TW202218224A - Artificial solid electrolyte interface cap layer for an anode in a li s battery system - Google Patents

Abstract

This disclosure provides a battery including a cathode and an anode positioned opposite the cathode. The anode includes a hybrid artificial solid-electrolyte interphase (A-SEI) layer encapsulating the anode. The hybrid A-SEI layer includes a first active component, a second active component disposed on the first active component, and a plurality of carbon-containing aggregates interwoven throughout the first and second active components and configured to inhibit growth of Li dendritic structures from the anode towards the cathode. A separator is positioned between the anode and the cathode. The cathode includes a porous carbon-based structure configured to expand in a presence of polysulfide (PS) shuttle within one or more portions of the battery. An electrolyte is dispersed between the anode and the cathode and in contact with both the anode and the cathode. The plurality of carbon-containing aggregates can include a polymer, which includes a cross-linked polymeric network.

Description

Artificial solid electrolyte interfacial capping for anodes in lithium-sulfur battery systems

Field of Invention

The present disclosure relates generally to inhibiting the formation of lithium (Li) dendrites on metallic lithium electrodes (anode), and more particularly to enabling stability and long life of Li-ion and lithium-sulfur (LiS) batteries.

Background of the Invention

Lithium-ion (Li-ion), lithium (Li) metal, and lithium-sulfur (LiS) battery packs are regarded as promising power sources for demanding applications such as electric vehicles (EVs), hybrid vehicles ( HEV) and modern portable electronic devices such as laptops and smart phones. Compared to other alkali metals, Li metal provides the highest specific capacity relative to any other metal or metal-intercalated compound used as an anode material. Therefore, Li metal batteries, such as Li metal batteries with solid Li metal foil anodes, have significantly higher energy and power densities than Li-ion batteries (traditionally characterized by graphite anodes with ionic Li sandwiched between them) . However, due to the highly reactive and explosive nature of elemental Li when exposed to the extreme forces experienced, for example, during vehicle crashes, cycling stability and safety issues remain an impediment characteristic for use in EV, HEV and microelectronic device applications A major factor in the wide-scale commercialization of Li metal or LiS batteries of solid Li metal foil anodes. And the specific cycling stability and safety issues of Li metal and LiS rechargeable batteries are primarily related to Li's high propensity to form dendrites that span the battery's self during repeated charge-discharge cycles or overcharge. The anode extends to the cathode and contributes to an internal electrical short and thermal runaway.

Conventional efforts to address the problems associated with dendrite growth during battery operation include implementing multi-layer spacers that include a porous membrane and an electroactive polymeric material contained within the spacer material. In addition to spacer improvements, intermediate electrodes or layers have been proposed that are located between the anode and cathode and are separated from the cathode and anode by a fiberglass paper spacer. This intermediate electrode comprises a carbon or graphite material disposed on the spacer surface and acts as a low capacity cathode that rapidly discharges any Li dendrites in contact with the getter layer. Surface layers (such as polynuclear aromatics and polyethylene oxides) capable of transferring metal ions from the metal anode to the electrolyte and back have also been proposed. The skin layer is also electronically conductive so that ions are uniformly attracted back to the metal anode during electrodeposition. It has also been shown that internal short circuits have been prevented by using multilayer metal oxide films as spacers with small pore sizes through which Li ions can pass and dendrite growth can be suppressed. The first thin film coating on the anode and the second thin film coating on the cathode can also effectively prevent the formation of dendrites, both of which are permeable to lithium ions. The first film may contain macrocyclic compounds, aromatic hydrocarbons, fluoropolymers, glassy metal oxides, cross-linked polymers, or conductive powder dispersions. Nonetheless, the dendrite prevention mechanism of these films remains to be clearly explained. Protective coatings for Li anodes such as glassy surface layers of _{LiI - Li3PO4 -} P2S5 can be obtained from plasma assisted deposition. Despite at least these and other previous efforts, rechargeable Li metal batteries or LiS batteries equipped with solid metal Li anodes have not yet achieved reliable commercial success, and there is a need to prevent Li metal batteries and other rechargeable batteries from being used in There is a need for simpler, more cost-effective and easier to implement methods of Li metal dendrite-induced internal short circuit and thermal runaway problems in groups.

Summary of Invention

This Summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This Summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter.

One innovative aspect of the subject matter described in this disclosure can be implemented as a lithium-sulfur (LiS) battery that includes a cathode and an anode positioned opposite the cathode. The anode includes a mixed artificial solid-electrolyte interphase (A-SEI) layer encapsulating the anode. The hybrid A-SEI layer includes: a first active element; a second active element disposed on the first active element; and a plurality of carbon-containing aggregates interwoven throughout the first active element and the second active element The device is configured to inhibit the growth of Li dendrites from the anode toward the cathode. The cathode may comprise a porous carbon-based structure assembled to amplify in the presence of polysulfide (PS) shuttles within one or more sections of the LiS battery. An electrolyte can be dispersed between and in contact with the anode and the cathode.

In some embodiments, the plurality of carbon-containing aggregates comprise a polymer comprising a cross-linked polymeric network. The cross-linked polymeric network can be formulated to control the amount of contact between the electrolyte and the anode. In some aspects, the first portion of the cross-linked polymeric network has a first cross-link density, and the second portion of the cross-linked polymeric network has a second, lower cross-link density that is different from the first cross-link density. The gradient can be defined by the crosslink density of the crosslinked polymeric network across the mixed A-SEI layer of the encapsulated anode. The cross-linked polymeric network may comprise any one or more of monomers or oligomers. The cross-linked polymeric network can be formulated to inhibit dissolution of the mixed A-SEI layer. The cross-linked polymeric network can have a defined Li wettability that is formulated to facilitate Li adhesion to the cross-linked polymeric network. The crosslinked polymeric network may include any one or more of vinyl, acrylate, methacrylate, or epoxy-based groups. Any or more of vinyl, acrylate, or methacrylate groups are formulated to be cured by any one or more of ultraviolet (UV) curing methods or thermal curing methods. Epoxy-based groups are formulated to cure by adding amine or amide groups.

In some embodiments, the first active component can include a barrier that can be configured to prevent direct contact between the Li metal in the anode and the electrolyte. The barrier can be configured to prevent unstable formation of A-SEI. The barrier can be configured to prevent electrolyte decomposition. In some aspects, a Li layer can be deposited on a second active element, which can be configured to ensure uniform deposition of the Li layer. The spacer can be configured to transport Li ions from the anode to the cathode through the spacer, which can be further configured to inhibit the growth of Li dendrites from the anode toward the cathode.

In some implementations, the anode further comprises a conductive matrix configured to support the hybrid A-SEI layer. The conductive matrix may include a copper current collector. In some aspects, the anode includes a metal foil having a thickness of between about 70 μm and 130 μm. The metal foil may comprise a Li layer between about 15 μm and 50 μm thick. The hybrid A-SEI layer may be conductive. The hybrid A-SEI layer can be assembled to electrochemically stabilize itself during operational cycling of the LiS battery. The hybrid A-SEI layer may include one or more flex points configured to cyclically expand and contract the volume of the hybrid A-SEI layer during an operational cycle of the LiS battery .

In some implementations, at least one of the first active component or the second active component includes a passivation layer, which can include an inorganic component including Al ₂ O ₃ , LiF, Li ₂ S ₆ , One or more _{of P2S5} , _Li3N , _SiO2 , MoS2, _Li2S3 , _LiF , _LiN3 , Li _- metal alloy, Li _- Si, _Li3PO4 , _LiI or _Li3PS4 By. The passivation layer can include one or more metal cross-linked carboxylates, the one or more metal cross-linked carboxylates include Zn, Sn, In, Al, Mo or other metal acrylate groups, methacrylate groups Group, higher analogs. In some aspects, the plurality of carbon-containing aggregates define a porous structure comprising a plurality of few-layer graphene (FLG) sheets fused together. The plurality of carbon-containing aggregates can include polymers that are formulated such that the plurality of carbon-containing aggregates are uniformly bound to each other. The polymer may include one or more of the following: cross-linked polydimethylsiloxane (PDMS), polystyrene (PS), bis(1-(methacryloyloxy)ethyl)phosphate , Adhesion promoters based on 2-hydroxyethyl methacrylate, glycerol dimethyl esters including any one or more of succinate, maleate phthalate or phosphate ester Acrylate maleate, polyethylene glycol (PEO), poly(3,4-ethylenedioxythiophene) (PEDOT), styrene-butadiene rubber (SBR), poly(vinylidene fluoride) Ethylene-co-hexafluoropropylene) (PVDF-HFP), polyvinylidene fluoride (polyvinylidene fluoride/polyvinylidene difluoride, PVDF).

In some embodiments, the porous structure includes carbon materials having a folded morphology that can be assembled to shrink the volume of the porous structure associated with cross-linking of polymers incorporated into a plurality of carbon-containing aggregates.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Various aspects of the novel systems, apparatus, and methods are described more fully herein with reference to the accompanying drawings. However, the disclosed teachings may be embodied in many different forms and should not be construed as limited to any specific structure or function presented throughout this disclosure. Rather, these aspects are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.

Based on the teachings herein, those skilled in the art should appreciate that the scope of the present disclosure is intended to encompass the novel systems, apparatus, and methods disclosed herein, whether or not implemented independently of or in combination with any other aspect of the present invention in any form. For example, an apparatus may be implemented, or a method may be practiced, using any number of the aspects set forth herein. Additionally, the scope of the invention is intended to encompass such apparatuses practiced using other structures, functions, or structures and functions in addition to or other than the various aspects of the invention set forth herein or method. Any aspect disclosed herein may be embodied by one or more elements of the claimed scope.

Although some examples and aspects are described herein, many variations and permutations of these examples are within the scope of this disclosure. Although some benefits and advantages of the preferred aspects are mentioned, the scope of this disclosure is not intended to be limited to benefits, uses, or objectives. Rather, aspects of the present disclosure are intended to apply broadly to carbon-based particles that self-nucleate in atmospheric pressure vapor streams of carbon-containing gases such as methane, including void spaces and ion conduits defined therein. Carbon-based particles of a plurality of conductive three-dimensional (3D) aggregates of graphene sheets, some of which are exemplified in the drawings and the description of the preferred aspects below. The detailed description and drawings merely illustrate rather than limit the disclosure, the scope of which is defined by the appended claims and their equivalents. Defining a Li -ion battery pack

Li-ion batteries are a type of secondary batteries that are alternatively referred to as rechargeable batteries. In recent years, this battery pack technology has shown great promise as a power source that can cause electric vehicles (EVs) to spin by facilitating the widespread implementation of EVs in many applications. Therefore, the development of novel materials for various components of Li-ion batteries is a research focus in the field of materials science. Li-ion battery packs power most modern portable devices and appear to have overcome the psychological hurdle of the consumer mass using these high energy density devices on a larger scale for more demanding applications such as EVs.

Regarding operation, in Li-ion batteries, Li ions (Li+) begin to migrate from the negative electrode, also known as the anode, through the electrolyte, which may be in either or more of the liquid or gel phase, during the discharge cycle. , reaches the positive electrode and returns during the charge cycle. Conventional Li-ion batteries may use intercalated Li compounds as forming materials at the positive electrode and graphite at the negative electrode. Such batteries can be characterized by their relatively high energy density, as measured by specific capacity in units of milliampere-hours per gram (mAh/g), with no "memory effect" - described where nickel-cadmium batteries are only partially Repeated recharging after discharge, then it gradually loses its maximum energy capacity - and low self-discharge. Unfortunately, unlike many non-Li conventional battery chemistries, Li-ion batteries can present safety concerns due to the highly reactive nature of elemental and ionic Li. Li battery packs can degrade unexpectedly, including explosions and fires through breakdown, frictional contact, or even overcharging. Despite these drawbacks, high energy density Li-ion batteries remain attractive because they allow for longer service life of hours between charge cycles and longer cycle life, which is defined as The current delivery or output performance of a given Li-ion battery over a number of repeated charge-discharge (such as partial or total charge depletion) cycles.

Overall, Li metal still exhibits due to its high theoretical specific capacity (3,860 mAh/g), low density (0.59 g cm ⁻³ ), and low negative electrochemical potential (such as −3.040 V) compared to standard hydrogen electrodes Ideal material for the negative electrode of secondary Li-ion batteries. However, problems such as dendrite growth, which refers to the growth of branched tree-like structures within the battery itself, possibly caused by Li precipitates, persist. Dendrites when grown from one electrode to contact the other can cause serious safety issues related to short circuits and limited Coulombic efficiency, which is a consequence of the deposition and lift-off operations inherent in Li-ion batteries A discussion of charging efficiency during the transfer of electrons in the battery pack. These challenges have previously hindered Li-ion battery applications.

The safety-related issues of earlier developed Li secondary batteries have led to the development and improvement of contemporary Li-ion secondary batteries. Such Li-ion batteries are typically characterized by carbonaceous materials used as anodes, such carbonaceous anode materials include: ● Graphite; ● Amorphous Carbon; and ● Graphitized Carbon. The three carbonaceous materials of the first type presented above include naturally occurring graphites and synthetic or artificial graphites (such as highly oriented pyrolytic graphite HOPG). Either form of graphite may have Li intercalated, such as Li obtained from a molten Li metal source. The resulting graphitic intercalation compound (GIC) can be represented as _LixC6 , where _X is typically less than 1. To limit or otherwise minimize the energy density loss due to Li metal replacement with GIC, _X in _LixC6 must be maximized and the irreversible capacity loss ( _Qir ) in the first charge of the battery must be minimize.

Therefore, it is generally believed that the maximum amount of Li that can be reversibly sandwiched into the gaps between the graphene planes of a perfect graphite crystal occurs in the expression represented by Li _x C ₆ (x=1) corresponding to the theoretical 372 mAh/g Graphite intercalation compound. However, such limited specific capacity is not sufficient to meet the demanding demands of modern electronic devices and the higher energy density power needs of EVs. Thus, carbon-based anodes such as graphite intercalated with Li can exhibit extended cycle life due to the presence of a surface-electrolyte interface (SEI) layer composed of Li and Li during initial charge-discharge cycles. Reactions between surrounding electrolytes or between Li and anode surface/edge atoms or functional groups arise. It means that the Li ions consumed in this reaction of SEI formation can be derived from some of the Li ions originally intended for charge transfer, which is when in a carbon-dominated structure, such as an anode with carbon sandwiched between The dissociation process of element Li.

As associated with the release and transport of electrons during the discharge cycle of a typical Li-ion battery to facilitate current conduction to power the load device, charge transfer can occur during the movement of Li ions in the electrolyte on the porous spacer to the cathode. During repeated Li-ion battery charge-discharge cycles, SEI forms, and some of the Li ions migrating through the electrolyte become part of the inert SEI layer and are described as becoming "irreversible" in that they are no longer available for charge The transferred active element or ion. Therefore, there is a need to minimize the amount of Li used to form an effective SEI layer. In addition to SEI formation, _Qir has also been attributed to graphite exfoliation caused by electrolyte/solvent co-intercalation and other side reactions.

Next, amorphous carbon contains no or very few micro- or nano-crystallites and can include "soft carbon" and "hard carbon." Soft carbon refers to carbon materials that can be graphitized at temperatures of about 2,500°C or higher. In contrast, hard carbon refers to carbon materials that cannot be graphitized at temperatures above 2,500°C.

In practice and industry, the so-called "amorphous carbon" commonly used as an anode active material may not be pure amorphous, but actually contain a certain amount of micro- or nano-crystallites, each of which is defined as a small number of graphene sheets , the few graphene sheets are oriented with the bottom surfaces stacked and bonded together by weak van der Waals forces. The number of graphene sheets can vary from one to several hundreds, resulting in c-direction dimensions such as thickness Le, typically _0.34 nm to 100 nm. The length or width (L _a ) of these crystallites is typically between tens of nanometers and micrometers. Among such carbon materials, soft carbon and hard carbon can be produced by low temperature pyrolysis (550-1,000°C) and exhibit reversible specific capacities of 400-800 mAh/g in the range of 0-2.5 V. So-called "house of cards" carbonaceous materials with enhanced specific capacities close to 700 mAh/g have been produced.

The research team has obtained enhanced specific capacities of up to 700 mAh/g by milling graphite, coke, or carbon fibers, and has explained the origin of the additional specific capacity under the assumption that in so-called "house of cards" materials containing some In the disordered carbon of dispersed graphene sheets, Li ions are adsorbed on both sides of a single graphene sheet. It has also been suggested that Li readily bonds to proton-passivated carbon, resulting in a series of edge-oriented Li and C-H bonds. This may provide some additional source of Li+ in the disordered carbon. Other studies have shown the formation of Li metal monolayers on outer graphene sheets with graphitic nanocrystallites. The amorphous carbon system in question is prepared by pyrolysis of epoxy resins and may be referred to as polymeric carbon. Anode materials based on polymer carbon have also been studied.

Chemistry, performance, cost, and safety features can vary among Li-ion battery variants. Handheld electronic devices may use Li polymer batteries that use polymer gels as electrolytes and Li cobalt oxide (LiCoO ₂ ) as cathode materials. Such assemblies can provide relatively high energy densities, but can present a safety risk, especially if compromised. Li iron phosphate (LiFePO ₄ ), Li-ion manganese oxide batteries (LiMn ₂ O ₄ , Li ₂ MnO ₃ or LMO), and Li nickel manganese cobalt oxide (LiNiMnCoO ₂ or NMC) all offer lower energy densities but longer Usable life and low probability of fire or explosion. Therefore, such battery packs are widely used in power tools, medical equipment, and other functions. In particular, NMC is often viewed as being used in automotive applications. Lithium (Li) -Sulfur (S) Battery Pack

Lithium-sulfur batteries, referred to herein as Li-S batteries, are a type of rechargeable battery known for its high specific energy. Relatively low atomic weights of Li and medium atomic weights of S cause Li-S batteries to be relatively light at about water densities.

Li-S batteries can replace Li-ion batteries due to their higher energy density and reduced cost due to the use of sulfur. Li-S batteries can provide a specific energy of about 500 Wh/kg, which is significantly better than many conventional Li-ion batteries, which are typically in the range of 150-250 Wh/kg. Li-S batteries with up to 1,500 charge and discharge cycles have been demonstrated. Despite presenting many advantages, the key challenge facing Li-S batteries is the polysulfide "shuttle" effect, which results in progressive leakage of active material from the cathode, resulting in a short overall battery life cycle . And extremely low conductivity sulfur cathodes require additional mass of conductive reagent to take advantage of the overall contribution of effective mass to capacity. The bulk expansion of the S cathode from elemental S to _Li2S and the large amount of electrolyte required are also problem areas requiring attention.

(方程式1) Chemical processes in Li-S cells include dissolution of Li from the anode surface and incorporation into alkali metal polysulfide salts during discharge and reverse plating of lithium to the anode during charging. At the anode surface, metallic lithium dissolution occurs, and electrons and lithium ions are generated during discharge and electrodeposition occurs during charging. The half-reaction is expressed as:

(Equation 1)

Similar to what has been observed in Li-ion batteries, dissolution and/or electrodeposition reactions may lead to unstable growth problems at the solid-electrolyte interface (SEI) over time, generating potential for Li nucleation and dendritic growth the effective site. Dendritic growth causes internal short circuits in Li batteries and causes the battery itself to die.

(E ° ≈ 2.15 V對Li / Li+)        (方程式2) In Li-S batteries, energy is stored in the sulfur electrode ( _S8 ) which is the cathode. During battery discharge cycles, Li ions in the electrolyte migrate from the anode to the cathode, where S is reduced to lithium sulfide ( _Li2S ). During the refill stage, the sulfur is reoxidized to _S8 . For explanatory purposes the half-reaction is expressed at a high level of abstraction as:

(E ° ≈ 2.15 V vs Li / Li+) (Equation 2)

(方程式3) In fact, the reduction of S to Li ₂ S is significantly more complex and involves the formation of several polysulfides of Li (Li ₂ S _x , 8 < x < 1 ) at decreasing chain lengths according to the following order:

(Equation 3)

The final product is a mixture of _Li2S2 and _Li2S rather _than just pure _Li2S due to the slow reduction kinetics of _Li2S . This situation is in contrast to conventional Li-ion batteries in which Li ions are sandwiched between the anode and cathode. For example, in a LiS battery system, each S atom can hold two Li ions. Typically, Li-ion batteries can accommodate only 0.5-0.7 lithium ions per host atom. Therefore, Li-S allows much higher Li storage densities. When the cell is discharged, the polysulfide (PS) is sequentially reduced on the cathode surface: S ₈ → Li ₂ S ₈ → Li ₂ S ₆ → Li ₂ S ₄ → Li ₂ S ₃ (Equation 4)

On the porous diffusion spacer, the S polymer is formed as a cell charge at the cathode: Li ₂ S → Li ₂ S ₂ → Li ₂ S ₃ → Li ₂ S ₄ → Li ₂ S ₆ → Li ₂ S ₈ → S ₈ ( Equation 5) These reactions can be similar to those in sodium (Na)-S batteries.

Major challenges with Li-S battery systems include the low relative low conductivity of S, its large volume change upon discharge, and finding a suitable cathode, such as any of the carbon-based structures disclosed by the present invention The constructed cathode is the first step in the commercialization of Li-S batteries. Currently, conventional LiS batteries use a carbon/sulfur cathode and a Li anode. Sulfur is naturally abundant and relatively low cost, but has practically no conductivity of 5×10 ^-30 S⋅cm ^-1 at 25°C. Carbon paint provides missing electrical conductivity. Carbon nanofibers provide efficient electronic conduction paths and structural integrity at the disadvantage of higher cost.

One problem with the Li-S design is that when S in the cathode absorbs Li, volume expansion of the LixS composition occurs, and the predicted volume expansion of _{Li2S is} almost 80% of the original S volume. This situation creates a large mechanical stress on the cathode, which is the main reason for the rapid decay. This process reduces the contact between carbon (C), S and prevents the flow of Li ions to the carbon surface.

The mechanical properties of the lithiated S compounds are largely dependent on the Li content, and the strength of the lithiated S compounds increases with increasing Li content, but the increase is not linear with Li. One of the major shortages of most Li-S batteries is related to undesirable reactions with electrolytes. While S and _Li2S are relatively insoluble in most electrolytes, many intermediate polysulfides (PS) are not intermediate polysulfides such that dissolution of _{Li2Sn into} the electrolyte may result in irreversible loss of effective S (PS). The use of highly reactive Li as a negative electrode results in the dissociation of most commonly used other types of electrolytes. The use of protective layers in the anode surface has been studied to improve battery safety, such as the use of Teflon coatings showing improved electrolyte stability, and LIPON, _Li3N also showing promising performance.

(方程式6) 其中 k _s、 q _up、[ S _tot]以及 I _c分別為動力學常數、貢獻於陽極平線區之比容量、總硫濃度以及充電電流。 以碳為主之材料之電導率 The "shuttle" effect has been observed to be the main cause of degradation in Li-S batteries. Li PS Li ₂ S _x (6 ≤ x ≤ 8) is highly soluble in electrolytes commonly used in Li-S batteries. It forms and leaks from the cathode, and it diffuses to the anode, where it is reduced to short-chain PS, and diffuses back to the cathode, where long-chain PS is formed again. This process results in continuous leakage of active material from the cathode, lithium corrosion, low coulombic efficiency, and short battery life due to battery self-discharge. Furthermore, the "shuttle" effect causes the characteristic self-discharge due to the slow dissolution of PS that also occurs in the quiescent state of Li-S batteries. The "shuttle" effect in Li-S batteries can be _quantified by the factor fc (0 < _{fc <} 1), which is evaluated by the extension of the charge voltage plateau . The factor fc is given by the following expression:

(Equation 6) where k _s , q _up , [ S _tot ], and I _c are the kinetic constant, the specific capacity contributing to the anode plateau, the total sulfur concentration, and the charging current, respectively. Conductivity of carbon-based materials

Advances in high-conductivity carbon materials such as carbon nanotubes (CNTs), graphene, amorphous carbon, and/or crystalline graphite in electronic devices allow the use of printed circuit boards without the need for In the case of materials or compounds that are toxic to humans, these materials are printed onto many types of surfaces. The use of high-conductivity carbon as a feedstock material or other material during any one or more of the above-described build-up fabrication methods may facilitate the use of microlattice structures suitable for enhanced functionality, power storage and delivery, and optimal efficiency Conducted battery pack manufacturing. Although many of the described devices can function as a power source such as a battery pack or capacitor, those skilled in the art will appreciate that printing techniques such as 3D printing can use materials such as carbon nanotubes (CNTs), graphene, amorphous carbon, or crystalline graphite. High conductivity carbon materials are assembled to form other electronic devices.

Printing techniques using high-conductivity carbon materials such as carbon nanotubes (CNTs), graphene, amorphous carbon, or crystalline graphite can be implemented and/or otherwise incorporated in the fabrication of the following devices: antennas, tuned antennas , sensors, biosensors, energy harvesters, photovoltaic cells and other electronic devices. Graphene

Graphene is an allotrope of carbon in the form of a monolayer of atoms in a two-dimensional hexagonal lattice in which one atom forms each vertex. It is the basic structural element of other allotropes including graphite, charcoal, carbon nanotubes and fullerenes. It can also be regarded as an infinitely large aromatic molecule, the ultimate example of the family of flat PAHs.

Graphene has a special set of properties that distinguish it from other elements. Proportional to its thickness, it is about 100 times stronger than the strongest steel. But its density is much lower than any other steel, where the surfacic mass, such as the surface-related mass, is 0.763 mg/m². It conducts heat and electricity extremely efficiently and is nearly transparent. Graphene has also been shown to be even larger than graphite and non-linearly diamagnetic and can be suspended by Nd-Fe-B magnets. Researchers have identified bipolar transistor effects, charge shock transport, and large quantum oscillations in materials. Its end-use applications are broad, finding unique implementations in advanced materials and composites, and as a forming material to build decorative scaffolds that can be used in Li-ion battery electrodes to enhance ion transport and current conduction, resulting in other Specific capacity and power delivery diagrams that cannot be achieved by conventional battery pack technologies. Graphene chemical functionalization

Functionalization refers to the process of adding new functions, features, capabilities or properties to a material or substance by altering the surface chemistry of the material. Functionalization is used throughout chemical reactions, materials science, bioengineering, textile engineering, and nanotechnology, and can be achieved by attaching molecules or nanoparticles to material surfaces with chemical bonds or via adsorption, from gases, liquids, or The adhesion of atoms, ions or molecules of the dissolved solid to the surface to create an adsorbate film on the adsorbent surface without forming covalent or ionic bonds to it is performed.

Functionalization and dispersion of graphene sheets can be of critical importance to their respective end-use applications. The chemical functionalization of graphene enables the material to be processed by solvent-assisted techniques such as layer-by-layer assembly, spin coating, and filtration and also prevents single-layer graphene (SLG) from cohesion during reduction and maintains graphene intrinsic properties.

Currently, graphene functionalization can be performed by covalent and non-covalent modification techniques. In both cases, surface modification of graphene oxide followed by reduction to obtain functionalized graphene has been performed. Both covalent and non-covalent modification techniques have been found to be extremely efficient in preparing processable graphene.

However, it has been observed that the electrical conductivity of functionalized graphene is significantly reduced compared to pure graphene. Furthermore, the surface area of functionalized graphene prepared by covalent and non-covalent techniques is significantly reduced due to destructive chemical oxidation of flake graphite followed by sonication, functionalization and chemical reduction. To overcome these problems, studies have reported the preparation of functionalized graphene directly from graphite in a one-step process. In all these cases, surface modification of graphene prevents cohesion and promotes stable dispersion formation. Surface-modified graphene can be used to fabricate polymer nanocomposites, Li-ion battery electrodes, ultracapacitor devices, drug delivery systems, solar cells, memory devices, transistor devices, biosensors, and more. graphite

As generally understood and as referred to herein, graphite means the crystalline form of the element carbon having atoms arranged in a hexagonal structure. Graphite occurs naturally in this form and is the most stable form of carbon under standard conditions such as atmospheric conditions. In addition, under high pressure and high temperature, graphite is converted into diamond. Graphite is used in pencils and lubricants. Its high conductivity makes it useful in electronic products such as electrodes, batteries and solar panels. Roll-to-roll (R2R) processing

R2R processing refers to a method of producing electronic devices on a roll of flexible plastic or metal foil. R2R processing can also refer to any method of applying a coating, printing, or performing other processes that start with a roll of flexible material and rewind after those processes to produce an output roll. These methods and others such as tabletting can be grouped together under the generic term "transformation". When the roll of material has been coated, laminated or printed, it can then be cut and/or slit to its finished size on a slit rewinder.

R2R processing of large area electronic devices can reduce manufacturing costs. Other applications may arise that take advantage of the flexible nature of substrates such as electronic devices embedded in sleeves, 3D printed Li-ion batteries, large area flexible displays, and roll-up portable displays. Oxidation -Reduction/Redox reaction

Redox is a type of chemical reaction in which the oxidation state of an atom has changed. Redox reactions are characterized by electron transfer between chemical species, most often with one species, the reducing agent, undergoing oxidation by losing electrons, while another species, such as the oxidizing agent, undergoing reduction by gaining electrons. The chemical species that are said to strip electrons have been oxidized, and the chemical species that are said to have added electrons have been reduced. between clips

Intercalation means the reversible inclusion or insertion of a molecule or ion into a material having a layered structure. Examples are found in graphite, graphene, and transition metal dichalcogenides. Li intercalation into bilayer or multilayer graphene

The electrical storage capacity of graphene and Li storage methods in graphite currently present challenges that require further development in the field of Li-ion batteries. Therefore, efforts have been made to further develop three-dimensional bilayer graphene foams with fewer defects and predominantly Bernal stacking assemblies, i.e. a type of bilayer graphene in which half of the atoms are directly in the lower part Within the hexagonal center and half of the atoms are within one atom in the graphene sheet; and study its Li storage capacity, method, kinetics and resistance. Li atoms can be stored only in the graphene interlayer. In addition, various physiochemical characterizations of segmented Li bilayer graphene products further reveal the regular Li intercalation phenomenon and exemplify the Li storage modes of these two sizes. Electrochemical Capacitor (EC)

Electrochemical capacitors (ECs), also known as ultracapacitors (supercapacitors), are considered for use in hybrid or full EVs. ECs can supplement or, in certain applications, replace conventional battery packs used in EVs to provide brief bursts of power (such as those required for forward propulsion and often required for rapid acceleration), including High-efficiency Li-ion battery pack. Conventional battery packs can still be used to provide uniform power for steady driving at normal highway speeds, but ultracapacitors, which have the ability to release energy much faster than battery packs, can be used at specific times, such as when a car so equipped needs to accelerate Activates and replenishes the power provided by the battery pack for purposes such as merging, passing, emergency maneuvers, and mountain climbing.

The EC must also store enough energy to provide an acceptable driving range such as 220-325 miles or more. And to be cost and weight efficient relative to the additional battery capacity, the EC must combine sufficient specific energy and specific power with long cycle life and also meet cost targets. Specifically, ECs for applications in EVs must store about 400 Wh of energy, be able to deliver about 40 kW of power for about 10 seconds and provide a long cycle life such as >100,000 cycles.

ECs such as high volumetric capacitance densities 10 to 100 times greater than conventional capacitors are derived from the use of porous electrodes that can incorporate scaffold-type graphene-based materials, feature them, and/or build from them to produce large effective" Plate Area" and is derived from storing energy in the diffusive bilayer. The thickness of this bilayer, which arises naturally at the solid-electrolyte interface when a voltage is applied, is only about 1-2 nm, thus creating a very small effective "plate separation". In some ECs, the stored energy is further augmented by pseudocapacitive effects that reoccur at the solid-electrolyte interface due to electrochemical phenomena such as redox charge transfer. Double layer capacitors are based on high surface area electrode materials such as activated carbon immersed in an electrolyte. Polarized bilayer systems form at the electrode-electrolyte interface, providing high capacitance. Overview - Preface

Technological advances in modern carbon-based materials such as graphene have subsequently enhanced the application of these materials in many end-use fields such as advanced secondary batteries. Such batteries may employ electrochemical Li intercalation or deintercalation to take advantage of the advantageous properties of carbon materials and carbon-based materials, which may vary significantly depending on their respective morphology, crystallinity, crystallite orientation, and defects. Certainly. For example, the electrical storage capacity of a Li-ion battery can be achieved by selecting and integrating materials such as graphite and graphene or nanoscale graphite, nanofibers, carbon nanostructures, each having small carbon nanostructures no greater than about 2 μm in size. Desirable nanostructured carbon materials such as carbon in specific allotropes of single-walled carbon nanotubes, nanospheres, and nanoscale amorphous carbon are enhanced.

