Cylindrical lithium-sulfur battery

Abstract

A lithium-sulfur battery includes a housing having a length and a width, the housing including at least an anode and a cathode wound into a jellyroll oriented parallel to the length of the housing; an electrolyte disposed in the lithium-sulfur battery; a negative terminal extending along the length of the housing; and a positive terminal extending along the length of the housing, the positive terminal and the negative terminal parallel to each other.

Description

[0001] Cross-reference to related applications

[0002] This patent application claims priority to U.S. Patent Application No. 18 / 137,028, filed April 20, 2023, entitled “CYLINDRICAL LITHIUM-SULFURBATTERIES,” which is a partial continuation of priority to U.S. Patent Application No. 17 / 726,753, filed April 22, 2022, entitled “LENGTH-WISE WELDED ELECTRODES INCORPORATED IN CYLINDRICALCELL FORMAT LITHIUM-SULFUR BATTERIES,” which is a continuation of priority to U.S. Patent Application No. 17 / 726,753, filed March 30, 2022, entitled “LITHIUM-SULFURBATTERY WITH A PROTECTIVE LAYER INCLUDING CARBON MATERIALSDECORATED WITH METAL-CONTAINING.” The U.S. patent application filed on March 14, 2022, entitled "METHOD OF MANUFACTURING TAB-LESS CYLINDRICAL CELLS", is a partial continuation of priority to U.S. Patent Application No. 17 / 694,407, entitled "METHOD OF MANUFACTURING TAB-LESS CYLINDRICAL CELLS". The U.S. patent application filed on February 16, 2022, entitled "PLASTICIZER-INCLUSIVE POLYMERIC-INORGANIC HYBRID LAYER FOR A LITHIUM ANODE IN A LITHIUM-SULFUR BATTERY", is a partial continuation of priority to U.S. Patent Application No. 17 / 672,960, entitled "PLASTICIZER-INCLUSIVE POLYMERIC-INORGANIC HYBRID LAYER FOR A LITHIUM ANODE IN A LITHIUM-SULFUR BATTERY". The U.S. patent application filed on February 8, 2022, is a partial continuation of priority to U.S. Patent Application No. 17 / 694,407, entitled "METHOD OF MANUFACTURING TAB-LESS CYLINDRICAL CELLS". ANODE, a partial continuation of priority to U.S. Patent Application No. 17 / 666,753, entitled "SOLID-STATE ELECTROLYTE FOR LITHIUM-SULFUR BATTERIES," filed January 26, 2022, entitled "SOLID-STATE ELECTROLYTE FOR LITHIUM-SULFUR BATTERIES," and U.S. Patent Application No. 17 / 578, entitled "LITHIUM-SULFUR BATTERY ELECTROLYTE COMPOSITIONS," filed January 18, 2022.The U.S. patent application is a partial continuation of priority to U.S. Patent Application No. 17 / 563,183, filed December 28, 2021, entitled “LITHIUM-SULFUR BATTERY CATHODE FORMED FROM MULTIPLE CARBONACEOUS REGIONS”, and is a partial continuation of priority to U.S. Patent Application No. 17 / 383,803, filed July 23, 2021, entitled “CARBONACEOUS MATERIALS FOR LITHIUM-SULFUR BATTERIES”. This patent application also claims priority to U.S. Patent Application No. 17 / 726,774, filed April 22, 2022, entitled “WOUND CYLINDRICAL LITHIUM-SULFUR BATTERY INCLUDING ELECTRICALLY-CONDUCTIVE CARBONACEOUS MATERIALS,” and U.S. Provisional Patent Application No. 63 / 235,892, filed August 23, 2021, entitled “LITHIUM SULFUR BATTERY.” All disclosures of the prior applications are assigned to their assigns and are considered part of this patent application, and are each incorporated herein by reference in their entirety. Technical Field

[0003] This disclosure generally relates to a lithium-sulfur battery, and more specifically to a method of manufacturing a lithium-sulfur battery as a jellyroll, wherein a carbonaceous material replaces one or more anode tabs, thereby providing increased conductivity relative to conventional jellyroll batteries. Background Technology

[0004] Recent advancements in batteries have enabled consumers to use electronic devices in many new applications. However, battery technology still needs further improvement. Summary of the Invention

[0005] This summary is provided to introduce, in a simplified form, some concepts further described below in the detailed description. 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.

[0006] One innovative aspect of the subject matter described in this disclosure can be implemented as a lithium-sulfur battery. In some implementations, the lithium-sulfur battery includes a housing having a length and a width, the housing including at least an anode and a cathode of a core wound parallel to the length of the housing; an electrolyte disposed in the lithium-sulfur battery; a negative terminal extending along the length of the housing; and a positive terminal extending along the length of the housing, the positive terminal and the negative terminal being parallel to each other. The electrolyte is configured to inhibit the transport of lithium polysulfide intermediates from the cathode to the anode. In some aspects, the core is welded along the length of the housing to one or both of the negative and positive terminals. In other aspects, one or both of the negative and positive terminals are formed of nickel.

[0007] In various implementations, multiple components also include an anode current collector coupled to the anode, a cathode current collector coupled to the cathode, and a ceramic separator disposed between the anode and the cathode. In some implementations, the cathode current collector includes a carbonaceous support formed of a material oriented at one or more defined angles relative to the cathode. In some aspects, the ceramic separator includes a plurality of holes configured to allow lithium ions to propagate between the anode and the cathode via the ceramic separator. In some cases, a positive terminal is longitudinally welded to the cathode current collector along the length of the housing, and a negative terminal is longitudinally welded to the anode current collector along the length of the housing. In other cases, the anode is configured to fold into the anode current collector, and the cathode is configured to fold into the cathode current collector. In some other cases, the cathode is formed of a plurality of interconnected non-hollow carbonaceous particles. In some aspects, the plurality of interconnected non-hollow carbonaceous particles collectively define a plurality of porous channels, at least some of which are configured to retain elemental sulfur.

[0008] In various implementations, the cathode can be coupled to a cathode current collector as a cathode laminate. The cathode may include one or more structured layers of spherical agglomerates of carbonaceous particles disposed on the surface of the cathode current collector. When wound into a core in a cylindrical lithium-sulfur battery, the average size of the agglomerates in one or more structured layers disposed on the side of the cathode current collector facing the battery casing may be greater than the average size of the agglomerates in one or more structured layers disposed on the side of the cathode current collector facing the mandrel.

[0009] Details of one or more implementations of the subject matter described in this disclosure are set forth in the accompanying drawings and the following description. Other features, aspects, and advantages will become apparent from this description, the drawings, and the claims. Note that the relative dimensions of the following figures are not drawn to scale. Attached Figure Description

[0010] Figure 1 The diagram illustrates an exemplary battery according to some implementation methods.

[0011] Figure 2A diagram depicting another exemplary battery according to some implementation methods is shown.

[0012] Figure 3 A diagram showing exemplary electrodes of a battery according to some implementations.

[0013] Figure 4 The diagram illustrates a portion of an exemplary battery including a protective lattice, according to some implementation methods.

[0014] Figure 5 The diagram illustrates an anode structure including a tin fluoride (SnF2) layer according to some implementation methods.

[0015] Figure 6 This shows the implementation methods. Figure 5 A magnified diagram of the anode structure.

[0016] Figure 7 A diagram illustrating the polymer network of a battery according to some implementations is shown.

[0017] Figure 8A The diagram illustrates an exemplary carbonaceous particle with graded porosity according to some implementations.

[0018] Figure 8B The diagram illustrates an example of a three-segment particle according to some implementation methods.

[0019] Figure 8C The diagram shows representations based on some implementation methods. Figure 8B An exemplary step function for three-segment particles.

[0020] Figure 8D A graph is shown depicting an exemplary distribution of the relationship between pore volume and pore width of exemplary carbonaceous particles according to some implementations.

[0021] Figure 9A and Figure 9B This shows the implementation methods. Figure 8A and / or Figure 8B Electron micrographs depicting exemplary carbonaceous particles, aggregates, and / or agglomerates.

[0022] Figure 10A and Figure 10B This image shows transmission electron microscopy (TEM) images of carbonaceous particles treated with carbon dioxide (CO2) according to some implementation methods.

[0023] Figure 11 The diagram illustrates the types of carbon pores found in the anode and / or cathode of this disclosure according to some implementations.

[0024] Figure 12A graph depicting the cumulative pore volume versus pore width of micropores and mesopores dispersed in the anode or cathode of a battery according to some implementations is shown.

[0025] Figure 13 The diagram shows battery performance based on the number of cycles, according to some implementation methods.

[0026] Figure 14 The diagram shows a bar chart depicting the capacity according to the number of cycles, based on some implementation methods.

[0027] Figure 15 The diagram shows battery performance based on the number of cycles, according to some implementation methods.

[0028] Figure 16 The diagram shows the battery discharge capacity according to the number of cycles, based on some implementation methods.

[0029] Figure 17 The diagram shows the battery discharge capacity according to the number of cycles, based on some implementation methods.

[0030] Figure 18 A graph depicts the specific discharge capacity of batteries containing various TBT-containing electrolyte mixtures according to some implementation methods.

[0031] Figure 19 The diagram depicts the implementation methods. Figure 1 A chart showing the battery's discharge capacity based on the number of cycles.

[0032] Figure 20 The illustration depicts a different implementation. Figure 2 A chart showing the battery's discharge capacity and discharge capacity retention capacity according to the number of cycles.

[0033] Figure 21 The illustration depicts a different implementation. Figure 2 A chart showing the battery's discharge capacity and discharge capacity retention capacity according to the number of cycles.

[0034] Figure 22 A diagram illustrating an exemplary cathode of a battery according to some implementations is shown.

[0035] Figure 23 –25 shows a graph depicting the specific discharge capacity according to the number of cycles, based on some implementation methods.

[0036] Figure 26A The diagram illustrates an exemplary battery according to some implementation methods.

[0037] Figure 26B A diagram depicting another exemplary battery according to some implementation methods is shown.

[0038] Figure 27 The diagram shows the voltage drop according to specific capacity based on some implementation methods.

[0039] Figure 28 A diagram depicting another exemplary battery according to some implementation methods is shown.

[0040] Figure 29 The diagram depicts the implementation methods. Figure 28 A diagram of an exemplary cathode of a battery.

[0041] Figure 30 The diagram depicts the implementation methods. Figure 28 A diagram of the protective layer of a battery.

[0042] Figure 31A Micrographs of exemplary baseline protection layers according to some implementations are shown.

[0043] Figure 31B This shows the implementation methods. Figure 28 A photomicrograph of the protective layer of the battery.

[0044] Figure 32 This shows the implementation methods. Figure 28 A photomicrograph of a cross-sectional view of the protective layer of the battery.

[0045] Figure 33A This shows the implementation methods. Figure 28 An exemplary crosslinking density of the protective layer of the battery.

[0046] Figure 33B This shows the implementation methods. Figure 28 Another exemplary crosslinking density of the battery's protective layer.

[0047] Figure 34 This illustrates triarylsulfonium salts (Ar3S) according to some implementations. + MtXn - An exemplary open-loop (ROP) mechanism.

[0048] Figure 35 This shows what is suitable for use according to some implementation methods. Figure 28 An exemplary onium salt of a cationic photoinitiator for the protective layer of a battery.

[0049] Figure 36 This demonstrates what is suitable for forming according to some implementation methods. Figure 28 Exemplary monomers of various cationic photopolymerizable compositions for the protective layer of batteries.

[0050] Figure 37This demonstrates what is suitable for forming according to some implementation methods. Figure 28 The protective layer of the battery can be cured by ultraviolet (UV) light.

[0051] Figure 38 This paper illustrates several exemplary non-reactive diluents suitable as battery additives according to some implementation methods.

[0052] Figure 39 Exemplary reactive diluents applicable as battery additives according to some implementations are shown.

[0053] Figure 40A A graph showing the relationship between capacity (initial %) and loop count for some implementations.

[0054] Figure 40B A graph showing the relationship between capacity (mAh / g) and cycle number for some implementations is provided.

[0055] Figure 41A Another graph showing the relationship between capacity (initial %) and loop number based on some other implementations.

[0056] Figure 41B Another graph showing the relationship between capacity (mAh / g) and cycle number for some other implementations.

[0057] Figure 42A The diagram illustrates an exemplary battery according to some other implementations.

[0058] Figure 42B This shows the implementation methods. Figure 42A The amplification section of the battery.

[0059] Figure 43 An exemplary battery system is shown according to some implementation methods.

[0060] Figure 44 This shows the implementation methods. Figure 1 An example battery within a battery system.

[0061] Figure 45A An exemplary electrode film applicable to the battery disclosed herein is shown according to some implementations.

[0062] Figure 45B An exemplary electrode film applicable to the battery disclosed herein is shown according to some other implementations.

[0063] Figure 46 Micrographs of exemplary electrode films according to some implementations are shown.

[0064] Figure 47Exemplary aggregates applicable to the batteries disclosed herein are shown according to some implementations.

[0065] Figure 48A Micrographs of exemplary secondary particles applicable to the batteries disclosed herein, according to some implementations, are shown.

[0066] Figure 48B A micrograph of another exemplary secondary particle applicable to the battery disclosed herein, according to some implementations, is shown.

[0067] Figure 49A A flowchart is shown illustrating exemplary operations for manufacturing a rollable cathode according to some implementations.

[0068] Figure 49B A flowchart is shown illustrating another exemplary operation for manufacturing a rollable cathode, according to some implementation methods.

[0069] Figure 49C A flowchart is shown illustrating another exemplary operation for manufacturing a rollable cathode, according to some implementation methods.

[0070] Figure 50A A flowchart is shown depicting exemplary operations for manufacturing coiled Li-S batteries according to some implementations.

[0071] Figure 50B A flowchart is shown depicting another exemplary operation for manufacturing a wound Li-S battery according to some implementation methods.

[0072] Figure 50C A flowchart is shown depicting another exemplary operation for manufacturing a wound Li-S battery according to some implementation methods.

[0073] Figure 51 A diagram of another lithium-sulfur battery according to other implementations is shown.

[0074] Figure 52 A flowchart is shown illustrating exemplary operations for manufacturing a jointless cylindrical battery cell according to some implementation methods.

[0075] Figure 53 A flowchart is shown depicting exemplary operations for winding a core according to some implementation methods.

[0076] Figure 54 A flowchart is shown illustrating exemplary operations for protecting the anode edge from lithium erosion, according to some implementation methods.

[0077] Figure 55 A flowchart is shown illustrating exemplary operations for protecting the bottom edge of the anode, according to some implementation methods.

[0078] Figure 56 A flowchart is shown illustrating exemplary operations for preventing lithium delamination according to some implementation methods.

[0079] Figure 57 A flowchart is shown illustrating exemplary operations for nucleating multiple carbon particles according to some implementation methods.

[0080] Figure 58 A flowchart is shown illustrating exemplary operations for functionalizing a viscous carbon-containing layer according to some implementation methods.

[0081] Figure 59 A flowchart is shown illustrating exemplary operations for crosslinking carbon atoms in a graphene-based material, according to some implementation methods.

[0082] Figure 60 A flowchart is shown depicting exemplary operations for generating a viscous carbonaceous layer according to some implementation methods.

[0083] Figure 61 A flowchart is shown illustrating an exemplary operation for inserting a core into a can, according to some implementation methods.

[0084] Figure 62 A flowchart is shown depicting exemplary operations for welding a sticky carbonaceous layer according to some implementation methods.

[0085] Figure 63 A flowchart is shown depicting exemplary operations for impregnating a core, according to some implementation methods.

[0086] Figure 64 A flowchart is shown depicting exemplary operations for configuring a viscous carbonaceous layer according to some implementation methods.

[0087] Figure 65 A flowchart illustrating exemplary operations for winding a core, according to some implementations, is shown.

[0088] Figure 66 A flowchart is shown illustrating exemplary operations for attaching one or more cathode tabs according to some implementations.

[0089] Figure 67 A flowchart is shown illustrating exemplary operations for welding or gluing one or more cathode tabs according to some implementations.

[0090] Figure 68 A flowchart is shown depicting exemplary operations for processing viscous carbonaceous layers according to some implementation methods.

[0091] Figure 69A flowchart is shown illustrating exemplary operations for functionalizing one or more exposed surfaces of one or more carbon allotropes, according to some implementation methods.

[0092] Figure 70 A flowchart is shown illustrating exemplary operations for increasing one or more of the mechanical or electrical properties of a viscous carbonaceous layer, according to some implementation methods.

[0093] Figure 71 A diagram depicting another exemplary battery according to some other implementation is shown.

[0094] Figure 72 The diagram depicts the implementation methods. Figure 71 A diagram of an exemplary cathode of a battery.

[0095] Figure 73 The diagram depicts the implementation methods. Figure 71 A diagram of the protective layer of a battery.

[0096] Figure 74 Micrographs of microwave energy-based wavy graphene and / or wrinkled graphene are shown, according to some implementation methods.

[0097] Figure 75 Micrographs of cobalt-decorated carbon-based growths applicable to the batteries disclosed herein, according to some implementation methods.

[0098] Figure 76 Exemplary geometries of batteries according to some implementations are shown.

[0099] Figure 77 Another exemplary geometry of a battery is shown, depending on some implementation.

[0100] Figure 78 An exemplary electrode film applicable to the battery disclosed herein is shown according to some implementations.

[0101] Figure 79 An exemplary electrode film applicable to the battery disclosed herein is shown according to some other implementations.

[0102] Figure 80 An exemplary electrode film applicable to the battery disclosed herein is shown according to some other implementations.

[0103] In the various figures, the same reference numerals and names indicate the same elements. Detailed Implementation

[0104] The following description relates to some exemplary implementations for the purpose of describing the innovative aspects of this disclosure. However, those skilled in the art will readily recognize that the teachings herein can be applied in many different ways. The described implementations can be implemented in any type of electrochemical cell, battery, or battery pack and can be used to overcome various performance-related drawbacks. Therefore, the disclosed implementations are not limited to the examples provided herein but cover all implementations covered by the appended claims. Furthermore, well-known elements of this disclosure will not be described in detail or will be omitted so as not to obscure the relevant details of this disclosure.

[0105] Batteries typically consist of multiple electrochemical cells that can be interconnected to power a wide variety of devices, such as (but not limited to) mobile phones, laptops, electric vehicles (EVs), factories, and buildings. Certain types of batteries, such as lithium-ion or lithium-sulfur batteries, can be limited in performance due to the type of electrolyte used or uncontrolled battery side reactions. Therefore, optimizing the electrolyte can improve the cycleability, specific discharge capacity, discharge capacity retention, safety, and lifespan of the corresponding battery. For example, in unused or “fresh” batteries, lithium-ion (Li₂) batteries... + After activation and later during initial and subsequent discharge cycles, the lithium cations (Li) are freely transported from the anode to the cathode. Then, during battery charging cycles, the lithium cations (Li) can be forced to... + The ions migrate from their electrochemically advantageous position in the cathode back to the anode, where they are stored for later use.

[0106] This cycle of discharge-charge associated with rechargeable batteries can lead to the generation of unwanted chemicals that can interfere with lithium cations (Li₂) during the corresponding discharge and charge cycles of the battery. + The transport of lithium cations back and forth between the cathode and cathode. Specifically, when lithium cations (Li...) + When lithium interacts with elemental sulfur (or, in some configurations, lithium sulfide, Li₂S) present in the cathode, it produces lithium-containing polysulfide intermediates (referred to herein as “polysulfides”). These polysulfides are soluble in the electrolyte and therefore diffuse throughout the battery during operating cycles, resulting in the loss of active material from the cathode. Excessive concentrations of polysulfides can lead to undesirable battery capacity decay and cell failure during operating cycles, potentially reducing the driving range of electric vehicles (EVs) and increasing the frequency with which such EVs require recharging.

[0107] In some cases, polysulfides participate in the formation of an inorganic layer in the solid electrolyte interphase (SEI) provided in the battery. In one example, the anode can be protected by forming a stable inorganic layer in the electrolyte containing 0.020 M Li₂S₅ (0.10 M sulfur) and 5.0 wt% LiNO₃. This is achieved using lithium fluoride and polysulfides (LiF-Li₂S₅).x The anode of a Li-Cu half-cell can enrich the SEI and produce a stable coulombic efficiency of 95% after 233 cycles, while preventing the formation of lithium dendrites or other uncontrolled lithium growth that can extend from the anode to the cathode and lead to cell failure or breakage. However, when polysulfides are generated at certain concentrations (such as greater than 0.50 M sulfur), SEI formation can be hindered. As a result, lithium metal from the anode can be undesirably etched, resulting in a rough and imperfect surface exposed to the electrolyte. This undesirable degradation (etching) of the anode due to relatively high concentrations of polysulfides may indicate that polysulfide dissolution and diffusion may limit battery performance.

[0108] In some implementations, the porosity of the carbonaceous cathode can be adjusted to achieve a desired balance between maximizing energy density and suppressing polysulfide migration into and / or throughout the battery electrolyte. As used herein, carbonaceous material can refer to a material containing one or more types or configurations of carbon or formed therefrom. For example, cathode porosity can be higher in sulfur-carbon composite cathodes compared to conventional lithium-ion battery electrodes. More compact electrodes with relatively low porosity can minimize electrolyte uptake, parasitic weight, and cost. Sulfur utilization can be limited by the solubility of polysulfides and the conversion rate of those polysulfides to lithium sulfide (Li₂S). The polysulfide-to-lithium sulfide conversion rate can be based on the accessible surface area of ​​the cathode.

[0109] Various aspects of the subject matter disclosed herein relate to a lithium-sulfur battery comprising a liquid-phase electrolyte, said electrolyte including a ternary solvent package and one or more additives. In some implementations, the lithium-sulfur battery may include a cathode, an anode positioned opposite the cathode, and an electrolyte. The cathode may include multiple regions, each defined by two or more carbonaceous structures that are adjacent to and in contact with each other. In some cases, the electrolyte may be distributed throughout the cathode and in contact with the anode. In some aspects, the electrolyte may include a ternary solvent package and 4,4'-thiobis(thiophenol) (TBT). In other cases, the electrolyte may include a ternary solvent package and 2-mercaptobenzothiazole (MBT).

[0110] In various implementations, each carbonaceous structure may include a relatively high-density shell region and a relatively low-density core region. In some aspects, the core region may be formed within an inner portion of the shell region. The shell region may have a carbon density between approximately 1.0 g / cc and 3.5 g / cc. The core region may have a carbon density between approximately 0.0 g / cc and 1.0 g / cc, or in some other range below the first carbon density. In other implementations, each carbonaceous structure may include a shell region and a core region having the same or similar density, for example, such that the carbonaceous structure does not include hierarchical porosity. The various regions of the cathode may include micropore channels, mesopore channels, and macropore channels interconnected to form a porous network extending from the shell region to the core region. For example, in some aspects, the porous network may include pores each having a principal size of approximately 1.5 nm.

[0111] In some implementations, one or more portions of the porous network may temporarily microscopically define an electroactive material within the cathode, such as (but not limited to) elemental sulfur, which can react with lithium cations (Li... + Ternary solvent packs can be combined to increase battery specific capacity. In some aspects, ternary solvent packs can have tunable polarity, tunable solubility, and the ability to transport lithium cations (Li). + Additionally, during the battery's charge-discharge cycle, the ternary solvent pack can at least temporarily suspend polysulfides (PS).

