plasma-pyrolyzed lithium into the solid carbon material to yield the lithium-carbon composite material.

[0281] Embodiment 23. A method of preparing a lithium-carbon composite material, the method comprising providing a pre-mixture of porous solid carbon material and solid lithium-containing precursor material in the plasma reactor, heating the pre-mixture of porous solid carbon material and solid lithium-containing precursor material to a temperature between 180.5°C and 1330°C to provide a mixture of porous solid carbon and plasma-pyrolyzed lithium, and holding the mixture of porous solid carbon and plasma- pyrolyzed lithium-containing precursor at 180.5°C and 1330°C for sufficient time to impregnate plasma-pyrolyzed lithium into the pores of the solid carbon material to yield the lithium-carbon composite material.

[0282] Embodiment 24. A method of preparing a lithium-carbon composite material, the method comprising providing a pre-mixture of non-porous solid carbon material and solid lithium-containing precursor material in the plasma reactor, heating the pre-mixture of solid carbon material and solid lithium material to a temperature greater than 1330°C to provide a mixture of non-porous solid carbon and the plasma-pyrolyzed lithium, and holding the mixture of non-porous solid carbon and plasma-pyrolyzed lithium-containing precursor at greater than 1330°C for sufficient time to impregnate the plasma-pyrolyzed lithium into the solid carbon material to yield the lithium-carbon composite material.

[0283] Embodiment 25. A method of preparing a lithium-carbon composite material, the method comprising providing a pre-mixture of porous solid carbon material and solid lithium-containing material in the plasma reactor, heating the pre-mixture of porous solid carbon material and solid lithium-containing precursor material to a temperature greater than 1330°C to provide a mixture of porous solid carbon and plasma-pyrolyzed lithium, and holding the mixture of non-porous solid carbon and plasma-pyrolyzed lithium at greater than 1330°C for sufficient time to impregnate the plasma-pyrolyzed lithium into the pores of the porous carbon material to yield the lithium-carbon composite material.

[0284] Embodiment 26. A method of preparing a lithium-carbon composite material, the method comprising providing non-porous solid carbon material in the plasma reactor and heating the non-porous solid-carbon material in the plasma reactor to a temperature between 180.5°C and 1330°C, providing solid lithium-containing precursor in the plasma reactor at a temperature between 180.5°C and 1330°C to provide for plasma-pyrolyzed lithium, contacting the plasma-pyrolyzed lithium and non-porous solid carbon in the plasma reactor to provide a mixture of non-porous solid carbon and plasma-pyrolyzed lithium, and holding the mixture of non-porous solid carbon and plasma-pyrolyzed lithium at 180.5°C and 1330°C for sufficient time to incorporate plasma-pyrolyzed lithium into the solid carbon material to yield the lithium-carbon composite material. Embodiment 27. A method of preparing a lithium-carbon composite material, the method comprising providing porous solid carbon material in the plasma reactor and heating the porous solid-carbon material in the plasma reactor to a temperature between 180.5°C and 1330°C, providing solid lithium-containing precursor in the plasma reactor at a temperature between 180.5°C and 1330°C to provide for plasma-pyrolyzed lithium, contacting the plasma-pyrolyzed lithium and porous solid carbon in the plasma reactor to provide a mixture of non-porous solid carbon and plasma-pyrolyzed lithium, and holding the mixture of non-porous solid carbon and plasma-pyrolyzed lithium at 180.5°C and 1330°C for sufficient time for impregnation of plasma-pyrolyzed lithium into the solid carbon material to yield the lithium-carbon composite material.

[0285] Embodiment 28. A method of preparing a lithium-carbon composite material, the method comprising providing non-porous solid carbon material in the plasma reactor and heating the non-porous solid-carbon material in the plasma reactor to a temperature above 1330°C, providing solid lithium-containing precursor in the plasma reactor at a temperature between above 1330°C to provide for plasma-pyrolyzed lithium, contacting the plasma-pyrolyzed lithium and non-porous solid carbon in the plasma reactor to provide a mixture of non-porous solid carbon and plasma-pyrolyzed lithium, and holding the mixture of non-porous solid carbon and plasma-pyrolyzed lithium above 1330°C for sufficient time to incorporate plasma-pyrolyzed lithium into the solid carbon material to yield the lithium-carbon composite material.