Known methods for making carbon and Li ion electrodes for rechargeable Li batteries include steps for forming carbon electrodes. Such carbon electrodes may be composed of graphitic carbon particles adhered to each other by an ethylene propylene diene monomer binder used to achieve a carbon electrode capable of intercalating Li ions. Subsequently, the carbon electrode is reacted with infiltrated lithium (Li) metal to incorporate Li ions obtained therefrom into the graphitic carbon particles of the electrode. A voltage can be repeatedly applied to the carbon electrode to initially induce surface reactions between Li ions, and repeatedly applied to the carbon and then to cause Li ions to intercalate into the crystalline layer of graphitic carbon particles. With repeated application of the voltage, a nip can be achieved to approach the theoretical maximum as may be required and to aid current conduction.

Other exfoliated graphite-based hybrid material compositions are related to: ● Micro- or nano-scale particles or coatings capable of absorbing and desorbing alkali metal or alkali metal ions, particularly Li ions; and • Exfoliated graphite flakes that are substantially interconnected to form a porous conductive graphite network comprising pores defined therein. Particles or coatings reside in mesh pores or are attached to mesh sheets. The amount of exfoliated graphite is in the range of 5 to 90% by weight and the number of particles or the amount of coating is in the range of 95 to 10% by weight.

In addition, the combination of high capacity silicon-based anode active material and high capacity Li-rich cathode active material has been shown to be effective. For some silicon-based active materials, Li supplementation has been shown to improve cycling performance and reduce irreversible capacity loss. Silicon-based active materials can be formed in composites with conductive coatings such as pyrolytic carbon coatings or metallic coatings, and composites can also be formed with other conductive carbon components such as carbon nanofibers and carbon nanoparticles .

And known rechargeable batteries with alkali metals with organic electrolytes experience very little capacity loss when the alkali metals are sandwiched between carbon-containing electrodes. The carbon-containing electrode may include a multiphase composition including a highly graphitized phase and a lower graphitization phase or may include a single phase highly graphitized composition subjected to Li intercalation above about 50°C. A conductive filamentary material such as carbon black interspersed closely with the carbon-containing composition minimizes capacity loss upon repeated cycling.

In addition, it is known that Li-based anode materials can be characterized by including a carbon-containing anode active material specific surface area of 1 m ² /g or more, a styrene-butadiene rubber binder, and fibers formed into 1,000-nanometer carbon fibers diameter. These anode materials are used in Li batteries that have desirable characteristics such as low electrode resistance, high electrode strength, electrolyte solutions with excellent permeability, high energy density, and high-speed charge/discharge. The negative electrode material contains 0.05 to 20 mass % of carbon fibers and 0.1 to 6.0 mass % of styrene. The butadiene rubber forms a binder and may further contain 0.3% by mass to 3% by mass of a thickener such as carboxymethyl methyl cellulose.

The prior art has been shown to be relevant to batteries having anode active materials that have performed the following: ● Pre-lithiation; and ● Pre-shredded. Such anodes can be prepared by methods including: ● Provide anode active material; ● Sandwich or absorb the required amount of Li into the anode active material to produce a pre-lithiated anode active material; Grind the pre-lithiated anode active material into fine particles with an average size of less than 10 µm, preferably < 1 µm and most preferably < 200 nm, by crushing, grinding, cutting, vibrating or other methods reducing solid material from an average particle size to a smaller average particle size; and ● Combining a plurality of fines of pre-lithiated anode active material with a conductive additive and/or binder material to form an anode. The prelithiated particles are protected by a Li-ion conducting matrix or coating material. The matrix material is reinforced with nanographene flakes.

Graphite nanofibers have also been disclosed and include tubular fullerenes (commonly referred to as "buckytubes"), nanotubes, and fibrils functionalized by chemical substitution for use as electrodes in electrochemical capacitors. Electrodes dominated by graphite nanofibers enhance the performance of electrochemical capacitors. Preferred nanofibers have a surface area greater than about ²⁰⁰ m2/gm and are substantially free of micropores.

And it is known that high surface area carbon nanofibers have an outer surface on which a porous high surface area layer is formed. A method of making high surface area carbon nanofibers includes pyrolyzing a polymer coating material disposed on the outer surface of the carbon nanofibers at a temperature below the melting temperature of the polymer coating material. Polymer coating materials for high surface area carbon nanofibers may include phenolic resins such as formaldehyde, polyacrylonitrile, styrene, divinylbenzene, cellulose polymers, and cyclotrimerdiethynylbenzene. High surface area polymers encompassing carbon nanofibers can be functionalized with one or more functional groups. Synthesis of the carbon disclosed in the present invention

As presented above, conventional carbon-based compositions or compounds intercalated with Li may include conventional battery electrode materials such as: graphene or multilayer 3D graphene particles; conductive carbon particles; Binders of binders provided in fluid form and/or in granular form that are formulated to retain carbon-based particles in their respective desired locations and provide overall structural integrity to carbon-based systems .

In the prior art, the particles are usually all deposited, such as dropwise, into existing current collectors comprising slurry cast electrodes made of metal foils such as copper. Slurries are usually prepared to contain an organic binder or binder material known as NMP, an organic compound consisting of 5-membered amides used as a solvent in the petrochemical and plastics industries for its non-volatile and ability to dissolve a wide variety of materials. compound. The ratio of active material to conductive carbon or carbon-based particles is typically 5 parts conductive carbon: the main balance also includes active material with a nominal amount of binder or binding material such as NMP. The relative amounts of binder and carbon conductive phase can be specified by creating one or more conductive paths between the larger particles of the active material in question.

Regarding the difficulties associated with the implementation and use of binders in secondary batteries, research has shown that developing high performance battery systems requires optimization of each battery component, from electrodes and electrolytes to binder systems. However, conventional strategies for fabricating battery electrodes by casting mixtures of active materials, non-conductive polymer binders, and conductive additives onto metal foil current collectors typically result in electrons or electrons due to randomly distributed conductive phases. Ionic bottlenecks and poor contacts, such electronic or ionic bottlenecks and poor contacts, can be problems that may be observed in the anode or cathode. And when high-capacity electrode materials are employed, the high stress generated during the electrochemical reaction may destroy the mechanical integrity of traditional binder systems, resulting in shortened battery cycle life. Thus, designs that exhibit structural integrity in the absence of binder use can provide reliable, low resistance, and continuous internal voids, microvoids, and pathways for when and where needed during battery charge-discharge cycles There is a critical need for novel and robust binder systems or scaffold-type carbon-based electrode structures that retain the active material and connect all areas of the electrode.

In contrast to conventional actions and addressing the binder performance shortcomings associated with reduced battery cycle life, the inventive composition of matter and method/process disclosed herein eliminates: any and all forms of binder phases; and Potential specific regions, characteristics and/or potential specific regions of the conductive phase bounded by larger carbon-based particles, such as larger carbon-based particles in the form of graphene including graphite and/or exfoliated extracted or otherwise produced from graphite or form.

This is done by fabricating particles in which interconnected 3D cohesives of multilayer graphene sheets are fused or sintered together, such as randomly or with controlled directionality (such as orthogonal) , or otherwise joined together to act as a type of internally self-supporting "adhesive" or as a bonding material that acts as an adhesive replacement, effectively allowing the elimination of separate traditional adhesive materials to achieve substantial weight savings. Such formats also allow for the elimination of separate and dedicated current collectors that are often a required component of many battery packs. Elimination of binder phases and/or current collectors provides beneficial and desirable features such as: ● Low production cost per unit with allowable quality manufacturability, ● High reversible specific capacity, ● Low irreversible capacity, ● Small granularity, such as those that permit high throughput/rate capacity, Compatibility with common electrolytes for ease of integration and use in commercial battery pack applications, and ● Long charge-discharge cycle life for consumer benefit across any number of demanding end-use applications including automotive, aircraft and spacecraft.

Notably, the techniques disclosed herein yield unexpectedly favorable results. It does not require traditional methods such as exfoliation of graphite to produce graphene sheets and instead synthesizes one or more multimodal carbon-dominated s from atmospheric plasma-dominated vapor streams. Synthesis of carbon-based particles can occur on-the-fly, either by nucleation from initially formed carbon-based homogeneous nucleation or during direct deposition onto a support or sacrificial substrate. Thus, any one or more of the techniques disclosed herein allow growth independent of the traditionally desired decorative carbon-based structures of seed particles on which nucleation occurs .

In the prior art, the production of functional graphene relies on the use of graphite as a starting material. Graphite, a conductive material, has been used as electrodes in batteries and other electrochemical devices. In addition to its function as an inert electrode, electrochemical methods have been employed to form graphitic intercalation compounds (GICs) and more recently to exfoliate graphite into less-layered graphene. As generally understood and as referred to herein, stripping means - in the context of intervening chemicals - complete separation of material layers and typically requires aggressive conditions involving highly polar solvents and aggressive agents. The electrochemical approach is attractive because it eliminates the use of chemical oxidants as a force for clipping or stripping, and the electrodynamic force for tunable GICs is controllable. More importantly, the extensive capabilities of electrochemical functionalization and modification enable the facile synthesis of functionalized graphene and its value-added nanohybrid.

Unlike exfoliation, including thermal exfoliation of graphite to produce graphene, the methods disclosed herein relate to one or more gaseous species including carbon, such as including methane (CH ₄ ), flowing to a microwave-based reactor or gaseous species comprising carbon in the reaction chamber of the thermal reactor. Upon receiving energy, such as that provided by electromagnetic radiation and/or thermal energy, the incoming gaseous species spontaneously crack to form allotropes with other cracked carbon from additional gaseous species supplied to the reactor to produce the initial Carbon-dominant sites, such as formed particles, that have or otherwise promote: ● additional particles that grow or nucleate based on the defects of their initially formed particles; or ● orthogonal fusion or sintering with additional carbon Primary particles, where there is sufficient local energy to combine at the point of collision for the colliding particles. System structure with carbon-dominated particles - detailed

Figure 1A shows a carbon-based particle 100A with controllable electrical and ionic conduction gradients therein, within which various aspects of the subject matter disclosed herein may be implemented. The carbon-based particles 100A can be synthesized via binder-independent self-assembly to be characterized by multimodal dimensions including various flow pores, conduits, voids, pathways, conduits, or the like, above. Any one or more are defined to have specific dimensions, such as mesopores. According to the IUPAC nomenclature, a mesoporous material means a material containing pores between 2 nm and 50 nm in diameter. For comparison purposes, IUPAC defines microporous materials as materials with pores less than 2 nm in diameter and macroporous materials as materials with pores greater than 50 nm in diameter.

Mesoporous materials may include various types of silica and alumina with mesopores of similar size. Niobium, tantalum, titanium, zirconium, cerium, and tin mesoporous oxides have been studied and reported. All variants of mesoporous materials, mesoporous carbons (such as carbon and carbon-based materials) have voids, orifices, pathways, conduits, or the like, of at least one mesopore size, that have achieved specific ridges, directly applied to in energy storage devices. Mesoporous carbon can be defined as having a porosity in the range of mesopores, and this significantly increases the specific surface area. Another commonly used mesoporous material is activated carbon, which refers to a form of carbon that has been treated to have small, low volume pores with increased surface area. In the case of mesoporosity, activated carbon is typically composed of carbon frameworks such as mesoporosity and microporosity depending on the conditions of its synthesis. According to IUPAC, mesoporous materials can be disordered or ordered in the mesostructure. In crystalline inorganic materials, the mesoporous structure significantly limits the number of lattice units, and this significantly alters the solid state chemistry. For example, the battery performance of a mesoporous electroactive material is significantly different from that of its bulk structure.

As seen in the prior art, carbon-based particles 100A nucleate and grow in an atmospheric plasma-based vapor stream of a reagent gaseous species such as methane ( _CH4 ) to form an initial carbonaceous and/or Carbon-based particles do not specifically or explicitly require a separate individual initial seed particle around which the carbon structure subsequently grows. In accordance with the disclosed embodiments of the present invention, initially carbon-dominant synthetic particles independent of individual seed particles can be subsequently amplified: - An operating description of the microwave plasma reaction chamber in accordance with Systematic coalescence of nucleation and/or growth by initial carbon-predominant homogeneous nucleation of seed particles of additional carbon-based material in the carbon gas atmosphere; or the amplification is by growth and/or Direct deposition into a thermal reactor such as a current collector support or sacrificial substrate is performed. Coalescing means a process in which two phase domains of the same composition come together and form a larger phase domain. In other words, a method that appears to pull two or more separate masses of miscible substances together if they are in least contact. The carbon-based particles 100A may alternatively be referred to simply as particles and/or any other similar term. As generally understood and as used herein, according to the International Union of Pure and Applied Chemistry (IUPAC) nomenclature, the term mesoporous can be defined as a material containing pores between 2 nm and 50 nm in diameter.

Synthesis and/or Growth of Carbon-Based Particles 100A in and/or Reaction Chambers otherwise Combined with Microwave-Based Reactors such as Reactors by Stowell et al. Man, "Microwave Chemical Processing Reactor," disclosed in US Pat. No. 9,767,992, which is incorporated herein by reference in its entirety. Synthesis can take place in systems other than microwave reactors, such as in thermal reactors, which generally refer to chemical reactors bounded by an enclosed volume in which temperature-dependent chemical reactors exist.

The carbon-based particle 100A, also shown in FIG. 1D as the carbon-based particle 100D, was synthesized as described herein in three dimensions (3D) comprising a combination of short-range localized nanostructures and long-range near fractal-characterized structures Hierarchical structure, which in this case refers to the formation of successive layers positioned orthogonally to each other. Orthogonal is defined herein as involving a 90 degree rotation of each successive layer relative to the layer below it, and the like, allowing vertical or substantially vertical layers and/or intermediate layers to be created.

Connected microstructures 107E suitable for incorporation in electrochemical cell cathodes for lithium-sulfur (LiS) secondary systems are shown in FIG. 1E , which itself shows the gap between the hierarchical pores 101A shown in FIGS. 1A and 1D . Enlarged and more detailed view. In some implementations, as shown in FIG. 1A , the contour and shape of the connected microstructures 107E can structurally define open porous scaffolds 102A and diffusion paths 109E suitable for use from anode to cathode during discharge-charge cycles Li ion transport. Connected microstructures 107E may include: a microporous framework bounded by dimensions 101E >50 nm that provides tunable Li ion channels, such as diffusion paths 109E ; Mesoporous channels defined by dimensions 102E of about 20 nm to about 50 nm (generally defined according to IUPAC nomenclature and referred to as mesoporous or mesoporous); and for charge storage and/or active materials such as LiS systems Sulfur (S) in the microporous texture bounded by <4 nm dimensions 103E, such as pores 105E.

Hierarchical porous network 100E, which includes diffusion paths 109E in addition to pores 105E for confining active materials and defining ion transport paths, can be assembled to define connected microstructures 107E for providing active Li sandwiches. Thus, the hierarchical porous network 100E with carbon-based particles 100D can be implemented in anodes or cathodes or, for example, Li ions or Li S with specific capacities rated between about 744 mAh/g to about 1,116 mAh/g in the battery pack system. For Li-ion or LiS assemblage, such as when provided by molten Li metal via capillary infusion, Li can infiltrate the open porous scaffold to chemically react, at least in part, with the exposed carbon therein in the reaction system.

One or more physical, electrical, chemical and/or material properties of the carbon-based particle 100A may be defined during its synthesis. In addition, dopants referring to trace impurity elements (such as Si, SiO, SiO2, Ti, TiO, Sn, Zn and/or the like) to be introduced into chemical materials to alter their original electrical or optical properties may be found in The carbon-based particles 100A are dynamically and at least partially affected during synthesis of material properties including electrical conductivity, wettability, and/or ion conduction or transport through the hierarchical porous network 100E. More generally, microporous textures with dimensions 103E and/or hierarchical porous networks 100E can be synthesized, prepared, or created to include smaller pores for micron confinement of chemicals such as sulfur (S), which Equally smaller pores are defined as ranging from 1 nm to 3 nm. Furthermore, the diameter (L _a ) of each graphene sheet such as shown in FIG. 1C may be in the range of 50 nm to 200 nm.

The open porous scaffold 102A can be synthesized onto metal foil current collectors in battery end-use applications without relying on binders such as traditional non-conductive polymer binders that are typically used in conjunction with conductive additives. Conventional formulations involving the use of adhesives may result in electron/current conduction related or ionic shrinkage and poor contact due to randomly distributed conductive phases. Furthermore, when high-capacity electrode materials are employed, the relatively high physical stress generated during the electrochemical reaction may destroy the mechanical integrity of traditional binder systems, thereby reducing battery cycle life thereafter.

The vapor stream stream used to synthesize the carbon-based particles 100A or the carbon-based particles 100A or the carbon-based particles 100D that may conform thereto may flow at least partially to the plasma, such as generating and/or flowing into the vicinity of the plasma in the reactor and/or chemical reaction vessel. Such plasma reactors can be configured to deliver microwave energy towards a vapor stream stream to at least partially assist in the synthesis of the carbon-based particles 100A, which can involve the formation of carbon-based gaseous species such as methane ( _CH4). )) and/or carbon particle-derived nucleation and growth, wherein the nucleation and growth can be carried out in the reactor independent of the initial formation of homogeneous carbon-based nucleation of seed particles actually happen. Such a reactor accommodates a gas-solid reaction control under non-equilibrium conditions, wherein the gas-solid reaction can be controlled at least in part by one or more of the following: and introduction into the reactor to synthesize carbon-based particles. The dissociative potential and/or thermal energy associated with the constituent carbon-dominated gaseous species; and/or the kinetic momentum associated with the gas-solid reaction.

The vapor stream stream may flow into the reactor and/or reaction chamber at substantially atmospheric pressure to synthesize carbon-based particles 100A. And the change in wettability of the carbon-based particle 100A and/or any constituent member such as the open porous scaffold 102A may involve, at least in part, the modulation of the polarity of the carbon matrix associated with the carbon-based particle 100A. Synthetic Procedure Microwave Reactor

A vapor stream stream comprising carbon-containing constituent species such as methane ( _CH4 ) can flow to one of two general types of reactors to produce carbon-based particles 100A: thermal reactor; or microwave-based the reactor. A suitable type of microwave reactor is disclosed by Stowell et al., "Microwave Chemical Processing Reactor", US Patent No. 9,767,992, filed September 19, 2017, which is incorporated herein by reference in its entirety.

The term running means that the novel chemical synthesis method is based on contacting particulate material derived from influent carbon-containing gaseous species such as methane ( _CH4 )-containing influent gaseous species to crack the gaseous species. As generally understood and as referred to herein, cracking means methane used to produce elemental carbon such as high quality carbon black and hydrogen without difficult to resolve carbon oxide pollution and with virtually no carbon dioxide emissions Pyrolysis technology method. The basic endothermic reaction that can occur in a microwave reactor to produce carbon-based particles 100A is shown by the following equation (7): CH ₄ + 74.85 kJ/mol ⟶ C + 2H ₂ (7)

Carbon derived from the cracking process described above and/or similar or dissimilar processes can be fused together while dispersed in the gas phase, said to be in operation, to produce carbon-predominant particles, structures, substantially 2D Graphene sheets, 3D cohesive bodies and/or pathways defined therein, including: ● The interconnected 3D cohesion of the multilayer graphene sheets 101C fused together as schematically depicted in FIG. 1C to form an open porous scaffold 102A that facilitates conduction along and across the contact points of the graphene sheets 101C as shown in FIG. 1B The bulk 101B and/or the monolayer graphene may comprise and/or refer to 5 to 15 layers of few-layer graphene oriented in a stack arrangement to have a vertical height called stack height (Lc); and Any one or more of the connected microstructures 107E interspersed with or otherwise shaped by the interconnected 3D cohesion 101B; in some configurations, the interconnected 3D cohesion may be prepared to include a single Layered graphene (SLG), defined as one or more of few-layered graphene (FLG) or multi-layered graphene (MLG) ranging from 5 to 15 layers of graphene.

As previously introduced, the interconnected 3D cohesives 101B of the multilayer graphene sheets are orthogonally fused together to act as a type of internal self-supporting adhesive or bonding material, allowing the elimination of separate traditional adhesive materials. As generally understood and as referred to herein, these procedures differ substantially from conventional sintering or firing, which means compacting and forming a solid mass of material by heat or pressure without melting it into which the material is A method of liquefaction points that meet each other at a specific acute angle.

Few-layer graphene (FLG), defined herein as ranging from 5 to 15 graphene sheets, fuses over time at angles that are not flat relative to other FLG sheets to nucleate at an angle and/or grow and thus self-assemble. In addition, processing conditions can be tuned to achieve carbon-based particles 100A, also referring to a plurality of carbon-based particles on components and/or wall surfaces within the reaction chamber or in contact with other carbon-based materials Synthesis, nucleation and/or growth that is fully running at the time.

The conductivity of the deposited carbon and/or carbon-based materials can be tuned by adding metal additions to the carbon phase in the first portion of the deposited phase or tuned to vary the ratios of the various particles in question. Other parameters and/or additives can be adjusted as part of the high energy deposition process so that a certain energy of deposited carbon and/or carbon-based particles will or will not stick together.

By nucleating and/or growing, or directly onto a support or sacrificial substrate, carbon-based particles 100A running in an atmospheric plasma-based vapor stream stream, in conventional Numerous steps and components found in batteries and conventional battery manufacturing methods can be eliminated. Furthermore, a great deal of adaptation and tunability can be enabled or otherwise added to the carbon and/or carbon-based materials discussed.

For example, conventional batteries may use a starting stock of active material, graphite, etc., available as a ready-made material to be mixed into a slurry. In contrast, the carbon-based particles 100A disclosed herein may be capable of on-the-fly adaptation and/or tuning of material properties as part of the carbon or carbon-based material synthesis and/or deposition process, when such The material is being synthesized and/or deposited onto the substrate on-the-fly. This capability presents an unexpected, unexpected, and substantially beneficial departure from what is currently available with respect to the generation of carbon-dominated scaffold-type electrode materials in the secondary battery field.

Stowell et al., "Microwave Chemical Processing Reactor", US Patent No. 9,767,992, filed Sep. 19, 2017 discloses reactors and/or reactor designs that can be adjusted, assembled, and/or adapted to control exposure to factors such as Desirable or undesirable nucleation sites on the inner surface of the reaction chamber for the carbon-based gaseous feedstock species of methane ( _CH4 ). The quality of the running particle can be affected by its solubility in the gaseous species in which it flows such that once a certain energy level is reached, the carbon is cracked off in the microwave reactor as described by thermal cracking and Forming its own solid is not unimaginable. Regulates Undesirable Carbon Buildup on Reaction Chamber Walls

Furthermore, tuning of the disclosed reactors and related systems can be performed to address the blockage associated with carbon-dominant microwave reactors, such as actively before observing undesired processing conditions and such as passively after observing such conditions the problem. For example, open surfaces, feed holes, hoses, pipes, and/or the like can accumulate undesirable carbon-based particulate matter as a by-product of the synthesis process performed to produce carbon-based particulate matter. Particle 100A. A central problem observed in microwave reactors may include this tendency to experience blockage in and/or along orifices due to exposure to walls and other surfaces of gaseous carbonaceous species in the flow that also have carbon solubility. Therefore, undesirable growth on the reaction chamber walls and/or on the outlet pipe is possible. Over time, these growths extend outward and eventually impinge on the flow and can shut down chemical reactions taking place within the reactor and/or reaction chamber. Such phenomena can be analogous to tubulars, such as exhaust gas, wall buildup from burning oil in high-efficiency or fast-running internal combustion engines, where instead of burning (such as burning) fossil-fuel-based gasoline, methane is used to create gas in the reaction chamber pores. Undesirable carbon deposits are created on the surface of the reaction chamber because the metal inside the reaction chamber itself has a carbon solubility level.

Although methane is primarily used to generate carbon _- based particles 100A, any carbon and/or hydrocarbon containing gas such as _C2 or acetylene or _C2H2 , _CH4 , butane, natural gas, biogas (such as derived from biomass Any one or more of decomposed biogas) are also used to provide a carbon-containing source.

The described uncontrollable and undesirable carbon growth within the exposed surfaces of microwave reactors can be compared to the carbon growth that occurs in an engine such as an internal combustion engine exhaust manifold opposite the cylinder bore, especially where such as will enter the plasma phase The hot and excited gas plasma plume is at the manifold start, and the scorching gas and carbon-dominant fragments travel down and up into the flow manifold, crossover conduits and catalytic converters, and outlet conduits. Thus, processing conditions can be actively tuned to accommodate and thus accommodate potential carbon buildup in the microwave reactor, which is dependent on the presence of plasma for hydrocarbon gas cracking. To maintain this plasma, a certain set of conditions must be maintained, otherwise a build-up of back pressure may destroy the plasma before its creation and subsequent ignition, etc. thermal reactor

In an alternative or addition to the synthesis of carbon-based particles 100A in microwave reactors, structured carbon can be produced by thermal cracking of hydrocarbons by application of heat in a reactor such as a thermal reactor. Exemplary configurations may include exposure of carbon-based gaseous species, such as any one or more of the aforementioned hydrocarbons, to a heating element similar to the wire in a light bulb.

The heating element heats the interior of the reaction chamber into which the carbon-containing gas is ionized. The carbonaceous gas does not burn due to the absence of sufficient oxygen to sustain combustion, but is instead ionized by contact with incoming thermal radiation, such as in the form of heat, to cause nucleation of constituent members of the carbon-predominant particles 100A, and ultimately Carbon-based particles 100A and/or carbon-based particles that are generally similar thereto are synthesized via nucleation. In thermal reactors, at least some of the observed nucleation of predominantly carbon particles can occur on the walls or on the heating element itself. Nonetheless, particles small enough to be fragmented by the velocity of the flowing gas can still nucleate, where the particles are trapped to assist in the production of carbon-based particles 100A.

The cracked carbon can be used to produce multishell fullerene carbon nano-onions (CNOs) and/or other fullerenes and smaller fractions of carbon with fullerene internal crystallography. In comparing the synthesis of carbon-based particles 100A via microwave and thermal reactors, the following differences have been observed: the microwave reactor can provide tuning capabilities suitable for providing a wider range of carbon allotropes; and • Thermal reactors tend to allow fine-tuning of process parameters such as heat flow, temperature, and/or the like to achieve the needs of the carbon-based particle 100A specific end-use application goals.

For example, thermal reactors are currently used to construct LiS electrochemical cell electrodes such as anodes and cathodes. Typical process temperatures are in the thousands of absolute temperature (Kelvin) range to produce electrical conductivity greater than 500 S/m or greater than 5,000 S/m or 500 S/m to 20,000 S/m or more when compressed Carbon-based particles 100A and/or carbon-based aggregates associated therewith. Optimum potency has been observed between 2,000-4,000 K. Carbon-Based Particles - Physical Properties and Implementation

Any of the carbon-based structures shown in FIGS. 1A-1F can be incorporated into secondary battery electrodes, such as electrodes of lithium (Li) ion batteries, as disclosed on June 6, 2019 Lanning et al., "Lithium Ion Battery and Battery Materials", US Patent Publication No. 2019/0173125, which is incorporated herein by reference in its entirety. The disclosed embodiments generally relate to Li incorporation or infusion within the anode, but carbon-based systems may be targeted to cathodes, especially where S-micron confinement is required to reduce undesirable polysulfide (PS) shuttling and cell self-discharge. The compatibility and integration of the cathode in the LiS system were modified.

Particulate carbon contained in and/or otherwise associated with carbon-based particles 100A can be implemented as structural and/or conductive materials in Li-ion battery anodes or cathodes and is characterized by a broad pore size distribution, as well as Hierarchical porous network 100E referred to as multimodal pore size distribution. For example, in addition to or as an alternative to the connected microstructures 107E as shown in Figure IE, particulate carbon may contain at least in part a multimodal distribution that further defines the open porous scaffold 102A having one or more diffusion paths 109E porosity. The pores may be 0.1 nanometers to 10 nanometers, 10 nanometers to 100 nanometers, 100 nanometers to 1 micrometer, and/or larger than 1 micrometer in size. The pore structure may contain pores with a multimodal size distribution, including smaller pores ranging from 1 nm to 4 nm in size and larger pores ranging in size from 30 nm to 50 nm. Such a multimodal pore size distribution in the carbon-dominated particles 100A can be beneficial in LiS battery system assembly, where the S-containing cathode in the LiS battery can be limited to having a size of about less than 1.5 nm or less. In pores 105E of size 103E in the range of 1 nm to 4 nm. S and/or generated S compounds in carbon-dominated cathodes comprising connected microstructures 107E in larger pores or pathways in the range of 30 nm to 50 nm in size, or pores larger than twice the size of solvated lithium ions Saturation and crystallinity control of ZnO can enable and/or promote rapid diffusion or mass transfer of solvated Li ions, such as lithium (Li) ions 108E, in the cathode.

As previously introduced, the lithium-sulfur battery, abbreviated as Li-S battery, is a type of rechargeable battery known for its high specific energy. The Li-S battery may include sulfur (S) infiltrated or impregnated to confine within the pores 105E and along the exposed surfaces of the connected microstructures 107E of the mesoporous particles 100D. Thus, S can infiltrate the open porous scaffold 102A for deposition on the inner surfaces of the carbon-dominated particles 100A, 100D and/or within the associated microstructures 107E when incorporated into the cathode of the LiS battery as follows 1E and by the schematic diagram 100F shown in FIG. 1F, which shows the intermediate steps associated with the reduction of sulfur to sulfide ions (S ²⁻ ). Carbon Dominated Particles - Formed to Address Polysulfide (PS) Related Challenges

In an attempt to address at least some of the challenges associated with these polysulfide (PS) systems, the carbon-based particles 100A and cathode active materials form a meta-particle framework, such as can be formed as shown in Figure IF The cathodic electroactive material of elemental sulfur of PS compound 100F shown in is disposed within carbon pores/channels, such as any one or more of the connected microstructures 107E shown in FIG. 1E, including pores 104E, 105E and Within path 106E and/or diffusion path 109E. For example, S may represent a loading level of 35-100% of the total weight/volume of the active material in the carbon-based particle 100A and/or 100E population substantially and within the associated microstructure 107E.

Organized particle frameworks of this type can provide low resistance electrical contact between insulating cathode electroactive materials such as element S and current collectors, while providing relatively high exposed surface area structures that are beneficial to overall specific capacity and Can assist, for example, by forming Li-ion micro-confinement enhanced by the formation of LiS compounds that temporarily remain in connected microstructures 107E, such as in pores 105E, to later control and direct current such as in battery electrodes and/or systems Conduction-dependent Li ion migration. The implementation of carbon-based particles 100A can also be achieved by using an adapted structure, such as that shown by the connected microstructure 107E, to effectively prevent it from undesirably migrating through the electrolyte to the anode, resulting in a self-consistency with the battery. Undesirable parasitic chemical reactions associated with the discharge to trap at least some portion of any polysulfides produced benefit cathodic as well as anodic stability. Migration of polysulfide (PS) during use of LiS battery system

As previously introduced, with reference to the PS shuttling mechanism observed in LiS battery electrodes and/or systems, PS dissolves well in the electrolyte. This move characterizes another Li-S battery, the shuttle mechanism. _The PS _Sn2 formed and dissolved at the cathode diffuses to the Li anode and is reduced to _Li2S2 and _Li2S . The PS species _Sn2- formed at the cathode during ^discharge dissolves in the electrolyte here. This causes the PS to diffuse towards the anode as the concentration gradient develops relative to the anode. PS is gradually distributed in the electrolyte. Subsequent higher PS species react with these compounds and form lower polysulfides S _(nx) . This means that the desired chemical reaction of sulfur at the cathode also occurs partly in an uncontrolled manner at the anode where chemical and electrochemical reactions are conceivable, which negatively affects overall cell characteristics.