[0112] In some implementations, the porous network formed by interconnecting micropores, mesopores, and macropores within the cathode may include multiple pores with numerous different pore sizes. In some implementations, the multiple pores may include micropores with a pore size less than approximately 2 nm, mesopores with a pore size between approximately 5 and 50 nm, and macropores with a pore size greater than approximately 50 nm. The micropores, mesopores, and macropores can collectively mitigate the unwanted migration or diffusion of polysulfides throughout the electrolyte. Since the polysulfide shuttle effect can lead to the loss of active material from the cathode, the ability to mitigate or reduce the polysulfide shuttle effect can increase battery performance.

[0113] In one implementation, the micropores may have a pore size of approximately 1.5 nm for elemental sulfur (S8, or smaller chains / fragments of sulfur, such as S2, S4, or S6) preloaded into the cathode, selectively microscopically confined. This microscopic confinement of elemental sulfur within the cathode allows TBT or MBT complexes generated during battery cycling to inhibit the migration of long-chain polysulfides within the mesopores of the cathode. The accumulation of these long-chain polysulfides within the mesopores of the cathode can cause the cathode to expand in volume to retain the polysulfides and thereby reduce the polysulfide shuttle effect. Therefore, lithium cations (Li... +Lithium ions (Li) can continue to be freely transported between the anode and cathode via the electrolyte without being blocked or hindered by polysulfides. In the absence of polysulfide interference, lithium ions (Li...) + Free movement throughout the electrolyte can increase battery performance.

[0114] Alternatively or additionally, one or more protective layers, sheaths, membranes, and / or regions (collectively referred to herein as “protective layers”) may be disposed on the anode and / or cathode and / or separator and in contact with the electrolyte. The protective layers may include materials capable of binding with polysulfides to impede polysulfide migration and prevent lithium dendrite formation. In some aspects, the protective layers may be arranged in different configurations and used with any electrolyte chemistry and / or composition disclosed herein, thereby enabling full tunability of the battery.

[0115] In one implementation, carbonaceous materials can be dendriticed using fluorinated polymers and deposited on one or more exposed surfaces of the anode. The fluorinated polymer chains can be crosslinked via a Wurtz reaction to form a polymer network in contact with lithium metal from the anode surface. The formation of the crosslinked polymer network can subsequently suppress anode-associated lithium metal dendrite formation and can also generate lithium fluoride. The fluorinated polymers within the polymer network can participate in chemical reactions during battery operating cycles to generate lithium fluoride. The formation of lithium fluoride can involve lithium cations (Li ions) from the electrolyte. + ( ) chemically combines with fluoride ions.

[0116] Alternatively or concurrently, the polymer network may be combined with any electrolyte chemicals and / or compositions disclosed herein and / or a protective sheath disposed on the cathode. In one implementation, the protective sheath may be formed by combining a compound containing a difunctional or higher-functionality epoxy with an amine or amide compound. Intermolecular crosslinking of the compounds results in the formation of a 3D network that exhibits high chemical resistance to dissolution in the electrolyte. The composition, for example, may include a trifunctional epoxy compound and a diamine-based oligomer compound, which may react with each other to produce a protective lattice that binds to polysulfides generated in the cathode and prevents their migration or diffusion into the electrolyte. Additionally, the protective lattice may diffuse through one or more cracks that may form in the cathode due to battery cycling. When the protective lattice diffuses in such cracks formed in the cathode, it increases the structural integrity of the cathode and reduces potential cracking of the cathode associated with volume expansion.

[0117] In various implementations, one or more of the disclosed battery components may be combined with a conformal coating disposed on the edge or surface of the anode exposed to the electrolyte. In some implementations, the conformal coating may include a hierarchical interface layer with a replaceable polymer network. In some aspects, the hierarchical interface layer may include a tin fluoride layer and a tin-lithium alloy region formed between the tin fluoride layer and the anode. In response to battery operating cycles, the tin-lithium alloy region may form a uniformly dispersed lithium fluoride layer between the anode and the tin fluoride layer.

[0118] In various implementations, lithium-sulfur batteries using various aspects of this disclosure may include electroactive materials extracted from external sources, such as underground sources and / or extraterrestrial underground sources. In such implementations, the cathode may be fabricated as a sulfur-free cathode comprising functional pores that microscopically define the electroactive material within the cathode. In some aspects, the cathode may include aggregates comprising a plurality of carbonaceous particles joined together, and may include agglomerates comprising a plurality of aggregates joined together. In one implementation, the carbonaceous material used to form the cathode (and / or anode) may be tuned to define unique pore sizes, pore size ranges, and volumes. In some implementations, the carbonaceous particles may include non-trisegmented particles having and not having trisegmented particles. In other implementations, the carbonaceous particles may not include trisegmented particles. Each trisegmented particle may include micropores, mesopores, and macropores, and both non-trisegmented and trisegmented particles may each have a predominant size in the approximate range of 20 nm to 300 nm. Each carbonaceous particle may include carbonaceous fragments nested together and separated from directly adjacent carbonaceous fragments by mesopores. In some respects, each carbonaceous particle may have a deformable periphery that varies in shape and coalesces with adjacent material.

[0119] Some pores may be distributed within the deformable periphery of multiple carbonaceous fragments and / or carbonaceous particles. In various implementations, mesopores may be dispersed throughout the aggregate, and macropores may be dispersed throughout multiple agglomerates. In one implementation, each mesopore may have a principal size between 3.3 nanometers (nm) and 19.3 nm, each aggregate may have a principal size in the approximate range between 10 nm and 10 micrometers (μm), and each agglomerate may have a principal size in the approximate range between 0.1 μm and 1,000 μm. As further described below, specific combinations of pore sizes matched to unique electrolyte formulations and protective layers can be used to reduce or mitigate the detrimental effects of unwanted polysulfide diffusion, thereby further increasing battery performance.

[0120] Furthermore, commercial lithium-ion batteries have been fabricated in cylindrical and wound-prism shape factors. Given the higher theoretical specific capacity and specific energy of Li-S batteries, it is desirable to manufacture cylindrical or wound-prism Li-S batteries. Conventional cylindrical or wound-prism battery cells require the cathode, anode, and separator to be formed into a wound core by radial bending. The cathode and anode must have robust mechanical structures to withstand the bending forces during the winding process, thereby preventing any internal short circuits or capacity degradation. Li-S batteries, which can power electric vehicles, energy storage systems, or satellites due to their high theoretical energy density, possess several undesirable characteristics. For example, the polysulfide shuttle effect can significantly reduce cycle stability, leading to irreversible sulfur loss and even severe lithium anode corrosion. During the discharge cycle of Li-S batteries, the volume expansion of the cathode active material caused by the cathode reaction can damage the cathode's mechanical structure and pose potential hazards. To address these issues, nanoscale porous carbon particles can be used as cathode support structures to carry sulfur within their pores. When cast as a slurry film on a current collector, porous carbon particles can provide the cathode with a conductive mechanical structure and electrolyte accessibility. Simultaneously, additives can be added to the porous carbon particles to chemically bind polysulfides, thereby reducing the polysulfide shuttle effect.

[0121] However, Li-S batteries with cathodes designed according to the above measures can have low volumetric energy density due to their high carbon content and limited space for sulfur. Therefore, to increase volumetric energy density, more nanoscale porous carbon particles need to be introduced, and these particles need to be densely packed within a given volume. Consequently, the densely packed nanoscale porous particles significantly increase the tortuosity within the cathode, thereby impairing the ion mobility required for Li-S batteries to operate at higher C rates. To address this issue, ion-conducting materials have been incorporated into the cathode manufacturing process. However, this practice compromises the gravimetric energy density of the Li-S battery because the ion-conducting materials add extra weight to the cathode. To increase the gravimetric energy density of Li-S batteries, the battery may have a thicker cathode to increase sulfur loading. However, thick cathodes typically result in low sulfur utilization and cracking and delamination during the drying step of the manufacturing process. Aggregates or clusters made of porous carbon particles have been used to increase sulfur loading, improve sulfur utilization, and reduce cracking. However, these aggregates or clusters are prone to deformation during slurry manufacturing and therefore cannot withstand the bending forces involved in the packaging of wound batteries.

[0122] The embodiments of the subject matter described in this disclosure can be used to manufacture cylindrical Li-S batteries or rolled-core prismatic Li-S batteries. Since both cylindrical and rolled-core prismatic shape factors require forming electrodes and separators into a rolled core, the disclosed invention can be described as a rolled-core Li-S battery. Rolled-core Li-S batteries have higher volumetric and gravimetric energy densities that are maintained at higher C-rates. In various embodiments, the Li-S battery contains a rolled core within a battery casing. In some aspects, the Li-S battery may include one or more tabs to connect the cathode and anode of the Li-S battery to the positive and negative terminals of the casing, respectively. In various embodiments, the rolled core comprises a lamination in which a cathode, a first barrier layer, an anode, and a second barrier layer are rolled into a cylinder having a cross-section of a circle, rectangle, square, triangle, or any other geometry. The cathode of the Li-S battery may be a film formed by co-bonding multiple micron-sized aggregates, which are produced by a suitable chemical method (e.g., spray drying or atomization). Multiple agglomerates are disposed on one or both surfaces of the current collector, and the agglomerates have various sizes determined based on the cathode thickness. In some cases, the diameter of a relatively large agglomerate may be in proportion to the cathode thickness, while the diameter of a relatively small agglomerate may be approximately one-third (1 / 3) the diameter of the relatively large agglomerate. In some aspects, the multiple agglomerates have a uniform shape. The shape may be spherical, elliptical, or other well-defined three-dimensional shape suitable for leaving gaps between adjacent agglomerates. The gaps between adjacent agglomerates define a first plurality of pores. In some aspects, the first plurality of pores may be micrometer-scale pores. In some aspects, the first plurality of pores are uniformly distributed within the cathode film.

[0123] In various implementations, each of the plurality of aggregates comprises a plurality of secondary particles interconnected by a carbon layer, and each of the plurality of secondary particles comprises a plurality of nanoscale primary particles covalently bonded to each other. The void spaces between adjacent secondary particles define a second plurality of pores. In some cases, the average size of the second plurality of pores may be smaller than the average size of the first plurality of pores. When the membrane is dried during the cathode fabrication process, the first plurality of pores and the second plurality of pores provide channels for the evaporation of the slurry solvent from the cast electrode membrane. In various implementations, each of the plurality of primary particles comprises nanoscale pores configured to define a cathode electroactive material, such as sulfur or lithium sulfur.

[0124] In some respects, each of the multiple aggregates may be encapsulated by a functional layer. The functional layer may be an ionically conductive layer configured to enhance the ion conductivity of the multiple aggregates. In some cases, the functional layer may contain one or more functional groups, one or more polar and ionically conductive additives, or combinations thereof.

[0125] Specific implementations of the subject matter described herein can achieve one or more of the following potential advantages. Existing cylindrical or wound-prism-shaped batteries are limited to lithium-ion battery chemistry. Regardless of research and development or breakthroughs in the constituent materials, such chemistry imposes limitations on battery capacity and energy density. Therefore, existing lithium-ion batteries may not be suitable for certain applications requiring high energy density, such as energy storage systems for powering satellites or electric vehicles with longer driving ranges. In some implementations, the techniques disclosed herein can be used to manufacture cylindrical or wound-prism-shaped Li-S batteries with significantly higher battery capacity and energy density compared to commercial lithium-ion batteries. Specifically, the techniques disclosed herein can be used to manufacture a cathode that can have a greater thickness than existing Li-S batteries for higher sulfur loading, while maintaining a robust mechanical structure capable of withstanding slurry preparation and winding processes. In this way, implementations of the subject matter disclosed herein can eliminate cracking and delamination currently associated with Li-S batteries, thereby enabling wound-prism Li-S batteries. Given the advantages of Li-S chemistry and structural design, the rolled Li-S batteries based on the topics disclosed herein can have higher volumetric and gravimetric energy densities, thus outperforming commercial cylindrical and rolled prismatic lithium-ion batteries.

[0126] Figure 1 An exemplary battery 100 according to some implementations is shown. Battery 100 may be a lithium-sulfur electrochemical cell, a lithium-ion battery, or a lithium-sulfur battery. Battery 100 may have a body 105 including a first substrate 101, a second substrate 102, a cathode 110, an anode 120 positioned opposite the cathode 110, and an electrolyte 130. In some aspects, the first substrate 101 may act as a current collector for the anode 120, and the second substrate 102 may act as a current collector for the cathode 110. The cathode 110 may include a first thin film 111 deposited on the second substrate 102, and may include a second thin film 112 deposited on the first thin film 111. In some implementations, the electrolyte 130 may be a liquid electrolyte comprising one or more additives, such as lithium nitrate, tin fluoride, lithium iodide, lithium bis(oxalate)borate (LiBOB), cesium nitrate, cesium fluoride, ionic liquids, lithium fluoride, fluorinated ethers, TBT, MBT, DPT, etc. Suitable solvent packages for these exemplary additives may include various dilution ratios, including 1:1:1 of 1,3-dioxolane (DOL), 1,2-dimethoxyethane (DME), tetraethylene glycol dimethyl ether (TEGDME), etc.

[0127] Although not shown for simplicity, in one implementation, a lithium layer may be electrodeposited on one or more exposed carbon surfaces of the anode 120. In some cases, the lithium layer may include elemental lithium provided by ex-situ electrodeposition of lithium on the exposed surface of the anode 120. In some aspects, the lithium layer may include lithium, calcium, potassium, magnesium, sodium, and / or cesium, wherein each metal may be ex-situ deposited onto the exposed carbon surface of the anode 120. During the operating cycle of the battery 100, the lithium layer can provide lithium cations (Li... + The lithium cations can be transported to and from the cathode 110. Therefore, the battery 100 may not require an additional lithium source for operation. Instead of using lithium sulfide, elemental sulfur (S8) can be preloaded into various pores or porous networks formed in the cathode 110. During the battery's operating cycles, the elemental sulfur can form lithium-sulfur complexes that microscopically confine (at least temporarily) a greater amount of lithium compared to conventional cathode designs. Therefore, the battery 100 can outperform batteries that rely on such conventional cathode designs.

[0128] In various implementations, during the discharge cycle of battery 100, the lithium layer can dissociate and / or separate into lithium cations (Li). + 125 and electrons 174. Lithium cation (Li + )125 can migrate from the anode 120 toward the cathode 110 via the electrolyte 130 to its electrochemically favorable location within the cathode 110, such as Figure 1 As shown in the example. With lithium cations (Li + 125 electrons move through the electrolyte 130, and 174 electrons from the lithium cation (Li) + Electrons 174 are released from anode 120 and become available to carry charge, thus conducting current between anode 120 and cathode 110. Therefore, electrons 174 can travel from anode 120 to cathode 110 via an external circuit to power external load 172. External load 172 can be any suitable circuit, device, or system, such as (but not limited to) light bulbs, consumer electronics, or electric vehicles (EVs).

[0129] In some implementations, battery 100 may include a solid electrolyte interfacial phase layer 140. In some cases, the solid electrolyte interfacial phase layer 140 may be artificially formed on anode 120 during the operating cycle of battery 100. In such cases, the solid electrolyte interfacial phase layer 140 may also be referred to as an artificial solid electrolyte interfacial phase or A-SEI. When formed as A-SEI, the solid electrolyte interfacial phase layer 140 may include tin, manganese, molybdenum, and / or fluorine compounds. Specifically, molybdenum can provide cations, and fluorine compounds can provide anions. Cations and anions can interact with each other to produce salts such as tin fluoride, manganese fluoride, silicon nitride, lithium nitride, lithium nitride, lithium nitride, lithium phosphate, manganese oxide, and lithium lanthanum zirconium oxide (LLZO, Li7La3Zr2O). 12 In some cases, A-SEI can respond to lithium cations (Li...). + )125 is formed by exposure to electrolyte 130, which may include a solvent-based solution comprising tin and / or fluorine.

[0130] In various implementations, the solid electrolyte interfacial phase layer 140 may be artificially provided on the anode 120 prior to activation of the battery 100. Alternatively, in one implementation, the solid electrolyte interfacial phase layer 140 may naturally form on the anode 120, for example, during operating cycles of the battery 100. In some cases, the solid electrolyte interfacial phase layer 140 may comprise an external shielding material layer that can be applied to the anode 120 as a microcoating. In this way, the formation of the solid electrolyte interfacial phase layer 140 on the portion of the anode 120 facing the electrolyte 130 may be caused by the electrochemical reduction of the electrolyte 130, which in turn may reduce uncontrolled decomposition of the anode 120.

[0131] In some implementations, the battery 100 may include a barrier layer 142 located on the side of the solid electrolyte interface phase layer 140, for example, as Figure 1 As shown. The barrier layer 142 may include a mechanical strength enhancer 144 coated and / or deposited on the anode 120. In some aspects, the mechanical strength enhancer 144 may provide structural support for the battery 100, preventing the formation of lithium dendrites from the anode 120, and / or preventing lithium dendrites from extending into the entire battery 100. In some implementations, the mechanical strength enhancer 144 may be formed as a protective coating on the anode 120 and may include one or more carbon allotropes, carbon nanotubes (CNO), nanotubes (CNT), reduced graphene oxide, graphene oxide (GO), and / or carbon nanodiamonds. In some cases, a solid electrolyte interfacial phase layer 140 may be formed within the mechanical strength enhancer 144.

[0132] In some implementations, the first substrate 101 and / or the second substrate 102 may be solid copper foil and may affect the energy capacity, rate performance, lifespan, and long-term stability of the battery 100. For example, to control the energy capacity and other performance properties of the battery 100, the first substrate 101 and / or the second substrate 102 may be subjected to etching, carbon coating, or other suitable treatments to increase the electrochemical stability and / or conductivity of the battery 100. In other implementations, depending on the end-use application and / or performance requirements of the battery 100, the first substrate 101 and / or the second substrate 102 may comprise or be formed of aluminum, copper, nickel, titanium, stainless steel, and / or carbonaceous materials. For example, the first substrate 101 and / or the second substrate 102 may be individually tuned or customized so that the battery 100 meets one or more performance requirements or metrics.

[0133] In some aspects, the first substrate 101 and / or the second substrate 102 may be at least partially based on or derived from a foam, and may be selected from any one or more of a metal foam, a metal mesh, a metal sieve, a porous metal, or a sheet-based three-dimensional (3D) structure. In other aspects, the first substrate 101 and / or the second substrate 102 may be a metal fiber pad, a metal nanowire pad, a conductive polymer nanofiber pad, a conductive polymer foam, a conductive polymer-coated fiber foam, a carbon foam, a graphite foam, or a carbon aerogel. In some other aspects, the first substrate 101 and / or the second substrate 102 may be a carbon dry gel, a graphene foam, a graphene oxide foam, a reduced graphene oxide foam, a carbon fiber foam, a graphite fiber foam, a peeled graphite foam, or any combination thereof.

[0134] Figure 2 Another exemplary battery 200 is shown according to some implementation methods. Battery 200 may be similar in many respects to... Figure 1 The battery 100 is described herein, so that the description of the same components will not be repeated here. In some implementations, the battery 200 may be a next-generation battery, such as a lithium metal battery and / or a solid-state battery having a solid electrolyte. In other implementations, the battery 200 may include an electrolyte 230 and may therefore include any protective layer and / or electrolyte chemicals or compositions disclosed herein.

[0135] In some other implementations, the electrolyte 230 may be solid or substantially solid. For example, in some cases, the electrolyte 230 may begin as a gel phase and then solidify after the battery 200 is activated. The battery 200 can reduce specific capacity or energy loss associated with the polysulfide shuttle effect by replacing a conventional carbon-supported anode with a single solid lithium metal layer deposited in an initially empty cavity. For example, although Figure 1 The anode 120 of the battery 100 may include a carbon support, but Figure 2The anode 220 of the battery 200 may be a lithium metal anode that does not contain any carbon material. In one implementation, the lithium metal anode may be formed as a single solid lithium metal layer and referred to as a "lithium metal anode".

[0136] Increased energy density associated with various cathode materials can be based on whether lithium metal is preloaded into the cathode 210 and / or whether said lithium metal is dominant in the electrolyte 230. The cathode 210 and / or electrolyte 230 can provide lithium that can be used to lithiate the anode 220. For example, a battery with a high-capacity cathode may require a thicker or more energy-dense anode to supply the increased amount of lithium needed for the high-capacity cathode. In some implementations, the anode 220 may include a scaffold carbonaceous structure capable of being progressively filled with lithium deposited therein. These carbonaceous structures may be able to retain a greater amount of lithium within the anode 220 compared to conventional graphite anodes, which may be limited to carrying only lithium embedded between alternating graphene layers or available for lithium electroplating. For example, a conventional graphite anode may use six carbon atoms to retain a single lithium atom. In contrast, by using a pure lithium metal anode, such as anode 220, the batteries disclosed herein can reduce or even eliminate the use of carbon in the anode 220, allowing the anode 220 to store a greater amount of lithium in a relatively small volume compared to conventional graphite anodes. In this way, the energy density of battery 200 can be greater than that of a conventional battery of similar size.

[0137] Lithium metal anodes (such as anode 220) can be fabricated to function in conjunction with a solid electrolyte designed to suppress the formation and growth of lithium dendrites from the anode. In some respects, separator 250 can further limit dendrite formation and growth. When Figure 1 While the electrolyte 130 still reduces lithium dendrite formation, the separator 250 can have similar ionic conductivity. In some respects, the separator 250 can be formed of a ceramic-containing material and therefore may not be chemically reactive with metallic lithium. Thus, the separator 250 can be used to control lithium-ion transport through pores distributed in the separator 250, while preventing short circuits by hindering the flow of electrons through or across the electrolyte 230.

[0138] In one implementation, void spaces (not shown for simplicity) may be formed in or near the anode 220 within the battery 200. In this implementation, operating cycles of the battery 200 may result in lithium deposition into the void spaces. Therefore, the void spaces may become or transform into lithium-containing regions (such as a solid lithium metal layer) and act as the anode 220. In some aspects, the void spaces may be generated in response to a chemical reaction between a metal-containing non-electroactive component of the battery 200 and a graphene-containing component. Specifically, during operating cycles, the graphene-containing component may chemically react with lithium deposited into the void spaces to produce lithiated graphite (LiC6) or patterned lithium metal. The lithiated graphite produced by the chemical reaction may generate or lead to lithium cations (Li... + The generation and / or release of ions or electrons, which can be used to carry charge or "current" between the anode 220 and the cathode 210 during the discharge cycle of the battery 200.

[0139] Furthermore, in the implementation where the anode 220 is a solid lithium metal layer, the battery 200 may be able to retain more electroactive material and / or lithium per unit volume (as compared to batteries with a carbon support and / or embedded lithium-based graphite anodes). In some aspects, when the anode 220 is fabricated as a solid lithium metal layer, it can result in the battery 200 having a higher energy density and / or specific capacity compared to batteries with a carbon support and / or embedded lithium-based graphite anodes, thereby producing a longer discharge cycle time and additional power output per unit time. In cases where the use of a solid electrolyte is not desirable or optimal, Figure 2 The electrolyte 230 of the battery 200 can be prepared using any liquid-phase electrolyte chemical substance and / or composition disclosed herein. Alternatively or concurrently, the electrolyte 230 may comprise lithium and / or lithium cations (Li₂). + It can be used for cyclic transport from anode 220 to cathode 210 and vice versa during discharge and charge cycles, respectively.