[0286] Embodiment 29. A method of preparing a lithium-carbon composite material, the method comprising providing porous solid carbon material in the plasma reactor and heating the porous solid-carbon material in the plasma reactor to a temperature above 1330°C, providing solid lithium-containing precursor in the plasma reactor at a temperature above 1330°C to provide for plasma-pyrolyzed lithium, contacting the plasma- pyrolyzed lithium and porous solid carbon in the plasma reactor to provide a mixture of non-porous solid carbon and plasma-pyrolyzed lithium, and holding the mixture of non- porous solid carbon and plasma-pyrolyzed lithium above 1330°C for sufficient time for impregnation of plasma-pyrolyzed lithium into the solid carbon material to yield the lithium-carbon composite material.

[0287] Embodiment 30. A method of preparing a lithium-carbon composite material, the method comprising providing solid lithium in the plasma reactor at a temperature between 180.5°C and 1330°C to yield plasma-liquified lithium, providing gaseous carbon-containing precursor in the plasma reactor at a temperature suitable to yield plasma-pyrolyzed carbon, mixing the plasma-liquified lithium with the plasma-pyrolyzed carbon; and holding the mixture of plasma-liquified lithium and plasma-pyrolyzed carbon material in the plasma reactor at a temperature between 180.5°C and 1330°C to yield the lithium-carbon composite material. Embodiment 31. A method of preparing a lithium-carbon composite material, the method comprising providing solid lithium in the plasma reactor at a temperature greater than 1330°C to yield plasma-vaporized lithium, providing gaseous carbon-containing precursor in the plasma reactor at a temperature suitable to yield plasma-pyrolyzed carbon, mixing the plasma-vaporized lithium with the plasma-pyrolyzed carbon; and holding the mixture of plasma-vaporized lithium and plasma-pyrolyzed carbon material in the plasma reactor at a temperature greater than 1330°C to yield the lithium-carbon composite material.

[0288] Embodiment 32. A method of preparing a lithium-carbon composite material, the method comprising providing solid lithium-containing precursor in the plasma reactor at a temperature above the melting point of the lithium-containing precursor to yield plasma- liquified lithium-containing precursor, mixing the plasma-liquified lithium-containing precursor with a gaseous carbon-containing precursor, and holding the mixture of plasma- liquified lithium-containing precursor and gaseous carbon-containing precursor in the plasma reactor at a temperature sufficient to accomplish co-plasma-pyrolysis of the mixture to yield the lithium-carbon composite material.

[0289] Embodiment 33. A method of preparing a lithium-carbon composite material, the method comprising providing solid lithium-containing precursor in the plasma reactor at a temperature above the boiling point of the lithium-containing precursor to yield plasma- vaporized lithium-containing precursor, mixing the plasma-vaporized lithium-containing precursor with a gaseous carbon-containing precursor, and holding the mixture of plasma- vaporized lithium-containing precursor and gaseous carbon-containing precursor in the plasma reactor at a temperature sufficient to accomplish co-plasma-pyrolysis of the mixture to yield the lithium-carbon composite material.

[0290] Embodiment 34. The method of any of the previous Embodiments, wherein the total pore volume of the porous carbon is between 0.01 and 2 cm3 / g.

[0291] Embodiment 35. The method of any of the previous Embodiments, wherein the total pore volume of the porous carbon is between 0.1 and 1.5 cm3 / g.

[0292] Embodiment 36. The method of Claims 15, 17, 19, 21, 23, 25, 27, or 29, wherein the total pore volume of the porous carbon is between 0.2 and 1.0 cm3 / g.

[0293] Embodiment 37. The method of any of the previous Embodiments, wherein the total pore volume of the porous carbon is between 0.4 and 0.8 cm3 / g.

