Dual-phase, ternary, and carbon-injected lithium alloys and self-supporting anodes for lithium-based batteries

Abstract

The self-supporting composite anode comprises a biphase Li-Mg-X ternary alloy. The composite anode features improved Li-ion transport and reduced dendrite formation. The biphase Li-Mg-X ternary alloy anode can be paired with an iron phosphate cathode. The amount of Li present can be from about 10 wt% to about 90 wt%. The amount of Mg present can be from about 5 wt% to about 50 wt%. One or more ternary alloy components may include calcium (Ca), gallium (Ga), boron (B), tin (Sn), aluminum (Al), indium (In), bismuth (Bi), antimony (Sb), tellurium (Te), carbon (C), silicon (Si), bismuth telluride (BiTe), antimony telluride (SbTe), zinc (Zn), etc., in amounts from about 1 wt% to about 90 wt%. The anode may contain one or more lithium-ion conducting materials: bismuth telluride (BiTe), antimony telluride (SbTe), lithium-doped tritelluride (LiTe3), lithium titanate (Li4Ti5O4), etc. 12 "LTO", lithium lanthanum zirconium oxide (Li7La3Zr2O) 12 Lithium phosphide (Li3P), molybdenum oxide (MoO), and molybdenum disulfide (MoS2) are also mentioned.

Description

[0001] Cross-references to related applications This international patent application is filed under the Patent Cooperation Treaty (PCT) and claims priority to the following: U.S. Provisional Patent Application No. 63 / 664,639, filed June 26, 2024, entitled "Biphasic, Three Dimensional Lithium-Based Alloys including Ternary Components and Applications Therefor"; U.S. Provisional Patent Application No. 63 / 658,087, filed June 10, 2024, entitled "Freestanding Lithium-Alloy Anodes For Lithium-based Batteries"; and U.S. Provisional Patent Application No. 63 / 658,087, filed January 2, 2024, entitled "Freestanding Lithium-Alloy Anodes For Lithium-based Batteries". The contents of each of the preceding applications are incorporated herein by reference in their entirety: U.S. Provisional Patent Application No. 63 / 616,995, filed December 29, 2023, entitled “Biphasic, Three Dimensional Lithium-Based Alloys including Ternary Components and Applications Therefor”; U.S. Provisional Patent Application No. 63 / 616,412, filed December 29, 2023, entitled “Graphitic Carbon Infused 3D Anode Composite Materials and Applications Therefor”; and U.S. Provisional Patent Application No. 63 / 616,427, filed December 29, 2023, entitled “Graphitic Carbon Infused 3D Anode Composite Materials and Applications Therefor”. Technical Field

[0002] This disclosure relates generally to batteries, and more specifically to lithium-based batteries that can provide a combination of high specific energy and energy density with long cycle life. Background Technology

[0003] Batteries, especially lithium-based batteries, are prone to failure due to various mechanisms, including the decomposition and reconstruction of one or more solid electrolyte interfaces (SEIs) that consume electrolytes, morphological changes that form highly porous structures in the anode, and the formation of dendritic deposits that may ultimately lead to internal short circuits within the electrochemical cell.

[0004] In particular, Li metal anodes undergo significant volume changes during repeated stripping and plating processes in normal cycling, due to the inherent hostless nature of the anode material. These severe volume changes can further destabilize the electrode-electrolyte interface, lead to persistent side reactions with the electrolyte, and cause electrode pulverization, thereby reducing its stability.

[0005] Furthermore, Li has the highest oxidation potential of all elements and can react with almost all substances present in electrolyte solutions (including solvents and salts) to form complex SEIs. SEIs are electronically insulated, but for Li... + Ions possess ionic conductivity, which allows for the partial blocking of reactions between Li metal and electrolytes. Therefore, SEIs provide kinetic protection for electrolytes that are normally thermodynamically reactive.

[0006] However, SEI is usually non-uniform, which can lead to uneven current distribution during deposition and may cause uneven Li deposition and cracking during cycling. This in turn exposes fresh Li metal to the electrolyte and leads to the consumption of active Li material and electrolyte.

[0007] Such localized, non-uniform Li deposition can manifest as dendrites, which pose serious problems for the safety and cycle life of Li metal battery cells. Dendrites may detach from the electrodes and form "dead" Li regions. Furthermore, Li dendrites can penetrate conventional polyolefin separators or even polymer / solid electrolyte separators, which has always been a major performance limiting factor for Li metal-based battery cells.

[0008] The problems mentioned above become further complicated in Li-S battery cells, where a large amount of soluble polysulfides are released from the cathode. These polysulfides can adversely participate in the formation of the SEI, thereby increasing SEI inhomogeneity, increasing anodic impedance, and exacerbating the corrosion of the Li metal anode. Therefore, repeated volume changes and corrosion continuously consume active Li and form a large amount of "dead Li," which detaches from the conductive substrate during cycling, resulting in poor recyclability of the Li-S battery.

[0009] Typically, it is the anode that causes cell failure, due to electrolyte depletion, for example, through corrosion or exhaustion during cycling. This type of failure is particularly common at high current densities, which are prevalent in high-energy Li-S pouch cells with dense cathodes, limited electrolytes, and limited anode reservoirs (or low N / P ratios).

[0010] Other problems encountered when using Li metal as the anode material are related to the current collector or substrate, which is traditionally copper. However, for Li-S battery cells, using a Cu substrate for the anode is disadvantageous because its mass reduces the specific energy of the cell (the mass fraction in Li-S battery cells is higher than that in Li-ion battery cells) and Cu corrosion may also occur due to polysulfides.

[0011] Substrate-free pure Li electrode design may partially solve some of the aforementioned challenges, but it carries significant risks due to the morphology and instability issues of the Li anode (as described above).

[0012] To address the issues of unstable Li metal anodes regarding volume changes and high reactivity to electrolytes and polysulfides, the use of Li alloys as anodes in Li-S battery cells has been proposed. Li can form alloys with several metals, including silicon, tin, magnesium, and aluminum, resulting in alloys that exhibit reversible electrochemical activity. Alloy-based anodes also exhibit higher electrode potentials relative to Li deposition; from a thermodynamic perspective, this higher electrode potential can inhibit corrosion reactions with electrolyte components. Simultaneously, the alloying elements can act as Li hosts to mitigate Li volume changes, thereby further stabilizing the electrode morphology and suppressing electrode pulverization. The alloy as a whole can form a more stable surface film on the anode, thus reducing uneven Li deposition.

[0013] However, using Li-based alloys as anode materials leads to a decrease in specific energy due to reduced capacity, and in some cases even a decrease in voltage. Furthermore, some alloying elements tend to undergo considerable volume changes during lithiation and delithiation (e.g., Si, Sn, and Ge), and therefore are not suitable candidates despite their high theoretical capacity. Moreover, alloys tend to exhibit reversibility within a limited compositional range (e.g., Li-Al), resulting in low capacity.

[0014] Furthermore, maximizing the full potential of Li metal and Li-based alloys (especially as anodic active materials in Li-based applications) presents formidable challenges that need to be overcome.

[0015] One such challenge involves the growth of dendritic lithium structures on the lithium-based anode during deposition. Dendrites can detach from the electrode, harmfully forming "dead" Li regions that reduce the amount of active material available for electrochemical operation. Furthermore, Li dendrites can penetrate conventional polyolefin membranes or even polymer / solid electrolyte membranes, which has been a major performance limiting factor for Li-based battery cells.

[0016] Some teams have attempted to address dendrite formation by incorporating metal foam into the anode composition or by forming the anode directly from metal foam. Other teams have addressed this issue similarly by incorporating or using self-supporting carbon films within the lithium metal or by using them as a three-dimensional host for the lithium metal. However, undesirably, these methods require the addition of significantly large amounts of inert material, thus reducing the energy density of the resulting battery. Furthermore, these techniques are not scalable and fail to meet the demands of modern high-energy battery systems.

[0017] Therefore, it is necessary to address these and / or other issues related to existing technologies. Summary of the Invention

[0018] This summary is provided to introduce a chosen concept in a simplified form, which will be further described in the detailed description section below. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter.

[0019] In some implementations, the composite anode associated with lithium-based batteries comprises a Li-Mg-X ternary alloy, a lithium-ion conductive material, and / or an electron-conducting material.

[0020] X refers to the tertiary component of the alloy, which, depending on various implementations, may comprise one or more tertiary components in an amount from about 1 wt% to about 90 wt%, such as about 1 wt%, about 2.5 wt%, about 3.33 wt%, about 5 wt%, about 6.66 wt%, about 7.5 wt%, about 10 wt%, about 12.5 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 33.3 wt%, about 35 wt%, about 40 wt%, about 50 wt%, about 60 wt%, about 66.6 wt%, about 70 wt%, about 75 wt%, about 80 wt%, about 90 wt%, or any value between these values ​​or in a subrange of the broader range from about 1 wt% to about 90 wt%. Furthermore, X may comprise one or more of the following: calcium (Ca), gallium (Ga), boron (B), tin (Sn), aluminum (Al), indium (In), bismuth (Bi), antimony (Sb), tellurium (Te), carbon (C), silicon (Si), bismuth telluride (BiTe), antimony telluride (SbTe), zinc (Zn), or any combination thereof. Preferably, the one or more tertiary components are substantially uniformly distributed throughout the bulk of the composite anode. Furthermore, the Li-Mg-X ternary alloy preferably comprises a Li-Mg alloy phase and a Li-X alloy phase. The weight ratio of the Li-Mg alloy phase to the Li-X alloy phase is between approximately 0.1 and approximately 20. In further embodiments, the lithium-ion conductive material may comprise: bismuth telluride (BiTe), antimony telluride (SbTe), lithium-doped tritelluride (LiTe3), lithium titanate (Li4Ti5O4), etc. 12 "LTO") or lithium lanthanum zirconium oxide (Li7La3Zr2O) 12 Lithium phosphide (Li3P), molybdenum oxide (MoO), molybdenum disulfide (MoS2), or any combination thereof.

[0021] Similarly, electron-conducting materials can contain carbon.

[0022] When the Li-Mg-X alloy contains carbon, the carbon can comprise: graphite, graphene, carbon nanotubes, hollow porous multi-nanochannel carbon fibers (HTCNF), non-graphitized carbon, carbon nanofibers, or any combination thereof. Notably, in some aspects, the carbon forms an electrochemically inert phase in the Li-Mg-X alloy. The carbon can also be substantially uniformly distributed throughout the bulk of the anode.

[0023] In various methods, the lithium content in the anode is between about 10 wt% and about 90 wt%, such as about 10 wt%, about 12.5 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 33.3 wt%, about 35 wt%, about 40 wt%, about 50 wt%, about 60 wt%, about 66.6 wt%, about 70 wt%, about 75 wt%, about 80 wt%, about 90 wt%, or any value between these values, or a subrange within the broader range of about 10 wt% to about 90 wt%.

[0024] Furthermore, the magnesium content in the anode or Li-Mg-X alloy is preferably a non-zero amount of up to about 50 wt%, such as about 1 wt%, about 2.5 wt%, about 3.33 wt%, about 5 wt%, about 6.66 wt%, about 7.5 wt%, about 10 wt%, about 12.5 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 33.3 wt%, about 35 wt%, about 40 wt%, about 50 wt%, or any value between these values, or a subrange within a broader range greater than about 0 wt% to about 50 wt%.

[0025] Furthermore, depending on the implementation method, the amount of lithium-ion conductive material can be between about 1 wt% and about 90 wt%, for example, about 1 wt%, about 2.5 wt%, about 3.33 wt%, about 5 wt%, about 6.66 wt%, about 7.5 wt%, about 10 wt%, about 12.5 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 33.3 wt%, about 35 wt%, about 40 wt%, about 50 wt%, about 60 wt%, about 66.6 wt%, about 70 wt%, about 75 wt%, about 80 wt%, about 90 wt%, or any value between these values, or a subrange within a broader range of about 1 wt% to about 90 wt%.

[0026] Therefore, in various implementations, the weight ratio of the Li-Mg-X alloy to the lithium-ion conductive material is preferably in the range of about 1 to about 9, or for example, a weight ratio of about 1, about 1.25, about 1.33, about 1.5, about 1.66, about 1.75, about 2, about 2.25, about 2.5, about 3, about 3.33, about 4, about 5, about 6, about 6.66, about 7, about 7.5, about 8, about 9, or any value or subrange in the broader range of about 1 to about 9.

[0027] In some methods, the composite anode may further comprise alumina (Al2O3) and / or titanium dioxide (TiO2).

[0028] In some methods, the composite anode can further contain a combination of such materials (e.g., LTO and titanium dioxide (TiO2, which is one of our formulations).

[0029] Composite anodes can be in the form of self-supporting three-dimensional monolithic materials.

[0030] In some methods, the composite anode of claim 1 may further include a polymer coating on one or more surfaces of the anode, said polymer coating comprising one or more of the following: polyvinylidene fluoride (PVDF), pentaerythritol tetraacrylate (PETEA), polyethylene glycol dimethacrylate (PEGDMA), or any combination thereof. The thickness of the polymer coating may be anywhere in the range of about 100 nm to about 10 µm, for example, about 100 nm, about 200 nm, about 250 nm, about 300 nm, about 333 nm, about 400 nm, about 450 nm, about 500 nm, about 600 nm, about 700 nm, about 800 nm, about 900 nm, about 1 µm, about 2 µm, about 3 µm, about 5 µm, about 6.66 µm, about 7.5 µm, about 10 µm, or any value between these values, or in a subrange within the broader range of about 100 nm to about 10 µm.

[0031] Similarly, according to a selected aspect of the inventive concept described in this invention, the overall thickness of the composite anode is approximately 100 μm.

[0032] The composite anode can be part of an electrochemical cell unit, characterized by a button-type configuration, a cylindrical configuration, a prismatic configuration, a pouch configuration, or any other suitable configuration as described herein, or its equivalent as understood by one of ordinary skill in the art upon reading this disclosure. In some methods, the electrochemical cell unit neither includes nor is coupled to any different structure serving as a current collector other than the three-dimensional (3D) monolithic material itself.

[0033] In some other aspects, the exemplary anode may further comprise one or more of alumina (Al₂O₃) or titanium dioxide (TiO₂). In some instances, the amount of lithium-ion conducting material in the anode may be between about 1 wt% and about 90 wt%. In some other instances, the weight ratio of the Li-Mg alloy to the lithium-ion conducting material may be between about 1 and about 9. In some implementations, the magnesium content in the Li-Mg alloy in the anode may be between about 5 wt% and about 50 wt%.

[0034] In some implementations, the electron-conducting material in the anode may comprise one or more of carbon, aluminum, or silicon. In some instances, the carbon may comprise graphite.

[0035] In some implementations, the anode associated with the lithium-based battery may comprise a lithium-magnesium ternary alloy. In other implementations, the anode associated with the lithium-based battery may comprise a Li-Al-Mg ternary alloy. In some instances, the aluminum content in the Li-Al-Mg ternary alloy may be between approximately 5 wt% and approximately 20 wt%. In some instances, the Li-Al-Mg ternary alloy may further comprise any of the lithium-ion conductive materials or fillers described earlier herein.

[0036] In some implementations, the anode associated with the lithium-based battery may comprise a Li-Si-Mg ternary alloy. In some instances, the silicon content in the Li-Si-Mg ternary alloy may be between approximately 5 wt% and approximately 20 wt%. In some instances, the Li-Si-Mg ternary alloy may further comprise any of the lithium-ion conducting materials described earlier herein.

[0037] In some other implementations, the anode associated with the lithium-based battery may comprise a Li-Mg / carbon alloy. In some instances, the carbon content in the Li-Mg / C alloy may be between approximately 1 wt% and approximately 20 wt%. In some instances, the Li-Mg / C alloy may further comprise any of the lithium-ion conducting materials described earlier herein.

[0038] In some implementations, the anode associated with the lithium-based battery may comprise a two-phase alloy comprising a Li-Mg alloy phase and a Li-x alloy phase. In some aspects, the Li-x alloy phase may comprise an alloy of lithium with one of calcium, boron, tin, aluminum, indium, bismuth, antimony, or zinc. In other aspects, the Li-x alloy phase may comprise a Li₂Ca (also referred to herein as CaLi₂) alloy phase. In some instances, the weight ratio of the Li-Mg alloy phase to the Li₂Ca alloy phase may be between approximately 0.1 and approximately 20.

[0039] In some implementations, the dual-phase alloy comprising the Li-Mg alloy phase and the Li2Ca alloy phase may be characterized by a lithium content between about 55 wt% and about 75 wt%, a magnesium content between about 15 wt% and about 30 wt%, and a calcium content between about 2 wt% and about 30 wt%.

[0040] In some implementations, any of the anodes described herein may include a polymer coating disposed on the anode, said polymer coating comprising one or more of polyvinylidene fluoride (“PVDF”), pentaerythritol tetraacrylate (“PETEA”), or polyethylene glycol dimethacrylate (“PEGDMA”). The thickness of the anode may be approximately 100 µm. The thickness of the polymer coating may be between approximately 1 µm and approximately 10 µm.

[0041] In some implementations, a lithium-based battery may include any of the anodes disclosed herein, and a fluorinated ether electrolyte comprising approximately 50:25:25 (volume%) of 1,2-dimethoxyethane (“DME”):1,3-dioxane (“DOL”):bis(2,2,2-trifluoroethyl) ether (“BTFE”), and containing approximately 0.4 M lithium bis(trifluoromethanesulfonyl) (LiTFSI) and approximately 2 wt% LiNO3. In some examples, the anode associated with the lithium-based battery may include an anode comprising a Li-Mg alloy, and one or more of lithium-ion conducting materials or electron conducting materials.

[0042] In some implementations, the fluorinated electrolyte in a Li-S cell, including any of the anodes described herein, may comprise approximately 50:25:25 (volume%) of DME:DOL:1,1,2,2-tetraethoxyethane (“TEE”) and approximately 0.4 M LiTFSI and approximately 2 wt% LiNO3.

[0043] In some implementations, the fluorinated electrolyte in a Li-S cell, including any of the anodes described herein, may comprise approximately 50:25:25 (volume%) of DME:DOL:1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether (“TFETFE”) and approximately 0.4 M LiTFSI and approximately 2 wt% LiNO3.

[0044] In some implementations, the fluorinated electrolyte in a Li-S cell, including any of the anodes described herein, may comprise approximately 60:20:10:10 (volume%) of DME:DOL:TEE:TFETFE and approximately 0.4 M LiTFSI and approximately 2 wt% LiNO3.

[0045] In some implementations, the fluorinated electrolyte in a Li-S cell, including any of the anodes described herein, may comprise approximately 50:25:25 (volume%) of DME:DOL:1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (“TTE”) and approximately 0.4 M LiTFSI and approximately 2 wt% LiNO3.

[0046] In some implementations, the fluorinated electrolyte in a Li-S cell, including any of the anodes described herein, may comprise approximately 50:25:25 (volume%) of DME:DOL:1 fluorinated 1,4-dimethoxybutane (“FDMB”), containing approximately 0.4 M LiTFSI and approximately 2 wt% LiNO3.

[0047] In some implementations, the fluorinated electrolyte in a Li-S cell containing any of the anodes described herein may be contained in approximately 1.0 M LiTFSI in an approximately 50:50 (volume %) DOL:BTFE composition.

[0048] In some implementations, an exemplary lithium-based battery may include a cathode disposed opposite to any of the anodes described herein. In some implementations, an exemplary cathode may include one or more porous carbon layers comprising porous carbon aggregates of porous primary carbon nanoparticles, wherein each porous primary carbon nanoparticle may include an inner porous shell disposed around the center of the respective porous primary carbon nanoparticle and encapsulating an inner porous carbon region; an outer porous shell encapsulating an outer porous carbon region disposed between the inner shell and the outer shell; and an interconnected porous network disposed within and in fluid communication with the inner and outer porous carbon regions.