[0140] To reduce the migration of polysulfides 282 generated from elemental sulfur 281 preloaded in the cathode 210 to the electrolyte 230, the battery 200 may include one or more unique polysulfide retention features. For example, given that polysulfides are soluble in the electrolyte 230, it is anticipated that some polysulfides may drift or migrate from the cathode 210 to the anode 220 due to differences in electrochemical potential, chemical gradients, and / or other phenomena. The migration of polysulfides 282 (especially long-chain polysulfides) may hinder the migration of lithium cations (Li). + The transfer of electrons from anode 220 to cathode 210 may reduce the number of electrons available to generate current that can power a load 272 such as an electric vehicle (EV). In some respects, lithium cations (Li... +)225 can be transported from one or more starting positions 226 at or near the anode 220 along the transport path to one or more final positions 227 at or near the cathode 210, such as Figure 2 The example depicts this.

[0141] In some implementations, a polymer network 285 may be disposed on the anode 220 to reduce uncontrolled migration of polysulfides 282 from the anode 220 to the cathode 210. The polymer network 285 may include one or more layers of carbonaceous material used as fluorinated polymer links that are cross-linked to each other via a Woods reaction after exposure to the lithium anode surface. The carbonaceous material of the polymer network 285, which may include (but is not limited to) graphene, few-layer graphene (FLG), and multilayer graphene (MLG), may be chemically grafted with fluorinated polymer chains containing carbon-fluorine (CF) bonds. These CF bonds can chemically react with lithium metal from the surface of the anode 220 to generate highly ionic carbon-lithium (C-Li) bonds. These formed C-Li bonds can then react with the CF bonds of the polymer chains to form new carbon-carbon bonds, which can also cross-link the polymer chains into (and thus form) a polymer network and produce lithium fluoride (LiF).

[0142] The resulting lithium fluoride can be uniformly distributed along the entire periphery of the polymer network 285, so that during battery cycling, the lithium cations (Li... + The lithium fluoride is consumed uniformly, thereby creating an interface layer 283 that may form or otherwise include lithium fluoride. The interface layer 283 may extend or partially extend along the surface of the anode 220 facing the cathode 210, such as... Figure 2 As shown. Therefore, lithium cations (Li + 225 are less likely to combine and / or react with each other and more likely to combine and / or react with fluorine atoms that can be provided by fluorinated polymer chains in polymer network 285. The resulting reduction in lithium-lithium chemistry reduces lithium-lithium bonding that leads to the formation of undesirable lithium-metal dendrites. Additionally, in some implementations, polymer network 285 may replace the interface phase layer 240 that is naturally or artificially formed between anode 220 and electrolyte 230.

[0143] In one implementation, the interface layer 283 of the polymer network 285 is in contact with the anode 220, and a protective layer 284 is disposed on top of the interface layer 283 (e.g., between the interface layer 283 and the interface phase layer 240). In some aspects, the interface layer 283 and the protective layer 284 may jointly define a gradient of cross-linked fluoropolymer chains with different densities, for example, as referenced. Figure 7 As described.

[0144] In some other implementations, battery 200 may include a protective lattice 280 disposed on cathode 210. Protective lattice 280 may include a trifunctional epoxy compound and a diamine-based oligomer compound that can chemically react with each other to produce nitrogen and oxygen atoms. The nitrogen and oxygen atoms available from protective lattice 280 may bond with polysulfide 282, thereby confining polysulfide 282 within cathode 210 and / or protective lattice 280. Either cathode 210 and / or protective lattice 280 may include carbon-carbon bonds and / or regions capable of flexing and / or expanding in volume during operating cycles of battery 200, thereby confining polysulfide 282 generated during operating cycles within cathode 210.

[0145] Figure 1 Electrolytes 130 and Figure 2 Electrolyte 230 can be prepared according to one or more formulations disclosed herein. For example, the ternary solvent package used in electrolyte 130 and / or electrolyte 230 may include DME, DOL, and TEGDME. In one implementation, the solvent mixture can be prepared by mixing 5800 μL of DME, 2900 μL of DOL, and 1300 μL of TEGDME and stirring at room temperature (77℉ or 25℃). Next, 0.01 mol (2,850.75 mg) of LiTFSI can be weighed. Subsequently, the 0.01 mol of LiTFSI can be dissolved in the solvent mixture by stirring at room temperature to prepare approximately 10 mL of 1 M LiTFSI in DME:DOL:TEGDME (volume:volume:volume 1:4:1). Finally, approximately 223 mg of LiNO3 can be added to 10 mL of solution to produce 10 mL of 1 M LiTFSI in DME:DOL:TEGDME (volume:volume:volume = 58:29:13) with approximately 2% by weight LiNO3.

[0146] Alternatively, the ternary solvent package used in electrolyte 130 and / or electrolyte 230 may include DME, DOL, TEGDME, and TBT or MBT. The solvent mixture can be prepared by mixing 2,000 μL of DME, 8,000 μL of DOL, and 2,000 μL of TEGDME and stirring at room temperature (68℉ or 25℃). Next, 0.01 mol (2,850.75 mg) of LiTFSI can be weighed and dissolved in approximately 3 mL of the solvent mixture by stirring at room temperature. Next, the dissolved LiTFSI and the additional solvent mixture (approximately 8,056 mg) can be mixed in a 10 mL volumetric flask to produce approximately 1 M LiTFSI in a DME:DOL:TEGDME (volume:volume:volume 1:4:1). Finally, approximately 0.05 mmol (approximately 12.5 mg) of TBT or MBT can be added to 10 mL of the solution to produce a 10 mL 5 M TBT or MBT solution.

[0147] Figure 3 An exemplary electrode 300 is shown according to some implementations. In various implementations, the electrode 300 may be... Figure 1 An example of the cathode 110 and / or anode 120 of the battery 100. In some other implementations, the electrode 300 may be... Figure 2 An example of the cathode 210 of the battery 200. When the electrode 300 is implemented as a cathode (e.g. Figure 1 When the cathode 110 of the battery 100 is used, the electrode 300 can temporarily microscopically confine an electroactive material such as elemental sulfur, which can reduce the amount of sulfur available for reaction with lithium to produce polysulfides. In some respects, the electrode 300 can provide an excess supply of lithium and / or lithium cations (Li₂O₃). + This can compensate for the first cycle operating losses associated with lithium-based batteries.

[0148] In some implementations, electrode 300 may be porous and accept a liquid electrolyte, such as... Figure 1 Electrolyte 130. Electrolyte-active substances suspended in electrolyte 130, such as lithium cations (Li... + )125, can chemically react with elemental sulfur preloaded into the pores of electrode 300 to produce polysulfides, which can then be retained in electrode 300 during battery cycling. In some aspects, electrode 300 can expand volutely along one or more flexure points to retain additional amounts of polysulfides generated during battery cycling. By confining polysulfides within electrode 300, aspects of the subject matter disclosed herein allow lithium cations (Li... +During the discharge cycle of battery 100, electrolyte 130 flows freely from anode 120 to cathode 110 (e.g., without being hindered by polysulfides). For example, when lithium cations (Li... + When 125 reaches the cathode 110 and reacts with elemental sulfur contained within or associated with the cathode 110, sulfur is reduced to lithium polysulfides (Li₂S) in decreasing chain lengths in the following order. x The sequence is: Li₂S₈→Li₂S₆→Li₂S₄→Li₂S₂→Li₂S, where 2≤x≤8). Higher polysulfides are soluble in various types of solvents and / or electrolytes, thereby interfering with lithium-ion transport necessary for healthy battery operation. Holding such higher polysulfides by electrode 300 allows lithium cations (Li₂S₈) to be transported. + )125 flows more freely through electrolyte 130, which in turn increases the number of electrons available to carry charge from anode 120 to cathode 110.

[0149] Electrode 300 may include a body 301 defined by a width 305, and may include a first film 310 and a second film 320. The first film 310 may include a plurality of first aggregates 312 bonded together to form a first porous structure 316 of electrode 300. In some cases, the first porous structure 316 may have a conductivity between approximately 0 and 500 S / m. In other cases, the first conductivity may be between approximately 500 and 1,000 S / m. In some other examples, the first conductivity may be greater than 1,000 S / m. In some aspects, the first aggregates 312 may include carbon nanotubes (CNTs), carbon nanotubes (CNO), sheet-like graphene, wrinkled graphene, graphene grown on a carbonaceous material, and / or graphene grown on graphene.

[0150] In some implementations, the first aggregate 312 may be decorated with a plurality of first nanoparticles 314. In some cases, the first nanoparticles 314 may include tin, lithium alloys, iron, silver, cobalt, semiconductor materials, and / or metals such as silicon. In some aspects, CNTs may be used as a support material for the first nanoparticles 314 due to their ability to provide a high exposed surface area per unit volume and stability at relatively high temperatures (such as 77℉ or above 25°C). For example, the first nanoparticles 314 may be fixed (e.g., by decoration, deposition, surface modification, or similar methods) to the exposed surface of CNTs and / or other carbonaceous materials. The first nanoparticles 314 may react with chemically available carbon on the exposed surface of CNTs and / or other carbonaceous materials.

[0151] The second thin film 320 may include a plurality of second aggregates 322 bonded together to form a second porous structure 326. In some cases, the electrical conductivity of the first porous structure 316 and / or the second porous structure 326 may be between approximately 0 S / m and 250 S / m. Where the first porous structure 316 includes aggregates at a higher concentration than the second porous structure 326, the first porous structure 316 may have a higher electrical conductivity than the second porous structure 326. In one implementation, the first electrical conductivity may be between approximately 250 S / m and 500 S / m, while the second electrical conductivity may be between approximately 100 S / m and 250 S / m. In another implementation, the second electrical conductivity may be between approximately 250 S / m and 500 S / m. In yet another implementation, the second electrical conductivity may be greater than 500 S / m. In some respects, the second aggregate 322 may include CNTs, CNOs, sheet graphene, wrinkled graphene, graphene grown on a carbonaceous material, and / or graphene grown on graphene.

[0152] The second aggregate 322 may be decorated with a plurality of second nanoparticles 324. In some implementations, the second nanoparticles 324 may include iron, silver, cobalt, semiconductor materials, and / or metals such as silicon. In some cases, CNTs may also be used as a support material for the second nanoparticles 324. For example, the second nanoparticles 324 may be fixed (e.g., by decoration, deposition, surface modification, or similar methods) to exposed surfaces of CNTs and / or other carbonaceous materials. The second nanoparticles 324 may react with chemically available carbon on the exposed surfaces of CNTs and / or other carbonaceous materials.

[0153] In some aspects, the first film 310 and / or the second film 320 (and any additional films disposed on their respective immediate adjoining the preceding film) may be formed as layers or regions of material and / or aggregates. The layers or regions may have thicknesses ranging from fractions of a nanometer to several micrometers, such as between approximately 0 and 5 micrometers, between approximately 5 and 10 micrometers, between approximately 10 and 15 micrometers, or greater than 15 micrometers. Any material and / or aggregate disclosed herein (such as CNO) may be incorporated into the first film 310 and / or the second film 320 to produce the described thickness levels.

[0154] In some implementations, the first thin film 310 can be deposited by chemical deposition or physical deposition. Figure 1The first film 310 may be grown layer-by-layer on the second substrate 102, or by techniques such as Frank-van der Merwe growth, Stranski-Krastonov growth, Volmer-Weber growth, etc. In other implementations, the first film 310 may be deposited on the second substrate 102 by epitaxy or other suitable thin film deposition methods involving epitaxial growth of the material. The second film 320 and / or subsequent films may be deposited on their respective adjacent films in a manner similar to that described with reference to the first film 310.

[0155] In various implementations, each of the first aggregate 312 and / or the second aggregate 322 can be a relatively large particle formed by bonding or fusing together a plurality of relatively small particles. Therefore, the outer surface area of ​​the relatively large particle can be significantly smaller than the combined surface area of ​​the plurality of relatively small particles. The forces holding the aggregates together can be, for example, covalent, ionic bonds, or other types of chemical bonds arising from the sintering or complex physical entanglement of the preceding primary particles.

[0156] As discussed above, first aggregates 312 may aggregate together to form a first porous structure 316, and second aggregates 322 may aggregate together to form a second porous structure 326. The conductivity of the first porous structure 316 may be based on the concentration level of the first aggregates 312 within the first porous structure 316, and the conductivity of the second porous structure 326 may be based on the concentration level of the second aggregates 322 within the second porous structure 326. In some aspects, the concentration level of the first aggregates 312 may result in the first porous structure 316 having a relatively high conductivity, and the concentration level of the second aggregates 322 may result in the second porous structure 326 having a relatively low conductivity (making the first porous structure 316 have a higher conductivity than the second porous structure 326). The resulting difference in conductivity between the first porous structure 316 and the second porous structure 326 may produce a conductivity gradient across the electrode 300. In some implementations, the conductivity gradient may be used to control or adjust the conductivity of the entire electrode 300 and / or Figure 1 One or more operations of the battery 100.

[0157] As used in this article, relatively small source particles can be referred to as "primary particles," and relatively large aggregates formed from primary particles can be referred to as "secondary particles." Figure 1As shown in Figures 8 to 10 and elsewhere throughout this disclosure, primary particles may be or comprise multiple graphene sheets, layers, regions, and / or nanosheets fused and / or bonded together. Thus, in some cases, carbon nanotubes (CNO), carbon nanotubes (CNT), and / or other tunable carbon materials may be used to form primary particles. In some aspects, some aggregates may have principal dimensions (such as length, width, and / or diameter) between approximately 500 nm and 25 μm. Additionally, some aggregates may comprise smaller assemblies of primary particles, referred to as “naturally formed particles,” of graphene sheets, layers, regions, and / or nanosheets bonded together at orthogonal angles. In some cases, these naturally formed particles may each have a corresponding size between approximately 50 nm and 250 nm.

[0158] The surface area and / or porosity of such naturally occurring particles can be imparted through secondary processes, such as carbon activation using one or more of the following thermal, plasma, or combined thermal-plasma processes: steam, hydrogen gas, carbon dioxide, oxygen, ozone, KOH, ZnCl2, H3PO4, or other similar chemical agents, either alone or in combination. In some implementations, the first porous structure 316 and / or the second porous structure 326 can be generated from a carbonaceous gaseous material, which can be controlled by a gas-solid reaction under unbalanced conditions. Generating the first porous structure 316 and / or the second porous structure 326 in this manner may involve the recombination of carbonaceous groups formed by the controlled cooling of a carbonaceous plasma material (which can be generated by the activation or compaction of a carbonaceous feed gaseous and / or plasma material in a suitable chemical reactor).

[0159] In some implementations, the first aggregate 312 and / or the second aggregate 322 may have a carbon content greater than 99% of the total carbon content of each respective aggregate, excluding hydrogen. In some cases, the median particle size of each aggregate may be between approximately 0.1 micrometers and 50 micrometers. The first aggregate 312 and / or the second aggregate 322 may also include a metallic organic framework (MOF).

[0160] In some implementations, the first porous structure 316 and the second porous structure 326 can jointly define the main structure 328, for example, as Figure 3 As shown. In some cases, the main structure 328 may be based on a carbon support and / or may include decorative carbon, for example, as shown in Figure 8. The main structure 328 may provide structural definition for the electrode 300. In some cases, the main structure 328 may be fabricated as a positive electrode and used for Figure 1 The cathode 110. In other implementations, the main structure 328 can be fabricated as a negative electrode and used for Figure 1The anode 120. In some other implementations, the main structure 328 may include pores of different sizes, such as micropores, mesopores, and / or macropores as defined by IUPAC. In some cases, at least some micropores may have a width of about 1.5 nm, which may be large enough to allow sulfur preloading into the electrode 300 and still small enough to define polysulfides within the electrode 300.

[0161] Main structure 328 when provided as Figure 3 When the electrode 300 is shown, it may include micropores, mesopores, and / or macropores created by the exposed surfaces and / or contours of the first porous structure 316 and / or the second porous structure 326. These channels may allow the main structure 328 to receive an electrolyte, for example, by passing lithium cations (Li... + The electrolyte 130 is transported to the cathode 110 of the battery 100. Specifically, the electrolyte 130 can wet various porous channels of the main structure 328 and is uniformly dispersed throughout the electrode 300 and / or other parts of the battery 100. The electrolyte 130's wetting into such regions of the main structure 328 allows lithium cations (Li₂O₃) to migrate from the anode 120 to the cathode 110. + )125 reacts with elemental sulfur associated with cathode 110 to form a lithium-sulfur complex. Therefore, elemental sulfur can retain an additional amount of lithium cations (Li). + Alternatively, it can be achieved using non-sulfur chemicals such as lithium cobalt oxide (LiCoO) or other lithium-ion cells.

[0162] In some aspects, each of the first porous structure 316 and / or the second porous structure 326 may have porosity based on one or more of a thermal, plasma, or combined thermal-plasma process using one or more of steam, hydrogen gas, carbon dioxide, oxygen, ozone, KOH, ZnCl2, H3PO4, or other similar chemical agents, either alone or in combination. For example, in one implementation, macropore channels may have a principal size greater than 50 nm, mesopore channels may have a principal size between approximately 20 nm and 50 nm, and micropore channels may have a principal size less than 4 nm. Thus, macropore channels and mesopore channels can provide for transporting lithium cations (Li... + The adjustable tubing of 125 and the microporous channel can confine the active material within the electrode 300.

[0163] In some implementations, electrode 300 may include one or more additional thin films (not shown for simplicity). Each of the one or more additional thin films may include individual aggregates interconnected across different thin films, wherein at least some films contain aggregates at different concentration levels. Therefore, the concentration level of any thin film can be varied (e.g., by a gradient) to achieve a specific resistance (or conductance) value. For example, in some implementations, the concentration level of the aggregates may gradually decrease between the first thin film 310 and the last thin film (e.g., in… Figure 1 The depicted direction 195 (upward), and / or individual films may have an average thickness between approximately 10 micrometers and approximately 200 micrometers. Alternatively or additionally, the first film 310 may have a relatively high concentration of carbonaceous aggregates, and the second film 320 may have a relatively low concentration of carbonaceous aggregates. In some aspects, a relatively high concentration of aggregates corresponds to a relatively low resistance, and a relatively low concentration of aggregates corresponds to a relatively high resistance.

[0164] The main structure 328 can be fabricated to have multiple active sites on the exposed surface of the first aggregate 312 and / or the second aggregate 322. These active sites, and the exposed surfaces of the first aggregate 312 and / or the second aggregate 322, can facilitate ectopic electrodeposition before the electrode 300 is incorporated into the battery 100. Electroplating is a process that produces a lithium layer 330 (including lithium on the exposed surface of the main structure 328) by applying and / or adjusting an electric current through the chemical reduction of metal cations. In the electrode 300 acting as... Figure 1 In the implementation of the anode 120 of the battery 100, the main structure 328 can be electroplated such that the lithium layer 330 has a thickness of approximately between 1 and 5 micrometers (μm), between 5 μm and 20 μm, or greater than 20 μm. In some cases, ex-situ electrodeposition can be performed at a location independent of the battery 100 before assembling the battery 100.

[0165] In various implementations, the excess lithium provided by the lithium layer 330 can increase the amount of lithium cations (Li) that can be transported in the battery 100. + The number of 125 increases the storage capacity, lifespan, and performance of battery 100 (compared to conventional lithium-ion and / or lithium-sulfur batteries).

[0166] In some respects, the lithium layer 330 can produce lithium-intercalated graphite (LiC6) and / or lithiated graphite based on chemical reactions with the first aggregate 312 and / or the second aggregate 322. Due to differences in electrochemical gradients during the operating cycles of the battery 100, the lithium intercalated between the alternating graphene layers can migrate or be transported within the electrode 300, which in turn can increase the energy storage and power delivery of the battery 100.

[0167] Figure 4The diagram illustrates a portion of an exemplary battery 400 including a protective lattice 402 according to some implementations. In some implementations, the protective lattice 402 may be disposed on the anode 220 of the battery 200. In other implementations, the protective lattice 402 may be disposed on the cathode 210 of the battery 200 (or other suitable battery). In some aspects, the protective lattice 402 may be... Figure 2 An example of a protective lattice 280. The protective lattice 402 can be used with many components (e.g., anode, cathode, associated current collector, carbonaceous material, electrolyte, and separator) to... Figure 1 100 and / or Figure 2 The battery 200 works in a similar way.

[0168] Protective lattice 402 may include trifunctional epoxy compounds and diamine-based oligomers that can chemically react with each other to produce a 3D lattice structure (e.g., as shown in the image). Figure 6 (As shown in Figure 8). In some respects, the protective lattice 402 can prevent the migration of polysulfides within the battery 400 by providing nitrogen and oxygen atoms that can chemically bind with lithium present in the polysulfides, thereby hindering the migration of polysulfides through the electrolyte 130. Therefore, lithium cations (Li... + )125 can be more free Figure 1 The anode 120 and cathode 110 are transported, thereby increasing the battery performance metrics.

[0169] Recycling of the cathode 110 can lead to the formation of cracks 404 that extend at least partially into the cathode 110. In one implementation, a protective lattice 402 may be dispersed throughout the crack 404, thereby reducing the susceptibility of the cathode 110 to breakage during volume expansion caused by the retention of polysulfides within the cathode 110 during recycling. In one implementation, based on a chemical reaction between a difunctional or higher-functionality epoxy compound and an amine or amide compound, Figure 4 The protective lattice 402 may have a cross-linked 3D structure. For example, the difunctional or higher-functionality epoxy compound may be trimethylolpropane triglycidyl ether (TMPTE), tris(4-hydroxyphenyl)methane triglycidyl ether, or tris(2,3-epoxypropyl)isocyanurate, and the difunctional or higher-functionality amine compound may be one of dihydrazide sulfoxide (DHSO) or polyetheramine, characterized, for example, by repeating oxypropylene units in the main chain. D-230.

[0170] In various implementations, the chemical compounds can be combined and reacted with each other in many quantities, amounts, ratios, and / or compositions to achieve different performance capabilities with respect to the combination with polysulfides generated during battery 400 operation. For example, in one implementation, 113 mg TMPTE and 134 mg D-230 polyetheramines can be mixed together and diluted with 1 mL to 10 mL of tetrahydrofuran (THF) or any other solvent. (Content: 113 mg TMPTE / 134 mg) An exemplary ratio of D-230 polyetheramine allows for the mixing of additional amounts of TMPTE and / or JEFFAMINE and dilution in THF or any other solvent. For this implementation, proof-of-concept (POC) documentation indicates that... Figure 4 The protective lattice 402 has Figure 1 Cathode 110 or Figure 2 The defined weight of cathode 210 is approximately 2.6 wt%. In other implementations, protective lattice 402 may have a weight of approximately 2 wt% to 21 wt% of cathode 110 and / or cathode 210, wherein an increase in impedance of cathode 110 and / or cathode 210 is expected at a weight level of approximately 10 wt% or more of protective lattice 402.