If lower PS species form near the anode, they diffuse to the cathode. When the battery is discharged, these _diffused species are further reduced to _Li2S2 or _Li2S . Thus, during the discharge process or more precisely during the self-discharge of the battery, the cathodic reaction takes place partly at the anode. Both are undesirable effects of reducing specific capacity. In contrast, diffusion to the cathode during the charging process is followed by reoxidation of PS species from low to high order. Subsequently, these PS diffused to the anode again. This cycle is generally referred to as a very obvious shuttle mechanism, and it is possible that the battery can accept an infinite charge for chemical shorting. In general, the shuttle mechanism results in the loss of parasitic sulfur active species. This is due to the uncontrolled _segregation of _Li2S2 and _Li2S outside the cathode region and it ultimately results in greatly reduced battery cycling capability and greatly shortened service life. Additional aging mechanisms may be heterogeneous segregation of _Li2S2 and _{Li2S on} the cathode due to volume changes during cell reaction or mechanical cathodic structure splitting. Pores of carbon-dominated particles confine sulfur and prevent PS shuttling to the anode

To address the PS shuttling phenomenon, any one or more of the connected microstructures 107E of the carbon-based particles 100A in the cathode may be provided with regions formed with appropriate dimensions, such as pores 105E having dimensions 103E of less than 1.5 nm, to The production of lower polysulfides such as S and _{Li2S is} driven, and thus the formation of higher soluble polysulfides LixSy (where _y is greater than 3) that promotes Li shuttling (such as loss to the anode) is prevented. As described herein, the structure of the particulate carbon and cathode material mixture can be tuned during the formation of the particulate carbon within a microwave plasma or thermal reactor. Additionally, the solubility and crystallinity of cathode electroactive materials, such as elemental sulfur, associated with Li phase formation can be confined to/within the microporous and/or mesoporous framework of the associated microstructures 107E of the carbon-dominated particles 100A was captured.

A multimodal pore size distribution may indicate that a structure has a high surface area and a large number of small pores that are effectively connected to the matrix and/or current collector through materials in the structure that have larger characteristic sizes to provide more conductive paths through the structure . Some non-limiting examples of such structures are fractal, dendritic, branched, and aggregated structures having interconnected channels of varying sizes composed of generally cylindrical and/or spherical pores and/or particles.

Exemplary particulate carbon materials for use in the Li-ion or Li S batteries described herein are described in US Patent No. 9,997,334 entitled "Seedless Particles with Carbon Allotropes," which is assigned the same assignment as the present application and incorporated herein by reference. The particulate carbon material may comprise a graphene-based carbon material comprising a plurality of carbon aggregates, each carbon aggregate having a plurality of carbon nanoparticles, each carbon nanoparticle comprising graphene, optionally a multi-wall spherical rich material. and optionally no seed particles, such as no nucleating particles. In some cases, particulate carbon materials are also produced without the use of catalysts. Graphene in the graphene-based carbon material has at most 15 layers. The ratio of carbon to elements other than hydrogen in the carbon aggregate is greater than 99%. The median size of the carbon aggregates is 1 to 50 microns or 0.1 to 50 microns. The surface area of the carbon aggregates is at least 10 m ² /g or at least 50 m ² /g or 10 m ² when measured using the Brunauer-Emmett-Teller (BET) method with nitrogen as the adsorbate /g to 300 m ² /g or 50 m ² /g to 300 m ² /g. When compressed, the carbon aggregates have electrical conductivity greater than 500 S/m or greater than 5,000 S/m or 500 S/m to 20,000 S/m. Differences between carbon-based particles and prior art

Conventional composite type Li-ion or LiS battery electrodes can be made from slurry cast mixtures of active materials including conductive materials such as fine carbon black and graphite used in battery cathodes in specific aspect ratios Additives and polymer-based binders optimized to produce unique self-assembled morphologies defined by interconnected percolating conductive networks. Whereas in conventional preparations or applications, additives and binders can be optimized to improve pass-through conductivity by, for example, providing lower interfacial impedance and thus corresponding electrical performance and delivery improvements, which means that the ratio must also be reduced (also known as gravitational) energy and density, ie parasitic bulk of the undesirable end result of today's demanding high-efficiency battery pack applications.

To minimize losses due to parasitic bulk, such as losses due to increased effective and/or ineffective ratios, and at the same time enable the electrolyte to reach the full surface of the electrode faster, the diffusion path 109E can be reoriented to effectively shorten Li-ion diffusion path length for charge transfer. Hierarchical pores 101A and/or open porous scaffolds 102A may be produced from carbon particles downsized and/or active materials downscaled to the nanoscale. Defined as the total surface area of the material/unit mass (units m ² /kg or m ² /g) or solid or total volume (units m ² /m ³ or m ⁻¹ ) outside the specific surface area (SSA) can be used to determine Physical values of any one or more of the carbon particles disclosed herein for material types and properties. For example, spherical SSA increases with decreasing diameter. However, as particle size drops into the nanometer size range, there are associated attractive Van der Waals forces that can hinder dispersion, promote cohesion, and thereby increase cell impedance and reduce power performance.

Another approach for shortening ion diffusion paths (referring to diffusion paths 109E shown in Figure 1E) is to uniquely engineer constitutive carbon-based particles, such as cohesives 101B used to create connected microstructures 107E The resulting internal porosity of the constituent carbon-dominated particles. Surface curvature may be referred to as a porosity if its cavity depth is greater than its width. Therefore, this definition must exclude many nanostructured carbon materials in which only the outer surface area is modified, or tightly packed particles in which voids such as interior specific spaces or regions are created between adjacent particles, as in conventional slurries The same is true in the case of cast electrodes.

With respect to the synthesis, production, formation and/or growth of carbon-based particles 100A as substantially previously described referring to running in a microwave-based reactor or via layer-by-layer deposition in a thermal reactor Engineered, the reactor process parameters can be adjusted to tune the size, geometry and distribution of hierarchical pores 101A and/or associated microstructures 107E within carbon-dominant particles 100A. Hierarchical pores 101A and/or associated microstructures 107E within carbon-based particle 100A can be tailored to achieve a performance map that is particularly well suited for implementation in high performance fast current delivery devices such as ultracapacitors.

As generally described earlier, a supercapacitor (SC), also known as an ultracapacitor, is a bridging electrolytic capacitor with a much higher capacitance value than other capacitors, but a lower voltage limit, and a rechargeable battery pack. gap high-capacity capacitors. They typically store 10 to 100 times more energy per unit volume or mass than electrolytic capacitors, can accept and deliver charge much faster than a battery pack, and accommodate many more charge and discharge cycles than a rechargeable battery pack.

In many of the readily available commercial carbons used in early ultracapacitor development work, there are narrow worm-like pores that become bottlenecks or disadvantageous conditions when operating at high current densities and fast charge and discharge rates because electrons may Difficulties in flow will be encountered in or around such structures or paths. Even though the pore size is extremely uniform yet can be tuned to accommodate a wide range of length scales, the truly achievable performance is still self-limiting based on the structural challenges inherent in worm-like narrow pores.

In contrast to conventional porous materials having uniform pore sizes tuned to a wide range of length scales, the 3D hierarchical porous materials disclosed herein, such as hierarchical pores 101A within carbon-based particles 100A and/or The 3D hierarchical porous material shown by connected microstructures 107E can be synthesized to have well-defined pore sizes, such as connected microstructures 107E including pores 104E, 105E and/or pathways 106E and/or diffusion pathways 109E and topologies to be Multimodal pores and/or channels with the following dimensions and/or widths are created to overcome the disadvantages of conventional single-sized porous carbon particles: ● Medium (2 nm < _dpores < 50 nm) pores; ● Large ( _dpores > 50 nm) nm) pores 201A to minimize diffusion resistance for mass transport; and Micro (d _pores < 2 nm) pores 202 to increase the surface area for active site dispersion and/or ion storage, and storage at a given pore size , the ion density and number-dependent capacitance within the pore size, such as that shown by pores 105E of size 103E in FIG. 1E.

Although a simple linear correlation between surface area and capacitance has not been established experimentally, the carbon-based particles 100A provide optimal pore size distributions and/or groups that differ for each intended end-use application and corresponding voltage window match. To optimize capacitive performance, carbon-based particles 100A can be synthesized with a very narrow pore size distribution (PSD); and larger pores are preferred as the required voltage increases. Regardless, current state-of-the-art ultracapacitors have provided a route to engineer the 3D hierarchically structured materials disclosed herein for specific end-use applications.

In ultracapacitors, capacitance and electrical performance are primarily governed by, for example, the surface area of the pore walls; the size of the pores; and the interconnectivity of the pore channels that affect the performance of the electric double layer.

In contrast, Li-ion and/or Li-S storage batteries undergo faradaic reduction/oxidation reactions within the active material and thereby may require techniques such as supercapacitors that effectively orient and/or shorten Li-ion diffusion paths. Many Li-ion transport parts. Regardless, in any application including supercapacitors and conventional Li-ion or LiS secondary batteries, 3D nanocarbon-dominated frameworks/architectures, such as the 3D nanocarbon-dominated architecture defining the open porous scaffold 102A The framework/framework may provide a continuous electrically conductive path, such as across and along the conductive interconnect cohesion 101B of the graphene sheets, alongside highly loaded active materials with, for example, high area and volume specific capacity. Carbon-based particles used as forming materials for cathodes

To address the prevalence of relatively low electrical and ionic conductivity, volume expansion, and polysulfide (PS) dissolution in current LiS cathode electrode designs, carbon-based particles 100A have carbon-based particles 100A formed therein to define open porous scaffolds 102A. Hierarchical pores 101A and/or connected microstructures 107E, the open porous scaffold 102A includes cavities having dimensions 103E suitable for confinement of elemental sulfur and/or LiS related compounds, such as cavities less than about 1.5 nm or 1-4 nm. Pores 105E of the microporous structure. The open porous scaffold 102A also provides a bulk scaffold-type structure when sulfur is confined to manage S amplification by, for example, in situ nitrogen (N) doping of carbon (C) adapted within the reactor to ensure trans-sulfur-carbon (SC) ) interface, such as electron conduction at the contact and/or interface region of S and C within pores 105E. Confining S within nanometer (nm)-scale cavities, such as pores 105E with a microporous texture 103E, advantageously modifies both: the equilibrium saturation, such as the solubility product; and the crystallization behavior of S, such that the apparent Desired electrical conduction upon dissociation of LiS compounds etc. may be required, S remains confined within a microporous texture or pores 105E with dimensions 103E without the external dynamics required to control the undesirable PS migration to the anode electrode .

Thus, the size 103E of the pores 105E results in no need to attempt to hinder polysulfide (PS) diffusion, while negatively affecting the cell impedance due to the combined effect of ohmic resistance and reactance and polarization, such as circuit or component resistance to alternating current Spacers for effective resistance. By using connected microstructures 107E with optimal and non-optimal multimodal pore distributions (referring to including pores 104E, 102E and/or 103E) or (alternatively (2) Carbon with a bimodal pore distribution, the carbon-dominant particles 100A exhibit a micron-confined operating principle in a properly optimized structure.

The optimized structures include incorporating agglomerates 101B, which themselves can be prepared to include parallel stacked graphene layers, such as from graphite having a strong (002) dimension to having a low (002) dimension Random few-layer (FL) graphene with nanoscale pores of dimensionality produces parallel stacked graphene layers. Figures 1G and 1H show the inter-system sandwiches of Li ions positioned in the individual graphene layer cells in Figure 1G and the carbon lattices and structures in the intervening and parallel graphene layers in Figure 1H. The assembly shown in Figure 1H can include multiple stages, including stages 1 through 3, each state representing graphitic layer planes of various sizes and pitch levels to yield a theoretical ratio of about 372 mAh/g or greater at the cathode capacity.

FIG. 2 shows the evolution of conventional contiguously stacked FL graphene layers beyond that shown in stages 1 to 3 in FIG. 1H , wherein cavities extending deep into several contiguous stacked FL graphene layers are formed, each layer having between about 3.34 Å Tunable D-spacing in the range of 4.0 Å or 3 Å to 20 Å. Thus, Li ions can be sandwiched between adjacent graphene layers and layered on the exposed surfaces of cavities, also known as nanoscale pores, to yield specific capacity ranges in excess of 750 mAh/g. According to some embodiments, when viewed together, an exemplary enlarged portion of a 3D self-assembled binderless carbon-based particle can coalesce to form a carbon-based structure that can include the ones shown in FIGS. 1A-1E . Any one or more of carbon-based networks, lattices, scaffolds or particles. The carbon-based network may include any one or more of a plurality of macropores or micropores 202 .

The carbon-based particles 100A also provide the ability to effectively support or impregnate the carbon scaffold 300 shown in FIG. 3 with elemental Li, such as that provided by molten Li metal or its vapor derivatives. The carbon scaffold 300 can be produced in the reactor by depositing a plurality of carbon-based particles 100A layer by layer by a slurry-based method; or, as shown by the plasma jet torch system 400B in FIG. 4B, by A set of plasma jet torches with successive sequences of sulfur such as elemental sulfur.

For LiS battery performance to reliably exceed conventional Li-ion batteries, industrially scalable technologies must achieve high S loadings, such as >70% sulfur/unit volume, relative to all additives and components of a given cathode template , while maintaining the natural specific capacity of the S active material. Attempts to incorporate S into the cathode body, such as by any one or more of electrolysis, wet chemistry, simple mixing, ball milling, spraying, and catholyte, have been incomplete with S or otherwise in the cathode body as desired. Not economically upgradable or manufacturable.

Unlike melt infiltration where small pores are thermodynamically unattainable, the disclosed synthetic methods can use isothermal vapor techniques introduced and reacted at substantially atmospheric pressure, where high surface free energy of nanoscale pores or surfaces drives sulfur-containing Spontaneous nucleation of the liquid until the conformal coating of sulfur and/or lithium condensate reaches the inward facing surface of the hierarchical pores 101A and/or the connected microstructures 107E. Essentially, the unique vapor infusion method infuses sulfur into fine pores such as hierarchical pores 101A and/or connected microstructures 107E and/or pores 104E, 105E at the core of carbon-dominated particles 100A and/or any one or more of path 106E and/or diffusion path 109E, and thus not only at its surface. Carbon-based particles for the production of conductive scaffolds

The carbon-based particles 100A can be manufactured in any number of ways using known techniques and the novel techniques disclosed herein, including: Slurry casting, which refers to where a liquid material is typically poured into a material having a desired shape Conventional metalworking, fabrication, and/or fabrication techniques in a mold with a hollow cavity and subsequent solidification; or a plasma jet torch system 400B, such as the plasma jet torch system 400B shown in FIG. 4B , which can be used A layer-by-layer deposition is performed to gradually grow the carbon-based particles 100A.

Any of the techniques as described above, or any other known or novel fabrication technique, can be used to produce the carbon scaffold 300 shown in FIG. 3 in a hierarchical manner. Control of the electrical gradient can result in carbon scaffolds 300 with varying degrees of conductivity, as specified at least in part by any one or more of an electrical gradient and an ionic conduction gradient as described below: an electrical gradient can be defined by graphene sheets 101B fused together substantially orthogonally to form open porous scaffold 102A, with electrical conduction occurring along and across the contact points of graphene sheets 101B; and Ion conduction gradients such as Li ion transport, movement or migration through hierarchical pores 101A and associated microstructures 107E may benefit in certain configurations of carbon-dominated particles 100 in vertical orientation as shown in Figure 3B Effective shortening of the diffusion paths 109E in the height direction A throughout the thickness of the carbon scaffold 300B, for example to allow Li ions sandwiched between adjacent few-layer graphene sheets such as graphene sheets 101B to be directed towards the carbon scaffold 300B The surrounding liquid electrolyte escapes en route and migrates to the cathode curing electrochemical cell discharge-charge cycle.

Throughout the disclosed embodiments, reference has been made to various forms of carbon that are synthesized on-the-fly within the reactor to produce graphene sheets 101B that are interconnected and conduct electricity along the contact points and Changes in shape, size, location, orientation and/or structure may occur. These variations can be affected in terms of crystallinity differences and one or more carbon allotropes of the particular type used to create the conductive interconnect aggregate 101B of the graphene sheets. Crystallinity means the degree of structural order in a solid. In a crystal, atoms or molecules are arranged in a regular periodic fashion. Therefore, crystallinity has a considerable effect on hardness, density, transparency and diffusion.

Thus, the carbon-based particles 100 can be produced outside the reactor in the form of organized scaffolds such as carbon-based scaffolds or during processing activities after the main synthesis takes place within the reactor.

As disclosed in Stowell et al., "Microwave Chemical Processing Reactor", US Pat. No. 9,767,992, issued Sep. 19, 2017, plasma processing and/or plasma-based processing can be performed in a reactor where supplying Gas systems are used to generate a plasma in the plasma zone to convert process input materials such as methane and/or other suitable hydrocarbons in the gas phase into separated components in the reaction zone to promote carbon-based materials The running synthesis.

As an alternative to synthesis by or within a microwave reactor as described above, thermal energy may be directed towards the carbon support 300 shown in Figure 3 towards or close to the carbonaceous feedstock material supplied in the gas phase Layers of carbon-based particles 100A are sequentially deposited on the sacrificial substrate 306 by, for example, the plasma jet torch system 400B shown in FIG. 4B. The particles can be fused together on-the-fly in a microwave reactor or deposited in a controlled manner in a thermal reactor to achieve varying levels of concentration of carbon-based particles 100A, and thus later achieved with the carbon scaffold 300 Graded conductivity proportional to the concentration level of carbon-based particles 100A. These procedures can be used to formulate porous carbon-based electrode structures such as carbon scaffold 300 that are highly tunable in conductivity and ion transport, while also eliminating many production steps and otherwise preserving the conventional external appearance.

An open porous scaffold 102A with an open honeycomb structure can be created such that liquid electrolyte can readily infiltrate into various pores therein, such as any one or more of the pathways, voids, and the like that connect the microstructures 107E. indivual. The frame portion of the open porous scaffold 102A may be referred to as a substrate or framework, and pores such as hierarchical pores 101A and/or connected microstructures 107E may be impregnated with fluids, liquids or gases, while the frame material is typically formed as a solid material. Porosity of carbon-based particles

Porous media such as carbon-based particles 100A may be characterized by their porosity. Other properties of the medium, such as permeability, tensile strength, electrical conductivity, and tortuosity, can be derived from its components, the solid matrix and fluid dispersed therein, and the corresponding properties of the medium's porosity and pore structure. Carbon-based particles 100A with interconnected microstructures 107E dispersed throughout can be generated outside the reactor to achieve the desired level of porosity that facilitates Li ion diffusion. In connection with this Li ion diffusion, graphene sheet 101B facilitates electron conduction along its contact points, while also allowing electrons to recombine with positive Li ions at the reaction site.

Regarding the porosity and torsion of the open porous scaffold 102A of the carbon-based particles 100A, marble analogs can be made in glass vials. In this example, porosity refers to the inter-marble spacing that allows the liquid electrolyte to penetrate into the inter-marble space similar to the interstitial spaces between the adjoining microstructures 107E that define the diffusion paths 109E within the predominantly carbon particle 100A. The marble itself can resemble Swiss cheese by allowing electrolyte to penetrate not only into the cracks between graphene sheets 101B, but also into each graphene sheet itself, individual graphene sheets are shown in Figure 1C. In this and other examples, the relative shortening of diffusion path 109E refers to the time it takes for Li ions to infiltrate therein by, for example, capillary action, to contact an active material such as S confined within pores 105E. Diffusion path 109E accommodates convenient and rapid wetting and diffusion of an electrolyte that may contain Li ions into carbon-based particles 100A, which may then be grown or otherwise further synthesized to produce graded conductivity The carbon support 300.

The shortening of the diffusion path 109E refers to the shortening of the diffusion length of the active material such as S within the open porous scaffold 102A in the carbon scaffold 300 through which Li ions move and does not have itself confined within the pores 105E of the connected microstructures 107E. This is in contrast to the prior art which requires shortening the diffusion length of the active material only by making the active material lesser/smaller. Diffusion paths 109E within connected microstructures 107E can act as Li ion buffer reservoirs by controlling Li ion flow and/or transport therein as can be beneficial for Li ion confinement, such as S-coated with pores 105 The Li ion transport in which the exposed carbon surface reacts and later Li ion transport during the charge-discharge cycle of the electrochemical cell provides a freer flow structure. Transport of Li ions across diffusion paths 109E in the general direction shown in Figure IE can occur in a liquid electrolyte that is initially perfused and trapped within open porous scaffold 102A, where this electrolyte perfusion occurs during discharge-charge cycles using a ring Before carbon support 300.

There are examples of allowing initial diffusion and distribution of liquid electrolyte in open porous scaffolds 102A of carbon-based particles 100A to fill and occupy hierarchical pores 101A and/or connected microstructures 107E, followed by deposition by layer-by-layer Carbon scaffold 300 synthesized or otherwise produced from carbon-based particles 100A. Vacuum or air may also be used to fill the hierarchical pores 101A and/or the connected microstructures 107E, which may allow or assist the electrolyte wetting of the exposed carbon-containing surfaces within the open porous scaffold 102A.

Li ions bounce from one location to another by a chain reaction, which is similar to a Newton's ball impact in which one ball hits to cause force transfer, which causes other balls to move. Similarly, individual Li ions travel relatively short distances, but remain capable of collectively moving large numbers of Li ions via chain reactions of this type as described. As can be a crystalline arrangement of Li ions and/or particles in, around, or within the agglomerates of graphene sheets 101B, individual Li ion mobility levels can be supplied together to the carbon scaffold 300B by infusion into the open porous scaffold 102A via capillaries The number of Li ions is affected. Electrochemical cell anode or cathode produced from carbon scaffolds

The carbon scaffold 300 shown in FIG. 3 can be integrated in battery or ultracapacitor applications, battery types including Li-ion batteries and LiS batteries. Carbon scaffolds 300 can be incorporated into anodes or cathodes for Li-ion and LiS battery systems, but require the preparation of connected microstructures 107E to confine S in pores 105E or elsewhere to accommodate polysulfide (PS) interactions. Generation and restriction and control of PS migration. An exemplary battery pack system may include electrochemical cells assembled to supply power to the system. An electrochemical cell may have an anode containing an anode active material, a cathode containing a cathode active material, a porous spacer disposed between the anode and the cathode, and an electrolyte in ionic contact with the anode active material and the cathode active material.

The anode and cathode may include a conductive sacrificial substrate 306, wherein a first layer is deposited on the first interconnected film having a first concentration of carbon-based particles 100A, which are shown in FIG. 3 is shown as carbon-based particle 302 so that redundant description thereof is omitted.

The porous configuration is formed in a carbon scaffold 300 as defined by carbon-based particles 302 that are synonymous with and used interchangeably with a plurality of carbon-based particles 100A contiguous together, And the smaller carbon particles 304 are dispersed throughout the carbon support 300 . The porous configuration of carbon scaffold 300 receives electrolyte dispersed therein for passage through interconnected hierarchical pores 101A and/or connected microstructures 107E that define one or more channels similarly to individual carbon-based particles 100A and/or 302 transport of Li ions, the one or more channels comprising: a microporous framework bounded by dimensions 101E >50 nm providing tunable Li ion channels; Li ion high-speed channels serving therein for fast Li ion transport is defined by a dimension 102E of about 20 nm to about 50 nm (generally defined according to IUPAC nomenclature and referred to as mesoporous or mesoporous ) mesoporous channels; and for charge storage and/or active material confinement by < Microporous texture defined by size 103E of 4 nm.

A first layer comprising a first concentration of carbon-based particles 100A and/or 302 can be formulated to exhibit electrical conductivity in the range of 500 S/m to 20,000 S/m. The second layer or any subsequent layer can be deposited on the first layer or any previous layer. The second layer can include a second contiguous film formed by a second concentration of carbon-based particles 100A and/or 302 in contact with each other to produce a range of 0 S/m to 500 S/m or otherwise A second conductivity lower than the first conductivity.

Carbon scaffold 300 can be prepared for subsequent Li infiltration, referred to herein as pre-lithiation, and later infused with Li ionic liquid solution via capillary action to produce lithiated carbon scaffold 400A as shown in Figure 4A. Film layers 406A, 408A, 410A, and 412A, each having a defined thickness in the vertical direction extending from the current collector, may be synthesized on-the-fly in a microwave reactor or deposited layer-by-layer in or out of a thermal reactor. Membrane layers 406A, 408A, 410A, and 412A have varying conductivities in a direction normal to and away from the current collector ranging from high, such as at layer 406A, to low, such as at layer 412A, which also Can be sacrificial and/or conductive substrates. In an exemplary configuration, layers of films 406A, 408A, 410A, and 412A with defined and gradually decreasing concentrations of carbon-based particles 302 may be produced to achieve specific resistance values, such as : Produces a layer 406A with a relatively high defined concentration of carbon-based particles 302 that facilitates low Li ion transport and low resistance < 1,000 Ω, Suitable for high conductivity; Produces layers 408A and 410A with systematically reduced conductivity by engineering carbon-based particles 302 to exhibit the desired interfacial surface tension to promote wetting of molten Li metal exposed carbon surfaces; and Produces a layer 412A with a relatively low defined concentration of carbon-based particles 302 that facilitates high Li ion transport and high >1,000-10,000 Ω resistance, suitable for high resistance.

The varying conductivity can be at least partially proportional to the interfacial surface tension of the Li ion solution infiltrated into the porous configuration of the open porous scaffold. Li ion solution infiltration, such as including Li ions 108E, can be performed via capillary infusion engineered to facilitate surface wetting of the open porous scaffold 102A exposed to the Li ion solution. Diffusion path 109E as shown in FIG. 1E ensures that one or more oxidation-reduction (also known as redox) reactions occur within carbon-based particles 100A and/or 302B The combined deposition and stripping operations were uniform. The electroactive material can reside in the pores 105E of the connected microstructures 107E when it is used to form the open porous scaffold 102A, which itself can be incorporated within any one or more of the anode and cathode. In some implementations, the connected microstructures 107E may be formed from or otherwise contain a single layer of graphene (SLG) as shown in FIG. 1C and/or as a cohesion of the multilayer graphene sheets 101C shown in FIG. 1B Few-layer graphene (FLG) of body 101B includes 1 to 10 graphene planes. Groups of graphene sheets 101C may be positioned along the vertical axis in substantially aligned orientations and fused together at substantially orthogonal angles. The anode active material or cathode active material may have a specific surface area of about 500 m ² /g to 2,675 m ² /g when measured in the dry state, and may contain a graphene material suitable for lithiation, the graphene material comprising the following Any one or more of: pre-lithiated graphene sheets, pristine graphene, graphene oxide, reduced graphene oxide, fluorinated graphene, chlorinated graphene, brominated graphene, iodized graphene, hydrogenated graphene Graphene, graphene nitride, boron-doped graphene, nitrogen-doped graphene, chemically functionalized graphene, its physically or chemically activated or etched versions, its conductive polymer-coated or grafted versions and/or its combination.

In any one or more of the examples discussed in relation to the lithiated carbon scaffold 400A, the conductive interconnecting aggregates 101B of graphene sheets are sintered together to form an open porous scaffold independent of the binder, however, there are Alternative examples of using adhesives. Formulations with or without binders may each involve an open porous scaffold 102A that acts as/serves as an active lithium inter-sandwich structure with a specific capacity of about 744 - 1,116 mAh/g or greater. Further, examples include the preparation of graphene sheets 101B using chemically functionalized graphene, the preparation involving functionalization of its surface, comprising imparting to the open porous scaffold 102A a compound selected from the group consisting of quinones, hydroquinones, quaternary ammonium arylamines, thiols, Functional groups of disulfides, sulfonates ( _-SO3 ), transition metal oxides, transition metal sulfides, other similar compounds, or combinations thereof.

The current collector shown in Figure 4A is, for example, at least partially foam-based or foam-derived and may be selected from any one or more of the following: metal foam, metal mesh, metal mesh , perforated metal, sheet-based 3D structures, metal fiber mats, metal nanowire mats, conductive polymer nanofiber mats, conductive polymer foams, conductive polymer coated fiber foams , carbon foam, graphite foam, carbon aerogel, carbon xerogel, graphene foam, graphene oxide foam, reduced graphene oxide foam, carbon fiber foam, graphite fiber foam Foams, exfoliated graphite foams, and combinations thereof.

Anode or cathode conducting or insulating materials, referred to herein as active materials, may include nanodisks, nanoflakes, nanofullerenes, carbon nanoonions (CNOs), nanocoatings or inorganic materials selected from the group consisting of: Any one or more of the nanosheets : bismuth selenide or bismuth telluride, transition metal dichalcogenide or trichalcogenide , transition metal sulfide, selenide or telluride; boron nitride or a combination thereof, including molten Li metal dispersed therein to provide a source of Li ions upon dissociation during normal electrochemical cell discharge-charge cycling, and the like.

The thickness of the nanodisks, nanoflakes, nanocoatings or nanosheets can be less than 100 nm. In other examples, the thickness of the nanoflakes can be less than 10 nm and/or the length, width or diameter can be less than 5 μm. Create an anode or cathode from the carbon structure

Exemplary methods for producing three-dimensional (3D) carbon-based electrodes, such as those produced by lithiated carbon scaffolds 400A, may include, for example, from one of the feedstock materials in which thermal energy is transmitted through a plasma and/or supplied in a gaseous state One or more plasma-based thermal reactors or torches deposit carbon-based particles 100A or 400A to form a first contiguous film layer on the substrate, such as layer 406A shown in FIG. 4A, wherein the first contiguous film The layer is characterized by a first conductivity. Each of the carbon-based particles comprises conductive three-dimensional (3D) aggregates or agglomerates 101B of graphene sheets. The aggregates can be fused together orthogonally to form the open porous scaffold 102A to facilitate electrical conduction along and across the contact points of the graphene sheets.

A porous configuration is formed in the open porous scaffold 102A, wherein the porous configuration helps to receive electrolyte dispersed therein for Li ions through interconnecting pores that define diffusion paths 109E, such as hierarchical pores 101A and/or connected microstructures 107E transportation. The average thickness of the first contiguous film layer is no greater than about 100-200 µm. In one example, the binder material is combined with the graphene sheet 101B to retain the graphene sheet 101B in the desired position to impart the structure to open the porous scaffold 102A. The binder can be or comprise a thermosetting resin or polymerizable monomer, wherein the resin is cured or polymerizable monomer is polymerized to form a solid resin or polymer with the aid of heat, radiation, initiators, catalysts, or combinations thereof. The binder can be initially a polymer, coal tar pitch, petroleum pitch, mesophase pitch, or organic precursor material and later thermally converted to a carbon material.

An additional amount of carbon-based particles 100A is deposited on the first contiguous film layer to form a second contiguous film layer thereon, the second contiguous film layer having a second conductivity lower than the first conductivity and closer to Electrolyte 414A is also located away from the current collector which may be a sacrificial matrix. The Li ion solution can be infiltrated into the open porous scaffold 102A, such as by capillary perfusion, to react with exposed carbon on its surface, which can comprise greater than about 100 m ² , to facilitate Li ion dissociation and current supply /gm of surface area.

The carbon-based particles 100A and/or the lithiated carbon scaffolds 400A can be synthesized on-the-fly in a microwave reactor or deposited or grown in a bottom-up manner in a thermal reactor in a bottom-up manner referred to as layer-by-layer deposition, and can then be Casting via a liquid slurry to be subsequently dried forms a carbon-based electrode suitable for implementation in or incorporation into a Li-ion battery. In some examples, such slurries may include chemical binders and conductive graphite and electrochemically active intrinsic carbon.

The term hierarchical means an arrangement of items in which items are represented as being above each other, below each other, or at the same level as each other. Here, the carbon-based particles 100A and/or the lithiated carbon scaffolds 400A can be grown by layer-by-layer deposition in a thermal reactor to produce a film such as from the conductive particles 100A, 302B, and/or 402A 406A-412A indicate one or more levels that refer to the electrical (referring to the contact points of the graphene sheet 101B) and the ionic (referring to the diffusion paths) through the entire thickness of the lithiated carbon scaffold 400A 109E) Levels produced by specific control of conduction gradients. The tuning of each of the individually deposited layers 406A-412A results in a relatively higher conductivity at the current collector interface and a progressively lower conductivity moving outward therefrom.