[0049] In some aspects, the internal and external carbon regions of exemplary porous carbon primary nanoparticles may be characterized by the average pore size and average pore density associated with each region. In other aspects, the average pore size may decrease radially from the center to the outer porous shell.

[0050] In some instances, exemplary porous carbon primary nanoparticles may further include one or more intermediate porous shells disposed between an inner porous shell and an outer porous shell, wherein each of the intermediate porous shells encapsulates a corresponding intermediate porous carbon region.

[0051] In some respects, porous carbon aggregates can be characterized by I D / I GThe Raman spectral characteristics are between approximately 0.95 and approximately 1.05. In some other respects, the porous carbon aggregates can be characterized by a Brunauer-Emmett-Teller (“BET”) surface area of ​​approximately 50 m², as measured using nitrogen. 2 / g and 300 m 2 Between / g. In some respects, porous carbon aggregates are characterized by an electrical conductivity between approximately 500 S / m and 20,000 S / m when compressed at a pressure of approximately 12,000 psi.

[0052] In some implementations, an exemplary cathode associated with a lithium-based battery may comprise porous carbon agglomerates of porous primary carbon nanoparticles, the porous carbon agglomerates comprising one or more interconnected bundles of conductive graphene layers. In some aspects, the graphene layers may be arranged as one or more stacks interconnected to each other and defining a 3D porous scaffold structure comprising mesopores. In some other aspects, the one or more stacks may be arranged substantially orthogonally to each other. In some instances, the graphene layers may be characterized by linear dimensions between approximately 50 nm and approximately 200 nm. In some other instances, the graphene layers may comprise one or more of monolayer graphene (“SLG”), few-layer graphene (“FLG”), or multilayer graphene (“MLG”). In some aspects, the porous carbon agglomerates may be characterized by a conductivity between approximately 500 S / m and 20,000 S / m when compressed at a pressure of approximately 12,000 psi.

[0053] In some implementations, the geometry of any of the previously described Li-S batteries can be cylindrical. A cylindrical battery can have a diameter of approximately 18 mm and a length of approximately 65 mm. In some implementations, a cylindrical battery can have a diameter of approximately 21 mm and a length of approximately 70 mm. In some implementations, a cylindrical battery can have a diameter of approximately 46 mm and a length of approximately 80 mm.

[0054] The accompanying drawings and the following description illustrate details of one or more implementations of the subject matter described in this disclosure. Other features, aspects, and advantages will become clear from the description, drawings, and claims. Note that the relative dimensions in the following drawings may not be drawn to scale. Attached Figure Description

[0055] Figure 1 A graph illustrating the cathode discharge capacity of an exemplary lithium-based coin cell according to some implementations is shown, the lithium-based coin cell comprising a self-supporting Li-Mg alloy anode with different Li-Mg compositions.

[0056] Figure 2A Exemplary X-ray diffraction (XRD) patterns of a dual-phase self-supporting anode alloy comprising a Li-Mg alloy phase and a Li2Ca alloy phase are shown according to some implementations.

[0057] Figure 2B A scanning electron microscope (SEM) image of a cross section of an exemplary biphase self-supporting anode alloy, comprising a Li-Mg alloy phase and a Li2Ca alloy phase, is shown according to some implementations.

[0058] Figure 2C Another SEM image of an exemplary dual-phase self-supporting anode alloy, comprising a Li-Mg alloy phase and a Li2Ca alloy phase, is shown according to some implementations.

[0059] Figure 3A A scanning electron microscope (SEM) image of a cross section of an exemplary biphase self-supporting anode alloy, comprising a Li-Mg alloy phase and a Li2Ca alloy phase, is shown according to some implementations.

[0060] Figures 3B to 3C The image shows an SEM-energy dispersive X-ray spectroscopy (EDS) elemental distribution image of an exemplary dual-phase self-supporting anode alloy, comprising a Li-Mg alloy phase and a Li2Ca alloy phase, according to some implementations.

[0061] Figure 4A The diagram illustrates voltage profiles of an exemplary lithium-based half-cell cell according to some implementations, the exemplary lithium-based half-cell cell including a self-supporting composite anode comprising a Li-Mg alloy and lithium titanate (“LTO”).

[0062] Figures 4B to 4C SEM images and SEM-EDS elemental distribution images of exemplary Li-Mg alloy anodes and self-supporting composite anodes containing Li-Mg alloy / LTO, according to some implementations, are shown respectively.

[0063] Figure 5A A schematic diagram of an exemplary porous carbon primary nanoparticle is shown, according to some implementation methods.

[0064] Figure 5B The image shown is a transmission electron microscope (TEM) image, which shows aggregates of porous carbon primary nanoparticles according to some implementations.

[0065] Figure 5CTEM images of aggregates of porous carbon primary nanoparticles are shown, according to some implementations.

[0066] Figure 5D TEM images of surface-etched aggregates of porous carbon primary nanoparticles are shown, according to some implementations.

[0067] Figure 5E A schematic diagram of another exemplary porous carbon primary nanoparticle is shown, according to some implementation methods.

[0068] Figure 6A A schematic diagram of aggregates of porous carbon primary nanoparticles is shown, according to some implementation methods.

[0069] Figure 6B The image shows scanning electron micrographs (SEM) of aggregates of porous carbon primary nanoparticles according to some implementation methods.

[0070] Figure 6C The image shows a TEM micrograph of aggregates of porous carbon primary nanoparticles according to some implementation methods.

[0071] Figure 7 A schematic diagram is shown, depicting an exemplary lithium-based cylindrical battery according to some implementations.

[0072] Figure 8A A diagram is shown illustrating the cathode discharge capacity of a lithium-based coin cell according to some implementations, the lithium-based coin cell including a biphase self-supporting anode comprising a Li-Mg alloy phase and a Li2Ca alloy phase.

[0073] Figure 8B Another diagram is shown, illustrating the cathode discharge capacity of a lithium-based coin cell according to some implementations, the lithium-based coin cell including a biphase self-supporting anode comprising a Li-Mg alloy phase and a Li2Ca alloy phase.

[0074] Figure 9A The diagram illustrates the rate performance of a lithium-based symmetric battery cell, comprising a self-supporting composite anode, according to several implementations, including a self-supporting composite anode containing a Li-Mg alloy and LTO.

[0075] Figure 9B A plot is shown illustrating the corrosion current after lithium stripping, measured using a lithium-symmetric cell according to some implementations, the lithium-symmetric cell including a self-supporting composite anode comprising a Li-Mg alloy and LTO.

[0076] Figure 9CA plot is shown illustrating the corrosion current after lithium deposition measured using a lithium-symmetric cell, according to some implementations, comprising a self-supporting composite anode containing a Li-Mg alloy and LTO.

[0077] Figure 10A A diagram is shown illustrating the cathode discharge capacity of a lithium-based coin cell, comprising a self-supporting composite anode, according to some implementations, wherein the self-supporting composite anode comprises a Li-Mg alloy and LTO.

[0078] Figure 10B The diagrams shown depict the discharge capacity, capacity retention, and coulombic efficiency of the exemplary Li-Mg / LTO alloy relative to the baseline Li-Mg.

[0079] Figure 10C The diagram shows the specific capacity and coulombic efficiency of several exemplary Li-Mg / LTO formulations with different magnesium contents compared to the baseline Li-Mg.

[0080] Figure 10D Several SEM images of the Li-Mg anode surface and the 3D Li-Mg-LTO anode surface after the first stripping and precipitation cycle, according to one implementation, are shown.

[0081] Figures 11A to 11B The diagram illustrates the cathode discharge capacity and capacity retention of a lithium-based coin cell, which includes a self-supporting Li-Al-Mg ternary alloy anode, according to some implementations.

[0082] Figures 12A to 12C The diagram illustrates the cathode discharge capacity, capacity retention, and coulombic efficiency of a lithium-based coin cell, which includes a self-supporting Li-Si-Mg ternary alloy anode, according to several implementations.

[0083] Figures 13A to 13F The diagram illustrates the cathode discharge capacity, capacity retention, polarization, and coulombic efficiency of a lithium-based coin cell, which includes a self-supporting Li-Mg / C alloy anode, according to several implementations.

[0084] Figure 14A A simplified schematic cross-sectional view of an electrochemical battery cell, characterized by a pouch cell arrangement, is shown as an embodiment of the inventive concept disclosed in this invention.

[0085] Figure 14B This is one embodiment of the inventive concept disclosed in this invention. Figure 14A A simplified schematic external view of the electrochemical battery cell shown.

[0086] Figure 14C A method according to the inventive concept disclosed in this invention is described. Figure 14B The diagram shows a simplified illustration of the arrangement of pouch cell units (wound into a core configuration).

[0087] Figure 15A This is a simplified schematic diagram of an electrochemical battery cell, which is characterized by a button cell arrangement, and is an implementation of the inventive concept disclosed in this invention.

[0088] Figure 15B An exploded view based on a simplified schematic is depicted. Figure 15A The various components of the button cell shown are arranged as illustrated.

[0089] Figure 16A This is a simplified schematic diagram of an electrochemical battery cell, one aspect of the inventive concept disclosed in this invention, characterized by a cylindrical battery cell arrangement.

[0090] Figure 16B This is one implementation of the inventive concept disclosed in this invention. Figure 16A The simplified schematic cross-sectional view of the exemplary components of the cylindrical battery cell arrangement shown is illustrated.

[0091] Figure 17 This is a simplified schematic diagram of an electrochemical battery cell, one aspect of the inventive concept disclosed in this invention, characterized by a cylindrical battery cell arrangement.

[0092] Figure 18 The diagram illustrates various forms of carbonaceous materials and methods for producing said materials from elemental carbon (e.g., charcoal), which may be incorporated into various components of an electrochemical battery cell, as shown in the aforementioned diagram.

[0093] The same reference numerals and symbols in the various figures denote the same elements. Detailed Implementation

[0094] The following description relates to some exemplary implementations, the purpose of which is to illustrate the innovative aspects of this disclosure. However, those skilled in the art will readily recognize that the teachings herein can be applied in a variety of different ways. The described implementations can be implemented in batteries for various applications and can be tailored as needed to compensate for various performance-related deficiencies. Therefore, the disclosed implementations are not limited to the examples provided herein, but cover all implementations contemplated by the appended claims. Furthermore, in order not to obscure relevant details of this disclosure, well-known elements of this disclosure will not be described in detail or will be omitted.

[0095] This document will describe in more detail various aspects of the novel components and methods with reference to the accompanying drawings. These aspects are provided so that this disclosure will be exhaustive and complete, and will enable those skilled in the art to fully understand the scope of this disclosure. Although some examples and aspects are described herein, many variations and arrangements of these examples fall within the scope of this disclosure. While some benefits and advantages of preferred aspects have been mentioned, the scope of this disclosure is not intended to be limited to benefits, uses, or purposes. The detailed description and accompanying drawings are illustrative only and not limiting of this disclosure, the scope of which is defined by the appended claims and their equivalents.

[0096] In this disclosure, primary carbon nanoparticles can be considered as spherical, non-discrete components or building blocks of aggregates, separable only by breakage from the aggregates. Multiple primary carbon nanoparticles produced by one or more methods (including thermal decomposition of hydrocarbon gases) can aggregate or combine to form aggregates of primary carbon nanoparticles. Carbon aggregates can be considered as discrete colloidal entities, which are the smallest dispersible units composed of aggregated primary carbon nanoparticles. Primary carbon nanoparticles can be linked together by one or more of van der Waals forces, covalent bonds, ionic bonds, metallic bonds, or other physical or chemical interactions. Multiple aggregates can be considered as agglomerates. Agglomerates of primary carbon nanoparticles can be prepared by one or more methods, including thermal decomposition of hydrocarbon gases. Exemplary porous carbon agglomerates of primary carbon nanoparticles may be characterized by a major size of at least about 1 µm.

[0097] In this publication, "graphene" refers to a carbon allotrope in the form of an atomically scaled hexagonal lattice, where each vertex is formed by a single atom. The carbon atoms in graphene can be sp... 2 Hybridized carbon atoms. Furthermore, the Raman spectrum of graphene exhibits two main peaks: one at approximately 1580 cm⁻¹. -1 The G-mode at approximately 1350 cm -1 The D-mode at the location (when using a 532 nm excitation laser). As used herein, carbonaceous materials can refer to materials containing one or more types or configurations of carbon or formed therefrom.

[0098] The commercialization of lithium-based (“Li-S”) batteries is hampered by a limited number of charge / discharge cycles of fewer than approximately 100. Root cause analysis indicates that Li metal anode failure is the primary cause of cell failure. During cycling, the Li metal anode undergoes significant volume changes due to repeated lithium stripping (during discharge) and deposition (during charging). These volume changes negatively impact anode stability, particularly for unsupported (or self-supported) Li metal anodes. In self-supported Li metal anodes, the anode is not supported on a metal substrate (such as a copper current collector). Anode stability is further affected by electrode-electrolyte interface instability and anode pulverization caused by volume changes during cycling, as lithium has a high oxidation potential (approximately 3.04 V) and can react with almost any electrolyte solution (with solvents or salts) to form a solid electrolyte interphase (“SEI”) layer.

[0099] The SEI layer is electronically insulating, but for Li + Ions possess ionic conductivity. Therefore, once the SEI layer forms, additional undesirable reactions between the Li metal anode and the electrolyte may be blocked or partially blocked by the SEI layer. However, the SEI layer is typically non-uniform, which leads to uneven current distribution during deposition and can cause uneven (or non-uniform) lithium deposition and anode cracking during cycling. Fresh lithium metal anodes may be exposed to the electrolyte, resulting in undesirable lithium consumption and thus reforming the SEI layer. Localized non-uniform lithium deposition and stripping can manifest as dendrites at the anode during deposition and as pits during stripping during charge / discharge cycles. Dendrites can cause serious safety issues and reduce the cycle life of lithium-ion batteries. Additionally, dendrites can detach from the anode, forming “dead” lithium regions. Lithium dendrites can penetrate the polyolefin separator or even the polymer / solid electrolyte separator between the battery anode and cathode, negatively impacting the safety and performance of the Li-ion battery.

[0100] The aforementioned problems are further exacerbated in lithium-based batteries (as understood herein, lithium-based batteries include electrochemical battery cells that utilize lithium, its alloys, its composites, etc., as active materials in one or more of their electrodes, especially those electrochemical battery cells in which lithium is the primary, dominant, or substantial component), particularly in Li-S batteries, which include sulfur confined in a porous carbon cathode as the active cathode material. Sulfur reacts with lithium ions to form polysulfides. During discharge cycling, Li ions migrate from the anode to the cathode through the electrolyte, where sulfur is reduced to lithium sulfide (Li₂S). The reduction of sulfur to Li₂S is complex and may involve several intermediate lithium polysulfides (Li₂S). xThe formation of polysulfides (“Li-PS”) (where 8 < x < 1) is possible. During battery discharge cycling, polysulfides may form as follows: S8 → Li2S8 → Li2S6 → Li2S4 → Li2S3 → Li2S2 → Li2S Ideally, Li-PS compounds would be oxidized back to sulfur during charge cycling. In practice, however, Li-PS compounds leak from the porous carbon cathode because they are highly soluble in the electrolyte, leading to sulfur loss and reduced cathode capacity. While sulfur and Li₂S are relatively insoluble in most electrolytes, many intermediate polysulfides (“Li-PS”) are soluble and cause irreversible loss of active sulfur from the cathode. To minimize the saturation effect of Li-PS dissolution in the electrolyte, a large electrolyte volume (E / S > 3) is required, which reduces the battery's specific energy. Higher-order polysulfides (Li₂S₈ and Li₂S₆) may diffuse to the anode and may be reduced to lower-order polysulfides (Li₂S₆ and Li₂S₄), which are subsequently re-oxidized at the cathode. At the anode, polysulfides participate in SEI formation, increasing SEI inhomogeneity, increasing anode impedance, and exacerbating corrosion of the Li metal anode. This cycling process, commonly known as "polysulfide shuttle," leads to poor coulombic efficiency and gradual leakage of active sulfur material from the cathode, which also reduces the battery's cycle life. Furthermore, elemental sulfur migrates to Li₂S… x The conversion of sulfur compounds is accompanied by a large volume expansion at the cathode (potentially up to 80%), which subjectes the cathode to significant mechanical stress, leading to rapid cathode degradation.

[0101] Additionally, the "shuttle effect" is a cause of self-discharge in Li-S batteries because Li-PS dissolves slowly during battery dormancy. Self-discharge reduces battery life and raises safety concerns. Repeated volume changes and corrosion reactions at the anode continuously consume active Li and form a large amount of "dead Li," which may detach during cycling, resulting in poor recyclability of the Li-S battery. As previously noted, it is typically the anode that causes cell failure, either through electrolyte depletion due to corrosion or through its depletion during cycling. These challenges limit the commercial viability of high-specific-energy Li-S batteries with dense cathodes, limited electrolytes, and limited anode capacity (or low N / P ratio). The N / P ratio can be defined as the ratio of the reversible capacity (mAh) of the negative electrode (anode) to the reversible capacity of the positive electrode (cathode), assuming complete sulfur utilization.

[0102] Therefore, excess electrolyte is used in Li-S batteries to mitigate conductivity loss due to dissolved Li-PS. Additionally, excess lithium metal is required at the anode to mitigate lithium metal loss due to SEI formation, pitting, and dendrite formation. These requirements hinder attempts to achieve or exceed the specific energy target of 500 Wh / kg for Li-S batteries. Li-S batteries typically require an electrolyte-to-sulfur ratio (“E / S ratio”) of approximately 5 μL / mgS and an N / P ratio greater than 2. In contrast, the N / P ratio of commercially available Li-ion batteries is between approximately 1.03 and 1.2. While the N / P ratio is important for offsetting potentially high anode material losses during cycling, areal capacity (mAh / cm²) is also crucial. 2 This is also crucial for reducing the current density at the anode and thus reducing the failure rate.

[0103] Li-S anodes typically use current collectors such as copper as anode supports. Copper significantly increases the weight of Li-S batteries and reduces their specific energy. Copper is also susceptible to corrosion by polysulfides. Therefore, there is great interest in developing substrate-free or self-supporting anodes. However, self-supporting anodes in Li-S batteries are challenging due to the morphology and instability issues of lithium metal (100% lithium) anodes. There is a need for self-supporting anode alloy compositions that are stable in Li-S batteries under cycling conditions and for coin cell cells at low E / S ratios of approximately 5 or less, and for pouch cell cells at 3 or less. There is also a need for self-supporting anode compositions that are stable in Li-S batteries under cycling conditions and at N / P ratios of approximately less than 2, thereby achieving a battery specific energy of 500 Wh / kg.

[0104] In some implementations, Li alloys can be used as self-supporting anodes instead of pure lithium metal anodes, thereby overcoming the previously mentioned anode instability issues related to volume changes during cycling and the high reactivity of Li metal anodes with electrolytes and polysulfides. Lithium can form alloys with several metals, including one or more of silicon, tin, magnesium, or aluminum. Li alloy anodes are characterized by a higher electrode potential than lithium and can inhibit corrosion at the anode caused by reactions between the anode and polysulfides and the electrolyte. Simultaneously, the alloying elements can act as lithium hosts for lithium deposition or precipitation (during charging cycles), absorbing volume changes during cycling and helping to stabilize the anode. The alloying elements can form a stable surface film on the anode, thereby reducing uneven lithium deposition during precipitation.

[0105] Some elements alloyed with lithium can reduce the capacity of Li-S batteries and subsequently decrease their specific energy (Wh / kg). Additionally, some alloying elements, such as silicon (Si), tin (Sn), and germanium (Ge), may undergo significant volume changes during lithiation (deposition during charging cycles) and delithiation (stripping during discharge) and may not be suitable candidates for Li-S battery anodes. Lithium can form Li-S alloys with elements such as silicon and tin. x M y These are intermetallic compounds of a certain type, characterized by high ionic bonding and therefore brittle and fragile. Other lithium alloys, such as lithium-aluminum alloys, are reversible only within a limited compositional range and may not be suitable for use in Li-S batteries.

