Lithium-sulfur battery cathode formed from multiple carbonaceous regions

Abstract

A composition of matter suitable for incorporation into a battery electrode is disclosed. In some embodiments, the composition of matter can include pores that can be defined by a number of carbonaceous particles. Each of the particles can have multiple regions such that adjacent regions are separated from one another by some of the pores. For example, deformable regions can be distributed throughout the periphery of each of the particles to accommodate the coalescence of multiple adjacent particles. The composition of matter can also include a plurality of aggregates and a plurality of agglomerates, where each aggregate includes a number of particles connected together and each agglomerate includes a number of aggregates connected together.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This patent application claims priority to U.S. patent application Ser. No. 17 / 563,183, entitled "LITHIUM-SULFUR BATTERY CATHODE FORMED FROM MULTIPLE CARBONACEOUS REGIONS," filed on December 28, 2021, which is a continuation-in-part application claiming priority to U.S. patent application Ser. No. 17 / 383,803, entitled "CARBONACEOUS MATERIALS FOR LITHIUM-SULFUR BATTERIES," filed on July 23, 2021, all of which are assigned to the assignee of the present application. This patent application is also related to U.S. patent application Ser. No. 17 / 383,735, filed on July 23, 2021, entitled "POWDERED MATERIALS INCLUDING CARBONACEOUS STRUCTURES FOR LITHIUM-SULFUR BATTERY CATHODES," U.S. patent application Ser. No. 17 / 383,744, filed on July 23, 2021, entitled "PROTECTIVE POLYMERIC LATTICES FOR LITHIUM ANODES IN LITHIUM-SULFUR BATTERIES," U.S. patent application Ser. No. 17 / 383,756, filed on July 23, 2021, entitled "BATTERY INCLUDING MULTIPLE PROTECTIVE LAYERS," U.S. patent application Ser. No. 17 / 383,757, filed on July 23, 2021, entitled "CARBON-SCAFFOLDED LITHIUM-SULFUR BATTERY CATHODES FEATURING A POLYMERIC No. 17 / 383,769, entitled "PROTECTIVE LAYER INCLUDING TIN FLUORIDE DISPOSED ON A LITHIUM ANODE IN A LITHIUM-SULFUR BATTERY," filed July 23, 2021, all of which are assigned to the assignee of the present application. The disclosures of the prior applications, in their respective entireties, are deemed to be part of and incorporated by reference into this patent application.

[0002] The present disclosure relates generally to batteries, and more specifically to lithium-ion batteries capable of compensating for operational cycle losses. [Background technology]

[0003] Recent developments in batteries are enabling consumers to use electronic devices in many new areas, however, further improvements in battery technology are desirable. Summary of the Invention

[0004] This summary is provided to introduce some 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.

[0005] One innovative aspect of the subject matter described in this disclosure can be implemented as a composition of matter comprising a plurality of pores. The composition of matter can be suitable for incorporation into a battery electrode and includes a plurality of particles, each of which includes a first zone comprising a plurality of first pores having a uniform pore size, and a second zone comprising a plurality of second pores. The second zone can be concentrically positioned with respect to the first zone and separated from the first zone by at least some of the plurality of first pores, where the plurality of second pores have a gradually decreasing pore size along a radial direction from the center of the particle to the boundary of the particle. The composition of matter can also include a plurality of aggregates, each of which includes a plurality of particles connected together, and a plurality of agglomerates, each of which includes a plurality of aggregates connected together.

[0006] In some embodiments, each of the particles may have a major dimension between 20 nanometers (nm) and 150 nm. Each of the aggregates may have a major dimension between 10 nanometers (nm) and 10 micrometers (μm). Each of the aggregates may have a major dimension between 0.1 μm and 1,000 μm. At least some of the pores may be dispersed throughout one or more of the particles or aggregates, where each of the pores may have a major dimension between 0 nm and 100 nm.

[0007] In one embodiment, each of the particles may include a first porosity region and a second porosity region positioned adjacent to the first porosity region. The first porosity region may have a first type of pores and the second porosity region may have a second type of pores such that the first porosity region has a different porosity than the second porosity region. Thus, the first type of pores may have a first pore density and the second type of pores may have a second pore density. For example, the first porosity region may have a first pore density of 0.0 cubic centimeters (cc) / g to 2.0 cc / g and the second porosity region may have a second pore density of 1.5 to 5.0 cc / g. In some embodiments, the second porosity region may be at least partially encapsulated by the first porosity region.

[0008] In some embodiments, some of the pores may be interspersed throughout the aggregate, where at least some of the pores have a major dimension between 1.3 nm and 32.3 nm. The conductive additive may be dispersed within at least some of the pores. In some embodiments, the composition of matter is at least 10 μm in diameter. 2 / g~3,000m 2 / g surface area and / or 10 m 2 / g~3,000m 2 / g (e.g., with sulfur microtrapped within the pores). In one embodiment, the composition of matter may have an electrical conductivity of 100 S / m to 20,000 S / m at a pressure of 12,000 pounds per square inch (psi). In one embodiment, the particles, aggregates, and / or agglomerates may include exposed carbon surfaces that may support sulfur nucleation, such that the composition of matter has a sulfur to carbon weight ratio of about 1:5 to 10:1. In some aspects, some of the aggregates are connected together with one or more polymeric binders.

[0009] Another innovative aspect of the subject matter described in this disclosure may be implemented as a battery. In some implementations, the battery may include an anode, a polymer network disposed on one or more exposed surfaces of the anode, a cathode positioned opposite the anode, an electrolyte at least partially dispersed throughout the cathode and in contact with the anode, an electrolyte configured to transport a plurality of alkali ions between the cathode and the anode, and a separator. In some implementations, the anode may include an alkali metal capable of releasing alkali ions during an operational discharge-charge cycle of the battery. The polymer network may include a carbonaceous material grafted with fluorinated polymer chains crosslinked to each other. The fluorinated polymer chains may generate an alkali metal-containing fluoride in response to an operational cycle of the battery. In one implementation, the formation of the alkali metal-containing fluoride may inhibit the formation of alkali metal dendrites from the anode, for example, such that lithium is consumed to form lithium fluoride rather than forming a structure of lithium-containing dendrites. The electrolyte may be at least partially dispersed throughout the cathode and in contact with the anode and may assist in the transport of alkali ions between the cathode and the anode. A separator may be positioned between the anode and the cathode.

[0010] In one embodiment, the carbonaceous material may include flat graphene, wrinkled graphene, carbon nanotubes (CNTs), and / or carbon nano-onions (CNOs). The fluorinated polymer chains may include monomers including 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl acrylate (DFHA), 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl methacrylate (HDFDMA), 2,2,3,3,4,4,5,5-octafluoropentyl methacrylate (OFPMA), tetrafluoropropyl methacrylate (TFPM), 3-[3,3,3-trifluoro-2-hydroxy-2-(trifluoromethyl)propyl]bicyclo[2.2.1]hept-2-yl methacrylate (HFA monomer), and / or vinyl-based monomers including 2,3,4,5,6-pentafluorostyrene (PFSt). The polymer network may have a thickness of about 0.001 μm to 5 μm.

[0011] In some embodiments, the fluorinated polymer chains can be grafted to the surface of the carbonaceous material, i.e., the grafting can be based on a radical initiator including at least one of benzoyl peroxide (BPO) or azobisisobutyronitrile (AIBN). The fluorinated polymer chains can react with alkali metal ions via the Wurtz reaction, which can be associated with the production of alkali metal fluorides. The graphene nanoplatelets can be dispersed throughout the polymer network, where the graphene nanoplatelets are isolated from one another within the polymer network. The dispersion of graphene nanoplatelets can include different concentration levels (of graphene nanoplatelets). In some embodiments, the dispersion of graphene nanoplatelets can include a carbonaceous material functionalized with at least some fluorinated polymer chains.

[0012] In one embodiment, the polymer network comprises about 0.001% to 2% by weight of fluorinated polymer chains. In some aspects, the polymer network comprises an interphase layer in contact with the anode and a protective layer disposed on top of the interphase layer. The interphase layer may be based on a Wurtz reaction at the interface between the anode and the polymer network. In some aspects, the crosslinked polymer network may comprise about 5% to 100% by weight of the carbonaceous material grafted with fluorinated polymer chains, with the remainder being a fluorinated polymer, a non-fluorinated polymer, or a crosslinkable monomer, or a combination thereof. In one embodiment, the carbonaceous material grafted with fluorinated polymer chains may comprise 5% to 50% by weight of the fluorinated polymer chains and the remainder being a carbonaceous material.

[0013] In some aspects, the polymer network may further define a density gradient associated with the self-healing properties of the interphase layer and / or protective layer, and may strengthen the polymer network, which may inhibit dendritic growth from the anode. In one embodiment, the anode may be an alkali metal layer and / or may include a surface exposed to the electrolyte, where each exposed surface may include an alkali metal-containing nanostructure or microstructure. In some aspects, the alkali metal-containing nanostructure or microstructure may include a carbonaceous particle, a number of aggregates each including a carbonaceous particle, or a number of aggregates each including several aggregates.

[0014] In one embodiment, each of the carbonaceous particles has a first porous region having a first pore density and a second porous region having a second pore density. The second porous region can be at least partially encapsulated by the first porous region, and the second density can be less than the first density. In some aspects, the second porous region can microtrap elemental sulfur at least temporarily as may be associated with an operational discharge-charge cycle of the battery.

[0015] In some embodiments, the anode may be structurally defined by a three-dimensional (3D) scaffold and / or structure, which may include adjacent graphene sheets that may interpose at least an alkali metal. For example, the anode may be formed as a lattice having adjacent graphene sheets with exposed surfaces for alkali metal electrodeposition and / or interlayers. In one embodiment, a film may be disposed on the cathode and may include a lattice having a trifunctional epoxy compound and a diamine oligomer compound chemically bonded to each other. The film may combine with the alkali metal-containing polysulfide intermediates generated during the operating discharge-charge cycle of the battery and may complement the polymer sheath disposed on the anode.

[0016] Another innovative aspect of the subject matter described in this disclosure may be implemented as a battery including an anode, a cathode positioned opposite the anode, a protective sheath disposed on the cathode, an electrolyte, and a separator. The polymer network may be disposed on the anode and may include a carbonaceous material grafted with a plurality of fluorinated polymer chains crosslinked within the lattice. In some aspects, the lattice may generate an alkali metal fluoride in response to an operating cycle of the battery. The alkali metal fluoride may be configured to inhibit the formation of alkali metal dendrites from the anode. Additionally, the anode may output alkali ions during an operating cycle of the battery. The protective sheath disposed on the cathode may include a trifunctional epoxy compound and a diamine oligomer-based compound, both of which may chemically react with each other. The electrolyte may be dispersed throughout the cathode and may be in contact with the anode. The separator may be positioned between the anode and the cathode.

[0017] In some embodiments, the polymer network may be deposited on one or more exposed surfaces of the anode. The carbonaceous material may include one or more of flat graphene, wrinkled graphene, carbon nanotubes (CNTs), or carbon nano-onions (CNOs). The fluorinated polymer chain may include multiple monomers, one or more of which may include vinyl-based monomers including 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl acrylate (DFHA), 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl methacrylate (HDFDMA), 2,2,3,3,4,4,5,5-octafluoropentyl methacrylate (OFPMA), tetrafluoropropyl methacrylate (TFPM), 3-[3,3,3-trifluoro-2-hydroxy-2-(trifluoromethyl)propyl]bicyclo[2.2.1]hept-2-yl methacrylate (HFA monomer), or 2,3,4,5,6-pentafluorostyrene (PFSt). The polymer network may have a thickness of about 0.001 μm to 5 μm. Fluorinated polymer chains may be grafted to the surface of each one of the carbonaceous materials.

[0018] In various embodiments, the fluorinated polymer chains can chemically interact with one or more surfaces of the alkali metal of the anode via the Wurtz reaction. In some aspects, the carbonaceous material can include graphene nanoplatelets dispersed throughout the polymer network. The graphene nanoplatelets can be isolated from one another within the polymer network. The dispersion of the multiple graphene nanoplatelets throughout the polymer network can have different concentration levels. The graphene nanoplatelets can be functionalized with fluorinated polymer chains.

[0019] In some embodiments, the polymer network includes about 0.001% to 2% by weight of fluorinated polymer chains. In one embodiment, the polymer network can include an interphase region in contact with the anode and a protective region disposed on top of the interphase region. The interphase region can be based on a Wurtz reaction at the interface between the anode and the polymer network. The interphase region can include one or more of a plurality of crosslinkable monomers including methacrylate (MA), acrylate, vinyl functional groups, or a combination of epoxy and amine functional groups. The protective region can be characterized by a density gradient, which can be related to the self-healing properties of the protective region. The density gradient can reinforce the polymer network. In this manner, the polymer network can inhibit dendritic growth from the anode.

[0020] In various embodiments, the anode can include exposed surfaces, where each exposed surface has alkali metal-containing nanostructures and / or microstructures, each of which can include a carbonaceous material. In one embodiment, the anode can have a three-dimensional (3D) structure, where several adjacent graphene sheets can have alkali metal ions interposed therebetween.

[0021] Another innovative aspect of the subject matter described in this disclosure may be implemented as a battery including an anode, a cathode, a protective sheath disposed on the cathode, a separator, and an electrolyte. The anode may be arranged in a lattice configuration and may include a carbonaceous material. The cathode may be positioned opposite the anode. The separator may be disposed between the anode and the cathode. The protective sheath disposed on the cathode may include a trifunctional epoxy compound and a diamine oligomer-based compound, both of which may chemically react with each other. In this manner, the protective sheath may prevent polysulfide migration within the battery based on chemical bonding between the protective sheath and one or more lithium-containing polysulfide intermediates. The electrolyte may be dispersed within the cathode and may contact the anode.

[0022] In one embodiment, a polymer network can be deposited on one or more exposed surfaces of the anode. The polymer network can have fluorinated polymer chains grafted with carbonaceous material and cross-linked to each other. In this manner, the polymer network can retain alkali metal-containing fluorides, which in turn can inhibit the formation of alkali metal dendrites associated with the anode.

[0023] In various embodiments, the cracks may extend into the cathode, where the protective sheath may be distributed across one or more cracks. In this manner, the protective sheath may be positioned to reduce the susceptibility of the cathode to rupture. In one embodiment, the protective sheath has a crosslinked three-dimensional structure based on a trifunctional epoxy compound and a diamine oligomer-based compound. In some examples, the trifunctional epoxy compound is one or more of trimethylolpropane triglycidyl ether (TMPTE), tris(4-hydroxyphenyl)methane triglycidyl ether, or tris(2,3-epoxypropyl)isocyanurate, and the diamine oligomer-based compound is one or more of dihydrazide sulfoxide (DHSO) or JEFFAMINE® D-230 polyetheramine. Additionally or alternatively, the protective sheath may include trimethylolpropane tris[poly(propylene glycol)] and an amine-terminated ether.

[0024] In some embodiments, the carbonaceous material can include flat graphene, wrinkled graphene, carbon nanotubes (CNTs), and / or carbon nano-onions (CNOs). In one embodiment, the cathode can include a host structure having one or more of flat graphene, wrinkled graphene, carbon nanotubes (CNTs), or carbon nano-onions (CNOs), where the anode includes a solid lithium metal layer.

[0025] In one embodiment, a tin fluoride layer can be disposed on the anode, and a lithium fluoride layer can be formed between the tin fluoride layer and the anode. The lithium fluoride layer can be associated with a chemical reaction between fluorine ions and lithium ions. In this manner, the lithium fluoride layer can inhibit lithium-containing dendritic growth from the anode. In some aspects, a solid electrolyte interphase can be disposed on the anode. The solid electrolyte interphase can include tin, manganese, molybdenum, fluorine compounds, tin fluoride, manganese fluoride, silicon nitride, lithium nitride, lithium nitrate, lithium phosphate, manganese oxide, and / or lithium lanthanum zirconium oxide (LLZO).

[0026] Another innovative aspect of the subject matter described in this disclosure may be implemented as a battery. In various embodiments, the battery may include an anode configured to output a plurality of lithium ions during cycling of the battery, a gradient layer disposed on the anode, a cathode positioned opposite the anode, an electrolyte dispersed throughout the cathode and the anode, and a separator positioned between the anode and the cathode. In some embodiments, the gradient layer may include a polymer network, which may include a density gradient formed of wrinkled graphene associated with graphene nanoplatelets dispersed throughout the polymer network and isolated from one another within the polymer network, at least some of the wrinkled graphene may be configured to expand in volume along one or more inflection points and retain polysulfides generated during cycling of the battery. In some cases, the polymer network comprises a plurality of fluorinated poly(meth)acrylates grafted onto one or more inflection points of at least some of the wrinkled graphenes; and a plurality of carbon-fluorine (CF) bonds in the polymer network, wherein at least some of the plurality of carbon-fluorine (CF) bonds are chemically reacted with at least some of the plurality of lithium ions via a Wurtz reaction and react with fluorine ions (F -) in the Wurtz reaction, and the conversion of multiple carbon-fluorine (CF) bonds to carbon-lithium (C-Li) bonds by replacing the fluorine ions (F - ) during the substitution of fluorine ions (F), the formation of carbon-carbon (CC) bonds being associated with cross-linking of the polymer network. - and lithium fluoride (LiF) formed in response to the replacement of Li with Li ions, where the lithium fluoride (LiF) is associated with consumption of at least some of the lithium ions.

[0027] In some cases, the battery may also include a solid electrolyte interphase formed on a surface of the anode exposed to the electrolyte during cycling of the battery. In other cases, the gradient layer may be configured to grow the solid electrolyte interphase during cycling of the battery. In some aspects, the gradient layer may be deposited on the anode by one or more of atomic layer deposition (ALD), chemical vapor deposition (CVD), or physical vapor deposition (PVD).

[0028] Another innovative aspect of the subject matter described in this disclosure may be implemented as a battery. In various embodiments, the battery may include an anode configured to output a plurality of lithium ions during cycling of the battery, a gradient layer disposed on the anode, a cathode positioned opposite the anode, an electrolyte dispersed throughout the cathode and the anode, and a separator positioned between the anode and the cathode. In some embodiments, the gradient layer may include a polymer network, which may include a density gradient formed of wrinkled graphene associated with graphene nanoplatelets dispersed throughout the polymer network and isolated from one another within the polymer network, at least some of the wrinkled graphene may be configured to expand in volume along one or more inflection points and retain polysulfides generated during cycling of the battery. In some cases, the polymer network comprises a plurality of fluorinated poly(meth)acrylates grafted onto one or more bending points of at least some of the wrinkled graphenes; and a plurality of carbon-fluorine (CF) bonds in the polymer network, wherein at least some of the plurality of carbon-fluorine (CF) bonds are configured to chemically react with at least some of the plurality of lithium ions and convert to carbon-lithium (C-Li) bonds by replacing fluorine ions (F-) during the Wurtz reaction. - ), and lithium fluoride (LiF) formed in response to the formation of at least some of the carbon-carbon (C-C) bonds, where the lithium fluoride (LiF) may be associated with consumption of at least some of the lithium ions.