The graphene sheets 101B within the carbon-based particles 100A can act as electrical conductors by conducting current through the contact points and/or regions and serve as a specific capacity 2 otherwise obtained from conventional graphite anodes, such as 372 mAh/g The active Li sandwich structure provides a source of anode electrode specific capacity of 744-1,116 mAh/g to 3 times. Thus, the interconnected 3D beams 102 of graphene sheets within the carbon-based particle 100A can be viewed as nanoscale electrodes that simultaneously enable a relatively high volume fraction of electrolytically active material and efficient 3D interpenetrating ion and electron paths.

The unique 3D structure of this carbon-based particle 100A enables, relative to conventional applications, to store charge via capacitive charge storage at its exposed surface for the desired high power delivery and also to provide Faradaic redox within its bulk ions for the required high electrical energy storage. As generally understood and as referred to herein, redox refers to a reduction-oxidation reaction in which the oxidation state of an atom has changed, involving electron transfer between chemical species, where most often one species undergoes oxidation while the other undergoes reduction .

As generally understood and as referred to herein, Faraday refers to a heterogeneous charge transfer reaction that occurs at the surface of an electrode prepared and/or otherwise incorporated with carbon-based particles 100A. For example, the pseudocapacitor method Raday-style storage of electrical energy by electron charge transfer between electrodes and electrolytes. This is achieved through electrosorption, redox reactions, and sandwiching methods, called pseudocapacitance. Roll-to-roll processing for battery electrodes produced from carbon scaffolds

With regard to manufacturing, lithiated carbon scaffolds 400A can be fabricated by sequentially, layer-by-layer (such as FIG. 4A ) of a concentration of carbon-based particles 100A and/or 100E via roll-to-roll (R2R) production methods Layers 406A-412A shown in ) are deposited onto moving substrates such as current collectors to fabricate and/or construct electrochemical cell electrodes such as cathodes and/or anodes in large scale. By consolidating the 3D carbon scaffold structure directly outside the microwave reactor, similar to the exiting plasma jet method, the electrode film can be used without the need for otherwise toxic solvents for the battery electrodes and in the slurry casting method. Continuous production in the case of adhesives. Thus, battery electrodes employing lithiated carbon scaffolds 400A can be more easily produced with controlled electrical, ionic, and chemical concentration gradients that are layer-by-layer by plasma jet-type methods and specific elements such as dopants can also be introduced into the plasma deposition process at different stages.

Furthermore, due to the pores 105E and/or the connected microstructures 107E interspersed throughout the carbon-based particle 100A, the lithiated carbon scaffold 400A may allow it to gravitationally (refer to the analytical properties used to quantify analytes based on their mass). The set of methods used in chemical reactions) are manufactured in a manner superior to known devices. That is, the carbon-based particles 100A having pores and/or voids in the 3D beam 102 and/or conducting carbon particles 104 defined throughout the graphene sheet can be lighter than those that do not include various pores and/or voids, etc. Equivalent battery electrode with mesoporous structure.

The carbon-based particles 100A may be characterized by an excellent ratio of active material to inactive material relative to the prior art, since larger amounts of active material are available relative to inactive and/or structural strengthening materials and prepared for conduction through electricity. Although the structural reinforcement material participates in defining the general structure of the carbon-based particles 100A, it may not be involved or as involved in the conductive interconnect aggregate 101B of the graphene sheets. Therefore, due to its high ratio of active material to inactive material, the carbon-based particles 100A can exhibit superior electrical conductivity characteristics relative to conventional batteries, and under conditions where carbon can be used to replace the heavier heavy metals traditionally used Significantly lighter than these conventional battery packs. Thus, carbon-based particles 100A may be particularly well suited for demanding end-use applications, automobiles, light trucks, etc., which may also benefit from their relatively low weight.

Carbon-dominant particles 100A can be produced to achieve percolation thresholds that rely on conductive interconnecting aggregates 101B of graphene sheets to describe the formation of long-range connectivity in random systems The mathematical concept of percolation theory. There are no gigantic connected components below the threshold value, but there are gigantic components above the threshold value that are about the size of the system. Thus, the 3D bundle 101B of the graphene conductive interconnected agglomerates of graphene sheets can conduct electricity from the current collector toward the electrolyte 414A as shown in FIG. 4A. Roll-to-Roll (R2R) Plasma Jet Torch Deposition System

When a variation relative to the disclosed atmospheric MW plasma reactors is used to produce particle-based outputs comprising integrated linked 3D hierarchical carbon scaffold films, torch configurations can be used to produce such Carbon-dominant structures, such as the carbon-dominant structures shown by the roll-to-roll (R2R) system 400V shown in Figure 4V. Similar to waveguide reactors, plasma torches allow material to be initially formulated and then accelerated into an impingement zone on a movable or stationary substrate surface. Each zone of the R2R process can provide unique control over the synthesis, formulation, consolidation, and integration (such as densification) of disparate mixed-phase or composite materials.

Plasma torches can be used to deposit carbon-based particles on a continuously moving substrate to enable additive process control at the location of the thermoplasma jet, depositing carbon-based particles beyond the plasma afterglow zone to the substrate impact zone. Various properties such as defect density, residual stress can be controlled by controlling the deposition thickness of the film, chemical and thermal gradients, phase transformations, and anisotropy. For electrochemical cell electrode fabrication, the atmospheric MW plasma torch not only produces formulated and integrated continuous 3D graphene films according to conventional slurry casting methods without the need for toxic solvents such as NMP and/or without the use of binders, Plasma torches can also be used to create integrated electrode/current collector film structures at reduced cost for enhanced performance.

4V shows a roll-to-roll (R2R) system 400V employing an exemplary arrangement of groups 444V of plasma jet torches 422V to 428V, such as 422V, 424V, 426V, and/or 428V, all configured to perform a case-by-case Layer deposition to incrementally fabricate (otherwise known as growth) the carbon-based scaffold 300B shown in FIG. 3B and/or variants thereof. A group 444V of plasma jet torches 414V to 420V is oriented in sequential order above an R2R processing apparatus 440V, which may include wheels and/or reels 434V and 439V to cause the transition of the sacrificial layer 402V to move forward 436V, on which the layer 442V of the carbon scaffold 436V can be deposited layer by layer to achieve progressive deposition of layers per unit volume (such as layers 406V-412V) ) is a graded electrical conduction gradient proportional to the concentration level of the carbon-based particles 100A contained in the region.

The deposition may involve placing a group 444V of plasma jet torches 414V-420V as shown in FIG. 4B of carbon support 300B on sacrificial layer 402V, initially in the direction of forward motion 436V, with torches 414V in a downward direction, Starting from the feedstock supply line 412V extending furthest towards the sacrificial layer 404V, the torch 414V is positioned to spray 422V the carbon-based material to deposit the initial layer 404V, which is also shown in FIG. 4A as the intermediate layer 406A , and so on. The initial layer 404V can be deposited to achieve the highest conductivity values, with each of the subsequent layers 406V-410V being characterized by the carbon-based scaffold 300B constituting the carbon-based scaffold 300B used to achieve the graded gradient for layer 442V. Proportionately less dense dispersion of primary particles 100A.

That is, as shown in FIG. 4V, plasma jet torches 414V-420V can be oriented to have gradually decreasing or otherwise varying heights such that each torch from group 444V can be tuned to jet (respectively). For injection 422V to 428V) the carbon-based feedstock material jet is supplied from feedstock supply line 412V. As a result, battery electrodes with controlled electrical, ionic, and chemical concentration gradients that are sequentially sequenced layer by layer as described herein with respect to the plasma jet torch system 400V can be more easily produced The plasma jet torch system 400V exhibits the desired characteristics of a plasma jet type method; and specific elements or additional components can also be used at different stages in the plasma-based jetting described by the plasma jet torch system 400V Introduced during deposition. This control may extend to the tunability of the plasma jet torch system 400V to achieve the target electric and/or electromagnetic field characteristics of any one or more of the layers 442V.

Group 444V of plasma jet torches 414V to 420V may employ plasma-based thermally enhanced carbon jetting technology to provide a carbon coating process in which molten or heated material is jetted onto a surface. The raw materials, which are coating precursors, are heated by electrical, plasma or arc or chemical means such as combustion and/or fire.

As compared to other coating methods such as electroplating, physical and chemical vapor deposition, thermal spraying with plasma spray torches 414V to 420V can provide high deposition rates over large areas with thicknesses approximately between Thick coatings in the range of 20 µm or more to a few mm. Coating materials available for thermal spraying include metals, alloys, ceramics, plastics and composites. It is fed in powder or wire form, heated to a molten or semi-molten state, and accelerated toward the matrix in the form of micron-sized particles. Combustion or arc discharge is often used as the energy source for thermal injection. The resulting coating is produced by accumulating many sprayed particles. The surface can heat up insignificantly, allowing the coating of flammable substances.

Coating quality is generally assessed by measuring its porosity, oxide content, macrohardness and microhardness, bond strength and surface roughness. In general, coating quality increases with increasing particle velocity. Carbon scaffolds implemented in LiS secondary batteries

The group 444B of plasma jet torches 414B-420B can be configured or tuned to spray carbon-based materials in a controlled manner to achieve a particular desired hierarchical and organized structure, such as is suitable for treating carbon-based The percent porosity of the particles 100A and/or 100D is determined by the open porous scaffold 102A and the associated microstructures 107E of the carbon-based particles 100A and/or 100E in which Li ions are infiltrated via capillary action. The total amount of S that can be infused into the connected microstructures 107E and/or deposited on the exposed surface area of the carbon-based particles 100A and/or 100D and other such similar structures may also depend on its porosity percentage , where the 3D fragmented structure provides larger pores, such as pores 105E, each of a size 103E that can be efficiently accommodated and micron-limited S for a desired period of time during electrochemical cell operation. There is permission to limit S at limits such as 0-5%, 0-10%, 0-30%, 0-40%, 0-50%, 0-60%, 0-70%, 0-80%, 0-90 % and/or 0-100% are examples where defined percentages are targeted purely by designing and growing structure S to combine S to prevent any resulting polysulfide (PS) from migrating out of pores 105E, such percentages Any one or more of the ranges successfully demonstrated a delay in the migration of polysulfides out of the electrode structure. Carbon scaffolds implemented in Li -air secondary batteries

Existing Li air cathodes can last for only 3-10 cycles, and thus are not generally understood to provide a very promising or reliable technology. In these cathodes, the air itself acts as the cathode, so a reliable and robust supply of air flowing through the cathode, such as through pores, orifices or other openings, is currently effectively excluded from consumer-grade portable electronic devices such as smartphones practical application.

The device could be fabricated with some air pumping mechanism, but since any amount of impurities prevalent in the air can and will react with available Li in parasitic side reactions, ultimately reducing the specific capacity of the overall electrochemical cell, air purification is still question. Furthermore, air provides only about 20.9% _O2 , and thus is not as effective as other alternative current advanced battery technologies.

Nonetheless, even in view of the challenges mentioned above, what is provided above regarding carbon-based particles 100A, 100D and/or any variation thereof implemented in carbon scaffold 300B and/or lithiated carbon scaffold 400A An example of this can be configured to operate in a 3D printed battery pack. Notably, steps can be taken to safeguard, such as by tuning to achieve desired structural reinforcement in specific targeted regions of the open porous scaffold 102A, to prevent unwanted and/or sudden collapse of the porous structure in order to avoid defining The passage in it is blocked. In an example, the carbon scaffold 300B can be decorated with a myriad of metal oxides to achieve this strengthening, which can also control or otherwise actively contribute to the mechanics of the structure itself once the lithium reacts with air to spontaneously form a solid from that state. tunneling etc. Conventional situations such as not performing special preparations for the disclosed carbon-based particles 100A and/or the like and implementation of Li air cathodes may otherwise involve the reaction of Li ions with carbon provided in gaseous form to make Li ions and carbonaceous gas to form expanded solids. And depending on where this amplification occurs, an overall carbon-dominated mesoporous scaffold structure, such as carbon scaffold 300B, can be mechanically degraded. Preparation of carbon-based particles for lithiation

To enable alternative non-Li or lithiated carbon-based scaffold cathodes on current lithium oxide compound cathodes, such as alternative non-Li or lithiated carbon-based scaffold cathodes that confine sulfur, oxygen, and vanadium oxide , and to accommodate the loss of first charge lithium in current Li-ion batteries, resulting in reduced Coulombic efficiencies, a scalable prelithiation approach for carbon-based structuring intended to be implemented in electrochemical cell electrodes may be required. Accordingly, various experimental attempts have been made on the carbon-based particles 100A, 100D and/or any derived structures based thereon including carbon scaffolds 300B, such as ball milling, post thermal annealing, and electrochemical reduction starting with additional electrodes. These results have been used for prelithiation, such as chemically preparing carbon-based structures to physically and/or chemically react with lithium and/or physically and/or chemically confine lithium, but have satisfied homogeneity, Lithium reactivity, cost, and scalability challenges.

Nonetheless, as substantially discussed previously, by fine-tuning the reactor process parameters, the carbon-based particles 100A, 100D, and/or carbon scaffolds 300B can be synthesized and/or fabricated by layer-by-layer deposition methods to function as The engineered surface chemistry, such as the inclusion of nitrogen and oxygen doping, promotes the rapid decomposition of oxides involving disproportionation of carbon-based host structures.

Upon thermal activation, which may include one or more spark formations, Li metal can infiltrate spontaneously, such as without a pressure gradient and not passively driven by capillary forces, to produce controlled prelithiated carbon structures or particle building blocks. These prelithiated particle building blocks can then be synthesized into integrated composite films with graded conductivity ranging from high conductivity at the plane after contact with the current collector, such as that shown by interlayer 406A, to Insulating ion conducting layer at the electrolyte/electrode plane. Surface chemistries such as can be related to non-reactive infiltration of Li metal can be optimized by the thermal reduction degree of oxides (such as exotherm) through the use of thermogravimetric analysis (TGA) or differential scanning calorimetry DSC analytical techniques And get tuned.

To address scalability issues such as those associated with transitioning from a low-volume laboratory testing and sample generation environment to a high-volume, large-scale factory capable of fulfilling multiple customer orders simultaneously, the pre-lithiation method described above can be combined with hardware such as Other liquid melt wetting methods of welding are similarly easily adaptable to the continuous roll-to-roll (R2R) format.

In the case of the torch method, in a controlled heat-drying environment, a thin-film Li-clad foil, which may include tantalum (Ta) or copper (Cu) in some configurations, may be loaded onto a heated calendering reel for contact with a Carbon-based particles 100A or carbon film. Heat retention, time, gradients, and applied pressure such as soaking can be adjusted and controlled to facilitate both: (1) activation; and (2) the soaking process step. Initiated lithiation of carbon scaffolds

Before developing Li metal infusion methods into carbon-based structures and/or coalesced particles, efforts have been made to evaluate the following two scenarios: Grow microwave graphene sheets with extended D-spacings that allow Li intercalation with much higher efficiency or faster rates than occurs in typical commercial graphene sheets occurs between individual graphene sheets; and grows the FLG in a manner that successfully and reproducibly achieves the higher de-spacing; and Use of wet liquid Li metal front surfaces delivered to hierarchical pores 101A and/or connected microstructures 107E defined by open porous scaffolds 102A of carbon-based particles 100A and/or 100D, where functionalized versus otherwise The attraction of Li metal to exposure to carbon-dominated surfaces to wetness is the same for carbon-dominated surfaces.

The disclosed thermal reactors may perform post-processing to produce highly organized and structured carbon that operates with molten Li metal and/or other species infiltration, such as aluminum to silicon carbide sintered materials Wetting in the particle surface is relevant and hammering the particle surface to promote frontal wetting of molten (Li) metal without additional pressure from an external source. These efforts allow for continuous wetting instead of using capillary pressure to push metal into the open porous scaffold 102A of carbon-based particles 100A and/or 100D.

FIG. 4A shows that from a number of interconnected carbon-based particles 402A similar in form and function to carbon-based particles 100A and/or 100E, concentrated from highest to lowest at varying concentration levels in membrane layers 406A-412A Concentration of synthesized and deposited lithiated carbon scaffolds. Membrane layers 406A-412A are all assembled to be impregnated with molten Li metal and/or Li ion solution in liquid or in liquid phase between graphene sheet pairs of graphene sheet 101B via a non-reactive capillary infusion method intercalate Li ions. Exemplary D-spacings of roughly 1 Å to 3 Å can be targeted during graphene sheet 101B synthesis to retain more Li ions between alternating graphene sheets than conventional stacks of graphene sheets.

Void 416A, denoting empty regions or spaces, between adjacent and/or contacting carbon-based particles 402A may be defined by the portion of lithiated carbon scaffold 400A positioned away from current collector 420A and facing the liquid electrolyte layer, passivation layer 418A. Passivation means that the material becomes passive, ie less susceptible to future use environment or corrosion. Additionally or alternatively, a Li-ion conducting insulating or graded mesophase layer may be deposited on layer 412A, such as at the same location as passivation layer 418A, facing electrolyte 414A so as to be free and/or physically and/or chemically unconnected The side reactions of Li in ionic form are minimized.

Any such capped layer Li, as provided by molten Li metal, may flow in liquid form into voids 416A defined by carbon-based particles 402A prior to deposition or placement to assist in the formation of interstices with the layers 406A-412A. An electrochemical gradient proportional to the concentration level of the carbon-based particles 402A.

Repeated or cyclic use of Li-ion electrodes (such as anodes or cathodes) in secondary batteries can lead to problems caused by the use of molten Li metal, such as volume expansion during redeposition in electroplating operations that are intended to Refers to the process of using an electrical current to reduce dissolved metal cations so that they form a thin coherent metal coating on an electrode. The term can also be used for the electrical oxidation of anions to solid substrates, as is the formation of silver chloride on silver wires used to make silver/silver chloride electrodes.

The method used in electroplating associated with the infiltration of Li ion solution into the lithiated carbon scaffold 400A may be referred to as electrodeposition, also known as electrophoretic deposition (EPD), and is similar to reverse acting concentration cells. Li-ion plating as described above may result in a volume expansion of about 400% or more of the lithiated carbon scaffold 400A. From a stability point of view, such amplification is not micromechanically required and results in the decay of many dead regions, meaning inactive regions or regions that are not chemically and/or electrically activated, thus ultimately preventing Longer lifetimes are derived from Li-ion batteries so equipped. In general, it is desirable to have a large number of plates of Li ion material, which means reduction onto a smooth and uniform surface to thus promote uniform deposition of Li ions. Removal is also smooth in a smooth flat interface.

In practice, Li, when infiltrated into carbon scaffold 400A, may tend to form undesirable dendrites, which are defined as crystals that develop in a typical multi-branched dendritic form. These Li ion dendrites, also in the form of acicular Li ion dendrites (acicular dendrites describe a crystal habit consisting of deposits of elongated needle-like crystals), grow away from surfaces on which, such as in individual Li ions are wetted on and/or between the graphene sheets 101B. In some cases, with sufficient battery charge-discharge cycles, the dendrites or protuberances can range from the anode within the electrochemical cell incorporating the lithiated carbon-based scaffold 400A to opposite the carbon-based scaffold The positioned cathode grows all the way to create a short line or short circuit, describing the presence of a low resistance connection between the two conductors supplying power to the circuit at this time. This can generate excess voltage string in the power source and cause excess current to flow. The current runs over the wire and causes a short circuit.

The capillary Li ion implantation into the lithiated carbon scaffold 400A technique can solve many of the described problems. However, ongoing problems encountered in Li-ion batteries include that conventional cathodes provide only a limited amount of specific capacity or specific energy capability. Likewise, on the anode side, reductions in specific capacity and specific energy density have also been observed. Thus, even with regard to relative desirability, Li-ion batteries may be compared to Li metal hydride or lead acid or Ni Cad batteries in terms of electrical energy storage capacity and current delivery, when incorporated herein by the disclosures Protection against or preventing the formation of undesirable lithium-based dendrites after lithiation of any one or more of the carbon-based materials, such as the lithiation of the carbon-based scaffold 400A, and even power storage and transport has further progressed to approach the theoretical capacity of pure Li metal with a specific capacity of about 3,800 mAh/g.

Other approaches have been undertaken, including the development of solid-state batteries that do not involve the liquid phase at all. However, attention has returned to Li metal due to the use of an oxidizing electrolyte to achieve and stabilize contact with lithium. And alternatives to Li metal including Si, Sn and various other alloys are also being explored. However, even after elimination of Li metal, a source of Li ions may still be required.

Alternative materials for lithium materials in Li-ion battery electrode structures can yield the following energy density values: oxide provides 260 mAh/g; and sulfur (S) provides 650 mAh/g. Due to its relatively high energy density capability, sulfur (S) needs to be confined in battery electrode applications so that it does not solubilize/dissolve in the surrounding electrolyte. To achieve this effect, sulfur micro-confinement is required, as previously described with respect to opening pores 105E of the connected microstructures 107E of porous scaffold 102A (as shown in Figure IE). A confinement (or micron confinement) liquid means a liquid that is geometrically confined at the nanoscale such that a majority of the molecules are close enough to the interface to sense some difference from standard bulk conditions. Typical examples are liquids in porous media or liquids in fusion shells.

Confinement and/or micron confinement refers to the confinement in the microscopic size region that regularly prevents crystallization, which enables the liquid to be supercooled below its homogeneous nucleation temperature, even though this is not possible in the bulk state. Therefore, in view of the various challenges presented above and others not discussed herein, the deposition of graphene with less than 15 layers can be accomplished by alternatively utilizing few-layer graphene (FLG) materials and/or structures (defined as graphene having less than 15 layers) or otherwise organized in a stacked architecture in which Li ions are sandwiched between stacked supports at defined intervals and/or concentration levels) to achieve various improvements over conventional graphene-based anodes. Any one or more of carbon-based particles 100A, 100D, and/or the like may be so prepared.

Thus, from graphite to FLG, the specific capacity of the carbon-based structure with Li interposed can be increased from about 380 to over 1,000 mAh/g. The disclosed materials can replace graphite with FLG to allow higher active surface area and can increase the spacing between individual graphene layers to wet up to 2 to 3 Li ions, whereas only 1 Li ion is typically seen elsewhere, such as As shown in FIG. 1I, it is shown that various graphite or graphene layer planes can be controlled according to the spacing to achieve various fits of Li ions between adjacent graphite or graphene layer planes.

In graphene, the hexagonal carbon structures in each graphene sheet can remain positioned on top of each other, which is called an A-A packing order rather than an A-B packing order. An exemplary carbon packing sequence is shown in the chemical structure diagram shown in Figure 1G, where Li ions can fit in the voids defined by carbon atoms arranged and bound in a hexagonal lattice structure. In particular, configurations of graphene sheets and/or few-layer graphene (FLG) are envisaged, where individual layers of graphene can be stacked directly on top of each other to obtain disproportionate, asymmetric and/or otherwise The irregular stacking, shown in stage 3 in Figure 1H, in turn allows for the addition of intervening Li ions between each graphene layer of the FLG structure.

Under conventional conditions and circumstances, top-down or bottom-up insertion of Li ions in hierarchical graphene structures can be extremely difficult in practice. Correspondingly, Li ions are more easily inserted between individual graphene layers separated by a definable distance. Therefore, the key is to manage and tune how much of the available edge area is available. In that regard, any of the carbon-based structures disclosed herein can be so tuned. And carbon in graphene is also conductive, so this feature serves a dual purpose by: (1) providing structural definition for FLG scaffold electrode structures, such as carbon scaffold 300B and/or lithiated carbon scaffold 400A; and (2) ) in the conduction path.

The fabrication techniques used to fabricate any one or more of the carbon-based structures disclosed herein may demonstrate the need to tune the edge lengths of individual graphene layers relative to their flat surfaces; furthermore, tuning between individual graphene stacks spacing may be possible. Graphene (in its two-dimensional structure) must provide significantly more surface area in which Li ions can be inserted. Thus, application of graphene sheets in accordance with various aspects of the subject matter disclosed herein may provide a natural evolution in the direction of enhanced energy storage density.

Individual graphene sheets are held in place as part of the plasma growth process. As previously described from FLG and/or combinations used to form particles such as carbon-based particles 100A, 100D, 402A, and/or the like, the carbon-based gumball-like structure is A defined long-range order is running self-assembly, which is defined as one in which the solid carbon material exhibits a crystalline phase structure. Once the positions of the carbon atoms and their neighbors are defined, the position of each carbon atom can be precisely defined throughout the crystalline phase structure so that the smaller structures cohere to form a substantially sphere-like structure.

The size dimension of such spherical structures describing individual carbon-dominated particles 100A and/or the like may be about 100 nm at their respective widest points. The larger cohesive particles forming the carbon lattice structure 1800 as shown in Figure 18 may be composed of multiple spherical structures with diameters of the order of magnitude larger, on the order of 20 microns to 30 microns, and are the films shown in Figure 4A One or more of layers 406A-412A provide structural definition.

In contrast, conventional battery electrode production methods typically use known deposition techniques (such as chemical vapor deposition (CVD) or other fabrication techniques, nanotubes, etc.) to grow structures away from a defined fixed substrate or surface, and thus There is no ongoing fusion of carbon-based particles in a substantially atmospheric vapor stream stream of carbon-containing gaseous species disclosed herein. Such known assembly processes and procedures can tend to be extremely labor-intensive, and they can also allow structures of limited thickness (200-300 microns thick) to be grown.

Graphene and graphene densification of multiple FLGs such as carbon-based particles 100A, carbon scaffolds 300B, lithiated carbon scaffolds 400A, and/or the like on pristine spherical carbon scaffolds can also result in energy density and Capacity increased. Such densification in targeted regions of the carbon scaffold may also be performed or otherwise achieved after the creation of larger cohesive particles comprising a plurality of carbon-based particles 100A. In general, Li ions can be plated onto electrodes prior to reduction, so depending on the battery chemistry, Li ions can transition from an ionic to a metallic state. Furthermore, in one embodiment, similar to electroplating, graphene can be grown on other materials, such as plastics, in a stacked fashion, and tuned to obtain a desired bright and/or smooth finish. Such electroplating processes are reversible and may include separate but related plating processes and stripping processes intended to place Li ions and/or atoms down and for their subsequent removal.

In continued cycling of secondary Li-ion batteries involving multiple charge-discharge-recharge cycles, the surface on which the carbon-dominated structures grow and/or build eventually becomes rough and thus undesired for dendrites Dendrite growth is susceptible to or prevents undesirable dendritic growth. In contrast, as discussed above, techniques for producing carbon-predominant particles 100A and/or the like can be achieved by using substantially impurity-free Li metal in conjunction with carbon-predominant graphene structures Higher specific capacity values, thereby substantially preventing the growth of such dendrites.

The use of graphene sheets allows for a relatively large exposed surface area, which can be used for plating or sandwich operations for infiltration involving non-reactive capillary infusion of Li ions. Therefore, any tendency to move to a certain point is eliminated; and basically, due to the higher surface area to volume ratio of graphene compared to other conventional carbon-based materials such as graphite, the occurrence of plating and exfoliation can be altered Way. Li ions can be introduced at least in part by relying on liquid Li; however, due to Li's ease of chemical reactivity with surrounding and/or surrounding elements, aqueous moisture and oxygen must be kept away. Similarly, the introduction of impurities has deleterious effects. With respect to the disclosed carbon-dominant structures, metal-matrix composites have been studied (with respect to Li metallization bonding or otherwise forming metal-matrix composites with C), thus providing refined insights into the reactivity at exposed surfaces Additional options for tuning and management.

Li in contact with C can result in that the free energy of Li at the contacting surface must be suppressed and/or controlled to avoid unintended consequences associated with spontaneous Li infiltration in carbon-based particles 100A and/or the like. Reactivity is required. Traditionally, Li in the liquid phase often forms carbonates and other formers due to the chemistry of the electrolyte. However, the examples of the present invention are concerned with the creation of a relatively stable solid electrolyte interface (SEI) prior to introduction of the liquid electrolyte.

In addition, various methods and/or processes to affect the Li-ion interfacial region may be available. For example, preparing the surface of liquid Li by alloying with Si and other elements will reduce reactivity and promote overall Li ion wetting of larger cohesive particles, each of which includes a plurality of carbon The main particle 100A. In one example, less than about 1.5% of Li was observed to preferentially move to exposed surfaces exposed to the electrolyte. 3D Hierarchical Graphene with Increased Specific Capacity

Commercial use of graphitic carbon materials for anode active materials and fine carbon black materials for electrical conduction is due to their relatively low cost, excellent structural integrity for insertion and extraction of Li+ ions, formation of dendrites with Li Unrelated safety and formation of protective passivation layers for many electrolytes, such as those associated with solid electrolyte interphase (SEI) formation or accumulation, are justified.

However, the lower specific capacity of graphite with stoichiometric _LiC6 at 372 mAh/g is a key limitation, and thus can potentially hinder the development of large-scale energy storage systems requiring high energy and power densities. Larger loadings of activity can be tuned by designing and applying three-dimensional (3D) graphene as disclosed herein by a compound electrode approach with Li and/or S sandwiched between any one or more of the preceding figures. anode material while promoting Li ion diffusion. In addition, 3D nanocarbon frameworks such as those defined by open porous scaffolds 102A and/or the like can impart: conductive pathways; and structural buffers for higher capacity non-carbon nanomaterials that result in enhanced Li-ion storage capacity. Both (1) and (2) enhance Li-ion storage capacity (>1,000 mAh/g) and enhanced cycling (stability) performance can be achieved using these 3D structures. Anode - electrolyte interface

The graphene and carbon derivative structures disclosed in the present invention can be incorporated into anodes, such as stacked graphenes with Li sandwiched therebetween, to enhance the performance of demanding Li-ion and LiS battery assemblies formed anode. Alternatively or additionally, conventional solid Li metal foil anodes can be used with carbon-based cathodes characterized by connected microstructures 107E (shown in FIG. 1E ) in the LiS battery system assembly. Nonetheless, problems associated with undesired chemical side reactions associated with solid-electrolyte interface (SEI) formation may be observed at Li anodes in LiS cells. In addition to electroplating and electrolytically dissolving Li in the core redox chemistry of the cell to release Li ⁺ cations into the electrolyte, the typical construction of the anode also provides a source of reducing agent species, while excess Li acts as a lightweight current collector and has Helps against poor coulomb efficiency. The resulting anode degradation greatly contributes to reduced cycle life and limits anode applications. If the energy density of the LiS cell is set at 400 Wh/kg, the thickness of Li metal is estimated at 1-200 μm, more preferably 20-50 μm (corresponding to 5-10 mAh/cm). In most cases, commercial foils are 70-130 µm.

Li is highly reactive and lightweight, which makes it an ideal candidate for battery technology designed for high gravitational energy densities. However, this reactivity allows Li to react with the many chemical species it contacts to form one or more undesirable by-products. These undesirable side reactions (and their corresponding resulting products) are often non-value added and may result in irreversible loss of Li and other electrolyte components. Depletion of the electrolyte or drying of the cell and/or loss of Li results in accelerated capacity fade. SEI formation

The chemical reaction of Li and electrolyte components forms SEI on the surface of the Li anode, which in turn slows the reaction of electrolyte components with the anode and can reduce degradation and thus improve cycle life. The SEI covers the anode surface and a first-order electrochemical reaction occurs through the SEI layer. The properties of the SEI layer affect the reaction kinetics and can reduce the cell voltage due to increased internal resistance. Regardless of this situation, the SEI layer and its properties are critical to anode performance and the focus of materials research related to anodes in LiS batteries. Although materials research in the electrolyte field has focused on the selection of stable solvent systems or reactive additives that promote favorable SEI composition, solvents are the main source of organic Li salts in SEI films.

The disordered structure promotes ionic conductivity, while the thickness of the SEI layer increases internal resistance. When electron transfer is blocked, typically in the order of tens of angstroms, the film stops growing. The tightly graded layer model is often used to describe the SEI on Li anodes. Considering that the surface film on the anode consists of a porous mesophase and a compact mesophase, the compact mesophase consists of sublayers. The porous outer layer closest to the solution is non-uniform because the reduction of solution species does not occur over the entire film-solution interface, but actually occurs at defects or holes where electrons can tunnel to the surface. The composition of the SEI gradually changes as it moves from solution/SEI to SEI/Li. Approaching the Li anode surface, lower oxidation states are found and the SEI can become tighter.