[0106] In some implementations, alloying lithium with a small amount of magnesium (Mg) can improve the stability of the Li-S battery anode in its reaction with the electrolyte and polysulfides, and increase the battery's cycle life. In lithium-magnesium (“Li-Mg”) alloy anodes, the magnesium alloying element can provide structural integrity to the anode during the volume changes associated with battery cycling, as magnesium does not undergo stripping and precipitation at the anode. Additionally, alloying lithium with a small amount of magnesium allows for self-supporting anode designs (without the need for a copper current collector substrate), thereby also increasing the battery's specific energy.

[0107] Li and Mg have comparable atomic radii and form extended single-phase (body-centered cubic or BCC) alloys in Li-Mg alloys over a wide compositional range of approximately 11.5–100 wt% lithium. Therefore, the capacity of Li-Mg alloy anodes can be tuned over a wide range without considering any alloy phase transformations. Li-Mg alloys can provide scaffold-like structures that facilitate Li-Mg anode formation during charge / discharge cycles in Li-S batteries. + Ion insertion and removal. The volume change associated with one mole of Li insertion into Mg can be approximately 80%, as calculated using the lattice parameters of the Li-Mg alloy, which is far lower than the volume change associated with the interaction of lithium with other alloying elements such as silicon, tin, and antimony. Li-Mg alloys exhibit very high ductility, allowing for direct fabrication of electrodes via rolling and annealing. When replacing a Li anode (100% lithium) with a Li-Mg anode at approximately 90% Li-rich composition, no voltage loss can be observed, as lithium stripping and deposition can occur near 0 V. Furthermore, due to the lithiophilic nature of magnesium, dispersed magnesium in the Li-Mg anode can serve as nucleation sites for uniform lithium deposition during charge cycling.

[0108] Because Li-Mg alloy anodes form a relatively stable SEI interface (compared to Li anodes), a relatively smooth anode surface morphology can be achieved during the cycling operation of Li-S batteries. Furthermore, after Li stripping, a lithium-poor Li-Mg alloy matrix with high electronic and ionic conductivity can be formed, providing an excellent anode current collector and host for subsequent Li deposition. Therefore, Li-Mg alloy anodes can be self-supporting and may not require a separate anode current collector.

[0109] As previously mentioned, lithium has a high oxidation potential (approximately 3.04 V) and can react with almost any electrolyte solution (in solvent or as a salt) to form a solid electrolyte interphase (“SEI”) layer. The stability of lithium anodes is further affected by electrode-electrolyte interphase instability and anode pulverization caused by volume changes during cycling. Alloying lithium with metals, including magnesium, can improve the stability of the anode in lithium-based battery cells, but this increase in stability typically requires increasing the number of formation cycles needed to achieve the target cathode discharge capacity.

[0110] Figure 1 Figure 100 illustrates the cathode discharge capacity of an exemplary lithium-based coin cell according to several implementations, the coin cell comprising a self-supporting Li-Mg alloy anode with varying Li-Mg compositions. The cells were tested at a charge / discharge rate of C / 3 after two cycles at C / 20 followed by one cycle at C / 10 (also referred to herein as activation) cycling. The magnesium content in the Li-Mg alloy ranged from approximately 10 wt% to approximately 28 wt%. The thickness of the Li-Mg self-supporting alloy anode was approximately 100 μm. The cathode loading was approximately 7.5 mg / cm³. 2 The cathode capacity in each case is approximately 4 mAh / cm³. 2 A Celgard PP2075 diaphragm is positioned between the cathode and anode. The anode does not include any polymer coating. The electrolyte comprises approximately 50:25:25 (volume%) 1,2-dimethoxyethane (“DME”):1,3-dioxane (“DOL”):bis(2,2,2-trifluoroethyl) ether (“BTFE”), and contains approximately 0.4 M lithium bis(trifluoromethanesulfonyl)imide (“LiTFSI”) and approximately 2 wt% LiNO3. The electrolyte to sulfur (“E / S”) ratio is approximately 5.

[0111] refer to Figure 1As the Mg content in the Li-Mg alloy anode increases beyond 12 wt%, the initial cathode discharge capacity at C / 20 rate decreases. With the 72Li-28Mg alloy anode (72 wt% Li and 28 wt% Mg), the measured initial discharge capacity is less than 200 mAh / g, a 3-fold decrease compared to the capacity measured with the 90Li-10Mg alloy anode. Under repeated formation cycles, the discharge capacity produced by a battery cell including the 85Li-15Mg alloy anode is comparable to that of the 90Li-10Mg anode. This extended formation cycle of approximately 25 cycles is impractical for several applications. A battery cell including the 72Li-28Mg alloy anode did not show a significant increase in discharge capacity after 40 long-term formation cycles. Therefore, increased anode stability in the Li-Mg alloy anode can be achieved at the expense of discharge capacity and formation cycle time. Improved anode stability and a high discharge capacity of approximately 600 mAh / g with fewer than approximately 5 formation cycles are required.

[0112] In some implementations, the self-supporting anode associated with a lithium-based battery may comprise a biphase alloy comprising a Li-Mg alloy phase and a Li-x alloy phase. In some aspects, the Li-x alloy phase may comprise an alloy of lithium with one of calcium, boron, tin, aluminum, indium, bismuth, antimony, or zinc. In other aspects, the Li-x alloy phase may comprise a Li₂Ca (also referred to herein as CaLi₂) alloy phase. In some instances, the weight ratio of the Li-Mg alloy phase to the Li₂Ca alloy phase may be between approximately 0.1 and approximately 20.

[0113] In some implementations, the biphase alloy comprising a Li-Mg alloy phase and a Li2Ca alloy phase may contain between approximately 55 wt% and approximately 75 wt% lithium, between approximately 15 wt% and approximately 30 wt% magnesium, and between approximately 2 wt% and approximately 30 wt% calcium. The cathode discharge capacity of an exemplary lithium-based coin cell is discussed below in Example 1, the coin cell comprising a self-supporting biphase alloy anode comprising a Li-Mg alloy phase and a Li2Ca alloy.

[0114] Figure 2AExemplary X-ray diffraction (“XRD”) pattern 200A of a dual-phase self-supporting anode alloy comprising a Li-Mg alloy phase and a Li2Ca alloy phase is shown according to some implementations. The elemental composition of the exemplary dual-phase anode alloy is approximately 55 wt% Li, approximately 17 wt% Mg, and approximately 28 wt% Ca. As can be seen, XRD pattern 200A confirms the presence of the Li-Mg alloy phase, based on the reference XRD fingerprint of a 90 wt% Li-10 wt% Mg alloy (“90Li-10Mg reference”, middle plot), whose characteristic peaks correspond to the (110) crystal plane, as indicated by the arrows pointing to the peaks in the sample and reference. Additionally, XRD pattern 200A confirmed the presence of the Li2Ca alloy phase, based on the reference XRD fingerprint of the Li2Ca alloy (“Li2Ca Reference”, bottom plot), whose fingerprint corresponds to the (100), (002), (101), (102), (110), (103), (200) and (112) crystal planes, as indicated by the circled peaks.

[0115] Figure 2B A scanning electron microscope (“SEM”) micrograph 200B is shown as a cross-section of an exemplary dual-phase self-supporting anode alloy, comprising a Li-Mg alloy phase and a Li2Ca alloy phase, according to some implementations. The elemental composition of the exemplary dual-phase anode alloy is approximately 55 wt% Li, approximately 17 wt% Mg, and approximately 28 wt% Ca. As can be seen, discrete Li2Ca alloy 201 is dispersed within a Li-Mg alloy matrix.

[0116] Figure 2C Another SEM micrograph 200C of an exemplary dual-phase self-supporting anode alloy, comprising a Li-Mg alloy phase and a Li2Ca alloy phase, is shown according to some implementations. SEM micrograph 200C was acquired in backscattered electron mode. As can be seen, the Li2Ca alloy 201 is uniformly dispersed within the Li-Mg alloy matrix. These observations corroborate the XRD pattern of the dual-phase alloy (see [link to XRD pattern]). Figure 2A Furthermore, it was confirmed that a dual alloy phase comprising a Li-Mg alloy phase and a Li2Ca alloy phase exists in the exemplary self-supporting anode. Those skilled in the art will understand that the micrographs are shown by way of example only, and other scales may exist without departing from the scope and spirit of this implementation.

[0117] Figure 3A A scanning electron microscope (SEM) micrograph 300A is shown of a cross section of an exemplary biphase self-supporting anode alloy according to some implementations, the exemplary biphase self-supporting anode alloy comprising a Li-Mg alloy phase and a Li2Ca alloy phase. Figures 3B to 3C SEM-EDS elemental distribution images 300B-300C of an exemplary dual-phase self-supporting anode, comprising a Li-Mg alloy phase and a Li₂Ca alloy phase, are shown according to some implementations. The elemental composition of the exemplary dual-phase anode alloy is approximately 55 wt% Li, approximately 17 wt% Mg, and approximately 28 wt% Ca. See also micrograph 200A (see...). Figure 2A Similarly, micrograph 300A shows the dispersion of the Li₂Ca alloy in the Li-Mg alloy matrix. Elements examined during EDS analysis included magnesium (shown in EDS image 300B, K-line) and calcium (shown in elemental dispersion image 300C, K-line). See also Figure 3C The discrete and substantially uniform calcium distribution indicates no cross-contamination between the Li-Mg and Li₂Ca dual-phase alloys. Furthermore, the dual-phase alloy was formed at approximately 300°C, significantly lower than the formation temperature of the Mg-Ca alloy, which is at least approximately 400°C. Therefore, the above observations suggest that calcium exists in the form of Li₂Ca alloy 301. The dual-phase alloy containing both the Li-Mg and Li₂Ca alloy phases also contains virtually no unalloyed calcium. The uniform distribution of Mg (see...) Figure 3B This indicates that the Li2Ca phase is distributed in the Li-Mg alloy phase of the dual-phase anode alloy.

[0118] In some implementations, any biphase self-supporting anode alloy previously disclosed herein may include a polymer coating disposed on the self-supporting anode, said polymer coating comprising one or more of the following: polyvinylidene fluoride (“PVDF”), pentaerythritol tetraacrylate (“PETEA”), or polyethylene glycol dimethacrylate (“PEGDMA”), or any combination thereof. The coating thickness may be between approximately 10 nm and approximately 10 µm.

[0119] In some other implementations, using a Li-Mg alloy composite anode can achieve high cathode discharge capacity (e.g., approximately 600 mAh / g) for lithium-based batteries without sacrificing anode stability and cell formation cycle time. In some implementations, the self-supporting composite anode associated with the lithium-based battery can comprise a Li-Mg alloy and a lithium-ion conductive material. In some aspects, the lithium-ion conductive material (also referred to herein as a lithium-ion conductive filler) can comprise lithium phosphide (Li3P), bismuth telluride (BiTe), antimony telluride (SbTe), lithium-doped tritelluride (LiTe3), lithium titanate (Li4Ti5O4), etc. 12 "LTO", lithium lanthanum zirconium oxide (Li7La3Zr2O) 12The self-supporting Li-Mg alloy composite anode may contain either LZO, molybdenum oxide (MoO), molybdenum disulfide (MoS2), or any combination thereof. In some other aspects, the exemplary self-supporting Li-Mg alloy composite anode may further comprise one of alumina (Al2O3) or titanium dioxide (TiO2). In some instances, the amount of lithium-ion conducting material in the self-supporting Li-Mg alloy composite anode may be between about 1 wt% and about 90 wt%. In some other instances, the weight ratio of the Li-Mg alloy composite anode to the lithium-ion conducting material may be between about 1 and about 9. The cathode discharge capacity of an exemplary lithium-based coin cell cell comprising a self-supporting dual-phase alloy anode containing a Li-Mg alloy phase and a Li2Ca alloy is discussed below in Example 3. Without being bound by any particular theory, lithium-ion conducting fillers may help control the grain size of Li-Mg in the Li-Mg alloy and promote lithium-ion diffusion across grain boundaries.

[0120] Figure 4A A voltage profile 400A of an exemplary lithium-based half-cell cell, according to some implementations, is shown. The exemplary lithium-based half-cell cell includes a self-supporting composite anode comprising a Li-Mg alloy and lithium titanate (“LTO”). At 0.2 mA / cm²... 2 The charging current and 1.3 mA / cm 2 Voltage curves of half-cell cells with self-supporting Li-Mg alloy anodes and Li-Mg alloy / LTO composite anodes were measured at the discharge current. Copper foil was used as the cathode. A glass fiber (GF / A) separator was used between the cathode and anode. The anode did not contain any polymer coating. The electrolyte contained approximately 50:25:25 (volume%) DME:DOL:BTFE and approximately 0.4 M LiTFSI and approximately 2 wt% LiNO3. Figure 4A As shown, under one discharge / charge cycle at C / 3 rate, the charge / discharge curve of the symmetrical cell containing the Li-Mg alloy / LTO composite anode is flatter than the charge / discharge curve measured using the Li-Mg alloy anode.

[0121] Figures 4B to 4C SEM images and SEM-EDS elemental distribution images 400B-400C are shown for exemplary Li-Mg alloy anodes and self-supporting composite anodes comprising Li-Mg alloy / LTO, according to some implementations. Based on the SEM-EDS imaging, the corresponding elements are examined... Figure 4A Related tests were conducted on Li-Mg alloy anode samples and Li-Mg alloy / LTO composite anode samples. See also... Figure 4BThe Li-Mg alloy anode exhibits a Li-rich layer 401 distributed on top of the α and Li-Mg alloy layers 402. This stratification gradient in the Li-Mg alloy composition may negatively affect anode stability. The target of the EDS analysis is magnesium (K-line). See, for comparison... Figure 4C The Li-Mg alloy / LTO composite anode exhibits a uniform Mg distribution, indicating lithium stripping and deposition. This result suggests that the Li-Mg alloy / LTO composite anode is more beneficial for improving anode stability compared to the Li-Mg alloy anode.

[0122] In some implementations, lithium-based batteries including self-supporting composite Li-Mg alloy anodes may experience delayed activation, requiring several activation cycles to reach rated discharge capacity. In some instances, prolonged activation can be observed when the Mg content in the Li-Mg alloy is greater than approximately 10 wt%. Prolonged battery activation is unsuitable for commercial lithium-based battery applications. To mitigate delayed activation, the Li-Mg alloy may contain one or more of the following: lithium-ion conductive fillers or electron conductive fillers, or combinations thereof. Li-ion conductive fillers may contain bismuth telluride (BiTe), antimony telluride (SbTe), lithium-doped tritelluride (LiTe3), lithium titanate (“LTO”), lithium lanthanum zirconium oxide (“LLZO”), lithium nitride (Li3N), or lithium phosphide (Li3P), molybdenum oxide (MoO), molybdenum disulfide (MoS2), or any combination thereof, or similar lithium-ion conductive materials, including ceramic materials. Electron conductive fillers may contain one or more of the following: carbon, aluminum, or silicon, or other similar electron conductive materials. The enhanced Li-ion conductivity or electronic conductivity of exemplary Li-Mg composite alloys containing lithium-ion conductive fillers or electron-conducting fillers can improve lithium utilization by reducing the impedance associated with charge transfer during deposition. Increasing the Mg content in the Li-Mg alloy can also reduce anode-related material costs and improve the safety of lithium-based batteries. Additional details related to the performance of a lithium-based coin cell including a Li-Mg / LTO anode are described below with reference to Example 3 and Figure 10.

[0123] Unbound by any particular theory, exemplary lithium-ion conductive fillers or electron-conducting fillers can be dispersed in the bulk alloy and reduce the grain size of Li-Mg domains or the Li content in the Li-Mg bulk alloy. + The diffusion length of ions is adjusted to promote faster lithium-ion diffusion across grain boundaries. With faster lithium-ion diffusion, lithium deposition / stripping during lithium-ion battery charge / discharge cycles may be more uniform and dendrite growth may be reduced. Dendrites can penetrate the polymer or ceramic separator in a Li-ion battery and create short circuits inside the battery, leading to a fire hazard.

[0124] In addition, a density of approximately 2 g / cm³ is used. 3 The filler material advantageously imparts a significant reduction in the overall density of the entire anode. Compared to using fillers with a density greater than 2 g / cm³... 3 Compared to the corresponding anode with filler, this results in less energy loss, especially when the filler content is at least about 20 wt%.

[0125] Furthermore, using fillers characterized by nanoscale particle size (diameter) can also impart similar capacity enhancements. For example, in an implementation involving titanium dioxide fillers, 10 wt% micron-sized LTO filler cannot activate a Li-Mg (92-8 wt%) anode within 20 cycles, but the corresponding 10 wt% nano-sized filler can. Indeed, increasing the filler concentration to 20 wt% still fails to achieve activation when the filler particles are characterized by micron-sized dimensions. Therefore, using nanoscale filler materials offers the opportunity to achieve lighter anode compositions without sacrificing capacity.

[0126] In some implementations, the diffusion coefficient of lithium in the Li-Mg / LTO composite alloy can be approximately 2.3 x 10⁻⁶. -8 cm 2 / s, which is about 3.8 x 10⁻⁶ for lithium in Li-Mg alloys. -9 cm 2 The diffusion coefficient is approximately one order of magnitude higher. Magnesium in the Li-Mg / LTO alloy primarily controls the alloy's reactivity or stability, while LTO reduces the size of Li-Mg domains and improves lithium-ion diffusion. Therefore, with Li-Mg alloys containing up to approximately 50 wt% Mg and up to approximately 90 wt% LTO, it is possible to improve the cycle life and discharge capacity of lithium-based batteries and reduce the N / P ratio to less than 2. Consequently, the lithium content in exemplary Li-Mg / LTO composite alloys can be reduced to between approximately 10 wt% and approximately 90 wt%, which in turn reduces the material costs associated with Li-ion battery anodes.

[0127] Additionally, the melting point of the Li-Mg / LTO composite alloy is approximately 210°C, higher than that of lithium, which is approximately 180°C. Battery safety is enhanced because the thermal runaway initiation point of the lithium-based battery increases from approximately 126°C for the 90 wt% Li-10 wt% Mg alloy to approximately 236°C for the Li-Mg / LTO alloy, thereby increasing the safe operating temperature of the lithium-based battery relevant to various aspects of the subject matter disclosed herein by approximately 110°C.

[0128] In some implementations, the magnesium content in the self-supporting Li-Mg alloy composite anode containing the lithium-ion conducting material can be between approximately 5 wt% and approximately 50 wt%. As previously noted, exemplary lithium-ion conducting materials (also referred to herein as lithium-ion conducting fillers) can comprise bismuth telluride (BiTe), antimony telluride (SbTe), lithium-doped tritelluride (LiTe3), and lithium titanate (Li4Ti5O4). 12 "LTO", lithium lanthanum zirconium oxide (Li7La3Zr2O) 12 The materials used may be lithium phosphide (Li3P), molybdenum oxide (MoO), molybdenum disulfide (MoS2), or any combination thereof, or any other suitable material described herein, or its equivalents as will be understood by one of ordinary skill in the art upon reading this disclosure. In some instances, the amount of lithium-ion conducting material in a self-supporting Li-Mg alloy composite anode may be between about 1 wt% and about 90 wt%. In some other instances, the weight ratio of Li-Mg alloy to lithium-ion conducting material may be between about 1 and about 9. In some other instances, the weight ratio of Li-Mg alloy to lithium-ion conducting material may be about 1.5.

[0129] In some implementations, the electron-conducting material in the self-supporting composite anode may comprise one or more of carbon, aluminum, or silicon. In some instances, the carbon may comprise graphite.

[0130] In some other implementations, the self-supporting anode associated with a lithium-based battery may comprise a Li-Mg ternary alloy. In some other implementations, the self-supporting anode associated with a lithium-based battery may comprise a Li-Al-Mg ternary alloy. In some instances, the aluminum content in the Li-Al-Mg ternary alloy may be between approximately 5 wt% and approximately 20 wt%. In some instances, the Li-Al-Mg ternary alloy may further comprise any of the lithium-ion conducting materials previously described herein. Without being bound by any particular theory, Li-Al intermetallic phases (e.g., Li3Al or Li9Al4) or similar phases may be embedded in the Li-Mg alloy microstructure of the Li-Al-Mg ternary alloy. These Li-Al intermetallic phases are lithiophilic and may reduce the local current density distribution, promote more uniform lithium deposition (or precipitation), and increase the lithium-ion diffusion rate.