[0294] Embodiment 38. The method of any of the previous Embodiments, wherein the micropore content as a fraction of the total pore volume is between 0% and 50% Embodiment 39. The method of any of the previous Embodiments, wherein the micropore content as a fraction of the total pore volume is between 50% and 100%

[0295] Embodiment 40. The method of any of the previous Embodiments, wherein the micropore content as a fraction of the total pore volume is between 70% and 100%

[0296] Embodiment 41. The method of any of the previous Embodiments, wherein the mesopore content as a fraction of the total pore volume is between 0% and 50%

[0297] Embodiment 42. The method of any of the previous Embodiments, wherein the mesopore content as a fraction of the total pore volume is between 50% and 100%

[0298] Embodiment 43. The method of any of the previous Embodiments, wherein the macropore content as a fraction of the total pore volume is between 0% and 50%

[0299] Embodiment 44. The method of any of the previous Embodiments, wherein the macropore content as a fraction of the total pore volume is between 50% and 100%.

[0300] Embodiment 45. The method of any of the previous Embodiments, wherein the micropores content is 50-100%, the mesopore content is 0-50%, and the macropore content is 0-50%,

[0301] Embodiment 46. The method of any of the previous Embodiments, wherein the gaseous carbon-containing precursor comprises methane, propane, butane, cyclohexane, ethane, propylene, ethylene or acetylene, or combinations thereof.

[0302] Embodiment 47. The method of any of the previous Embodiments, wherein plasms-pyrolysis is carried out in the plasma reactor at a temperature between 100°C and 500°C.

[0303] Embodiment 48. The method of any of the previous Embodiments, wherein plasms-pyrolysis is carried out in the plasma reactor at a temperature between 500°C and 1000°C.

[0304] Embodiment 49. The method of any of the previous Embodiments, wherein plasms-pyrolysis is carried out in the plasma reactor at a temperature between 1000°C and 2000°C.

[0305] Embodiment 50. The method of any of the previous Embodiments, wherein plasms-pyrolysis is carried out in the plasma reactor at a temperature between 2000°C and 3000°C.

[0306] Embodiment 51. The method of any of any of the previous Embodiments, wherein plasms-pyrolysis is carried out in the plasma reactor at a temperature above 3000°C. Embodiment 52. The method of any of the previous Embodiments, wherein the lithium-containing precursor comprises lithium acetylsalicylate, lithium amide, lithium bromide, lithium tetraborohydride, lithium chloride, lithium hydride, lithium hydroxide, lithium carbonate, lithium acetate, lithium fluoride, lithium hydrogen sulfate, lithium dihydrogen phosphate, lithium nitrate, lithium phosphate, lithium sulfate, lithium sulfide, or lithium disulfide lithium sulfite, or combinations there.

[0307] The various embodiments described above can be combined to provide further embodiments. All of the U.S. patents, U.S. patent application publications, U.S. patent applications, foreign patents, foreign patent applications and non-patent publications referred to in this specification and / or listed in the Application Data Sheet, including U.S. Provisional Patent Application No. 63 / 601,988, filed November 22, 2023, are incorporated herein by reference, in their entirety. Aspects of the embodiments can be modified, if necessary to employ concepts of the various patents, applications and publications to provide yet further embodiments. From the foregoing it will be appreciated that, although specific embodiments of the disclosure have been described herein for purposes of illustration, various modifications may be made without deviating from the spirit and scope of the disclosure.

Claims

CLAIMS1. A reactor comprising: a housing; a plasma torch configured to produce plasma within the housing; and one or more nozzles configured to introduce silicon, a silicon-containing precursor, lithium, a lithium-containing precursor, carbon, or a carbon-containing precursor in a solid state, a vapor state, a liquid state, or a combination thereof into the housing resulting in lithium or silicon infiltrating into pores of a carbon material, depositing on the carbon material, or reacting with the carbon material.

2. The reactor of Claim 1, wherein the housing comprises a first chamber receiving the plasma and a second chamber being cooler than the first chamber.

3. The reactor of Claim 2, wherein one of the nozzles includes an output port adjacent to a transition point between the first chamber and the second chamber.

4. The reactor of Claim 3, further comprising an input port disposed at the second chamber, the input port configured to inject one of a carbon-based gas or a lower temperature inert quenching gas.

5. The reactor of Claim 4, further comprising a second input port disposed at the second chamber, the second input port configured to inject a dopant material.

6. The reactor of Claim 2, wherein the second chamber comprises: a first stage section configured to evaporate, melt, and / or condensate lithium; and a second stage section configured to receive a carbon-based gas and cause reaction of the carbon-based gas with melted or condensed lithium.