[0171] In various implementations, the protective lattice 402 can be manufactured based on the molar and / or molar ratio of -NH2 groups and epoxy groups, and can be further adapted to various crosslinking forms between difunctional or higher-functionality epoxy compounds and amine or amide compounds. In some aspects, such crosslinking forms may include a fully crosslinked stage, for example, where one -NH2 group is chemically bonded to two epoxy groups, and can be further extended to include a configuration comprising one NH2 group chemically bonded to only one epoxy group. Furthermore, in one or more implementations, a mixture comprising an excessive amount (higher than the ratio presented herein) of -NH2 groups can be prepared to provide additional polysulfide bonding capability to the protective lattice 402.

[0172] In some other implementations, this can be achieved by varying the TMPTE content from 201g to between 109g and 283g. D-230 polyetheramine is mixed to prepare protective lattice 402. The resulting mixture can then be diluted with 1 L to 20 L of a chosen solvent (such as THF). The resulting diluted solution can be deposited and / or otherwise disposed on cathode 110 to achieve a crosslinking agent content between 1 wt% and 10 wt%. (The dosage ranges from 201 g TMPTE / 109 g to 283 g). An exemplary ratio of D-230 polyetheramine can be used to mix additional TMPTE and / or JEFFAMINE together and dilute in THF or another suitable solvent.

[0173] In another implementation, the protective lattice 402 can be prepared by mixing 201g of TMPTE with between 74g and 278g of DHSO. The resulting mixture can then be diluted with 1L to 20L of a chosen solvent (such as THF). The resulting diluted solution can be deposited and / or otherwise disposed on the cathode 110 to achieve a crosslinking agent content between 1% and 10% by weight. (201g TMPTE / 201g to 278g) An exemplary ratio of D-230 polyetheramine can be used to mix additional TMPTE and / or JEFFAMINE together and dilute in THF or another suitable solvent.

[0174] In one implementation, a difunctional or higher-functionality epoxy compound may chemically react with a difunctional or higher-functionality amine compound to produce a 3D cross-linked protective lattice 402, which may include the functional epoxy compound and amine-containing molecules. In some aspects, the protective lattice 402 is deposited on... Figure 1 Cathode 110 or Figure 2 When applied to the cathode 210, it can have a thickness between approximately 1 nm and 5 μm.

[0175] In some implementations, the protective lattice 402 can increase the structural integrity of the cathode 110 or cathode 210, reduce surface roughness, and retain polysulfides within the cathode. For example, in one implementation, the protective lattice 402 can act as a sheath on the exposed surface of the cathode and bind to the polysulfides to prevent their migration and diffusion into the electrolyte 130. In this way, aspects of the subject matter disclosed herein can prevent (or at least reduce) battery capacity decay by suppressing the polysulfide shuttle effect. In some aspects, the protective lattice 402 can also fill... Figure 4 Cracks 404 are formed in the cathode to improve the integrity of the cathode coating. In various implementations, the protective lattice 402 can be prepared by a drop casting process in the presence of a solvent, wherein the resulting solution can penetrate into the cracks 404 of the cathode 110 and bind to the polysulfides in the cathode 110 to prevent their migration and / or diffusion into the entire electrolyte 130.

[0176] In various implementations, the protective lattice 402 provides nitrogen and / or oxygen atoms that can chemically bond with lithium in the polysulfides generated during battery cycling. In one example, the polysulfides may be bonded to available nitrogen atoms provided, for example, by DHSO. In another example, the polysulfides may be bonded to available oxygen atoms provided, for example, by DHSO. In yet another example, the polysulfides may be bonded to other available oxygen atoms.

[0177] In some other implementations, the formulation described above can be modified by replacing TMPTE with tris(4-hydroxyphenyl)methane triglycidyl ether 910 and / or tris(2,3-epoxypropyl)isocyanurate. In various implementations, the diamine oligomer-based compound may be (or may include) D-230, or other polyether amines containing a polyether backbone typically based on propylene oxide (PO), ethylene oxide (EO), or a mixture of PO / EO structures, such as D-400 T-403. The protective lattice 402 may also include inert molecules at various concentration levels, such as polyethylene glycol chains of various lengths, which allows for fine-tuning of the mechanical properties of the protective lattice and the chemical bonding of various atoms with lithium present in the polysulfides.

[0178] Figure 5 A diagram is shown illustrating an anode structure 500 including a tin fluoride (SnF2) layer according to some implementations. Specifically, the diagram depicts a cross-sectional schematic of the anode structure 500, wherein all components associated with a first region A have identical counterparts in a second region B, wherein the first region A and the second region B have opposite orientations around the current collector 520. Therefore, the description of the components in the first region A described below also applies to the components in the second region B. In some aspects, the anode 502 may be... Figure 1 Anode 120 and / or Figure 2 An example of an anode 220.

[0179] As discussed, lithium-sulfur batteries, such as Figure 1 100 batteries and Figure 2 The battery 200 operates as a conversion chemistry type electrochemical cell, wherein sulfur pre-loaded into the cathode can rapidly dissolve into the electrolyte before and during operation. Lithium, which can be supplied by the lithiation anode and / or can be predominantly present in the electrolyte, dissociates into lithium cations (Li). + Lithium cations (Li) are suitable for transport from the anode to the cathode via an electrolyte. + The generation of electrons is related to the corresponding release of electrons, which can flow through external circuits to power the load, as shown in the reference. Figure 1 As described above. However, when lithium dissociates into lithium cations (Li... + ) and electrons (e - When ), some lithium cations (Li) + The cathode may undesirably react with polysulfides generated in the cathode, and therefore may no longer be usable for generating output current or voltage. Polysulfides react with lithium cations (Li... + This consumption reduces the host cell or the total capacity of the battery, and may also promote anode corrosion, which can lead to cell failure.

[0180] In some implementations, the protective layer 516 may be provided as a passivating coating that reduces the chemical reactivity of the anode 502 during cell assembly or formation. In some aspects, the protective layer 516 may be suitable for lithium cations (Li... + It is permeable to the anode 502, while protecting it from lithium cations (Li). + Corrosion caused by chemical reactions between the protective layer and polysulfides. In other implementations, the protective layer 516 may be an artificial solid electrolyte interphase (A-SEI), which may replace naturally occurring SEI and / or other types of conventional A-SEI. In various implementations, the protective layer 516 may be deposited as a liner disposed on top of one or more films on the anode 502. In some aspects, the protective layer 516 may be a self-generated layer formed during electrochemical reactions associated with the operating cycle of the battery. In some aspects, the protective layer 516 may have a thickness of less than 5 micrometers. In other aspects, the protective layer 516 may have a thickness between 0.1 and 1.0 micrometers.

[0181] In various implementations, one or more engineered additives that facilitate the formation and / or deposition of the protective layer 516 on the anode 502 may be provided within the battery electrolyte. In other implementations, the engineered additives may be the active components of the protective layer 516. In some aspects, the protective layer 516 may be provided with tin ions and / or fluorine anions, which may prevent unwanted lithium growth from the first edge 5181 and the second edge 5182 of the anode.

[0182] A hierarchical layer 514 may be formed and / or deposited on the anode 502 below the protective layer 516. In various implementations, the hierarchical layer 514 prevents lithium contained in or associated with the anode 502 from engaging in undesirable chemical interactions and / or reactions with the electrolyte 540 that could lead to the growth of lithium-containing dendrites from the anode 502. The hierarchical layer 514 may also facilitate the dissociation of lithium cations (Li... + Lithium fluoride is produced by a chemical reaction between lithium ions and fluoride ions. As discussed, the presence of lithium fluoride in or near anode 502 can reduce the polysulfide shuttle effect. For example, the formation of lithium fluoride (e.g., by the availability of lithium cations (Li)) is achieved through a chemical reaction between lithium ions and fluoride ions. + Lithium ions (Li₂) and fluoride ions can occur uniformly across the entire first edge 5181 and / or second edge 5182 of the anode. In this way, localized regions of high lithium concentration in the electrolyte 540 near the anode 502 are substantially suppressed. Therefore, the formation of lithium-lithium bonds leading to the formation of lithium-containing dendrite structures extending longitudinally from the anode is correspondingly suppressed, thereby causing lithium cations (Li₂) to... +Lithium is freely transported from the anode 502 to the electrolyte (e.g., as encountered during battery operating cycles). In some aspects, uniform distribution of lithium throughout the hierarchical layer 514 can increase the uniformity of lithium-ion flux during battery operating cycles. In some aspects, the hierarchical layer 514 may be approximately 5 nanometers (nm) thick.

[0183] In one or more implementations, the hierarchical layer 514 can structurally reinforce the main cell in a way that not only reduces or prevents the growth of lithium-containing dendrites from the anode 502, but also increases the ability of the anode 502 to expand and contract without cracking during the operating cycles of the main cell. In some aspects, the hierarchical layer 514 has a 3D architecture with a hierarchical concentration gradient (e.g., one or more constitutive materials and / or components, including carbon, tin, and / or fluorine), which facilitates rapid lithium-ion transport. Therefore, the hierarchical layer 514 significantly improves overall battery efficiency and performance.

[0184] In some implementations, the hierarchical layer 514 provides an electrochemically desirable surface on which the protective layer 516 can be grown or deposited. For example, in some aspects, the hierarchical layer 514 may comprise compounds and / or organometallic compounds including (but not limited to) aluminum, gallium, indium, nickel, zinc, chromium, vanadium, titanium, and / or other metals. In other aspects, the hierarchical layer 514 may comprise oxides, carbides, and / or nitrides of aluminum, gallium, indium, nickel, zinc, chromium, vanadium, titanium, and / or other metals.

[0185] In some implementations, the hierarchical layer 514 may comprise a carbonaceous material, including (but not limited to) sheet-like graphene, few-layer graphene (FLG), carbon nano-onions (CNO), graphene nanosheets, or carbon nanotubes (CNTs). In other implementations, the hierarchical layer 514 may comprise carbon, oxygen, hydrogen, tin, fluorine, and / or other suitable chemical compounds and / or molecules derived from tin fluoride, along with one or more carbonaceous materials. The hierarchical layer 514 may be prepared directly or indirectly at varying concentration levels and / or deposited on the anode 502. For example, the hierarchical layer 514 may comprise 5% by weight of carbonaceous material and the remainder of 95% by weight of tin fluoride, which may result in relatively uniform dissociation of fluorine atoms and / or fluoride anions from tin fluoride.

[0186] Other suitable ratios include: 5% carbonaceous material with 95% tin fluoride; 10% carbonaceous material with 90% tin fluoride; 15% carbonaceous material with 85% tin fluoride; 20% carbonaceous material with 80% tin fluoride; 25% carbonaceous material with 75% tin fluoride; 30% carbonaceous material with 70% tin fluoride; 35% carbonaceous material with 65% tin fluoride; 40% carbonaceous material with 60% tin fluoride; 45% carbonaceous material with 55% tin fluoride; and 50% carbonaceous material with 50% tin fluoride. 55% tin fluoride, 55% carbonaceous material with 45% tin fluoride, 55% carbonaceous material with 45% tin fluoride, 60% carbonaceous material with 40% tin fluoride, 65% carbonaceous material with 35% tin fluoride, 70% carbonaceous material with 30% tin fluoride, 75% carbonaceous material with 25% tin fluoride, 80% carbonaceous material with 20% tin fluoride, 85% carbonaceous material with 15% tin fluoride, 90% carbonaceous material with 10% tin fluoride, 95% carbonaceous material with 5% tin fluoride. Then, fluorine atoms and / or fluoride anions can react with lithium cations (Li... + The reaction and combination are homogeneous to form lithium fluoride, as discussed further below.

[0187] In some implementations, the anode 502 and the cathode ( Figure 5 Lithium cations (Li not shown) cycling between (not shown in the image) + A tin-lithium alloy region 512 can be formed within the hierarchical layer 514. In some respects, the operating cycles of the main cell can result in a uniform dispersion of lithium fluoride within the tin-lithium alloy region 512. This uniform dispersion of lithium fluoride facilitates the defluorination reaction of at least some tin(II) fluoride (SnF2) within the tin fluoride layer 510 (as well as additional tin fluoride that can be dispersed into the hierarchical layer 514 and / or the protective layer). The fluorine atoms and / or fluoride anions provided by the defluorination reaction can react with at least some lithium cations (Li) present in or near the anode 502. + Chemical bonding is used to produce lithium fluoride (LiF) and thereby correspondingly prevent at least some lithium cations (Li) from forming. + They bond with each other and generate lithium dendrite growth from the anode 502.

[0188] For example, at least a portion of the fluorine atoms and / or fluorine anions present in tin fluoride can dissociate from the protective layer 516 and generate tin cations (Sn) via one or more chemical reactions. 2+ ) and fluoride anion (2F - Fluorine atoms and / or fluorine anions dissociated from protective layer 516 can chemically bond to at least some lithium cations (Li) present in electrolyte 540 and / or dispersed throughout protective layer 516 or hierarchical layer 514. + In some respects, the dissociated fluorine atoms can form Li-F bonds or Li-F compounds in the tin-lithium alloy region 512. In other respects, the dissociated fluorine atoms can form a tin fluoride layer 510 within the hierarchical layer 514.

[0189] In another implementation, at least some of the defluorinated tin fluoride may be uniformly dispersed throughout the hierarchical layer 514 to produce lithium fluoride (LiF) crystals. The lithium fluoride crystals may act as electrical insulators and prevent electrons from flowing from the anode 502 to the electrolyte 540 through the first edge 5181 and / or the second edge 5182 of the anode 502.

[0190] In various implementations, the hierarchical layer 514 can be deposited on the anode 502 via one or more of atomic layer deposition (ALD), chemical vapor deposition (CVD), or physical vapor deposition (PVD). For example, ALD can be used to deposit a protective film on the anode 502, such as an ALD film that reacts at least partially with the electrolyte 540 during a high-voltage bonding process. Thus, using atomic planes suitable for lithium transfer, the ALD film can be used to generate either a protective layer 516 or a hierarchical layer 514. This lithium transfer can, in principle, be similar to the transfer observed for few-layer graphene (FLG) or graphite, where alternating graphene layers in FLG or graphite are intercalated with various forms of lithium cations (Li). + This includes lithium in the form of lithium titanium oxide (LTO) and lithium iron phosphate (PO3) (LFP). The described forms of intercalated lithium (e.g., LTO and / or LFP) can be oriented to facilitate rapid lithium atom and / or lithium-ion transport and / or diffusion, which can be beneficial for the formation and / or synthesis of lithium fluorides (e.g., in the tin fluoride layer 510 and / or elsewhere), as previously described. Additional forms of intercalated lithium (e.g., lithium lanthanum perovskite titanate (LLTO)) can also function to store lithium within the anode 502.

[0191] In some implementations, the hierarchical layer 514 may comprise various types and / or forms of carbon and / or carbonaceous materials, each having one or more physical properties that can be selected or configured to modulate the reactivity of carbon with contaminants (such as polysulfides) present in the electrolyte 540 and / or anode 502. In some aspects, selectable physical properties may include (but are not limited to) porosity, surface area, surface functionalization, or electrical conductivity. Additionally, the hierarchical layer 514 may include a binder or other additives that can be used to modulate one or more physical properties of the carbonaceous material to achieve the desired reactivity of the carbon supplied by the carbonaceous material with the polysulfides present in the electrolyte 540 and / or anode 502.

[0192] In one implementation, the carbonaceous material within the hierarchical layer 514 can trap undesirable contaminants and thereby prevent them from chemically reacting with available lithium at the exposed surface of the anode 502. Alternatively, undesirable contaminants (e.g., polysulfides) can chemically react with various exposed surfaces of the carbonaceous material within the hierarchical layer 514 (e.g., through carbon-lithium interactions). In some implementations, the carbonaceous material within the hierarchical layer 514 can be bonded to available lithium. The carbonaceous material reacts with lithium cations (Li... + The degree of adhesion between the layers can be selected or altered via a chemical reaction induced during the preparation of the hierarchical layer 514.

[0193] In some implementations, various carbon allotropes may be incorporated within the hierarchical layer 514 (such as in one or more portions of the tin-lithium alloy region 512 and / or the tin fluoride layer 510). These carbon allotropes may be functionalized with one or more reactants and used to form a sealant layer and / or region at the interface between the carbon nanodiamonds within the hierarchical layer 514 and the electrolyte 540. In some aspects, the carbon nanodiamonds may increase the mechanical robustness of the anode 502 and / or the hierarchical layer 514. In other aspects, the carbon nanodiamonds may also provide exposed carbonaceous surfaces, which can be used to reduce polysulfide shuttle effects by microscopically defining and / or bonding polysulfides present in the electrolyte 540 to polysulfides in a defined region outside the anode 502 of the battery.

[0194] Alternatively, in other implementations, the carbon nanodiamonds within the hierarchical layer 514 can be replaced with those having specific L... A Size (e.g., sp) 2 The carbon and / or carbonaceous materials on the surface and / or in the region of the hybrid carbon, reduced graphene oxide (rGO), and / or graphene. In some aspects, the use of the carbonaceous materials disclosed herein within the battery can increase carbon stacking and layer formation within the hierarchical layer 514. Exfoliated and oxidized carbonaceous materials can also produce a more uniform layered structure within the hierarchical layer 514 (compared to unexfoliated and oxidized carbonaceous materials). In some aspects, solvent treatments such as tetrabutylammonium hydroxide (TBA) and / or dimethylformamide (DMF) can be applied to the carbonaceous materials disclosed herein to increase the wetting of exposed carbonaceous surfaces within the hierarchical layer 514.

[0195] In some implementations, the paste used to form the hierarchical layer 514 may be doped to improve or otherwise affect the crystal structure of the carbonaceous material within the hierarchical layer 514. For example, adding certain dopants may affect the crystal structure of the carbonaceous material in a corresponding manner, and functional groups may be added within the hierarchical layer 514 (e.g., via grafting onto exposed carbon atoms within the carbonaceous material).

[0196] In some implementations, a carbonaceous material having an exposed surface functionalized with one or more fluorine- or silicon-containing functional groups may be included within the hierarchical layer 514. In other implementations, the carbonaceous material having an exposed surface functionalized with one or more fluorine- or silicon-containing functional groups may be deposited beneath the hierarchical layer 514 to form a stable SEI at the interface between the hierarchical layer 514 and the anode 502. In one implementation, the stable SEI may replace the protective layer 516. In some implementations, the hierarchical layer 514 may be slurry-cast and / or deposited onto the anode 502 having a lithium and carbon interfacial phase, either of which may be functionalized with silicon and / or nitrogen to inhibit polysulfide diffusion and migration to the exposed surface of the anode 502. Additionally, specific polymers and / or crosslinking agents may be incorporated into the hierarchical layer 514 to mechanically strengthen the hierarchical layer 514, improve lithium-ion transport across the hierarchical layer 514, or increase the uniformity of lithium-ion flux across the hierarchical layer 514. Exemplary polymers and / or polymeric materials suitable for incorporation into the hierarchical layer 514 may include poly(ethylene oxide) and poly(ethyleneimine). Exemplary crosslinking agents suitable for incorporation into the hierarchical layer 514 may include inorganic crosslinking agents (e.g., borates, aluminates, silicates), multifunctional organic molecules (e.g., diamines, glycols), polyurea, or high molecular weight (MW) (e.g., >10,000 Daltons) carboxymethyl cellulose (CMC).

[0197] Various manufacturing methods can be used to produce the graded layer 514. In one implementation, direct coating of the interface between the anode 502 and the electrolyte 540 prior to deposition and / or formation of the graded layer 514 can be performed by dispersing carbonaceous materials and other chemicals dissolved in a carrier (e.g., solvent, binder, polymer). In another implementation, deposition of the graded layer 514 can be performed as a standalone operation, or various other active ingredients (e.g., metals, carbonaceous materials, tin fluoride, etc.) can be added to a slurry that can be cast onto the anode 502. Alternatively, in another implementation, the protective layer 516 can be directly transferred onto the anode 502 via a calendering roll lamination process. The protective layer 516 and / or the graded layer 514 may also incorporate a partially cured lithium-ion conductive epoxy resin to better increase adhesion to lithium, for example, during the calendering roll lamination process.

[0198] In one implementation, a carbon-containing layered structure ( Figure 5 (Not shown) may be disposed on anode 502 to replace hierarchical layer 514. The carbon-containing hierarchical structure may include atomic planes available for lithium transfer and may guide the formation of lithium fluoride in various parts of the battery, transferring lithium cations (Li₂O₃) provided by electrolyte 540. +The carbon-containing layered structure may be uniformly transported throughout the protective layer 516. In various implementations, the carbon-containing layered structure may include one or more arrangements of few-layer graphene (FLG) or graphite and / or may be intercalated with lithium, and produce one or more reaction products, including lithium tin oxide (LTO), lithium iron phosphate (LFP), or lithium lanthanum titanate perovskite (LLTO).

[0199] In some implementations, the tin fluoride layer 510 may act as a protective layer against corrosion, including corrosion of the copper-containing surface and / or areas of the protective layer 516, the hierarchical layer 514, or the anode 502. In some aspects, the tin fluoride layer 510 may also provide a uniform seed layer suitable for lithium deposition, thereby inhibiting dendrite formation. Additionally, in some implementations, the tin fluoride layer 510 may include one or more lithium-ion intercalation compounds, any one or more of which have a low voltage penalty. Suitable lithium-ion intercalation compounds may include graphitic carbon (e.g., graphite, graphene, reduced graphene oxide rGO). In one implementation, during the fabrication of the anode 502, before being plated onto the exposed carbonaceous surface within the tin fluoride layer 510, lithium cations (Li... + The tin fluoride layer 510 can be embedded. In this way, before the lithium plating and / or electroplating operation begins, the tin fluoride layer 510 has a uniform Li distribution ready to serve as a seed layer.

[0200] In one implementation, one or more conformal coatings may be applied to portions of the anode 502 such that the resulting conformal coatings contact and conform to a first edge 5181 and / or a second edge 5182 of the anode 502. In some aspects, the conformal coatings may begin as a first spacer edge protection region 5301 and a second spacer edge protection region 5302, which react with or otherwise combine with one or more of a protective layer 516, a tin-lithium alloy region 512, and / or a tin fluoride layer 510 to form a conformal coating 544 that at least partially seals and protects the surfaces and / or interfaces between lithium in the anode 502 and various substances (e.g., copper (Cu)) suspended in the electrolyte. In some aspects, the dissociation of fluorine atoms from tin fluoride present in the conformal coating 544 may react with lithium in the anode 502 to form lithium fluoride, rather than to form or grow lithium dendrites. In this manner, the conformal coating 544 may reduce the formation or growth of lithium dendrites from the anode 502.

[0201] The conformal coating 544 can be deposited or disposed on the anode 502 in many different thicknesses. In some aspects, the conformal coating 544 can be less than 5 μm thick. In others, the conformal coating 544 can be less than 2 μm thick. In still others, the conformal coating 544 can be less than 1 μm thick. During battery cycling, these thickness levels can hinder the migration of polysulfides to the anode 502, thereby preventing at least some lithium cations (Li) from being deposited or disposed on the anode 502. +Lithium cations (Li) react with polysulfides. Lithium cations (Li) do not react with polysulfides. + It can be used to transfer from the anode to the cathode during battery discharge cycles.