[0029] In some embodiments, the first plurality of mesopores has a first mesopore density and the second plurality of mesopores has a second mesopore density different from the first mesopore density. In other embodiments, the first plurality of macropores has a first pore density and the second plurality of macropores has a second pore density different from the first pore density. In some other embodiments, one or more of the first porous carbonaceous region or the second porous carbonaceous region may be configured to nucleate sulfur.

[0030] In some embodiments, the cathode comprises a plurality of pores and may include a plurality of non-tri-zone particles, a plurality of tri-zone particles, a plurality of aggregates each including a number of tri-zone particles connected together, a plurality of mesopores interspersed throughout the plurality of aggregates, a plurality of agglomerates each including a number of aggregates connected to each other, and a plurality of macropores interspersed throughout the plurality of aggregates. In some cases, each tri-zone particle may include a plurality of carbon fragments intertwined with each other and separated from each other by mesopores, and a deformable perimeter configured to merge with one or more adjacent non-tri-zone particles or tri-zone particles. In some embodiments, each aggregate may have a major dimension within a range of 10 nanometers (nm) to 10 micrometers (μm), each mesopore may have a major dimension between 3.3 nanometers (nm) and 19.3 nm, each aggregate may have a major dimension within an approximate range of 0.1 μm to 1,000 μm, and each macropore may have a major dimension between 0.1 μm and 1,000 μm.

[0031] In some cases, one or more of the first or second porous carbonaceous regions may also include a selectively permeable shell configured to form a separated liquid phase on the first or second porous carbonaceous region, respectively. In some embodiments, the first porous carbonaceous region has a conductivity in the approximate range of 500 S / m to 20,000 S / m at a pressure of 12,000 pounds per square inch (psi). In other embodiments, the second porous carbonaceous region has a conductivity in the approximate range of 0 S / m to 500 S / m at a pressure of 12,000 pounds per square inch (psi). In some other embodiments, one or more of the first or second plurality of aggregates may include aggregates connected to one another with one or more polymeric binders.

[0032] In some embodiments, each of the tri-zone particles may include a first porous region located about a center of each of the tri-zone particles, the first porous region including a first pore, and a second porous region surrounding the first porous region, the second porous region including a second pore. In some cases, the first pores define a first pore density and the second pores define a second pore density different from the first pore density. In other embodiments, the cathode may also include one or more additional porous carbonaceous regions, at least one of which is combined with the second porous carbonaceous region. In some cases, the one or more additional porous carbonaceous regions are positioned to provide a stepwise decreasing concentration level of carbonaceous material away from the first porous carbonaceous region.

[0033] Another innovative aspect of the subject matter described in this disclosure can be implemented as a composition of matter comprising a plurality of pores. In various embodiments, the composition of matter can comprise a plurality of non-tri-zone particles, a plurality of aggregates, each aggregate comprising a number of tri-zone particles connected together, each aggregate having a major dimension within a range of 10 nanometers (nm) to 10 micrometers (μm), a plurality of mesopores dispersed throughout the plurality of aggregates, each mesopore having a major dimension between 3.3 nanometers (nm) and 19.3 nm, a plurality of aggregates, each aggregate comprising a number of interconnected aggregates, each aggregate having a major dimension within an approximate range of 0.1 μm to 1,000 μm, and a plurality of macropores dispersed throughout the plurality of aggregates, each macropore having a major dimension between 0.1 μm to 1,000 μm. In some embodiments, each tri-zone particle may include a plurality of carbon fragments intertwined with one another and separated from one another by mesopores and a deformable periphery configured to merge with one or more adjacent non-tri-zone or tri-zone particles, and in some aspects, each of the pores has a major dimension in the approximate range of 0 nanometers (nm) to 32.3 nm. In other aspects, the composition of matter has a conductivity in the approximate range of 100 S / m to 20,000 S / m at a pressure of 12,000 pounds per square inch (psi).

[0034] In various embodiments, the composition of matter may also include a selectively permeable shell configured to form a separate liquid phase on one or more exposed surfaces of the composition of matter. In other embodiments, the composition of matter may also include an electrolyte dispersed within the composition of matter. In some cases, at least some of the aggregates are connected to one another with one or more polymeric binders.

[0035] The details of one or more embodiments of the subject matter described in this disclosure are set forth in the accompanying drawings and the following description. Other features, aspects, and advantages will become apparent from the description, drawings, and claims. It should be noted that the relative dimensions of the following figures may not be drawn to scale. [Brief description of the drawings]

[0036] [Figure 1] 1 shows a diagram depicting an exemplary battery, according to some embodiments. [Diagram 2] 1 shows a diagram depicting another exemplary battery, according to some embodiments. [Diagram 3] 1 illustrates a schematic diagram of an exemplary electrode of a battery, according to some embodiments. [Figure 4] 1 illustrates a simplified diagram of a portion of an exemplary battery including a protective grid, according to some embodiments. [Diagram 5] 1 shows a schematic diagram of an anode structure including a tin fluoride (SnF2) layer according to some embodiments. [Figure 6] 6 shows a schematic diagram of an enlarged portion of the anode structure of FIG. 5 according to some embodiments. [Figure 7] 1 shows a schematic diagram of a polymer network of a battery, according to some embodiments. [Figure 8A] 1 shows a schematic diagram of an exemplary carbonaceous particle having gradient porosity, according to some embodiments. [Figure 8B] 1 shows a schematic diagram of an example tri-zone particle, according to some embodiments. [Figure 8C] 8C illustrates an exemplary step function representing the tri-zone particle of FIG. 8B, according to some embodiments. [Figure 8D] 1 shows a graph depicting an exemplary distribution of pore volume versus pore width for an exemplary carbonaceous particle, according to some embodiments. [Figure 9] 8A and 8B show electron micrographs of exemplary carbonaceous particles, aggregates, and / or agglomerates depicted in FIG. 8A and / or FIG. 8B, according to some embodiments. [Figure 10] 1A and 1B show transmission electron microscope (TEM) images of carbonaceous particles treated with carbon dioxide (CO2), according to some embodiments. [Figure 11] 1 shows a schematic diagram depicting the carbon porous type commonly used in the anode and / or cathode of the present disclosure, according to some embodiments. [Figure 12] 1 shows a graph depicting cumulative pore volume versus pore width for micropores and mesopores distributed throughout a battery anode or cathode, according to some embodiments. [Figure 13] 1 shows a graph depicting battery performance over cycle number, according to some embodiments. [Figure 14] 1 shows a bar graph depicting capacity per cycle number according to some embodiments. [Figure 15] 1 shows a graph depicting battery performance over cycle number, according to some embodiments. [Figure 16] 1 shows a graph depicting battery discharge capacity per cycle number according to some embodiments. [Figure 17] 1 shows a graph depicting battery discharge capacity per cycle number according to some embodiments. [Figure 18] 1 shows a graph depicting battery specific discharge capacity for various TBT-containing electrolyte mixtures, according to some embodiments. [Figure 19] 2 shows a graph depicting battery specific discharge capacity versus cycle number for the battery of FIG. 1 according to some embodiments. [Figure 20] 3 shows a graph depicting battery specific discharge capacity and discharge capacity retention over cycle number for the battery of FIG. 2 according to another embodiment. [Figure 21] 3 shows a graph depicting battery specific discharge capacity and discharge capacity retention over cycle number for the battery of FIG. 2 according to some other embodiments. [Figure 22] 1 shows a schematic diagram of an exemplary cathode of a battery, according to some embodiments.

[0037] Like reference numbers and designations in the various drawings indicate like elements. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0038] The following description is directed to several exemplary embodiments for the purpose of illustrating the innovative aspects of the present disclosure. However, those skilled in the art will readily recognize that the teachings herein can be applied in many different ways. The described embodiments can be implemented in any type of electrochemical cell, battery, or battery pack and can be used to compensate for various performance-related deficiencies. Thus, the disclosed embodiments should not be limited by the examples provided herein, but rather encompass all embodiments contemplated by the appended claims. Additionally, known elements of the present disclosure will not be described or will be omitted so as not to obscure the relevant details of the present disclosure.

[0039] Batteries typically include several electrochemical cells that can be connected together to provide power to a wide variety of devices, such as, but not limited to, mobile phones, laptops, electric vehicles (EVs), factories, and buildings. Certain types of batteries, such as lithium-ion or lithium-sulfur batteries, may be limited in performance by the type of electrolyte used or by uncontrolled battery side reactions. As a result, optimization of the electrolyte may improve the cycleability, specific discharge capacity, discharge capacity retention, safety, and lifespan of the respective batteries. For example, in an unused or "new" battery, lithium ions are freely transported from the anode to the cathode at start-up and then during initial and subsequent discharge cycles. Then, during the charging cycle of the battery, the lithium ions may be forced from their electrochemically favored position in the cathode back to the anode, where they are stored for subsequent use. This cyclical discharge-charge process associated with rechargeable batteries may result in the generation of undesirable chemical species that may interfere with the transport of lithium ions to and from the cathode during each discharge and charge of the battery. Specifically, lithium-containing polysulfide intermediate species (referred to herein as "polysulfides") are produced when lithium ions interact with elemental sulfur (or, in some configurations, lithium sulfide, Li2S) present in the cathode. These polysulfides are soluble in the electrolyte and, as a result, diffuse throughout the battery during an operating cycle, thereby resulting in loss of active material from the cathode. The production of excessive concentration levels of polysulfides can result in undesirable battery capacity fade and cell failure during an operating cycle, potentially reducing the driving range of electric vehicles (EVs) and increasing the frequency with which such EVs require recharging.

[0040] In some cases, polysulfides are involved in the formation of an inorganic layer at the solid electrolyte interphase (SEI) provided in the battery. In one example, the anode may be protected by a stable inorganic layer formed in the electrolyte and containing 0.020M Li2S5 (0.10M sulfur) and 5.0 wt.% LiNO3. Lithium fluoride and polysulfide (LiF-Li2S x Anodes with 0.1M sulfur may concentrate the SEI to provide a stable coulombic efficiency of 95% after 233 cycles for Li-Cu half cells while simultaneously preventing the formation of lithium dendrites or other uncontrolled lithium growths that may extend from the anode to the cathode and result in failed or ruptured cells. However, when polysulfides are produced at certain concentrations (such as greater than 0.50M sulfur), the formation of the SEI may be impeded. As a result, lithium metal from the anode may be undesirably etched away, creating a rough and incomplete surface exposed to the electrolyte. This undesirable degradation (etching) of the anode due to a relatively high concentration of polysulfides may indicate that polysulfide dissolution and diffusion may be limiting battery performance.

[0041] In some implementations, the porosity of the carbonaceous cathode may be tailored to achieve a desired balance between maximizing energy density and inhibiting polysulfide migration into and / or throughout the battery electrolyte. As used herein, the term carbonaceous may refer to a material that contains or is formed of one or more types or compositions of carbon. For example, the porosity of the cathode may be higher in a sulfur and carbon composite cathode than in a conventional lithium-ion battery electrode. A denser electrode with relatively low porosity may minimize electrolyte intake, parasitic weight, and cost. Sulfur utilization may be limited by the solubility of polysulfides and their conversion to lithium sulfide (Li2S). The conversion of polysulfides to lithium sulfide may be based on the accessible surface area of ​​the cathode. Aspects of the present disclosure recognize that the cathode porosity may be tailored based on the electrolyte constituent materials to maximize the battery volumetric energy density. Additionally or alternatively, one or more protective layers or regions can be added to the surfaces of the cathode and / or anode exposed to the electrolyte to adjust the cathode porosity level, and in some embodiments, these protective layers or regions can inhibit undesirable migration of polysulfides throughout the battery.

[0042] Various aspects of the subject matter disclosed herein are directed to a lithium-sulfur battery including a liquid phase electrolyte, which may include a ternary solvent package and one or more additives. In some embodiments, the lithium-sulfur battery may include a cathode, an anode positioned opposite the cathode, and an electrolyte. The cathode may include several regions, each region defined by two or more carbonaceous structures adjacent and in contact with one another. In some cases, the electrolyte may be interspersed throughout the cathode and in contact with the anode. In some aspects, the electrolyte may include a ternary solvent package and 4,4'-thiobisbenzenethiol (TBT). In other cases, the electrolyte may include a ternary solvent package and 2-mercaptobenzothiazole (MBT).

[0043] In various embodiments, the ternary solvent package may include 1,2-dimethoxyethane (DME), 1,3-dioxolane (DOL), tetraethylene glycol dimethyl ether (TEGDME), and one or more additives, which may include lithium nitrate (LiNO3), all of which may be in a liquid phase. In some embodiments, the ternary solvent package may be prepared by mixing about 5,800 microliters (μL) of DME, 2,900 microliters (μL) of DOL, and 1,300 microliters (μL) of TEGDME together to create a mixture. About 0.01 moles of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) may be dissolved in the ternary solvent package to produce a dilute level of about 1 M LiTFSI in DME:DOL:TEGDME in a volume ratio of 2:1:1 with about 2 weight percent (wt%) lithium nitrate. In other embodiments, the ternary solvent package may be prepared with 2,000 microliters (μL) of DME, 8,000 microliters (μL) of DOL, and 2,000 microliters (μL) of TEGDME and may include about 0.01 molar dissolved lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). In some aspects, the ternary solvent package may be prepared at a first approximate dilution level of 1 molar (M) LiTFSI in a mixture of DME:DOL:TEGDME. In other cases, the ternary solvent package may be prepared at a second approximate dilution level of about 1 M LiTFSI in DME:DOL:TEGDME in an approximate volume ratio of 1:4:1 and may include either the addition of a 5 M TBT solution, or the addition of a 5 M MBT solution, or the addition of other additives and / or chemicals.

[0044] In various embodiments, each carbonaceous structure can include a relatively high density shell region and a relatively low density core region. In some aspects, the core region can be formed within an inner portion of the shell region. The shell region can have a carbon density of about 1.0 grams per cubic centimeter (g / cc) to 3.5 g / cc. The core region can have a carbon density of about 0.0 g / cc to 1.0 g / cc, or some other range of carbon densities lower than the first carbon density. In other embodiments, each carbonaceous structure can include a shell region and a core region having the same or similar densities, such that, for example, the carbonaceous structure does not include gradient porosity.

[0045] The various regions of the cathode can include micro-, meso-, and macro-porous channels that are interconnected to form a porous network that extends from the shell region to the core region. For example, in some embodiments, the porous network can include pores each having a major dimension of about 1.5 nm.

[0046] In some embodiments, one or more portions of the porous network may temporarily microconfine electroactive materials, such as (but not limited to) elemental sulfur in the cathode, which may increase the battery specific capacity by complexing with lithium ions. In some aspects, the ternary solvent package may have tunable polarity, tunable solubility, and may be capable of transporting lithium ions. Additionally, the ternary solvent package may at least temporarily suspend polysulfide (PS) during the charge-discharge cycle of the battery.

[0047] Certain embodiments of the subject matter described in this disclosure may be implemented to realize one or more potential advantages. In some embodiments, the porous network formed by the interconnection of microporous, mesoporous, and macroporous channels in the cathode may have a plurality of pores having a number of different pore sizes. In some embodiments, the plurality of pores may include micropores having a pore size of less than about 2 nm, may include mesopores having a pore size of about 5-50 nm, and may include macropores having a pore size of greater than about 50 nm. The micropores, mesopores, and macropores may collectively mitigate undesirable migration or diffusion of polysulfides throughout the electrolyte. Because the polysulfide shuttle effect may result in loss of active material from the cathode, the ability to mitigate or reduce the polysulfide shuttle effect may increase battery performance.

[0048] In one embodiment, the micropores may have a pore size of about 1.5 nm selected to microconfine elemental sulfur (S8, or smaller chains / fragments of sulfur, e.g., in the form of S2, S4, or S6) pre-loaded in the cathode. The microconfinement of elemental sulfur in the cathode may allow the TBT or MBT complexes generated during battery cycling to inhibit the migration of long-chain polysulfides in the mesopores of the cathode. The accumulation of these long-chain polysulfides in the mesopores of the cathode may cause the cathode to volumetrically expand and retain the polysulfides, thereby reducing the polysulfide shuttle effect. Thus, lithium ions may continue to freely transport between the anode and cathode through the electrolyte without being blocked or impeded by polysulfides. The free movement of lithium ions throughout the electrolyte without interference from polysulfides may increase battery performance.

[0049] Additionally or alternatively, one or more protective layers, sheaths, films, and / or regions (collectively referred to herein as "protective layers") may be disposed on the anode and / or cathode and / or separator and in contact with the electrolyte. The protective layers may include materials capable of binding with polysulfides to impede polysulfide migration and prevent lithium dendrite formation. In some embodiments, the protective layers may be arranged in different configurations and used with any of the electrolyte chemistries and / or compositions disclosed herein, which in turn may provide full tunability of the battery.

[0050] In one embodiment, the carbonaceous material may be grafted with fluorinated polymer chains and deposited on one or more exposed surfaces of the anode. The fluorinated polymer chains may be crosslinked into a polymer network upon contact with lithium metal from the anode surface via the Wurtz reaction. The formation of the crosslinked polymer network may in turn inhibit the formation of lithium metal dendrites associated with the anode and may also produce lithium fluoride. The fluorinated polymer within the polymer network may participate in a chemical reaction during the battery operation cycle to produce lithium fluoride. The formation of lithium fluoride may require chemical bonding of lithium ions with fluorine ions from the electrolyte.

[0051] Additionally or alternatively, the polymer network may be combined with any of the electrolyte chemistries and / or compositions disclosed herein and / or a protective sheath disposed on the cathode. In one embodiment, the protective sheath may be formed by combining compounds containing difunctional or higher functional epoxy compounds and amine or amide compounds. Their intermolecular crosslinking will result in the formation of a 3D network with high chemical resistance to dissolution in the electrolyte. The composition may include, for example, trifunctional epoxy compounds and diamine oligomer-based compounds, which may react with each other to form a protective lattice that can bond to the polysulfides formed in the cathode and prevent their migration or diffusion into the electrolyte. Additionally, the protective lattice may diffuse through one or more cracks that may form in the cathode due to battery cycling. When the protective lattice is diffused across such cracks formed in the cathode, it may increase the structural integrity of the cathode and reduce potential rupture of the cathode associated with volume expansion.

[0052] In various embodiments, one or more of the disclosed battery components may be combined with a conformal coating material disposed on the edge or surface of the anode exposed to the electrolyte. In some embodiments, the conformal coating material may include a gradient interfacial layer that may replace the polymer network. In some aspects, the gradient interfacial layer may include a tin fluoride layer and a tin-lithium alloy region formed between the tin fluoride layer and the anode. The tin-lithium alloy region may form a uniformly distributed lithium fluoride layer between the anode and the tin fluoride layer in response to cycles of operation of the battery.