7. The reactor of Claim 1, wherein the housing comprises a crucible disposed proximate to the plasma.

8. The reactor of Claim 1, further comprising a fixed bed or a fluidized bed configured to receive a porous carbon material.

9. The reactor of Claim 1, wherein the one or more nozzles comprises a nozzle configured to direct material directly into the plasma.

10. The reactor of Claim 1, wherein the plasma is directed tangentially into the first chamber for generating a flow of gases.

11. The reactor of Claim 1, further comprising a graphite tube configured to receive a hot vapor or liquid.

12. The reactor of Claim 1, further comprising a porous separator configured to allow condensation to occur thereby forming droplets.

13. The reactor of Claim 12, wherein the droplets comprise II2C2 droplets.

14. A method of preparing a lithium-carbon composite material, the method comprising: a] providing a pre-mixture of non-porous solid carbon material and solid lithium material in the plasma reactor; b] heating the pre-mixture of non-porous solid carbon material and solid lithium material to a temperature between 180.5°C and 1330°C to provide a mixture of non-porous solid carbon and plasma-liquified lithium; and c] holding the mixture of non-porous solid carbon and plasma-liquified lithium at 180.5°C and 1330°C for sufficient time to incorporate liquid lithium into the solid carbon material to yield the lithium-carbon composite material.

15. A method of preparing a lithium-carbon composite material, the method comprising: a] providing a pre-mixture of porous solid carbon material and solid lithium material in the plasma reactor; b] heating the pre-mixture of porous solid carbon material and solid lithium material to a temperature between 180.5°C and 1330°C to provide a mixture of porous solid carbon and liquid lithium; and c] holding the mixture of porous solid carbon and plasma-liquified liquid lithium at 180.5°C and 1330°C for sufficient time to impregnate liquid lithium into the pores of the solid carbon material to yield the lithium-carbon composite material.

16. A method of preparing a lithium-carbon composite material, the method comprising: a) providing a pre-mixture of non-porous solid carbon material and solid lithium material in the plasma reactor; b] heating the pre-mixture of non-porous solid carbon material and solid lithium material to a temperature greater than 1330°C to provide a mixture of non-porous solid carbon and plasma-vaporized lithium; andc] holding the mixture of non-porous solid carbon and plasma-vaporized lithium at greater than 1330°C for sufficient time to incorporate the plasma-heated lithium into the solid carbon material to yield the lithium-carbon composite material.

17. A method of preparing a lithium-carbon composite material, the method comprising: a] providing a pre-mixture of porous solid carbon material and solid lithium material in the plasma reactor; b] heating the pre-mixture of porous solid carbon material and solid lithium material to a temperature greater than 1330°C to provide a mixture of non-porous solid carbon and plasma-vaporized lithium; and c] impregnating of plasma-vaporized lithium into the pores of the solid carbon material to yield the lithium-carbon composite material.

18. A method of preparing a lithium-carbon composite material, the method comprising: a] providing non-porous solid carbon material in the plasma reactor and heating the non-porous solid-carbon material in the plasma reactor to a temperature between 180.5°C and 1330°C; b] providing solid lithium in the plasma reactor at a temperature between 180.5°C and 1330°C to convert the solid lithium material to plasma-liquified lithium; c] contacting the plasma-liquified lithium and non-porous solid carbon in the plasma reactor to provide a mixture of non-porous solid carbon and plasma-liquified lithium; and d] holding the mixture of non-porous solid carbon and plasma-liquified lithium at 180.5°C and 1330°C for sufficient time to incorporate liquid lithium into the solid carbon material to yield the lithium-carbon composite material.

19. A method of preparing a lithium-carbon composite material, the method comprising: a] providing porous solid carbon material in the plasma reactor and heating the porous solid-carbon material in the plasma reactor to a temperature between 180.5°C and 1330°C; b] providing solid lithium in the plasma reactor at a temperature between 180.5°C and 1330°C to convert the solid lithium material to plasma-liquified lithium; c] contacting the plasma-liquified lithium and porous carbon in the plasma reactor to provide a mixture of porous solid carbon and plasma-liquified lithium; and d] holding the mixture of porous solid carbon and plasma-liquified lithium at 180.5°C and 1330°C for sufficient time for the plasma-liquified lithium to impregnate into the pores of the solid carbon material to yield the lithium-carbon composite material.