[0202] The conformal coating 544 (along with the protective layer 516 and the hierarchical layer 514) uniquely modulates the lithium-ion flux toward the first edge 5181 and / or the second edge 5182 of the anode 502, thereby preventing corrosion of the anode 502. This modulation can function in a similar manner to the gate spacers used during the fabrication of polysilicon (poly-Si) gates. Specifically, during the fabrication of integrated circuits (ICs), gate spacers or gate sidewall structures are used to protect and mechanically support polysilicon gates. Similarly, the conformal coating 544 provides... Figure 5 The edge protection provided by the anode 502 regulates the lithium-ion flux toward the first edge 5181 and / or the second edge 5182 of the anode 502, and thereby prevents corrosion of the anode 502. This type of edge protection provided to the anode 502 by the conformal coating 544 is equally applicable to other battery and / or electrochemical cell formats and / or configurations, such as (but not limited to) cylindrical cells, stacked cells, etc., where various constructs are specifically engineered to suit the parameters of each in such designs.

[0203] In some implementations, the fabrication and / or deposition of the conformal coating 544, protective layer 516, and / or hierarchical layer 514 on the anode 502 may depend on the type of battery or cell assembly incorporating the anode 502, for example, a cylindrical cell compared to a pouch cell and / or a prismatic cell. In one implementation, for a cylindrical cell, the metal anode may be composed of an electroactive material, typically lithium metal and / or lithium-containing alloys, such as graphite and / or other carbonaceous composites including lithium, and any fully homogeneous or multilayered material sheet. In one example, a solid lithium metal foil serving as the anode 502 may be attached to a copper substrate serving as a current collector 520 to facilitate electron transfer via the tab 546 to an external load, such as... Figure 5 As depicted in the example. In other implementations, the anode structure 500 may include an anode 502 in the absence of a current collector 520, wherein the carbonaceous material contained within the anode 502 may provide a conductive medium for coupling with the circuit.

[0204] In some implementations, the anode structure 500 can be incorporated into the electrochemical cell and / or battery by winding around a mandrel. Cylindrical cell layouts typically use bifacial anodes, such as the anode structure 500. In some implementations, the cylindrical cell construction employing the anode structure 500 can use a conformal coating 544 to protect the first edge 5181 and / or the second edge 5182 of the anode 502. The uniform protection provided by the conformal coating 544 may be referred to herein as “edge protection.” In one implementation, edge protection can be incorporated into the cell using the anode structure 500 by extending the size and / or area of ​​the protective layer 516 to superimpose any geometrically induced edge effects (e.g., surface roughness) of the anode.

[0205] In other implementations, the anode structure 500 can be incorporated into pouch cells and / or prismatic cells. Generally, two constructions can be used to manufacture pouch cells and / or prismatic cells, including (1) a wound-core cell (e.g., present in the industry as a lithium-polymer battery), where two mandrel-wound electrodes can be produced in a manner similar to that of cylindrical cells as previously discussed; and (2) a stacked-plate cell, which can be cut from a pre-cast and / or pre-laminated anode sheet, such that the unprotected edges of, for example, the anode 502 (when prepared in a stacked-plate configuration) are exposed and susceptible to corrosion, rapid ion flux, and exposure within the cell. In the stacked-plate configuration, a conformal coating 544 protects the anode 502 and prevents oversaturation of lithium in the electrolyte 540. In this way, the conformal coating 544 controls lithium plating on the anode 502 during battery operation cycles.

[0206] In some implementations, during cell assembly or cell rest periods, one or more chemical reactions (involving solvent decomposition and / or addition reactions) may occur between the electrolyte 540 and the anode 502. These chemical reactions may contribute to the formation of the conformal coating 544. In some aspects, higher and / or lower temperatures (e.g., relative to room temperature and / or 20°C) may be used as a stimulus for lithium-induced polymerization of the conformal coating 544. For example, lithium-induced polymerization may occur in the presence of one or more catalysts and / or by using lithium metal and its associated chemical reactivity as an initiator to initiate radical-based polymerization of component materials within any one or more layers of the anode structure 500 and / or the conformal coating 544. Additionally, electrochemical reactions under forward or reverse electrical bias may be used to fabricate and / or deposit the conformal coating 544 on the anode 502, using auxiliary metals and / or salts as additives that can decompose to form alloys on the first edge 5181 and / or the second edge 5182 of metallic lithium in the anode 502 exposed to the electrolyte 540. For example, suitable additives may contain one or more metallic substances, such as those required for co-alloying with lithium or intended to be used as barrier layers to reduce lithium transfer to the first edge 5181 and / or the second edge 5182 of the anode 502.

[0207] Figure 6 This shows the implementation methods. Figure 5 A schematic diagram of a magnified portion 600 of the anode structure 500. The magnified portion 600 shows a first spacer edge protection region 5301 and a second spacer edge protection region 5302. Figure 6 The arrangement of the edge protection area (referred to as edge protection area 530) in a direction orthogonal to the first edge 5181 and / or the second edge 5182, such as Figure 5 As shown. Therefore, the edge protection region 530 of the carbonaceous material 610, which may be organized into a structure and / or lattice, can prevent lithium cations (Li... + Undesirably, lithium ions escape from the anode 502 across the edge protection region 530. In this way, lithium ion dissociation, flux, transport, and / or other movement can occur. Figure 6 The entire amplification portion 600 (and Figure 5 The anode structure 500 is effectively guided, thereby producing optimal battery operating cycles. In some implementations, the carbonaceous material 610 used to generate the edge protection region may include few-layer graphene (FLG), multilayer graphene (MLG), graphite, carbon nanotubes (CNTs), carbon nanotubes (CNO), etc. The carbonaceous material 610 (e.g., Figure 8A , Figure 8B , Figure 9A , Figure 9B , Figure 10A and / or Figure 10B(As shown in the diagram) can be synthesized at different concentration levels, self-nucleated, or otherwise bonded together to provide full tunability of the edge protection region 530. For example, the density, thickness, and / or composition can be designed to minimize lithium-ion permeation compared to the protective layer 516 or the hierarchical layer 514, thereby guiding lithium-ion permeation accordingly. In some implementations, the edge protection region 530 may be less than 5 μm thick. In others, the edge protection region 530 may be less than 2 μm thick. In still others, the edge protection region 530 may be less than 1 μm thick. In some implementations, conductive additive 640, like binder 620, may be added to carbonaceous material 610.

[0208] Figure 7 A diagram illustrating a polymer network 710 according to some implementations is shown. In some aspects, the polymer network 710 may be... Figure 2 An example of polymer network 285. Polymer network 710 may be disposed on anode 702. Anode 702 may be formed as an alkali metal layer having one or more exposed surfaces comprising a plurality of nanostructures or microstructures containing alkali metals. Alkali metals may include (but are not limited to) lithium, sodium, zinc, indium, and / or gallium. During battery operation cycles, anode 702 may release alkali metal cations.

[0209] A carbonaceous material layer 714 may be grafted with a fluorinated polymer and deposited on one or more exposed surfaces of the anode 702. Grafting may be based on (e.g., starting with) activating the carbonaceous material with one or more free radical initiators, such as benzoyl peroxide (BPO) or azobisisobutyronitrile (AIBN), followed by a reaction with monomer molecules. A polymer network 710 may be based on cross-linked fluorinated polymer chains and the carbonaceous material of layer 714, such that layer 714 is consumed during the generation of the polymer network 710. In some implementations, the polymer network 710 may have a thickness between about 0.001 μm and 5 μm and comprise between about 0.001 wt% and 2 wt% of fluorinated polymer chains. In some other implementations, the polymer network 710 may comprise between about 5 wt% and 100 wt% of a variety of carbonaceous material grafted with fluorinated polymers, with the remainder being fluorinated polymers or one or more non-fluorinated polymers or one or more cross-linkable monomers or combinations thereof. In one implementation, the carbonaceous material linked by the fluorinated polymer may comprise 5% to 50% by weight of the fluorinated polymer chain and the remainder is carbonaceous material.

[0210] During battery cycling, the carbon-fluorine bonds within the polymer network 710 can chemically react with newly formed lithium metal and transform into carbon-lithium bonds (C-Li). These C-Li bonds can then react with the carbon-fluorine bonds within the polymer network 710 via a Woods reaction 750 to further crosslink the polymer network through newly formed C-Li bonds and form alkali metal-containing fluorides (such as lithium fluoride (LiF)). The additional polymer network crosslinking resulting in the uniform formation of alkali metal-containing fluorides can thereby suppress the formation of alkali metal dendrites 740 associated with the anode 702, thereby improving battery performance and lifespan. In one implementation, grafting fluorinated methyl acrylate (FMA) onto one or more exposed graphene surfaces of the carbonaceous material in layer 714 can be performed in an organic solution, for example, resulting in the formation of graphene-grafted-poly-FMA, etc. Incorporating carbon-fluorine bonds into the exposed graphene surfaces allows the Woods reaction 750 to occur between the carbon-fluorine bonds and the metal surface of the alkali metal (e.g., lithium) provided by the anode 702. In this manner, completing the Woods reaction 750 can lead to the formation of a polymer network 710. In some aspects, the polymer network 710 may include a density gradient 716 following the completion of the Woods reaction 750. The density gradient 716 may include interconnected graphene sheets and may be infused with one or more in-situ formed metal fluoride salts. Furthermore, the layer porosity and / or mechanical properties may be tuned by a combination of carbon-loaded and / or functionalized carbons, each having a unique and / or different physical structure.

[0211] In some implementations, the carbonaceous material within the density gradient 716 may include one or more of flat graphene, wrinkled graphene, multiple carbon nanotubes (CNTs), or multiple carbon nanotubes (CNOs) (e.g., as shown in the image). Figure 8A and / Figure 8B Describing and as Figures 9A-9B and Figures 10A-10B (A micrograph is shown). In one implementation, graphene nanosheets are dispersed throughout the polymer network 710 and isolated from each other. The dispersion of the graphene nanosheets includes one or more different concentration levels. In one implementation, the dispersion of the graphene nanosheets may include at least some carbonaceous material functionalized with at least some fluorinated polymer chains.

[0212] For example, the fluorinated polymer chain may include one or more acrylate or methacrylate monomers, including 2,2,3,3,4,4,5,5,6,6,7,7-dodecylfluoroheptyl acrylate (DFHA), 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptafluorodecyl methacrylate (HDFDMA), 2,2,3,3,4,4,5,5-octafluoropentyl methacrylate (OFPMA), tetrafluoropropyl methacrylate (TFPM), 3-[3,3,3-trifluoro-2-hydroxy-2-(trifluoromethyl)propyl]bicyclo[2.2.1]hept-2-yl methacrylate (HFA monomer) or vinyl-based monomers (including 2,3,4,5,6-pentafluorostyrene (PFSt)).

[0213] In some implementations, fluorinated polymer chains can be grafted onto the surface of a carbonaceous material layer and thereby chemically interact with one or more surfaces of the alkali metal of the anode via the Woods reaction 750. In organic chemistry, organometallic chemistry, and inorganic main group polymers, the Woods reaction is a coupling reaction in which two alkyl halides react with metallic sodium (or some other metal) in a dry ether solution to form higher alkanes. In this reaction, the alkyl halides are treated with an alkali metal (e.g., metallic sodium) in a dry ether (water-free) solution to produce higher alkanes. In the case of sodium, the intermediate of the Woods reaction is a highly polar and highly reactive carbon-sodium metallic bond, which then reacts chemically with the carbon-halogen bond to produce newly formed C-C bonds and sodium halides. The formation of new carbon-carbon bonds allows the use of the Woods reaction to prepare higher alkanes containing an even number of carbon atoms, for example:

[0214] 2R-X + 2Na → R-R + 2Na + X - (Equation 1)

[0215] Other metals are also used to influence Woods coupling, particularly silver, zinc, iron, activated copper, indium, and mixtures of manganese chloride and copper chloride. The related reaction for treating aryl halides is called the Wurtz–Fittig reaction. This can be explained by the formation of a radical intermediate and its subsequent disproportionation to yield an alkene. The Wurtz reaction 750 occurs via a radical mechanism that makes the side reaction leading to the alkene product possible. In some implementations, the chemical interactions associated with the Wurtz reaction as described above can form alkali metal fluorides, such as lithium fluoride.

[0216] In one implementation, the polymer network 710 may include an interface layer 718 in contact with the anode 702. A protective layer 720 may be disposed on top of the interface layer 718, which may be based on a Woods reaction 750 at the interface between the anode 702 and the polymer network 710. The interface layer 718 may have a relatively high crosslink density (e.g., fluorinated polymers, etc.), a high metal-fluoride concentration, and a relatively low carbon-fluorine bond concentration. Compared to the interface layer 718, the protective layer 720 may have a relatively low crosslink density, a low metal-fluoride concentration, and a high carbon-fluorine bond concentration.

[0217] In some implementations, the interface layer 718 may comprise crosslinkable monomers, such as methacrylate (MA), acrylate, vinyl functional groups, or combinations of epoxy and amine functional groups. In one implementation, the protective layer 720 may be characterized by a density gradient 716. In this manner, the density gradient 716 may be associated with one or more self-healing properties of the protective layer 720 and / or may reinforce the polymer network 710. In some implementations, the protective layer 720 may further suppress the formation 740 of alkali metal dendrites from the anode 702 during battery cycling.

[0218] Operationally, the interface layer 718 can suppress the formation of alkali metal dendrites 740 associated with the anode 702 by uniformly generating a metal fluoride (e.g., lithium fluoride) at the interface across the length of the anode 702. Uniform generation of the metal fluoride, for example via conversion to a metal fluoride, leads to the dissolution of the dendrite surface, ultimately suppressing the formation of alkali metal dendrites 740. Additionally, crosslinking of the fluorinated polymer chains on the remaining dendrites can further suppress the formation of alkali metal dendrites 740. In some implementations, the density gradient 716 can be tuned to control the degree of crosslinking between the fluorinated polymer chains.

[0219] Figure 8A A simplified cross-sectional view is shown of an exemplary carbonaceous particle 800 with hierarchical porosity according to some implementations. The carbonaceous particle 800 can be synthesized in a reactor and output in a controlled manner to produce Figure 1 Cathode 110 and / or anode 120, Figure 2 Cathode 210 and / or anode 220 or Figure 3The electrode 300. The carbonaceous particles 800, also referred to as the subject composition, include a plurality of nested regions. Each region may include at least a first porosity region 811 and a second porosity region 812. The first porosity region 811 may include a plurality of first pores 801, and the second porosity region 812 may include a plurality of second pores 802. In some aspects, each region may be separated from directly adjacent regions by at least some first pores 801. The first pores 801 may be dispersed throughout the first porosity region 811 of the carbonaceous particles 800, and the second pores 802 may be dispersed throughout the second porosity region 812 of the carbonaceous particles 800. In this way, the first pores 801 may be associated with a first pore density, and the second pores 802 may be associated with a second pore density different from the first pore density. In some aspects, the first pore density may be between approximately 0.0 cc / g and 2.0 cc / g, and the second pore density may be between approximately 1.5 and 5.0 cc / g. In some aspects, the first pore 801 may be configured to retain polysulfides 820, and the second pore 802 may provide an exit channel from the carbonaceous particles 800.

[0220] A group of carbonaceous particles 800 may aggregate together to form a carbonaceous aggregate (not shown for simplicity), and a group of carbonaceous aggregates may aggregate together to form a carbonaceous agglomerate (not shown for simplicity). In some implementations, first pores 801 and second pores 802 may be dispersed throughout the aggregate formed by the respective group of carbonaceous particles 800. In some aspects, a first porosity region 811 may be at least partially encapsulated by a second porosity region 812, such that the respective agglomerate may include some of the first pores 801 and / or some of the second pores 802.

[0221] In some implementations, the carbonaceous particles 800 may have a principal size "A" in the approximate range of 20 nm to 150 nm, the aggregates formed by a group of carbonaceous particles 800 may have a principal size in the approximate range of 20 nm to 10 μm, and the agglomerates formed by a group of aggregates may have a principal size in the approximate range of 0.1 μm to 1,000 μm. In some aspects, at least some of the first pores 801 and second pores 802 have a principal size in the approximate range of 1.3 nm to 32.3 nm. In one implementation, each first pore 801 has a principal size in the approximate range of 0 nm to 100 nm.

[0222] The carbonaceous particles 800 may also include a plurality of deformable regions 813 distributed along a periphery 810 of the carbonaceous particles 800. The carbonaceous particles 800 may conduct electricity along a junction boundary (such as the periphery 810) having one or more other carbonaceous particles. The carbonaceous particles 800 may also define polysulfides 820 within the first pore 801 and / or at one or more barrier regions 822, thereby inhibiting the migration of polysulfides 820 to the anode and increasing lithium cations (Li). + The rate at which the anode of the autonomous battery is transported to the cathode.

[0223] In some implementations, carbonaceous particles 800 can have a size of 10m. 2 / g to 3,000m 2 The surface area of ​​exposed carbon surfaces is within an approximate range of / g. In other implementations, the carbonaceous particles 800 may have a composite surface area, including sulfur 824 microscopically defined within a plurality of first pores 801 and / or a plurality of second pores 802. As used herein, the first pores 801 and / or second pores 802 microscopically defining the polysulfide 820 may be referred to as “functional pores.” In some aspects, one or more of the carbonaceous particles, aggregates formed from carbonaceous particles of the corresponding group, or agglomerates formed from aggregates of the corresponding group may include one or more exposed carbon surfaces configured to nucleate sulfur 824. The composite surface area may be approximately 10 m². 2 / g to 3,000m 2 The sulfur to carbon weight ratio can be between 1:5 and 10:1. In some respects, the carbonaceous particles 800 can have a conductivity in the approximate range of 100 S / m to 20,000 S / m at a pressure of 12,000 psi.

[0224] In some implementations, the carbonaceous particles 800 may include surfactants or polymers, including one or more of styrene-butadiene rubber, polyvinylidene fluoride, polyacrylic acid, carboxymethyl cellulose, polyvinylpyrrolidone, and / or polyvinyl acetate, which may act as an adhesive to bond a group of carbonaceous particles 800 together. In other implementations, the carbonaceous particles 800 may include a gel-phase electrolyte or a solid-phase electrolyte disposed within at least some of the first pores 801 or second pores 802.

[0225] Figure 8B The diagram illustrates examples of three-segment particles 850 according to some implementations. In various implementations, the three-segment particle 850 may be... Figure 8AAn example of carbonaceous particles 800. Three-segment particles 850 may include three discrete segments, such as (but not limited to) a first segment 851, a second segment 852, and a third segment 853. In some aspects, each of segments 851–853 surrounds and / or encapsulates the preceding segment. For example, the first segment 851 may be surrounded or encapsulated by the second segment 852, and the second segment 852 may be surrounded or encapsulated by the third segment 853. The first segment 851 may correspond to an inner region of the three-segment particle 850, the second segment 852 may correspond to an intermediate transition region of the three-segment particle 850, and the third segment 853 may correspond to an outer region of the three-segment particle 850. In some aspects, the three-segment particle 850 may include a permeable shell 855 that deforms in response to contact with one or more adjacent non-three-segment particles and / or three-segment particles 850.

[0226] In some implementations, the first segment 851 may have relatively low density, relatively low electrical conductivity, and relatively high porosity; the second segment 852 may have medium density, medium electrical conductivity, and medium porosity; and the third segment 853 may have relatively high density, relatively high electrical conductivity, and relatively low porosity. In some aspects, the first segment 851 may have a carbonaceous material density between approximately 1.5 g / cc and 5.0 g / cc; the second segment 852 may have a carbonaceous material density between approximately 0.5 g / cc and 3.0 g / cc; and the third segment 853 may have a carbonaceous material density between approximately 0.0 and 1.5 g / cc. In other aspects, the first segment 851 may include pores with a width between approximately 0 and 40 nm; the second segment 852 may include pores with a width between approximately 0 and 35 nm; and the third segment 853 may include pores with a width between approximately 0 and 30 nm. In some other implementations, the second segment 852 may not be defined for the three-segment particle 850. In one implementation, the first segment 851 may have a major size D1 between approximately 0 nm and 100 nm, the second segment 852 may have a major size D2 between approximately 20 nm and 150 nm, and the third segment 853 may have a major size D3 of approximately 200 nm.

[0227] All aspects of this disclosure recognize that the unique layout of the three-segment particle 850 and the relative sizes, porosity, and conductivity of the first segment 851, the second segment 852, and the third segment 853 can be selected and / or modified to achieve a desired balance between minimizing the polysulfide shuttle effect and maximizing the specific capacity of the main cell. Specifically, in some aspects, the pore size and volume can be reduced between one segment and another. In some implementations, the three-segment particle may consist entirely of a single segment having a range of pore sizes and pore distributions (e.g., pore density). Figure 8BFor example, pores 861 associated with the first segment 851 or the first porosity region have a relatively large width and can be defined as macropores, pores 862 associated with the second segment 852 or the second porosity region have a medium width and can be defined as mesopores, and pores 863 associated with the third segment 853 or the third porosity region have a relatively small width and can be defined as micropores.

[0228] A group of three-segment particles 850 may aggregate to form an aggregate (not shown for simplicity), and a group of aggregates may aggregate to form a flocculent (not shown for simplicity). In some implementations, a plurality of mesopores may be dispersed throughout the aggregate formed by the respective groups of carbonaceous particles 800. In some aspects, a first porosity region 811 may be at least partially encapsulated by a second porosity region 812, such that the respective aggregate may include one or more mesopores and one or more macropores. In one implementation, each mesopore may have a principal size between 3.3 nanometers (nm) and 19.3 nm, and each macropore may have a principal size between 0.1 μm and 1,000 μm. In some cases, the three-segment particles 850 may include carbon fragments interwoven with each other and spaced apart from each other by at least some mesopores.

[0229] In some implementations, the three-segment particles 850 may include surfactants or polymers, including one or more of styrene-butadiene rubber, polyvinylidene fluoride, polyacrylic acid, carboxymethyl cellulose, polyvinylpyrrolidone, and / or polyvinyl acetate, which may act as an adhesive to bond a group of carbonaceous materials together. In other implementations, the three-segment particles 850 may include a gel-phase electrolyte or a solid-phase electrolyte disposed within at least some of the pores.

[0230] In some implementations, the three-segment particle 850 can have a size of 10m. 2 / g to 3,000m 2 The surface area of ​​exposed carbonaceous surfaces and / or 10m² within an approximate range between / g. 2 / g to 3,000m 2 The composite surface area (including sulfur microscopically confined within the pores) is in the approximate range between / g. In one implementation, the subject composition comprising a plurality of three-segment particles 850 may have an electrical conductivity in the approximate range between 100 S / m and 20,000 S / m at a pressure of 12,000 psi and a sulfur to carbon weight ratio of approximately 1:5 to 10:1.