The formation of SEI offers benefits as well as challenges depending on specific chemical and physical properties. For example, rough and heterogeneous SEI such as the disordered mosaic type derived from immersion promotes better growth through cracks and in regions where the SEI is thinner. Intact and smooth SEI with largely eliminated local defects effectively inhibits intrinsic Li dendrite growth and induced Li dendrite growth, which is desirable for Li-ion and LiS battery pack battery performance needs. Ideally, the SEI should be chemically stable, Li-ion conducting, compact, uniform, and mechanically rigid and elastic to accommodate the volume changes associated with PS shuttling encountered in typical LiS system cycling. Anode morphology

In addition to the formation of SEI during charge and discharge, Li exfoliation and electroplating also cause morphological changes over time. Natural defects in soft Li metal anodes can act as Li dendrite nucleation sites, and uneven exfoliation and electroplating of Li over time can increase the surface area of Li anodes and correspondingly introduce porosity, such as in the form of a defined plurality of fillers. Form of interstitial pore volume. This phenomenon is called "three-dimensional (3D) moss-like growth". Although this process increases the anodic reactive surface area for electrochemistry, it also promotes the continued fragmentation and reorganization of the SEI. This cycling process depletes the electrolyte components of the battery that form reactive SEI over time. And during cycling, irreversible side reactions may consume the Li anode active material and detract from the Li anode's ability to act as a current collector.

Moss-like growth is 3D omnidirectional moss or bush-like growth. 1D growth forms 3D growth by widening and branching during filamentous growth. This omnidirectional growth can be explained by the "raisin bread" expansion model, where there is no preferred direction and the distance between raisins increases as the bread loaf expands. The growth model does not have a growth center, but Li dendrite movement can be limited due to the available structural supports, where the Li metal anode can act as a substrate on which any growing moss is attached. Since Li atoms can be inserted over the entire Li anode structure, growth does not necessarily occur at the exposed ends of the Li anode surface and also does not necessarily occur at distributed growth points or regions. The growth and dissolution of the Li moss structure is a nonlinear dynamic process, in which the motion associated with the formation of the Li dendritic structure appears to be random and not governed by any direction of the electric field in the constructing electrolyte. During dissolution, a substantial portion of any Li dendrites formed can become electrically disconnected, and even though the Li dendrites remain attached to their original positions at the SEI layer, the Li dendrites extend from the SEI layer, as described above. This can still happen because the electrical contact sites are replaced by insulating and passivating SEI layers.

The surface of the Li anode exposed to the surrounding electrolyte must generally be relatively smooth to ensure the formation of a uniform SEI layer. The effect of controlling the initial Li surface roughness may depend on the nature of the native SEI. Simple spool pressing can be used to form artificial SEI with controlled surface modification, which can provide the effect of reducing overpotentials for plating and de-plating in symmetrical cells. barrier layer on anode

Excess Li can be used to act as a current collector in solid Li metal foil anodes such as in LiS systems to combat low coulombic efficiencies. In Li-ion batteries using Li metal, the formation of Li dendrites (also referred to interchangeably as dendrites) poses safety concerns due to the potential for internal short circuits, such as rapid self-susceptibility of the affected batteries. On discharge, dendrites extend from the anode to the cathode in the affected cell, creating a fast path for the electrical or ionic charge, while the non-electric or ionic charge travels fast through the intended path to power the load. The term dendrite encompasses a series of structures including needle-like, snowflake-like, tree-like, bush-like, whisker-like and moss-like structures. In most LiS systems, only moss-like growth has been observed in practice, and internal shorting due to dendritic growth has not been reported as a practical problem, however, these potential problems do present a concern for future high-demand applications . Accordingly, barrier or capping layer methods, such as layers that at least partially encapsulate the Li anode to prevent unwanted Li dendrites from growing from it, have been advanced to handle Li dendrite growth that has the potential for Li dendrite growth The potential of ionic technology to penetrate the spacer, some of these methods can be applied to LiS technology to combat shuttling and other degradation processes.

Most approaches to preventing dendrites in rechargeable Li batteries have focused on SEI stability and uniformity through the use of electrolyte additives. As previously discussed, these methods are often short-lived because Li metal is thermodynamically unstable in organic solvents. Nonetheless, its scale-up and simplicity of commercialization make it attractive.

And an alternative approach is to form an off-site mechanical barrier on the Li foil anode that is configured to prevent Li dendrite growth from the Li anode surface exposed to the electrolyte. Examples include polymer coatings or ceramics with high shear modulus to reduce damage to the protective layer and repair that would otherwise deplete reactive components in the electrolyte. Reel-to-reel coating techniques can be developed for Li coatings; these techniques are used, for example, in the semiconductor industry.

Barriers rely on the formation of a strong mechanical layer while attempting to reduce the impact on the occurrence of first-order electrochemical reactions. If the barrier layer blocks electrochemical activity, this method can easily create high internal resistance within the cell. The polymer layer can be cast onto Li and dried; the advantage is that the flexibility of the polymer makes it robust against volume changes during cycling. The problem is finding conductive polymers or achieving thin coatings that do not significantly increase the internal resistance in the battery. The polymer layer is required to be insoluble in the electrolyte and stable in the presence of polysulfides, nucleophiles and free radicals.

SEIs formed from organic solvents are generally brittle and thus cannot withstand mechanical deformation, leading to crack formation. Cracks enhance Li ion flux and lead to dendrite formation and new SEI formation. Cyclic rupture and repair of SEI consumes Li and electrolyte, resulting in battery pack failure. Volume variation is a major problem that renders most methods used to form stable SEIs ineffective. Elastic smart SEI layers have been developed using an in situ reaction between Li and polyacrylic acid (Li PAA). Li PAA has good uniform adhesive properties and is flexible enough to adapt to Li deformation. Mechanically Strengthened Hybrid Artificial Solid - Electrolyte Interface (A - SEI)

Distinguishing from attempted and partially successful approaches to efforts in developing effective barrier or capping layers suitable for limiting Li dendrite growth from Li anodes, the following solutions have been proposed: incorporating, for example, any of the binding schemes or Any one or more of the carbon-containing aggregates discussed in many of the nucleated graphene flakes can be used with polymers to generate the barrier layer. The disclosed carbon can act as a type of mechanical strength enhancer for solid Li metal foil anodes or carbon-based anodes with Li sandwiched between them to effectively inhibit lithium dendrites on exposed metallic lithium on the anode Form and enable Li-S batteries to be stable and have a long life. Such efforts may be used independently of or in conjunction with any or more conventional Li dendrite growth reduction techniques, including: ‧ Use of electrolytes or electrolytes with additives, which can help to develop a stable and uniform SEI layer inside the Li anode; ‧ External coating of artificial SEI (A-SEI) layer on Li anode prior to battery assembly; and • Preparation of carbon and Li composites by infusing Li into 3D structural materials of a given carbon-dominated scaffold structure.

The techniques disclosed in the present invention seek to combine multiple active components with mechanical strength enhancers such as polymers combined with the disclosed carbon to fabricate A-SEI films to produce ultrastable systems suitable for implementation in Li-S battery systems Li anode. The proposed A-SEI is ideal in many aspects and provides at least the following characteristics: • Operable on Li metal, electrolyte, and other battery components at typical Li-ion or LiS ranges such as temperature, pressure, current, and voltage Chemical and electrochemical stability under conditions such as contact; ‧ Mechanical strength formulated to inhibit Li dendrite formation from the Li anode; ‧ Adaptation attributable to the LiS battery system The flexibility or elasticity of the volume change of the polysulfide (PS) shuttle encountered during charge-discharge operational cycles; by substantially surrounding and adhering exposed to the surrounding electrolyte such as a solid Li metal foil anode or its intermediate sandwich Conformity and uniformity of any and all surfaces of anodes with Li-based carbon-based anodes; and ‧ High ionic conductivity for desired Li ⁺ ion transport throughout the cell, resulting in enhanced power Delivery and battery life.

Alternatively or additionally, inorganic chemicals can be added to the proposed barrier layer in order to incorporate the polymer into the carbon. Such inorganic chemicals may include, but are not limited to, any one or more of the following: alumina (Al ₂ O ₃ ), lithium fluoride (LiF), polysulfides (such as Li ₂ S ₆ ), phosphorus pentasulfide ( P ₂ S ₅ ), lithium phosphate (Li ₃ PO ₄ ), lithium nitride (Li ₃ N), silicon dioxide (SiO ₂ ), molybdenum disulfide (MoS ₂ ), Li ₂ S ₃ , any of the above Or more can provide a material suitable for forming a passivation layer due to relatively high chemical stability (such as becoming "passive," ie, a material that is less susceptible to environmental impact or corrosion in future use). However, if the resulting barrier layer with at least some of these inorganic chemicals is too thick, then these inorganic chemicals can, for example, also potentially interfere with the desired and necessary Li ions (Li ⁺ ) from anode to cathode. delivery. Polymers can be added to the mixture including these inorganic chemicals and together with any one or more of the carbon derivatives disclosed herein to form the barrier layer. These polymers may include cross-linked variants of polydimethylsiloxane (PDMS), polystyrene (PS), bis(1-(methacryloyloxy)ethyl)phosphate, including Adhesion promoter based on 2-hydroxyethyl methacrylate, glycerol dimethacrylate of any one or more of succinate, maleate phthalate or phosphoric acid ester Maleate, polyethylene glycol (PEO), poly(3,4-ethylenedioxythiophene) (PEDOT), styrene-butadiene rubber (SBR), poly(vinylidene fluoride- Co-hexafluoropropylene) (PVDF-HFP), polyvinylidene fluoride (polyvinylidene fluoride/polyvinylidene difluoride, PVDF). These polymers are elastic and self-healing, and thus can accommodate substantial volume changes during battery cycling. However, its lack of rigidity may not be sufficient to inhibit dendrite formation over extended durations of use.

To best incorporate the beneficial features of inorganic A-SEIs and/or polymer-based A-SEIs, while further enhancing the mechanical strength and/or integrity of barrier layers prepared as thin films, hybrid A-SEIs are disclosed. Hybrid A-SEI layers can be prepared to include any or more of the following: • Active inorganic components, such as any of the previously presented active inorganic components and/or including LiF, _LiN3 , Li-metal Alloys, Li-Si, Li ₃ PO ₄ , LiI, Li ₃ PS ₄ ; higher cross-linkable analogs of Zn, Sn, Sr, Ln, Al or Mo and/or their analogs; Primary and mechanical reinforcements, including any one or more of the disclosed carbon-based structures incorporating a polymeric binder (such as SBR) therein to provide structural reinforcement and flexural materials; and the like.

Fabrication techniques suitable for producing a hybrid A-SEI layer may include any or more of drop casting, knife coating, spray coating, UV curing, thermal curing, and the like.

4B shows a schematic diagram of a simplified schematic of an A-SEI protected anode 4B00 that can be used as an example of the carbon-based electrode structure shown in FIG. 3 . In some other implementations, and unlike the electrode shown in Figure 3, the electrode shown here in Figure 4B can be prepared without carbon and as solid Li metal supported by copper foil current collector 4B14 Foil anode 4B12. According to some embodiments, solid Li metal foil anode 4B12 has an exemplary hybrid artificial solid-electrolyte interphase (A-SEI) layer deposited thereon, where hybrid A-SEI consists of two active component layers, the first The active device layer 4B04 is deposited on the second active device layer 4B06, the two layers substantially encapsulate the solid Li metal foil anode 4B12. Any of the active element layers may include or be formed from the active element (or other active element) presented and any combination of polymer-based and mechanical enhancers. The first active device layer 4B04 may primarily act as a physical barrier layer or cap layer and prevent direct contact between the Li metal contained within the solid Li metal foil anode 4B12 and the electrolyte 4B02 surrounding the solid Li metal foil anode 4B12. Such confirmation of the first active device layer 4B04 prepared as a barrier layer prevents unstable SEI formation, electrolyte decomposition and drying, which can be beneficial for maintaining high efficiency over the lifetime of the Li-S battery and allowing the electrolyte to interact with each other. The sulfur (E/S) ratio can be relatively low (such as about 4.2 μL/mg).

Complementing the preparation of the first active device layer 4B04 as a physical barrier layer or cap layer, the second active device layer 4B06 can be prepared primarily to enable the surface of the solid Li metal foil anode 4B12 exposed to the electrolyte 4B02, such as by being formed on Uniform Li deposition in the apertures and/or void areas in any or more of the first active device layer 4B04 and the second active device layer 4B06 to correspondingly inhibit Li dendrites extending from the solid Li metal foil anode 4B12 formation of crystals. A mechanical strength enhancer comprising any one or more of the disclosed carbon-based aggregates, such as a plurality of graphene flakes fused together substantially orthogonally, can comprise the first formulation 4B08 and optionally the The second set 4B10 is displaced relative to the position of the first set 4B08. The mechanical strength enhancers comprising and with reference to the first set 4B08 and the second set 4B10, respectively, can be formulated to assist, at least in part, in retaining the A-SEI in the desired location, location, or set necessary to cause extended battery pack life. match. In addition, the first set 4B08 and the second set 4B10 can be prepared to together increase the strength of the A-SEI (such as the first component layer 4B04 and the second component layer 4B06), such as the Young's modulus of the hybrid A-SEI ( Young's modulus) (> 6 GPa), thus preventing Li dendrite growth.

4C shows the example shown in FIG. 4B prepared with an anode formed from the multilayer carbon-based scaffold structure shown in FIG. 3 , according to some embodiments. The same drawing reference numerals in Figure 4B refer to the same components in Figure 4B, except that the solid Li metal foil anode 4B12 is replaced by the porous carbon-based scaffold structure first shown and described in Figures 3 and 4A, This structure can be impregnated with Li to provide many insights into the solid Li metal foil anode 4B12 that provides Li ions (Li ⁺ ) suitable for ion transport associated with electrochemical transport required for proper Li ion and/or LiS cell cycling operation. Anode-like capabilities or characteristics. Given that the ubiquitous Li within the carbon-based scaffold structure shown in Figure 4C can theoretically also form dendritic structures, any one or more of the disclosed components related to hybrid A-SEI can also Reconfigured to substantially encapsulate such carbon-based anodes and protect such carbon-based anodes from undergoing Li dendritic growth.

Figure 4D shows a Table 4D00 of various exemplary conventional chemical adhesive materials or substances, also referred to as "adhesives," any one or more of which may be used to be included in Figures 4B and 4D, according to some embodiments. Parts of the carbonaceous material in the hybrid A-SEI layer shown in Figure 4C are bonded and/or bonded together to enhance Li dendrite formation protection. This article discusses the need and proposed solutions for binder systems and mechanical strength additives for the manufacture of mechanically strengthened hybrid artificial SEIs.

The need to substantially encapsulate the Li anode surface with a thin, uniform, and mechanically robust A-SEI layer that prevents direct contact between Li metal and the host electrolyte while enabling rapid Li ⁺ transport, uniform Li deposition, and suppression of dendrite formation A carefully designed formulation comprising the following characteristics: ‧ Desired chemical resistance to electrolytes; ‧ Desired Li wetting and adhesion; ‧ Minimal shrinkage during drying or curing; High packing density of mechanical strength enhancers; and ‧ High Li ⁺ permeability of encapsulation layer.

It is desirable to provide an A-SEI layer formed with a flexible polymeric matrix that is filled with the active components listed above and has a relatively high Young's modulus additive that provides good adhesion to Li surfaces. Styrene-butadiene rubber (SBR) linear polymers are examples of well-known flexible polymeric binders that can be used.

As has been experimentally demonstrated, the SBR-based mixed layer coating significantly improves Li-S full battery cycling compared to cells with untreated Li anodes. However, when such linear polymers are used as binders for protective A-SEI layers, their prolonged exposure to the electrolyte may cause the polymer to dissolve over time and cause the corresponding protective layer to degrade.

The stability of the protective A-SEI layer applied to the anode can be achieved by incorporating one or more functional groups such as -OH, -COOH, _-NH2 or other functional groups into the flexible polymeric structure This is enhanced by providing and promoting the binding of ions to the metal surface to increase the adhesion of the A-SEI layer to the Li surface exposed to the electrolyte. For example, dicarboxy-terminated polybutadienes and copolymers thereof, including poly(ethylene-co-acrylic acid) copolymers, may be used, which may combine flexible polyethylene units with PAA units and Li has strong affinity and is another good example of an improved linear polymeric binder.

An optimal solution for achieving good chemical resistance to electrolytes may include forming a cross-linked polymeric network, where the polymer chains are interconnected into the 3D network, preventing the polymer chains from dissolving over time. Variations in crosslink density and monomer and/or oligomeric blend composition will also allow tuning of A-SEI coating flexibility, good Li wetting and adhesion, and chemical resistance to electrolytes. Various types of curing, including UV curing or thermal curing, can be performed on any one or more of vinyl, acrylate groups, methacrylate groups. Additionally or alternatively, epoxy-based curing can be used to form a cross-linked polymeric network.

For example, the following monofunctional and difunctional acrylate and methacrylate monomers and combinations thereof can be used to form UV-curable or thermally-curable cross-linked polymeric networks: • Polybutadiene diacrylates, which can be used to impart improved flexibility to polymer blends; • Trimethylolpropane triacrylate, which can be used to impart crosslink density control to polymer blends; and • Bis[2-(methacryloyloxy)ethyl]phosphate and its monofunctional analogs, which can be used to impart improved adhesion and lithium adhesion to polymer blends.

These acrylate/methacrylate monomer based blends with initial low viscosity can eliminate the need to add solvent to the protective A-SEI layer composition and allow formation with optimum flexibility , Li wetting and adhesion, A-SEI coating for electrolyte chemical resistance and Li ⁺ permeability.

Examples such as those involving linear polymer chains with one or more monomers that will have the desired functionality, such as flexibility and adhesion (PAA, etc.) and lithium-adhesion capabilities (PEO, etc.), as can be provided by SBR, PBD, etc., can also be implemented. A symbiotic approach to solvent blending. Although the use of individual linear polymer chains as binders can cause them to dissolve over time, retention of the linear polymer chains in the cross-linked network prevents such dissolution. In addition, the long polymer chains can simultaneously minimize film shrinkage after curing. And in contrast to (meth)acrylate systems that may require an inert environment to form cross-networks, similar concepts as described above can be extended to epoxy-based systems that are curable at ambient conditions.

4E shows Example 4E00 formed of zinc acrylate as a mechanical strength enhancing additive for the A-SEI shown in FIGS. 4B and 4C , according to some embodiments. Another important aspect of A-SEI formation as previously described is shaping A-SEI to have high mechanical strength and to provide good dispersion of filler materials potentially useful in A-SEI formation as well as good dispersion within A-SEI Defect-free (such as without pores or cracks) films of high carbon particle packing density. Both preferences can take advantage of the use of nanofillers. Nanoscale materials with high Young's modulus, such as nanofillers, may be most beneficial for use as mechanical strength enhancers in the final A-SEI film.

For example, when ultra-thin (< 2 µm) coatings are required, the morphology of the nanofiller particles can become critical. Mechanical strength enhancers with substantially 2D morphology (such as graphene, nanoclays) composed of nanoflakes aligned under applied shear forces compared to 3D nanofillers with more spherical particle geometries , mica) may be more beneficial in terms of imparting mechanical strength or other beneficial properties such as filler dispersibility to A-SEI.

Graphene, such as when organized as a plurality of graphene flakes fused together at substantially orthogonal angles, can provide optimal mechanical strength enhancement due to its very high Young's modulus. Therefore, such high Young's modulus graphene materials can be used as strength enhancing additives in A-SEI fabrication. Unique graphene materials with substantially folded or wrinkled morphologies can be particularly beneficial for this application due to the structure incorporating highly crystalline and rigid graphene sp ^- bound carbon domains with softer and more flexible "wrinkled" regions particularity. Such incorporation would allow the graphene structure to accommodate the volume shrinkage of the A-SEI protective layer in fabrication while undergoing cross-linking to form the polymer.

Graphene allotropes can be functionalized with epoxy, amine, thiol, carboxylic acid, (meth)acrylate, vinyl, and -Si-H groups, any or more of which can be combined into the blend to further enhance film integrity. These functionalized graphenes can be covalently incorporated into the matrix and cross-linked via epoxy, free radical initiated vinyl or (meth)acrylate groups with difunctional molecules containing double bonds at either end or -Si-H group crosslinking or a combination of these curing methods to cure.

Notably, the same material may provide multiple functions, such as any one or more of the following: ‧ Encapsulating the Li surface so as to act as a physical barrier to prevent direct contact between the Li metal and the electrolyte; ‧ Enables uniform deposition of Li; and • Inhibits dendrite formation by acting as a mechanical strength enhancer for A-SEI.

Examples of such materials are curable organic salts of Zn, Sn, In and other metals. For example, zinc acrylate deposited on Li surface and cross-linked via UV or heat can result in a zinc polyacrylate layer that is excellent due to its high compressive strength at >4.5 pH and good chemical resistance. Often referred to as "dental cement". Such cured films can provide mechanical robustness, while the Zn2 ⁺ ions will be exchanged for Li ⁺ ions to enable their transport through the film.

4F shows an exemplary formation path 4F00 of metal polyacrylates suitable for protecting Li electrodes, such as anodes, according to some embodiments. This exemplary metal polyacrylate can be incorporated into any or more of the exemplary A-SEI formulations discussed previously to obtain any or more of the discussed benefits, such as fortification, to provide, for example, Self-standing, UV-cured, semi-interpenetrating polymer network. example

Figure 4G shows a pair of images of exemplary _SnF2 /SBR coatings on a control Hohsen Li anode with a Cu foil current collector (referred to as "Hohsen Li/Cu foil"), 4G00 and 4G02, respectively, according to some embodiments . Films were fabricated on Hohsen Li/Cu foils by doctor blade technology and baked at 60°C to accelerate the associated chemical reactions and drying processes. Yields of 0.3 mg and 2.3 µm SnF ₂ /SBR coatings were achieved. Photo 4G00 shows SnF ₂ /SBR coating on Hohsen Li/Cu foil after blade coating; and Photo 4G02 shows SnF ₂ /SBR on Hohsen Li/Cu foil after baking at 60°C for 20 hours coating.

4H shows the specific discharge capacity (in mAh/g) of an exemplary LiS full battery with a LiF/Li-Sn alloy mixed A-SEI treated Li anode and an intact Hohsen Li control foil and cathode according to some embodiments unit) of the scheme 4H00. A significant improvement in the performance of the SNF2/SBR-Li hybrid A-SEI combination with Li-S full cells with LiF/Li-Sn alloys is shown over the conventional _Hohsen Li control.

4I shows a photograph _4I00 of an exemplary Si3N4/SBR _A -SEI coating on a control Hohsen Li/Cu foil according to some embodiments. Films were fabricated by doctor blade on Hohsen Li/Cu foil and baked at 60°C to accelerate the associated chemical reactions and drying process. Yields of 0.3 mg and 1.6 μm Si ₃ N ₄ /SBR coatings were achieved.

4J shows the specific discharge capacity (in mAh/g) of an exemplary Li-S full battery prepared with a _LiN3 /Li-Si mixed A-SEI treated Li anode and an intact Hohsen Li control according to some embodiments ) of the schema 4J00. A _- SEI covered Li anodes (referred to as at least Si3N4 _- Li) were tested in Li-S full cells and showed significantly improved stability in early cycling.

4K shows a photograph 4K00 of an exemplary graphitic fluoride/SBR A-SEI coating in a control Hohsen Li/Cu foil anode according to some embodiments. LiF and graphite were combined to form A-SEI with SBR polymer binder. Films were fabricated by doctor blade on Hohsen Li/Cu foil and baked at 60°C to speed up the reaction and drying process. A yield of less than 0.1 mg and about 1.3 µm graphite fluoride (GF)/SBR coating was achieved.

4L shows the specific discharge capacity (in mAh/g) of an exemplary Li-S full battery prepared with LiF/graphite hybrid A-SEI treated Li anode and intact Hohsen Li control and cathode according to some embodiments schema. The ASEI covered anode (graphene-F, shown as GF-Li) was tested in a Li-S full cell and showed significantly improved stability in early cycling. Protective carbon interface layer for lithium metal anode protection

There are alternative or additional configurations for the A-SEI discussed to address various current limitations in Li-ion and LiS batteries. Notable challenges can be attributed to the volume expansion observed in the cathode and parasitic reactions observed in traditional (such as unprotected) solid Li metal foil anodes. Exemplary undesired parasitic reactions to try to prevent may include at least the following: Excessive formation of SEI, which may lead to electrolyte depletion; Li dendrite formation due to uneven current distribution, which results in internal short circuits and inactivity or """dead"Li; ‧Lithium metal surface corrosion (i.e. polysulfide dissolution) caused by reactants entering the electrolyte; and ‧Suppression or elimination of parasitic reactions associated with solid foil Li metal anodes may enable applications in many end-use applications Safe, cost-effective and higher energy density battery packs useful in the field.

Conventional battery manufacturers have encountered challenges associated with parasitic side reactions observed in conventional batteries with Li metal anodes that contribute to potentially unwanted Li dendrite growth. Attempts to address these parasitic side reactions may include, for example: Replacing the liquid electrolyte in the system with a solid electrolyte composed of different polymers, such as lithium phosphorus oxynitride, ceramics or polymers and/or ceramics, which tend to include High ionic conductivity materials such as fluoride/sulfide in some combination; Direct introduction of a protective barrier or cap layer on Li metal made of polymers and ceramics to protect Li metal itself from liquid electrolytes Influence, these protective layers include LiF, LiO, _Li2S and other common lithium alloying or conductive materials; ‧Create a patterned layer on top of the solid Li metal foil anode to redistribute the electrochemical current in the electrode; • Addition of metallic Li alloying additives such as titanium (Ti), tin (Sn), or silicon (Si) has been used to help reduce parasitic reactions; and • Addition of a mechanically stable layer that prevents outgrowth of dendrites into the current collector.

4M is an illustrative schematic diagram of a protected electrode (anode) 4M00 comprising a carbon-containing layer of carbon allotropes, such as an electrically insulating sheet carbon layer 4M04. In some examples, the electrically insulating sheet carbon layer 4M04 can be deposited on, around, or substantially encapsulate the naturally occurring SEI to prevent unstable formation of the naturally occurring SEI. The carbon allotrope particle size can be incorporated into an electrically insulating sheet carbon layer 4M04, which is shown laminated on top of a lithium sheathed current collector foil 4M06 supporting a conventional solid Li metal foil anode 4M10. Alternatively, in some configurations, the lithium sheathed current collector foil 4M06 can be assembled as a functional anode. Still further, alternatively, an electrically insulating sheet-like carbon layer 4M04 can be laminated to a carbon-based anode comprising a graphite scaffold or sheet of few-layer graphene with Li sandwiched therebetween. material. Any or more of these described configurations are suitable for use in Li-ion or LiS batteries. The electrically insulating sheet carbon layer 4M04 may have a thickness between about 0.1 µm and 50 µm and include one or more carbon allotropes (such as two different isotopes, with or without doping or functionalization). Prism) or functionalized carbon (such as graphene oxide and carbon nanoonions, which can define various interstitial pore volumes that are interspersed throughout the electrically insulating sheet carbon layer 4M04, allowing access via paths 4M14 and Li ⁺ ions are transported therethrough via the electrolyte 4M08, as may be necessary for proper cell operation). The carbon allotrope particle size can be in the range of 0.01-10 μm. An electrically insulating sheet-like carbon layer 4M04 is added to act as a "carbon sheath" to protect the solid Li metal foil anode 4M10 (in some configurations, it can alternatively be a carbon scaffold comprising a plurality of graphene sheets with Li sandwiched between them The Li metal contained in the anode) is free from interaction with the electrolyte. The electrically insulating sheet carbon layer 4M04 does this by providing the SEI (or alternatively, A-SEI such as the A-SEI discussed earlier) the desired surface to grow on, preventing polysulfides (PS) to the lithium metal anode, improving the uniformity of Li ion flux during normal battery operable charge-discharge cycles and adding mechanical benefits for preventing Li dendrites extending from the anode towards the cathode and assisting in volume Regulation of expansion and contraction.

To suppress Li dendrite growth starting from the solid Li metal foil anode 4M10 during the operational cycle of the battery, the electrically insulating sheet carbon layer 4M04 can be formed as a uniform thin film layer with a Young's modulus of about >6 GPa. Graphene oxide, which is a material with a Young's modulus of 380-470 GPa, is an example of a suitable carbon-based candidate to achieve proper Li dendrite suppression. Compared to conductive graphene, graphene oxide is electrically insulating and prevents Li dendrite deposition on top of the electrically insulating sheet carbon layer 4M04. Instead, any Li present will be deposited under the electrically insulating sheet carbon layer 4M04 due to its barrier and insulating properties, more precisely, some Li ⁺ ions 4M 12 will adhere to the electrically insulating sheet carbon The underside of layer 4M04 instead forms long dendritic structures extending towards the cathode. The graphene oxide flakes can be overlapped with each other to form an electrically insulating sheet-like carbon layer 4M04 as a conformal film. However, this conformal graphene oxide film may induce high impedance. Thus, the addition of a collection of carbon nanoonions 4M12 can create gaps within the bulk graphene oxide stack (and thus the electrically insulating sheet carbon layer 4M04), a reduction due to enhanced Li transport (via, for example, one or more orientations) The impedance of the path 4M14) of the cathode 4M02 and allow better release of the film from the PET matrix.

Carbon nanoonions with relatively high surface areas of, for example, about 10 m ² /g-90 m ² /g, more preferably about 30 m ² /g, will facilitate polysulfide (PS) adsorption, thereby preventing PS Anions reach the Li metal anode surface and undergo chemical reduction to form _Li2S (S), which will result in irreversible sulfur and lithium capacity loss.

The electrically insulating sheet carbon layer 4M04 can be prepared in a substantially binder-free manner. The two-dimensional shape of graphene oxide results in a more efficient packing between individual graphene oxide sheets when compared to films composed of individual particles held together with a binder, resulting in formation of π- A denser film where the pi bonds are strongly held together. Furthermore, the sheet-like stacking of graphene oxide inhibits crack growth due to the complex, high surface area pathways required to expand the cracks in the direction perpendicular to the graphene oxide sheets, thereby improving the integrity of the film. Additionally, conventional binders will fill the voids between the carbon particles, resulting in high impedance for lithium ion transport. In addition, graphene oxide can react with Li metal and form LiOH in the intermediate phase as a stable SEI. Since graphene oxide is insulating, it will not interact with the electrolyte to form SEI on the carbon surface.

The electrically insulating sheet carbon layer 4M04 can optionally include various types of carbon with variable porosity, surface area, surface functionalization and electronic conductivity to influence the interaction of the carbon with that from the surrounding environment (outside the solid Li metal foil anode 4M10). Reactivity of contaminants, such as components of electrolytes in Li batteries, such as PS, and the layer may include binders or be used to supplement the carbon sheath to produce materials with variable density, porosity, carbon fraction, Other additives for reactive, electronically conductive sheaths and can readily conduct lithium ions or lithium-containing molecules to facilitate lithium shuttle between cathode and anode. The best use of the carbon disclosed herein is to trap the undesirable contaminants prevalent in the electrolyte and prevent the contaminants from reacting with the Li surface, which reacts with the surface of the electrically insulating sheet carbon layer 4M04. This layer must have excellent adhesion to Li, as determined by the method of manufacture and composition of the electrically insulating sheet carbon layer 4M04, which mainly contains carbon.

FIG. 4N is an exemplary schematic diagram of a roll-to-roll apparatus 4N00 prepared for the manufacture of carbon/lithium anodes such as the protected electrode 4M00 of FIG. 4M showing electrically insulating sheet carbon deposited on solid Li metal foil anode 4M10 Layer 4M04. The roll-to-roll apparatus 4N00 can be configured to utilize any compression method such as roll-to-roll lamination and release to transfer the carbon-containing coating (for generating or providing the electrically insulating sheet carbon layer 4M04 ) from another substrate to Li On surfaces such as the surface of solid Li metal foil anode 4M10 that will be exposed to electrolyte 4M08 after fabrication is complete.