[0131] In some implementations, the self-supporting anode associated with the lithium-based battery may comprise a Li-Si-Mg ternary alloy. In some instances, the silicon content in the Li-Si-Mg ternary alloy may be between approximately 5 wt% and approximately 20 wt%. In some instances, the silicon content in the Li-Si-Mg ternary alloy may be approximately 20 wt%. In some instances, the Li-Si-Mg ternary alloy may further comprise any of the lithium-ion conducting materials previously described herein.

[0132] In some other implementations, the self-supporting composite anode associated with lithium-based batteries may include a Li-Mg / C composite anode. In some instances, the carbon content in the Li-Mg / C composite anode may be between about 1 wt% and about 20 wt%. In some other instances, the carbon may comprise graphite. In some instances, the carbon content in the exemplary Li-Mg / C alloy may be about 15 wt%. In some instances, the Li-Mg / C alloy may further comprise any of the lithium-ion conducting materials described above herein.

[0133] In some other implementations, the carbon in the exemplary Li-Mg / C alloy may comprise one or more of the following: carbon nanotubes (“CNTs”), carbon nano-onions (“CNO”), carbon nanofibers, or fullerenes. In some instances, the carbon can be surface-functionalized using CO2 etching and other methods to introduce functional groups containing surface oxygen. Unbound by any particular theory, carbon, and especially graphite, is an electronically conductive additive and can also function as a current collector, which can significantly increase the active surface area of ​​the anode and mitigate dendrite growth. Therefore, in Li-ion batteries and lithium-based batteries, the addition of carbon can increase lithium utilization, discharge capacity, rate performance, and cycle stability.

[0134] In some implementations, the grain size of Li-Mg domains in any of the Li-Mg alloys described herein can be manipulated through annealing or rapid quenching operations associated with the heat treatment and machining of the Li-Mg alloy. For example, grain growth of Li-Mg domains can be mitigated by annealing the Li-Mg alloy at 70% of its melting point. In some implementations, annealing the anode-related Li-Mg alloy for a lithium-based battery at approximately 150°C can improve the capacity retention and coulombic efficiency of the lithium-based battery. Annealing or rapid quenching can also change the orientation of the body-centered cubic (“BCC”) grain structure in the Li-Mg alloy to a preferred orientation, such as the (110) or (200) crystal plane. In some implementations, after annealing, the grain size of Li-Mg domains in the Li-Mg alloy or any of the Li-Mg composite alloys described herein can be less than approximately 175 µm.

[0135] Any of the self-supporting anode implementations described above can also be used in other lithium-ion battery chemistry systems, including but not limited to nickel manganese cobalt (“NMC”) batteries, lithium iron phosphate (“LFP”) batteries, or nickel cobalt aluminum oxide (“NCA”) batteries.

[0136] In some implementations, any self-supporting Li-Mg alloy / anode previously disclosed herein may include an anodic protective polymer coating disposed on the self-supporting anode, said anodic protective polymer coating comprising one or more of the following: polyvinylidene fluoride (“PVDF”), pentaerythritol tetraacrylate (“PETEA”), or polyethylene glycol dimethacrylate (“PEGDMA”), or any combination thereof. The coating thickness may be between approximately 10 nm and approximately 10 µm.

[0137] In some implementations, exemplary lithium-based batteries may include any of the self-supporting anodes and fluorinated ether electrolytes described earlier herein. The thickness of the self-supporting anode can be up to approximately 100 µm. In some instances, the self-supporting anode may include any biphase alloy anode comprising a Li-Mg alloy phase and a Li₂Ca alloy phase. In some other instances, the self-supporting anode may include any Li-Mg alloy composite anode comprising a lithium-ion conductive material or an electronically contained material.

[0138] In some implementations, the exemplary fluorinated ether electrolyte may contain one or more of lithium nitrate (LiNO3) or lithium bis(trifluoromethanesulfonyl)imide (“LiTFSI”). In some implementations, the concentration of LiTFSI in the fluorinated electrolyte may be between about 0.1 M and about 2 M. In some other implementations, the concentration of LiNO3 in the fluorinated ether electrolyte may be between about 2 wt% and about 6 wt%.

[0139] In some implementations, an exemplary fluorinated ether electrolyte may comprise approximately 50:25:25 (volume%) of 1,2-dimethoxyethane (“DME”):1,3-dioxane (“DOL”):bis(2,2,2-trifluoroethyl) ether (“BTFE”), and approximately 0.4 M LiTFSI and approximately 2 wt% LiNO3. In some other implementations, an exemplary fluorinated ether electrolyte may comprise approximately 50:25:25 (volume%) of DME:DOL:1,1,2,2-tetraethoxyethane (“TEE”), and approximately 0.4 M LiTFSI and approximately 2 wt% LiNO3.

[0140] In some implementations, the exemplary electrolyte may comprise approximately 50:25:25 (volume%) of DME:DOL:1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether (“TFETFE”) and approximately 0.4 M LiTFSI and approximately 2 wt% LiNO3. In some other implementations, the exemplary electrolyte may comprise approximately 60:20:10:10 (volume%) of DME:DOL:TEE:TFETFE and approximately 0.4 M LiTFSI and approximately 2 wt% LiNO3.

[0141] In some implementations, an exemplary electrolyte may comprise approximately 50:25:25 (volume%) of DME:DOL:1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (“TTE”) and approximately 0.4 M LiTFSI and approximately 2 wt% LiNO3. In some other implementations, an exemplary fluorinated ether electrolyte may comprise LiTFSI at a concentration between approximately 0.1 M and approximately 1 M and LiNO3 at a concentration between approximately 1 wt% and 6 wt%. In some other implementations, an exemplary fluorinated ether electrolyte may comprise approximately 50:25:25 (volume%) of DME:DOL:1-fluorinated 1,4-dimethoxybutane (“FDMB”) and approximately 0.4 M LiTFSI and approximately 2 wt% LiNO3. In some other implementations, the electrolyte may comprise approximately 1.0 M LiTFSI in approximately 50:50 (volume%) of DOL:BTFE.

[0142] Additives in fluorinated ether electrolytes, including lithium nitrate (LiNO3), may dissociate to produce lithium ions (Li... + Alternatively, additives in the electrolyte (including LiTFSI) may dissociate to produce lithium ions (Li). + ) and TFSI - Anions. Additives in the electrolyte that may dissociate into lithium ions may also include one or more of the following: lithium lanthanum zirconium oxide (“LLZO”), oxynitrides (e.g., lithium phosphorus oxynitride or “LIPON”), NASICON-type conductors (e.g., lithium titanium aluminum phosphate) or lithium tin phosphide sulfide (“LSPS”).

[0143] In some exemplary implementations, any of the previously described self-supporting biphase Li-Mg alloy and Li-x alloy anodes, or any Li-Mg alloy composite anode containing Li ion-conducting materials, electron-conducting materials, or fillers, may be coated with a surface coating that can react with lithium in the alloy to form a protective layer and further improve the stability of the anode during cycling. In some instances, the anode protective layer may comprise one or more of the following: polyvinylidene fluoride (“PVDF”), pentaerythritol tetraacrylate (“PETEA”), or polyethylene glycol dimethacrylate (“PEGDMA”), or any combination thereof, disposed on the self-supporting anode. In some other instances, the thickness of the anode coating may be between approximately 100 nm and approximately 10 µm.

[0144] Unbound by any particular theory, PVDF can react with lithium in a self-supporting Li-Mg alloy anode to form LiF dispersed in a polymer matrix. - Lithium ions. The protective layer can improve the lithium ion concentration during cycling. + Transport from and to the anode and / or may be associated with improvements in said transport. Reducing the growth of lithium dendrites in the anode of a Li-S battery can increase charge rate, discharge rate, energy density, cycle life, or any combination thereof. The polymer matrix may partially capture TFSI generated by the dissociation of additives, including LiTFSI, in the electrolyte. - Anions.

[0145] In some implementations, an exemplary lithium-based battery may include a cathode disposed opposite to the anode. See below for reference. Figures 5A to 5E In some implementations, an exemplary cathode may include one or more porous carbon layers comprising porous carbon aggregates of porous primary carbon nanoparticles. In some instances, the corresponding porous primary carbon nanoparticles may include an inner porous shell arranged around the center of the corresponding porous primary carbon nanoparticle and encapsulating an inner porous carbon region; an outer porous shell encapsulating an outer porous carbon region disposed between the inner shell and the outer shell; and an interconnected porous network disposed within and in fluid communication with the inner and outer porous carbon regions.

[0146] In some aspects, the internal and external carbon regions of exemplary porous carbon primary nanoparticles may be characterized by the average pore size and average pore density associated with each region. In other aspects, the average pore size may decrease radially from the center to the outer porous shell.

[0147] In some instances, exemplary porous carbon primary nanoparticles may further include one or more intermediate porous shells disposed between an inner porous shell and an outer porous shell, wherein each of the intermediate porous shells encapsulates a corresponding intermediate porous carbon region.

[0148] In some respects, porous carbon aggregates can be characterized by I D / I G The Raman spectral characteristics are between approximately 0.95 and approximately 1.05. In some other respects, the porous carbon aggregates can be characterized by a Brunauer-Emmett-Teller (“BET”) surface area of ​​approximately 50 m², as measured using nitrogen. 2 / g and 300 m 2 Between / g. In some respects, porous carbon aggregates are characterized by an electrical conductivity between approximately 500 S / m and 20,000 S / m when compressed at a pressure of approximately 12,000 psi.

[0149] Figure 5A A schematic diagram 500A of an exemplary porous primary carbon nanoparticle 505 is shown, according to some implementations. In some aspects, the porous primary carbon nanoparticle 505 may resemble a carbon nano-onion (“CNO”). Figure 5A As illustrated in the example, porous primary carbon nanoparticles 505 may include a core (internal) porous carbon region 511 defined by a first porosity and encapsulated within an inner porous shell 513. The internal porous carbon region 511 (also referred to herein as the first porosity region) may contain a plurality of first pores 501 dispersed therein. An external porous carbon region 512 (also referred to herein as the second porosity region) may be disposed between the inner porous shell 513 and the outer porous shell 510, and may contain a plurality of second pores 502 dispersed therein. The internal porous carbon region 511 and the external porous carbon region 512 may be interconnected through one or more first pores 501 or one or more second pores 502, thereby connecting the first porosity region and the second porosity region. That is, the internal porous carbon region 511 may be configured to be in fluid communication with the external porous carbon region 512 through an interconnected porous network. The internal porous carbon region 511 can be defined by a first pore density, and the external porous carbon region 512 can be defined by a second pore density, which may be similar to or different from the first pore density.

[0150] The exemplary porous primary carbon nanoparticle 505 may be characterized by an average size or major size (diameter, length, width) of less than approximately 200 nm. In some implementations, the average pore size may gradually decrease radially from the center 516 of the nanoparticle 505 to the outer boundary 513 of the nanoparticle 505. In some implementations, the porous primary carbon nanoparticle 505 may be characterized by the range of pore size and pore size distribution in each region. A first pore 501 may be configured to retain polysulfides 520, and a second pore 502 may provide channels or pathways for the transport of lithium ions (not shown for simplicity) into and out of the porous primary carbon nanoparticle 505, and for preloading sulfur 524 into the nanoparticle.

[0151] Figure 5B A transmission electron microscope (“TEM”) micrograph 500B of an aggregate 540 of porous primary nanoparticles 505 according to some implementations is shown. Those skilled in the art will understand that the micrograph is shown by way of example only, and other scales may exist without departing from the scope and spirit of this implementation. An exemplary carbon aggregate 540 may comprise an interconnected porous network disposed between adjacent carbon nanoparticles 505. The aggregate 540 may contain multiple porous carbon primary nanoparticles 505 and in some instances may resemble a “string of pearls.” In some implementations, the size or main size of the aggregate 540 may be between approximately 50 nm and approximately 500 nm.

[0152] Figure 5C TEM image 500C of aggregates 545 of porous primary carbon nanoparticles 505, according to some implementations, is shown. The aggregates 545 of porous primary carbon nanoparticles 505 are characterized by a Brunauer-Emmett-Teller (“BET”) surface area of ​​approximately 50 m², measured using nitrogen gas. 2 / g and approximately 300 m 2 Between / g. In some implementations, the exemplary aggregate 545 may be spherical. In some implementations, the aggregate 545 may have any shape, including one or more of the following: spherical, near-spherical, dumbbell-shaped, cylindrical, elongated cylindrical, rectangular prism, disk-shaped, linear, or irregular shapes.

[0153] Figure 5DTEM image 500D of a surface-etched agglomerate 542 of porous primary carbon nanoparticles according to some implementations is shown. The exemplary agglomerate 545 can be surface-etched using a method including CO2 etching to form pores on the outer surface of the agglomerate 545 and increase the surface area of ​​the carbon agglomerate 545 to produce the surface-etched agglomerate 542. After etching, the surface-etched agglomerate 542 may comprise three-dimensional graphene carbon (“3DG carbon”), which includes graphene layers (not shown for simplicity) interconnected as a three-dimensional (“3D”) graphene structure. The surface-etched agglomerate 542 of porous primary carbon nanoparticles may be characterized by I D / I G The Raman spectral characteristics are approximately between 0.95 and 1.05. In some instances, surface-etched agglomerates 542 can be assembled into rigid porous carbon agglomerates through processes including spray drying.

[0154] Figure 5E A schematic diagram 500E of another exemplary porous primary carbon nanoparticle 505 is shown according to some implementations. The exemplary three-region porous primary nanoparticle 505 may include a first core (internal) carbon region or region 551 nested within a second intermediate carbon region or region 552, which in turn is nested within a third outer carbon region or region 553. The exemplary first region 551 may contain pores 561 with an average or major size (diameter, length, width) less than about 40 nm, the second region 552 may contain pores 562 with an average or major size less than about 35 nm, and the third region 553 may contain pores 563 with an average or major size less than about 30 nm. In some exemplary implementations, the pores 561 may be characterized as macropores, the pores 562 in the intermediate region 552 may be characterized as mesopores, and the pores 563 in the outer region 552 may be characterized as micropores.

[0155] In some implementations, the principal size D1 of the first region 551 can be less than about 100 nm, the principal size D2 can be less than about 150 nm, and the principal size D3 of the third region 553 can be about 200 nm. The relative sizes, porosity, and conductivity of the first region 551, the second region 552, and the third region 553 can be adjusted to achieve a desired balance between minimizing the polysulfide shuttle effect and maximizing the specific capacity of the host cell. The first region (core region) 551 can have a carbon density of less than about 1 g / cc. The carbon density of the third region (outer region) 553, defined by the periphery of particle 205 or the outer shell 555, can have a carbon density between about 1 g / cc and 3.5 g / cc. The second region (intermediate region) 552 can have a carbon density between about 0.5 g / cc and 3 g / cc. Each region 551, 552, and 553 can be characterized by the average pore size and average pore density associated with each region. The average pore size associated with each region 551 to 553 can decrease radially from the center of the porous primary carbon nanoparticle 505 to the outer porous shell 555.

[0156] In some implementations, methods including CO2 etching can be used to surface-etch aggregates of porous primary carbon nanoparticles 505 to form pores on the outer surface of the aggregates and increase the surface area of ​​the carbon aggregates. After etching, the aggregates may contain three-dimensional graphene carbon (“3DG carbon”), which includes graphene layers interconnected as a three-dimensional (“3D”) graphene structure. The resulting surface-etched aggregates of porous primary carbon nanoparticles 505 can be characterized by I D / I G The Raman spectral characteristics are between approximately 0.95 and 1.05. In some implementations, the resulting aggregates can be produced by the thermal cracking of hydrocarbon feedstocks as disclosed in commonly owned U.S. Patent Nos. 9,862,602, 10,112,837, 11,053,121, and / or U.S. Patent Publication No. 2021 / 0292170, all of which are incorporated herein by reference in their entirety.

[0157] The porous carbon agglomerates described above can be used to produce carbon-sulfur composites (“CSCs”) by sulfurizing the carbon agglomerates. The weight ratio of sulfur to carbon can be between approximately 1:5 and 10:1. The weight ratio of sulfur to carbon can be approximately 3. A slurry comprising the carbon-sulfur composite and one or more polymer binders can be cast onto a suitable substrate to form one or more layers or films of carbon material to form a cathode in an exemplary Li-S battery. The cathode substrate may include a cathode current collector. The cathode current collector may contain aluminum. The carbon agglomerates can resist deformation under high shear mixing and thus produce a carbon film or layer with the desired porosity, thickness, and packing density. In some implementations, the cathode is characterized by a packing density of carbon material on a substrate (containing sulfur, binders, and other components) of at least approximately 7 mg / cm³. 2 This, in turn, increases the sulfur loading at the cathode and can reduce the N / P ratio in the Li-S cell.

[0158] In some implementations, such as those disclosed herein, porous carbon agglomerates can resist deformation under high-shear mixing, thus producing carbon films or layers with desired porosity, thickness, and packing density. In some implementations, porous carbon agglomerates can be mixed in a high-shear mixer within at least 500 s of a slurry containing porous carbon agglomerates. -1 It resists deformation at shear rates. The slurry can be arranged as one or more porous carbon layers on the cathode substrate (also referred to as the cathode current collector in this paper).

[0159] In some implementation methods, see the following references. Figures 6A to 6C The exemplary cathode for a lithium-based battery may comprise porous carbon aggregates of porous primary carbon nanoparticles, the porous carbon aggregates comprising one or more interconnected bundles of conductive graphene layers. In some aspects, the graphene layers may be arranged as one or more stacks interconnected to each other and defining a 3D porous scaffold structure comprising mesopores. In some other aspects, the one or more stacks may be arranged substantially orthogonally to each other. In some instances, the graphene layers may be characterized by a linear size between approximately 50 nm and 200 nm. In some other instances, the graphene layers may comprise one or more of monolayer graphene (“SLG”), few-layer graphene (“FLG”), or multilayer graphene (“MLG”).

[0160] Figure 6AA schematic diagram of mesoporous carbon nanoparticles 600A, according to some implementations, is shown, the mesoporous carbon nanoparticles having interconnected bundles of conductive graphene layers arranged to form a 3D open porous scaffold structure. Nanoparticles 600A and porous carbon agglomerates containing nanoparticles 600A can be produced by high-flux, low-cost pyrolysis of hydrocarbon gases (such as natural gas) in an atmospheric pressure microwave plasma reactor. An exemplary microwave plasma reactor is disclosed in commonly owned U.S. Patent No. 9,767,992, which is incorporated herein by reference in its entirety. For example, within a microwave plasma reactor chamber, agglomerates can form and grow in flight by adding additional carbon-based material derived from the incoming carbon-containing gas.

[0161] The carbon nanoparticles 600A may include three-dimensional (“3D”) multimodal mesoporous carbon nanoparticles. According to IUPAC nomenclature, as commonly understood and referred to herein, mesoporous materials include materials containing pores with diameters between 2 nm and 50 nm. For comparative purposes, IUPAC defines microporous materials as materials with pore diameters less than 2 nm and macroporous materials as materials with pore diameters directly greater than 50 nm. In some instances, the mesoporous carbon particles 600A may be characterized by a three-dimensional (“3D”) hierarchical porous structure comprising pores 680 (blank spaces between carbon nanoparticles 600A). In some aspects, at least a portion of the hierarchical porous structure may further define a 3D open porous scaffold structure 681.