[0053] In various embodiments, lithium sulfur batteries using various aspects of the present disclosure may include electroactive materials extracted from external sources, such as subterranean and / or extraterrestrial sources. In such embodiments, the cathode may be prepared as a sulfur-free cathode that includes functional pores that may microscopically confine the electroactive materials within the cathode. In some embodiments, the cathode may include aggregates that include multiple carbonaceous particles connected together, and may include agglomerates that include multiple aggregates connected together. In an embodiment, the carbonaceous material used to form the cathode (and / or anode) may be tailored to define specific pore sizes, size ranges, and volumes. In some embodiments, the carbonaceous particles may include non-tri-zone particles with or without tri-zone particles. In other embodiments, the carbonaceous particles may not include tri-zone particles. Each tri-zone particle may include micropores, mesopores, and macropores, and both the non-tri-zone and tri-zone particles may each have a major dimension within the approximate range of 20 nm to 300 nm. Each of the carbonaceous particles may include carbonaceous fragments that are nested within one another and separated from immediately adjacent fragments by mesopores, hi some aspects, each of the carbonaceous particles may have a deformable periphery that changes shape and coalesces with adjacent material.

[0054] Some of the pores may be distributed throughout the deformable perimeter of the carbonaceous fragments and / or carbonaceous particles. In various embodiments, the mesopores may be interspersed throughout the aggregates, and the macropores may be interspersed throughout the aggregates. In one embodiment, each mesopore may have a major dimension between 3.3 nanometers (nm) and 19.3 nm, each aggregate may have a major dimension within the approximate range of 10 nm to 10 micrometers (μm), and each aggregate may have a major dimension within the approximate range of 0.1 μm to 1,000 μm. As further described below, a specific combination of pore sizes compatible with a unique electrolyte formulation and protective layer may be used to reduce or mitigate the deleterious effects of undesirable polysulfide diffusion, which may further increase battery performance.

[0055] FIG. 1 illustrates an exemplary battery 100 according to some embodiments. The battery 100 can be a lithium-sulfur electrochemical cell, a lithium-ion battery, or a lithium-sulfur battery. The battery 100 can have a body 105 including a first substrate 101, a second substrate 102, a cathode 110, an anode 120 positioned opposite the cathode 110, and an electrolyte 130. In some embodiments, the first substrate 101 can function as a current collector for the anode 120 and the second substrate 102 can function as a current collector for the cathode 110. The cathode 110 can include a first thin film 111 deposited on the second substrate 102 and can include a second thin film 112 deposited on the first thin film 111. In some implementations, the electrolyte 130 may be a liquid phase electrolyte including one or more additives such as lithium nitrate, tin fluoride, lithium iodide, lithium bis(oxalate)borate (LiBOB), cesium nitrate, cesium fluoride, ionic liquids, lithium fluoride, fluorinated ethers, TBT, MBT, DPT, etc. Suitable solvent packages for these exemplary additives may include various dilution ratios including 1:1:1 with 1,3-dioxolane (DOL), 1,2-dimethoxyethane (DME), tetraethylene glycol dimethyl ether (TEGDME), etc.

[0056] Although not shown for simplicity, in one embodiment, a lithium layer may be electrodeposited on one or more exposed carbon surfaces of the anode 120. In some cases, the lithium layer may include elemental lithium provided on the exposed surface of the anode 120 by ex situ electrodeposition of lithium. In some aspects, the lithium layer may include lithium, calcium, potassium, magnesium, sodium, and / or cesium, where each metal may be deposited ex situ on the exposed carbon surface of the anode 120. The lithium layer may provide available lithium ions for transport to and from the cathode 110 during the operating cycle of the battery 100. As a result, the battery 100 may not require an additional lithium source for operation. Instead of using lithium sulfide, elemental sulfur (S8) may be pre-packed within the various pores or porous networks formed within the cathode 110. During the operating cycle of the battery, the elemental sulfur may form lithium-sulfur complexes that can micro-trap (at least temporarily) greater amounts of lithium than conventional cathode designs. As a result, battery 100 may outperform batteries that rely on such conventional cathode designs.

[0057] In various implementations, the lithium layers may dissociate and / or separate into lithium ions 125 and electrons 174 during a discharge cycle of the battery 100. The lithium ions 125 may migrate from the anode 120 through the electrolyte 130 to the cathode 110 to their electrochemically favored locations within the cathode 110, as depicted in the example of FIG. 1. As the lithium ions 125 move through the electrolyte 130, the electrons 174 are released from the lithium ions 125 and become capable of carrying charge, thus conducting current between the anode 120 and the cathode 110. As a result, the electrons 174 may move through an external circuit from the anode 120 to the cathode 110 to power a load 172. The load 172 may be any suitable circuit, device, or system, such as, but not limited to, an incandescent light bulb, an appliance, or an electric vehicle (EV).

[0058] In some implementations, the battery 100 may include a solid electrolyte interphase layer 140. This solid electrolyte interphase layer 140 may, in some cases, be artificially formed on the anode 120 during the operating cycle of the battery 100. In such cases, the solid electrolyte interphase layer 140 may also be referred to as an artificial solid electrolyte interphase or A-SEI. The solid electrolyte interphase layer 140, when formed as an A-SEI, may include tin, manganese, molybdenum, and / or fluorine compounds. Specifically, the molybdenum may provide the cations and the fluorine compounds may provide the anions. The cations and anions may interact with each other to form tin fluoride, manganese fluoride, silicon nitride, lithium nitride, lithium nitrate, lithium phosphate, manganese oxide, lithium lanthanum zirconium oxide (LLZO, Li7La3Zr2O 12 In some cases, the A-SEI may form in response to exposure of lithium ions 125 to an electrolyte 130, which may include a solvent-based solution containing tin and / or fluorine.

[0059] In various embodiments, the solid electrolyte interphase layer 140 may be artificially provided on the anode 120 prior to activation of the battery 100. Alternatively, in one embodiment, the solid electrolyte interphase layer 140 may naturally form on the anode 120, for example, during an operating cycle of the battery 100. In some cases, the solid electrolyte interphase layer 140 may include an outer layer of a shielding material that may be applied to the anode 120 as a microcoating material. In this manner, forming the solid electrolyte interphase layer 140 on a portion of the anode 120 facing the electrolyte 130 may result in an electrochemical reduction of the electrolyte 130, which in turn may reduce uncontrolled decomposition of the anode 120.

[0060] In some implementations, as shown in FIG. 1, for example, the battery 100 can include a barrier layer 142 that protects the sides of the solid electrolyte interphase layer 140. The barrier layer 142 can include a mechanical strength enhancing material 144 coated and / or deposited on the anode 120. In some aspects, the mechanical strength enhancing material 144 can provide structural support for the battery 100, prevent lithium dendrite formation from the anode 120, and / or prevent lithium dendrite protrusion throughout the battery 100. In some implementations, the mechanical strength enhancing material 144 can be formed as a protective coating on the anode 120 and can include one or more of carbon allotropes, carbon nano-onions (CNO), nanotubes (CNT), reduced graphene oxide, graphene oxide (GO), and / or carbon nanodiamonds. In some cases, the solid electrolyte interphase layer 140 can be formed within the mechanical strength enhancing material 144.

[0061] In some implementations, the first substrate 101 and / or the second substrate 102 may be solid copper metal foils, which may affect the energy capacity, rate capability, life, and long-term stability of the battery 100. For example, to control the energy capacity and other performance attributes of the battery 100, the first substrate 101 and / or the second substrate 102 may be subjected to etching, carbon coating, or other suitable treatments to increase the electrochemical stability and / or electrical conductivity of the battery 100. In other implementations, the first substrate 101 and / or the second substrate 102 may include or be formed from a selection of aluminum, copper, nickel, titanium, stainless steel, and / or carbonaceous materials depending on the end use application and / or performance requirements of the battery 100. For example, the first substrate 101 and / or the second substrate 102 may be separately tuned or adapted to allow the battery 100 to meet one or more performance requirements or metrics.

[0062] In some embodiments, the first substrate 101 and / or the second substrate 102 may be at least partially foam-based or foam-derived and may be selected from any one or more of metal foam, metal foil, metal sieve, porous metal, or sheet-based three-dimensional (3D) structures. In other embodiments, the first substrate 101 and / or the second substrate 102 may be a metal fiber mat, a metal nanowire mat, a conductive polymer nanofiber mat, a conductive polymer foam, a conductive polymer coated fiber foam, a carbon foam, a graphite foam, or a carbon aerogel. In some other embodiments, the first substrate 101 and / or the second substrate 102 may be a carbon xerogel, a graphene foam, a graphene oxide foam, a reduced graphene oxide foam, a carbon fiber foam, a graphite fiber foam, an exfoliated graphite foam, or any combination thereof.

[0063] 2 illustrates another exemplary battery 200, according to some embodiments. Battery 200 can be similar in many respects to battery 100 of FIG. 1, and thus the description of similar elements will not be repeated herein. In some embodiments, battery 200 can be a lithium metal battery and / or a next generation battery, such as a solid-state battery featuring a solid electrolyte. In other embodiments, battery 200 can include a liquid phase electrolyte 230 and thus can include any of the protective layer and / or electrolyte chemistries or compositions disclosed herein.

[0064] In some other implementations, the electrolyte 230 may be solid or substantially solid. For example, in some cases, the electrolyte 230 may begin in a gel phase and then subsequently solidify upon activation of the battery 200. The battery 200 may reduce the specific capacity or energy loss associated with the polysulfide shuttle effect by replacing a conventional carbon scaffold anode with a single solid metallic layer of lithium deposited in the initially empty cavities. For example, the anode 120 of the battery 100 of FIG. 1 may include a carbon scaffold, while the anode 220 of the battery 200 of FIG. 2 may be a lithium metal anode lacking any carbon material. In one implementation, the lithium metal anode may be formed as a single solid lithium metal layer and may be referred to as a "lithium metal anode."

[0065] The energy density gains associated with various cathode materials may be based on whether lithium metal is pre-packed in the cathode 210 and / or prevalent in the electrolyte 230. Either the cathode 210 and / or the electrolyte 230 may provide lithium available for lithiation of the anode 220. For example, a battery with a high-capacity cathode may require a thicker or more energetically dense anode to supply the increased amount of lithium required for use with the high-capacity cathode. In some implementations, the anode 220 may include a scaffolded carbonaceous structure that may be incrementally loaded with lithium deposited therein. These carbonaceous structures may be capable of holding a greater amount of lithium in the anode 220 compared to conventional graphite anodes, which may be limited to hosting lithium alone intercalated between alternating graphene layers or may be electroplated with lithium. For example, conventional graphite anodes may use six carbon atoms to hold a single lithium atom. In contrast, by using a pure lithium metal anode, such as anode 220, the batteries disclosed herein may reduce or even eliminate the use of carbon in anode 220, which may allow anode 220 to store greater amounts of lithium in a relatively smaller volume than conventional graphite anodes. In this manner, the energy density of battery 200 may be greater than conventional batteries of similar size.

[0066] Lithium metal anodes, such as anode 220, can be prepared to function with a solid electrolyte designed to inhibit the formation and growth of lithium dendrites from the anode. In some embodiments, separator 250 can further limit the formation and growth of dendrites. Separator 250 can have an ionic conductivity similar to electrolyte 130 of FIG. 1, but still reduce the formation of lithium dendrites. In some embodiments, separator 250 can be formed from a ceramic-containing material, and as a result, cannot chemically bond with metallic lithium. As a result, separator 250 can be used to control lithium ion transport through pores dispersed across separator 250 while simultaneously preventing short circuits by impeding the flow or passage of electrons through electrolyte 230.

[0067] In one embodiment, void space (not shown for simplicity) may be formed in the battery 200 at or near the anode 220. An operating cycle of the battery 200 in this embodiment may result in the deposition of lithium in the void space. As a result, the void space may become or convert to a lithium-containing region (such as a solid lithium metal layer) and function as the anode 220. In some aspects, the void space may be created in response to a chemical reaction between a metal-containing, electrically inactive component and a graphene-containing component of the battery 200. Specifically, the graphene-containing component may chemically react with the lithium deposited in the void space during an operating cycle to produce lithiated graphite (LiC6) or patterned lithium metal. The lithiated graphite produced by the chemical reaction may produce or induce the production and / or release of lithium ions and / or electrons that may be used to carry charge or “current” between the anode 220 and the cathode 210 during a discharge cycle of the battery 200.

[0068] And in embodiments where the anode 220 is a solid lithium metal layer, the battery 200 may be able to retain more electroactive material and / or lithium per unit volume (compared to batteries with scaffolded carbon and / or intercalated lithiated graphite anodes). In some aspects, the anode 220, when prepared as a solid lithium metal layer, may result in the battery 200 having a higher energy density and / or specific capacity than batteries with scaffolded carbon and / or intercalated lithiated graphite anodes, thereby resulting in longer discharge cycle times and additional power output per unit time. In cases where a solid electrolyte is not desired or optimal, the electrolyte 230 of the battery 200 of FIG. 2 may be prepared using any of the liquid phase electrolyte chemistries and / or compositions disclosed herein. Additionally or alternatively, the electrolyte 230 may include lithium and / or lithium ions available for cyclical transport from the anode 220 to the cathode 210 and vice versa during discharge and charge cycles, respectively.

[0069] To reduce migration of polysulfides 282 generated in the electrolyte 230 from elemental sulfur 281 preloaded in the cathode 210, the battery 200 may include one or more inherent polysulfide retention features. For example, assuming polysulfides are soluble in the electrolyte 230, some polysulfides may be expected to drift or migrate from the cathode 210 toward the anode 220 due to differences in electrochemical potentials, chemical gradients, and / or other phenomena. Migration of polysulfides 282, particularly long-chain polysulfides, may impede the transport of lithium ions from the anode 220 to the cathode 210, which in turn may reduce the number of electrons available to generate a current that can power a load 272, such as an electric vehicle (EV). In some embodiments, lithium ions 225 can be transported along a transport path from one or more starting locations 226 in or near the anode 220 to one or more ending locations 227 in or near the cathode 210, as depicted in the example of FIG. 2.

[0070] In some implementations, the polymer network 285 may be disposed on the anode 220 to reduce uncontrolled migration of the polysulfide 282 from the anode 220 to the cathode 210. The polymer network 285 may include one or more layers of carbonaceous material grafted with fluorinated polymer chains crosslinked to each other via a Wurtz reaction upon exposure to the lithium anode surface. The carbonaceous material in the polymer network 285 may include, but is not limited to, graphene, few-layer graphene, FLG, multilayer graphene, and MLG, and may be chemically grafted with fluorinated polymer chains containing carbon-fluorine (CF) bonds. These CF bonds may chemically react with lithium metal from the surface of the anode 220 to generate highly ionic carbon-lithium bonds (C-Li). These formed C-Li bonds may then react with the CF bonds of the polymer chains to form new carbon-carbon bonds that can crosslink (and thereby form) the polymer chains into a polymer network and generate lithium fluoride (LiF).

[0071] The resulting lithium fluoride may be distributed uniformly along the entire circumference of the polymer network 285 so that lithium ions are consumed uniformly to produce an interfacial layer 283 that may form or otherwise contain lithium fluoride during battery cycling. The interfacial layer 283 may extend along the surface or portion of the anode 220 that faces the cathode 210, as shown in FIG. 2. As a result, the lithium ions 225 are less likely to bond and / or react with each other and more likely to bond and / or react with fluorine atoms made available by the fluorinated polymer chains in the polymer network 285. The resulting reduction of lithium-lithium chemical reactions reduces lithium-lithium bonds that are responsible for the formation of undesirable lithium metal dendrites. Additionally, in some embodiments, the polymer network 285 may replace a naturally or artificially created interphase layer 240 between the anode 220 and the electrolyte 230.

[0072] In one embodiment, the interfacial layer 283 of the polymer network 285 is in contact with the anode 220, and the protective layer 284 is disposed on top of the interfacial layer 283 (e.g., between the interfacial layer 283 and the interphase layer 240). In some aspects, the interfacial layer 283 and the protective layer 284 may collectively define a gradient of crosslinked fluorinated polymer chains of varying degrees of density, for example, as described with reference to FIG.

[0073] In some other embodiments, the battery 200 may include a protective grid 280 disposed on the cathode 210. The protective grid 280 may include a trifunctional epoxy compound and a diamine oligomer-based compound that may chemically react with each other to generate nitrogen and oxygen atoms. The nitrogen and oxygen atoms made available by the protective grid 280 may bond with the polysulfide 282, thereby trapping the polysulfide 282 within the cathode 210 and / or the protective grid 280. Either the cathode 210 and / or the protective grid 280 may include carbon-carbon bonds and / or regions that may bend and / or expand in volume during the operating cycle of the battery 200, which may trap the polysulfide 282 generated during the operating cycle in the cathode 210.

[0074] Electrolyte 130 of FIG. 1 and electrolyte 230 of FIG. 2 may be prepared according to one or more recipes disclosed herein. For example, the ternary solvent package used in electrolyte 130 and / or electrolyte 230 may include DME, DOL, and TEGDME. In one embodiment, a solvent mixture may be prepared by mixing 5800 μL of DME, 2900 μL of DOL, and 1300 μL of TEGDME and stirring at room temperature (77° F. or 25° C.). Next, 0.01 moles (2,850.75 mg) of LiTFSI may be weighed out. Then, 0.01 moles of LiTFSI may be dissolved in the solvent mixture by stirring at room temperature to prepare about 10 mL of 1 M LiTFSI in DME:DOL:TEGDME (vol:vol:vol 1:4:1). Finally, about 223 mg of LiNO3 can be added to 10 mL of solution to produce 10 mL of 1 M LiTFSI in DME:DOL:TEGDME (vol:vol:vol = 58:29:13) with about 2 wt% LiNO3.

[0075] Additionally or alternatively, the ternary solvent package used in electrolyte 130 and / or electrolyte 230 may include DME, DOL, TEGDME, and TBT or MBT. A solvent mixture may be prepared by mixing 2,000 μL of DME, 8,000 μL of DOL, and 2,000 μL of TEGDME and stirring at room temperature (68° F. or 25° C.). 0.01 moles (2,850.75 mg) of LiTFSI may then be weighed and dissolved in about 3 mL of the solvent mixture by stirring at room temperature. The dissolved LiTFSI and the added solvent mixture (about 8,056 mg) may then be mixed in a 10 mL volumetric flask to produce about 1 M LiTFSI in DME:DOL:TEGDME (vol:vol:vol 1:4:1). Finally, about 0.05 mmol (about 12.5 mg) of TBT or MBT can be added to the 10 mL solution to produce 10 mL of a 5 M TBT or MBT solution.