The carbon/lithium anode can be fabricated by using any known technique using any compression method, such as roll-to-roll lamination and release. The carbon-containing coating represented by the carbon interface 4N06 on the release film 4N04 of the mold film was transferred from another substrate to the Li surface. For example, an electrically insulating sheet carbon layer 4M04 including graphene oxide and carbon nanoonions can be prepared by first mixing to form a slurry, then casting the slurry onto a PET release such as a release film 4N04 on the film and dried under vacuum at 60°C. After drying, the film is then transferred via roll-to-roll lamination (such as by rotating the first roll 4N02 and the second roll 4N12, respectively) to the lithium sheath formed by compressing the Li layer 4N08 onto the copper foil 4N10 in a drying room environment on copper foil.

Applying pressure to transfer the carbon interface 4N06 from the release film 4N04 to the Li layer 4N08 can be accomplished by, for example, calendering the carbon interface 4N06 (such as when prepared as a protective carbon layer) onto the Li layer 4N08 and subsequently releasing the release film 4N04 to achieve. After doing the above actions, the carbon interface 4N06 will firmly adhere to the Li layer 4N08 due to the inherent adhesion properties within the Li metal. Therefore, the binder Li metal will assist in releasing the carbon interface 4N06 from the release film 4N04, thereby completing the fabrication of the protected electrode 4M00 shown in FIG. 4 .

In addition to the arrangement of protected electrodes 4M00 shown in Figure 4M produced by roll-to-roll apparatus 4N00, several alternative arrangements are possible. For example, CNO can be substituted or added to and including one or more other carbon allotropes, each carbon allotrope exhibiting different chemical and mechanical properties. Nanodiamonds (also referred to as "diamond nanoparticles") can include diamonds with a size below 1 micron, can be dispersed throughout, and thus strengthen the electrically insulating sheet carbon layer 4M04 and enhance capabilities including mechanical robustness, electrical insulation The various properties of this are non-SEI-forming and protect from the intrusion of polysulfide (PS) species into the solid Li metal foil anode 4M10 (or carbon-based anodes containing Li). In addition to or in place of nanodiamond, other carbon-based substances that may be dispersed throughout the electrically insulating sheet carbon layer 4M04 may include: such as SP mixed carbon, reduced graphene ^oxide (rGO) and/or Graphene carbon in various forms or types, which can lead to improved stacking and layer formation of one or more layers of the electrically insulating sheet carbon layer 4M04 ; Exfoliation and carbon oxides, which are formulated to incorporate electrically insulating sheet carbon layer 4M04 to give it a more uniform layered structure; solvents such as tetrabutylammonium hydroxide (TBA) and dimethylformamide (DMF) solvent treatments can be applied to incorporate into the electrically insulating sheet carbon layer 4M04 Exfoliation and carbon oxidation to give carbon better wetting, thereby achieving better carbon dispersion uniformity in the entire electrical insulating sheet carbon layer 4M04 ; Fluorinated graphene, which is added to the carbon slurry, The carbon paste includes any one or more of the 3D hierarchical carbon structures or cohesion disclosed herein to enhance the SEI formation reaction between the carbon exposed thereto and Li metal, all while not interfering with the protected electrode Layered structure of 4M00; ‧Adding dopants to the crystalline structure of carbon incorporated into the electrically insulating sheet carbon layer 4M04; one or more functional groups can also be added to the electrically insulating sheet carbon layer 4M04 incorporated Among them, the carbon-based scaffold or one or more doped carbons in the matrix; ‧Adding functionalized carbon, especially functionalized carbon with F and Si groups, to the electrically insulating sheet-like carbon layer 4M04, which Can be included or deposited under layered carbon barriers to form stable SEIs on Li and carbon mesophases; and • addition of functionalized carbons such as silicon hydride and/or hydride nitrogen functionalized carbons to electrically insulating sheets In the carbon layer 4M04, it is included or deposited over the electrically insulating sheet carbon layer 4M04 to block the diffusion and migration of polysulfide (PS) to the surface of the Li metal exposed to the electrolyte 4M08.

In addition, the addition of specific polymers/crosslinkers, such as any or more of the polymers/crosslinkers referenced by Table 4D00 shown in Figure 4D, can improve the mechanical properties of the electrically insulating sheet carbon layer 4M04 , enhances Li ion transport and/or flux in the electrically insulating sheet carbon layer 4M04 (as shown by one or more paths 4M14 in Figure 4M). Additional examples of polymers that enhance Li ion transport include poly(ethylene oxide) and poly(ethyleneimine), while examples of linkers that can be used to crosslink carbons together include inorganic linkers such as borates, aluminates, silicates), multifunctional organic molecules (such as diamines, diols), polyureas, and high molecular weight (MW) carboxymethyl cellulose CMC.

Additional or alternative methods of making and/or depositing the electrically insulating sheet carbon layer 4M04 onto the protected electrode 4M00 include spraying; slurry casting the carbon layer onto a perforated film for better release ; The carbon layer slurry is then cast onto the spacer without release for direct cell assembly; and the electrically insulating sheet carbon layer 4M04 is vacuumed with or without calendering-lamination Filter onto spacers.

Either or more of the A-SEIs described with reference to the A-SEI protected anode 4B00 shown in FIG. 4B or the protected electrode 4M00 (protected by the electrically insulating sheet carbon layer 4M04 ) can be removed from the competitor's cell to Interfacial coatings on the anode surface are revealed, which can be further analyzed by various test methods such as: Using X-ray powder diffraction (XRD), mass spectrometry and by observation using scanning electron microscopy Disassembly analysis by visual inspection will reveal material properties such as flake-like morphologies of included carbon inherent in the structures observed or evaluated; and Mechanical testing of competitor anodes will reveal protections as disclosed in the present invention Similarity of any one or more of the carbon interfacial layers. example

4O is a photograph of an exemplary Protective Carbon Interface (PCI) 4O00 suitable for deposition on a Li anode, such as the Li anode shown by the protected electrode 4M00 in FIG. 4M, in accordance with some embodiments. The PCI layer may comprise ratios of different carbon allotropes mixed together to produce a homogeneous dispersion, followed by direct transfer of the homogeneous dispersion by roll-to-roll transfer on Li metal foil, such as shown in Figure 4N. The reel transfer described in the roll-to-roll apparatus 4N00 shown in . The PCI layer 4000 maintains a relatively stable average charge voltage, which indicates that no unwanted parasitic side reactions occur within the battery cells so equipped during cycling operation.

4P shows a graph 4P00 of electrode specific capacity performance versus cycle number for Li anodes protected by the Protective Carbon Interface (PCI) 4000 shown in FIG. 40 , compared to a reference pure Li metal electrode, according to some embodiments. As shown, the reference Li metal electrode exhibits a dramatic decrease in capacity after about 25 cycles. The dramatic reduction in capacity is caused by parasitic reactions occurring on the surface of the Li anode exposed to the electrolyte, resulting in dendrite formation on the surface of the Li anode and a corresponding increase in the resistance of the anode. In contrast, the PCI layer prevents the sudden sharp drop in capacity caused by the high impedance that the interface layer can prevent.

4Q shows a graph 4Q00 of coulombic efficiency versus cycle number for Li anodes protected by the Protective Carbon Interface (PCI) 4000 shown in FIG. 40 compared to a reference pure Li metal electrode, according to some embodiments. The Coulombic efficiencies shown in Figure 4Q indicate that the reference Li metal electrode experienced a sharp anomaly (such as a decrease) in efficiency starting at cycle 30 (as shown by the unstable behavior of the data points), while PCI 4O00 maintained a stable efficiency bit throughout the cycle allow. The unstable efficiency data in the reference Li metal electrodes correspond to high levels of Li dendritic growth. This is further confirmed by the average charge voltage data shown in Figure 4R.

4R shows a graph 4R00 of average charge voltage versus cycle number for a protected carbon interface (PCI) protected Li anode compared to a reference pure Li metal electrode according to some embodiments. As shown, the average charge voltage of the reference Li metal electrode increases rapidly, while the PCO layer (corresponding to PCI 4O00 shown in Figure 4O) remains relatively constant, indicating the absence of Li dendrite growth.

FIG. 4S shows another graph 4S00 of cycle data for various full cells (with a limited supply of lithium), each in coin cell format. According to some embodiments, the electrode specific capacity (in mAh/g) performance versus cycle number of a Li anode protected by a Protected Carbon Interface (PCI) was compared to a nanodiamond layer, a reference pure Li metal electrode, and a non-uniform interface layer for comparison. As shown, the reference Li decays rapidly without the protective interfacial layer. The protective carbon interface layer (corresponding to PCI 4O00 shown in Figure 4O) showed the best capacity retention, followed by the nanodiamond layer. A heterogeneous (carbon) interfacial layer with visible defects on the surface actually performed worse than the reference Li Li, indicating that uniform coverage of the Li surface and integrity of the interfacial layer are key parameters.

Figure 4T shows a photograph of reference cell disassembly 4T00 of an exemplary reference lithium pouch cell showing a high degree of dendritic growth into the spacer (shown in area 4T02). Here, dendritic growth is shown as the transfer (growth) of the black moss-like structure in region 4T02.

Figure 4U shows a photo of a disassembled 4U00 of an exemplary carbon-containing layer protected Li anode, such as the protected electrode 4M00 shown in Figure 4M, which shows the absence of the region of the reference cell disassembly 4T00 shown in Figure 4T The moss-like black protrusions shown in 4T02. Instead, disassembly of 4U00 shows only a few trace spots of layered PCI adhering to the spacer upon deconstruction.

Conversely, the spacer depicted in Figure 6 is not without any moss-like black protrusions found in the reference cell. More precisely, it has several spots of layered LPCI that stick to the spacer when deconstructed.

FIG. 5 shows an exemplary Li-ion or LiS secondary electrochemical cell system 500 having an anode 501 and a cathode 502 separated by a spacer 517 . Any one or more of anode 501 and cathode 502 may be formed substantially from the lithiated carbon scaffold 400A shown in FIG. 4A, and represented here in simplified representations of larger and smaller carbon particles 509, all of which The isocarbon particles each at least partially confine the Li ion conducting electrolyte solution 518 containing the dissociated Li ion conducting salt 505 as shown. Spacers (porous membranes that electrically isolate anode 501 and cathode 502 from each other) are also located where shown. A single Li ion migrates back and forth between the electrodes of the Li-ion battery during the discharge-charge cycle via pathway 507 and is sandwiched into the carbon-based active material to form any one or more of anode 501 and cathode 502. Alternatively, if necessary, it is limited to obtain the best secondary electrochemical cell 500 performance.

Electrolytes such as electrolyte solution 518 can generally be divided into several broad categories, including liquid electrolytes and solid electrolytes. Liquid electrolytes are the most common electrolyte system for many conventional batteries due to their higher ionic conductivity, lower surface tension, lower interfacial impedance, and good wettability within the electrodes. In LiS battery systems, the liquid electrolyte predominates because it helps compensate for the poor electrochemical kinetics of large amounts of potentially encountered S and lithium sulfide ( _Li2S ). In LiS systems, liquid electrolytes containing ether-based solvents can be used because, unlike carbonates, ether-based solvents do not react adversely with S and generally have better Li ion transport properties. Potential disadvantages of using ether-based electrolytes include the solubility of long-chain polysulfides (PS), which can eventually lead to degradation of LiS electrochemical cells due to PS shuttling, electron migration, and volume expansion of the cathode, thereby damaging its structure completeness.

Outside of conventional liquid phase electrolytes, solid electrolytes can potentially be configured to stop the formation and growth of Li dendrites, and stop PS when the solid electrolyte effectively converts the LiS system from a multiphase system to a single phase system Shuttle without causing internal short circuits, electrolyte leakage and non-flammability. A solid polymer electrolyte can be defined as a porous membrane with the ability to transport Li ions on the membrane. Solid electrolytes can be further classified into solid polymer electrolytes, gel polymer electrolytes, and non-polymer electrolytes. The solid polymer electrolyte may consist of a lithium salt dissolved in a high molecular weight polymer host. Common polymer hosts used are polyethylene glycol (PEO), polyvinylidene fluoride or polyvinylidene fluoride (PVDF), poly(paraphenylene oxide) or poly(PPO), poly(vinylidene fluoride) Ethylene-co-hexafluoropropylene) (PVDF-HFP) and poly(methyl methacrylate) (PMMA), etc.

Gel polymer electrolytes can be similar to solid polymer electrolytes in that they have higher molecular weight polymers and also include liquid components tightly trapped within the polymer matrix. In some embodiments, gel polymer electrolytes are developed to compensate for the poor ionic conductivity observed in solid polymer electrolytes. Compared to other forms of solid electrolytes, non-polymer solid electrolytes have the advantage of higher thermal and chemical stability.

Non-polymer solid electrolytes are composed of ceramics and commonly found non-polymer electrolytes include superionic conductors (LISICON), Li ₇ La ₃ Zr ₂ O ₁₂ (LLZO), Li ₇ La _2.75 Ca _0.25 Zr _1.75 Nb _0.25 O ₁₂ (LLCZN ), Garnet, and Ge-doped Li _0.33 La _0.56 TiO ₃ (Ge-LLTO) perovskite, etc., and thicknesses can range from about 0.5 μM to 40 μM, which can be formulated to substantially prevent Li dendrites Either or more of crystal formation or growth. Nonetheless, some solid electrolytes may have certain challenges, including relatively poor Li ion conductivity and weight. At the thicknesses required to prevent Li dendrite growth, the observed ionic impedance may be so high that a Li-ion or LiS battery so equipped may not function as desired, while it is necessary to have acceptable Li-ion At a thickness of conductivity, Li dendrite growth may not be avoided.

During discharge, Li is sandwiched from the anode 501 . The active material of cathode 502 may include mixed oxides. The active material of anode 501 may include primarily graphite and amorphous carbon compounds, including those presented herein. These materials are materials with Li interposed.

Li ion conducting salt 505 can dissociate to provide mobile Li ions that can be intercalated into any one or more of the unique carbon-based structures disclosed herein, which can be incorporated into anode 501 or in any one or more of the cathodes 502 as a structural material to achieve specific capacity retention in excess of 1,100 mAh/g or higher, as facilitated by the connected microstructures 107E. Li ions form complexes and/or compounds with S in the LiS system and are temporarily limited during charge-discharge cycles to levels not otherwise achievable with conventional unorganized carbon structures (needs to be defined and combined by adhesion), It can also inhibit overall battery pack performance and durability, as discussed earlier.

Pores 105E of connected microstructures 107E shown in FIG. 1E that can form carbon-based particles 100A, 100D, 402A and/or the like and used to create either or more of anode 501 or cathode 502 A conductive graded membrane layer that can be defined during synthesis to include a micropore volume (pores < 1.5 nm). Sulfur (S) is infused into pores 105E via capillary forces, where S is confined. Successful micron confinement of sulfur will prevent dissolved polysulfide (PS) (as presented earlier for LiS systems) from generally reprecipitating outside of its original pores. To achieve an activated carbon composite capable of retaining achievable amounts of S, a pore volume of 1.7 cc/g may be required, all 1.7 cc/g such that the opening of the pores is <1.5 nm.

FLG + Li+ e- Operationally, in a Li ion or Li S system, Li ions migrate from anode 501 to cathode 502 via electrolyte 518 and spacer 517 . Here, as shown in magnified regions 516 and 513, molten Li metal 514 microns is confined to those associated with either of the disclosed carbon-based structures used as structures for anode 501 or cathode 502. within the few-layer graphene sheet 515 . Molten Li metal can dissociate in anode 501 according to the following equation (8): (8) FLG-Li

FLG + Li + e-

LiCoO ₂。 Equation (1) shows that electrons 506 and 511 discharge 508 to power an external load so that Li ions 512 that migrate to cathode 502 return to thermodynamically favorable locations within the cobalt oxide-dominated lattice according to equation (9) below: (9) xLi ⁺ + xe ^- +Li _1-x CoO ₂

LiCoO ₂ .

During charging, the process is reversed, where Li ions 505 are transferred from cathode 502 to anode 501 via electrolyte 518 and spacer 517 .

The disclosed carbon-based structures are fabricated by the unique multimodal hierarchical structure of carbon-based particles 100A, 100D and/or derivatives thereof, including carbon scaffolds 300B and lithiated carbon scaffolds 400A With the unexpectedly favorable specific capacity values, any one or more of these structures can be assembled to yield the traditional advantages offered by Li-ion technology. Relatively small Li ions exhibit significantly faster kinetics in different oxidizing cathode materials compared to sodium or potassium ions. Another difference includes that Li ions are reversibly intercalated and deintercalated in graphite and silicon (Si), as opposed to other alkali metals. And the lithiated graphite electrode enables higher battery voltage. Thus, the disclosed carbon-based material enhances the reversible intercalation and desorption of Li ions due to the unique stacking of few-layer graphene (FLG), such as 5 to 15 layers of graphene in the general horizontal stack configuration 101C. The simplicity of being sandwiched between graphene sheets, as employed in carbon-based particles 100A and/or the like, is suitable for hard case, pouch battery, and solar applications. Stabilization of artificial solid - electrolyte interface (SEI) films by doping

Currently, current Li-ion batteries form a protective passivation layer (such as the passivation layer shown in Figure 4A) at the electrode surfaces exposed to the electrolyte during the preconditioning step when the electrolyte is first introduced followed by the initial discharge and charge steps. 418A) or solid electrolyte interface (SEI). Although electrolyte chemistry and pretreatment schemes such as charge/discharge rates and overvoltages can be adjusted to optimize film passivation, conventional film layers incorporated into electrodes can be chemically and mechanically unstable, with reference to SEI formation .

Referring now to FIG. 6A, a specific element 602A can be introduced into the aforementioned carbon material 600A by doping. Elements such as silicon, sulfur, nitrogen, phosphorus 602A at example exposed electrode surfaces 601A can be coated onto carbon-structured electrode surfaces 601A with a contoured coverage at specified levels, such as loosely decorated to full contoured coverage. Preferential formation of stable solid-state electrolyte ion-conducting layers has been reported in the literature; see sulfur-based _thioLISCON , which is defined as a lithium-sulfur conductor with the _{formula Li3.25Geo.25P0.75S4} , and phosphate-based _NASCION , such as sodium (Na) superionic conductors, which generally refer to the family of solids having the formula Na _1+x Zr ₂ Si _x P _3−x O ₁₂ (0<x<3), and abbreviations are also used for analogous compounds in which Na, Zr and/or Si are substituted with the same valence element. As explained herein, the formation of the stable solid-state passivation layer includes doping with specific elements 602A, and the electrode surface 601A can be engineered prior to battery assembly so that the formation of the stable solid-state ion-conducting layer is the same as that which occurs when in contact with the electrolyte. Decoupling of reduction/oxidation events, as encountered in current Li-ion battery fabrication, still often suffers from long-term stable operation.

In combination with conductive particles such as carbon black and optional polymeric binders and solvents such as NMP, any one or more of the tuned 3D hierarchical graphene-based particles disclosed herein can be incorporated directly To the following conventional slurry cast electrode fabrication processes: in the case of the anode, active graphene-based (FLG) replaces the graphite particles; and/or in the case of the cathode, infused with active sulfur (S).

3D graphene particles provide higher specific capacity graphene building blocks with interconnected mesoporous ion-conducting channels for fast Li ion transport as well as carbon black and binder to ensure conductive paths, such as for use as a continuous microstructure 107E Defined by graphene sheets 101B of structural material, it also provides mechanical integrity.

The disclosed carbon materials can be pre-lithiated by ball milling and/or after thermal annealing and electrochemical reduction from the third electrode at relatively low concentrations to counteract the first charge Li loss of conventional oxide cathode cells; or The slurries were then cast into the electrodes at relatively high concentrations to increase the overall specific capacity of both the oxidation and alternative cathode assemblies.

6B1 and 6B2 show schematic diagrams comparing chemically non-reactive system 600B1 to chemically reactive system 600B2 with active material wetting and lithium (Li) confinement within the active material, according to some embodiments. While molten Li metal infiltrates the assembly of any one or more of the presently disclosed carbon-based structures shown in FIGS. 1A-1E , such as the connected microstructures 107E, alternative or additional embodiments provide Molten Li metal droplets are poured into pores, such as pores 105E, in the gas phase. In chemically non-reactive system 600B1, Li metal droplets were prepared, or expected to fail to react with carbon when in contact with exposed carbon surfaces due to, for example, the Li hydrophobicity of carbon. In any event, impregnating vapor-phase Li droplets with an internal contact angle (θ) of between about 50° and 90° may provide a balance between competing liquid and solid adhesion forces, such as in liquid phase molten Li droplets (such as with Adhesion observed between those providing Li ions 108E) and the solid phase carbon (γ _sl ), which is proportional to the (γ _lv ) adhesion in the liquid.

Wetting that occurs between gas-phase Li and solid-phase carbon is defined as the ability of a liquid to maintain contact with a solid surface, resulting from intermolecular interactions when the two are brought together, where the degree of wetting or wettability can be determined by adhesion The force balance between the force and the adhesive force is determined. The desired degree of wetting can occur when the adhesive energy is close to the adhesive energy, such as with tightly held bonds, such as in liquid metals dispersed on solid metals, or in cases including silicon (Si), Found in semiconductors of germanium (Ge) or silicon carbide (SiC), and ceramics including any one or more of carbides, nitrides, or borides, which can exhibit metallic-like properties close to exposed surfaces. And the use of liquid phase metals with relatively high solubility for atmospheric pollutants such as oxygen (O), nitrogen (N) or moisture (H ₂ O vapor) or carbon can reduce the rate at contaminated solid surfaces or at pure carbon surfaces. The observed or desired contact angle during wetting.

In chemically reactive system 600B2, wetting of carbon surface layer 602B2, such as on the surface of Li metal-exposed carbon-based particles 100A, may be accompanied by chemical reactions occurring at that interface, such as dissolving solid carbon materials Either a new 3D layer 604B2 is formed or a compound involved in at least partial depletion of the underlying carbon surface layer 604B2. Addition of dopants tuned by type and concentration at carbon surface layer 602B2 can also affect the degree of wetting, as shown by the various fluid locations 606B2, 608B2, and 610B2, shown with minimal wetting at location 606B2 and respectively at Positions 608B2 and 610B2 have progressively larger wetted molten Li droplets. In some implementations, the formation of the new 3D layer 604B2 can alter the properties of the underlying carbon surface layer 602B2, including electrical conductivity, or can otherwise (by pinch off) confine the reaction product by forming volume expansion (shown Wetted into the porous medium for the new 3D layer 604B2).

For either chemically non-reactive system 600B1 or chemically reactive system 600B2, reducing the contact angle of liquid Li metal droplet beads, such as the droplet beads shown in location 610B2, may promote wetting of the underlying carbon surface layer 602B2. And for combinations of carbon surface layer 602B2 with adsorbed or chemically bonded oxygen (O), adding elements with higher O solubility, such as also known as getters, can reduce or otherwise control the new 3D layer 604B2 O activity at the site. For the solid variant of the carbon surface layer 602B2, the addition of elements such as nickel (Ni), iron (Fe), or other elements to liquid phase metals with higher carbon solubility can ensure relatively higher surface activity or affinity.

7 shows an example process workflow in which molten Li metal is infiltrated into void spaces between carbon agglomerates to initiate reactions at exposed carbon surfaces, according to some embodiments. Considerations for infiltrating Li metal 704, 706 into encapsulated carbon scaffold 702 are shown in infiltration process workflow schematic 700, and these considerations may be incorporated into any one or more of the carbon-based structures disclosed herein ( Such structural materials are provided within or otherwise, such as the carbon particles 100A shown in Figure 1A or the connected microstructures 107E shown in Figure 1E). The surface conditions of the carbon scaffold 702 can be tuned prior to infiltration by molten Li metal, either by capillary infusion using molten Li metal in the liquid phase or infusion of molten Li metal droplets suspended in air. One or more enters into the carbon support 702, thereby forming Li metal vapor. Precise tuning of the following conditions at the surface of the carbon support 702 exposed to incoming Li, including control of: Atmospheric contaminants such as moisture ( _H2O vapor), oxygen (O), nitrogen (N) and a combination of Hydrocarbons that limit or contain physiosorbent or chemisorbed O; ● Nitrogen bond formation on surfaces during plasma post-processing; and ● Li metal purity, such as control of prevalent surface oxides, nitrides, and carbonates.

Li infiltration can be initiated by capillary infusion of molten Li metal 704 , 706 to spread and fill within carbon scaffold 702 , forming lithiated carbon compound 708 , encapsulating the voids of carbon scaffold 702 . The procedure can be followed by non-reactive Li wetting and post-reactive treatments. There are various specific method options by which Li can be infiltrated into the carbon scaffold 702, including:

8A shows equations that model the rate of Li wetting into any one or more of the porous regions of presently present carbon-dominated structures such as Pores 105E and connecting paths 107E shown in FIG. 1E of carbon-based particle 100A shown in FIG. 1A . The rate of wetting can be controlled by the non-reactive viscous resistance of the liquid metal, such as molten Li metal, followed by the chemical reaction between the liquid metal and the carbon contact according to Washburn's equation 800A shown in FIG. 8A . Carbide, where σ and η are the surface tension and viscosity of the liquid, respectively, θ is the contact angle, and r _eff is the effective pore radius of pores such as pores 105E shown in FIG. A predominant scaffold, such as in the carbon predominant scaffold 702 shown in FIG. 7 . Thus, as can be seen from the various coefficients used in Washburn's equation 800A, capillary flow is described by modeling the carbon-dominant preform structure as a theoretical bundle of parallel cylindrical tubes, effectively representing infiltration into the porous material.

8B shows a non-reactive system 800B including a non-wetting assembly 802B and a spontaneously wetting assembly 804B, according to some embodiments. For example: • In non-wetting configuration 802B, pressure (P ₀ ) is applied to overcome capillary pressure, such as two immiscible solutions in a thin tube caused by the interaction of forces between the liquid and solid walls of the tube pressure between the bodies, and may be limited by viscous friction, such as that established and characterized by Washburn's equation 800A; L may represent a liquid phase Li layer, such as that provided by molten Li metal , S can represent the solid carbon surface exposed to L, θ can represent the contact angle of L and S, and V can represent viscous friction, and is characterized by Washburn's equation 800A at the contact area of L and S; In wetting configuration 804B, θ is maintained at an angle of <60° to achieve non-reactive Li infiltration of carbon-based scaffolds; and ● either non-wetting configuration 802B or spontaneously wetting configuration 804B One or more may be incorporated into or otherwise implemented in the exemplary carbon-based scaffold 806B, which may be a forming part of any one or more of the carbon-based structures disclosed herein.

8C shows a reactive system 800C including a wettable reactive product layer assembly 802C and a non-wettable surface layer assembly 804B, according to some embodiments. The wettable reactive product layer assembly 802C may involve forming a new 3D layer 806C similar to the layers previously discussed in relation to the chemically reactive system 600B2 shown in FIG. 6B2, wherein the new 3D layer 604B2 or compound formation involves At least partial consumption of the base carbon surface layer 604B2. Herein, the solid carbon material S may be at least partially consumed to manufacture or generate a new 3D layer 806C which may be or include LiC ₆ . In contrast, in the assembly 804B for a non-wettable surface layer of S, such as a surface that faces directly in the vertical direction, L is not reactive so that invasion of L into the capillary tubular open area causes a depletion reaction with S to occur. A new 3D layer 808C is created only along those capillary open areas.

9 shows a flow diagram 900 of a method of lithiation and alloying of carbon-based structures, according to some embodiments. At block 902, oxide thermal decomposition can be used to initiate surface interfacial reactions via lithium (Li) vapor pressure to activate carbon surfaces in the encapsulated preform. At block 904, in the instance where the Li film is wetted into the metal matrix, the surface active element compound may be vaporized to decompose the oxide flux and/or promote wetting. At block 906, as part of the wetting process, alloying elements such as silicon (Si), aluminum (Al), and potassium (K) may be incorporated to facilitate wetting/manage oxygen activity at the interface.

10A shows a flow diagram of a method 1000A of preparing a carbon-based structure to undergo a lithiation operation, according to some embodiments. At block 1002A, a procedure for testing the lithium foil/powder preform can be established. At block 1004A, alternative metal powder preforms can be used to facilitate non-reactive wetting while understanding reproducible schemes for managing lithium such as surface pretreatment/impurity management. At block 1006A, carbon surface activity/pretreatment schemes can be evaluated by measuring thermal activation reactions through various techniques including thermogravimetric analysis (TGA) and/or differential scanning calorimetry (DSC).

10B shows a flow diagram of another method 1000B of making Li materials suitable for use in lithiation operations, according to some embodiments. At block 1002B, the heated platen can be calibrated and thermal profiling of the material can be performed. At block 1004B, the glove box environment, such as conditions or settings involving humidity and oxygen, can be determined before, during, and after testing. At block 1006B, a sample may be prepared from any one or more of vaporized lithium, carbon powder, and other substances on the lithium foil and/or metal foil.

10C shows a flowchart of a method 1000C of nucleating a plurality of carbon particles at a first concentration level. At block 1002C, a first concentration level configured to form a first film on a sacrificial substrate can nucleate a plurality of carbon particles, each of which includes a plurality of few-layer graphenes fused together Multiple aggregates of flakes. At block 1004C, a porous structure may be formed based on a plurality of few-layer graphene sheets fused together. At block 1006C, molten Li metal can be infused into the porous structure.

10D shows a flowchart of a method 1000D of nucleating a plurality of carbon particles at a second concentration level. At block 1002D, carbon particles may be nucleated at the second concentration level on the first film. At block 1004D, a second film may be formed based on the carbon particles at a second concentration level.

Figure 10E shows a flow diagram of a method 1000E of growing carbon particles. At block 1002, carbon particles can be grown on roll-to-roll processing equipment.

Figure 1OF shows a flow diagram of a method 1000F of vaporizing molten Li metal. At block 1002E, molten Li metal can be vaporized onto the metal foil. At block 1004E, molten Li metal can be rolled from the metal foil into the porous structure.

Figure 10G shows a flow diagram of a method 1000G of preparing an anode to participate in the reversible transport of Li ions. At block 1002G, the anode can be prepared to participate in the reversible transport of Li ions along with the cathode. The cathode is prepared by any one or more of chemical functionalization or vulcanization.

10H shows a flow diagram of a method 1000H of densifying a plurality of graphene flakes. At block 1002H, the plurality of graphene flakes can be densified over the void structure.

10I shows a flowchart of a method 1000I of depositing a first plurality of carbon particles to form a first film. At block 1002I, a first plurality of carbon particles can be deposited to form a first film on the substrate, the first film assembled to provide a first conductivity. At block 1004I, a plurality of 3D aggregates formed from few-layer graphene sheets that can be orthogonally fused together are assembled to define a porous structure. At block 1006I, a porous configuration can be formed in the porous structure. At block 1008I, molten Li metal can be infused into the void structure.

10J shows a flow diagram of a method 1000J of depositing a second plurality of carbon particles. At block 1002J, a second plurality of carbon particles may be deposited on the first film. At block 1004J, a second film may be formed based on the second plurality of carbon particles.

Figure 10K shows a flow diagram of a method 1000K of infiltrating molten Li metal. At block 1002K, molten Li metal in the gas phase can be infiltrated into the void structure. At block 1004K, a chemical reaction may be initiated between any one or more Li ions provided by molten Li metal and one or more exposed surfaces of the void structure. At block 1006K, one or more lithiophilic surfaces may be formed from one or more exposed surfaces.

10L shows a flow diagram of a method 1000L of coating any one or more of lithiophilic surfaces. At block 1002L, any one or more of the lithiophilic surfaces may be coated with an active element including any one or more of a halogen and an oxide getter including titanium (Ti).

10M shows a flow diagram of a method 1000M of coating any one or more of lithiophilic surfaces. At block 1002M, any one or more of the lithiophilic surfaces may be coated with any one or more elements including silicon (Si) or aluminum (Al) having a surface energy lower than Li. At block 1004M, Li wetting enhancement of any one or more of the lithiophilic surfaces may be promoted with any one or more elements having a surface energy lower than that of Li.

Figure 10N shows a flow diagram of a method 1000N of producing an adhesive. At block 1002N, the binder may be produced by incorporating any one or more of metal powders or metal-containing compounds including silicon carbide (SiC) into the carbon scaffold.