[0162] Nanoparticles 600A may comprise one or more interconnected conductive graphene layers or bundles 682. Each interconnected bundle 682 may comprise one or more graphene layer stacks 683. Each stack 683 may comprise multiple graphene layers 686, which are typically horizontally stacked, as more clearly shown in stacks 684. The one or more graphene layer stacks 686 683 may be arranged to form a 3D porous scaffold structure 681 containing mesopores. That is, multiple conductive graphene layer stacks 686 683 can be sintered together to define a 3D open porous scaffold structure 681 (in... Figure 6A In some implementations, the structure includes mesopores 680. In some implementations, one or more stacks 683 may be substantially orthogonally connected to each other. An open porous support structure 681 may be configured to provide conductivity between contact points (not shown for simplicity) of the graphene layer 686 stack. In some implementations, each graphene layer 686 may be characterized by a diameter or linear dimension (“L”). a The wavelength is between approximately 50 nm and approximately 200 nm. In some implementations, the graphene stack 683 may contain few-layer graphene ("FLG"), which may consist of 5 to 15 graphene layers.

[0163] Multiple porous carbon primary nanoparticles 600A can aggregate or combine to form porous carbon agglomerates of porous carbon primary nanoparticles. In this disclosure, three-dimensional graphene carbon (“3DG carbon”) includes porous carbon agglomerates of mesoporous nanoparticles 600A. In some implementations, the exemplary 3DG carbon material described herein may be characterized by a Brunauer-Emmett-Teller (“BET”) surface area, measured using nitrogen, of approximately 50 to 300 m². 2 / g. In some implementations, 3DG carbon is characterized by a graphene to amorphous carbon ratio between approximately 1% and 95%. In some implementations, 3DG carbon is characterized by a carbon purity of at least 99.9%. 3DG carbon is characterized by an electrical conductivity between approximately 500 S / m and approximately 20,000 S / m when compressed at approximately 12,000 psi. The open porous scaffold structure 681 provides a host scaffold structure while confining sulfur to manage volume expansion caused by the formation of long-chain polysulfides.

[0164] In some implementations, sulfur can be confined within the pores 680 of the open porous support structure 681. In some implementations, sulfur can also be confined within the support structure space 685 formed by a stack of orthogonally connected graphene layers 684 683.

[0165] In some implementations, the porous carbon primary nanoparticles 600A can comprise multiple interconnected wrinkled 3D graphene sheets, multiple non-hollow carbon spherical particles (“NHCS”), flat graphene, wrinkled graphene, or multiple carbon nano-onions (“CNO”). In some implementations, the porous carbon primary nanoparticles 600A can comprise corrugated or flexible graphene layers resembling creased paper and can be produced using a microwave process. The graphene layers can be flexible because they are saturated with silica gel. 2 sp 3 The defects may merge together.

[0166] Figure 6B SEM micrographs 600B of porous carbon aggregates 402 are shown according to some other implementations. In some instances, plasma-based processing conditions applied or performed in a reactor (such as a microwave reactor) can be highly tunable to achieve densification of the porous carbon aggregates and graphene on graphene, resulting in complex 3D carbon materials 602. The porous carbon aggregates 602 can be surface-etched using methods such as CO2 etching to form pores on the outer surface of the aggregates and increase the surface area of ​​the aggregates.

[0167] The porous carbon aggregates described herein and characterized using Raman spectroscopy exhibit high order and structural homogeneity. In this publication, "graphene" refers to a carbon allotrope in the form of a two-dimensional, atomically scaled hexagonal lattice, where each vertex is formed by one atom. The carbon atoms in graphene can be sp... 2 Hybridized carbon atoms. Furthermore, the Raman spectrum of graphene exhibits two main peaks: one at approximately 1580 cm⁻¹. -1 The G-mode at approximately 1350 cm -1 The D mode at the location (when using a 532 nm excitation laser). The characteristics of porous carbon aggregates can be found in I... D / I G The Raman spectral characteristics are between approximately 0.95 and approximately 1.05.

[0168] Figure 6C A TEM micrograph 600C of a porous carbon aggregate is shown according to some implementations. As shown, the 3D few-layer graphene (“FLG”) structure 604 can be considered as a porous carbon aggregate at a scale of 50 nm. Those skilled in the art will understand that the micrograph is shown by way of example only, and other scales may exist without departing from the scope and spirit of this implementation.

[0169] Any of the Li-S battery cathode or anode implementations described above can be configured or arranged for cylindrical, prismatic, pouch cell, or any other suitable geometry. Cylindrical Li-S cells can be sized to match 18650 (approximately 18 mm diameter x approximately 65 mm length), 21700 (approximately 21 mm diameter x approximately 70 mm length), or 4680 (approximately 46 mm diameter x approximately 80 mm length) cells. In some implementations, the Li-S cell can have a prismatic shape factor that can match the size of the CP3553 cell. For example, an exemplary Li-S cell can have a height between approximately 56 mm and approximately 58 mm, a length between approximately 34 mm and approximately 36 mm, and a width between approximately 6 mm and approximately 8 mm.

[0170] Figure 7A schematic diagram 700 is shown, depicting an exemplary cylindrical battery 700 according to some implementations. The battery 700 may include a housing 710 and a core 720. The housing 710 may have a longitudinal axis as indicated by AA' in FIG. 4, and the core 720 may be disposed within the housing 710 along the longitudinal axis AA'. The core 720 may have a cross-section in the form of a circle, rectangle, square, triangle, or any other geometry. The core 720 may include an anode 722, a first barrier layer (or separator layer) 724, a cathode 726, and a second barrier layer 728, each in the form of a rollable sheet. The anode 722, the first barrier layer 724, the cathode 726, and the second barrier layer 728 may be stacked one on top of the other. Thus, the anode 722 and the cathode 726 may be separated by the first and second barrier layers to prevent undesirable short circuits from occurring inside the battery 700. In some other implementations, a center pin or mandrel (for simplicity) may be used. Figure 7 (Not shown) can be attached to the inner edge of the anode 722, and the stack of cathode-first barrier layer-anode-second barrier layer can be radially wound or rolled up around the central pin to form core 720. Anode current collector 702 (in the case that the anode is not a self-supporting anode) and cathode current collector 704 can be integrated into the anode layer and cathode layer, respectively.

[0171] In some implementations, the anode 722, the first barrier layer 724, the cathode 726, and the second barrier layer 728 may share the same dimensions, and during winding, the sheets may be aligned with each other so that no sheet protrudes from the core 720. The current collector for the anode 722 or cathode 726 may include current collector tabs that protrude after the sheets are wound into the core 720. Tabs 723 can connect the anode 722 or cathode 726 to the negative or positive terminal, respectively, via any suitable process (including mechanical welding). Figure 7 (Not shown in the image). In some implementations, tab 723 may be a cathode current collector tab. The anode current collector (not shown for simplicity) may be disposed on the outer edge of the core 720, and the cathode current collector tab 723 may be disposed approximately at the center of the core 720.

[0172] In some implementations, either electrode (e.g., anode 722 or cathode 726) may be misaligned with the other electrode and the first barrier layer 724 and the second barrier layer 728 during winding, such that a portion 725 may protrude beyond the core 720. In some aspects, the electronically conductive adhesive (for simplicity, Figure 7(Not shown) can be arranged inside the housing 710 at the top and bottom of the housing 710. The protruding portion 725 can be connected to the negative or positive terminal of the housing 710 by electronically conductive adhesive, thus eliminating the need for mechanical welding. In some implementations, the anode 722, anode current collector (not shown), first barrier layer 724, cathode 726, cathode current collector 704, and second barrier layer 728 can be stacked one on top of the other. A center pin or mandrel (for simplicity) Figure 7 (Not shown) can be configured as a cathode terminal and can be attached to the cathode current collector 704. When arranged as a core, the anode current collector can be arranged at the outer edge of the core 720, and the cathode current collector 404 can be arranged approximately at the center of the core 720.

[0173] In various implementations, the anode 722 can be any suitable material typically used as the anode in a Li-S battery. For example, the anode 722 can be a lithium foil or a lithium substrate. In some instances, the anode 722 may include a current collector to support the lithium foil or lithium substrate. In some aspects, the anode 722 may include any type of self-supporting Li alloy anode, including the Li-Mg composite anode described earlier herein.

[0174] In some implementations, cathode 726 may comprise one or more membranes or CSC layers containing any of the previously described rigid porous carbon agglomerates comprising metal nanoparticles. Cathode 726 may be disposed on cathode current collector 704. The cathode membrane may cover both sides of the current collector (such as aluminum foil) to provide maximum cathode capacity. The cathode CSC containing any of the previously described rigid porous carbon agglomerates with metal nanoparticles may contain multiple pores to microscopically confine sulfur as the cathode electroactive material. The electroactive material (sulfur) may comprise between approximately 60 wt% and 90 wt% of the cathode membrane. The electroactive material of cathode 726 may comprise other suitable sulfur-containing materials, such as lithium sulfide.

[0175] Battery 700 may have an electrolyte incorporated into core 720 (for simplicity, Figure 7(Not shown in the image). In some implementations, the battery 700 may have a liquid electrolyte, which may be added to the housing 710 after the core 720 is laid in the housing 710. In some other implementations, the battery 700 may include a non-aqueous electrolyte such as a solid electrolyte, gel electrolyte, or polymer membrane electrolyte, which is incorporated into the core 720. For example, between the first barrier layer 724 and the second barrier layer 728, one barrier layer may function as a separator, and the other may function as a non-aqueous electrolyte membrane. In some other implementations, each of the first barrier layer 724 and the second barrier layer 728 may function as both a separator and a non-aqueous electrolyte membrane. The electrolyte may include any of the electrolyte compositions described herein.

[0176] In some implementations, a microporous monolayer polypropylene membrane can be used as a diaphragm, which is disposed between the anode 722 and the cathode 726. Exemplary diaphragms (e.g., Celgard) R The porosity of the membrane (2500) can be approximately 55%. The membrane can have similar ionic conductivity to the electrolyte, but can be used to reduce the formation of lithium dendrites. The membrane can be formed of a ceramic-containing material that does not chemically react with metallic lithium. Therefore, a membrane with a ceramic-containing material can be used to control the transport of lithium ions through the pores dispersed across the membrane, while simultaneously preventing short circuits by hindering the flow or channels of electrons through the electrolyte. The membrane layer may include a mechanical strength enhancer coated and / or deposited on the anode. The mechanical strength enhancer can provide structural support for the battery, can prevent the formation of lithium dendrites from the anode, and / or can prevent lithium dendrites from protruding throughout the battery. In some exemplary implementations, ceramic particles may be impregnated in a microporous monolayer polypropylene membrane. In some exemplary implementations, the membrane may include a ceramic-coated membrane.

[0177] In cylindrical Li-ion batteries, the dense packing of layers in the core 720 and volume changes during charge-discharge cycles can cause mechanical stress and aging in the battery 700. As previously mentioned, volume changes can originate from uneven lithium deposition and dendrite formation at the anode, polysulfide "shuttle effect," and growth at the solid electrolyte interface. Dendrites can even cause fires due to localized heating. Furthermore, pitting on the anode 722 leads to non-uniform transport of Li ions from the anode 722 to the cathode 726 and also causes cracking of the protective coating / layers applied to the anode. Similarly, during charge cycles, lithium dendrites may form on the metal anode due to non-uniform transport and deposition of Li ions from the cathode to the anode. Pitting and / or dendrite formation leads to uneven stress and volume expansion in the core 720, which, over time, causes the layers of the core 720 to lose close contact with each other, exacerbating these problems and leading to accelerated degradation / capacity decay. A cathode comprising any of the previously described CSC materials (including any of the previously described porous carbon agglomerates), a self-supporting anode comprising any of the previously described Li-Mg alloys, and any of the previously described electrolyte compositions can mitigate the polysulfide shuttle effect and mechanical stress effect, and increase the cycle life of the Li-S battery.

[0178] As noted above, according to various embodiments, the inventive concept of this invention includes the use of Li-Mg alloys and Li-Mg-X alloys containing a tertiary component as active anode materials. Due to the wide range of possible compositions, according to various embodiments, the solid solution phase of these Li-Mg alloy-based anodes can provide a high specific energy of 500 Wh / kg, wherein the Mg content is as high as about 50 wt% (or about 18 at%).

[0179] Indeed, due to the inherent chemical and electrochemical stability of the Li-Mg alloy anode during cycling in our battery electrolyte, the Li-Mg alloy anode exhibits a significant (e.g., >2x) improvement in the lifetime of the Li / S battery cell of this invention. This indicates that they function well with lower electrolyte content (electrolyte to sulfur ratio) and reduced anode stockpile (lower anode to cathode capacity ratio), both of which contribute to higher specific energy. The use of Li-Mg alloys also enables substrate-free (particularly copper-free) anode designs, which leads to a further increase in specific energy (i.e., about 10%). Although some implementations of the inventive concept may contain smaller amounts of Mg (e.g., about 10 wt% or less), analysis shows that higher Mg contents, up to about 50 wt% (or about 18 at%) of Mg in the Li-Mg alloy, can be used without sacrificing the benefits of higher specific energy.

[0180] Without being bound by any particular theory, the inventors have observed, as described herein, that the inclusion of magnesium and / or tertiary components advantageously reduces the grain size of the resulting alloys (and thus increases the number and dispersion of grain boundaries). Since grain boundaries serve as ion conduction channels and, in particular, as high-velocity channels for lithium diffusion, the alloys of the present invention presented herein are able to perform as well as, or even better than, conventional lithium-based anodes.

[0181] Even with higher Mg content, improved anode stability and cycle life can be achieved. Furthermore, as described herein, as the amount of magnesium and / or tertiary components (such as aluminum, silicon, graphene, calcium (Ca), gallium (Ga), boron (B), tin (Sn), aluminum (Al), indium (In), bismuth (Bi), antimony (Sb), tellurium (Te), carbon (C), silicon (Si), bismuth telluride (BiTe), antimony telluride (SbTe), zinc (Zn), and combinations thereof) increases, the resulting anode composition advantageously improves mechanical strength, even when the total mass of the anode remains constant in various duplex alloys and alloys containing tertiary components. In various implementations, the amount of tertiary component in the composition can be anywhere in the range of about 1 wt% to about 90 wt%, or any value in between, or a subrange thereof.

[0182] Furthermore, compared to pure lithium or anode compositions with relatively high lithium content, increasing the amount of secondary and / or tertiary components in the alloy can substantially reduce overall costs and simplify supply chain logistics.

[0183] Reducing the amount of lithium present in electrochemical battery cells can also reduce the amount of undesirable reactions (e.g., parasitic reactions) and the amount of lithium used during normal cycling. As the data presented in this paper show, the result is improved cycle life and stability (both during cycling and during long-term storage).

[0184] However, it is worth noting that in developing the inventive concept described herein, the inventors encountered serious kinetic problems in several embodiments, including those with high Mg content (i.e., greater than about 5 wt%). With Mg content exceeding 5 wt%, the inventors observed low cell capacity in the first few cycles, indicating that the anode required some form of activation to achieve the desired high capacity.

[0185] Activation lasts approximately 2–20 cycles, depending on the amount of Mg in the anode. Higher Mg content results in greater activation, which we believe is a consequence of the slow diffusion of Li into the Mg-rich solid solution (see Figure 2 and the corresponding description below). This is indeed a drawback, as alloys with higher Mg content are expected to exhibit electrochemical stability and improved cycle life. High-Mg alloys are also expected to have mechanical stability and less volume change during cycling than that experienced by Li metal.

[0186] Another advantage of using Li alloys (especially low-cost Li alloys) instead of pure Li metal lies in the cost and availability of Li metal for the large-scale production of lithium-based battery cells. Lithium metal has been identified as a key resource material for Li metal batteries. Although concerns about its availability have been partially alleviated with the recent discovery of new Li resources, producing sufficient quality elemental Li for battery use remains a significant challenge and a major contributor to the overall cost of electrochemical battery cells using lithium-based anodes.

[0187] Mechanistically, during the initial discharge of a Li-Mg / Li-Mg symmetric battery cell, a slow activation process promoting the Li-Mg alloy with over approximately 10 wt% Mg is evident. This activation occurs during the lithium stripping process. The stripping efficiency is approximately 5 mAh / cm³. 2 After Li, the anodic potential rises by about 300-500 mV, indicating that it has transitioned to the second Mg-rich phase (with a higher redox potential).

[0188] This voltage shift occurred during the initial discharge, even at low rates, and is likely due to the slow diffusion of Li within the alloy. Interestingly, this potential shift disappeared from the second cycle onwards, suggesting that the alloy had been activated.

[0189] To address the aforementioned problem of poor Li diffusion, the inventive concept disclosed herein includes the use of a tertiary component in the anode, preferably a metallic component or a ceramic component that forms an alloy with Li in a separate phase. However, other components (such as carbon-based, silicon-based, etc.) may also be used as the tertiary component without departing from the scope of the inventive concept disclosed herein.

[0190] Unlike pure Li-Mg alloys, the addition of one or more tertiary components transforms the alloy into a two-phase alloy. Therefore, compositions comprising alloyed Li and Mg, as well as at least one tertiary component, are interchangeably referred to herein as “two-phase alloys” or “Li-Mg-X” alloys. It should also be noted that, according to preferred embodiments, the two-phase alloys of the present invention as described herein are characterized by a monolithic three-dimensional structure. However, those skilled in the art will understand that the structure of the two-phase alloys of the present invention, particularly as described herein, can be arranged in any suitable configuration or manner that will be understood by those skilled in the art upon reading this disclosure. For example, the structure may be porous, may have a substantially lattice-like or mesh-like configuration, may comprise multiple monolithic materials arranged according to a predetermined two-dimensional or three-dimensional pattern, may be hollow, etc., as will be understood by those skilled in the art upon reading this specification.

[0191] The tertiary compound is preferably well dispersed in the anode and separates the Li-Mg alloy into well-distributed smaller particles with shorter diffusion lengths compared to pure Li-Mg alloys. By thus overcoming the slow diffusion of Li, the dual-phase alloy of the present invention does not suffer from the activation problems discussed with Li metal-based materials and conventional Li alloy-based materials. In the presence of these tertiary additives, a high Mg content of up to 50 w% (or about 18 at%) can be used in the Li-Mg alloy, resulting in a battery with improved performance relative to pure Li-Mg alloys and other conventional Li alloy compositions.

[0192] The following describes some of the key aspects of these dual-phase Li-Mg-X alloys.

[0193] Li and Mg are diagonally related in the periodic table and have comparable atomic radii, leading to increased solid solubility. A single BCC phase solid solution exists in Li-Mg when the Li content is 11.5-100 wt%.

[0194] The dual-phase Li-Mg-X alloy represents a true 3D anode structure. Even under deep delithiation conditions, the second phase can act as a scaffold-like structure, maintaining the mechanical integrity of the anode and promoting Li-carboxylation during charge / discharge cycles. + Ion insertion and removal.

[0195] Volume changes during cycling can be reduced to about 10%-15%, which will have benefits, including minimizing morphology-related failures.

[0196] Furthermore, after Li stripping, a Li-depleted Li-Mg alloy matrix with high electrical conductivity and ionic conductivity can be formed, which can act as an excellent current collector and host for subsequent Li precipitation. Most importantly, due to the conductive matrix, the microstructure and bulk integrity can be maintained during cycling.

[0197] Tertiary additives improve the effective diffusion coefficient of lithium in the alloy and can support high discharge (lithiation rate). Similarly, due to the ionicity of tertiary additives added to Li-Mg alloys (especially when the tertiary component is or contains Si), the SEI of the dual-phase anode will have favorable precipitation kinetics.

[0198] These tertiary additives enhance the stability of the solid electrolyte interface, thereby improving cycle life.

[0199] In summary, the most significant benefit of these biphase Li-Mg-X alloys is likely the reduction in Li content without any performance loss. Importantly, Li in Li-Mg-X is replaced with more abundant and cheaper materials (higher Mg, Si, C, and LTO) without any performance loss (i.e., Li is used more efficiently in these alloys), as lithium is considered a critical material in terms of both cost and supply. This will be a significant benefit not only for Li-S battery cells but for all Li metal battery cells.