[0076] FIG. 3 illustrates an exemplary electrode 300, according to some embodiments. In various embodiments, the electrode 300 can be an example of the cathode 110 and / or anode 120 of the battery 100 of FIG. 1. In some other embodiments, the electrode 300 can be an example of the cathode 210 of the battery 200 of FIG. 2. When the electrode 300 is implemented as a cathode (such as the cathode 110 of the battery 100 of FIG. 1), the electrode 300 can temporarily trap electroactive materials, such as elemental sulfur, in a microscopic manner, thereby reducing the amount of sulfur available to react with lithium to form polysulfides. In some embodiments, the electrode 300 can provide an excess supply of lithium and / or lithium ions that can compensate for the first cycle operational losses associated with lithium-based batteries.

[0077] In some implementations, the electrode 300 may be porous and may readily accept a liquid-phase electrolyte, such as the electrolyte 130 of FIG. 1. Electroactive species, such as lithium ions 125, suspended in the electrolyte 130 may chemically react with elemental sulfur pre-packed in the pores of the electrode 300 to produce polysulfides, which in turn may be trapped in the electrode 300 during battery cycling. In some embodiments, the electrode 300 may volumetrically expand along one or more inflection points to hold additional amounts of polysulfides created during battery cycling. By trapping polysulfides within the electrode 300, embodiments of the subject matter disclosed herein may allow the lithium ions 125 to flow freely from the anode 120 through the electrolyte 130 to the cathode 110 (e.g., without being impeded by polysulfides) during a discharge cycle of the battery 100. For example, when lithium ions 125 reach the cathode 110 and react with elemental sulfur contained within or associated with the cathode 110, the sulfur forms lithium polysulfides (LiS) of decreasing chain length according to the sequence Li2S8 → Li2S6 → Li2S4 → Li2S2 → Li2S. x ) where 2≦x≦8. Higher polysulfides can be soluble in various types of solvents and / or electrolytes, thereby impeding lithium ion transport necessary for healthy battery operation. Retention of such higher polysulfides by electrode 300 can allow lithium ions 125 to flow more freely through electrolyte 130, which in turn can increase the number of electrons available to carry charge from anode 120 to cathode 110.

[0078] The electrode 300 may include a body 301 defined by a width 305 and may include a first thin film 310 and a second thin film 320. The first thin film 310 may include a plurality of first aggregates 312 that are coupled together to form a first porous structure 316 of the electrode 300. In some cases, the first porous structure 316 may have a conductivity of about 0-500 S / m. In other cases, the first conductivity may be about 500-1,000 S / m. In some other cases, the first conductivity may be greater than 1,000 S / m. In some embodiments, the first aggregates 312 may include carbon nanotubes (CNTs), carbon nano-onions (CNOs), flaky graphene, wrinkled graphene, graphene grown on carbonaceous materials, and / or graphene grown on graphene.

[0079] In some implementations, the first assembly 312 can be decorated with a plurality of first nanoparticles 314. In some cases, the first nanoparticles 314 can include metals such as tin, lithium alloys, iron, silver, cobalt, semiconductor materials, and / or silicon, and / or the like. In some aspects, CNTs can be used as a support material for the first nanoparticles 314 due to their large exposed surface area per unit volume and their ability to provide stability at relatively high temperatures (e.g., above 77° F. or 25° C.). For example, the first nanoparticles 314 can be immobilized (by decoration, deposition, surface modification, etc.) on the exposed surfaces of the CNTs and / or other carbonaceous materials. The first nanoparticles 314 can react with chemically available carbon on the exposed surfaces of the CNTs and / or other carbonaceous materials.

[0080] The second thin film 320 can include a plurality of second aggregates 322 that are connected together to form a second porous structure 326. In some cases, the electrical conductivity of the first porous structure 316 and / or the second porous structure 326 can be between about 0 S / m and 250 S / m. In cases where the first porous structure 316 includes a higher concentration of aggregates than the second porous structure 326, the first porous structure 316 can have a higher electrical conductivity than the second porous structure 326. In one embodiment, the first electrical conductivity can be between about 250 S / m and 500 S / m, whereas the second electrical conductivity can be between about 100 S / m and 250 S / m. In another embodiment, the second electrical conductivity can be between about 250 S / m and 500 S / m. In yet another embodiment, the second electrical conductivity can be greater than 500 S / m. In some embodiments, the second assemblies 322 can include CNTs, CNO, exfoliated graphene, wrinkled graphene, graphene grown on carbonaceous materials, and / or graphene grown on graphene.

[0081] The second assemblies 322 can be decorated with a plurality of second nanoparticles 324. In some implementations, the second nanoparticles 324 can include metals such as iron, silver, cobalt, semiconductor materials, and / or silicon, and / or the like. In some cases, the CNTs can also be used as a support material for the second nanoparticles 324. For example, the second nanoparticles 324 can be immobilized (by decoration, deposition, surface modification, etc.) on exposed surfaces of the CNTs and / or other carbonaceous materials. The second nanoparticles 324 can react with chemically available carbon on exposed surfaces of the CNTs and / or other carbonaceous materials.

[0082] In some embodiments, the first thin film 310 and / or the second thin film 320 (as well as any additional thin films disposed on their respective immediately preceding thin films) may be created as layers or regions of materials and / or aggregates. The layers or regions may range in thickness from a tenth of a nanometer to several microns, e.g., about 0-5 microns, about 5-10 microns, about 10-15 microns, or greater than 15 microns. Any of the materials and / or aggregates disclosed herein, e.g., CNO, may be incorporated into the first thin film 310 and / or the second thin film 320 to provide the thickness levels described.

[0083] In some embodiments, the first thin film 310 may be deposited on the second substrate 102 of FIG. 1 by multiple layers grown alternatingly via techniques such as chemical deposition, physical deposition, or Frank-van der Merwe growth, Stranski-Krastonov growth, Volmer-Weber growth, etc. In other embodiments, the first thin film 310 may be deposited on the second substrate 102 by epitaxy or other suitable film deposition process involving epitaxial growth of a material. The second thin film 320 and / or subsequent thin films may be deposited on their respective immediately preceding thin films in a manner similar to that described with reference to the first thin film 310.

[0084] In various embodiments, each of the first aggregates 312 and / or the second aggregates 322 can be a relatively large particle formed by many relatively small particles bonded or fused together. As a result, the external surface area of ​​the relatively large particle can be significantly less than the combined surface area of ​​the many relatively small particles. The forces holding the aggregates together can be, for example, covalent bonds, ionic bonds, or other types of chemical bonds that cause sintering or complex physical entanglement of the original primary particles.

[0085] As discussed above, the first aggregates 312 may connect together to form the first porous structure 316, and the second aggregates 322 may connect together to form the second porous structure 326. The electrical conductivity of the first porous structure 316 may be based on the concentration level of the first aggregates 312 within the first porous structure 316, and the electrical conductivity of the second porous structure 326 may be based on the concentration level of the second aggregates 322 within the second porous structure 326. In some embodiments, the concentration level of the first aggregates 312 may cause the first porous structure 316 to have a relatively high electrical conductivity, and the concentration level of the second aggregates 322 may cause the second porous structure 326 to have a relatively low electrical conductivity (such that the first porous structure 316 has a greater electrical conductivity than the second porous structure 326). The resulting difference in the conductivity of the first porous structure 316 and the second porous structure 326 may create a conductivity gradient between the electrodes 300. In some implementations, the conductivity gradient may be used to control or regulate electrical conduction throughout one or more operations of the electrodes 300 and / or the battery 100 of FIG.

[0086] As used herein, the relatively small source particles may be referred to as "primary particles" and the relatively larger aggregates formed by the primary particles may be referred to as "secondary particles." As shown in FIG. 1, FIG. 8-10, and elsewhere throughout this disclosure, the primary particles may be or may include multiple graphene sheets, layers, regions, and / or nanoplatelets fused and / or connected together. Thus, in some cases, carbon nano-onions (CNO), carbon nanotubes (CNT), and / or other tunable carbon materials may be used to form the primary particles. In some embodiments, some aggregates may have major dimensions (such as length, width, and / or diameter) of about 500 nm to 25 μm. Also, some aggregates may include an aggregate of smaller natively formed primary particles, referred to as "native particles," of graphene sheets, layers, regions, and / or nanoplatelets connected together at orthogonal angles. In some cases, these native particles may each have a respective dimension of about 50 nm to 250 nm.

[0087] The surface area and / or porosity of these native particles may be imparted by secondary processes such as carbon activation by thermal, plasma, or combined thermal plasma processes using one or more of steam, hydrogen gas, carbon dioxide, oxygen, ozone, KOH, ZnCl2, H3PO4, or other similar chemicals, alone or in combination. In some embodiments, the first porous structure 316 and / or the second porous structure 326 may be generated from carbonaceous gas species that can be controlled by gas-solid reactions under non-equilibrium conditions. Generating the first porous structure 316 and / or the second porous structure 326 in this manner may involve recombination of carbon-containing radicals formed from controlled cooling of carbon-containing plasma species (which may be generated by excitation or compression of feedstock carbon-containing gas species and / or plasma species in a suitable chemical reactor).

[0088] In some embodiments, the first assemblies 312 and / or the second assemblies 322 may have a ratio of carbon to other elements, excluding hydrogen, within each respective assemblies of greater than 99%. In some cases, the median size of each assemblies may be between about 0.1 microns and 50 microns. The first assemblies 312 and / or the second assemblies 322 may also include metal-organic frameworks (MOFs).

[0089] In some implementations, the first porous structure 316 and the second porous structure 326 can collectively define a host structure 328, for example, as shown in FIG. 3. In some cases, the host structure 328 can be based on a carbon scaffold and / or can include decorated carbon, for example, as shown in FIG. 8. The host structure 328 can provide structural definition to the electrode 300. In some cases, the host structure 328 can be fabricated as a positive electrode and used in the cathode 110 of FIG. 1. In other implementations, the host structure 328 can be fabricated as a negative electrode and used in the anode 120 of FIG. 1. In some other implementations, the host structure 328 can include pores having different sizes, such as micropores, mesopores, and / or macropores as defined by IUPAC. In some cases, at least some of the micropores may have a width of about 1.5 nm, which may be large enough to allow sulfur to be pre-packed into the electrode 300, yet small enough to confine polysulfides within the electrode 300.

[0090] When provided within the electrode 300, the host structure 328 may include microporous, mesoporous, and / or macroporous pathways created by the exposed surfaces and / or contours of the first porous structure 316 and / or the second porous structure 326, as shown in FIG. 3. These pathways may allow the host structure 328 to receive an electrolyte, for example, by transporting lithium ions toward the cathode 110 of the battery 100. Specifically, the electrolyte 130 may permeate the various porous pathways of the host structure 328 and be uniformly distributed throughout the electrode 300 and / or other portions of the battery 100. The permeation of the electrolyte 130 into such regions of the host structure 328 may allow lithium ions 125 migrating from the anode 120 toward the cathode 110 to react with elemental sulfur associated with the cathode 110 to form lithium-sulfur complexes. As a result, elemental sulfur can hold additional amounts of lithium ions that would otherwise be achievable using non-sulfur chemistries such as lithium cobalt oxide (LiCoO) or other lithium-ion cells.

[0091] In some embodiments, each of the first porous structure 316 and / or the second porous structure 326 may have a porosity based on one or more of a thermal process, a plasma process, or a hybrid thermal plasma process using one or more of steam, hydrogen gas, carbon dioxide, oxygen, ozone, KOH, ZnCl2, H3PO4, or other similar chemicals, alone or in combination. For example, in one embodiment, the macroporous pathways may have a major dimension greater than 50 nm, the mesoporous pathways may have a major dimension between about 20 nm and 50 nm, and the microporous pathways may have a major dimension less than 4 nm. In this manner, the macroporous pathways and the mesoporous pathways may provide tunable conduits for transporting lithium ions 125, and the microporous pathways may confine the active material within the electrode 300.

[0092] In some implementations, the electrode 300 may include one or more additional thin films (not shown for simplicity). Each of the one or more additional thin films may include separate aggregates interconnected with each other across different thin films, at least some of which have different concentration levels of aggregates. As a result, the concentration level of any thin film may be varied (such as by gradation) to achieve a particular electrical resistance (or conductance) value. For example, in some implementations, the concentration level of the aggregates may be gradually decreased between the first thin film 310 and the last thin film (such as in the direction 195 depicted in FIG. 1 ), and / or the individual thin films may have an average thickness of about 10 microns to about 200 microns. Additionally or alternatively, the first thin film 310 may have a relatively high concentration of carbonaceous aggregates and the second thin film 320 may have a relatively low concentration of carbonaceous aggregates. In some embodiments, a relatively high concentration of aggregates corresponds to a relatively low electrical resistance, and a relatively low concentration of aggregates corresponds to a relatively high electrical resistance.

[0093] The host structure 328 may be prepared with a plurality of active sites on the exposed surfaces of the first and / or second assemblies 312 and / or 322. These active sites, as well as the exposed surfaces of the first and / or second assemblies 312 and / or 322, may facilitate ex situ electrodeposition prior to assembly of the electrode 300 into the battery 100. Electroplating is a process that may create a lithium layer 330 (including lithium on the exposed surfaces of the host structure 328) via chemical reduction of metal cations by application and / or modulation of an electric current. In an embodiment in which the electrode 300 serves as the anode 120 of the battery 100 of FIG. 1, the host structure 328 may be electroplated such that the lithium layer 330 has a thickness of about 1 to 5 micrometers (μm), 5 μm to 20 μm, or greater than 20 μm. In some cases, ex situ electrodeposition may be performed at a location separate from the battery 100 prior to assembly of the battery 100.

[0094] In various embodiments, the excess lithium provided by lithium layer 330 may increase the number of lithium ions 125 available for transport within battery 100, thereby increasing the storage capacity, life, and performance of battery 100 (compared to conventional lithium-ion and / or lithium-sulfur batteries).

[0095] In some embodiments, the lithium layer 330 may produce lithium intercalated graphite (LiC6) and / or lithiated graphite upon chemical reaction with the first masses 312 and / or the second masses 322. The lithium intercalated between the alternating graphene layers may migrate or be transported within the electrode 300 due to differences in electrochemical gradients during the operating cycle of the battery 100, which in turn may increase the energy storage and power delivery of the battery 100.

[0096] 4 shows a schematic diagram of a portion of an exemplary battery 400 including a protective grid 402, according to some embodiments. In some embodiments, the protective grid 402 may be disposed over the anode 220 of the battery 200. In other embodiments, the protective grid 402 may be disposed over the cathode 210 of the battery 200 (or other suitable battery). In some aspects, the protective grid 402 may be an example of the protective grid 280 of FIG. 2. The protective grid 402 may function with many of the components (e.g., the anode, cathode, associated current collectors, carbonaceous material, electrolyte, and separator) in a manner similar to the battery 100 of FIG. 1 and / or the battery 200 of FIG. 2.

[0097] The protective lattice 402 may include trifunctional epoxy compounds and diamine oligomer-based compounds that can chemically react with each other to generate a 3D lattice structure (e.g., as shown in Figures 6 and 8). In some embodiments, the protective lattice 402 may prevent polysulfide migration within the battery 400 by providing nitrogen and oxygen atoms that can chemically bond with lithium present within the polysulfide, thereby hindering polysulfide migration through the electrolyte 130. As a result, lithium ions 125 may be more freely transported from the anode 120 and cathode 110 of Figure 1, thereby increasing a measure of battery performance.

[0098] Cyclic use of the cathode 110 can cause the formation of cracks 404 that extend at least partially into the cathode 110. In one embodiment, the protective grid 402 can be dispersed throughout the cracks 404, thereby reducing the susceptibility of the cathode 110 to rupture during volumetric expansion of the cathode 110 caused by retention of polysulfides within the cathode 110 during cyclic use. In one embodiment, the protective grid 402 of FIG. 4 can have a crosslinked 3D structure based on a chemical reaction between a di- or higher-functional epoxy compound and an amine or amide compound. For example, the difunctional or higher functionality epoxy compound can be trimethylolpropane triglycidyl ether (TMPTE), tris(4-hydroxyphenyl)methane triglycidyl ether, or tris(2,3-epoxypropyl)isocyanurate, and the difunctional or higher functionality amine compound can be dihydrazide sulfur oxide (DHSO), or one of the polyether amines, such as JEFFAMINE® D-230, which features repeating oxypropylene units in the backbone.

[0099] In various embodiments, the compounds may be combined and reacted with one another in any number of amounts, total amounts, ratios, and / or compositions to achieve different performance capabilities associated with binding with polysulfides generated during operation of the battery 400. For example, in one embodiment, 113 mg of TMPTE and 134 mg of JEFFAMINE® D-230 polyetheramine may be mixed together and diluted with 1 mL to 10 mL of tetrahydrofuran (THF) or any other solvent. Additional amounts of TMPTE and / or JEFFAMINE may be mixed together and diluted in THF or any other solvent in an exemplary ratio of 113 mg of TMPTE for every 134 mg of JEFFAMINE® D-230 polyetheramine. For this embodiment, proof-of-concept (POC) data indicates that the guard grid 402 of FIG. 4 has a defined weight of about 2.6% of the cathode 110 of FIG. 1 or the cathode 210 of FIG. 2. In other embodiments, the guard grid 402 may have a weight of about 2% to 21% by weight of the cathode 110 and / or cathode 210, where an increase in impedance of the cathode 110 and / or cathode 210 may be expected at weight levels of about 10% or greater by weight of the guard grid 402.

[0100] In various embodiments, the protective grid 402 may be manufactured based on the molar and / or molar ratio of -NH2 groups and epoxy groups, and may further accommodate various forms of crosslinking between difunctional or higher functional epoxies and amine or amide compounds. In some aspects, such forms of crosslinking may include a fully crosslinked stage, for example, where one -NH2 group is chemically bonded to two epoxy groups, and may further extend to a configuration including one -NH2 group chemically bonded to only one epoxy group. Still further, in one or more embodiments, a mixture containing an excess amount (above the ratios presented herein) of -NH2 groups may be prepared to provide additional polysulfide binding capacity to the protective grid 402.

[0101] In some other embodiments, the guard grid 402 may be prepared by mixing 201 g of TMPTE with 109 g to 283 g of JEFFAMINE® D-230 polyetheramine. The resulting mixture may then be diluted with 1 L to 20 L of a selected solvent, such as THF. The resulting diluted solution may be deposited and / or otherwise disposed on the cathode 110 to achieve a crosslinker content of 1% to 10% by weight. Additional TMPTE and / or JEFFAMINE may be mixed together and diluted in THF or another suitable solvent in an exemplary ratio of 201 g of TMPTE for every 109 g to 283 g of JEFFAMINE® D-230 polyetheramine.