Figure 10O shows a flow diagram of a method 1000O of adding an amount of dopant. At block 1002O, an amount of dopant may be at the interface. At block 1004O, the degree of Li wetting corresponding to this amount of dopant can be affected.

Figure 10P shows a flow chart of a method 1000P for controlling hydroxy/hydroxyl (OH) adsorption. At block 1002P, hydroxyl (OH) adsorption can be controlled at any of one or more exposed surfaces of the void structure.

FIG. 11A shows a flowchart of a method 1100A of infusing lithium. At block 1102A, the lithium may be injected by using roll-to-roll boiler brazing or spontaneous infiltration. At block 1104A, a two-dimensional (2D) analog with a 2D liquid gap filler may be used. At block 1106A, the infused lithium metal can be chemically reacted with the exposed carbon surface at the liquid and solid interface, and the flux for activation, surface tension increased and/or decreased, and thermodynamic dynamics controlled. At block 1108A, rapid screening of lithium wettability can be performed by using a halogen interlayer to decompose _Li2O with a Li foil/carbon particle stack on a hot plate.

FIG. 11B shows a flow diagram of a method 1100B of vaporizing lithium (Li) onto a metal foil. At block 1102B, lithium can be vaporized onto a metal foil, which can act as a thermal conductor. At block 1104B, copper may optionally be used as a current collector and/or tantalum may be used for release to achieve minimal chemical interaction. At block 1106B, a film thickness commensurate with the pore volume in the encapsulated carbon-dominant particles and/or structures can be tuned.

Figure 11C shows yet another flow diagram of a method 1100C of preparing carbon particles for lithiation, such as via a method known as pre-lithiation. At block 1102C, a pre-lithiated and/or pre-formed foil may be oriented on top of a packed bed of carbon particles or pre-lithiated and/or pre-formed in dry room ambient conditions with a load to be applied, such as a calendered reel type. At block 1104C, overall isothermal-like conditions (such as at about 180°C and/or immediately below the Li melting point) can be created across Li and encapsulated particles with rapid thermal spikes at the concentrated load location. At block 1106C, an exothermic reaction can be used using principles related to Darcy's law with variable permeability, Washburn, etc. to induce wetting followed by capillary-driven fluid flow in the porous carbon medium. Capillary driven fluid flow assumes no appreciable reaction product formation/stacking.

12 shows a flowchart of a method 1200 of performing Li infusion of carbon particles during formation of carbon particles from vaporized Li, according to some embodiments. At block 1202, a metal (such as copper and/or tantalum) foil may be coated with lithium, such as in a vacuum; the measured Li volume, such as thickness and density, may be commensurate with the pore volume in the encapsulated particle layer . At block 1204, the particles can be assembled into the encapsulated film without a binder, such as via size enlargement, from fine particles to a coarse-grained material such as a film, where assembly techniques can include tumbling, pressure pressing Tightening, thermal reaction, fusing, drying, cohesion by liquid suspension, and electrostatics to form coin hole sized discs. At block 1206, intrinsic carbon particles may be formed. At block 1208, the ^sp2 / ^sp3 ratio of carbon during formation can be optimized to correspondingly increase lithium (Li) insertion and/or intercalation. At block 1210, impurity contamination, such as from acetylene and other post-plasma aromatics, may be reduced. At block 1212, post-processing operations may be performed.

13 shows a schematic diagram illustrating an idealized anode 1300 assembly having 3D graphene-based nanostructures 1302 incorporated therein to provide structural definition for the anode 1300, according to some embodiments. The 3D graphene-based nanostructures 1302 can be incorporated into or provide structural definition to any one or more of the carbon-based structures disclosed herein that are The dominant structure includes pores 105E and/or connecting paths 107E, both shown in FIG. 1E, and may confine or otherwise retain metal dopants 1312 such as silicon (Si) and create surface-activated diffusion paths 1316 for disposal Volume expansion during Li-ion 1306 alloying-dealloying cycles and also restricts electrolyte entry. As shown in path 1310, the silicon can be redistributed into defects, pores or wrinkles in at least one graphene sheet and into a binder 1304 such as highly polar polyacrylonitrile (PAN) in path 1308. Sulfur (S) doping can be performed or occur at the graphene 1314 and silicon contact regions or surfaces to assist Li recombination and associated charge-discharge cycling in LiS battery systems to achieve any of the performance graphs cited herein or more, including a specific capacity greater than 372 mAh/g, which can generally be achieved with graphite alone as the theoretical maximum. In some embodiments, graphene oxide can be used in addition to or as an alternative to few-layer graphene, and the LiS system can be immersed in a LiPF ₆ liquid phase electrolyte.

Anode 1300 may be assembled with existing or upcoming future carbon-based materials, which provide reverse compatibility. Surface activated diffusion paths 1316 can accommodate Li metal, and Li can also be sandwiched between pairs of few-layer graphene sheets. The pore size of the carbon material can be tuned in anode 1300 to achieve a specific distribution or containment level of Li and Li ion flow reversibility, and can be created in either amorphous or crystalline carbon structures.

Pre-lithiation of anode 1300 may initially include molten Li metal electrochemistry or direct contact with molten Li metal to later transition to direct vapor infusion techniques. As substantially previously described, the carbon structures used as the forming material for constructing the anode 1300 can be deposited directly as a particle film or from a powder as a particle film. The rate of Li exudation can be matched to the rate of Li insertion within anode 1300 to avoid excessive exposure to Li deposition or condensed carbon surfaces entering Li. And production and cost metric considerations for anode 1300 may include: ● Produce carbon-based materials as low-cost powders rather than films, which are formulated to be dropwise added to existing Li-ion or LiS battery fabrication; ● Direct deposition of carbon-based films on the drum independent of adhesives; and ● Impregnation of Li into carbon-based particles and structures such as slurry cast films/binders. Evaporation techniques can be used to purify or dry the carbon.

Li infusion of anode 1300 may include the following procedures established by known roll-to-roll boiler brazing and/or spontaneous infiltration techniques, including any one or more of the following: Using a liquid gap with 2D Two-dimensional (2D) analogs of fillers; ● chemical reaction of liquid to solid using flux for activation; ● increasing proportion of solid to viscous surface area and decreasing proportion of liquid to viscous surface area to control and Tuning surface tension and/or thermodynamic dynamics; and • Screening Li wettability using a halogen interlayer with a Li foil/carbon particle stack on a hot plate to decompose any lithium oxide ( _Li2O ) formed.

Li impregnation of anode 1300 may also include the following procedures, techniques, or implementations related to the vaporization of Li onto metal foils configured to act as thermal conductors: ● Copper (Cu) is selected for use as a current collector in Li-ion or LiS battery systems incorporating anode 1300; ● Tantalum (Ta) dispersed within anode 1300 for Li ion release, resulting in minimal overall chemical interaction; and ● Produces a carbon-dominated film thickness commensurate with the pore volume in the encapsulated particles.

Additionally, the Li infusion of the anode 1300 may also include the following procedures, techniques or implementations related to the orientation of the Li and Ta foils on top of the carbon particles encapsulated in a bed assembly that may be in dry room ambient conditions Prepared to accept the load or pressure provided by a rotating calendering reel-type drum: ● Forward rotation of a calendering reel or drum coated with a layer of Ta foil and further wrapped in Li foil compresses the carbon particles prepared in the form of a thin layer material, which is placed on the copper foil, wherein applying heat from the calendering reel and to the Cu foil to melt the Li and produce molten Li metal infiltrated into the carbon particles; ● Creation of overall isothermal conditions such as at about 180°C, just below the melting point of Li, across infiltrated Li and encapsulated carbon particles; ● Rapid thermal spikes observed at concentrated Li load locations; and ● As Li infiltration with exothermic reactions and capillary-driven melting in porous carbon media governed by any one or more of Darcy's law with variable permeability, Washburn's equation, etc. Li metal fluid flows, and the method assumes no appreciable reaction product formation or buildup.

In addition, the Li infusion of the anode 1300 may also include the following procedures, techniques or implementations: ● Coating metal (such as copper (Cu) and/or tantalum (Ta)) foils with lithium Li in a vacuum; controlling Li such as thickness and density commensurate with the pore volume in the encapsulated carbon particle layer or film volume; ● Assembling carbon particles into encapsulated films without binder, but assuming that there is no interaction with molten Li and the proposed binder can be easily removed after Li infiltration, binder options can be considered; ● Amplification and/or production of coarse carbon materials (such as films) from carbon fines, such as by tumbling, pressure pressing, thermal reaction, fusion, drying, cohesion by liquid suspensions, and for generating It is shaped into the static electricity of the coin hole size structure of the wafer; ● Collect or screen any of the foregoing materials in the reactor; ● Post-microwave sintering or fusion is performed; and ● Do not rely on carbon molds to perform partial compaction into wafers or ingots.

Intrinsic carbon particle formation for few-layer graphene and other carbons used to form anode 1300 may include: ● Optimizing ^sp2 and/or ^sp3 carbon structure formation to increase lithium insertion/intercalation; and ● Reduction such as acetylene and others Impurity contamination of aromatics after plasma.

Post-processing methods can include: ● Washing aromatics, such as removing aromatics; ● bake the carbon at about 500°C for a duration of about 3 hours to remove adsorbed humidity and/or oxygen; and ● Nitrid and/or treat carbon with silicon monoxide.

Factors affecting the infiltration of Li into the carbon structure of anode 1300 may include precursor volume; melting temperature such as about 180°C to 380°C; post-processing of particles such as at carbon surfaces exposed to Li contact; mechanical pressure; graphene properties, few layer or sheet size; carbon structure morphology including pore size, volume, distribution; and surface activation.

The carbon structure response to Li infiltration can include: spontaneous infiltration; accumulation of excess Li material to achieve an equilibrium mass proportional to Li input; and degree of infiltration based on the ratio of carbon surface area exposed to Li entry based on the comparison of the total volume of the control carbon structure .

14 shows silicon and carbon (Si-C) anode performance comparing anode specific capacity in mAh/g over a number of charge-discharge cycles, according to some embodiments. The various series shown, including 426, 459, 462, 486, 487, and 401, may include the carbon shown in FIGS. 1A-1F with the anode 1300 shown in FIG. 13 or within a Li-ion or LiS system anode Any one or more similar changes and/or preparations in the structures. As shown, the disclosed carbon structures can uniformly produce specific capacity values significantly higher than the 372 mAh/g typically associated with graphite anodes.

Figures 15 and 16 show schematic diagrams associated with the idealized cathode assembly 1500 shown in Figure 15, characterized by being held together by a PAN-type adhesive and immersed in a LiTFSI electrolyte solution for convenience, according to some embodiments Reduction and control of dispersed lithium sulfide ( _Li2S ) nanoparticles in graphene sheets for Li ion transport and electrical conduction and polysulfide (PS) generation during charge-discharge cycling of LiS battery systems. In a LiS battery system, the idealized cathode assembly 1500 may be implemented at least in part with any one or more of the carbon structures disclosed herein. are included to form pores 105E and/or connected microstructures 107E as shown in FIG. 1E.

16 shows an exemplary in situ 3D nanostructured few-layer graphene material 1600 that may be incorporated to provide structural definition to any one or more of the carbon structures disclosed herein. In some implementations, the few-layer graphene sheet stack 1602 can include milled sulfur-impregnated graphene heated in a two-stage high temperature (HT) process to 250°C and 350°C. The few-layer graphene sheet stack 1602 can be wetted with Li, such as from a solution of lithium triethylborohydride ( _LiEt3BH ) in THF or placed in an inert argon (Ar) atmosphere by the aforementioned Li wetting technique Any one or more of them provide Li provided by the n-butyllithium of the Li source 1604. Li-wetted stack 1602 of few-layer graphene sheets can undergo HT vacuum treatment at 110° C. for 10 hours to form _Li2S in situ in pores, such as pores 105E shown in FIG. 1E, where the _Li2S participates in as Li S electrochemical cell operation as previously described.

17A shows an enlarged perspective cross-sectional view of carbon-based particles 100A, 100E, and/or the like. Individual ties 1702A formed from contact surfaces and/or regions between conductive interconnect agglomerates 101B of graphene sheets as discussed in conjunction with carbon-based particles 100A shown in FIGS. 1A-1E may extend to form portions Lattice and/or dendritic branches of 1700A through which Li ions (Li+) 1704A can be sandwiched, intercalated into individual gradient layers of portion 1700A of 3D beam 101B comprising graphene sheets between. Electric current can be carried out via electron flow through the contact surfaces and/or regions between the interconnected 3D beams 101B of the graphene sheets. Li ions can flow through pores 1710A sized to the larger size of about 20 nm to 50 nm with a bimodal distribution of voids or pores as depicted in Figures 1A-1E, or limited in size, such as via chemical micron confinement Generally about 1 to 3 nanometers in the pores.

Thus, Li ion flow can be finely controlled in carbon-dominated particles 100A as desired or tuned to, for example, diametrically opposed to electron flow to facilitate contact points and/or regions that can pass through the 3D beam 101B of the graphene sheet The galvanic gradient necessary for electrical conduction and/or electron flow. The spacing between individual carbon-dominated bonds can be set to 0.1 µm. Those skilled in the art will appreciate that a size of 0.1 μm is provided by way of example only, and that other suitable similar or dissimilar sizes may be present in portion 1700A of carbon-based particle 100A.

Portion 1700A may be formed from 3D bundles 101B of graphene sheets sintered together to form an assembly in which there are no fully open channels such that electricity must conduct through the contacts and/or regions of the interconnected 3D bundles of graphene sheets 101B . Thus, the conductive properties of the liquid and carbon-carbon bonds through the void 1704A facilitate the interaction of carbon-based materials with other carbon-based materials when chemical binders and/or chemical bonding materials or reagents are not necessary. Linking, many of the chemical binders and/or chemical bonding materials or agents produce undesirable chemical properties of the carbon-based particle 100A or side effects with respect to its function.

The open porous scaffold 102A of the carbon-based particles 100A presents a deviation from traditional industry standard battery electrodes, which may involve slurry cast boulders, relatively large particles, randomly organized on a substrate, These boulders typically require adhesives to be held together to conduct electricity through them. The open porous scaffold 102A defined by the hierarchical pores 101A and/or the connected microstructures 107E of the carbon-based particles 100A allows for improved electrical conduction therein.

Figure 17B shows the carbon-based particle of Figure 17A with graphene-on-graphene densification. For the example of FIG. 17B, the surface 1700B shown in FIG. 17B and/or the surface 1708A shown in FIG. 17A at the edge region can be densified upon application, deposition, or other growth of multiple additional graphene layers, The edge regions are at least partially flat surfaces of the branched tree-like structure of the portion 1700A of the predominantly carbon particle 100A. These densification processes/methods and/or procedures allow for the creation of intricate, multi-layered and potentially nearly infinitely tunable 3D carbon structures of combinations of 3D beams 101B comprising graphene sheets. Thus, the fine tunability achieved by graphene-on-graphene densification can facilitate reaching particular conductivity values when integrating carbon-based particles 100 into battery electrodes.

Figures 18A-18C show, respectively, any one or more of the carbon structures disclosed herein, including the carbon-based particles 100A and/or associated microstructures 107E shown in Figures 1A and 1E, respectively, in various increments Actual micrographs 1800A, 1800B and 1800C at magnification level.

Figure 18D shows a micrograph 1800D in which the composite carbon agglomerate has an internal structure similar to that described for the carbon-based particle 100A, complete with pores 105E and associated microstructures 107E, and of uniform size and composition It has been prepared to be incorporated into the cathode of a Li-ion system, but can also be adapted to the method and create a cage of Li for use on the anode. Randomly sized and shaped agglomerates can be used to fabricate any one or more of the electrodes disclosed herein. Nonetheless, the tuning procedure may allow the production of carbon agglomerates and/or particles that are also of regular desired size, potentially providing ease of handling and processing advantages.

Figure 18E shows a micrograph 1800E in which the activated carbon structure is used as described by at least any one or more of the carbon-based structures disclosed herein, including the connected microstructure 107E shown in Figure 1E Infiltration of sulfur (S) used in the cathode of the LiS system. The activated carbon structure shown in micrograph 1800E to infiltrate sulfur (S) can be produced by incorporating screw conveyor systems or through other different steps. Thermal reactor-generated materials have been shown to be more lithiophilic than undoped and/or unfunctionalized microwave-generated carbon structures. In some embodiments, the prevalence of organic and/or hydrocarbon-based contamination on the surface of the few-layer graphene produced in the reactor may require additional post-processing improvement steps to be performed.

19A shows a schematic depiction 1900A of a 3D graphene-particle cathode scaffold such as a carbon scaffold 300B featuring sulfur (S) micron confinement therein suitable for scale-up and/or as disclosed herein Any one or more of the carbons are incorporated, including as a forming material for producing the connected microstructures 107E shown in FIG. 1E . In the example of Figure 19A, graphene-based sheets and/or structures containing sulfur entrainment and/or confinement 1902A in various 3D cathode scaffold-type structures or assemblies are shown with various thicknesses 1904A and 1906A. S includes providing the desired charge storage and retention in graphene-based battery chemistries, the desired charge storage and retention measured in milliamp-hours, further by using carbon black The synthesis of graphene-sulfur composites by nanoparticle-decorated mildly oxidized graphene oxide sheets coated with poly(ethylene glycol) (PEG)-coated submicron sulfur particles is described.

600 mAh/g之高且穩定比容量，表示用於具有高能量密度之可充電Li電池組之有前景陰極材料。其他研究已顯示，已製造具有各種比表面積、孔隙體積以及平均孔隙尺寸之活化石墨烯(AG)且作為硫之基質施用。系統地研究AG孔隙結構參數及硫負載量對Li-硫電池組之電化效能之影響。 PEG and graphene coatings are important for accommodating the volume expansion of the coated sulfur particles during discharge, trapping soluble polysulfide intermediates, and making the sulfur particles conductive. The resulting graphene-sulfur composites show up to 100 cycles

The high and stable specific capacity of 600 mAh/g represents a promising cathode material for rechargeable Li batteries with high energy density. Other studies have shown that activated graphene (AG) with various specific surface areas, pore volumes, and average pore sizes have been fabricated and applied as a matrix for sulfur. The effects of AG pore structure parameters and sulfur loading on the electrochemical performance of Li-sulfur batteries were systematically studied.

The results show that the specific capacity, cycle efficiency and Coulombic efficiency of the battery pack are closely related to the pore structure and sulfur loading. The AG3 sized (S) composite electrode with high sulfur loading of 72 wt.% exhibits excellent long-term cycling stability at 50% capacity retention and ultra-low capacity decay rate (0.05%/cycle within 1,000 cycles) ). Additionally, the AG3/S electrode exhibited similar capacity retention at ~98% within 1,000 cycles and high Coulombic efficiency when _LiNO3 was used as the electrolyte additive. The excellent electrochemical performance of the AG3/S electrode series is attributed to the mixed micro/mesoporous structure, high surface area, and good conductivity of the AG matrix and well-distributed sulfur within the micro/mesopores, which is beneficial for cycling During electrical and ion transfer.

19B shows a 3D few-layer graphene anode scaffold, such as carbon scaffold 300 prepared and used in or as a forming material for Li-ion or LiS system anodes with Li intercalation between graphene layers and /or lithiated carbon support 400A. In the example of Figure 19B, Li ions (Li+) are shown in various configurations 1900B, including sandwiched into the FLG 1902B and Li metal reversibly included in a carbon-based host scaffold 1904B. Intercalation of Li into bilayer graphene can relate to and solve the following: the true capacity of graphene and Li storage methods in graphite, which presents a problem in the field of Li-ion batteries.

Theoretical calculations confirm that various physiochemical characterizations of segmented lithium bilayer graphene products further reveal the regular Li intercalation phenomenon and thus fully exemplify this fundamental two-dimensional lithium storage mode. These findings not only enable commercial graphite to be the first electrode with a clear lithium storage method, but also lead to the development of graphene materials in Li-ion batteries. Li absorption and intercalation in monolayer graphene and few-layer graphene is different from the Li absorption and intercalation associated with bulk graphite. For single-layer graphene, a cluster amplification method was used to systematically explore the lowest energy ion assembly as a function of absorbed Li content. It is predicted that unless a monolayer graphene surface includes defects, there is no Li arrangement that stabilizes Li absorption on that surface. From this result it is concluded that defective monolayer graphene exhibits significantly poorer capacity compared to bulk graphite.

In some embodiments, in addition to any one or more of the sacrificial membrane matrix and the supporting membrane matrix, the carbon-based particle membrane can include at least the following particle-like properties: tunable velocity of the matrix; self-implantation to Tunable impact energy for adsorption; tunable thickness; and tunable porosity; any one or more of the above properties can be integrated with additive manufacturing capabilities.

In some implementations, any one or more of the carbon and carbon-based structures disclosed herein may enable advantages over current Numerous battery performance advantages of Li-ion and/or Li S batteries are available, including: to achieve a range including about 400 to 650 (W·h)/kg with a maximum theoretical value of 850 (W·h) Energy density per kg and also includes 650 (MAh)/g of sulfur and/or sulfur intercalated cathode aspect and graphene sheet 102A and/or conductive carbon particle aspect interspersed with it to define pores and/or voids Any one or more of physical and/or electrical energy storage and/or conductivity values, etc., ultimately achieving an energy density storage of 900 to 2,000 (mAh)/g with intervening ionic Li (Li+) value.

Figure 20A shows cathode specific capacity levels within cycles and various representative sulfur nanoconfinements and their derived graphs and images as representative of the application and/or use of systems based on or using carbon-based particles 100A. The modified cathode specific capacity, electrode level, as measured in mAh/g, is shown in Figure 2008a for various compositions and/or compounds, any one or more of these compositions and/or compounds At least a portion of the carbon-based particles 100A are formed with s integrated therewith to enhance the cathode specific capacity.

Figures 20B and 20C show graphs for accelerated carbon tuning for reducing polysulfide (PS) shuttle-related problems, the graphs indicating increasing porosity for carbon-based materials, carbon-based particles 100A, and variations thereof Reduced PS shuttling, defined as the case where sulfur S reaches the negative electrode surface and undergoes chemical reduction, resulting in undesirable self-discharge of auto-electrochemical cells. Graph 2002B, shown in Figure 20B, shows the average strength change for low porosity carbon, which is generally at a higher level than high porosity carbon. Graph 2002C shown in FIG. 20C shows that high porosity carbons generally have higher percentage levels of capacity retention over repeated battery life cycles relative to low porosity carbons.

Carbon-based particle 100A tuning enables more efficient manufacturing including: Li utilization and potential increase in the ratio of active to inactive materials in battery electrodes, binder reduction, improved homogeneity, and controlled electrochemical reactions, Such as battery conductivity and/or activity. The parameters of the carbon-based particle 100A can be tuned to achieve specific performance characteristics as a function of Li loading percentage per unit area or volume of the carbon-based particle 100A, including: ● At low load levels less than capacity, the first charge loss is compensated/more efficient SEI formation; at saturation/matching load, the current is coupled to the Li-rich region of carbon, ● Oxidizes the material when in contact with the electrolyte and intercalates Li and/or Li ions through the intercalation between the graphene layers; ● Infiltration of metallic Li into the engineered host carbon at an excess loading level; the host is assembled to accommodate/stabilize Li amplification and suppress dendrite formation due to increased Li surface area, enabling specific capacity Compatible with pure Li: > 2,000 mAh/g; and ● The preparation of Li-ion method (process/methodology) that can be directly transferred to Li-ion hybrid capacitors.

Ongoing challenges associated with thermal and/or liquid impregnation of Li and/or Li ions into carbon-based structures such as carbon-based particles 100A as outlined in Listing 2900E may include issues related to the solid-liquid electrolyte interface Li reactivity management at surface tension, wettability; capillary Li and/or S wetting kinetics management, electrical gradient engineering through electrode thickness, Li wetting for highest Li at the current collector and migration towards the electrolyte interface. Grading of transitions to higher ionic conductivity concentrations and/or levels and carefully tuned engineering of surface chemistry by promoting stable SEI formation in contact with electrolyte and minimizing reactivity with air.

The disclosed aspects can be built upon conventional two-dimensional (2D) plating, which can be similar to brighteners in electroplating. In electroplating, the addition of chemical additives can often increase polarization, decrease current density; such as redirecting current density to low regions such as as opposed to high regions such as protrusions; produce relatively high nucleation rates, and produce moderate charges transfer rate. In the case of plating or stripping for battery charge and discharge cycles, for batteries having electrodes equipped with carbon-based particles 100A as shown in FIGS. 1A-1E , the carbon film can serve as a useful A flexible carrier is formed at the SEI and redirects the current density to a low area as opposed to a high area.

For use herein in the context of producing carbon-based particles 100A and integrating them with Li-ion batteries, cementation may be used in any one or more of the disclosed fabrication techniques. Cementing means a method of modifying a metal by heating the metal in contact with a powdered solid, precipitation in copper production may refer to and/or may involve a heterogeneous process. Such methods can mean conditions where the reactants are components of two or more phases, such as solids and gases, solids and liquids, two immiscible liquids; or where one or more reactants experience an interface , a chemical change on the surface of a solid catalyst; where ions are reduced to zero valence at the solid metal surface, such as Cu ions on the surface of Fe particles; and where iron is oxidized and copper is reduced, such as with Li vs. C, copper on the current series Relatively high.

The fusion of molten metals including Li metal can be managed such that any one or more of the techniques mentioned can be functionally integrated with the carbon-based particles 100A and/or used to produce carbon-based particles 100A to enhance Li Ion or Li S battery pack efficiency. Such auxiliary methods and/or techniques include: reactive metal management via welding; classical metal inert gases for joining reactive metals such as Ti and Al via liquid metal methods using inert shielding gases, such as by welding (MIG), Gas Tungsten Arc Welding (GTAW) also known as Tungsten Inert Gas (TIG), and Submerged Arc Welding (SAW). Examples include the use of an inert shielding gas without oxidation to form a liquid pool of reactive metals where the ΔGf of oxides such as _TiO2 , _Al2O3 is on par with the ΔGf of _Li2O . Oxygen and humidity can be effectively managed in the presence of reactive liquid metals through the controlled use of inert shielding gases around the reactive metals. In these environments and conditions, liquid Li can be infiltrated into the carbon-based structure of the carbon-based particles 100A through controlled shielding gas composition and operation.

Figure 21 shows Raman spectra of 3D N -doped FL graphene including initial carbon and N -doped carbon maps. In the example of FIG. 21, the Raman spectrum of 3D N -doped FL graphene 2100 includes a 2D peak 2102 at about 2730 cm ^- 1 and a D peak 2104 at about 1600 cm ^-1 and 1400 cm ^-1 , respectively, 2106.

22 shows various properties associated with bilayer graphene 2200. In the example of Figure 22, a sample bilayer graphene base structure 2200 is shown with bilayer graphene oriented in the positions shown, which positions are understood to be devices containing only one, two or three atomic layers. Schematic 2202 shows approximate spacing measurements of 1.42 Å, 1.94 Å and/or 3.35 Å between individual graphene sheets. Schematic 2204 shows various exemplary defect sites 2206 and/or 2208 that may exist within defined adjacent regions of the edge plane and/or aid in the creation of one or more graphene sheets comprising a predominantly carbon particle structure. Schematic 2210 shows various model diagrams 2212 of top views of hard spherical carbon particle models.

In some embodiments, reactor tuning can be performed to, for example, perform any one or more of the following: increase FL graphene spacing, decrease Van der Waals forces; control doping; promote carbon vacancy formation; and reduce Li Adsorption energy and/or increase Li capacity. Li-ion intercalation can, for example, displace the stack of graphene sheets from the A-B group to A with increasing spacing to accommodate intercalation, where for example in graphite, A-A can be displaced back to A with deintercalation A-B; and in FL graphene, in FL graphene, the AA stack is preserved with deintercalation, such as by maintaining the increased spacing. These stacking arrangements can be associated with the carbon-based particles 100A shown in Figures 1A-1E.

23 shows an exemplary flow diagram for depicting exemplary operations 2300 for preparing a 3D scaffold-type membrane containing carbon-based particles. In the example of FIG. 23 , method 3300 includes preparing a 3D scaffold film having carbon-based particles therein at operation 2304 by providing the 3D scaffold film to a roll-to-roll processing device or apparatus at operation 2306 . The carbon-rich electrode can be deposited on the 3D scaffold-type membrane at operation 2308; and the 3D scaffold-type membrane can be processed on a roll-to-roll processing apparatus or equipment independent of the application of a chemically inactive binder material can be at operation 2312 This occurs at operation 2310 before method 2300 ends.

In the foregoing specification, the present disclosure has been described with reference to specific examples. It will be evident, however, that various modifications and changes may be made thereto without departing from the broader spirit and scope of the present disclosure. For example, the process flow described above is described with reference to a particular ordering of method actions. However, the ordering of many of the described method acts may be changed without affecting the scope or operation of the present disclosure. The specification and drawings are to be regarded in an illustrative rather than a restrictive sense.