[0200] Adding graphite flakes also provides an improved pathway for lithium-ion transport. Morphology (plate-like structure) is also an important optimization factor for promoting graphene embedding into the lithium bulk. Crystal orientation also appears to be important and can be determined based on composition and processing conditions.

[0201] This also improves lithium diffusion during the stripping process, as well as lithium ion diffusion between electrodes throughout the battery.

[0202] According to Sander's time equation 1 The growth of Li dendrites can be controlled by increasing the effective surface area of ​​the lithium-based anode. in: It is the current density. It is the transition time (defined as the period during which the Li+ concentration in the electrolyte is close to zero at the electrode surface). It is the number of electrons per unit. It is Faraday's constant. It is the salt concentration, and It is the diffusion constant.

[0203] Therefore, the inventive concept described in this invention includes novel anode compositions for lithium-based electrochemical battery cells, and more particularly, three-dimensional (3D) composite anodes comprising both electronically conductive and Li-based composites. + Materials with ion conductivity.

[0204] Suitable materials include carbon-based additives, such as non-graphitized carbon (also known as "hard carbon") and carbon nanofibers. While these materials meet the conductivity requirements of the inventive concept disclosed herein, forming alloys with lithium has proven difficult because carbon-based additives cannot be readily infused into lithium (especially molten lithium).

[0205] Therefore, the inventive concept described herein also includes lithiation of graphite carbon and the introduction of graphite as an electrochemically inert phase to facilitate diffusion and reduce or prevent dendrite formation in the resulting Li-C alloy anode material.

[0206] Using pure lithium metal as the active anode material has proven infeasible because the morphology (especially volume) changes and chemical reactivity increases at medium to high current densities. However, at medium current densities, dendrite growth is less likely in the case of lithified graphite than in pure Li metal and common Li alloys.

[0207] Furthermore, porous electrodes with high surface area are preferred, as they can maintain a smoother precipitation and exfoliation morphology.

[0208] According to the inventive concept described in this invention, lithium is embedded in graphite to form an electrochemically inert phase. This electrochemically inert phase does not participate in the charging or discharging reaction but acts as a scaffold to promote uniform nucleation on the anode surface, thereby preventing the accumulation of lithium deposits on the surface and thus mitigating or preventing dendrite growth within the electrochemical battery cell. These advantages can be amplified by using Li-Mg alloy anode active materials.

[0209] In addition, carbon, especially graphitic carbon, intercalation into lithium advantageously provides an ion conduction pathway and allows graphitic carbon to be used as an active material and / or lithium reservoir.

[0210] Therefore, in a preferred embodiment, the composite anode material comprises a Li-Mg alloy. In a particularly preferred embodiment, the composite anode material comprises an alloy combination of Li, Mg, and C. According to various embodiments, the composition may include a Li-Mg alloy component, a Li-C component, or a combination thereof.

[0211] During the initial stripping cycle of a Li-Mg alloy anode, diffusion limitations exist, making some lithium inaccessible. Similarly, according to the inventive concept described in this invention, graphite acts as an electronic conductor and, when included in the Li-Mg alloy anode, promotes lithium diffusion.

[0212] Not wanting to be bound by any particular theory, the inventors propose that the interface between carbon particles and lithium in the composite anode composition is Li + The conduction provides additional ion pathways, thereby enhancing diffusion both in the bulk and on the anode surface.

[0213] Example In the embodiments described below, the electrolyte used in the Li-S battery implementation comprises approximately 50:25:25 (volume%) DME:DOL:BTFE and contains approximately 0.4 M LiTFSI and approximately 2 wt% LiNO3. For symmetric half-cell Li-S battery testing, an exemplary electrolyte may contain approximately 1 M lithium polysulfide Li2S6.

[0214] Example 1. Cathode discharge capacity of a lithium-based button cell at a C / 3 discharge rate, wherein the lithium-based button cell includes a self-supporting dual-phase alloy anode, and the self-supporting dual-phase alloy anode comprises a Li-Mg alloy and a Li2Ca alloy.

[0215] Figure 8A Figure 800A illustrates the cathode discharge capacity of a lithium-based coin cell, comprising a self-supporting biphase anode, according to several implementations, including a Li-Mg alloy phase and a Li2Ca alloy phase. The cathode discharge capacity of an exemplary lithium-based coin cell at C / 3 rate is compared to that of a cell comprising a 72Li-28Mg alloy (72 wt% lithium, 28 wt% magnesium) anode. Four biphase alloys with Li-Mg-Ca contents (wt%) of (a) 61% Li, 21% Mg, 18% Ca, (b) 55% Li, 17% Mg, 28% Ca, (c) 67% Li, 25% Mg, 8% Ca, and (d) 70% Li, 26% Mg, and 4% Ca were evaluated as candidates for self-supporting anode alloys. The weight ratio of the Li-Mg alloy to the Li2Ca alloy is between approximately 0.1 and approximately 20. The anode thickness in each case is approximately 100 µm. The formation cycle consisted of two discharge / charge cycles at a C / 20 rate and one cycle at a C / 10 rate. The cathode loading was approximately 7.5 mg / cm³. 2 The cathode capacity in each case is approximately 4 mAh / cm³. 2 A Celgard PP2075 diaphragm is used between the cathode and anode. The anode does not contain any polymer coating. The E / S ratio is approximately 5.

[0216] See Figure 8A When compared to the 72Li-28Mg alloy, which requires approximately 100 formation cycles to achieve a discharge capacity of approximately 400 mAh / g, the battery cell with a dual-phase alloy anode (containing 61% Li, 21% Mg, 18% Ca and 55% Li, 17% Mg, 28% Ca) provides a discharge capacity of at least 400 mAh / g at approximately 150 cycles.

[0217] To examine the effect of calcium content on discharge capacity, alloys were prepared in which the calcium content varied from 2 at% (atomic %) to 10 at% in a two-phase alloy comprising Li-Mg alloy and Li2Ca alloy. Figure 8BAnother drawing, Figure 800B, illustrates the cathode discharge capacity of a lithium-based coin cell, comprising a biphase self-supporting anode containing a Li-Mg alloy phase and a Li₂Ca alloy phase, according to some implementations. As shown, achieving a discharge capacity of approximately 600 mAh / g requires a calcium content of at least 5 at% . Without being bound by any particular theory, it appears that even in the case of a Mg-rich Li-Mg alloy in the biphase alloy, increasing the calcium content in the exemplary biphase alloy anode leads to a significant enhancement in discharge capacity.

[0218] Example 2. Rate performance test of a lithium-based symmetric battery cell, wherein the lithium-based symmetric battery cell includes a self-supporting composite anode, the self-supporting composite anode comprising a Li-Mg alloy and LTO.

[0219] Figure 9A Figure 900A illustrates the rate performance test results of a lithium-symmetric battery cell, comprising a self-supporting composite anode, according to several implementations, including a Li-Mg alloy and LTO. The rate performance is 0.4 mA / cm². 2 Up to 13 mA / cm 2 Rate capability testing of symmetrical battery cells was conducted at a surface current density. In the symmetrical battery cells, Li-Mg or Li-Mg / LTO electrodes were separated by a Celgard PP2075 separator. Rate capability testing can be used to monitor voltage drop as current density increases. Negligible voltage drop or polarization indicates that the battery cell can achieve high discharge capacity. Figure 9A It can be seen that, compared with battery cells with Li-Mg alloy anodes, battery cells with Li-Mg / LTO composite anodes achieve a lower efficiency of 0.4 mA / cm². 2 Up to 13 mA / cm 2 At current densities of 13 mA / cm², it exhibits negligible voltage drop. 2 At current densities of [value missing], the symmetrical cell with a Li-Mg / LTO composite anode exhibits a voltage drop of only about 0.12 V, which is about one-third of the overpotential of about 0.3 V measured using the symmetrical cell with a Li-Mg anode.

[0220] Figure 9B Figure 900B is shown, illustrating the corrosion current after lithium stripping measured using a lithium-symmetric cell according to some implementation, the lithium-symmetric cell including a self-supporting composite anode comprising a Li-Mg alloy and LTO. Figure 9CFigure 900C is shown, illustrating the post-deposition corrosion current measured using a lithium-symmetric cell, according to some implementations, comprising a self-supporting composite anode containing a Li-Mg alloy and LTO. The post-deposition and post-peeling corrosion currents were obtained using a Tafel plot (not shown). Reference Figure 9B There was no significant difference in the post-stripping corrosion current between battery cells with Li-Mg anodes and Li-Mg / LTO composite anodes. However, the significantly higher corrosion current associated with battery cells including lithium metal anodes suggests that battery cells with Li-Mg anodes may lead to better cycle stability compared to those with lithium metal anodes.

[0221] See Figure 9C The corrosion current following lithium deposition suggests that the low reactivity of the Li-Mg / LTO composite anode may be a promising candidate for increasing the cycle stability of lithium-based batteries. (As previously referenced...) Figure 9A The discussed value is at 0.4 mA / cm 2 Up to 13mA / cm 2 At current densities of [value missing], battery cells with Li-Mg / LTO composite anodes also exhibit negligible voltage losses, indicating high discharge capacity.

[0222] Example 3. Cathode discharge capacity of a lithium-based button cell at a C / 3 discharge rate, wherein the lithium-based button cell includes a self-supporting Li-Mg / LTO composite anode.

[0223] Figure 10A Figure 1000A illustrates the cathode discharge capacity of a lithium-based coin cell according to some implementations, the lithium-based coin cell including a self-supporting Li-Mg / LTO composite anode comprising a Li-Mg alloy and LTO.

[0224] The cathode discharge capacity of an exemplary lithium-based coin cell with a Li-Mg / LTO composite anode at C / 3 rate was compared with that of a cell having a 72Li-28Mg alloy anode (72 wt% lithium, 28 wt% magnesium) and a 90Li-10Mg alloy anode (90 wt% lithium, 10 wt% magnesium). Two Li-Mg / LTO composite anode compositions were evaluated: 72Li-28Mg / LTO and 90Li-10Mg / LTO. The anode thickness was approximately 100 µm in each case. Formation cycling included two discharge / charge cycles at C / 20 rate and one cycle at C / 10 rate. The cathode loading was approximately 7.5 mg / cm³. 2 The cathode capacity in each case is approximately 4 mAh / cm³.2 A Celgard PP2075 diaphragm is used between the cathode and anode. The anode does not contain any polymer coating. The E / S ratio is approximately 5. The anode does not contain any polymer coating.

[0225] refer to Figure 10A Compared to the performance of the 72Li-28Mg alloy anode, the battery cell with the 72Li-28Mg / LTO composite anode is characterized by higher reactivity and a cycle improvement of approximately 200 cycles. The battery cell with the 72Li-28Mg / LTO composite anode also exhibits better cycle stability than the battery cell with the 90Li-10Mg / LTO anode, indicating that the addition of LTO leads to improved cycle stability at a high discharge capacity of approximately 600 mAh / g, and confirming the superior performance of the 72Li-28Mg / LTO composite anode. Figures 9A to 9C Related observations: Optimizing the Li-Mg composition (e.g., increasing the Mg content) and screening lithium-ion conductive fillers can further improve the cycle stability of lithium-based batteries without sacrificing discharge capacity.

[0226] Continuing to refer to Li-Mg / LTO alloys, Figure 10B Figures 1000B, 1000C, and 1000D are shown, depicting the discharge capacity, capacity retention, and coulombic efficiency of exemplary Li-Mg / LTO alloys containing approximately 43 wt% lithium, approximately 17 wt% magnesium, and 40 wt% LTO relative to a baseline Li-Mg alloy. As previously stated, the inclusion of LTO in the alloy composition extends cycle life and also improves the discharge capacity, capacity retention, and coulombic efficiency of the corresponding electrochemical cell.

[0227] like Figure 10C As shown in Figures 1000E and 1000F, when LTO is used as the tertiary component, the specific capacity and coulombic efficiency of the dual-phase alloy of the present invention increase with increasing magnesium content, even after more than 200 cycles.

[0228] According to various embodiments, the LTO component of the Li-Mg-LTO dual-phase alloy can contain any suitable amounts of Li, Ti, and O, and can have any suitable crystal structure known in the art, belonging to the general category of "lithium titanium oxide" or "lithium titanate," which includes, but is not limited to, lithium titanate, lithium titanate spinel, lithium metatitanate, primary lithium titanate, orthorhombic manganese oxide lithium titanate, etc., as will be understood by those skilled in the art upon reading this disclosure. Generally, the LTO component can have the chemical formula Li x Ti y O zWhere x is a value in the range of about 1 to about 17, y is a value in the range of about 1 to about 28, and z is a value in the range of about 2 to about 56. According to several illustrative embodiments, the LTO component may have the chemical formula Li4Ti5O. 12 Li7Ti5O 12 Li2TiO3, Li4TiO4, etc., as will be understood by one of ordinary skill in the art upon reading this disclosure. Table 1 below provides other exemplary chemical formulations considered within the scope of "LTO" as referenced herein.

[0229] Table 1 - Exemplary LTO Formulations Furthermore, in various implementations, the LTO component of the Li-Mg-LTO alloy can be doped with one or more dopants selected from the following: K + Ag + Sn 2+ Mg 2+ Ca 2+ Zn 2+ AI 3+ Ni 2+ Ga 3+ Cr 3+ Co 3+ La 3+ Y 3+ Zr 4+ Ru 4+ Mo 4 + Mn 4+ V 5+ Ta 5+ 、Nb 5+ 、Sr 2+ Or any combination thereof. Furthermore, the one or more dopants may be present in any suitable amount, as will be understood by those skilled in the art upon reading this disclosure. For example, in selected implementations, the one or more dopants may be present in any amount ranging from about 0.01 at% to about 3.0 at%, such as about 0.01 at%, about 0.023 at%, about 0.04 at%, about 0.23 at%, about 0.47 at%, about 0.95 at%, about 1.19 at%, about 1.42 at%, about 2.38 at%, about 2.85 at%, about 3.0 at%, etc.

[0230] As noted above, stripping and precipitation can have a significant impact on battery performance, especially in terms of dendrite formation in Li-Mg-based electrochemical cell cells. Figure 10DThis demonstrates that this effect may largely depend on the morphology of the anode surface, and the more uniform 3D Li-Mg-LTO anode realization exhibits significantly less dendrite growth than the corresponding baseline Li-Mg anode composition. Specifically, SEM image 1000G depicts the surface of a conventional Li-Mg anode after the first exfoliation cycle, and the anode surface remains remarkably flat and uniform after such exfoliation. However, as shown in SEM image 1000H, after the first precipitation cycle, the surface exhibits a substantially non-uniform morphology, with large areas and gaps extending from and within the anode. In contrast, from a morphological perspective, the 3D anode composition disclosed herein remains much more uniform after the first cycles of exfoliation (SEM image 1000I) and precipitation (SEM image 1000M). Since dendrite formation (as defined by the Sandel time equation given above) is significantly influenced by the morphology of the exfoliation / precipitation process, using the 3D Li-Mg-LTO anode composition disclosed herein significantly reduces dendrite formation and correspondingly increases battery cycle life. In one exemplary embodiment, compared to a corresponding Li-Mg anode composition (100 μm thick) exhibiting a cycle life of approximately 250 cycles, the Li-Mg-LTO 3D anode composition (120 μm thick) of the present invention exhibits a cycle life of approximately 310 cycles (i.e., maintaining a capacity discharge retention rate of over 70%). Therefore, embodiments including the Li-Mg-LTO 3D anode composition and structure are characterized by improved stability, safety, and lower cost compared to conventional Li-Mg anodes.

[0231] Example 4. Cathode discharge capacity and capacity retention of a lithium-based coin cell including a self-supporting Li-Al-Mg ternary alloy anode.

[0232] Figures 11A to 11B Figures 1100A-1100B illustrate the cathode discharge capacity and capacity retention of a lithium-based coin cell, comprising a self-supporting Li-Al-Mg ternary alloy anode, according to some implementations. The aluminum content in the exemplary Li-Al-Mg ternary alloy anode is approximately 15 wt%. The magnesium content in the exemplary Li-Al-Mg ternary alloy anode is approximately 15 wt%. Therefore, the lithium content in the exemplary Li-Al-Mg alloy anode is approximately 70 wt%.

[0233] The cathode discharge capacity and capacity retention of an exemplary lithium-based coin cell with a self-supporting Li-Al-Mg ternary alloy anode at C / 3 rate were compared with those of a cell including a self-supporting 90 wt% Li-10 wt% Mg alloy anode. The cathode loading was approximately 7 mg / cm³. 2A Celgard PP2075 diaphragm is placed between the cathode and anode. The E / S ratio is approximately 5 ml / g sulfur. The N / P ratio is between approximately 2.4 and approximately 2.6.

[0234] refer to Figures 11A to 11B The cathode discharge capacity and capacity retention associated with the lithium-based battery cell having a self-supporting Li-Al-Mg ternary alloy anode are comparable to those of a battery cell including a reference self-supporting 90 wt% Li-10 wt% Mg alloy anode. At approximately 80% capacity retention, the discharge capacity is greater than approximately 500 mAh / g after approximately 150 cycles. Therefore, the lithium content in the self-supporting Li-Mg alloy can be reduced to approximately 70 wt% by including a ternary alloying element (including aluminum). Furthermore, no undesirable prolonged activation was observed during testing of a lithium-based coin cell containing a Li-Al-Mg alloy with approximately 70 wt% lithium content.

[0235] Example 5. Cathode discharge capacity and capacity retention of a lithium-based coin cell including a self-supporting Li-Si-Mg ternary alloy anode.

[0236] Figures 12A to 12C Figures 1200A-1200C illustrate the cathode discharge capacity, capacity retention, and coulombic efficiency of a lithium-based coin cell, comprising a self-supporting Li-Si-Mg ternary alloy anode, according to several implementations. The silicon content in the exemplary Li-Si-Mg ternary alloy anode is approximately 20 wt%. The magnesium content in the exemplary Li-Al-Mg ternary alloy anode is between approximately 15 wt% and approximately 25 wt%. Therefore, the lithium content in the exemplary Li-Si-Mg ternary alloy anode is between approximately 55 wt% and approximately 65 wt%.

[0237] The cathode discharge capacity and capacity retention of an exemplary lithium-based coin cell with a self-supporting Li-Si-Mg ternary alloy anode at C / 3 rate were compared with those of a cell including a self-supporting 90 wt% Li-10 wt% Mg alloy anode. The cathode loading was approximately 7 mg / cm³. 2 A Celgard PP2075 diaphragm is placed between the cathode and anode. The E / S ratio is approximately 5 ml / g sulfur. The N / P ratio is approximately 2.4.

[0238] refer to Figures 12A to 12CThe cathode discharge capacity associated with a lithium-based battery cell having a self-supported Li-Si-Mg ternary alloy anode is comparable to that of a battery cell including a reference self-supported 90 wt% Li-10 wt% Mg anode. The discharge capacity is greater than approximately 500 mAh / g at approximately 80% capacity retention. However, after approximately 175 cycles, the battery cell including the reference self-supported 90 wt% Li-10 wt% Mg alloy anode is relatively more stable. Therefore, the lithium content in the self-supported Li-Mg alloy can be reduced to between approximately 55 wt% and approximately 65 wt% by including a ternary alloying element (including silicon). Furthermore, no undesirable prolonged activation was observed during testing of lithium-based coin cell cells containing the Li-Si-Mg alloy. Figure 12C As can be seen, the dual-phase Li-Mg-Si alloy of the present invention also exhibits similar coulombic efficiency characteristics to the baseline pure Li-Mg alloy containing approximately 90 wt% lithium and approximately 10 wt% magnesium. Although the efficiency varies slightly with different ratios of Li, Mg, and Si, for example, different embodiments have 10 wt% Mg-20 wt% Si, 15 wt% Mg-20 wt% Si, or 20 wt% Mg-20 wt% Si with the balance being lithium, all exhibit slightly lower coulombic efficiency compared to the reference 90 wt% Li-10 wt% Mg alloy anode.