[0102] In yet another embodiment, the guard grid 402 may be prepared by mixing 201 g of TMPTE with 74 g to 278 g of DHSO. The resulting mixture may then be diluted with 1 L to 20 L of a selected solvent, such as THF. The resulting diluted solution may be deposited and / or otherwise disposed on the cathode 110 to achieve a crosslinker content of 1% to 10% by weight. Additional TMPTE and / or JEFFAMINE may be mixed together and diluted in THF or another suitable solvent in an exemplary ratio of 201 g of TMPTE for every 201 g to 278 g of JEFFAMINE® D-230 polyetheramine.

[0103] In one embodiment, a difunctional or higher functional epoxy compound can be chemically reacted with a difunctional or higher functional amine compound to produce a 3D crosslinked morphology of the protective grid 402, which can include both functional epoxy compounds and amine-containing molecules. In some embodiments, the protective grid 402 can have a thickness of about 1 nm to 5 μm when deposited on the cathode 110 of FIG. 1 or the cathode 210 of FIG. 2.

[0104] In some embodiments, the protective grid 402 may increase the structural integrity of the cathode 110 or cathode 210, reduce surface roughness, and retain polysulfides within the cathode. For example, in one embodiment, the protective grid 402 may act as a sheath on the exposed surface of the cathode and bind with the polysulfides to prevent their migration and diffusion into the electrolyte 130. In this manner, aspects of the subject matter disclosed herein may prevent (or at least reduce) battery capacity fade by suppressing the polysulfide shuttle effect. In some embodiments, the protective grid 402 may also fill cracks 404 formed in the cathode of FIG. 4 to improve the integrity of the cathode coating material. In various embodiments, the protective grid 402 can be prepared by a drop casting process in the presence of a solvent, and the resulting solution can penetrate into the cracks 404 of the cathode 110 and bond with the polysulfides in the cathode 110 to prevent their migration and / or diffusion throughout the electrolyte 130.

[0105] In various implementations, the protective grid 402 can provide nitrogen and / or oxygen atoms that can chemically bond with lithium in polysulfides generated during the operating battery cycle. In one example, the polysulfides can bond with available nitrogen atoms provided, for example, by DHSO. In another example, the polysulfides can bond with available oxygen atoms provided, for example, by DHSO. In yet another example, the polysulfides can bond with other available oxygen atoms.

[0106] In some other embodiments, the recipe described above can be modified by replacing TMPTE with tris(4-hydroxyphenyl)methane triglycidyl ether 910 and / or tris(2,3-epoxypropyl)isocyanurate. In various embodiments, the diamine oligomer-based compound can be (or can include) JEFFAMINE® D-230, which is typically based on either propylene oxide (PO), ethylene oxide (EO), or mixed PO / EO structures, or other polyetheramines containing a polyether backbone, such as JEFFAMINE® D-400, JEFFAMINE® T-403. The protective grid 402 can also include various concentration levels of inert molecules, such as polyethylene glycol chains of various lengths, which can make it possible to fine-tune the mechanical properties of the protective grid, the chemical bonding of various atoms to the lithium present in the polysulfide.

[0107] 5 shows a schematic diagram of an anode structure 500 including a tin fluoride (SnF2) layer according to some embodiments. Specifically, the diagram depicts a cutaway schematic diagram of the anode structure 500 in which all of the components associated with the first region A have identical counterparts in the second region B, where the first and second regions A and B have opposite orientations around the current collector 520. As such, the following description with reference to the components of the first region A is equally applicable to the components of the second region B. In some embodiments, the anode 502 can be an example of the anode 120 of FIG. 1 and / or the anode 220 of FIG. 2.

[0108] As discussed, lithium-sulfur batteries, such as battery 100 of FIG. 1 and battery 200 of FIG. 2, operate as conversion chemistry type electrochemical cells in that sulfur preloaded in the cathode can rapidly dissolve in the electrolyte before and during operation. Lithium, which may be provided by the lithiated anode and / or may be prevalent in the electrolyte, dissociates into lithium ions (Li+) suitable for transport from the anode through the electrolyte to the cathode. As described with reference to FIG. 1, the production of lithium ions is associated with a corresponding release of electrons, which can flow through an external circuit to power a load. However, once the lithium dissociates into lithium ions and electrons, some of the lithium ions may react undesirably with the polysulfides produced at the cathode and thus may no longer be available to generate an output current or voltage. This consumption of lithium ions by the polysulfides reduces the overall capacity of the host cell or battery and may also promote corrosion of the anode, which may result in cell failure.

[0109] In some embodiments, the protective layer 516 may be provided as a passivation coating material that may reduce the chemical reactivity of the anode 502 during cell assembly or formation. In some aspects, the protective layer 516 may be permeable to lithium ions while simultaneously protecting the anode 502 from corrosion caused by chemical reactions between the lithium ions and polysulfides. In other embodiments, the protective layer 516 may be an artificial solid electrolyte interphase (A-SEI) that may replace the natural SEI and / or other types of conventional A-SEI. In various embodiments, the protective layer 516 may be deposited as a liner on top of one or more films disposed on the anode 502. In some aspects, the protective layer 516 may be a self-generated layer that forms during electrochemical reactions associated with the operation cycle of the battery. In some aspects, the protective layer 516 may have a thickness that is less than 5 microns. In other aspects, the protective layer 516 may have a thickness between 0.1 microns and 1.0 microns.

[0110] In various embodiments, one or more engineering additives can be provided in the battery's electrolyte that can facilitate the formation and / or deposition of protective layer 516 on anode 502. In other embodiments, the engineering additive can be an active component of protective layer 516. In some aspects, protective layer 516 can provide tin ions and / or fluoride ions that can prevent unwanted lithium growth from first edge 5181 and second edge 5182 of the anode.

[0111] The gradient layer 514 may be formed and / or deposited on the anode 502 beneath the protective layer 516. In various implementations, the gradient layer 514 may prevent lithium contained within or associated with the anode 502 from participating in undesirable chemical interactions and / or reactions with the electrolyte 540 that may result in the growth of lithium-containing dendrites from the anode 502. The gradient layer 514 may also facilitate the production of lithium fluoride based on a chemical reaction between dissociated lithium ions and fluoride ions. As discussed, the presence of lithium fluoride in or near the anode 502 may reduce the polysulfide shuttle effect. For example, the formation of lithium fluoride (e.g., the formation of available lithium and fluorine ions) may occur uniformly throughout the first edge 5181 and / or second edge 5182 of the anode. In this manner, localized regions of high lithium concentration in the electrolyte 540 near the anode 502 are substantially inhibited. As a result, lithium-lithium bonds that contribute to the formation of lithium-containing dendritic structures extending longitudinally from the anode are correspondingly inhibited, thereby allowing lithium ions to pass freely from the anode 502 to the electrolyte (e.g., as encountered during battery operation cycles). In some embodiments, the uniform distribution of lithium throughout the gradient layer 514 can increase the uniformity of lithium ion flux during battery operation cycles. In some embodiments, the gradient layer 514 can be about 5 nanometers (nm) thick.

[0112] In one or more embodiments, the gradient layer 514 may structurally reinforce the host battery to reduce or prevent lithium-containing dendritic growth from the anode 502 as well as increase the ability of the anode 502 to expand and contract during the host battery's operating cycles without bursting. In some aspects, the gradient layer 514 has a 3D structure with a stepped concentration gradient (e.g., one or more forming materials and / or components including carbon, tin, and / or fluorine), which facilitates rapid lithium ion transport. As a result, the gradient layer 514 significantly improves overall battery efficiency and performance.

[0113] In some implementations, the gradient layer 514 can provide an electrochemically desirable surface upon which the protective layer 516 can be grown or deposited. For example, in some aspects, the gradient layer 514 can include compounds and / or organometallic compounds including, but not limited to, aluminum, gallium, indium, nickel, zinc, chromium, vanadium, titanium, and / or other metals. In other aspects, the gradient layer 514 can include oxides, carbides, and / or nitrides of aluminum, gallium, indium, nickel, zinc, chromium, vanadium, titanium, and / or other metals.

[0114] In some implementations, the gradient layer 514 may include carbonaceous materials, including, but not limited to, flake graphene, few-layer graphene (FLG), carbon nano-onions (CNO), graphene nanoplatelets, or carbon nanotubes (CNTs). In other implementations, the gradient layer 514 may include molecules derived from carbon, oxygen, hydrogen, tin, fluorine, and / or other suitable chemical compounds, and / or tin fluoride and one or more carbonaceous materials. The gradient layer 514 may be prepared and / or deposited directly or indirectly on the anode 502 at different concentration levels. For example, the gradient layer 514 may include 5% by weight of a carbonaceous material with the balance being 95% by weight of tin fluoride, which may result in a relatively uniform dissociation of fluorine atoms and / or fluoride ions from the tin fluoride.

[0115] Other suitable ratios include 5% carbonaceous material with 95% tin fluoride, 10% carbonaceous material with 90% tin fluoride, 15% carbonaceous material with 85% tin fluoride, 20% carbonaceous material with 80% tin fluoride, 25% carbonaceous material with 75% tin fluoride, 30% carbonaceous material with 70% tin fluoride, 35% carbonaceous material with 65% tin fluoride, 40% carbonaceous material with 60% tin fluoride, 45% carbonaceous material with 55% tin fluoride, 50% carbonaceous material with 50% tin fluoride. material, 55% carbonaceous material with 45% tin fluoride, 55% carbonaceous material with 45% tin fluoride, 60% carbonaceous material with 40% tin fluoride, 65% carbonaceous material with 35% tin fluoride, 70% carbonaceous material with 30% tin fluoride, 75% carbonaceous material with 25% tin fluoride, 80% carbonaceous material with 20% tin fluoride, 85% carbonaceous material with 15% tin fluoride, 90% carbonaceous material with 10% tin fluoride, 95% carbonaceous material with 5% tin fluoride. The fluorine atoms and / or fluoride ions may then react and combine homogeneously with the lithium ions to form lithium fluoride, as further described below.

[0116] In some implementations, lithium ions circulating between the anode 502 and the cathode (not shown in FIG. 5) may generate tin-lithium alloy regions 512 in the gradient layer 514. In some aspects, operating cycles of the host battery may result in a uniform distribution of lithium fluoride in the tin-lithium alloy regions 512. The uniform distribution of lithium fluoride may facilitate a defluorination reaction of at least some of the tin(II) fluoride (SnF2) in the tin fluoride layer 510 (as well as additional tin fluoride that may be dispersed in the gradient layer 514 and / or protective layer). The fluorine atoms and / or fluoride ions made available by the defluorination reaction may chemically bond with at least some of the lithium ions present in or near the anode 502 to create lithium fluoride (LiF), and accordingly, may prevent at least some of the lithium ions from bonding with each other and creating lithium dendritic growth from the anode 502.

[0117] For example, at least a portion of the fluorine atoms and / or fluoride ions present in tin fluoride dissociate from the protective layer 516 and form tin ions (Sn 2+ ) and fluorine ion (2F - ) The fluorine atoms and / or fluoride ions dissociated from the protective layer 516 may be present in the electrolyte 540 and / or chemically bonded to at least some of the lithium ions dispersed throughout the protective layer 516 or the gradient layer 514. In some embodiments, the dissociated fluorine atoms may form Li-F bonds or Li-F compounds in the tin-lithium alloy region 512. In other embodiments, the dissociated fluorine atoms may form a tin fluoride layer 510 in the gradient layer 514.

[0118] Additionally, in one embodiment, at least a portion of the defluorinated tin fluoride may be uniformly dispersed throughout the gradient layer 514 to produce lithium fluoride (LiF) crystals that may act as electrical insulators and prevent electrons from flowing from the anode 502 through the first edge 5181 and / or second edge 5182 of the anode 502 and into the electrolyte 540.

[0119] In various implementations, the gradient layer 514 may be deposited on the anode 502 by one or more of atomic layer deposition (ALD), chemical vapor deposition (CVD), or physical vapor deposition (PVD). For example, ALD may be used to deposit a protective film, such as an ALD film, on the anode 502 that at least partially reacts with the electrolyte 540 during the high pressure bonding process. Thus, the ALD film may be used to create the protective layer 516 or the gradient layer 514 using atomic planes available for lithium migration. Such lithium migration may be similar in principle to that observed for few-layer graphene (FLG) or graphite, where alternating graphene layers in FLG or graphite mediate various forms of lithium ions, including lithium titanium oxide (LTO), lithium iron phosphate (PO3) (LFP). The intercalated lithium, e.g., the described forms of LTO and / or LFP, may be oriented to facilitate rapid transport and / or diffusion of lithium atoms and / or lithium ions, which may promote the formation and / or synthesis of lithium fluoride (e.g., in the tin fluoride layer 510 and / or elsewhere), as previously described. Additional forms of intercalated lithium, e.g., perovskite lithium lanthanum titanate (LLTO), may also function to store lithium within the anode 502.

[0120] In some implementations, the gradient layer 514 may include a variety of different types and / or forms of carbon and / or carbonaceous materials, each having one or more physical attributes that can be selected or configured to tailor the reactivity of the carbon with contaminants (such as polysulfides) present in the electrolyte 540 and / or anode 502. In some aspects, the selectable physical attributes may include, but are not limited to, porosity, surface area, surface functionalization, or electrical conductivity. Additionally, the gradient layer 514 may include binders or other additives that can be used to tailor one or more physical attributes of the carbonaceous material to achieve a desired reactivity of the carbon provided by the carbonaceous material with the polysulfides present in the electrolyte 540 and / or anode 502.

[0121] In one embodiment, the carbonaceous material in the gradient layer 514 can trap unwanted contaminants, thereby preventing the contaminants from chemically reacting with the lithium available at the exposed surfaces of the anode 502. Instead, the unwanted contaminants (e.g., polysulfides) can chemically react with various exposed surfaces of the carbonaceous material in the gradient layer 514 (e.g., via carbon-lithium interactions). In some embodiments, the carbonaceous material in the gradient layer 514 can agglomerate to the available lithium. The degree of agglomeration between the carbonaceous material and the lithium ions can be selected or modified via chemical reactions induced during preparation of the gradient layer 514.

[0122] In some embodiments, various carbon allotropes can be incorporated into the gradient layer 514 (e.g., into one or more portions of the tin-lithium alloy region 512 and / or the tin fluoride layer 510). These carbon allotropes can be functionalized with one or more reactants and used to form sealant layers and / or regions at the interface of the gradient layer 514 and the carbon nanodiamonds in the electrolyte 540. In some aspects, the carbon nanodiamonds can increase the mechanical robustness of the anode 502 and / or the gradient layer 514. In other aspects, the carbon nanodiamonds can also provide exposed carbonaceous surfaces that can be used to reduce the polysulfide shuttle effect by micro-confining and / or binding polysulfides present in the electrolyte 540 in a manner that keeps the polysulfides within a defined area of ​​the battery outside the anode 502.

[0123] Alternatively, in other embodiments, the carbon nanodiamonds in the gradient layer 514 have a specific L A Dimensions (e.g., sp 2The carbonaceous material may be replaced with carbon and / or carbonaceous materials, including surfaces and / or regions having hybrid orbital carbon, reduced graphene oxide (rGO), and / or graphene. In some embodiments, using the carbonaceous materials disclosed herein in a battery may increase carbon lamination and layer formation in the gradient layer 514. The exfoliated and oxidized carbonaceous material may also result in a more uniform layered structure in the gradient layer 514 (compared to non-exfoliated and non-oxidized carbonaceous material). In some embodiments, a solvent, such as tetrabutylammonium hydroxide (TBA) and / or dimethylformamide (DMF), may be applied to the carbonaceous materials disclosed herein to increase wetting of exposed carbonaceous surfaces in the gradient layer 514.

[0124] In some embodiments, the slurry used to form the gradient layer 514 may be doped to improve or otherwise affect the crystal structure of the carbonaceous material in the gradient layer 514. For example, the addition of a particular dopant may affect the crystal structure of the carbonaceous material in a particular corresponding manner and may add functional groups within the gradient layer 514 (e.g., via grafting to exposed carbon atoms within the carbonaceous material).

[0125] In some embodiments, a carbonaceous material having an exposed surface functionalized with one or more of a fluorine-containing or silicon-containing functional group may be included in the gradient layer 514. In other embodiments, a carbonaceous material having an exposed surface functionalized with one or more of a fluorine-containing or silicon-containing functional group may be deposited under the gradient layer 514 to form a stable SEI on the interface between the gradient layer 514 and the anode 502. In one embodiment, the stable SEI may replace the protective layer 516. In some embodiments, the gradient layer 514 may be slurry cast and / or deposited on the anode 502 using other techniques with lithium and carbon interphases, any of which may be functionalized with silicon and / or nitrogen to inhibit diffusion and migration of polysulfides toward the exposed surface of the anode 502. Additionally, certain polymers and / or cross-linking agents can be incorporated into the gradient layer 514 to mechanically strengthen the gradient layer 514, improve lithium ion transport across the gradient layer 514, or increase the uniformity of lithium ion flux across the gradient layer 514. Exemplary polymers and / or polymeric materials suitable for incorporation into the gradient layer 514 can include poly(ethylene oxide) and poly(ethyleneimine). Exemplary cross-linking agents suitable for incorporation into the gradient layer 514 can include inorganic linkers (e.g., borates, aluminates, silicates), polyfunctional organic molecules (e.g., diamines, diols), polyureas, or high molecular weight (MW) (e.g., >10,000 Daltons) carboxyl methyl cellulose (CMC).

[0126] Various manufacturing methods for producing the gradient layer 514 may be used. In one embodiment, prior to deposition and / or formation of the gradient layer 514, direct coating of the interface between the anode 502 and the electrolyte 540 may be performed using a dispersion of carbonaceous material and other chemicals dissolved in a carrier (e.g., solvent, binder, polymer). In another embodiment, deposition of the gradient layer 514 may be performed as a separate operation, or various other active ingredients (e.g., metals, carbonaceous materials, tin fluoride, etc.) may be added into a slurry that can be cast onto the anode 502. Alternatively, in another embodiment, the protective layer 516 may be transferred directly onto the anode 502 by a calendar roll lamination process. The protective layer 516 and / or the gradient layer 514 may also incorporate a lithium ion conductive epoxy that is partially cured to better increase adhesion with lithium during, for example, the calendar roll lamination process.

[0127] In one embodiment, a carbon-inclusive layer structure (not shown in FIG. 5 ) can be disposed on the anode 502 as a replacement for the gradient layer 514. This carbon-inclusive layer structure can include atomic planes available for lithium migration and can uniformly transport lithium ions provided by the electrolyte 540 throughout the protective layer 516 in a manner that can induce the formation of lithium fluoride in various portions of the battery. In various embodiments, the carbon-inclusive layer structure can include one or more arrangements of few-layer graphene (FLG) or graphite and / or can intercalate lithium to produce one or more reaction products including lithium tin oxide (LTO), lithium iron phosphate (LFP), and perovskite lithium lanthanum titanate (LLTO).