20. A method of preparing a lithium-carbon composite material, the method comprising: a] providing non-porous solid carbon material in the plasma reactor and heating the non-porous solid-carbon material in the plasma reactor to a temperature above 1330°C; b] providing solid lithium in the plasma reactor at a temperature above 1330°C to convert the solid lithium material to plasma-vaporized lithium; c] contacting the plasma-vaporized lithium and non-porous solid carbon in the plasma reactor to provide a mixture of non-porous solid carbon and plasma-vaporized lithium; and d] holding the mixture of non-porous solid carbon and plasma-vaporized lithium at greater than 1330°C for sufficient time to incorporate plasma-vaporized lithium into the solid carbon material to yield the lithium-carbon composite material.

21. A method of preparing a lithium-carbon composite material, the method comprising: a] providing porous solid carbon material in the plasma reactor and heating the porous solid-carbon material in the plasma reactor to a temperature above 1330°C; b] providing solid lithium in the plasma reactor and heating the solid lithium in the plasma reactor to a temperature above 1330°C to convert the solid lithium material to plasma-vaporized lithium; c] contacting the plasma-vaporized lithium and porous solid carbon in the plasma reactor to provide a mixture of porous solid carbon and plasma-vaporized lithium; and d] holding the mixture of porous solid carbon and plasma-vaporized lithium at greater than 1330°C for sufficient time to impregnate plasma-vaporized lithium into the pores of the porous solid carbon material to yield the lithium-carbon composite material.

22. A method of preparing a lithium-carbon composite material, the method comprising: a] providing a pre-mixture of non-porous solid carbon material and solid lithium-containing precursor material in the plasma reactor; b] heating the pre-mixture of non-porous solid carbon material and solid lithium material to a temperature between 180.5°C and 1330°C to provide a mixture of non-porous solid carbon and plasma-pyrolyzed lithium; and c] holding the mixture of non-porous solid carbon and plasma-pyrolyzed lithium at 180.5°C and 1330°C for sufficient time to incorporate plasma-pyrolyzed lithium into the solid carbon material to yield the lithium-carbon composite material.

23. A method of preparing a lithium-carbon composite material, the method comprising: a] providing a pre-mixture of porous solid carbon material and solid lithium- containing precursor material in the plasma reactor; b] heating the pre-mixture of porous solid carbon material and solid lithium- containing precursor material to a temperature between 180.5°C and 1330°C to provide a mixture of porous solid carbon and plasma-pyrolyzed lithium; and c] holding the mixture of porous solid carbon and plasma-pyrolyzed lithium- containing precursor at 180.5°C and 1330°C for sufficient time to impregnate plasma- pyrolyzed lithium into the pores of the solid carbon material to yield the lithium-carbon composite material.

24. A method of preparing a lithium-carbon composite material, the method comprising: a] providing a pre-mixture of non-porous solid carbon material and solid lithium-containing precursor material in the plasma reactor; b] heating the pre-mixture of solid carbon material and solid lithium material to a temperature greater than 1330°C to provide a mixture of non-porous solid carbon and the plasma-pyrolyzed lithium; and c] holding the mixture of non-porous solid carbon and plasma-pyrolyzed lithium-containing precursor at greater than 1330°C for sufficient time to impregnate the plasma-pyrolyzed lithium into the solid carbon material to yield the lithium-carbon composite material.

25. A method of preparing a lithium-carbon composite material, the method comprising: a] providing a pre-mixture of porous solid carbon material and solid lithium- containing material in the plasma reactor; b] heating the pre-mixture of porous solid carbon material and solid lithium- containing precursor material to a temperature greater than 1330°C to provide a mixture of porous solid carbon and plasma-pyrolyzed lithium; and c] holding the mixture of non-porous solid carbon and plasma-pyrolyzed lithium at greater than 1330°C for sufficient time to impregnate the plasma-pyrolyzed lithium into the pores of the porous carbon material to yield the lithium-carbon composite material.