[0239] Example 6. Cathode discharge capacity, capacity retention and polarization of a lithium-based coin cell including a self-supporting Li-Mg / C alloy anode.

[0240] Figures 13A to 13E Figures 1300A-1300F illustrate the cathode discharge capacity, capacity retention, polarization, and coulombic efficiency of a lithium-based coin cell, comprising a self-supporting Li-Mg / C alloy anode, according to several implementations. Graphite is used as the representative carbon material. The graphite content in the exemplary Li-Mg / C anode is approximately 13 wt%.

[0241] The cathode discharge capacity and capacity retention of an exemplary lithium-based coin cell with a self-supporting Li-Mg / C alloy anode at C / 3 rate were compared with those of a cell including a self-supporting 90 wt% Li-10 wt% Mg alloy anode. The cathode loading was approximately 7.4 mg / cm³. 2 A Celgard PP2075 diaphragm is placed between the cathode and anode. The E / S ratio is approximately 5 ml / g sulfur. The N / P ratio is approximately 3.5.

[0242] refer to Figures 13A to 13BThe cathode discharge capacity associated with the lithium-based battery cell including a self-supporting Li-Mg / C alloy anode is comparable to that of a battery cell including a reference self-supporting 90 wt% Li-10 wt% Mg alloy anode. At approximately 80% capacity retention, the discharge capacity is approximately 400 mAh / g. Furthermore, no undesirable prolonged activation was observed during testing of the lithium-based coin cell containing the Li-Mg / C alloy.

[0243] refer to Figures 13C to 13E Reduced cell polarization was observed at 1C rate in battery cells incorporating Li-Mg / C alloy anodes. This indicates that adding carbon to the Li-Mg alloy reduces overpotential, mitigates energy density loss during cycling, and improves the electrochemical performance of lithium-based batteries. Notably, graphite is characterized by its three-dimensional (3D) geometry, which advantageously provides improved accessibility to the anode. Graphite acts as an electron filler, reducing diffusion confinement within the anode structure bulk. Furthermore, polarization is reduced relative to the baseline Li-Mg alloy composition.

[0244] To further evaluate the potential of the Li-Mg-C 3D anode composite material of this invention, at approximately 24 mA / cm², 2 Rate testing was conducted on symmetrical battery cells at very high current densities. Figure 13E As shown, the Li-Mg-C graphite 3D composite material can maintain a very high current density while still producing a lower impedance than the baseline Li-Mg composition. Indeed, in the 4C-6C range, and especially at charge / discharge rates of 4C-5C, the potential generated by the Li-Mg-C alloy anode is significantly more stable than that generated by the baseline Li-Mg alloy.

[0245] refer to Figure 13F It is evident that the exemplary Li-Mg / C alloy anode is characterized by a coulombic efficiency substantially similar to that of the reference self-supporting 90 wt% Li-10 wt% Mg alloy anode.

[0246] In various methods, the structures, compositions, configurations, etc., of the present invention described herein can be implemented in various types of electrochemical battery cells for practical use in a wide variety of applications. Without limitation, any exemplary electrochemical battery cell configuration utilizing any combination of the features described herein can take the form of: pouch, button, prismatic battery cell, cylindrical configuration, or any suitable one or more equivalent forms that will be understood by one of ordinary skill in the art upon reading this disclosure.

[0247] Reference is made to an electrochemical cell with a pouch cell arrangement of 1400 and as per [reference to] Figures 14A to 14CAs shown in the exemplary embodiment, the electrochemical battery cell includes a cathode 1410a and an anode 1410b, which are positioned on opposite sides of a pouch cell arrangement 1400 and separated by a separator 1410c (physical and / or chemical). The anode 1410b and cathode 1410a are electronically coupled via an electrolyte 1410f present in the pouch cell arrangement 1400. Furthermore, each electrode is electronically coupled to the external environment of the pouch cell arrangement 1400 via a current collector and a corresponding terminal; that is, the cathode 1410a is electronically coupled to the external environment via a cathode current collector 1410d and a cathode terminal 1406a, while the anode 1410b is coupled via an anode current collector 1410e and an anode terminal 1406b. The aforementioned structure is encapsulated, packaged, or otherwise spatially fixed and housed by a pouch 1402 surrounding the component.

[0248] According to various embodiments, the flexible package 1402 may take any suitable form that a person skilled in the art would understand after reading this disclosure, such as wrapping, coating, shell (soft or hard), compression structure (such as metal strip or mesh), etc., as a person skilled in the art would understand after reading this disclosure.

[0249] In addition, such as Figure 14B As shown, the anode terminal 1406b and cathode terminal 1406a extend through the pouch 1402, providing electronic coupling between the internal and external environments of the pouch cell arrangement 1400. Note that the anode terminal 1406b may alternatively be positioned on the same side or opposite side of the pouch cell arrangement 1400 relative to the cathode terminal 1406a. Furthermore, according to alternative implementations and without departing from the inventive concept described herein, the relative positions of the anode terminal 1406b and cathode terminal 1406a may be relative to... Figure 14B and Figure 14C The arrangement shown is switched.

[0250] like Figure 14A and Figure 14B As indicated, the illustrative pouch cell arrangement 1400 can be wound around, for example, its longitudinal axis to form a spiral, fold, pleat, coil, or otherwise at least partially overlapping configuration of the electrochemical cell components referenced above. In a preferred implementation, winding the pouch cell arrangement 1400 produces a configuration 1420 referred to as a "core". Figure 14C As shown schematically in the diagram.

[0251] Now go to Figure 15A and Figure 15B It depicts a simplified schematic diagram of an electrochemical cell cell arrangement according to a button cell cell arrangement 1500, the button cell cell arrangement being as follows: Figure 15AIt is aptly named for its substantially flat cylindrical shape. According to various implementations, the cylindrical battery cell arrangement 1500 includes a housing 1502 and a cap 1504, which protect the components placed therein from mechanical damage, chemical damage (e.g., corrosion, oxidation, etc.), electrical damage, etc., and also prevent compounds within the cylindrical battery cell arrangement 1500 from leaking into the environment.

[0252] The anode terminal 1506b is coupled to the cap 1504, and similarly, the cathode terminal 1506a is coupled to the housing 1502. Figure 15B (Not shown in the diagram). Preferably, these terminals have a configuration suitable for conducting electricity generated within the button cell arrangement 1500 to a properly connected or coupled output and can be inserted into a circuit to provide power thereto, as will be understood by one of ordinary skill in the art upon reading this specification. Exemplary configurations suitable for cathode terminal 1506a and anode terminal 1506b include conductive metals as known in the art, such as copper, nickel, etc.; conductive carbonaceous materials as known in the art, such as graphene, etc.; or any other suitable equivalent thereof as will be understood by one of ordinary skill in the art upon reading this disclosure.

[0253] Now go to Figure 15B An exploded view, consistent with various embodiments of the inventive concept described herein, illustrates multiple components that may be included in the button cell arrangement 1500. It should be understood that components indicated by dashed outlines (such as washers / springs 1520, spacers 1522, and gaskets 1524) are optional and may, but are not required, be included according to the inventive concept disclosed herein. However, it should also be understood that, depending on the intended application of the button cell arrangement 1500, washers / springs 1520, spacers 1522, and / or gaskets 1524 can advantageously impart mechanical strength or advantageous electrical properties to the button cell arrangement 1500. For example, washers / springs 1520 and / or gaskets 1524 can help secure other depicted components in place, thereby facilitating the desired operation of the button cell arrangement 1500. Similarly, according to Figure 15B In the configuration shown, the spacer 1522 can buffer the anode 1510b from the frictional or compressive forces of the washer / spring 1520, and / or is formed of a material that facilitates the conduction of heat and / or electricity from within the coin cell arrangement 1500 to the anode terminal 1506b. Of course, those skilled in the art will understand that various advantages can be achieved in various implementations, based on knowledge generally available at the date of this filing, by including the washer / spring 1520, the spacer 1522, and / or the gasket 1524.

[0254] Continue to refer to Figure 15BThe illustrative button cell arrangement 1500 is characterized by its internal components, including an anode 1510b positioned at opposite ends of the button cell arrangement (as cathode 1510a), and a separator 1510c and an electrolyte 1510f positioned therebetween. As... Figures 14A to 17 All electrochemical cell cell arrangements shown and consistent with their corresponding descriptions provided herein, the respective features of the anode 1510b, cathode 1510a, separator 1510c, and electrolyte 1510f may be in any composition as known in the art or as described herein, which those skilled in the art will understand, upon reading this disclosure and without departing from the scope of the inventive concept set forth herein, as suitable for their respective functions in the electrochemical cell. Several such exemplary compositions are provided below, and other compositions may be described elsewhere in the detailed description of the inventive concept set forth hereto. Unless expressly acknowledged as known in the art, it should be understood that any such exemplary compositions described with respect to any component of the electrochemical cell cell arrangements 14A-17 are not considered so well known, but are considered part of the inventive concept set forth herein.

[0255] In other methods, the electrochemical cell unit may be characterized by a cylindrical cell arrangement of 160° (e.g., as per [reference to other methods]). Figure 16A (External view) and Figure 16B (The illustrative implementation shown in the sectional view) includes a housing 1602 and a cap 1604, said housing and cap being arranged in accordance with the present document's provisions regarding the arrangement of button cell cells, such as... Figure 15A and Figure 15B The button cell arrangement 1500 shown herein houses and protects other components within the cylindrical battery cell configuration in a similar manner. Also similar to other arrangements described herein, according to various embodiments and as will be understood by those skilled in the art upon reading this disclosure, the cap 1604 and housing 1602 each include terminals configured to conduct electricity generated within the cylindrical battery cell arrangement 1600 to the external environment, output devices electrically coupled to the cylindrical battery cell arrangement 1600, etc. Figure 16B As shown, cap 1604 includes cathode terminal 1606a, while housing 1602 includes anode terminal 1606b. Figure 16B (Not shown in the diagram), which is positioned at substantially opposite ends of the cylindrical battery cell arrangement 1600. Of course, according to an alternative embodiment of the cylindrical battery cell arrangement 1600, the relative positions of the cathode terminal 1606a and the anode terminal 1606b can be interchanged.

[0256] Continue to refer to Figure 16BThe illustrative cylindrical battery cell arrangement 1600 includes similar components as described herein with reference to other electrochemical battery cell arrangements, but arranged structurally in a unique manner. Most notably, while one or more cathodes 1610a and one or more anodes 1610b are spatially separated by one or more separators 1610c, multiple such structures are arranged in a substantially layered configuration and wound around the central longitudinal axis of the cylindrical battery cell arrangement 1600. In this way, the one or more cathodes 1610a and one or more anodes 1610b are not positioned near opposite ends of the cylindrical battery cell arrangement 1600 as in the pouch cell arrangement 1400 and the button cell arrangement 1500, but rather exist throughout the entire volume of the cylindrical battery cell arrangement 1600. Nevertheless, consistent with the pouch cell arrangement 1400, the cylindrical battery cell arrangement 1600 includes a cathode current collector 1610d (… Figure 16B (Not shown in the text) and anode current collector 1610e, the cathode current collector and anode current collector being positioned at opposite ends of the cylindrical battery cell arrangement 1600 and electrically coupled to corresponding terminals (i.e., cathode terminal 1606a or anode terminal 1606b), as will be understood by one of ordinary skill in the art upon reading this disclosure.

[0257] Now targeting Figure 17 According to one aspect of the inventive concept disclosed in this invention, a simplified schematic diagram of an electrochemical battery cell implemented in a prismatic arrangement 1700 is shown. Like other electrochemical battery cell arrangements described above, the prismatic battery cell arrangement 1700 includes a housing 1702 and a cap 1704. Unlike the prismatic battery cell arrangement 1700, as... Figure 17 The housing 1702 and cap 1704 shown are substantially cuboid in shape; however, those skilled in the art will understand that a unique advantage of the prismatic battery cell arrangement considered herein is the near-infinite flexibility in the spatial configuration of the housing 1702 and cap 1704. The only limitation to such a spatial configuration is the ability to completely enclose and accommodate the internal components, as shown in an exemplary embodiment, reference electrode and separator arrangement 1710. This flexibility is largely due to the implementation of the electrode and separator arrangement 1710, characterized by a layered structure comprising one or more anodes 1710b and one or more cathodes 1710a physically and / or chemically separated by one or more separators 1710c. Although Figure 17The specific electrode and diaphragm arrangement 1710 shown is a multilayer structure (e.g., composed of a series of thin films deposited sequentially one on top of another), but those skilled in the art will understand that, depending on various implementations, the components of the electrode and diaphragm arrangement 1710 (which may include components other than the anode 1710b, cathode 1710a, and diaphragm 1710c, without departing from the scope of the inventive concept disclosed herein) can be arranged in a “wound” configuration, such as... Figure 14C and Figure 16B As shown, or arranged in a folded configuration, a pleated configuration, or any other configuration in which at least one or more portions of the components of the electrode and diaphragm arrangement 1710 at least partially overlap themselves, overlap each other, or both. Furthermore, combinations of overlapping arrangements may be implemented in the electrode and diaphragm arrangement 1710 without departing from the scope of the inventive concept disclosed herein.

[0258] Back Figure 17 The exemplary prismatic battery cell arrangement 1700 shown has a cap 1704. In one illustrative implementation, multiple terminals, including a cathode terminal 1706a and an anode terminal 1706b, are arranged on the outer surface of the cap 1704 and electrically coupled to the electrode and separator arrangement 1710, for example, through one or more current collectors. Figure 17 (Not shown) This shall be implemented using any suitable means and / or mechanisms that a person skilled in the art would understand upon reading this specification.

[0259] refer to Figures 14A to 17 Several exemplary electrochemical battery cell arrangements are shown and described, and should be understood as illustrative rather than limiting the scope of the inventive concepts presented herein. Furthermore, some arrangements are depicted as including or omitting certain components not shown or described with reference to other arrangements (such as gasket / spring 1420, spacer 1422, gasket 1424, electrolyte 1410f, current collectors 1410d and 1410e, see reference). Figure 14A Other arrangements not explicitly shown or described herein are illustrated but referenced in this text. Although Figures 14A to 17 The specific components are shown, but it should be understood that any electrochemical cell arrangement (whether based on...) Figures 14A to 17 (Whether it is a different arrangement of electrochemical cell units) may include any suitable combination of components described with reference to any single figure or any components not shown in the figure, but those skilled in the art will understand upon reading this specification as suitable for producing a functional electrochemical cell unit.

[0260] Of course, according to Figures 14A to 17The various exemplary embodiments of the electrochemical battery cells with different configurations shown and described above are provided for illustrative purposes and should not be construed as limiting the scope of electrochemical battery cells in which the anode structures and compositions of the present invention can be implemented. For example, in various approaches, different electrochemical battery cell configurations can be used together in any combination to provide power to one or more machines.

[0261] Furthermore, the exemplary electrochemical battery cell configuration described above can be modified in any suitable manner known in the art without departing from the scope of the inventive concept described herein. For example, the above... Figures 14A to 17 The various components shown can be modified, replaced, omitted, supplemented, etc., in any way that a person skilled in the art who reads this disclosure will understand as suitable for producing a working electrochemical cell without departing from the scope of the inventive concept described herein.

[0262] For example, according to various embodiments, an electrochemical battery cell implemented according to the inventive concept described herein may include one or more (preferably at least two) electrodes, which may individually be one or more anodes or one or more cathodes, for example, according to the electrochemical function within the entire battery cell, and may be formed of any one or more suitable materials known in the art, and is understood upon reading this disclosure to be suitable for combination with other structures and compositions in exemplary electrochemical battery cells and consistent with the inventive concept provided herein.

[0263] In some methods, one or two electrode types can be configured as a “self-supporting” three-dimensional monolithic structure. In other words, a “self-supporting” electrode is “structurally self-supporting” such that when deposited, positioned, or otherwise placed in an operating environment (such as an electrochemical cell), the monolithic material does not require a separate substrate, frame, support, foam, matrix, current collector, support fluid, etc., to support its own weight and maintain defined physical characteristics (e.g., density, volume, porosity, physical dimensions, shape, chemical composition, etc.). Of course, the inventive concepts presented herein should not be construed as limiting in any way to including or claiming one or more “self-supporting” electrodes, but should be understood as permissible where such structures are advantageous to one or more particular applications or intended for use in the electrochemical cell of interest of the present invention.

[0264] When implementing a "self-supporting" electrode structure, depending on the chosen implementation method, the corresponding electrochemical cell unit can omit, and preferably omit, different current collectors (or at least different anode current collectors). Indeed, even in the absence of a "self-supporting" electrode structure, the electrochemical cell unit according to the inventive concept described herein can still omit different current collector structures or components.

[0265] For example, depending on certain implementations, the electrode itself can be used as a current collector, or one or more separators can be used as current collectors in addition to performing other functions described herein with respect to the separator, such as isolating the various components of the electrochemical battery cell from each other in a physical, chemical, electrical, or other manner to avoid undesirable chemical reactions, physical phenomena, etc. (as will be understood by one of ordinary skill in the art upon reading this disclosure). Similarly, according to various embodiments, the inventive concepts presented herein should be understood to include, but not require, the omission of different current collector components.

[0266] Therefore, the electrodes of the illustrative electrochemical cell implementation can have different structures, such as three-dimensional monolithic materials, which may optionally be porous, with one or more surfaces functionalized to enhance, suppress, or otherwise modify their functional characteristics (such as permeability, reactivity, etc., to select for chemical substances present within the electrochemical cell), without limitation. The electrodes may optionally or additionally include indeterminate structures, such as solutions exhibiting the functional characteristics of a monolithic electrode structure but present partially or entirely in solution form. Furthermore, the electrodes can be physically arranged in various configurations, such as thin films that can be sprayed or deposited on a suitable substrate; one or more (planar) layers that can be sprayed or deposited on a suitable substrate or as a self-supporting structure; or as multiple rows and / or channels (e.g., they may be formed in a suitable electrode material, or they may be formed as a result of stacked layers of electrochemical cell units, wound multilayer electrochemical cell units, etc.), as will be understood by one of ordinary skill in the art upon reading this disclosure.

[0267] Optionally, the electrode may be coated with a protective layer designed to promote or mitigate predetermined chemical or physical interactions with other components of the electrochemical cell unit, such as reactions that consume electrode active material, form dendritic structures extending from the electrode, etc., as will be understood by one of ordinary skill in the art upon reading this disclosure. Similarly, the electrode may comprise a plurality of particles (e.g., active material particles) dispersed within or throughout a binder such as a polymer matrix, and the binder may be or contain one or more materials that respectively promote or mitigate desired or undesirable interactions within the electrochemical cell unit. In further embodiments, one or more electrolytes may be operatively, chemically, or electrically coupled to one or more membranes configured (e.g., based on physical characteristics such as porosity, lack of porosity, spatial arrangement, surface area, etc., or chemical configuration, such as based on the chemical composition (e.g., of one or more surfaces of the membrane), specific functionalization, etc.) to separate the electrolyte and / or chemicals formed or derived therefrom from other components of the electrochemical cell unit.

[0268] In a particularly preferred method, the electrode may comprise one or more carbonaceous materials, such as Figure 18 The carbonaceous material described herein and described in more detail below.

[0269] It should be understood that, taking into account the specific context of the electrochemical battery cell, such as the chemical composition and structural arrangement of the various other components included in the electrochemical battery cell, the electrolyte of the inventive concept disclosed in this invention may have any suitable chemical composition that will be understood by those skilled in the art.

[0270] Similarly, one or more electrolytes present in various electrochemical battery cells may be in liquid form, may be or contain one or more solid electrolyte compositions, may be or contain a gel phase or gel-based electrolyte (such as a gel polymer electrolyte), or any combination thereof as will be understood by one of ordinary skill in the art upon reading this disclosure. Similarly, electrolytes may comprise semi-solid compositions, such as gels, slurries, suspensions, etc., as will be understood by one of ordinary skill in the art upon reading this disclosure.