[0128] In some embodiments, the tin fluoride layer 510 can act as a protective layer against corrosion, including corrosion of the protective layer 516, the gradient layer 514, or copper-containing surfaces and / or regions of the anode 502. In some aspects, the tin fluoride layer 510 can also provide a uniform seed layer suitable for lithium deposition, thereby inhibiting the formation of dendrites. Additionally, in some embodiments, the tin fluoride layer 510 can include one or more lithium ion intercalation compounds, any one or more of which have a low voltage penalty. Suitable lithium ion intercalation compounds can include graphitic carbon (e.g., graphite, graphene, reduced graphene oxide (rGO). In one embodiment, during the manufacture of the anode 502, lithium ions can tend to intercalate before plating onto exposed carbonaceous surfaces in the tin fluoride layer 510. In this way, the tin fluoride layer 510 will have a uniform Li distribution to easily act as a seed layer prior to the initiation of lithium plating and / or electroplating operations.

[0129] In one embodiment, one or more conformal coating materials may be applied over a portion of the anode 502, with the resulting conformal coating material contacting and conforming to the first edge 5181 and / or second edge 5182 of the anode 502. In some aspects, the conformal coating material may begin as a first spacer edge protection region 5301 and a second spacer edge protection region 5302 that react with or otherwise combine with one or more of the protective layer 516, the tin-lithium alloy region 512, and / or the tin fluoride layer 510 to form a conformal coating material 544 that at least partially seals and protects the surfaces and / or interfaces between the lithium in the anode 502 and various materials suspended in the electrolyte, such as copper (Cu). In some embodiments, dissociation of fluorine atoms from tin fluoride present in conformal coating material 544 may react with lithium in anode 502 to form lithium fluoride rather than forming or growing lithium dendrites. In this manner, conformal coating material 544 may reduce the formation or growth of lithium dendrites from anode 502.

[0130] The conformal coating material 544 may be deposited or disposed on the anode 502 in any number of different thicknesses. In some embodiments, the conformal coating material 544 may be less than 5 μm thick. In other embodiments, the conformal coating material 544 may be less than 2 μm thick. In some other embodiments, the conformal coating material 544 may be less than 1 μm thick. These thickness levels may impede migration of polysulfides toward the anode 502 during battery cycling, thereby preventing at least some of the lithium ions from reacting with the polysulfides. Lithium ions that do not react with the polysulfides are available for transport from the anode to the cathode during a discharge cycle of the battery.

[0131] The conformal coating material 544 (as well as the protective layer 516 and the gradient layer 514) can uniquely tailor the lithium ion flux toward the first edge 5181 and / or the second edge 5182 of the anode 502, thereby preventing corrosion of the anode 502. Such tailoring can function in a manner similar to gate spacers used during the fabrication of polysilicon (poly-Si) gates. Specifically, gate spacers or gate sidewall structures can be used to protect and mechanically support polysilicon gates during the fabrication of integrated circuits (ICs). Similarly, the edge protection provided by the conformal coating material 544 for the anode 502 of FIG. 5 tailors the lithium ion flux toward the first edge 5181 and / or the second edge 5182 of the anode 502, thereby preventing corrosion of the anode 502. This type of edge protection provided by the conformal coating material 544 for the anode 502 may be equally applicable to other battery and / or electrical cell formats and / or configurations, such as (but not limited to) cylindrical cells, stacked cells, and / or others likewise, with the various configurations being specifically designed to fit within the parameters of each of these designs.

[0132] In some embodiments, the fabrication and / or deposition of the conformal coating material 544, protective layer 516, and / or gradient layer 514 on the anode 502 may depend on the type of battery or cell configuration in which the anode 502 is incorporated, e.g., cylindrical cells compared to pouch-shaped and / or prismatic cells. In one embodiment, for cylindrical cells, the metallic anode may be comprised of an electroactive material, typically metallic lithium, and / or lithium-containing alloys, e.g., graphite and / or other carbonaceous composites containing lithium, as well as any single unitary or multi-layered sheet material. In one example, as depicted in the example of FIG. 5, a solid metallic lithium foil used as the anode 502 may be attached to a copper substrate used as a current collector 520 to facilitate the transfer of electrons to an external load via tab 546. In other embodiments, the battery 500 may include an anode 502 without a current collector 520, where a carbonaceous material contained within the anode 502 may provide a conductive medium coupled to the circuit.

[0133] In some implementations, the anode structure 500 can be incorporated into an electrochemical cell and / or battery by winding it around a mandrel. Cylindrical cell layouts typically use double-sided anodes such as the anode structure 500. In some implementations, a cylindrical cell structure using the anode structure 500 can use a conformal coating material 544 to protect the first edge 5181 and / or the second edge 5182 of the anode 502. The uniform protection provided by the conformal coating material 544 can be referred to herein as "edge protection." In one implementation, this edge protection can be incorporated into a cell using the anode structure 500 by extending the size and / or area of ​​the protective layer 516 to overlap beyond any geometrically induced edge effects, e.g., surface roughness, of the anode.

[0134] In other embodiments, the anode structure 500 can be incorporated into a pouch-type cell and / or a prismatic cell. Generally, two configurations of pouch-type cell and / or prismatic cell can be manufactured, including: (1) a jelly-roll type cell (e.g., seen in the industry as a lithium polymer battery), in which two rod-wound electrodes can be manufactured in a manner similar to the cylindrical cell, as previously described; and (2) a stacked plate type cell, which can be cut from a sheet of pre-cast and / or pre-stacked prepared anode, e.g., the unprotected edge of the anode 502 (when prepared in a stacked plate type configuration) is exposed and vulnerable to corrosion, fast ion flux, and exposure within the cell. The conformal coating material 544 of the stacked plate type configuration can protect the anode 502 and prevent supersaturation of lithium in the electrolyte 540. In this manner, the conformal coating material 544 can control lithium plating on the anode 502 during the operating cycle of the battery.

[0135] In some implementations, one or more chemical reactions may occur between the electrolyte 540 and the anode 502 during cell assembly or cell rest periods (involving solvent decomposition and / or additive reactions). These chemical reactions may assist in the formation of the conformal coating material 544. In some aspects, elevated and / or reduced temperatures (e.g., relative to room temperature and / or 20° C.) may be used as a stimulus for lithium-induced polymerization of the conformal coating material 544. For example, lithium-induced polymerization may occur in the presence of one or more catalysts and / or by using lithium metal and its associated chemical reactivity as an inducer, which initiates free radical-based polymerization of constituent species within any one or more layers of the anode structure 500 and / or the conformal coating material 544. Additionally, a conformal coating material 544 can be produced and / or deposited on the anode 502 using electrochemical reactions under either a forward or reverse electrical bias, and a secondary metal and / or salt can be used as an additive that can decompose and form an alloy on the metallic lithium at the first edge 5181 and / or second edge 5182 in the anode 502 exposed to the electrolyte 540. For example, suitable additives can contain one or more metal species desired, for example, to co-alloy with lithium or to be used as a blocking layer to reduce lithium migration to the first edge 5181 and / or second edge 5182 of the anode 502.

[0136] FIG. 6 shows a schematic diagram of an enlarged portion 600 of the anode structure 500 of FIG. 5 according to some embodiments. The enlarged portion 600 illustrates the arrangement of the first spacer edge protection region 5301 and the second spacer edge protection region 5302 (collectively referred to as edge protection region 530 in FIG. 6) in a direction perpendicular to the first edge 5181 and / or the second edge 5182 as shown in FIG. 5. As a result, the edge protection region 530 may include a carbonaceous material 610 organized into a structure and / or lattice, which may block lithium ions from undesirably escaping the anode 502 across the edge protection region 530. In this manner, dissociation, flux, transport, and / or other movement of lithium ions may be effectively channeled throughout the enlarged portion 600 of FIG. 6 (as well as the anode structure 500 of FIG. 5), thereby resulting in an optimal battery operation cycle. In some implementations, the carbonaceous material 610 used to generate the edge protection region may include few-layer graphene (FLG), multi-layer graphene (MLG), graphite, carbon nanotubes (CNT), carbon nano-onions (CNO), and the like. The carbonaceous material 610 (e.g., as shown in Figures 8A, 8B, 9A, 9B, 10A, and / or 10B) may be synthesized, self-nucleated, or otherwise joined together at various concentration levels to provide perfect tailoring of the edge protection region 530. For example, its density, thickness, and / or composition may be designed to reduce lithium ion permeation across the protection layer 516 or gradient layer 514 and promote lithium ion permeation accordingly. In some implementations, the thickness of the edge protection region 530 may be less than 5 μm. In other aspects, the thickness of the edge protection region 530 may be less than 2 μm. In some other aspects, the thickness of the edge protection region 530 may be less than 1 μm. In some embodiments, the conductive additive 640 may be added to the carbonaceous material 610 as well as the binder 620 .

[0137] 7 shows a schematic diagram of a polymer network 710, according to some embodiments. In some aspects, the polymer network 710 can be an example of the polymer network 285 of FIG. 2. The polymer network 710 can be disposed on an anode 702. The anode 702 can be formed as an alkali metal layer having one or more exposed surfaces that include any number of alkali metal-containing nanostructures or microstructures. The alkali metals can include, but are not limited to, lithium, sodium, zinc, indium, and / or gallium. The anode 702 can release alkali ions during the operating cycle of the battery.

[0138] A layer 714 of carbonaceous material may be grafted with fluorinated polymer chains and deposited on one or more exposed surfaces of the anode 702. The grafting may be based on (e.g., initiated by) activating the carbonaceous material with one or more radical initiators, such as benzoyl peroxide (BPO) or azobisisobutyronitrile (AIBN), and subsequently reacting with monomer molecules. The polymer network 710 may be based on the fluorinated polymer chains crosslinked together with each other and the carbonaceous material of the layer 714, such that the layer 714 is consumed during the production of the polymer network 710. In some embodiments, the polymer network 710 may have a thickness of about 0.001 μm to 5 μm and may include about 0.001% to 2% by weight of fluorinated polymer chains. In some other embodiments, the polymer network 710 may comprise a plurality of carbonaceous materials grafted with about 5% to 100% by weight of fluorinated polymer chains, and the remainder being a fluorinated polymer, or one or more non-fluorinated polymers, or one or more crosslinkable monomers, or combinations thereof. In one embodiment, the carbonaceous material grafted with fluorinated polymer chains may comprise 5% to 50% by weight of fluorinated polymer chains, and the remainder being carbonaceous material.

[0139] During battery cycling, the carbon-fluorine bonds in the polymer network 710 may chemically bond with newly formed lithium metal and convert to carbon-lithium bonds (C-Li). These C-Li bonds may in turn react with the carbon-fluorine bonds in the polymer network 710 via a Wurtz reaction 750 to further crosslink the polymer network with the newly formed C-C bonds and form alkali metal-containing fluorides (such as lithium fluoride (LiF)). The additional polymer network crosslinking leading to the uniform formation of alkali metal-containing fluorides may thereby suppress the formation 740 of alkali metal dendrites associated with the anode 702, thereby improving battery performance and life. In one embodiment, grafting of a fluorinated m / acrylate (FMA) to one or more exposed graphene surfaces of the carbonaceous material in layer 714 may be performed in an organic solution leading to the formation of, for example, graphene-grafted poly-FMA. The incorporation of carbon-fluorine bonds on the exposed graphene surface may allow a Wurtz reaction 750 to occur between the carbon-fluorine bonds and the metal surface of the alkali metal (e.g., lithium) provided by the anode 702. Completion of the Wurtz reaction 750 may thus result in the formation of a polymer network 710. In some embodiments, the polymer network 710 may include a density gradient 716 following completion of the Wurtz reaction 750. This density gradient 716 may include interconnected graphene flakes and may be infused with one or more metal fluoride salts formed in situ. Additionally, the porosity and / or mechanical properties of the layer may be tailored by a combination of carbon loading and / or functionalized carbon, each with a unique and / or distinct physical structure.

[0140] In some implementations, the carbonaceous material in the density gradient 716 may include one or more of flat graphene, wrinkled graphene, carbon nanotubes (CNTs), or carbon nanoonions (CNOs) (e.g., as depicted in FIG. 8A and / or FIG. 8B and as shown in the micrographs of FIGS. 9A-9B and 10A-10B). In one implementation, the graphene nanoplatelets may be dispersed throughout the polymer network 710 and isolated from one another within the polymer network. The dispersion of graphene nanoplatelets may include one or more different concentration levels. In one implementation, the dispersion of graphene nanoplatelets may include at least some of the carbonaceous material functionalized with at least some of the fluorinated polymer chains.

[0141] For example, the fluorinated polymer chain may include one or more acrylate or methacrylate monomers, including vinyl-based monomers including 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl acrylate (DFHA), 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl methacrylate (HDFDMA), 2,2,3,3,4,4,5,5-octafluoropentyl methacrylate (OFPMA), tetrafluoropropyl methacrylate (TFPM), 3-[3,3,3-trifluoro-2-hydroxy-2-(trifluoromethyl)propyl]bicyclo[2.2.1]hept-2-yl methacrylate (HFA monomer), or 2,3,4,5,6-pentafluorostyrene (PFSt).

[0142] In some embodiments, fluorinated polymer chains can be grafted onto the surface of a layer of carbonaceous material, thereby chemically interacting with one or more surfaces of the alkali metal of the anode via the Wurtz reaction 750. In organic chemistry, organometallic chemistry, and inorganic main group polymers, the Wurtz reaction is a coupling reaction whereby two alkyl halides react with sodium metal (or some other metal) in a dry ether solution to form a higher alkane. In this reaction, an alkyl halide is treated with an alkali metal, e.g., sodium metal, in a dry ether (water-free) solution to form a higher alkane. If the sodium intermediate of the Wurtz reaction is a highly polar and reactive carbon-sodium metal bond, this in turn chemically reacts with the carbon-halide bond to result in a newly formed C-C bond and a sodium halide. The formation of new carbon-carbon bonds allows the Wurtz reaction to be used for the preparation of higher alkanes containing an even number of carbon atoms, e.g., as follows: 2R-X+2Na → R-R+2Na + X - (Formula 1)

[0143] Other metals have also been used to affect the Wurtz bond, particularly mixtures of silver, zinc, iron, activated copper, indium, and manganese with copper chloride. A related reaction involving aryl halides is called the Wurtz-Fittig reaction. This can be explained by the formation of a free radical intermediate and subsequent disproportionation reaction to produce an alkene. The Wurtz reaction 750 occurs through a free radical mechanism that allows for a side reaction to produce an alkene product. In some embodiments, the chemical interaction associated with the Wurtz reaction described above can form an alkali metal fluoride, such as lithium fluoride.

[0144] In one embodiment, the polymer network 710 can include an interfacial layer 718 in contact with the anode 702. The protective layer 720 can be disposed on top of the interfacial layer 718, which can be based on a Wurtz reaction 750 at the interface between the anode 702 and the polymer network 710. The interfacial layer 718 can have a relatively high crosslink density (e.g., a fluorinated polymer), a high metal fluoride concentration, and a relatively low carbon-fluorine bond concentration. In contrast to the interfacial layer 718, the protective layer 720 can have a relatively low crosslink density, a low metal fluoride concentration, and a high carbon-fluorine bond concentration.

[0145] In some embodiments, the interfacial layer 718 may include crosslinkable monomers, such as methacrylate (MA), acrylate, vinyl functional groups, or a combination of epoxy and amine functional groups. In one embodiment, the protective layer 720 may be characterized by a density gradient 716. In this manner, the density gradient 716 may be associated with one or more self-healing properties of the protective layer 720 and / or may enhance the polymer network 710. In some embodiments, the protective layer 720 may further inhibit the formation 740 of alkali metal dendrites from the anode 702 during battery cycling.

[0146] In operation, the interfacial layer 718 can suppress alkali metal dendrite formation 740 associated with the anode 702 by uniformly generating metal fluoride, e.g., lithium fluoride, at the interface along the length of the anode 702. This uniform metal fluoride generation can cause decomposition of the dendrite surface, e.g., via conversion to metal fluoride, ultimately suppressing alkali metal dendrite formation 740. Additionally, cross-linking of fluorinated polymer chains on remaining dendrites can further suppress alkali metal dendrite formation 740. In some implementations, the density gradient 716 can be adjusted to control the degree of cross-linking between fluorinated polymer chains.

[0147] 8A shows a simplified cross-sectional view of an exemplary carbonaceous particle 800 having gradient porosity, according to some embodiments. The carbonaceous particle 800 may be synthesized in a reactor and output in a controlled manner to produce the cathode 110 and / or anode 120 of FIG. 1, the cathode 210 and / or anode 220 of FIG. 2, or the electrode 300 of FIG. 3. The carbonaceous particle 800, which may also be referred to as a composition of matter, also includes multiple regions nested within each other. Each region may include at least a first porosity region 811 and a second porosity region 812. The first porosity region 811 may include a plurality of first pores 801, and the second porosity region 812 may include a plurality of second pores 802. In some embodiments, each region may be separated from an immediately adjacent region by at least some of the first pores 801. The first pores 801 can be distributed throughout a first porous region 811 of the carbonaceous particle 800, and the second pores 802 can be distributed throughout a second porous region 812 of the carbonaceous particle 800. In this manner, the first pores 801 can be associated with a first pore density and the second pores 802 can be associated with a second pore density that is different from the first pore density. In some embodiments, the first pore density can be between about 0.0 cubic centimeters (cc) / g and 2.0 cc / g, and the second pore density can be between about 1.5 and 5.0 cc / g. In some embodiments, the first pores 801 can be configured to retain polysulfides 820, and the second pores 802 can provide an exit path for the carbonaceous particle 800.

[0148] Groups of carbonaceous particles 800 can be connected together to form carbonaceous aggregates (not shown for simplicity), and groups of carbonaceous aggregates can be connected together to form carbonaceous agglomerates (not shown for simplicity). In some implementations, the first pores 801 and the second pores 802 can be dispersed throughout the aggregates formed by each group of carbonaceous particles 800. In some aspects, the first porosity region 811 can be at least partially encapsulated by the second porosity region 812, such that each aggregate can include some of the first pores 801 and / or some of the second pores 802.

[0149] In some embodiments, the carbonaceous particles 800 may have a major dimension "A" in the approximate range of 20 nm to 150 nm, the aggregates formed by the group of carbonaceous particles 800 may have a major dimension in the approximate range of 20 nm to 10 μm, and the aggregates formed by the group of aggregates may have a major dimension in the approximate range of 0.1 μm to 1,000 μm. In some aspects, at least some of the first pores 801 and the second pores 802 have a major dimension in the approximate range of 1.3 nm to 32.3 nm. In one embodiment, each of the first pores 801 has a major dimension in the approximate range of 0 nm to 100 nm.