[0231] Figure 8C The diagram shows representations based on some implementation methods. Figure 8BAn exemplary step function 800C of the average pore volume in each region of the three-segment particle 850. As discussed, pores distributed throughout the three-segment particle 850 may have different sizes, volumes, or distributions. In some implementations, the average pore volume may be reduced based on the distance between the center of the three-segment particle 850 and adjacent segments, for example, such that pores associated with the first segment 851 or the first porosity region have relatively large volumes or pore sizes, pores associated with the second segment 852 or the second porosity region have medium volumes, and pores associated with the third segment 853 or the third porosity region have relatively small volumes. The inner regions have higher pore volumes compared to the regions near the periphery. Regions with higher pore volumes provide higher sulfur loading, while the outer regions with lower pore volumes mitigate polysulfide migration during cell cycling. Figure 8C In the example, the average pore volume in the inner region is approximately 3 cc / g, the average pore volume in the outermost region is -0.5 cc / g, and the average pore volume in the middle region is between 0.5 cc / g and 3 cc / g.

[0232] Figure 8D A graph 800D illustrates an exemplary distribution depicting the relationship between pore volume and pore width of the carbonaceous particles described herein. As depicted in Figure 800D, pores associated with relatively high pore volumes may have relatively low pore widths, for example, such that the pore width generally increases as the pore volume decreases. In some aspects, pores having a pore width of less than about 1.0 nm can be referred to as micropores, pores having a pore width between about 3 and 11 nm can be referred to as mesopores, and pores having a pore width greater than about 24 nm can be referred to as macropores.

[0233] Figure 9A Micrographs 900 are shown of multiple carbonaceous structures 902 according to some implementations. In some implementations, each of the carbonaceous structures 902 may have a substantially hollow core region surrounded by various integral carbon growths and / or layerings. In some aspects, integral carbon growths and / or layerings may be referenced. Figure 8A and Figure 8B Examples of overall carbon growth and / or layering are described. In some cases, the carbonaceous structure 902 may comprise multiple concentric multilayer fullerenes organized at different density and / or concentration levels and / or similarly shaped carbonaceous structures. For example, the actual final shape, size, and graphene configuration of each in the carbonaceous structure 902 may depend on various manufacturing methods. In some aspects, the carbonaceous structure 902 may exhibit poor water solubility. Therefore, in some implementations, nonvalent functionalization may be used to modify one or more dispersibility properties of the carbonaceous structure 902 without affecting the intrinsic properties of the underlying carbon nanomaterial. In some aspects, the underlying carbon nanomaterial may be a constitutive sp 2Carbon nanomaterials. In some implementations, each of the carbonaceous structures 902 may have a diameter between approximately 20 and 500 nm. In various implementations, the groups of carbonaceous structures 902 may aggregate and / or bond together to form aggregates 904. Additionally, the groups of aggregates 904 may aggregate and / or bond together to form agglomerates 906. In some aspects, one or more of the carbonaceous structures 902, aggregates 904, and / or agglomerates 906 may be used to form... Figure 1 100 batteries Figure 2 200 or Figure 3 The anode and / or cathode of electrode 300.

[0234] Figure 9B A micrograph 950 is shown of an aggregate 960 formed from carbonaceous material according to some implementations. In some implementations, the aggregate 960 may be... Figure 9A An example of one of the aggregates 904. In one implementation, the outer carbonaceous shell structure 952 may be fused with carbon provided by other carbonaceous shell structures 954 to form a carbonaceous structure 956. A group of carbonaceous structures 956 may aggregate and / or join with each other to form an aggregate 1010. In some aspects, the core region 958 of each of the carbonaceous structures 956 may be tunable, for example, because the core region 958 may include various interconnected graphene structures defining concentration levels, as referenced Figure 8A and / or Figure 8B As described. In some implementations, some carbonaceous structures 956 may have a first concentration of interconnected carbon between approximately 0.1 g / cc and 2.3 g / cc at or near the outer carbonaceous shell structure 952. Each of the carbonaceous structures 956 may have an inwardly extending lithium cation (Li... + Transmitted to the pores of core region 1008.

[0235] In some implementations, the pores in each of the carbonaceous structures 956 may have a width or dimension between approximately 0.0 nm and 0.5 nm, between approximately 0.0 nm and 0.1 nm, between approximately 0.0 nm and 6.0 nm, or between approximately 0.0 nm and 35 nm. Each carbonaceous structure 956 may also have a second concentration different from the first concentration at or near the core region 958. For example, the second concentration may comprise a plurality of concentrically arranged, relatively low-density carbonaceous regions. In one implementation, the second concentration may be lower than the first concentration, between approximately 0.0 g / cc and 1.0 g / cc, or between approximately 1.0 g / cc and 1.5 g / cc. In some aspects, the relationship between the first and second concentrations can be used to confine sulfur or polysulfides within the respective electrode and to enable lithium cations (Li... +A balance must be struck between maximizing the transport of sulfur and / or polysulfides. For example, during the operating cycle of a lithium-sulfur battery, sulfur and / or polysulfides can travel through a first concentration and are at least temporarily confined to and / or dispersed throughout a second concentration.

[0236] In some implementations, at least some of the carbonaceous structures 956 may include CNO oxides grown integrally and / or interconnectedly and generated in a thermal reactor. For example, the carbonaceous structure 956 may be decorated with cobalt nanoparticles according to the following example formulation: cobalt(II) acetate (C4H6CoO4), a cobalt salt of acetate (typically present as tetrahydrate Co(CH3CO2)2·4H2O, which may be abbreviated as Co(Oac)2·4H2O), which may flow into the thermal reactor at a ratio of approximately 59.60 wt% corresponding to 40.40 wt% carbon (referring to carbon in the form of CNO), resulting in the cobalt functionalization of active sites on the CNO oxides, correspondingly showing cobalt-decorated CNO at a 15,000x level. In some implementations, a suitable gas mixture for generating carbon #29 and / or cobalt-decorated CNO may include the following steps:

[0237] ●Ar purging at 0.75 standard cubic feet per minute (scfm) for 30 minutes;

[0238] ● Change the Ar purge to 0.25 scfm for operation;

[0239] ●Temperature increase: 25℃ to 300℃ for 20 minutes; and

[0240] ●Temperature increase: 300°–500°C for 15 minutes.

[0241] refer to Figure 9A and Figure 9B The described carbonaceous materials may include one or more examples of graphene or otherwise formed therefrom, which may comprise a monolayer of carbon atoms, wherein each atom is bonded to three adjacent atoms in a honeycomb structure. The monolayer may be a loosely oriented material limited to one dimension, such as within a condensed phase or at a surface. For example, graphene may grow outward only in the x and y planes (but not in the z plane). In this way, graphene may be a two-dimensional (2D) material comprising one or more layers, wherein atoms in each layer are strongly bonded to (e.g., through multiple carbon-carbon bonds) adjacent atoms within the same layer.

[0242] In some implementations, graphene nanosheets (e.g., constitutive structures included in each carbonaceous structure 956) may comprise multiple examples of graphene, such as a first graphene layer, a second graphene layer, and a third graphene layer, all stacked together vertically. Each of the graphene nanosheets, which may be referred to as GNPs, may have a thickness between 1 nm and 3 nm and may have lateral dimensions in the range of approximately 100 nm to 100 μm. In some implementations, graphene nanosheets may be produced using multiple sequentially arranged plasma spray guns via roll-to-roll (R2R) production. In some aspects, R2R production may include deposition on a continuous substrate processed into rolled sheets, including transferring 2D material to individual substrates. In some cases, R2R production may be used to form Figure 3 The first thin film 310 and / or the second thin film 320 of the electrode 300 are configured such that the concentration level of the first aggregate 312 in the first thin film 310 is different from the concentration level of the second aggregate 322 in the second thin film 320. That is, the plasma spraying gun used in the R2R process can spray carbonaceous material at different concentration levels to produce the first thin film 310 and / or the second thin film 320 using graphene nanosheets at specific concentration levels. Therefore, the R2R process can be used for... Figure 1 100 and / or Figure 2 The 200 battery offers a fine level of tunability.

[0243] Figure 10A and Figure 10B The images shown are transmission electron microscope (TEM) images 1000 and 1050 of carbonaceous particles treated with carbon dioxide (CO2) according to some implementations. Figure 10A and Figure 10B The carbonaceous particles shown may include one or more examples of graphene or otherwise formed therefrom, which may include a monolayer of carbon atoms, wherein each atom is bonded to three adjacent atoms in a honeycomb structure.

[0244] Figure 11 A diagram 1100 is shown depicting the carbon porosity types of various carbonaceous aggregates according to several implementations. In each implementation, reference is made to... Figure 11 The carbonaceous aggregates described can be Figure 9A Aggregates 904 and / or Figure 9B An example of the carbonaceous structure 956. In some respects, refer to... Figure 11 The described carbonaceous aggregates can be used to form Figure 3 Electrode 300. As discussed, the aggregate may be formed of or may include a set of carbonaceous structures, such as Figure 9A The carbonaceous structure of 902 or Figure 9B The carbonaceous structure is 956. In some respects, the carbonaceous structure can be CNO.

[0245] Carbonaceous structures can be used to form electrodes with any porosity type shown in Figure 1100 (such as...). Figure 3 The electrode 300. For example, the electrode may include any one of porosity type I 1110, porosity type II 1120, and porosity type III 1130. In some implementations, porosity type I 1110 may include a first pore 1111, a second pore 1112, and a third pore 1113, all sized with a principal size of less than 5 nm to retain polysulfides within the electrode. Some polysulfides may grow to a larger size after forming larger complexes and become permanently retained within the pores of porosity type I 1110. In some implementations, aggregates may aggregate to create pores of porosity type II 1120 and / or porosity type III 1130, which can retain larger polysulfides and / or polysulfide complexes.

[0246] Figure 12 A graph 1200 is shown depicting the pore size versus pore size distribution of exemplary electrodes according to some implementations. As used herein, "carbon 1" refers to a structured carbonaceous material that primarily comprises micropores (such as less than 5 nm in major size), and "carbon 2" refers to a structured carbonaceous material that primarily comprises mesopores (such as between approximately 20 nm and 50 nm in major size). In some implementations, electrodes suitable for use in one of the batteries disclosed herein may be fabricated to have the pore size versus pore size distribution depicted in graph 1200.

[0247] Figure 13 A first graph 1300 and a second graph 1310 are shown depicting battery performance according to cycle number based on some implementations. Specifically, the first graph 1300 shows the specific discharge capacity of an exemplary battery using the electrolyte 1302 disclosed herein, relative to the specific discharge capacity of a conventional battery using a conventional electrolyte. The second graph shows the capacity retention capability of a battery using electrolyte 1302, relative to the capacity retention capability of a battery using a conventional electrolyte. In some aspects, electrolyte 1302 may be... Figure 1 Electrolyte 130 or Figure 2 An example of electrolyte 230. In the first chart 1300 and the second chart 1310, the conventional electrolyte is prepared as 1M LiTFSI in DME:DOL:TEGDME (volume:volume:volume = 1:1:1) with 2 wt% LiNO3.

[0248] Figure 14Bar graph 1400 illustrates battery performance per cycle number according to some implementations. Specifically, bar graph 1400 depicts the specific discharge capacity per cycle number of an exemplary battery using the electrolyte 1402 disclosed herein, relative to the specific discharge capacity per cycle number of a conventional battery using a conventional electrolyte. In some aspects, electrolyte 1402 may be... Figure 1 Electrolyte 130 or Figure 2 An example of electrolyte 230. In bar chart 1400, a conventional electrolyte is prepared as 1M LiTFSI in DME:DOL:TEGDME (volume:volume:volume = 1:1:1). Bar chart 1400 shows the performance of an exemplary battery (such as...) compared to a battery using a conventional electrolyte. Figure 1 100 or Figure 2 Using electrolyte 1402 in the battery (200) can increase the battery's specific discharge capacity by approximately 28% at the 3rd cycle, approximately 30% at the 50th cycle, and approximately 39% at the 60th cycle.

[0249] Figure 15 A first graph 1500 and a second graph 1510 depict battery performance per cycle number according to some implementations. Specifically, the first graph 1500 shows the electrode discharge capacity per cycle number of an exemplary lithium-sulfur coin cell using the electrolyte 1502 disclosed herein, relative to the electrode discharge capacity per cycle number of an exemplary lithium-sulfur coin cell using a conventional electrolyte, and the second graph 1510 shows the capacity retention capability per cycle number of a lithium-sulfur coin cell using electrolyte 1502, relative to the electrode discharge capacity per cycle number of a lithium-sulfur coin cell using a conventional electrolyte. In some aspects, electrolyte 1502 may be... Figure 1 Electrolyte 130 or Figure 2 An example of electrolyte 230. The lithium-sulfur button cell is cycled at a discharge rate of 1C (such as complete discharge in one hour), at 100% depth of discharge (DOD), and maintained at approximately room temperature (68℉ or 20℃). The conventional electrolyte is prepared as 1M LiTFSI in DME:DOL:TEGDME (volume:volume:volume = 1:1:1) with 2 wt% LiNO3.

[0250] Figure 16 A graph 1600 is shown depicting the electrode discharge capacity per cycle number according to some implementations. Specifically, graph 1600 depicts the electrode discharge capacity per cycle number of an exemplary battery using the electrolyte 1602 disclosed herein, relative to the electrode discharge capacity of a conventional battery using a conventional electrolyte. In some aspects, electrolyte 1602 may be... Figure 1 Electrolyte 130 or Figure 2An example of electrolyte 230. The conventional electrolyte is prepared as 1M LiTFSI in DME:DOL:TEGDME (volume:volume:volume = 1:1:1) with 2 wt% LiNO3, and electrolyte 1602 is prepared as 1M LiTFSI in DME:DOL:TEGDME (volume:volume:volume = 58:29:13) with 2 wt% LiNO3.

[0251] Figure 17 Another graph 1700 is shown depicting the electrode discharge capacity per cycle number according to some implementations. Specifically, graph 1700 depicts the electrode discharge capacity per cycle number of an exemplary battery using the electrolyte 1702 and solvent pack 1704 disclosed herein, relative to the electrode discharge capacity of a conventional battery using a conventional electrolyte and solvent pack. The conventional electrolyte is prepared as 1M LiTFSI in DME:DOL:TEGDME (volume:volume:volume = 1:1:1) having about 2 wt% LiNO3, and electrolyte 1702 is prepared as 1M LiTFSI in DME:DOL:TEGDME (volume:volume:volume = 58:29:13) having 2 wt% LiNO3. The conventional solvent coating was prepared as 1M LiTFSI in DME:DOL:TEGDME (volume:volume:volume = 1:1:1), and the solvent package 1704 was prepared as 1M LiTFSI in DME:DOL:TEGDME (volume:volume:volume = 58:29:13).

[0252] Figure 18 Chart 1800 illustrates the specific discharge capacity per cycle number for various TBT-containing electrolyte mixtures according to some implementations. As shown in Chart 1800, "181" indicates an electrolyte with no TBT added, resulting in a 0 MTBT concentration level, "181-25TBT" indicates an electrolyte prepared at a 25 MTBT concentration level, and so on. In some implementations, a 5 MTBT concentration level can result in an increase in discharge capacity of approximately 70 mAh / g compared to an electrolyte with no TBT added.

[0253] Figure 19A first graph 1900 depicting electrode discharge capacity per cycle number according to some implementations and a second graph 1910 depicting electrode capacity retention capability per cycle number. Specifically, the first graph 1900 depicts electrode discharge capacity per cycle number for exemplary batteries excluding the protective lattice disclosed herein, and for exemplary batteries including the protective lattice disclosed herein. The second graph 1910 depicts electrode capacity retention capability per cycle number for exemplary batteries excluding the protective lattice disclosed herein, and for exemplary batteries including the protective lattice disclosed herein. In some aspects, the protective lattice may be... Figure 4 An example of the protective lattice 402. The performance results in the first graph 1900 and the second graph 1910 include the use of an electrolyte prepared as having 2 wt% LiNO3 in a 1 M LiTFSI in DME:DOL:TEGDME (volume:volume:volume = 58:29:13).

[0254] Figure 20 A first graph 2000 depicting electrode discharge capacity according to a number of cycles, and a second graph 2010 depicting electrode capacity retention capability according to a number of cycles, are shown according to other implementations. Specifically, the first graph 2000 depicts including... Figure 7 The exemplary battery of the polymer network shows the electrode discharge capacity according to the number of cycles. The second figure 2010 depicts the electrode discharge capacity of the battery including... Figure 7 The exemplary battery of the polymer network exhibits its discharge capacity retention capability according to the number of cycles. The battery may be... Figure 1 100 or Figure 2 An example of battery 200. The performance results of the first graph 2000 and the second graph 2010 include the use of an electrolyte prepared as having 2 wt% LiNO3 in 1 M LiTFSI in DME:DOL:TEGDME (volume:volume:volume = 58:29:13).

[0255] Figure 21 A first graph 2100 depicting electrode discharge capacity according to a number of cycles, based on some other implementations, and a second graph 2110 depicting electrode capacity retention capability according to a number of cycles. Specifically, the first graph 2100 depicts including... Figure 5 The exemplary battery with protective layer 516 shows the electrode discharge capacity according to the number of cycles. The second figure 2110 depicts the electrode discharge capacity of the battery including... Figure 5 The exemplary battery with protective layer 516 exhibits its discharge capacity retention capability according to the number of cycles. The battery may be... Figure 1 100 or Figure 2An example of battery 200. The performance results of the first chart 1900 and the second chart 1910 include the use of an electrolyte prepared as having 2 wt% LiNO3 in a 1 M LiTFSI in DME:DOL:TEGDME (volume:volume:volume = 58:29:13).

[0256] Figure 22 An exemplary cathode 2200 with a body 2201 and a width 2205 is shown according to some implementations. In some implementations, the cathode 2200 may be... Figure 3 An example of electrode 300. Cathode 2200 may be similar in many respects to... Figure 3 The electrode 300 is described in such a way that the description of the same element will not be repeated here. In one implementation, the cathode 2200 includes a first porous carbonaceous region 2210 and a second porous carbonaceous region 2220 positioned adjacent to the first porous carbonaceous region 2210. The first porous carbonaceous region 2210 may be formed of a carbonaceous material at a first concentration level, and the second porous carbonaceous region 2220 may be formed of a carbonaceous material at a second concentration level different from the first concentration level. For example, the second porous carbonaceous region 2220 may have a carbonaceous material at a lower concentration level than the first porous carbonaceous region 2210, such as... Figure 22 As shown. In some respects, additional porous carbonaceous regions (for simplicity, Figure 22 (Not shown in the image) can be coupled to at least a second porous carbonaceous region.

[0257] Specifically, these additional porous carbonaceous regions can be arranged in a direction away from the first porous carbonaceous region 2210, in order of progressively decreasing carbonaceous material concentration levels, to provide full ion transport and current tunability. That is, in one implementation, the second porous carbonaceous region 2220 can face the bulk electrolyte (e.g., provided in a liquid phase), and the first porous carbonaceous region 2210 of the cathode 2200 can be connected to a current collector (for simplicity, Figure 22 (Not shown in the image) coupling. In this way, compared to conventional lithium-ion batteries, denser carbonaceous regions (such as the first porous carbonaceous region 2210) can facilitate higher electrical conductivity levels between adjacent contact points of the carbonaceous material. Figure 22 The text is displayed as "e" - Furthermore, sparser carbonaceous regions (such as the second porous carbonaceous region 2220) can facilitate higher levels of lithium-ion transport associated with increased lithium-sulfur battery discharge-charge cycles. In some implementations, additional carbonaceous regions coupled to and located adjacent to the second porous carbonaceous region 2220 may have a lower density of carbonaceous material than the second porous carbonaceous region 2220. In this way, the lower-density additional carbonaceous regions can accommodate higher levels of lithium-ion transport to, for example, allow for tuning of various performance characteristics of the electrode 300.

[0258] In one implementation, the first porous carbonaceous region 2210 may include first non-trisegmented particles 2211. The configuration of the first non-trisegmented particles 2211 within the first porous carbonaceous region is an exemplary configuration. Other arrangements, orientations, alignments, etc., are possible for the non-trisegmented particles. In some aspects, each non-trisegmented particle may be an example of one or more carbonaceous materials disclosed elsewhere in this disclosure. The first porous carbonaceous region 2210 may also include, for example, […]. Figure 22 The first three-segment particles 2212 shown are either dispersed throughout the first non-three-segment particles 2211 or positioned in any other arrangement, orientation, or configuration. Each first three-segment particle 2212 may be... Figure 8B An example of a three-segment particle 850. Alternatively, each first three-segment particle 2212 may include first carbon segments 2213 interwoven with each other and spaced apart from each other by a central hole 2214. Each three-segment particle may have a first deformable periphery 2215 configured to coalesce with adjacent first non-three-segment particles 2211 and / or first three-segment particles 2212.

[0259] The first porous carbonaceous region 2210 may also include first aggregates 2216, each aggregate comprising a plurality of first three-segment particles 2212 joined together. In one or more specific examples, each first aggregate may have a principal size in the range of 10 nanometers (nm) to 10 micrometers (μm). Mesopores 2214 may be dispersed throughout the first plurality of aggregates, each mesopore having a principal size in the range of 3.3 nanometers (nm) to 19.3 nm. Additionally, the first porous carbonaceous region 2210 may include first agglomerates 2217, each agglomerate comprising a plurality of first aggregates 2216 joined together. In some aspects, each first agglomerate 2217 may have a principal size in the approximate range of 0.1 μm to 1,000 μm. Macropores 2218 may be dispersed throughout the first aggregates 2216, each macropore having a principal size in the range of 0.1 μm to 1,000 μm. In some implementations, one or more of the carbonaceous materials, allotropes, and / or structures discussed above may be used. Figure 9A and Figure 9B One or more examples are shown in the figure.

[0260] The second porous carbonaceous material may include a second non-tertiary particle 2221, which may be an example of the first non-tertiary particle 2211. The second porous carbonaceous region 2220 may include second tertiary particles 2222, each of which may be an example of each of the first tertiary particles 2212 and / or may be an example of... Figure 8BAn example of a three-segment particle 850. Alternatively, each second three-segment particle 2222 may include second carbon segments 2223 interwoven with each other and spaced apart from each other by a central hole 2214. Each second three-segment particle 2222 may have a second deformable periphery 2225 configured to coalesce with one or more adjacent second non-three-segment particles 2221 or second three-segment particles 2222.

[0261] Additionally, the second porous carbonaceous region 2220 may include second aggregates 2226, each of which may include a plurality of second three-segment particles 2222 joined together. In one or more specific examples, each second aggregate 2226 may have a principal size in the range of 10 nanometers (nm) to 10 micrometers (μm). Mesopores 2214 may be dispersed throughout the second aggregates 2226, each mesopore having a principal size in the range of 3.3 nanometers (nm) to 19.3 nm. Furthermore, the second porous carbonaceous region 2220 may include second agglomerates 2227, each of which may include a plurality of second aggregates 2226 joined together, each agglomerate having a principal size in the approximate range of 0.1 μm to 1,000 μm. Macropores 2218 may be dispersed throughout the plurality of second aggregates, each macropore having a principal size in the range of 0.1 μm to 1,000 μm. In some implementations, one or more of the carbonaceous materials, allotropes, and / or structures discussed above may be used. Figure 9A and Figure 9B One or more examples are shown in the figure.