Various embodiments of the present disclosure relate to the following numbered items: 1. A battery comprising: a cathode; an anode positioned opposite the cathode, the anode comprising a hybrid artificial solid-electrolyte encapsulating the anode an intermediate phase (A-SEI) layer, the hybrid A-SEI layer comprising: a first active element; a second active element disposed on the first active element; and a plurality of carbon-containing aggregates interwoven in throughout the first active element and the second active element and configured to inhibit the growth of Li dendrites from the anode toward the cathode; and a spacer located between the anode and the cathode. 2. The battery of clause 1, wherein the cathode comprises a porous carbon-based structure configured for the presence of a polysulfide (PS) shuttle within one or more portions of the battery. case expansion. 3. The battery of clause 1, further comprising an electrolyte dispersed between and in contact with the anode and the cathode. 4. The battery of clause 3, wherein the plurality of carbon-containing aggregates comprise a polymer comprising a cross-linked polymeric network. 5. The battery of clause 4, wherein the cross-linked polymeric network is assembled to control an amount of contact between the electrolyte and the anode. 6. The battery of clause 4, wherein a first portion of the cross-linked polymeric network has a first cross-link density, and a second portion of the cross-linked polymeric network has a different cross-link density than the first cross-link density. One of the link densities has the second lowest cross-link density. 7. The battery of clause 4, further comprising a gradient defined by a crosslink density across the crosslinked polymeric network of the hybrid A-SEI layer encapsulating the anode. 8. The battery of clause 4, wherein the cross-linked polymeric network comprises any one or more of a monomer or an oligomer. 9. The battery of clause 4, wherein the cross-linked polymeric network is formulated to inhibit dissolution of the mixed A-SEI layer. 10. The battery of clause 4, wherein the cross-linked polymeric network has Li wettability formulated to promote Li adhesion to the cross-linked polymeric network. 11. The battery of clause 4, wherein the cross-linked polymeric network comprises any one of a vinyl group, an acrylate group, a methacrylate group, or an epoxy-based group or many. 12. The battery of clause 11, wherein any one or more of the vinyl group, the acrylate group, or the methacrylate group is formulated to be cured by an ultraviolet (UV) curing method or a thermal any one or more of the methods to cure. 13. The battery of clause 11, wherein the epoxy-based group is formulated to be cured by adding an amine group or an amide group. 14. The battery pack of clause 1, wherein the first active element includes a barrier rib. 15. The battery of clause 14, wherein the barrier is configured to prevent direct contact between the Li metal in the anode and the electrolyte. 16. The battery of clause 14, further comprising a naturally occurring solid-electrolyte interface (SEI), wherein the barrier is configured to prevent an unstable formation of the naturally occurring SEI. 17. The battery of clause 14, wherein the barrier is configured to prevent decomposition of the electrolyte. 18. The battery of clause 1, further comprising a Li layer deposited on the second active element. 19. The battery of clause 18, wherein the second active component is configured to ensure uniform deposition of one of the Li layers. 20. The battery of clause 1, wherein the spacer is configured to transport Li ions from the anode to the cathode through the spacer. 21. The battery of clause 20, wherein the spacer is further configured to inhibit the growth of the Li dendrites from the anode toward the cathode. 22. The battery of clause 1, wherein the anode further comprises a conductive matrix assembled to support the hybrid A-SEI layer. 23. The battery of clause 22, wherein the conductive substrate comprises a copper current collector. 24. The battery of clause 1, wherein the anode comprises a metal foil. 25. The battery of clause 24, wherein one of the metal foils is between about 1 µm and 250 µm thick. 26. The battery of clause 25, wherein the metal foil comprises a Li layer having a thickness of between about 15 μm and 50 μm. 27. The battery of clause 1, wherein the hybrid A-SEI layer comprises a component comprising a plurality of carbon nanoonions (CNOs), wherein the component is conductive. 28. The battery of clause 1, wherein the hybrid A-SEI layer is configured to electrochemically stabilize itself during operational cycles of the battery. 29. The battery of clause 1, wherein the hybrid A-SEI layer can include one or more flex points configured to cyclically during an operable cycle of the battery A volume of the mixed A-SEI layer was expanded and contracted. 30. The battery of clause 1, wherein at least one of the first active element or the second active element comprises a passivation layer. 31. The battery of clause 30, wherein the passivation layer comprises an inorganic component. 32. The battery of clause 31, wherein the inorganic component comprises one or more of the following: Al ₂ O ₃ , LiF, Li ₂ S ₆ , P ₂ S ₅ , Li ₃ N, SiO ₂ , MoS ₂ , Li ₂ S ₃ , LiF, LiN ₃ , Li-metal alloys, Li-Si, Li ₃ PO ₄ , LiI or Li ₃ PS ₄ . 33. The battery of clause 30, wherein the passivation layer comprises one or more metal cross-linked carboxylates comprising Zn, Sn, Sr, In, Al or Mo. Acrylate group, methacrylate group or higher crosslinkable analogs. 34. The battery of clause 1, wherein the plurality of carbon-containing aggregates define a porous structure comprising a plurality of few-layer graphene (FLG) sheets fused together. 35. A battery comprising: a cathode; an anode positioned opposite the cathode; a mixed artificial solid-electrolyte interphase (A-SEI) layer deposited on the anode and comprising a plurality of active components; a blend material interwoven throughout the plurality of active components and configured to inhibit growth of lithium (Li) dendrites from the anode to the cathode, the blend material comprising: crystalline sp of graphene sheets ² binding carbon domains in combination with one of a plurality of flexible pleated regions located at the junctions of two or more of the crystalline sp ² binding carbon domains of the graphene sheets; and a polymeric matrix composed of The plurality of active components and the blend material are bonded together; an electrolyte is in contact with the hybrid A-SEI and the cathode; and a spacer is located between the anode and the cathode. 36. The battery of clause 35, wherein the blend material comprises any one or more curable metal carboxylates comprising one or more of the following: zinc, strontium , tin, indium, aluminum or molybdenum acrylate, methacrylate or higher curable carboxylates analogs. 37. The battery of clause 35, wherein the combination further comprises one or more flex points configured to shrink one of the A-SEI layers during cross-linking of the polymeric matrix volume. 38. The battery of clause 35, wherein the cathode comprises a porous structure assembled to amplify in the presence of polysulfide (PS) shuttles within one or more portions of the battery . 39. The battery pack of clause 35, wherein the plurality of active components comprises: a first active component; and a second active component disposed on the first component. 40. The battery of clause 39, wherein at least one of the first active element or the second active element comprises a passivation layer. 41. The battery of clause 40, wherein the passivation layer comprises an inorganic component. 42. The battery of clause 41, wherein the inorganic component comprises one or more of: Al ₂ O ₃ , LiF, Li ₂ S ₆ , P ₂ S ₅ , Li ₃ N, SiO ₂ , MoS ₂ , Li ₂ S ₃ , LiF, LiN ₃ , Li-metal alloys, Li-Si, Li ₃ PO ₄ , LiI or Li ₃ PS ₄ . 43. The battery of clause 39, wherein the first component comprises a barrier configured to prevent direct contact between the Li metal in the anode and the electrolyte. 44. The battery of clause 43, further comprising a naturally occurring solid-electrolyte interface (SEI) formed between the anode and the electrolyte, wherein the barrier is configured to prevent one of the naturally occurring SEIs unstable formation. 45. The battery of clause 43, wherein the barrier is configured to prevent decomposition of the electrolyte. 46. The battery of clause 39, further comprising a Li layer deposited on the anode. 47. The battery of clause 46, wherein the second active component is configured to ensure uniform deposition of one of the Li layers on the anode. 48. The battery of clause 35, wherein the spacer is configured to transport Li ions from the anode to the cathode through the spacer. 49. The battery of clause 35, wherein the spacer is configured to inhibit the growth of the Li dendrites from the anode toward the cathode. 50. The battery of clause 35, wherein the anode further comprises a conductive matrix assembled to support the hybrid A-SEI layer. 51. The battery of clause 50, wherein the conductive substrate comprises a copper current collector. 52. The battery of clause 35, wherein the anode comprises a metal foil. 53. The battery of clause 52, wherein one of the metal foils is between about 1 µm and 250 µm thick. 54. The battery of clause 53, wherein the metal foil comprises a Li layer having a thickness of between about 15 μm and 50 μm. 55. The battery of clause 35, wherein the hybrid A-SEI layer is ionically conductive and configured to conduct preferentially upon addition of conductive carbon. 56. The battery of clause 35, wherein the hybrid A-SEI layer is configured to electrochemically stabilize itself during operational cycles of the battery. 57. The battery of clause 35, wherein the polymeric matrix comprises one or more of the following: cross-linked polydimethylsiloxane (PDMS), polystyrene (PS), bis(2-(methyl) Acryloyloxy)ethyl)phosphate, including one or more of succinate, maleate phthalate or phosphoric acid ester, mainly 2-hydroxyethyl methacrylate Adhesion promoter, glycerol dimethacrylate maleate, polyethylene glycol (PEO), poly(3,4-ethylenedioxythiophene) (PEDOT), styrene-butadiene rubber (SBR), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), polyvinylidene fluoride (polyvinylidene fluoride/polyvinylidene difluoride, PVDF). 58. The battery of clause 35, wherein the polymeric matrix comprises a cross-linked polymeric network configured to control an amount of contact between the electrolyte and the anode. 59. The battery of clause 58, wherein a first portion of the cross-linked polymeric network has a first cross-link density, and a second portion of the cross-linked polymeric network has a different cross-link density than the first cross-link density. One of the link densities has the second lowest cross-link density. 60. The battery of clause 58, further comprising a gradient defined by a crosslink density across the crosslinked polymeric network of the hybrid A-SEI layer encapsulating the anode. 61. The battery of clause 58, wherein the cross-linked polymeric network comprises any one or more of a monomer or an oligomer. 62. The battery of clause 58, wherein the cross-linked polymeric network is formulated to inhibit dissolution of the mixed A-SEI layer. 63. The battery of clause 58, wherein the cross-linked polymeric network has a defined Li wettability associated with Li adhesion to the cross-linked polymeric network. 64. The battery of clause 58, wherein the cross-linked polymeric network comprises any one or more of a vinyl group, an acrylate group, a methacrylate group, or an epoxy-based group. By. 65. The battery of clause 64, wherein any one or more of the vinyl group, the acrylate group, or the methacrylate group is formulated to be cured by an ultraviolet (UV) curing method or a thermal any one or more of the methods to cure. 66. The battery of clause 64, wherein the epoxy-based group is formulated to be cured by adding an amine group or an amide group. 67. The battery of clause 35, wherein the combination further comprises a plurality of three-dimensional (3D) carbon-based aggregates, each 3D aggregate comprising one or more functionalized graphene allotropes. 68. The battery of clause 67, wherein each of the one or more functionalized graphene allotropes comprises an epoxy, an amine, a thiol, a carboxylic acid, a mono(methyl) group ) any one or more of acrylate functional groups, monovinyl functional groups or -Si-H functional groups. 69. The battery of clause 67, wherein the one or more functionalized graphene allotropes are assembled to enhance a mechanical property of the combination. 70. The battery of clause 67, wherein the one or more functionalized graphene allotropes are assembled to form covalent bonds with the polymeric matrix. 71. The battery of clause 70, wherein the covalent bonds comprise an epoxy-based crosslink, a free-radically initiated vinyl or (meth)acrylate-based crosslink, or a One or more of the -Si-H group crosslinks of the bifunctional molecules. 72. The battery of clause 67, wherein the one or more functionalized graphene allotropes are assembled to enhance adhesion between the hybrid A-SEI layer and Li metal in the anode. 73. The battery of clause 67, wherein the one or more functionalized graphene allotropes are assembled to enable uniform deposition of Li on the anode. 74. The battery of clause 67, wherein the one or more functionalized graphene allotropes are formulated to at least partially inhibit polysulfide (PS) in a bulk phase of the electrolyte and polysulfides in the anode. direct contact between Li. 75. A battery comprising: a cathode; an anode positioned opposite the cathode; a carbon interface layer comprising: an electrically insulating sheet carbon layer conformally encapsulating the anode; and a plurality of carbon nanoonions (CNOs) defining interstitial pore volumes interspersed throughout the electrically insulating sheet carbon layer; an electrolyte in contact with the carbon interface layer and the cathode; and a spacer, It is located between the anode and the cathode. 76. The battery of clause 75, wherein the electrically insulating sheet carbon layer comprises graphene oxide (GO). 77. The battery of clause 75, wherein the plurality of interstitial pore volumes are configured to transport lithium between the anode and the cathode through the plurality of interstitial pore volumes in a bulk phase of the electrolyte (Li) ions. 78. The battery of clause 75, wherein a thickness of the carbon interface layer is between about 0.1 µm and 20 µm. 79. The battery of clause 75, wherein the cathode further comprises a porous carbon-based structure configured to cyclically expand and contract a volume of the cathode during operational cycles of the battery. 80. The battery of clause 75, wherein the carbon interface layer further comprises a thin film with a Young's modulus greater than about 6 GPa. 81. The battery of clause 75, wherein the carbon interface layer is configured to inhibit growth of Li dendrites from the anode toward the cathode. 82. The battery of clause 75, wherein the spacer is configured to transport Li ions between the anode and the cathode through the spacer. 83. The battery of clause 75, wherein a surface area of any one or more of the plurality of CNOs is from about 10 m ² /g to 90 m ² /g. 84. The battery of clause 83, wherein the plurality of CNOs are assembled to adsorb polysulfide (PS) onto the exposed surface of each CNO. 85. The battery of clause 84, wherein the plurality of CNOs are further assembled to inhibit PS anions from contacting the anode. 86. The battery of clause 75, wherein the anode comprises a metal foil. 87. The battery of clause 75, wherein the anode comprises a carbon-based composite structure comprising a plurality of carbon nanoonions or a plurality of graphene flakes fused together. any one or more. 88. The battery of clause 87, wherein the carbon-based composite structure is assembled to be infiltrated with a molten lithium (Li) metal. 89. The battery of clause 88, wherein the molten Li metal comprises one or more Li-containing droplets, domains, or mono- or polycrystalline domains. 90. The battery of clause 86, wherein a thickness of the metal foil is between about 1 µm and 70 µm. 91. The battery of clause 86, wherein the metal foil comprises a Li layer having a thickness of between about 25 μm and 50 μm. 92. The battery of clause 75, wherein the electrically insulating sheet carbon layer comprises interlayer π-π bonds. 93. The battery of clause 92, wherein the electrically insulating sheet carbon layer comprises a stack comprising two or more electrically insulating sheet carbon films, wherein each electrically insulating sheet carbon film is substantially flat and is assembled to accommodate the formation of the stack. 94. The battery of clause 93, wherein the stack is configured to inhibit crack growth in the anode. 95. The battery of clause 93, wherein the stack further comprises a plurality of gap regions, wherein each gap region is located between a corresponding pair of adjacent electrically insulating sheet carbon films within the stack. 96. The battery of clause 95, wherein each gap region is configured to receive an adhesive. 97. The battery of clause 96, wherein the adhesive is formulated to bond together two or more electrically insulating sheet carbon films. 98. The battery of clause 75, wherein the electrically insulating sheet carbon layer is configured to react with a Li metal provided by the anode. 99. The battery of clause 98, wherein the electrically insulating sheet carbon layer is assembled to produce lithium hydroxide (LiOH) based on a chemical reaction with one of the Li metals. 100. The battery of clause 99, wherein the lithium hydroxide is formulated to produce a solid-electrolyte interphase (SEI) between the anode and the electrolyte. 101. The battery of clause 75, wherein the carbon interface layer further comprises one or more carbon derivatives. 102. The battery of clause 101, wherein each of the one or more carbon derivatives comprises a first moiety having a first pore concentration and comprises a moiety having a second pore concentration different from the first pore concentration A second part. 103. The battery of clause 101, wherein each of the one or more carbon derivatives includes a first moiety having a first surface area, and includes a first moiety having a second surface area different from the first surface area. One second. 104. The battery of clause 101, wherein the one or more carbon derivatives are formulated to react with a contaminant. 105. The battery of clause 104, wherein the contaminant comprises any one or more of a polysulfide (PS), a binder, or an additive. 106. The battery of clause 105, wherein the carbon interface layer is at least partially incorporated with the additive. 107. The battery of clause 105, wherein the additive is formulated to conduct Li ions during an operational cycle of the battery. 108. The battery of clause 104, wherein one or more carbon derivatives of the carbon interface layer are formulated to chemically react with the contaminant. 109. The battery of clause 75, wherein the carbon interface layer is configured to adhere to Li metal provided by the anode. 110. A method of making a lithium (Li) anode, the method comprising: forming a slurry by mixing a plurality of electrically insulating sheet carbons and a plurality of carbon nanoonions (CNOs) with each other; casting the slurry onto a release film; drying the slurry; and transferring the dried slurry on the release film to a lithium sheathed copper foil of the Li anode by roll-to-roll lamination. 111. The method of clause 110, wherein the roll-to-roll lamination comprises: applying pressure to the dry slurry on the release film; forming a protective coating based on applying pressure to the dry slurry on the release film a carbon layer; extending the protective carbon-containing layer onto the Li anode; and releasing the release film from the protective carbon-containing layer while maintaining adhesion between the carbon-containing layer and the Li anode.

In the foregoing specification, the present disclosure has been described with reference to specific examples. It will be evident, however, that various modifications and changes may be made thereto without departing from the broader spirit and scope of the present disclosure. For example, the process flow described above is described with reference to a particular ordering of method actions. However, the ordering of many of the described method acts may be changed without affecting the scope or operation of the present disclosure. The specification and drawings are to be regarded in an illustrative rather than a restrictive sense.

100, 302: Carbon-based particles 100A, 302B: Carbon-based particles, conductive particles 100D: Carbon-based particles, mesoporous particles 100E: Hierarchical porous network 100F: PS compound, schematic diagram 101A: Hierarchical Pores, Interconnected Hierarchical Pores 101B: Interconnected 3D Aggregates, Graphene Sheets, Cohesives, Conductive Interconnect Aggregates of Graphene Sheets, 3D Bundles of Graphene Sheets, Interconnects of Graphene Sheets 3D bundle 101C: Graphene sheets, horizontally stacked assemblage 101E: Dimensions 102: Interconnection of graphene sheets 3D bundles 102A: Open porous scaffolds 102E: Dimensions, pores 103E: Dimensions, microporous texture, pores 108E: Lithium (Li (Li) ) ions 104: conductive carbon particles 105, 104E, 105E, 1710A: pores 106E, 507, 1308, 1310, 4M14: path 107E: connected microstructure, connected path 109E: diffusion path 1800A, 1800B, 1800C, 1800D, 1800E: microscopic Figure 201A: macropores 202: macropores or micropores 300B: carbon scaffolds, carbon-based scaffolds 300: carbon scaffolds, annular carbon scaffolds 304: smaller carbon particles 306: sacrificial matrix 400A: lithiated carbon scaffolds, with Carbon-based particles, lithiated carbon-based scaffolds, carbon scaffolds 402A: conductive particles, interconnected carbon-based particles, carbon-based particles 406A: film layer, intermediate layer, layer, separate deposition Build-up layers 408A, 410A, 412A: layers, layers, individually deposited layers 414A, 4B02, 4M08: electrolyte 416A: voids 418A: passivation layer 420A: current collectors 4B00: anode protected by A-SEI 4B04: first active component layer, First assembly layer 4B06: Second active assembly layer, Second assembly layer 4B08: First assembly 4B10: Second assembly 4B12, 4M10: Solid Li metal foil anode 4B14: Copper foil current collector 4D00: Table 4E00: Example 4F00 : Forming path 4G00, 4G02, 4I00, 4K00: Photo 4H00, 4J00, 4P00, 4Q00, 4R00, 4S00: Pattern 4M00: Protected electrode (anode) 4M02, 502: Cathode 4M04: Electrically insulating sheet carbon layer 4M06: Lithium Sheathed Current Collector Foil 4M12: Carbon Nano Onion 4N00: Roll-to-Roll Equipment 4N02: First Reel 4N04: Release Film 4N06: Carbon Interface 4N08: Li Layer 4N10: Copper Foil 4N12: Second Reel 4O00: Protective Carbon Interface (PCI), PCI Layer 4T00: Reference Battery Disassembly 4T02: Area 4U00: Disassembly 400V: Plasma Jet Torch System, Roll-to-Roll (R2R) System 402V: Sacrificial Layer 404V: Sacrificial Layer, Initial Layer 406V, 408V, 410V: Subsequent layer 412V: raw material supply line 414V: plasma jet torch, torch 416V, 418V, 420V: Plasma Jet Torch 422V, 424V, 426V, 428V: Jet, Plasma Jet Torch 430V, 432V: Direction 434V: Wheel and/or Reel 436V: Forward Movement, Carbon Support 440V: R2R Processing Equipment 442V: Layer 444V: Group 500: Secondary electrochemical battery system, Secondary electrochemical battery 501: Anode 505: Dissociated Li ion conductive salt, Li ion conductive salt, Li ion 506, 511: Electron 508: Discharge 509: Carbon particles 512, 1306: Li ion 513, 516: Enlarged area 514: Molten Li metal 515: Few-layer graphene sheet 517: Spacer 518: Li ion conducting electrolyte solution, electrolyte solution, electrolyte 600A: Carbon material 601A: Exposed electrode surface, electrode surface 602A: Specific element 600B1: Chemical non- Reactive System 600B2: Chemical Reactive System 700: Schematic Workflow of Infiltration Process 702: Encapsulated Carbon Scaffolds, Carbon Scaffolds, Carbon-Based Scaffolds 704, 706: Li Metal, Molten Li Metal 708: Lithium Carbon Compounds 800A: Washber Equation 800B: Non-reactive systems 802B: Non-wetting assemblies 804B: Spontaneous wetting assemblies, non-wettable surface layer assemblies 806B: Carbon-dominated scaffolds 800C: Reactive systems 802C: Wettable reactivity Product Layer Assembly 806C, 808C: 3D Layer 900: Flowchart 1004I,1006I,1008I,1002J,1004J,1002K,1004K,1006K,1002L,1002M,1004M,1002N,1002O,1004O,1002P,1102A,1104A,1106A,1108A,1102B,1104B,1106B,1102C,1104C,1106C, 1202, 1204, 1206, 1208, 1210, 1212: Blocks 1000A, 1000B, 1000C, 1000D, 1000E, 1000F, 1000G, 1000H, 1000I, 1000J, 1000K, 1000L, 1000M, 1000N, 1000O, 100B0 1100C, 1200, 3300: Method 1300: Anode, Idealized Anode 1302: 3D Graphene-Based Nanostructures 1304: Binders 1312: Metal Dopants 1314: Graphene 1316: Surface Activated Diffusion Paths 1500: Ideal Chemical Cathode Assembly 1600: In Situ 3D Nanostructured few-layer graphene material 1602: few-layer graphene sheet stack, Li-wetted stack of few-layer graphene sheets 1604: Li source 1700A: part 1702A: individual bonds 1704A: Li ions (Li+), voids 1708A: Surface 1900A: Schematic depiction 1900B: Assembly 1902A: Sulfur entrainment and/or confinement 1902B: Intercalation into FLG 1904A, 1906A: Thickness 1904B: Li metal reversibly included in carbon-dominant host scaffold 2008A: Figure 2002B , 2002C: Graph 2100: 3D N -doped FL Graphene 2102: 2D Peak 2104, 2106: D Peak 2200: Bilayer Graphene, Bilayer Graphene Basic Structure 2202, 2204, 2210: Schematic 2206, 2208: Defective Sites Point 2212: Model Diagram 2300: Methods, Operations 2304, 2306, 2308, 2310, 2312: Operations A: Vertical Height Direction L: Liquid Li Layer S: Solid Carbon Surface V: Viscous Friction θ: Contact Angle

The details of the subject matter described in this disclosure are set forth in the accompanying drawings and the description below. Other features, aspects, and advantages of the subject matter will become apparent from the description, drawings, and claims.

1A-1E show diagrams of carbon-based particles with various defined regions for electrical conduction and ion transport, according to some aspects of the present disclosure.

Figure 1F shows a representative schematic of intermediate steps for reducing sulfur and/or forming polysulfides (PS), according to some embodiments.

1G and 1H show schematic diagrams of placement and/or intercalation of Li ions in carbon lattices and structures, according to some embodiments.

2 shows a schematic diagram of a cavity formed to extend deep into several adjoining stacked FL graphene layers, according to some implementations.

3 shows a schematic diagram of a multilayer carbon-based scaffold-type structure according to some embodiments.

4A shows a schematic diagram of the structure shown in FIG. 3 with lithium (Li) metal infused into nanoscale gaps therein, according to some embodiments.

4B shows a schematic diagram of a simplified version of the structure shown in FIG. 3 prepared as an anode with a mixed artificial solid-electrolyte interphase (A-SEI) layer encapsulating the anode, according to some embodiments.

4C shows the example shown in FIG. 4B prepared with an anode formed from the multilayer carbon-based scaffold structure shown in FIG. 3 , according to some embodiments.

Figure 4D shows a table of various adhesives that can be used to strengthen the hybrid A-SEI layer shown in Figures 4B and 4C, according to some implementations.

4E shows an example of the mechanical strength enhancing additive shown in FIGS. 4B and 4C for A-SEI, according to some embodiments.

4F shows an exemplary formation pathway for metal polyacrylates suitable for protecting Li electrodes, such as anodes, according to some embodiments.

4G shows a photograph of an exemplary _SnF2 /SBR coating on a control Hohsen Li/Cu foil according to some embodiments.

4H shows a graph of the specific discharge capacity of an exemplary LiS full battery with LiF/Li-Sn alloy mixed A-SEI treated Li anode and intact Hohsen Li control foil and cathode, according to some embodiments.

4I shows a photograph of an exemplary Si3N4/SBR _{A -} SEI coating on a control Hohsen Li/Cu foil according to some embodiments.

4J shows a graph of the specific discharge capacity of an exemplary Li-S full battery prepared with a LiN3/Li-Si mixed A-SEI treated Li anode and an intact Hohsen Li control, according to some embodiments.

4K shows a photograph of an exemplary graphitic fluoride/SBR A-SEI coating in a control Hohsen Li/Cu foil anode according to some embodiments.

4L shows a graph of the specific discharge capacity of an exemplary Li-S full battery prepared with a LiF/graphite hybrid A-SEI treated Li anode and an intact Hohsen Li control and cathode in accordance with some embodiments.

4M is an exemplary schematic diagram of a carbon-containing layer including carbon allotropes, with or without doping, as a functional anode for Li-ion or LiS batteries, according to some embodiments Hetero or functionalized, with particle sizes in the 0.01-10 µm range, laminated on top of a lithium sheathed current collector foil.

4N is an exemplary schematic diagram of a roll-to-roll apparatus prepared for the manufacture of carbon/lithium anodes utilizing any compression method, such as roll-to-roll lamination and release, to coat carbon-containing anodes in accordance with some embodiments. The layer is transferred from another substrate onto the lithium surface.

40 is a photograph of an exemplary protective carbon interface (PCI) suitable for implementation in or on an anode, such as the anode shown in FIG. 4M, according to some embodiments.

4P shows a graph of electrode specific capacity performance versus cycle number for a Protected Carbon Interface (PCI) protected Li anode compared to a reference pure Li metal electrode, according to some embodiments.

4Q shows a graph of Coulombic efficiency versus cycle number for a Protected Carbon Interface (PCI) protected Li anode compared to a reference pure Li metal electrode, according to some embodiments.

4R shows a graph of average charge voltage versus cycle number for a protected carbon interface (PCI) protected Li anode compared to a reference pure Li metal electrode, according to some embodiments.

4S shows another variation of electrode specific capacity performance versus cycle number for Li anodes protected by Protected Carbon Interface (PCI) compared to nanodiamond layers, a reference pure Li metal electrode, and a heterogeneous interface layer according to some embodiments figure.

4T shows a disassembled photograph of an exemplary reference lithium pouch cell showing a high degree of dendritic growth into the spacer indicated by the transfer of black moss-like structures, according to some embodiments.

4U shows a photograph of a disassembly of an exemplary carbon-containing layer-protected Li anode, such as the Li anode shown in FIG. 4M , showing the lack of that in the reference cell disassembly shown in FIG. 4T , according to some embodiments. Moss-like black protrusions were found, and instead showed only a few spots of layered LPCI with spacers pasted upon deconstruction.

4V shows a schematic diagram of a series of plasma jet torches positioned in a continuous sequence above a roll-to-roll (R2R) processing apparatus, according to some embodiments.

5 shows a schematic diagram of an exemplary Li-ion or LiS electrochemical cell according to some embodiments.

6A shows a schematic diagram of the incorporation of metal powder into carbon particles for Li wetting and wetting, according to some embodiments.

6B and 6C show schematic diagrams of chemically non-reactive and chemically reactive systems, respectively, according to some embodiments.

7 shows an exemplary method workflow in which molten Li metal is infiltrated into void spaces between carbon agglomerates, according to some embodiments.

8A shows equations for wetting rates for carbon-based structures, according to some embodiments.

8B and 8C show non-reactive and reactive systems with respect to infiltration of Li into carbon structures, according to some implementations.

9 shows a flow diagram depicting an exemplary operation for lithiation and alloying of carbon-based structures, according to some embodiments.

10A shows a flow diagram depicting an exemplary operation for preparing a carbon-based structure, according to some embodiments.

10B shows a flow diagram depicting exemplary operations for preparing Li materials, according to some embodiments.

10C-10P show flow diagrams depicting exemplary operations for fabricating electrochemical cell electrodes, according to some implementations.

11A-11C show exemplary operations depicting the preparation of carbon particles for lithiation, according to some embodiments.

12 shows a flowchart depicting exemplary operations for performing Li infusion of carbon particles, according to some embodiments.

13 shows a schematic diagram of an anode according to some embodiments.

14 shows silicon and carbon anode performance over multiple use cycles, according to some embodiments.

15 and 16 show schematic diagrams related to idealized cathode assemblies of graphene with lithium sulfide ( _Li2S )-containing nanoparticles dispersed therein, according to some embodiments.

17A and 17B show enlarged portions of the carbon-based particles of FIGS. 1A-1F, according to some embodiments.

18A-18E are micrographs of carbon particle portions according to some embodiments.

19A shows a schematic diagram of a 3D carbon-based cathode according to some embodiments.

19B shows a schematic diagram of a 3D carbon-based anode according to some embodiments.

20A shows discharge and charge cycles of an exemplary LiS electrochemical cell according to some implementations.

20B and 20C show battery performance graphs for batteries equipped with electrodes including carbon, according to some implementations.

21 shows Raman spectra of 3D N -doped FL graphene according to some embodiments.

22 shows a schematic diagram of bilayer graphene according to some embodiments.

Figure 23 shows a method for making a 3D scaffold-type membrane, according to some embodiments.

The same reference numerals and names in the various figures refer to the same elements.

4B00: Anode protected by A-SEI

4B02: Electrolyte

4B04: The first active component layer, the first component layer

4B06: Second Active Component Layer, Second Component Layer

4B08: The first set

4B10: The second set

4B12: Solid Li metal foil anode

4B14: Copper foil current collector

Claims (20)

A battery pack comprising: a cathode; an anode positioned opposite the cathode, the anode comprising a mixed artificial solid-electrolyte interphase (A-SEI) layer encapsulating the anode, the mixed A-SEI layer comprising: a first active component; a second active component disposed on the first active component; and a plurality of carbon-containing aggregates interwoven throughout the first active element and the second active element and assembled to inhibit the growth of Li dendrites from the anode toward the cathode; and a spacer between the anode and the cathode. The battery of claim 1, wherein the cathode comprises a porous carbon-based structure configured to shuttle polysulfide (PS) in one or more portions of the battery in the presence of Amplification. The battery of claim 1, further comprising an electrolyte dispersed between the anode and the cathode and in contact with the anode and the cathode. The battery of claim 3, wherein the plurality of carbon-containing aggregates comprise a polymer comprising a cross-linked polymeric network. The battery of claim 4, wherein the cross-linked polymeric mesh is assembled to control an amount of contact between the electrolyte and the anode. The battery of claim 4, wherein a first portion of the cross-linked polymeric network has a first cross-link density, and a second portion of the cross-linked polymeric network has a different cross-link density than the first cross-link density One of the second lowest crosslink density. The battery of claim 4, further comprising a gradient defined by a crosslink density across the crosslinked polymeric network of the hybrid A-SEI layer encapsulating the anode. A battery comprising: a cathode; an anode positioned opposite the cathode; a hybrid artificial solid-electrolyte interphase (A-SEI) layer deposited on the anode and including a plurality of active components; a composite material interwoven throughout the plurality of active components and assembled to inhibit the growth of lithium (Li) dendrites from the anode to the cathode, the blend material comprising ^: crystalline sp bonding of graphene sheets a combination of carbon domains with one of a plurality of flexible pleated regions located at the junctions of two or more of the crystalline sp ^- bound carbon domains of the graphene sheets; and a polymeric matrix assembled with The plurality of active components are bonded together with the blend material; an electrolyte in contact with the hybrid A-SEI and the cathode; and a spacer between the anode and the cathode. The battery of claim 8, wherein the blend material comprises any one or more curable metal carboxylates, the one or more curable metal carboxylates comprising one or more of the following: zinc, strontium, tin , indium, aluminum or molybdenum acrylate, methacrylate or higher curable carboxylate analogs. The battery of claim 8, wherein the combination further comprises one or more flex points configured to shrink a volume of the A-SEI layer during crosslinking of the polymeric matrix. The battery of claim 8, wherein the cathode comprises a porous structure configured to expand in the presence of polysulfide (PS) shuttles within one or more portions of the battery. The battery pack of claim 8, wherein the plurality of active components comprise: a first active component; and A second active component is disposed on the first component. The battery pack of claim 12, wherein at least one of the first active element or the second active element includes a passivation layer. The battery of claim 13, wherein the passivation layer includes an inorganic component. A battery pack comprising: a cathode; an anode positioned opposite the cathode; a carbon interface layer, the carbon interface layer comprising: an electrically insulating sheet carbon layer that conformally encapsulates the anode; and a plurality of carbon nano-onions (CNOs) defining a plurality of interstitial pore volumes interspersed throughout the electrically insulating sheet carbon layer; an electrolyte in contact with the carbon interface layer and the cathode; and a spacer between the anode and the cathode. The battery of claim 15, wherein the electrically insulating sheet carbon layer comprises graphene oxide (GO). The battery of claim 15, wherein the plurality of interstitial pore volumes are configured to transport lithium (Li (Li) through the plurality of interstitial pore volumes in a bulk phase of the electrolyte between the anode and the cathode )ion. The battery of claim 15, wherein a thickness of the carbon interface layer is between about 0.1 μm and 20 μm. A method of making a lithium (Li) anode, the method comprising: forming a slurry by mixing a plurality of electrically insulating sheet carbons and a plurality of carbon nanoonions (CNOs) with each other; Casting the slurry onto a release film; drying the slurry; and The dry slurry on the release film was transferred to a Li-sheathed copper foil of the Li anode by roll-to-roll lamination. The method of claim 19, wherein the roll-to-roll lamination comprises: applying pressure to the dry slurry on the release film; forming a protective carbon-containing layer based on applying pressure to the dry slurry on the release film; extending the protective carbon-containing layer onto the Li anode; and The release film is released from the protective carbon-containing layer while maintaining adhesion between the carbon-containing layer and the Li anode.

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