26. A method of preparing a lithium-carbon composite material, the method comprising:a] providing non-porous solid carbon material in the plasma reactor and heating the non-porous solid-carbon material in the plasma reactor to a temperature between 180.5°C and 1330°C; b] providing solid lithium-containing precursor in the plasma reactor at a temperature between 180.5°C and 1330°C to provide for plasma-pyrolyzed lithium; c] contacting the plasma-pyrolyzed lithium and non-porous solid carbon in the plasma reactor to provide a mixture of non-porous solid carbon and plasma-pyrolyzed lithium; and d] holding the mixture of non-porous solid carbon and plasma-pyrolyzed lithium at 180.5°C and 1330°C for sufficient time to incorporate plasma-pyrolyzed lithium into the solid carbon material to yield the lithium-carbon composite material.

27. A method of preparing a lithium-carbon composite material, the method comprising: a] providing porous solid carbon material in the plasma reactor and heating the porous solid-carbon material in the plasma reactor to a temperature between 180.5°C and 1330°C; b] providing solid lithium-containing precursor in the plasma reactor at a temperature between 180.5°C and 1330°C to provide for plasma-pyrolyzed lithium; c] contacting the plasma-pyrolyzed lithium and porous solid carbon in the plasma reactor to provide a mixture of non-porous solid carbon and plasma-pyrolyzed lithium; and d] holding the mixture of non-porous solid carbon and plasma-pyrolyzed lithium at 180.5°C and 1330°C for sufficient time for impregnation of plasma-pyrolyzed lithium into the solid carbon material to yield the lithium-carbon composite material.

28. A method of preparing a lithium-carbon composite material, the method comprising: a] providing non-porous solid carbon material in the plasma reactor and heating the non-porous solid-carbon material in the plasma reactor to a temperature above 1330°C; b] providing solid lithium-containing precursor in the plasma reactor at a temperature between above 1330°C to provide for plasma-pyrolyzed lithium; c] contacting the plasma-pyrolyzed lithium and non-porous solid carbon in the plasma reactor to provide a mixture of non-porous solid carbon and plasma-pyrolyzed lithium; and d] holding the mixture of non-porous solid carbon and plasma-pyrolyzed lithium above 1330°C for sufficient time to incorporate plasma-pyrolyzed lithium into the solid carbon material to yield the lithium-carbon composite material.

29. A method of preparing a lithium-carbon composite material, the method comprising: a] providing porous solid carbon material in the plasma reactor and heating the porous solid-carbon material in the plasma reactor to a temperature above 1330°C; b] providing solid lithium-containing precursor in the plasma reactor at a temperature above 1330°C to provide for plasma-pyrolyzed lithium; c] contacting the plasma-pyrolyzed lithium and porous solid carbon in the plasma reactor to provide a mixture of non-porous solid carbon and plasma-pyrolyzed lithium; and d] holding the mixture of non-porous solid carbon and plasma-pyrolyzed lithium above 1330°C for sufficient time for impregnation of plasma-pyrolyzed lithium into the solid carbon material to yield the lithium-carbon composite material.

30. A method of preparing a lithium-carbon composite material, the method comprising: a] providing solid lithium in the plasma reactor at a temperature between 180.5°C and 1330°C to yield plasma-liquified lithium; b] providing gaseous carbon-containing precursor in the plasma reactor at a temperature suitable to yield plasma-pyrolyzed carbon; c] mixing the plasma-liquified lithium with the plasma-pyrolyzed carbon; and d] holding the mixture of plasma-liquified lithium and plasma-pyrolyzed carbon material in the plasma reactor at a temperature between 180.5°C and 1330°C to yield the lithium-carbon composite material.

31. A method of preparing a lithium-carbon composite material, the method comprising: a] providing solid lithium in the plasma reactor at a temperature greater than 1330°C to yield plasma-vaporized lithium; b] providing gaseous carbon-containing precursor in the plasma reactor at a temperature suitable to yield plasma-pyrolyzed carbon; c] mixing the plasma-vaporized lithium with the plasma-pyrolyzed carbon; and d] holding the mixture of plasma-vaporized lithium and plasma-pyrolyzed d] carbon material in the plasma reactor at a temperature greater than 1330°C to yield the lithium-carbon composite material.

32. A method of preparing a lithium-carbon composite material, the method comprising: a) providing solid lithium-containing precursor in the plasma reactor at a temperature above the melting point of the lithium-containing precursor to yield plasma- liquified lithium-containing precursor;b] mixing the plasma-liquified lithium-containing precursor with a gaseous carbon-containing precursor; and c] holding the mixture of plasma-liquified lithium-containing precursor and gaseous carbon-containing precursor in the plasma reactor at a temperature sufficient to accomplish co-plasma-pyrolysis of the mixture to yield the lithium-carbon composite material.