[0262] In one implementation, the first porous carbonaceous region 2210 and / or the second porous carbonaceous region 2220 may include a selectively permeable shell (for simplicity, Figure 22 (Not shown in the diagram), which can form a separated liquid phase on the first porous carbonaceous region 2210 or the second porous carbonaceous region 2220, respectively. An electrolyte (such as any electrolyte disclosed in this disclosure) can be dispersed in the first porous carbonaceous region and / or the second porous carbonaceous region for lithium-ion transport associated with the discharge-charge operation cycle of the lithium-sulfur battery.

[0263] In one or more specific examples, the first porous carbonaceous region 2210 may have an electrical conductivity in the approximate range of 500 S / m to 20,000 S / m at a pressure of 12,000 psi. The second porous carbonaceous region 2220 may have an electrical conductivity in the approximate range of 0 S / m to 500 S / m at a pressure of 12,000 psi. The first aggregate 2217 and / or the second aggregate 2227 may comprise aggregates linked together by one or more polymer-based adhesives.

[0264] In some respects, each first three-segment particle 2212 may have a first porosity region located around the center of the first three-segment particle 2212 (for simplicity, Figure 22 (Not shown in the image). Similarly, each second-third segment particle 2222 may have a first porosity region located around the center of the second-third segment particle 2222 (for simplicity, Figure 22 (Not shown in the image). The first porosity region may include the first pores. The second porosity region (for simplicity, ...) Figure 22 (Not shown) may enclose a first porosity region. A second porosity region may include second pores. In one implementation, the first pores may define a first pore density, and the second pores may define a second pore density different from the first pore density.

[0265] In some respects, the central hole 2214 can be grouped into a first central hole and a second central hole (for simplicity, both are referred to as such). Figure 22 (Not shown in the image). In one or more specific examples, the first mesopore may have a first mesopore density, and the second mesopore may have a second mesopore density different from the first mesopore density. Additionally, the macropores 2218 may be grouped into first macropores that may have a first pore density and second macropores that may have a second pore density different from the first pore density (for simplicity, both are shown in the image). Figure 22 (Not shown in the text).

[0266] In one implementation, the first porous carbonaceous region 2210 and / or the second porous carbonaceous region 2220 can nucleate sulfur, such as that required for the operation of any lithium-sulfur battery disclosed herein during discharge-charge cycling. For example, the cathode 2200 may have a sulfur to carbon weight ratio of approximately 1:5 to 10:1. In some aspects, one or more conductive additives may be dispersed within the first porous carbonaceous region 2210 and / or the second porous carbonaceous region 2220 to, for example, accordingly affect the discharge-charge cycle performance of the cathode 2200. Additionally, a protective sheath (such as...) Figure 4 The protective lattice 402 can be placed on the cathode.

[0267] In one implementation, Figure 22 The exemplary cathode 2200 and / or any battery configuration presented in this disclosure (such as battery 100 and / or 200) can be prepared using an electrolyte (such as electrolyte 130 and / or 230) dispersed throughout the respective battery configuration. Alternatively or additionally, electrolyte 130, electrolyte 230, etc., can be formulated according to the following numbered examples:

[0268]

[0269]

[0270]

[0271]

[0272] In some respects, such as when prepared according to any or more of the examples presented above, the lithium cations (Li) transported throughout the electrolyte 130 + The ionic conductivity of electrolyte 125 can depend on the molecular structure of the various component substances of electrolyte 130. For example, hydrophobic substances with low polarity may have a lower ionic conductivity value. Hydrophilic substances with higher polarity may have a higher ionic conductivity value. In this way, the component materials in the above-mentioned electrolyte formulation examples used for electrolyte 130 can be ordered from lowest to highest ionic conductivity as follows: DMTS, TOL, TFETFE, MPB, MTBE, TrigDME, THF, TEE, TMU, DMSO, DMF, ACN.

[0273] In the electrolyte components disclosed in Examples 1–20 above, lithium nitrate (LiNO3) can dissociate into lithium cations (Li... + (Li) + ) and nitrate anion (NO3) - In this way, lithium nitrate (LiNO3) can produce nitrogen-oxygen compounds (not shown in the figure for simplicity), which can be derived from and / or based on nitrate anions (NO3). - When prepared according to any or more of the examples presented above, the electrolyte 130 prevents the diffusion of nitrogen-containing compounds generated during the operating discharge-charge cycle of the battery 100. Additionally, some nitrate anions (NO3) - A solvation sheath (not shown in the figure for simplicity) can be formed on the anode 120. In this way, an electrolyte 130 can be prepared to allow the nitrogen-oxygen additive to at least partially coat the anode 120 and thereby prevent dendrites from the anode 120 from extending through the electrolyte 130 to the cathode 110. The solvation sheath can be formed in the electrolyte 130 by reacting LiTFSI with lithium cations (Li... + Coordination complexes are formed between 125 and 1. These complexes may include a central atom or ion, which may be a metal and can be referred to as a "coordination center" (such as a lithium cation, Li). + )125) and the surrounding array of bound molecules or ions that may be called ligands or complexing agents.

[0274] The prevention of dendrite formation provided by the solvation sheath can be at least partially impaired by the continuous reduction of nitrogen compounds, which are dominant in nitrogen-oxygen additives, such as those forming nitrites (NO2). -This can generate gases in electrolyte 130 that cause bubble formation. These bubbles can interfere with lithium cations (Li... + The transport of lithium ions can cause swelling of the battery 100 and can also lead to undesirable obstacles to lithium-ion transport. To address these limitations, the electrolyte formulation of example 18 presented above can be prepared without the addition of lithium nitrate (LiNO3) and / or other types of nitrogen-oxygen-containing additives.

[0275] Figure 23 –25 shows a graph depicting the specific discharge capacity of one or more of the previously presented Examples 1–20 according to the number of cycles, based on some implementation. Figure 23 Show depiction Figure 1 Figure 2300 shows the performance improvements of battery 100 and / or other battery configurations disclosed herein, with respect to specific discharge capacity (mAh / g) per cycle number. Regarding Figure 2300, "Control" refers to electrolyte 130 prepared according to Example 1, "Toluene" refers to electrolyte 130 prepared according to Example 3, and "TMU" refers to electrolyte 130 prepared according to Example 5. In some aspects, the toluene in electrolyte 130 prepared according to Example 3 is based on its non-polar properties and accordingly with, for example... Figure 1 The poor interaction of polysulfide 128 with B can provide favorable, unintended results. That is, toluene has a unique chemical structure that, when prepared according to Example 3, may hinder the easy transport of polysulfide 128 through electrolyte 130. The benefits associated with using different concentrations or dilution levels of toluene in, for example, liquid solvent mixtures (also known as ternary solvent packs) can be significantly increased in proportion to the cycling rate. That is, when observing lithium-sulfur batteries discharged at a C / 3 rate (corresponding to a full cell discharge over a 1-hour period) compared to a conventional 1C discharge rate (corresponding to a full cell discharge over a 3-hour period), the use of toluene can be even more beneficial in terms of cathode capacity retention, as shown in Figure 2300. In this way, toluene is particularly well-suited for end-use applications where longer battery life or discharge time is involved, such as electric vehicles (EVs).

[0276] Based on its chemical structure and nonpolar properties, and possessing an approximate ionic conductivity of 5.128026 (mS / cm), toluene is uniquely suited to outperform other solvents. In this manner, such as when prepared according to Example 3, toluene in the electrolyte 130 can release, during battery cycling, a substance that can be used to transport lithium cations (Li₂O₃) by hindering the movement of polysulfides 128 within the electrolyte 130. +The increased volume of electrolyte 130 in the cell 125 contributes to higher specific capacity and increased capacity retention. Alternatively, toluene can act as a favorable solvent for elemental sulfur 126 when preloaded (e.g., via capillary infusion or some other suitable technique) into cathode 110 or cathode 2200. In one implementation, toluene can help depassivate cathode 110 or cathode 2200 to pre-condition cell 100, thereby preventing it from dropping below its minimum design voltage once external load 172 is applied.

[0277] Toluene improves sulfur retention and overall sulfur-related kinetics within the cathode 110 by hindering the movement of polysulfides 128 in the electrolyte 130, that is, in relation to lithium cations (Li... + Sulfur utilization during the formation of coordination complexes 125. Toluene also improves the interfacial region between the anode 120 and the electrolyte 130 by preventing the migration of polysulfides 128 to contact the anode 120. Additionally, toluene can increase the boiling point of the electrolyte 130 and / or reduce its volatility, thereby improving the safety and reliability of the electrolyte 130. Furthermore, toluene can lower the freezing point of the electrolyte 130, thus contributing to the low-temperature performance of the battery 100. Toluene can also reduce the density of the electrolyte 130, which can improve specific energy, since the mass of the electrolyte 130 can affect the performance and / or efficiency of the battery 100.

[0278] In some implementations, the ability of toluene to improve the performance of electrolyte 130 may depend at least in part on toluene's ability to dissolve certain forms of elemental sulfur, such as cyclooctasulfide (S8). In some respects, at an S8 solubility level of approximately 0.0275 mol / L, toluene may have a normalized first-cycle discharge capacity (Ah / g) between approximately 0.6 (Ah / g) and 0.8 (Ah / g). These values ​​provide a significant improvement compared to, for example, ACN, which has a normalized first-cycle discharge capacity (Ah / g) between approximately 0.37 (Ah / g) and 0.41 (Ah / g) at an S8 solubility level of approximately 0.0075 mol / L, indicating that toluene tends to solubilize S8 better and provide a correspondingly improved discharge capacity.

[0279] Figure 24 Show depiction Figure 1 Figure 2400 shows the performance improvements of battery 100 and / or other battery configurations disclosed herein, in terms of specific discharge capacity (mAh / g) per cycle number. Regarding Figure 2400, "MPB" refers to electrolyte 130 prepared according to Example 7, "TrigDME" refers to electrolyte 130 prepared according to Example 9, and "TEE" refers to electrolyte 130 prepared according to Example 8.

[0280] Figure 25Show depiction Figure 1 Chart 2500 shows the performance improvements of battery 100 and / or other battery configurations of A, based on the specific discharge capacity (mAh / g) per cycle number. Regarding Chart 2500, "TFETFE" refers to electrolyte 130 prepared according to Example 13, "DMTS" refers to electrolyte 130 prepared according to Example 11, "MTBE" refers to electrolyte 130 prepared according to Example 10, and "ACN" refers to electrolyte 130 prepared according to Example 12.

[0281] In some respects, the cathode (such as Figure 22 The cathode 2200 can be used with the anode (such as...) Figure 1 The anode 120 is positioned relative to the cathode and has an overall porosity between 40% and 70%. In one example, the cathode 2200 may comprise non-hollow carbon spherical (NHCS) particles bonded together. Each NHCS particle may be... Figure 22 The first and third section particles 2212, Figure 22 Particles 2222 in the second and third sections Figure 8A An example of carbonaceous particles, such as 800. At least some NHCS particles can aggregate together and thus collectively form tubular NHCS particle aggregates, which can be Figure 9B An example of aggregate 960. Each NCHS particle may have a diameter between 30 nanometers (nm) and 60 nm, and may include a first region and a second region. In one implementation, the first region may be... Figure 8A The first pore 801 defines the region, and the second region can be defined by... Figure 8A The second region is defined by a second pore 802. In this way, the first region may be adjacent to the center of the corresponding NHCS particle and may have a carbonaceous material of a first density, while the second region may be adjacent to the surface of the corresponding NHCS particle. The second region may encapsulate the first region and has a second density of carbonaceous material lower than the first density of the carbonaceous material. The first region and the second region may be in fluid communication with each other.

[0282] Additionally, the cathode 2200 may include interconnected channels defined in shape by adjacent NHCS particles (for simplicity, Figure 22 (Not shown in the image). Some interconnecting channels may be preloaded with elemental sulfur and hold polysulfides (PS) based on one or more of a first-density or second-density carbonaceous material. An electrolyte that can be prepared by any of the formulations presented in Examples 1–20 may be distributed throughout the cathode and in contact with the anode. A separator may be positioned between the anode and the cathode.

[0283] Figure 26AAn exemplary battery 2600A according to some other implementations is shown. Battery 2600A may be an example of other battery configurations disclosed herein. In one implementation, battery 2600A may be implemented as a lithium-sulfur battery and may include an anode 2620 (e.g., an anode active material comprising lithium foil), a cathode 2610, and a solid electrolyte 2630. In some cases, solid electrolyte 2630 may replace one or more electrolyte solution compositions presented in Examples 1-20. Cathode 2610 may be an example of other cathode configurations disclosed herein, such as... Figure 1 Cathode 110, Figure 2 Cathode 210 and / or Figure 22 The cathode is 2200. In some aspects, the cathode can be loaded with 3 mg / cm³. 3 ) elemental sulfur. In other aspects, the cathode 2610 can be loaded with 3 mg / cm³, suitable for maximizing the discharge-charge cycle efficiency of the 2600A battery. 3 Other concentrations of elemental sulfur. In some aspects, the cathode 2610 may be porous and composed of a subject composition comprising multiple pores 2612 (for simplicity, Figure 26A (Not shown in the image) Formation. The subject composition may be one example of various carbonaceous materials and / or structures disclosed herein, such as Figure 22 The first and third section particles 2212, Figure 22 Particles 2222 in the second and third sections Figure 8A Carbonaceous particles 800, Figure 9B One or more examples of aggregate 960, etc.

[0284] The solid electrolyte 2630 may be dispersed in at least the entire pore 2612 of the cathode 2610 and may also be in contact with the anode 2620. In some aspects, the solid electrolyte 2630 may be formed as a membrane, thereby providing contact with the separator (e.g., Figure 1 The ion conductivity associated with the separator 150. In one implementation, the solid electrolyte 2630 may be formed of and / or comprise said polymer matrix 2631, which may be formed of glass fibers 2633 interconnected with each other. In some aspects, the polymer matrix 2631 may have ion conductivity (e.g., conduction of lithium cations (Li... + It may include between 8 wt.% and 12 wt% of polyethylene oxide (PEO) 2632, between 13 wt% and 17 wt% of polyvinylidene fluoride (PVDF) 2634, and between 3 wt% and 7 wt% of polyvinylidene fluoride having repeating oxypropylene units in its main chain (for simplicity, Figure 26A (not shown) polyetheramine 2535 and one or more lithium-containing salts between 5% and 10% by weight (for simplicity) Figure 26A(Not shown in the image), the lithium-containing salt includes one or more of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) or lithium iodide (LiI). In some implementations, at least some of the lithium-containing salts are dissociable into lithium cations (Li... + This also facilitates lithium-ion transport between the anode 2620 and the cathode 2610 during the operating discharge-charge cycle of the battery 2600A.

[0285] Similar to other lithium-sulfur battery configurations disclosed herein, during the operational discharge-charge cycle of battery 2600A, battery 2600A may produce undesirable lithium-containing polysulfide substances (for simplicity, Figure 26A (Not shown in the image). In some cases, the cathode 2610 may at least partially trap and / or retain lithium-containing polysulfide material, thereby preventing blockage of lithium transport channels (e.g., as shown as charging cycle flow 2625) within the solid electrolyte 2630. In some aspects, the anode 2620 may be configured to provide lithium cations (Li₂O₃) after activation of the battery 2600A. + The lithium layer provides lithium cations (Li₂O₃) during the 2600A operation discharge-charge cycle of the battery. + In other respects, during the operating charging cycle of battery 2600A, cavity 2622 can receive lithium deposits from cathode 2610. That is, lithium cations (Li... + The charge cations can travel along the charging cycle flow 2624 from the cathode 2610 to the cavity 2622, which can be associated with the return of electrons 2674 to the battery 2600A, the return being related to or occurring during battery charging and / or recharging cycles. In this way, the cavity 2622 can be converted into an anode 2620, which can again be used to return lithium cations (Li₂C₃) to the battery 2600A during its operating discharge cycle. + This provides it with a corresponding electrochemically favorable position in the cathode 2610.

[0286] In one implementation, the subject composition for forming the cathode 2610 may be formed from and / or comprise one or more non-three-segment particles, three-segment particles, aggregates, or agglomerates as disclosed herein. In some aspects, the cathode 2610 may be... Figure 22An example of cathode 2200. That is, each three-segment particle in cathode 2610 may comprise carbon fragments interwoven with each other. At least some carbon fragments may be separated from each other by mesopores. A deformable periphery may be defined after the aggregation of one or more adjacent non-three-segment particles or three-segment particles. Each aggregate may comprise a plurality of three-segment particles joined together and have a principal size in the range of 10 nanometers (nm) to 10 micrometers (μm). Mesopores may be distributed throughout the aggregate. Each mesopore may have a principal size between 3.3 nanometers (nm) and 19.3 nm. Each agglomerate may be formed from a plurality of aggregates joined together and have a principal size in the approximate range of 0.1 μm to 1,000 μm. Macropores may be distributed throughout the aggregate, wherein each macropore has a principal size between 0.1 μm and 1,000 μm.

[0287] In some implementations, when a film is formed and / or deposited on the anode 2620 (for simplicity, Figure 26A When (not shown), the ionic conductivity of the solid electrolyte 2630 can be based on the relative concentration level of one or more lithium-containing salts doped into the polymer matrix 2631. In this way, the ionic conductivity of the solid electrolyte 2630 at temperatures between 18°C ​​and 22°C can reach 0.97 × 10⁻⁶. -3 Siemens' S / m is 1.03 × 10 -3 In other implementations, the membrane can be coated onto the anode 2620, resulting in an ionic conductivity of 3.97 × 10⁻⁶ S / m at temperatures between 18°C ​​and 22°C. -6 Siemens' S / m is 4.03 × 10 -6 Between S / m. In some respects, higher amounts of one or more lithium-containing salts may be associated with an increase in the ionic conductivity of the polymer matrix 2631.

[0288] In one implementation, the solid electrolyte 2630, when formed as a film, has a thickness between 10 micrometers (μm) and 50 μm, and can have a uniform density throughout its thickness. For example, in some cases, the solid electrolyte 2630 can have a density of 2 g / cm³. 3 ) and 3g / cm 3 The density between. In some respects, the film can be coated onto the sacrificial polymer (for simplicity, Figure 26A (Not shown in the image) The polymer can be disposed on the anode 2620 facing the solid electrolyte 2630. In this way, the solid electrolyte 2630 can prevent electrons from traveling from the anode 2620 to the cathode 2610 through the solid electrolyte 2630. In addition, the contact point between the solid electrolyte 2630 and the anode 2620 can prevent the impedance of the battery 2600A from increasing.

[0289] In one implementation, the cathode 2610 has a thickness between 50 micrometers (μm) and 150 μm, and a thickness of 5 grams per cubic centimeter (g / cm³). 3 ) and 15g / cm 3 The density between [specific parameters]. In some aspects, the solid electrolyte 2360 can be prepared without a liquid electrolyte, such as Examples 1-20 disclosed herein. Alternatively or concurrently, the solid electrolyte 2630 can position lithium-containing polysulfide material within the cathode 2610 and / or prevent the growth of lithium-containing dendrite structures from the anode 2620. In some aspects, during the operational discharge-charge cycle of the battery 2600A, the anode 2620 can expand in volume between 5% and 20% of its initial size. In some cases, during the operational discharge-charge cycle of the battery 2600A, the solid electrolyte 2630 can provide interfacial stability between the anode 2620 and the solid electrolyte 2630, for example, to reduce or limit the volume expansion of the anode 2620.

[0290] Figure 26B Another exemplary battery 2600B is shown according to some other implementations. In one implementation, battery 2600B may be another example of battery 2600A. In some aspects, cavity 2622 may replace anode 2620, and during the operational discharge-charge cycle of battery 2600B, it may be progressively filled with lithium supplied from cathode 2610. In this way, once Figure 26B The cavity 2622 is filled with lithium to become Figure 26A With the anode 2620, the battery 2600B can function in a similar or identical manner to the battery 2600A.

[0291] Figure 27 The illustration shows a depiction based on some implementation methods. Figure 26A Chart 2700 shows an exemplary configuration of battery 2600A according to voltage drop based on specific capacity. Regarding chart 2700, battery 2600A is rated at 3 mg / cm³. 3 The battery 2600A is fabricated with a sulfur loading level and is in the form of a button cell. Additionally, the battery 2600A is fabricated with a solid electrolyte 2630 at a thickness of 18 micrometers (μm). Region 2702 can represent the unique voltage drop behavior associated with the formation and / or dissociation of lithium-containing polysulfide intermediates generated during the discharge-charge operation cycle of the battery 2600A.

[0292] Figure 28Another exemplary battery 2800 according to some other implementations is shown. Battery 2800 may be an example of other battery configurations disclosed herein. In one implementation, battery 2800 may be implemented as a lithium-sulfur battery and may include a cathode 2810, an anode structure 2822 including an anode 2820 (e.g., an anode active material comprising lithium foil) positioned opposite the cathode, a separator 2850 positioned between the anode 2820 and the cathode 2810, and an electrolyte 2830. In some aspects, electrolyte 2830 may be formulated by mixing at least two or more solvents, such as those disclosed in Examples 1-20 previously presented. Electrolyte 2830 may be dispersed throughout cathode 2810 and in contact with anode 2820. In some aspects, anode 2820 may be a single solid lithium metal foil. In this manner, at least some lithium cations (Li₂O₃) output from anode 2820 are... + Lithium cations (Li2825) can participate in dissociation and / or combination reactions during the operating discharge-charge cycle of battery 2800. That is, during the discharge cycle of battery 2800, lithium cations (Li2825) output from anode 2820... + )2825 can be transported through electrolyte 2830 and remain in its electrochemically advantageous position within cathode 2810 (for simplicity, Figure 28 (Not shown in the image). Then, during the charging cycle of battery 2800, after exposure to an external current source, lithium cations (Li...) can be forced... + )2825 returns to anode 2820.

[0293] Additionally, a solid electrolyte interface phase 2840 may be formed on the anode 2820. In this manner, a protective layer 2860 may be formed at least partially within and / or on the solid electrolyte interface phase 2840 and facing the cathode 2810. In some aspects, based on the involvement of lithium cations (Li... + One or more redox reactions of the solid electrolyte interfacial phase 2840 with one or more solvents of the electrolyte 2830 can form one or more compounds on the anode 2820. In some implementations, the protective layer 2860 may be at least partially formed of a carbonaceous material including one or more of planar graphene, wrinkled graphene, carbon nanotubes (CNTs), carbon nanotubes (CNO), or non-hollow carbon spherical particles (NHCS), wherein one or more of the carbonaceous materials may be... Figure 9B An example of the carbonaceous structure 956.