[0271] One or more separators (which may also be omitted according to certain aspects of the inventive concept described herein) may be or comprise any suitable composition or structure known in the art, and those skilled in the art will understand that such composition or structure is compatible with the composition and / or structure of the invention described herein. For example, one or more separators may comprise an impermeable solid structure, a semi-permeable membrane, or a selectively permeable composition (i.e., a composition permeable to one or more predetermined chemicals but impermeable or substantially impermeable to selected or all other chemicals, according to various embodiments). For example, separators may be configured to physically, chemically, electrically, or otherwise functionally separate or isolate different components of an electrochemical battery cell from each other to avoid undesirable chemical reactions (such as parasitic reactions between the electrolyte or its derivatives and the electrodes, polysulfide shuttle, dendrite formation, etc., as will be understood by those skilled in the art upon reading this specification).

[0272] Additionally, any exemplary electrochemical battery cell in any configuration described herein or in its equivalent form, as would be understood by one of ordinary skill in the art upon reading this disclosure, may include one or more mechanisms for mitigating or preventing polysulfide shuttling, dendrite formation, parasitic reactions between one or more electrodes and one or more electrolytes (and substances formed or derived by the electrodes or electrolytes during operation of the electrochemical battery cell), or other chemical substances present in the electrochemical battery cell environment. These mechanisms may be inherent to one or more of the exemplary structures described above (e.g., electrodes, separators, electrolytes, etc.) or may be specifically configured through specific modifications, functionalizations, structural arrangements, etc., of specific components of the electrochemical battery cell. Any such features, whether inherent or specifically configured, are described in more detail herein according to various exemplary embodiments of the inventive concept disclosed in this invention.

[0273] From the foregoing general description and the corresponding figures, those skilled in the art will understand that, depending on the implementation, the electrochemical battery cell described herein comprises various components, each playing a specific core role in the overall function of the electrochemical battery cell (e.g., electrodes facilitate electrical contact between the electrolyte and the external environment of the electrochemical battery cell; a separator isolates or separates the various components and chemicals within the electrochemical battery cell environment; and the electrolyte facilitates charge transfer between the electrodes of the electrochemical battery cell). These components may optionally provide or impart one or more additional functions to the electrochemical battery cell. For example, and as mentioned above, in addition to their respective core functions, electrodes or separators may also function as current collectors, thereby allowing the omission of a separate (typically heavy metal) structure specifically designed to collect the current generated by the electrochemical battery cell.

[0274] In all respects, any one or more components of the electrochemical cell arrangement described herein may include one or more carbonaceous materials, including but not limited to... Figure 18 Those shown. For example, some components may contain carbonaceous materials, in addition to those shown in the reference. Figures 14A to 17 In addition to the various components shown and described, carbonaceous materials may also be included, or both, as will be understood by those skilled in the art upon reading this disclosure. In numerous embodiments, exemplary carbonaceous materials may include, but are not limited to, carbon black, carbon nanotubes (CNO), necked CNO, carbon nanospheres, graphite, pyrolytic graphite, graphene, graphene nanoparticles, graphene sheets, three-dimensional (3D) graphene, graphene oxide, fullerene, mixed fullerene, single-walled nanotubes, multi-walled nanotubes, carbon dots, carbon spheres, porous carbon, carbon fibers, etc., as will be understood by those skilled in the art upon reading this specification. (Li et al., “Synthesis, modification strategies and applications of coal-based materials”) Fuel Processing Tech. Reference 230:1, 107203 (June 2022) (https: / / doi.org / 10.1016 / j.fuproc.2022.107203) provides additional details on the fabrication and characteristics of the selected carbonaceous material, particularly... Figure 18 Those shown in the image.

[0275] Furthermore, according to various embodiments, exemplary components of the electrochemical battery cell described above, particularly as shown in Figures 14 to 15, are... Figure 17Those shown can exist in a single battery cell "stack" (e.g., two opposing electrodes with corresponding separators, electrolytes, etc. arranged between them) or in a repeating (e.g., layered) structure. For example, a simplified repeating structure may include a first cathode (optionally coupled to a first cathode current collector) at one end of an electrochemical battery cell, the first cathode being adjacent to a first electrolyte, the first electrolyte being adjacent to a first separator, the first separator being adjacent to a second electrolyte, and the second electrolyte being adjacent to a first anode (optionally coupled to a first anode current collector) positioned at the opposite end of the electrochemical battery cell (as the first cathode), together forming a single electrochemical battery cell layer. The repeating structure may further include additional electrolyte, separator, and electrode structures in a similar manner to form a multilayer repeating pattern within the resulting electrochemical battery cell.

[0276] Regardless of whether repeating structures are included, in various methods, electrochemical battery cells can be manipulated, configured, arranged, etc., during the fabrication of larger structures (such as batteries). For example, and as those skilled in the art will understand upon reviewing the inventive concept described herein, in some methods, electrochemical battery cells (such as...) Figure 14B (As shown) can be "wound" around a central axis to form a so-called "core" configuration, according to one implementation such as Figure 14C As shown, the configuration may be particularly suitable for certain arrangements or applications, such as for cylindrical or prismatic electrochemical cell cell implementations and other implementations that a person skilled in the art will recognize upon review of this disclosure.

[0277] While the aforementioned electrode, electrolyte, and separator components are the most common and critical aspects of the exemplary electrochemical battery cell described herein, it should be understood that, depending on various implementations, the electrochemical battery cell may include or exclude any suitable combination or arrangement of additional or alternative components such as membranes, housings, caps, shells, wrappers, springs, wires, spacers, tabs, contacts, leads, gaskets, compression structures, or mechanisms, as will be understood by one of ordinary skill in the art upon reading this specification.

[0278] Furthermore, it should be understood that, without departing from the scope of the inventive concept described herein, those skilled in the art can employ various electrochemical battery cell embodiments described herein in any effective arrangement or combination, including but not limited to button cell arrangements, cylindrical cell arrangements, pouch cell arrangements, prismatic cell arrangements, etc., or any one or more suitable equivalent forms that those skilled in the art will understand after reading this disclosure. For example, multiple identical arrangements, combinations of different arrangements, or both may be used, for example, to form a battery or component (e.g., a battery module or battery pack, as will be understood by those skilled in the art after reading this disclosure).

[0279] For example, those skilled in the art will understand that the different arrangements described herein may have different advantages or disadvantages in the context of different applications, and the most advantageous arrangement for a particular application of interest can be selected. Additionally or alternatively, those skilled in the art may include different arrangements to provide robustness to the resulting structure under different application or operating conditions, providing flexibility of use, redundant failure points, or other advantages that those skilled in the art will understand based on the specific application considered.

[0280] As a specific example, cylindrical battery cells are more prone to cracking compared to other arrangements described herein. Therefore, cylindrical battery cell arrangements (such as...) Figure 16A and Figure 16B The configuration shown may not be suitable for prismatic battery cell configurations (such as...). Figure 17 (as shown) or compatible therewith, depending on the intended application of the given electrochemical cell, such as applications involving large and / or frequent application of mechanical forces (e.g., rapid acceleration / deceleration, vibration, etc., as often experienced in vehicle applications). Similarly, pouch cell arrangements are particularly sensitive to volume expansion and contraction that occur during the natural operation and cycling of the electrochemical cell and may require or benefit from additional support, such as compression structures or internal mechanisms (e.g., polymer support networks, such as those described in U.S. Patent No. 12,009,953, issued June 11, 2023, entitled “Internally enclosed support system for batteries, fabrication techniques and applications for the same,” the contents of which are incorporated herein by reference).

[0281] Furthermore, while the exemplary electrochemical battery cell arrangements explicitly described herein and shown in various figures include pouch cell arrangements, button cell arrangements, cylindrical cell arrangements, and prismatic cell arrangements, other arrangements and / or components may be used without departing from the scope of the inventive concept set forth in this disclosure. For example, an electrochemical battery cell arrangement may additionally or alternatively include components or arrangements characterized by, for example, a chassis, tray, bag, module, component, housing, etc., as will be understood by one of ordinary skill in the art upon reading this disclosure.

[0282] Of course, according to various embodiments, the electrochemical battery cell described herein may include one or more external components at least partially surrounding the electrochemical battery cell. For example, exemplary external components may be selected from an outer casing encapsulating the electrochemical battery cell, a module operatively coupled to the electrochemical battery cell, an assembly operatively coupled to the electrochemical battery cell, a package encapsulating the electrochemical battery cell, a pouch encapsulating the electrochemical battery cell, a housing encapsulating the electrochemical battery cell, a tray operatively coupled to the electrochemical battery cell, a disc operatively coupled to the electrochemical battery cell, and combinations thereof. The components may include: parallel components, series components, or battery cell chassis components. In yet another embodiment, the electrochemical battery cell may be integrated into or become part of a structural component of a device that supplies power to it, such as integration into a structural component of an electric vehicle.

[0283] The inventive concept described in this invention includes the use of additive manufacturing techniques, injection molding techniques, compression molding techniques, hybrid injection / compression molding techniques, preforming techniques, manual stacking techniques, casting techniques, injection techniques, sintering techniques, or any combination thereof, as will be understood by a person skilled in the art upon reading this disclosure, to manufacture various types of electrochemical battery cells.

[0284] As used herein, the phrase “at least one” or “one or more” in a list of items refers to any combination of these items, including a single member. For example, “at least one of a, b, or c” is intended to cover the possibilities of: only a, only b, only c, 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. Unless otherwise specified in this disclosure, the margin of error relating to the terms “about” or “approximately” is ±10% of the value indicated in this disclosure in order to interpret the range of the terms “about” or “approximately”. The margin of error relating to values ​​disclosed in percentage form is ±1% of the indicated percentage. The word “substantially” used before a particular term includes the meanings of “comparable to the specified range” and “largely but not entirely specified”.

[0285] Those skilled in the art will readily recognize the various modifications to the implementations described in this disclosure, and the basic principles defined herein can be applied to other implementations without departing from the spirit or scope of this disclosure. Therefore, the claims are not intended to be limited to the implementations shown herein, but should be accorded the widest scope consistent with this disclosure, the principles disclosed herein, and the novel features.

[0286] Furthermore, the various features described in this specification in the context of individual implementations can also be implemented in combination in a single implementation. Conversely, the various features described in the context of a single implementation can also be implemented individually or in any suitable sub-combination in multiple implementations. Thus, although features may be described in combination with each other above and even initially claimed in this way, one or more features from a claimed combination may, in some cases, be decoupled from said combination, and the claimed combination may be for sub-combinations or variations thereof.

[0287] Similarly, when operations are depicted in a specific order in the accompanying drawings, this should not be construed as requiring such operations to be performed in the specific order shown or sequentially, or to perform all illustrated operations to achieve the desired result. Furthermore, the drawings may schematically depict one or more embodiment processes in the form of flowcharts or block diagrams. However, other operations not depicted may be incorporated into the schematically illustrated embodiment processes. For example, one or more additional operations may be performed before, after, simultaneously with, or between any illustrated operation. In some cases, multitasking and parallel processing may be advantageous. Moreover, the separation of the various system components in the above implementations should not be construed as requiring such separation in all implementations, and it should be understood that the described program components and systems can generally be integrated together into a single product or packaged in multiple products.

Claims

1. A composite anode related to lithium-based batteries, the composite anode comprising a Li-Mg-X ternary alloy and one or more of a lithium-ion conductive material or an electron conductive material.

2. The composite anode of claim 1, wherein X is the third component in the Li-Mg-X ternary alloy, and wherein the content of the third component in the Li-Mg-X ternary alloy is between about 1 wt% and about 90 wt%.

3. The composite anode of claim 1, wherein X comprises one or more tertiary components selected from the following: calcium (Ca), gallium (Ga), boron (B), tin (Sn), aluminum (Al), indium (In), bismuth (Bi), antimony (Sb), tellurium (Te), carbon (C), silicon (Si), bismuth telluride (BiTe), antimony telluride (SbTe), zinc (Zn), or any combination thereof.

4. The composite anode of claim 3, wherein one or more third-component components are substantially uniformly distributed throughout the entire body of the composite anode.

5. The composite anode as described in claim 1, wherein the Li-Mg-X ternary alloy comprises a Li-Mg alloy phase and a Li-X alloy phase.

6. The composite anode of claim 5, wherein the weight ratio of the Li-Mg alloy phase to the Li-X alloy phase is between about 0.1 and about 20.

7. The composite anode of claim 1, wherein the lithium-ion conductive material comprises: bismuth telluride (BiTe), antimony telluride (SbTe), lithium-doped tritelluride (LiTe3), and lithium titanate (Li4Ti5O4). 12 LTO), lithium lanthanum zirconium oxide (Li7La3Zr2O) 12 Lithium phosphide (Li3P), molybdenum oxide (MoO), molybdenum disulfide (MoS2), or any combination thereof.

8. The composite anode of claim 1, wherein the electron-conducting material comprises carbon.

9. The composite anode of claim 1, wherein the Li-Mg-X alloy comprises carbon.

10. The composite anode of claim 9, wherein the carbon comprises: graphite, graphene, carbon nanotubes, hollow porous multi-nanochannel carbon fibers (HTCNF), non-graphitized carbon, carbon nanofibers, or any combination thereof.

11. The composite anode of claim 9, wherein the carbon forms an electrochemically inert phase in the Li-Mg-X alloy.

12. The composite anode of claim 9, wherein the carbon is substantially uniformly distributed throughout the entire body of the anode.

13. The composite anode of claim 1, wherein the lithium content in the anode is between about 10 wt% and about 90 wt%.

14. The composite anode of claim 1, wherein the magnesium content in the anode is a non-zero amount of up to about 50 wt%.

15. The composite anode of claim 1, wherein the composite anode further comprises one or more of alumina (Al2O3) or titanium dioxide (TiO2).

16. The composite anode of claim 1, wherein the amount of the lithium-ion conductive material is between about 1 wt% and about 90 wt%.

17. The composite anode of claim 1, wherein the weight ratio of the Li-Mg alloy to the lithium-ion conductive material is between about 1 and about 9.

18. The composite anode of claim 1, wherein the magnesium content in the Li-Mg alloy is between about 5 wt% and about 50 wt%.

19. The composite anode of claim 1, wherein the composite anode is a self-supporting three-dimensional monolithic material.

20. The composite anode of claim 1, further comprising a polymer coating disposed on the composite anode, the polymer coating comprising one or more of polyvinylidene fluoride (PVDF), pentaerythritol tetraacrylate (PETEA), or polyethylene glycol dimethacrylate (PEGDMA).

21. The composite anode of claim 20, wherein the thickness of the polymer coating is between about 100 nm and about 10 µm.

22. The composite anode of claim 1, wherein the thickness of the composite anode is approximately 100 μm.

23. An electrochemical cell unit, the electrochemical cell unit comprising the composite anode as described in claim 1.

24. The electrochemical cell unit of claim 23, wherein the electrochemical cell unit is characterized by a button-type configuration.

25. The electrochemical cell unit of claim 23, wherein the electrochemical cell unit is characterized by a cylindrical configuration.

26. The electrochemical cell unit of claim 23, wherein the electrochemical cell unit is characterized by a prismatic configuration.

27. The electrochemical battery cell of claim 23, wherein the electrochemical battery cell is characterized by a pouch configuration.

28. The electrochemical cell unit of claim 23, wherein the electrochemical cell unit neither includes nor is coupled to any different structure other than the three-dimensional (3D) monolithic material used as a current collector.

29. A lithium-based battery, the lithium-based battery comprising: The self-supporting composite anode comprises a Li-Mg-X ternary alloy and one or more of lithium-ion conductive materials or electron conductive materials; as well as Fluorinated ether electrolyte.

30. The lithium-based battery of claim 29, wherein the fluorinated ether electrolyte comprises one or more of the following: The composition is approximately 50:25:25 (volume%) of 1,2-dimethoxyethane (DME):1,3-dioxane (DOL):bis(2,2,2-trifluoroethyl) ether (BTFE), and contains approximately 0.4 M LiTFSI and approximately 2 wt% LiNO3; The composition is approximately 50:25:25 (volume%) of DME:DOL:1,1,2,2-tetraethoxyethane (TEE) and contains approximately 0.4 M LiTFSI and approximately 2 wt% LiNO3; Approximately 50:25:25 (volume%) of DME:DOL:1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether (TFETFE), and containing approximately 0.4 M LiTFSI and approximately 2 wt% LiNO3; The composition is approximately 60:20:10:10 (volume %) of DME:DOL:TEE:TFETFE, and contains approximately 0.4 M LiTFSI and approximately 2 wt% LiNO3; Approximately 50:25:25 (volume%) of DME:DOL:1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), and containing approximately 0.4 M LiTFSI and approximately 2 wt% LiNO3; Approximately 50:25:25 (volume%) of DME:DOL:1 fluorinated 1,4-dimethoxybutane (FDMB), and containing approximately 0.4 M LiTFSI and approximately 2 wt% LiNO3; or Approximately 1.0 M LiTFSI in approximately 50:50 (volume %) DOL:BTFE.

31. The lithium-based battery of claim 29, wherein the thickness of the composite anode is approximately 100 μm.

32. The lithium-based battery of claim 29, wherein the lithium-based battery further comprises a polymer coating disposed on the composite anode.

33. The lithium-based battery of claim 32, wherein the polymer coating comprises one or more of polyvinylidene fluoride (PVDF), pentaerythritol tetraacrylate (PETEA), or polyethylene glycol dimethacrylate (PEGDMA).

34. The lithium-based battery of claim 32, wherein the thickness of the polymer coating is between about 100 nm and about 10 µm.

35. The lithium-based battery of claim 29, wherein the lithium-based battery further comprises a cathode disposed opposite to the composite anode.

36. The lithium-based battery of claim 35, wherein the cathode comprises: One or more porous carbon layers, the one or more porous carbon layers comprising porous carbon aggregates of porous primary carbon nanoparticles, wherein the corresponding porous primary carbon nanoparticles include: An internal porous shell, wherein the internal porous shell is arranged around the center of the corresponding porous carbon primary nanoparticle and encapsulates the internal porous carbon region. An outer porous shell encapsulates an outer porous carbon region, the outer porous carbon region being disposed between the inner shell and the outer shell; and An interconnected porous network is arranged within the inner porous carbon region and the outer porous carbon region and is in fluid communication with them.

37. The lithium-based battery of claim 36, wherein the inner carbon region and the outer carbon region are characterized by an average pore size and an average pore density associated with each region.

38. The lithium-based battery of claim 37, wherein the average pore size decreases radially from the center to the outer porous shell.

39. The lithium-based battery of claim 36, further comprising one or more intermediate porous shells disposed between the inner porous shell and the outer porous shell, wherein each of the intermediate porous shells encapsulates a corresponding intermediate porous carbon region.

40. The lithium-based battery of claim 36, wherein the porous carbon aggregates are characterized by I D / I G a Raman spectral feature that is between about 0.95 and about 1.

05.

41. The lithium-based battery of claim 36, wherein the porous carbon aggregates are characterized by a Brunauer-Emmett-Teller (BET) surface area of ​​approximately 50 m², as measured using nitrogen. 2 / g and 300 m 2 Between / g.

42. The lithium-based battery of claim 36, wherein the porous carbon aggregate is characterized in that its conductivity is between approximately 500 S / m and 20,000 S / m when compressed at a pressure of approximately 12,000 psi.

43. The lithium-based battery of claim 36, wherein the porous carbon agglomerates of the porous carbon primary nanoparticles comprise one or more interconnected conductive graphene bundles.

44. The lithium-based battery of claim 43, wherein the graphene layers are arranged in one or more stacks, the one or more stacks being interconnected and defining a 3D porous support structure comprising mesopores.

45. The lithium-based battery of claim 44, wherein the one or more stacks are arranged substantially orthogonally to each other.

46. ​​The lithium-based battery of claim 45, wherein the graphene layer is characterized in that its linear size is between approximately 50 nm and 200 nm.

47. The lithium-based battery of claim 43, wherein the graphene layer comprises one or more of single-layer graphene (SLG), few-layer graphene (FLG), or multilayer graphene (MLG).

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