[0150] The carbonaceous particle 800 may also include a plurality of deformable regions 813 distributed along the perimeter 810 of the carbonaceous particle 800. The carbonaceous particle 800 may conduct electricity along connected boundaries with one or more other carbonaceous particles (such as the perimeter 810). The carbonaceous particle 800 may also confine polysulfide 820 within the first pores 801 and / or in one or more blocking regions 822, thereby inhibiting migration of the polysulfide 820 to the anode and increasing the rate at which lithium ions may be transported from the anode to the cathode of the host battery.

[0151] In some embodiments, the carbonaceous particles 800 are 10 2 / g~3,000m 2In another embodiment, the carbonaceous particle 800 may have a composite surface area including sulfur 824 microtrapped within some of the first pores 801 and / or some of the second pores 802. As used herein, the first pores 801 and / or the second pores 802 that microtrap the polysulfides 820 may be referred to as "functional pores." In some aspects, one or more of the carbonaceous particles, the aggregates formed by a corresponding group of the carbonaceous particles, or the aggregates formed by a corresponding group of the aggregates may include one or more exposed carbon surfaces configured to nucleate sulfur 824. The composite surface area may be greater than 10 m2. 2 / g~3,000m 2 / g, and the carbonaceous particles 800 may have a sulfur to carbon weight ratio of about 1:5 to 10:1. In some embodiments, the carbonaceous particles 800 may have a conductivity in the approximate range of 100 S / m to 20,000 S / m at a pressure of 12,000 pounds per square inch (psi).

[0152] In some embodiments, the carbonaceous particles 800 may include a surfactant or polymer, including one or more of styrene butadiene rubber, polyvinylidene fluoride, polyacrylic acid, carboxymethyl cellulose, polyvinylpyrrolidone, and / or polyvinyl acetate, that may act as a binder linking together groups of carbonaceous particles 800. In other embodiments, the carbonaceous particles 800 may include a gel or solid phase electrolyte disposed within at least some of the first pores 801 or the second pores 802.

[0153] FIG. 8B shows a schematic diagram of an example of a tri-zone particle 850, according to some embodiments. In various embodiments, the tri-zone particle 850 can be an example of the carbonaceous particle 800 of FIG. 8A. The tri-zone particle 850 can include three distinct zones, such as, but not limited to, a first zone 851, a second zone 852, and a third zone 853. In some embodiments, each of the zones 851-853 surrounds and / or encapsulates the previous zone. For example, the first zone 851 can be surrounded or encapsulated by the second zone 852, which can be surrounded or encapsulated by the third zone 853. The first zone 851 may correspond to an interior region of the tri-zone particle 850, the second zone 852 may correspond to a middle transition region of the tri-zone particle 850, and the third zone 853 may correspond to an exterior region of the tri-zone particle 850. In some embodiments, the tri-zone particle 850 may include a permeable shell 855 that deforms in response to contact with one or more adjacent non-tri-zone particles and / or tri-zone particles 850.

[0154] In some embodiments, the first zone 851 can have a relatively low density, a relatively low conductivity, and a relatively high porosity, the second zone 852 can have an intermediate density, an intermediate conductivity, and an intermediate porosity, and the third zone 853 can have a relatively high density, a relatively high conductivity, and a relatively low porosity. In some aspects, the first zone 851 can have a density of the carbonaceous material between about 1.5 g / cc and 5.0 g / cc, the second zone 852 can have a density of the carbonaceous material between about 0.5 g / cc and 3.0 g / cc, and the third zone 853 can have a density of the carbonaceous material between about 0.0 and 1.5 g / cc. In other aspects, the first zone 851 may include pores having a width of about 0-40 nm, the second zone 852 may include pores having a width of about 0-35 nm, and the third zone 853 may include pores having a width of about 0-30 nm. In some other embodiments, the second zone 852 may not be defined for the tri-zone particle 850. In one embodiment, the first zone 851 may have a major dimension D1 of about 0 nm-100 nm, the second zone 852 may have a major dimension D2 of about 20 nm-150 nm, and the third zone 853 may have a major dimension D3 of about 200 nm.

[0155] Aspects of the present disclosure recognize that the unique layout of the tri-zone particle 850 and the relative dimensions, porosity, and conductivity of the first zone 851, second zone 852, and third zone 853 can be selected and / or modified to achieve a desired balance between minimizing the polysulfide shuttle effect and maximizing the specific capacity of the host battery. Specifically, in some aspects, the size and volume of the pores may decrease from one zone to the other. In some implementations, the tri-zone particle may be entirely composed of one zone having a range of pore sizes and pore distributions (e.g., pore density). In the example of FIG. 8B, the pores 861 associated with the first zone 851 or first porous region have a relatively large width and may be defined as macropores, the pores 862 associated with the second zone 852 or second porous region have a medium sized width and may be defined as mesopores, and the pores 863 associated with the third zone 853 or third porous region have a relatively small width and may be defined as micropores.

[0156] Groups of tri-zone particles 850 may be connected together to form aggregates (not shown for simplicity), and groups of aggregates may be connected together to form agglomerates (not shown for simplicity). In some embodiments, a plurality of mesopores may be interspersed throughout the aggregates formed by each group of carbonaceous particles 800. In some aspects, the first porous region 811 may be at least partially enclosed by the second porous region 812 such that each aggregate may include one or more mesopores and one or more macropores. In one embodiment, each mesopore may have a major dimension between 3.3 nanometers (nm) and 19.3 nm, and each macropore may have a major dimension between 0.1 μm and 1,000 μm. In some cases, the tri-zone particle 850 may include carbon fragments that are intertwined with each other and separated from each other by at least some of the mesopores.

[0157] In some embodiments, the tri-zone particle 850 may include a surfactant or polymer, including one or more of styrene butadiene rubber, polyvinylidene fluoride, polyacrylic acid, carboxymethyl cellulose, polyvinylpyrrolidone, and / or polyvinyl acetate, that can act as a binder linking the groups of carbonaceous material together. In other embodiments, the tri-zone particle 850 may include a gel or solid phase electrolyte disposed within at least some of the pores.

[0158] In some embodiments, the tri-zone particle 850 is 10 mm 2 / g~3,000m 2 / g and / or 10 m 2 / g~3,000m 2 / g. In one embodiment, a composition of matter comprising a multiplicity of tri-zone particles 850 may have a conductivity in the approximate range of 100 S / m to 20,000 S / m at a pressure of 12,000 pounds per square inch (psi) and a sulfur to carbon weight ratio of about 1:5 to 10:1.

[0159] FIG. 8C illustrates an exemplary step function 800C that represents the average pore volume in each of the regions of the tri-zone particle 850 of FIG. 8B, according to some embodiments. As described, the pores distributed throughout the tri-zone particle 850 may have different sizes, volumes, or distributions. In some embodiments, the average pore volume may decrease based on the distance between the center of the tri-zone particle 850 and adjacent zones, so that, for example, the pores associated with the first zone 851 or first porosity region have a relatively large volume or pore size, the pores associated with the second zone 852 or second porosity region have an intermediate volume, and the pores associated with the third zone 853 or third porosity region have a relatively small volume. The interior regions have a larger pore volume than the regions near the periphery. The regions with larger pore volumes provide a high sulfur loading, while the outer regions of smaller pore volumes mitigate polysulfide migration during cell cycling. In the example of FIG. 8C, the average pore volume in the inner region is about 3 cc / g, the average pore volume in the outermost region is −0.5 cc / g, and the average pore volume in the middle region is between 0.5 cc / g and 3 cc / g.

[0160] 8D shows a graph 800D depicting an exemplary distribution of pore volume versus pore width for carbonaceous particles described herein. As depicted in graph 800D, pores associated with a relatively large pore volume may have a relatively small pore width, such that, for example, pore width generally increases as pore volume decreases. In some embodiments, pores having a pore width less than about 1.0 nm may be referred to as micropores, pores having a pore width of about 3-11 nm may be referred to as mesopores, and pores having a pore width greater than about 24 nm may be referred to as macropores.

[0161] FIG. 9A shows an electron micrograph 900 of a plurality of carbonaceous structures 902 according to some embodiments. In some embodiments, each of the carbonaceous structures 902 can have a substantially hollow core region surrounded by various monolithic carbon growths and / or layering. In some aspects, the monolithic carbon growths and / or layering can be examples of the monolithic carbon growths and / or layering described with reference to FIGS. 8A and 8B. In some cases, the carbonaceous structures 902 can include several concentric multi-layered fullerenes and / or similarly shaped carbonaceous structures organized at various levels of density and / or concentration. For example, the actual final shape, size, and graphene configuration of each of the carbonaceous structures 902 can depend on various manufacturing processes. The carbonaceous structures 902 can exhibit poor water solubility in some embodiments. Thus, in some embodiments, non-covalent functionalization can be utilized to modify one or more dispersibility properties of the carbonaceous structures 902 without affecting the intrinsic properties of the underlying carbon nanomaterial. In some embodiments, the underlying carbon nanomaterial is sp 2 3. The carbonaceous structures 902 may form a carbon nanomaterial. In some embodiments, each of the carbonaceous structures 902 may have a diameter of about 20-500 nm. In various embodiments, groups of the carbonaceous structures 902 may coalesce and / or link together to form aggregates 904. Additionally, groups of the aggregates 904 may coalesce and / or link together to form aggregates 906. In some embodiments, one or more of the carbonaceous structures 902, aggregates 904, and / or aggregates 906 may be used to form the anode and / or cathode of the battery 100 of FIG. 1, the battery 200 of FIG. 2, or the electrode 300 of FIG. 3.

[0162] FIG. 9B shows an electron micrograph 950 of an aggregate formed of a carbonaceous material, according to some embodiments. In some embodiments, the aggregate 960 can be an example of the aggregate 904 of FIG. 9A. In one embodiment, the outer carbonaceous shelled structure 952 can be fused with carbon provided by other carbonaceous shelled structures 954 to form a carbonaceous structure 956. A group of carbonaceous structures 956 can coalesce and / or connect with each other to form an aggregate 1010. In some aspects, the core region 958 of each of the carbonaceous structures 956 can be tunable in that the core region 958 can include various defined concentration levels of interconnected graphene structures, for example, as described with reference to FIG. 8A and / or FIG. 8B. In some embodiments, some of the carbonaceous structures 956 can have a first concentration of interconnected carbon at or near the outer carbonaceous shelled structure 952, between 0.1 g / cc and 2.3 g / cc. Each of the carbonaceous structures 956 can have pores for transporting lithium ions that extend inwardly toward the core region 1008.

[0163] In some embodiments, each pore of the carbonaceous structures 956 can have a width or dimension of about 0.0 nm to 0.5 nm, about 0.0 to 0.1 nm, about 0.0 to 6.0 nm, or about 0.0 to 35 nm. Each carbonaceous structure 956 can also have a second concentration at or near the core region 958 that is different from the first concentration. For example, the second concentration can include several relatively low density carbonaceous regions arranged in a concentric pattern. In one embodiment, the second concentration can be less than the first concentration, at about 0.0 g / cc to 1.0 g / cc or about 1.0 g / cc to 1.5 g / cc. In some embodiments, the relationship between the first and second concentrations can be used to achieve a balance between trapping sulfur or polysulfides within the respective electrodes and maximizing lithium ion transport. For example, sulfur and / or polysulfides may migrate through the first concentration and may be at least temporarily trapped within the second concentration and / or may be interspersed throughout the second concentration during the operating cycle of the lithium-sulfur battery.

[0164] In some embodiments, at least some of the carbonaceous structures 956 may comprise CNO oxides organized as monolithic and / or interconnected growths and produced in a thermal reactor. For example, the carbonaceous structures 956 may be decorated with cobalt nanoparticles according to the following exemplary recipe, in which cobalt (II) acetate (C4H6CoO4), i.e., the cobalt salt of acetate (often found as the tetrahydrate Co(CH3CO2)2·4H2O, which may be abbreviated as Co(OAc)2·4H2O), may be flowed into the thermal reactor in a ratio of about 59.60% by weight, corresponding to 40.40% by weight of carbon (referring to carbon in the CNO form), resulting in functionalization of the active sites on the CNO oxide with cobalt, respectively, which represents a 15,000-fold level of cobalt-decorated CNO. In some embodiments, a suitable gas mixture used to generate carbon #29 and / or cobalt decorated CNO may include the following steps: · Ar purge at 0.75 standard cubic feet per minute (scfm) for 30 minutes; · Ar purge changed to 0.25scfm for run; Temperature increase: 25℃~300℃ for 20 minutes; and Temperature increase: 300℃~500℃ in 15 minutes.

[0165] The carbonaceous material described with reference to Figures 9A and 9B may include or be otherwise formed from one or more instances of graphene, which may include a monolayer of carbon atoms with each atom bonded to three neighboring lattices in a honeycomb structure. The monolayer may be a discrete material confined to one dimension, such as within or at the surface of a condensed phase. For example, graphene may grow outward only in the x- and y-planes (and not in the z-plane). In this manner, graphene may be a two-dimensional (2D) material that includes one or several layers with atoms of each layer strongly bonded (such as by multiple carbon-carbon bonds) to neighboring atoms in the same layer.

[0166] In some implementations, the graphene nanoplatelets (e.g., the forming structures included in each of the carbonaceous structures 956) may include multiple instances of graphene, such as a first graphene layer, a second graphene layer, and a third graphene layer, all stacked vertically on top of each other. Each of the graphene nanoplatelets, which may be referred to as GNPs, may have a thickness of 1 nm to 3 nm and lateral dimensions ranging from about 100 nm to 100 μm. In some implementations, the graphene nanoplatelets may be produced by roll-to-roll (R2R) production, by multiple plasma spray torches arranged in sequence. In some aspects, R2R production may include deposition on a continuous substrate that is processed as a rolled sheet, including the transfer of the 2D material(s) to a separate substrate. In some cases, R2R production can be used to form the first thin film 310 and / or the second thin film 320 of the electrode 300 of FIG. 3, such that, for example, the concentration level of the first aggregates 312 in the first thin film 310 is different from the concentration level of the second aggregates 322 in the second thin film 320. That is, the plasma spray torch used in the R2R process can spray the carbonaceous material at different concentration levels to create the first thin film 310 and / or the second thin film 320 with a particular concentration level of graphene nanoplatelets. Thus, the R2R process can provide a fine level of tailoring capability for the battery 100 of FIG. 1 and / or the battery 200 of FIG. 2.

[0167] 10A and 10B show transmission electron microscope (TEM) images 1000 and 1050, respectively, of carbonaceous particles treated with carbon dioxide (CO2), according to some embodiments. The carbonaceous particles shown in Figures 10A and 10B may include or be otherwise formed from one or more instances of graphene, which may include a single layer of carbon atoms with each atom bonded to three neighbors in a honeycomb structure.

[0168] FIG. 11 shows a schematic diagram 1100 depicting various carbonaceous aggregate carbon porosity types, according to some embodiments. In various embodiments, the carbonaceous aggregate described with reference to FIG. 11 can be an example of the aggregate 904 of FIG. 9A and / or the carbonaceous structure 956 of FIG. 9B. In some aspects, the carbonaceous aggregate described with reference to FIG. 11 can be used to form the electrode 300 of FIG. 3. As described, the aggregate can be formed from or can include a group of carbonaceous structures, such as the carbonaceous structure 902 of FIG. 9A or the carbonaceous structure 956 of FIG. 9B. In some aspects, the carbonaceous structure can be CNO.

[0169] The carbonaceous structure can be used to form an electrode having any of the porosity types shown in schematic diagram 1100 (such as electrode 300 in FIG. 3). For example, the electrode can include any of porosity type I 1110, porosity type II 1120, and porosity type III 1130. In some embodiments, porosity type I 1110 can include a first pore 1111, a second pore 1112, and a third pore 1113, all of which are sized with major dimensions less than 5 nm to hold the polysulfides within the electrode. Some polysulfides can grow in size as they form larger complexes and become immobilely contained within the pores of porosity type I 1110. In some embodiments, the aggregates can be connected together to create pores of porosity type II 1120 and / or porosity type III 1130 that can hold larger polysulfides and / or polysulfide complexes.

[0170] 12 shows a graph 1200 depicting pore size versus pore distribution of an exemplary electrode, according to some embodiments. As used herein, "carbon 1" refers to a structured carbonaceous material that contains mostly micropores (e.g., major dimensions less than 5 nm) and "carbon 2" refers to a structured carbonaceous material that contains mostly mesopores (e.g., major dimensions between about 20 nm and 50 nm). In some embodiments, an electrode suitable for use in one of the batteries disclosed herein can be prepared to have the pore size versus pore distribution depicted in graph 1200.

[0171] FIG. 13 shows a first graph 1300 and a second graph 1310 depicting battery performance over cycle number, according to some embodiments. Specifically, the first graph 1300 shows the specific discharge capacity of an exemplary battery using an electrolyte 1302 disclosed herein versus the specific discharge capacity of a conventional battery using a conventional electrolyte. The second graph shows the capacity retention of a battery using the electrolyte 1302 versus the capacity retention of a battery using a conventional electrolyte. In some embodiments, the electrolyte 1302 can be an example of the electrolyte 130 of FIG. 1 or the electrolyte 230 of FIG. 2. In the first graph 1300 and the second graph 1310, the conventional electrolyte is prepared as 1M LiTFSI in DME:DOL:TEGDME (vol:vol:vol=1:1:1) with 2 wt. % LiNO3.

[0172] FIG. 14 shows a bar graph 1400 depicting battery performance over cycle number according to some embodiments. Specifically, bar graph 1400 depicts the specific discharge capacity over cycle number of an exemplary battery using electrolyte 1402 disclosed herein versus the specific discharge capacity over cycle number of a conventional battery using a conventional electrolyte. In some embodiments, electrolyte 1402 can be an example of electrolyte 130 of FIG. 1 or electrolyte 230 of FIG. 2. In bar graph 1400, the conventional electrolyte is prepared as 1 M LiTFSI in DME:DOL:TEGDME (volume:volume:volume=1:1:1). Bar graph 1400 shows that using electrolyte 1402 in an exemplary battery (such as battery 100 of FIG. 1 or battery 200 of FIG. 2) can increase the specific discharge capacity of the battery by about 28% at the 3rd cycle number, by about 30% at the 50th cycle number, and by about 39% at the 60th cycle number, compared to a battery using a conventional electrolyte.