33. A method of preparing a lithium-carbon composite material, the method comprising: a] providing solid lithium-containing precursor in the plasma reactor at a temperature above the boiling point of the lithium-containing precursor to yield plasma- vaporized lithium-containing precursor; b] mixing the plasma-vaporized lithium-containing precursor with a gaseous carbon-containing precursor; and c] holding the mixture of plasma-vaporized lithium-containing precursor and gaseous carbon-containing precursor in the plasma reactor at a temperature sufficient to accomplish co-plasma-pyrolysis of the mixture to yield the lithium-carbon composite material.

34. The method of Claims 15, 17, 19, 21, 23, 25, 27, or 29, wherein the total pore volume of the porous carbon is between 0.01 and 2 cm3 / g.

35. The method of Claims 15, 17, 19, 21, 23, 25, 27, or 29, wherein the total pore volume of the porous carbon is between 0.1 and 1.5 cm3 / g.

36. The method of Claims 15, 17, 19, 21, 23, 25, 27, or 29, wherein the total pore volume of the porous carbon is between 0.2 and 1.0 cm3 / g.

37. The method of Claims 15, 17, 19, 21, 23, 25, 27, or 29, wherein the total pore volume of the porous carbon is between 0.4 and 0.8 cm3 / g.

38. The method of Claims 15, 17, 19, 21, 23, 25, 27, or 29, wherein the micropore content as a fraction of the total pore volume is between 0% and 50%.

39. The method of Claims 15, 17, 19, 21, 23, 25, 27, or 29, wherein the micropore content as a fraction of the total pore volume is between 50% and 100%.

40. The method of Claims 15, 17, 19, 21, 23, 25, 27, or 29, wherein the micropore content as a fraction of the total pore volume is between 70% and 100%.

41. The method of Claims 15, 17, 19, 21, 23, 25, 27 , or 29, wherein the mesopore content as a fraction of the total pore volume is between 0% and 50%.

42. The method of Claims 15, 17, 19, 21, 23, 25, 27, or 29, wherein the mesopore content as a fraction of the total pore volume is between 50% and 100%.

43. The method of Claims 15, 17, 19, 21, 23, 25, 27, or 29, wherein the macropore content as a fraction of the total pore volume is between 0% and 50%.

44. The method of Claims 15, 17, 19, 21, 23, 25, 27, or 29, wherein the macropore content as a fraction of the total pore volume is between 50% and 100%.

45. The method of Claims 15, 17, 19, 21, 23, 25, 27, or 29, wherein the micropores content is 50-100%, the mesopore content is 0-50%, and the macropore content is 0-50%.

46. The method of any of Claims 30-33, wherein the gaseous carbon-containing precursor comprises methane, propane, butane, cyclohexane, ethane, propylene, ethylene or acetylene, or combinations thereof.

47. The method of any of Claims 15-33, wherein plasms-pyrolysis is carried out in the plasma reactor at a temperature between 100°C and 500°C.

48. The method of any of Claims 15-33, wherein plasms-pyrolysis is carried out in the plasma reactor at a temperature between 500°C and 1000°C.

49. The method of any of Claims 15-33, wherein plasms-pyrolysis is carried out in the plasma reactor at a temperature between 1000°C and 2000°C.

50. The method of any of Claims 15-33, wherein plasms-pyrolysis is carried out in the plasma reactor at a temperature between 2000°C and 3000°C.

51. The method of any of Claims 15-33, wherein plasms-pyrolysis is carried out in the plasma reactor at a temperature above 3000°C.

52. The method of any of Claims 22-29, 32, or 33, wherein the lithium-containing precursor comprises lithium acetylsalicylate, lithium amide, lithium bromide, lithium tetrab orohydride, lithium chloride, lithium hydride, lithium hydroxide, lithium carbonate, lithium acetate, lithium fluoride, lithium hydrogen sulfate, lithium dihydrogen phosphate,lithium nitrate, lithium phosphate, lithium sulfate, lithium sulfide, or lithium disulfide lithium sulfite, or combinations there.

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