[0173] FIG. 15 shows a first graph 1500 and a second graph 1510 depicting battery performance over cycles, according to some embodiments. Specifically, the first graph 1500 shows electrode discharge capacity over cycles for an exemplary lithium-sulfur coin cell using an electrolyte 1502 disclosed herein versus electrode discharge capacity over cycles for an exemplary lithium-sulfur coin cell battery using a conventional electrolyte, and the second graph 1510 shows capacity retention over cycles for a lithium-sulfur coin cell battery using an electrolyte 1502 versus electrode discharge capacity over cycles for a lithium-sulfur coin cell battery using a conventional electrolyte. In some embodiments, the electrolyte 1502 can be an example of the electrolyte 130 of FIG. 1 or the electrolyte 230 of FIG. 2. The lithium-sulfur coin cell battery is cycled at 100% depth of discharge (DOD) at a discharge rate of 1C (e.g., fully discharged within 1 hour) and maintained at approximately room temperature (68° F. or 20° C.). The conventional electrolyte was prepared as 1 M LiTFSI in DME:DOL:TEGDME (vol:vol:vol = 1:1:1) with 2 wt% LiNO3.

[0174] FIG. 16 shows a graph 1600 depicting electrode discharge capacity per cycle number according to some embodiments. Specifically, graph 1600 depicts electrode discharge capacity per cycle number for an exemplary battery using an electrolyte 1602 disclosed herein versus electrode discharge capacity for a conventional battery using a conventional electrolyte. In some embodiments, electrolyte 1602 can be an example of electrolyte 130 of FIG. 1 or electrolyte 230 of FIG. 2. The conventional electrolyte was prepared as 1 M LiTFSI in DME:DOL:TEGDME (vol:vol:vol=1:1:1) with 2 wt. % LiNO3, and electrolyte 1602 was prepared as 1 M LiTFSI in DME:DOL:TEGDME (vol:vol:vol=58:29:13) with about 2 wt. % LiNO3.

[0175] 17 shows another graph 1700 depicting electrode discharge capacity per cycle number according to some embodiments. Specifically, graph 1700 depicts electrode discharge capacity per cycle number for an exemplary battery using an electrolyte 1702 and solvent package 1704 disclosed herein versus electrode discharge capacity for a conventional battery using a conventional electrolyte and solvent package. The conventional electrolyte was prepared as 1 M LiTFSI in DME:DOL:TEGDME (vol:vol:vol=1:1:1) with about 2 wt. % LiNO3, and electrolyte 1702 was prepared as 1 M LiTFSI in DME:DOL:TEGDME (vol:vol:vol=58:29:13) with 2 wt. % LiNO3. The conventional solvent package is prepared as 1 M LiTFSI in DME:DOL:TEGDME (vol:vol:vol = 1:1:1) and solvent package 1704 is prepared as 1 M LiTFSI in DME:DOL:TEGDME (vol:vol:vol = 58:29:13).

[0176] 18 shows a graph 1800 depicting the specific discharge capacity per cycle number for various TBT-containing electrolyte mixtures, according to some embodiments. As shown in graph 1800, "181" refers to an electrolyte without any TBT added, resulting in a 0 M TBT concentration level, "181-25TBT" refers to an electrolyte prepared with a TBT concentration level of 25M, and so on. In some embodiments, a TBT concentration level of 5M can result in an increase in discharge capacity of about 70 mAh / g relative to an electrolyte without any TBT added.

[0177] FIG. 19 shows a first graph 1900 depicting electrode discharge capacity per cycle number and a second graph 1910 depicting electrode capacity retention per cycle number according to some embodiments. Specifically, the first graph 1900 depicts electrode discharge capacity per cycle number for an exemplary battery including a protective grid disclosed herein versus electrode discharge capacity for an exemplary battery not including a protective grid disclosed herein. The second graph 1910 depicts electrode capacity retention per cycle number for an exemplary battery including a protective grid disclosed herein versus electrode capacity retention for an exemplary battery not including a protective grid disclosed herein. In some embodiments, the protective grid can be an example of the protective grid 402 of FIG. 4. The performance results for both the first graph 1900 and the second graph 1910 include the use of an electrolyte prepared with 1 M LiTFSI in DME:DOL:TEGDME (vol:vol:vol=58:29:13) with 2 wt. % LiNO3.

[0178] FIG. 20 shows a first graph 2000 depicting electrode discharge capacity per cycle number and a second graph 2010 depicting electrode capacity retention per cycle number according to another embodiment. Specifically, the first graph 2000 depicts electrode discharge capacity per cycle number for an exemplary battery including the polymer network of FIG. 7. The second graph 2010 depicts discharge capacity retention per cycle number for an exemplary battery including the polymer network of FIG. 7. The battery can be an example of the battery 100 of FIG. 1 or the battery 200 of FIG. 2. The performance results of both the first graph 2000 and the second graph 2010 include the use of an electrolyte prepared with 1 M LiTFSI in DME:DOL:TEGDME (vol:vol:vol=58:29:13) with 2 wt. % LiNO3.

[0179] FIG. 21 shows a first graph 2100 depicting electrode discharge capacity per cycle number and a second graph 2110 depicting electrode capacity retention per cycle number according to some other embodiments. Specifically, the first graph 2100 depicts electrode discharge capacity per cycle number for an exemplary battery including the protective layer 516 of FIG. 5. The second graph 2110 depicts discharge capacity retention per cycle number for an exemplary battery including the protective layer 516 of FIG. 5. The battery can be an example of the battery 100 of FIG. 1 or the battery 200 of FIG. 2. The performance results of both the first graph 1900 and the second graph 1910 include the use of an electrolyte prepared with 1 M LiTFSI in DME:DOL:TEGDME (vol:vol:vol=58:29:13) with 2 wt. % LiNO3.

[0180] FIG. 22 illustrates an exemplary cathode 2200 having a body 2201 and a width 2205, according to some embodiments. In some embodiments, the cathode 2200 may be an example of the electrode 300 of FIG. 3. The cathode 2200 may be similar to the electrode 300 of FIG. 3 in many respects, and thus a description of similar elements will not be repeated herein. In one embodiment, the cathode 2200 includes a first porous carbonaceous region 2210 and a second porous carbonaceous region 2220 positioned adjacent to the first porous carbonaceous region 2210. The first porous carbonaceous region 2210 may be formed of a first concentration level of carbonaceous material, and the second porous carbonaceous region 2220 may be formed of a second concentration level of carbonaceous material that is different from the first concentration level of carbonaceous material. For example, the second porous carbonaceous region 2220 may have a lower concentration level of carbonaceous material than the first porous carbonaceous region 2210, as shown in Figure 22. In some embodiments, additional porous carbonaceous regions (not shown in Figure 22 for simplicity) may be combined with at least the second porous carbonaceous region.

[0181] Specifically, these additional porous carbonaceous regions can be arranged to provide a stepwise decreasing concentration level of carbonaceous material in a direction away from the first porous carbonaceous region 2210 to provide full ion transport and current regulation capabilities. That is, in one embodiment, the second porous carbonaceous region 2220 can face the bulk electrolyte (e.g., provided in a liquid phase) and the first porous carbonaceous region 2210 of the cathode 2200 can be coupled to a current collector (not shown in FIG. 22 for simplicity). In this manner, a higher concentration carbonaceous region, such as the first porous carbonaceous region 2210, can provide a higher level of electrical conduction between adjacent contact points of the carbonaceous material (referred to in FIG. 22 as "e"). -"), whereas a more sparse carbonaceous region such as the second porous carbonaceous region 2220 can promote higher levels of lithium ion transport associated with improved lithium-sulfur battery discharge-charge cycling versus conventional lithium ion batteries. In some implementations, an additional carbonaceous region associated with and positioned adjacent to the second porous carbonaceous region 2220 can have a lower density of carbonaceous material than the second porous carbonaceous region 2220. In this manner, the lower density additional carbonaceous region can accommodate a higher level of lithium ion transport, for example, allowing for tuning of various performance characteristics of the electrode 300.

[0182] In one embodiment, the first porous carbonaceous region 2210 may include first non-tri-zone particles 2211. The configuration of the first non-tri-zone particles 2211 within the first porous carbonaceous region is one exemplary configuration. Other arrangements, orientations, alignments, etc. are possible for the non-tri-zone particles. In some aspects, each non-tri-zone particle may be one or more examples of carbonaceous materials disclosed elsewhere in this disclosure. The first porous carbonaceous region 2210 may also include first tri-zone particles 2212 interspersed throughout the first non-tri-zone particles 2211, as shown in FIG. 22, or positioned in any other arrangement, orientation, or configuration. Each first tri-zone particle 2212 may be an example of a tri-zone particle 850 of FIG. 8B. Additionally or alternatively, each of the first tri-zone particles 2212 may include first carbon fragments 2213 intertwined with one another and separated from one another by mesopores 2214. Each tri-zone particle can have a first deformable perimeter 2215 configured to merge with an adjacent first non-tri-zone particle 2211 and / or first tri-zone particle 2212.

[0183] The first porous carbonaceous region 2210 may also include first aggregates 2216, where each aggregate includes a number of first tri-zone particles 2212 connected together. In one or more particular examples, each first aggregate may have a major dimension within a range of 10 nanometers (nm) to 10 micrometers (μm). The mesopores 2214 may be interspersed throughout the first plurality of aggregates, where each mesopore has a major dimension between 3.3 nanometers (nm) and 19.3 nm. Additionally, the first porous carbonaceous region 2210 may include first aggregates 2217, where each aggregate includes a number of first aggregates 2216 connected together. In some embodiments, each first aggregate 2217 may have a major dimension within an approximate range of 0.1 μm to 1,000 μm. Macropores 2218 may be interspersed throughout the first mass 2216, where each macropore may have a major dimension between 0.1 μm and 1,000 μm. In some embodiments, one or more of the carbonaceous materials, allotropes, and / or structures described above may be one or more of the examples shown in FIGS. 9A and 9B.

[0184] The second porous carbonaceous region may include a second non-tri-zone particle 2221, which may be an example of the first non-tri-zone particle 2211. The second porous carbonaceous region 2220 may include a second tri-zone particle 2222, which may be an example of each of the first tri-zone particles 2212, and / or an example of the tri-zone particle 850 of FIG. 8B. Additionally or alternatively, each second tri-zone particle 2222 may include second carbon fragments 2223 intertwined with each other and separated from each other by mesopores 2214. Each second tri-zone particle 2222 may have a second deformable perimeter 2225 configured to coalesce with one or more adjacent second non-tri-zone particles 2221 or second tri-zone particles 2222.

[0185] Additionally, the second porous carbonaceous region 2220 may include second aggregates 2226, where each second aggregate 2226 may include a number of second tri-zone particles 2222 connected together. In one or more specific examples, each second aggregate 2226 may have a major dimension within a range of 10 nanometers (nm) to 10 micrometers (μm). The mesopores 2214 may be interspersed throughout the second aggregates 2226, where each mesopore may have a major dimension between 3.3 nanometers (nm) and 19.3 nm. Furthermore, the second porous carbonaceous region 2220 may include second aggregates 2227, where each second aggregate 2227 may include a number of second aggregates 2226 connected together, where each aggregate may have a major dimension within an approximate range of 0.1 μm to 1,000 μm. The macropores 2218 can be interspersed throughout the second plurality of aggregates, where each macropore has a major dimension between 0.1 μm and 1,000 μm. In some embodiments, one or more of the carbonaceous materials, allotropes, and / or structures described above can be one or more of the examples shown in FIGS. 9A and 9B.

[0186] In one embodiment, the first porous carbonaceous region 2210 and / or the second porous carbonaceous region 2220 may include a selectively permeable shell (not shown in FIG. 22 for simplicity) that may form a separate liquid phase on the first porous carbonaceous region 2210 or the second porous carbonaceous region 2220, respectively. An electrolyte, such as any of the electrolytes disclosed in this invention, may be dispersed within the first porous carbonaceous region and / or the second porous carbonaceous region for lithium ion transport associated with a lithium-sulfur battery discharge-charge operating cycle.

[0187] In one or more specific examples, the first porous carbonaceous region 2210 can have a conductivity in the approximate range of 500 S / m to 20,000 S / m at a pressure of 12,000 pounds per square inch (psi). The second porous carbonaceous region 2220 can have a conductivity in the approximate range of 0 S / m to 500 S / m at a pressure of 12,000 pounds per square inch (psi). The first agglomerates 2217 and / or the second agglomerates 2227 can include aggregates connected together with one or more polymeric binders.

[0188] In some aspects, the first tri-zone particle 2212 or the second tri-zone particle 2222 may each include a first porous region (not shown in FIG. 22 for simplicity) located about a center of the respective first tri-zone particle 2212 or second tri-zone particle 2222. The first porous region may include first pores. The second porous region (not shown in FIG. 22 for simplicity) may surround the first porous region. The second porous region may include second pores. In one embodiment, the first pores may define a first pore density and the second pores may define a second pore density different from the first pore density.

[0189] In some embodiments, the mesopores 2214 may be grouped into first mesopores and second mesopores (both not shown in FIG. 22 for simplicity). In one or more particular examples, the first mesopores may have a first mesopore density and the second mesopores may have a second mesopore density that is different from the first mesopore density. Additionally, the macropores 2218 may be grouped into first macropores, which may have a first pore density, and second macropores, which may have a second pore density that is different from the first pore density (both not shown in FIG. 22 for simplicity).

[0190] In one embodiment, the first porous carbonaceous region 2210 and / or the second porous carbonaceous region 2220 may nucleate sulfur as necessary to facilitate the operational discharge-charge cycle of any of the lithium-sulfur batteries disclosed by the present invention. For example, the cathode 2200 may have a sulfur-to-carbon weight ratio of about 1:5 to 10:1. In some embodiments, one or more conductive additives may be dispersed within the first porous carbonaceous region 2210 and / or the second porous carbonaceous region 2220 to, for example, affect the discharge-charge cycle performance of the cathode 2200 accordingly. Additionally, a protective sheath, such as the protective grid 402 of FIG. 4, may be disposed over the cathode.

[0191] As used herein, a reference to "at least one" or "one or more" of a list of items refers to any combination of those items, including single members. For example, "at least one of a, b, or c" is intended to cover the possibilities of a only, b only, c only, a combination of a and b, a combination of a and c, a combination of b and c, and a combination of a, b, and c.

[0192] The various illustrative components, logic circuits, logic blocks, modules, circuits, operations, and algorithmic processes described in connection with the embodiments disclosed herein, including the structures disclosed herein and structural equivalents thereof, may be implemented as electronic hardware, firmware, software, or a combination of hardware, firmware, or software. Interoperability of hardware, firmware, and software has generally been described in terms of functionality and is illustrated in the various illustrative components, blocks, modules, circuits, and processes described above. Whether such functionality is implemented in hardware, firmware, or software depends on the application and design constraints imposed on the overall system.

[0193] Various modifications to the embodiments described in this disclosure may be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the present disclosure. Thus, the claims are not intended to be limited to the embodiments shown herein, but are to be accorded the widest scope consistent with the invention, principles, and novel features disclosed herein.

[0194] Additionally, various features described herein in the context of separate embodiments can also be implemented in combination in a single embodiment. Conversely, various features described in the context of a single embodiment can also be implemented in multiple embodiments separately or in any suitable subcombination. Thus, although features may be described above in combination with each other, and may even be initially claimed as such, one or more features from the claimed combination may, in some cases, be cut out from the combination, and the claimed combination may be directed to a subcombination or a variation of the subcombination.

[0195] Similarly, while operations are depicted in the figures in a particular order, this should not be understood as requiring such operations to be performed in the particular order or sequential order shown, or that all of the illustrated operations be performed, to achieve a desired result. Additionally, the figures may generally depict another exemplary process in the form of a flow chart or flow diagram. However, other operations not depicted may be incorporated into the generally illustrated exemplary process. For example, one or more additional operations may be performed before, after, simultaneously with, or between any of the illustrated operations. In some circumstances, multitasking and parallel processing may be advantageous. Additionally, the separation of various system components in the above-described embodiments should not be understood as requiring such separation in all embodiments, and it should be understood that the program components and systems described may generally be integrated together in a single product or packaged into multiple products.

Claims

1. A composition of a substance containing a plurality of pores, wherein the composition of the substance comprises: a plurality of particles, each of the particles comprising: a first zone containing a plurality of first pores, the plurality of first pores having a uniform pore size, the first zone; and a second zone containing a plurality of second pores, the second zone being positioned concentrically with respect to the first zone and being separated from the first zone by at least some of the plurality of first pores, the plurality of second pores having a pore size that gradually decreases along the radial direction from the center of the particle to the boundary of the particle, the second zone; the plurality of particles; a plurality of aggregates, each comprising a number of the particles linked together; a plurality of agglomerates, each comprising a number of the aggregates linked together; The composition of the substance comprising

2. The composition of the substance according to claim 1, wherein each of the particles has a major dimension in the approximate range of 20 nanometers (nm) to 150 nm.

3. The composition of the substance according to claim 1, wherein each of the aggregates has a major dimension in the approximate range of 10 nanometers (nm) to 10 micrometers (μm).

4. The composition of the substance according to claim 1, wherein each of the agglomerates has a major dimension in the approximate range of 0.1 micrometer (μm) to 1,000 μm.

5. The composition of the substance according to claim 1, wherein each of the pores has a major dimension in the approximate range of 0 nanometers (nm) to 100 nm.

6. The composition of the substance according to claim 1, wherein the first zone has a first porosity and the second zone has a second porosity different from the first porosity.

7. The composition of the substance according to claim 1, wherein the first zone has a first density and the second zone has a second density different from the first density.

8. The composition of the substance according to claim 1, wherein the first zone has a first pore density of 0.0 cubic centimeters (cc) / g to 2.0 cc / g.

9. The composition of the substance according to claim 1, wherein the second zone has a second pore density of 1.5 cubic centimeters (cc) / g to 5.0 cc / g.

10. The composition of the substance has a conductivity within a range of approximately 100 Siemens (S) / m to 20,000 S / m at a pressure of 12,000 pounds per square inch (psi), the composition of the substance according to claim 1.

11. The composition of the substance according to claim 1, wherein at least some of the aggregates are connected to each other by one or more polymer-based binders.

12. The composition of the substance according to claim 1, further comprising one or more conductive additives dispersed inside at least some of the plurality of pores.

13. Each of the particles of the composition of the substance according to claim 1 comprises one or more of flat graphene, wrinkled graphene, a plurality of carbon nanotubes (CNTs), or a plurality of carbon nano-onions (CNOs).

14. Each of the particles further comprises a third zone disposed concentrically on the second zone with respect to the center of each respective particle and separated from the second zone by at least some of the plurality of pores, the third zone comprising a plurality of third pores, the composition of the substance according to claim 1.

15. The plurality of first pores are macropores, the plurality of second pores are mesopores, and the plurality of third pores are micropores, the composition of the substance according to claim 1.

16. Each of the particles further comprises one or more additional zones disposed concentrically on the second zone with respect to the center of each respective particle, each of the one or more additional zones being separated from directly adjacent zones by at least some of the plurality of pores, the composition of the substance according to claim 1.

17. The pore size of the pores among the plurality of second pores gradually decreases along the radial direction, the composition of the substance according to claim 1.

Images