[0294] Figure 29 The diagram illustrates an exemplary cathode 2900 according to some implementation methods. Cathode 2900 may be one example of other cathode configurations disclosed herein, such as... Figure 22 Cathode 2200 and / or Figure 28The cathode 2810. In some implementations, the cathode 2900 may include a porous structure 2915 having interconnected channels 2916 defined by adjacent and interconnected non-hollow carbon spherical particles (NHCS) 2917, each of which may be Figure 8B Three-section particles 850, Figure 9B An example of aggregate 960 and / or other carbonaceous materials described in this disclosure. In this way, in, for example... Figure 28 Prior to the activation and discharge-charge cycle of the battery 2800, at least some interconnecting channels 2916 may be loaded with elemental sulfur 2926 from the cathode 2900. Elemental sulfur 2926 may react with at least some lithium cations (Li... + )2825 forms a coordination complex to increase the specific capacity of the cathode 2900, for example, compared to conventional lithium-ion chemistry. In some aspects, the cathode 2900 may have a width 2910 formed by a first region 2911 disposed on a substrate 2902 (e.g., a copper or other metal current collector), and may have multiple additional regions, such as a second region 2912 positioned adjacent to the first region 2911. This includes the first region 2911, the second region 2912, and / or additional subsequent regions positioned adjacent to the second region 2912 (for simplicity, Figure 29 Each of the regions (not shown) can be defined in shape, size, and orientation by a corresponding concentration level of NHCS particles 2917. That is, in some respects, the first region 2911 can be prepared with a relatively high concentration of NHCS particles 2917, thereby resulting in increased conductivity between adjacent graphene flakes within each NHCS particle, as desired near or at the substrate 2902. In contrast, the second region 2912 can be prepared with a relatively low concentration of NHCS particles 2917, thereby allowing lithium-ion (Li...)... + )2925 is additionally transmitted to the width 2910 of the cathode 2900 to complex with elemental sulfur 2926 contained in the interconnect channel 2916.

[0295] Figure 30 The diagram depicts the implementation methods. Figure 28 Figure 3000 shows region "A" of the protective layer 2860 of the battery. In some aspects, region "A" may be one example of various anode protective layers (including protective layer 2860) disclosed herein. In one implementation, region "A" may be formed at least partially of a polymeric material, such as a first polymer chain 3010 having carbon atoms 3014 provided by at least some carbonaceous material. Oxygen anions (O 2- 3022, fluoride anion (F - )3012 and nitrate anion (NO 3-3024 may be uniformly dispersed throughout region "A" and grafted onto one or more of the carbon atoms 3014. Region "A" may also include a second polymer chain 3020, which includes at least some carbon atoms 3014, said carbon atoms may also be provided by a carbonaceous material. Similar to the first polymer chain 3010, the carbon atoms 3014 of the second polymer chain 3020 may also be grafted onto oxygen anions (O). 2- 3022, fluoride anion (F - )3012 and nitrate anion (NO 3- One or more of the anions 3024 may be uniformly dispersed throughout the protective layer 2860. In some aspects, the second polymer chain 3020 may be positioned relative to the first polymer chain 3010. Additionally, in one implementation, the first polymer chain 3010 and the second polymer chain 3020 may be configured based on exposure to one or more nitrogen-containing groups such as nitrate anions (NO3-). 3- )3024 and they are interconnected.

[0296] In some respects, inorganic and / or ionic conductors 3018, such as lithium-containing salts including lithium bis(trifluoromethanesulfonyl)imine (LiTFSI), can be uniformly dispersed throughout the electrolyte 2830 and / or protective layer 2860, and subsequently dissociate into lithium cations (Li... + )2825 and TFSI - Anion 2826. Additionally, upon exposure to environment 3050, the first polymer chain 3010 and the second polymer chain 3020 may at least partially crosslink with each other and form carbon-carbon bonds 3026. In some cases, environment 3050 may include a polymerization initiator and / or ultraviolet (UV) radiation.

[0297] Specifically, exposing the first polymer chain 3010 and the second polymer chain 3020 to a polymerization initiator and / or UV radiation can cause region “A” to form a three-dimensional (3D) lattice with a crosslinking density defined by the number of crosslinking points per unit volume. In some aspects, the crosslinking points can be configured to be at least partially trapped within the TFSI generated after the dissociation of LiTFSI. -Anion 2826. For example, the number of crosslinking points per unit volume can limit the redissolution of the lithium-containing additive in region "A" into the electrolyte 2830. In some aspects, the crosslinking density of the protective layer 2860 can, for example, suppress swelling exceeding 10% of the initial volume of the protective layer 2860 by preventing the absorption of at least one of the solvents in the electrolyte 2830. In some other aspects, the crosslinking density of the protective layer 2860 can control the swelling to between 10% and 50% of the initial volume of the protective layer 2860 by controlling the absorption of at least one solvent. In this way, the crosslinking density of the protective layer 2860 can improve lithium-ion (Li+) transport throughout the anode structure 2822 and the electrolyte 2830 and / or may be associated with the improvement of said transport.

[0298] In one implementation, the protective layer 2860 may have an elastic modulus between 3 gigapascals (GPa) and 100 GPa, a glass transition temperature above 60 degrees Celsius (°C), and be curable at a temperature below 81 degrees Celsius (°C). After activating the battery 2800, lithium fluoride (LiF) may be applied based on one or more chemical reactions (e.g., Figure 7 It is formed by the Woods reaction. For example, lithium fluoride (LiF) can be configured based on fluoride anions (F-) and lithium cations (Li). + It is formed by the combination of fluoride anions (F-) and lithium cations (Li-). In some aspects, fluoride anions (F-) and lithium cations (Li-) are involved. + The combination of these can produce lithium oxide (Li₂O), lithium nitrate (LiNO₃), and / or nitrogen-containing oxides. In one implementation, lithium fluoride (LiF) can be based on lithium cations (Li₂O) output from the anode 2820. + )2825 and fluoride anions (F-)3012 grafted onto the first polymer chain 3010 and / or the second polymer chain 3020 Figure 30 It is formed by the combination of lithium cations (Li). In some respects, lithium cations (Li...) + )2825 and fluoride anion (F - The combination of 3012 can consume at least some of the lithium cations (Li) output from the anode 2820. + )2825, thereby reducing the growth of lithium dendrites from the anode 2820 (for simplicity, Figure 28 (Not shown in the image). Reducing lithium dendrite growth from the anode can further increase the charging rate, discharging rate, energy density, cycle life, or any combination thereof of the battery 2800. Additionally, lithium fluoride (LiF), lithium oxide (Li₂O), lithium nitrate (LiNO₃), or nitrogen-oxygen-containing additives can form one or more regions across one or more of the anode 2820 or the solid electrolyte interface phase 2840.

[0299] In some aspects, the inorganic and / or ionic conductor 3018 of the protective layer 2860 may include additives such as lithium salts, including lithium nitrate (LiNO3), and / or inorganic ionic conductive ceramics, including lithium lanthanum zirconium oxide (LLZO), NASICON-type oxides, etc. 1+x Al x Ti 2–x One or more of (PO4)3 (LATP) and / or lithium tin phosphide sulfide (LSPS), and / or nitrogen-oxygen-containing additives. At least some of these additives dispersed throughout region “A” and / or protective layer 2860 are dissociable to generate lithium cations (Li). + )2825. In this way, the presence of at least some additives within the protective layer 2860 can increase the charging rate, discharging rate, and / or energy density of the lithium-sulfur battery 2800.

[0300] In one implementation, the first polymer chain 3010 may be composed of a first plurality of interconnected monomer units "C" (e.g., Figure 36 and 37 The first plurality of interconnecting monomer units "C" and the second plurality of interconnecting monomer units "D" may be formed, and the second polymer chain 3020 may be formed from the second plurality of interconnecting monomer units "D". In some aspects, the first plurality of interconnecting monomer units "C" and the second plurality of interconnecting monomer units "D" may be the same. In other aspects, the first plurality of interconnecting monomer units "C" and the second plurality of interconnecting monomer units "D" may be different from each other.

[0301] In some aspects, the first polymer chain 3010 and the second polymer chain 3020 may be based on exposure to nitrogen-containing groups (e.g., nitrate ions NO3). - They are cross-linked with each other, and some of the nitrogen-containing groups can be cured in the epoxy resin and / or include amine-containing groups. Alternatively or additionally, the first polymer chain 3010 and / or the second polymer chain 3020 can be prepared to comprise a liquid bisphenol A epichlorohydrin-based epoxy resin having an average molecular weight of 500 M n The protective layer 2860 comprises PEG-DEG-500 (polyoxyethylene bis(glycidyl ether)) and polyoxypropylene diamine. For example, in one implementation, the protective layer 2860 can be prepared to include 2-5 wt% of a bifunctional bisphenol A / epichlorohydrin-derived liquid epoxy resin and 15-25 wt% of an average M0 of 500. nThe composition includes polyoxyethylene bis(glycidyl ether) (PEG-DEG-500), 20%-25% diaminopolypropylene glycol, 5%-15% poly(propylene glycol)bis(2-aminopropyl ether), 5%-15% lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and 40%-60% lithium lanthanum zirconium oxide (LLZO). In some other aspects, a protective layer 2860 can be prepared comprising 2%-5% bifunctional bisphenol A / epichlorohydrin-derived liquid epoxy resin, 15%-25% of an average M of 500... n The composition includes polyoxyethylene bis(glycidyl ether), 5%-15% 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (ECC), 15%-20% bis(trifluoromethanesulfonyl)imide lithium (LiTFSI), 40%-60% lithium lanthanum zirconium oxide (LLZO), and 1%-5% diphenylmonium hexafluorophosphate (DPIHFP). Additionally, the protective layer 2860 can be applied and / or deposited on the anode 2820 using a roll-to-roll apparatus. For example, the protective layer can be one or more of the following methods applied to the anode: spray coating, gravure coating, microgravure coating, slot die coating, doctor blade coating, and / or Mayer bar spiral coating.

[0302] In some implementations, the battery 2800 may be arranged in one or more additional configurations. For example, based on exposure to one or more ultraviolet (UV) curing accelerators (including one or more cationic photoinitiators), the first polymer chain 3010 and the second polymer chain 3020 may participate in one or more crosslinking polymerization reactions to form a protective layer 2860. As discussed, the UV curing accelerator may be provided by an environment 3050, which may include an ultraviolet (UV) radiation source.

[0303] In some aspects, one or more crosslinking polymerization reactions may include ring-opening polymerization (ROP). Additionally, one or more ultraviolet (UV) curing accelerators include various onium salts, which may include one or more triphenylsulfonium salts, one or more diazonium salts, one or more diarylmonium salts, one or more ferrocene onium salts, and / or one or more metallocene compounds. In some aspects, one or more UV curing accelerators may include one or more antimony salts and / or polyols that can act as reactive diluents.

[0304] In some aspects, the protective layer 2860 may be formed from multiple polymers uniformly mixed together and / or crosslinked (e.g., via cationic polymerization and / or ultraviolet (UV curing)) to form a three-dimensional (3D) lattice. The protective layer 2860 may be formulated according to one or more formulations disclosed in the following formulation examples 21-22:

[0305] Example 21: For amine-curable epoxy resin-based film compositions

[0306]

[0307] Example 22: For amine-curable epoxy resin-based film compositions

[0308]

[0309] In some respects, the protective layer 2860 may be prepared following the steps of Example 23, which are exemplary procedures for preparing 30 mL sample-scale dispersions of any one or more of the formulations provided by Examples 21-22 and / or 24-28 disclosed herein.

[0310] Example 23: Procedure for preparing a protective layer

[0311]

[0312] When prepared according to Example 21, the protective layer 2860 has an initial curing temperature of 68°C and a glass transition temperature of -16°C (T0). g In some aspects, the protective layer 2860 may have one or more openings, also known as "pinholes," by... Figure 31A As shown in pinhole 3102A, it is formed in protective layer 2860, allowing polysulfides 2882 to... Figure 28 The direction "B" faces the anode 2820 and is not desired to pass through. Polysulfide 2882 can at least partially coat the anode 2820 and thereby hinder lithium cations (Li... + The free movement and / or transport of 2825 between the anode 2820 and the cathode 2810 can thus facilitate the discharge-charge cycle operation of the battery 2800. To address the undesirable formation of pinholes in the protective layer 2860 when prepared according to Example 21, the protective layer 2860 can be prepared according to Example 22. In this configuration, the protective layer 2860 has an initial curing temperature of 81°C, a peak curing temperature of 124°C, a curing enthalpy of 104 J / g, and a Tg of 63°C. g Variations of Example 21 or Example 22 are possible, wherein the component loading level is adjusted to + / - 3% of the listed levels. However, any formulation may be prepared to produce protective layer 2860 such that it generates a temperature greater than 60°C. g A curing start temperature of less than 81°C or a curing peak of less than 124°C is used to cure at room temperature (e.g., 18°C-22°C). Additionally, the protective layer 2860 may be provided on the anode 2820 with a thickness between 100 nm and 3 μm, according to Example 23.

[0313] The protective layer 2860 can be formulated according to either Example 21 or Example 22, following the procedure listed in Example 23, to address operational challenges commonly encountered in conventional lithium-sulfur batteries. For example, in conventional lithium-sulfur batteries using a liquid electrolyte solution, unnecessary and uncontrolled dissolution of polysulfides due to polysulfide shuttle can cause battery failure. In one or more specific examples, polysulfide attack on lithium can lead to rapid battery capacity reduction due to the growth of a continuous solid electrolyte interphase (SEI). This growth consumes lithium cations, resulting in less lithium available for transport to the cathode for healthy discharge-charge cycles in conventional lithium-sulfur batteries. Additionally, due to the gradient of electrochemical potential, for example, which is beneficial to lithium-lithium metal bonding, remaining lithium cations can adhere to other lithium cations, thereby creating lithium-containing dendrite structures that grow from the anode and extend from the anode to the cathode, potentially causing short circuits in conventional lithium-sulfur batteries.

[0314] To protect the lithium contained in the anode 2820 from the effects of polysulfides migrating from the cathode 2810 to the anode 2820, and to suppress the formation of lithium dendrites, a protective layer 2860 can be directly coated onto the anode 2820 prior to activation and operational discharge-charge cycles of the battery 2800. Therefore, the protective layer 2860 can be prepared to include a first polymer chain 3010 and a second polymer chain 3020. Each of the first polymer chain 3010 and the second polymer chain 3020 may have (e.g., Figure 36 and 37 The protective layer 2860 consists of repeating monomer units, which may be identical or different from each other. Additionally, in some aspects, when the protective layer 2860 is formulated according to Example 21 or Example 22, at least some carbon atoms 3014 on each polymer chain may form carbon-carbon bonds with each other via ring-opening (ROP) cationic polymerization (e.g., optionally catalyst-based), thereby forming an amine-curable epoxy-based film. In some other aspects, when the protective layer 2860 is formulated according to one of Examples 24 to 28 (presented below), at least some carbon atoms 3014 on each polymer chain may form carbon-carbon bonds 3026 with each other via ultraviolet (UV) curable ROP cationic polymerization.

[0315] Furthermore, catalyst-based or UV-curing of difunctional and / or multifunctional components can initiate and / or facilitate cross-linking of the first polymer chain 3010 and the second polymer chain 3020 via carbon-carbon bonds 3026, thereby effectively protecting the anode 2820. (Functional groups, for simplicity) Figure 28 or Figure 30(Not shown) can be attached to at least some inorganic and / or ionic conductors 3018 to achieve additional tunability of the protective layer 2860. In this way, the protective layer 2860 can provide several advantages when formulated with any of the formulations disclosed in Examples 21 to 28, compared to conventional anodic protective layers that typically have only one component.

[0316] In some implementations, the protective layer 2860 can be formulated to include multiple polymer components, such as where the first polymer chain 3010 and the second polymer chain 3020 are different from each other, allowing the protective layer 2860 to cure relatively more flexibly on and over the anode 2820 after spray coating. This flexibility prevents the protective layer 2860 from disintegrating during the manufacturing process. Additionally, directly coating the protective layer 2860 onto the anode 2820 allows for the uniform stripping and deposition of at least some lithium cations (Li+) 2825 during the operating discharge-charge cycle of the battery 2800, thereby minimizing lithium dendrite formation. In some aspects, the inorganic and / or ionic conductor 3018 (such as LLZO) dispersed throughout the protective layer 2860 can be ionicly conductive and designed to minimize impedance growth in the battery 2800. Furthermore, UV curing can be used to replace conventional heat drying processes to accelerate the curing of the protective layer 2860 and minimize the potential adverse effects of the processing time of the protective layer 2860 on the anode 2820.

[0317] Figure 31A A micrograph is shown of an exemplary baseline protection layer 3100A according to some implementations. The baseline protection layer 3100A may be... Figure 28 An example of the protective layer 2860 is prepared according to the previously provided example 21, thereby resulting in the formation of pinhole 3102A. In some aspects, pinhole 3102A can be as follows: Figure 31A The set size is shown. In some other respects, the pinhole 3102A can be smaller or larger than, for example... Figure 31A The dimensions are shown. Additionally, the baseline protective layer 3100A may have multiple examples of pinholes 3102A, which can collectively and adversely interfere with the healthy operation of the battery 2800 during discharge-charge cycles. For example, pinholes 3102A may allow at least some polysulfides 2882 to be transmitted through pinholes 3102 to contact the anode 2820 and / or otherwise interfere with the formation of the solid electrolyte interface phase 2840, thereby reducing the cycle efficiency of the battery 2800.

[0318] Figure 31B A micrograph of an exemplary protective layer 3100B according to some implementation is shown. Protective layer 3100B may be prepared according to Example 22 using the method disclosed in Example 23. Figure 28An example of the protective layer 2860 of the battery. The protective layer 3100B minimizes pinhole formation so that there are no pinholes or one or more smaller pinholes 3102B, thereby reducing the risk of at least some polysulfides 2882 contacting the anode 2820 and correspondingly improving the operational discharge-charge performance of the battery 2800.

[0319] Figure 32 This shows the implementation methods. Figure 28 A photomicrograph of a cross-sectional view 3200 of the protective layer 2860 of the battery 2800. The protective layer 2860 may be prepared according to Example 21 by the method disclosed in Example 23. In some other aspects, the protective layer 2860 may be prepared according to other formulations disclosed in the examples (including Example 22).

[0320] Figure 33A This shows the implementation methods. Figure 28 An exemplary crosslinking density 3300A is given for the protective layer 2860 of the battery 2800. The crosslinking density 3300A may be an example of the crosslinking density of the protective layer 2860 when prepared according to Example 21 by the method disclosed in Example 23, and thus having a certain number (e.g., 9) of crosslinking points 3306A per unit area of ​​3302A. In this way, each crosslinking point 3306A may be spaced apart from adjacent crosslinking points 3306A by a dimension 3304A.

[0321] Figure 33B This shows the implementation methods. Figure 28 Another exemplary crosslinking density 3300B is provided for the protective layer 2860 of the battery 2800. The crosslinking density 3300B may be an example of the crosslinking density of the protective layer 2860 when prepared according to Example 22 using the method disclosed in Example 23, and thus having a certain number (e.g., 25) of crosslinking points 3306B per unit area 3302B. In this manner, each crosslinking point 3306B may be separated from adjacent crosslinking points 3306B by a size 3304B that may be smaller than the size 3304A, and is thus configured to be retained in the electrolyte 2830 after the dissociation of LiTFSI and / or included in at least some TFSI in the protective layer 2860. - Anion 2826. By retaining at least some TFSI - Within a crosslinking density of 3300B, the anionic 2826 and protective layer 2860 can function to prevent the retention of TFSI. - Anion 2826 blocks lithium cations (L + The transfer and / or contact anode 2820 of 2825 improves the operating discharge-charge cycle performance of battery 2800.

[0322] Figure 34This illustrates triarylsulfonium salts (Ar3S) according to some implementations. + MtXn - An exemplary ring-opening (ROP) mechanism 3400 is described. Generally, using a UV initiator to initiate ROP polymerization via crosslinking the first polymer chain 3010 with the second polymer chain 3020 can accelerate the curing of the protective layer 2860 from a maximum of 24 hours to 1 to 3 seconds, which is desirable for large-scale manufacturing processes. In some aspects, the use of a UV initiator can accelerate the epoxy crosslinking of existing epoxy systems (e.g., Examples 21-22 and / or Examples 24-28 to be disclosed herein) without the need to introduce additional new chemicals. Additionally, the UV initiator selected to achieve epoxy crosslinking can be a cationic UV initiator. In this way, when various epoxy compounds are exposed to UV radiation, they can generate relatively strong Lewis acids and / or Brinzyl-Lorey acids. –Lowry acid), which can then accordingly initiate ROP of epoxy groups.

[0323] For triarylsulfone salts (Ar3S) that can represent inorganic and / or ionic conductors 3018 incorporated into protective layer 2860 + MtXn - The ROP mechanism 3400 is illustrated. In some aspects, HMtXn is a Lewis acid (e.g., HBF4, HPF6, HAsF6, HSbF6) and M is a monomer (e.g., Figure 36 and 37 And / or include epoxy groups). Unlike free radical polymerization, cationic polymerization (e.g., including UV-initiated cationic ROPs) is not inhibited by oxygen. However, polymer chain growth and crosslinking reactions can be inhibited by trace amounts (e.g., less than 0.1% by weight) of water and / or chemicals (e.g., amines and / or urethanes). However, the initiating moiety in UV-initiated cationic ROPs is relatively chemically stable for a long duration (e.g., greater than 24 h). In this way, polymerization in UV-initiated cationic ROPs can continue even in the absence of visible light. In addition, depending on the amount of the protective layer 2860 being prepared, some monomers (e.g., Figure 36 and 37 () and / or oligomers can be cured with a lower UV dose.

[0324] Figure 35 This illustrates what is suitable for use in some implementations. Figure 28Various exemplary onium salts 3500 of the cationic photoinitiator of the protective layer 2860 of the battery. The onium salt 3500 may be an example of an inorganic and / or ionic conductor 3018 and may thus be used to initiate crosslinking of a first polymer chain 3010 with a second polymer chain 3020 to form the protective layer 2860. In some aspects, the onium salt 3500 may include diphenylmonium onium salts and / or triphenylsulfonium salts (both in… Figure 35 (as shown in the image), as well as diazonium salts, diarylmonium salts, ferroceneium salts and / or various other metallocene compounds (for simplicity, ...). Figure 35 (Not shown in the image). The efficiency of onion salt 3500 as a cationic photoinitiator can depend at least in part on its corresponding solubility in protective layer 2860 (e.g., when formed as a resin) and / or its corresponding polarity and / or surface charge. Generally, solubility increases with increasing size of the anion in the corresponding onion salt 3500, because the charge dissipates over the relatively large surface area of ​​the anion, thereby reducing the hydrophilicity of the corresponding onion salt 3500. In this way, the solubility and reactivity of at least some onion salts 3500 in nonionic resins can be determined according to tetrafluoroborate (BF) ions. 4- )< hexafluorophosphate (PF6) 6- )< hexafluoroarsenate (AsF 6- )<Fluoronium (SbF) 6- The order of these factors increases. In some respects, antimony salts (e.g., including fluoroonium anions) are most often chosen as cationic photoinitiators due to their relatively higher solubility and reactivity compared to the other listed salts. Additionally, besides solubility alone, spectral properties such as light absorption range and / or bond cleavage efficiency can affect the initiation rate of monomer polymerization in the first polymer chain 3010 and / or the second polymer chain 3020.

[0325] Figure 36 This illustrates the suitability for forming based on some implementation methods. Figure 28 Various exemplary monomers 3600 are used in a variety of cationic photopolymerizable compositions for the protective layer of batteries. Monomer 3600 can be individually... Figure 30 An example of a repeating monomer unit "C" and / or "D" is provided, and thus can be used to initiate crosslinking of the first polymer chain 3010 with the second polymer chain 3020 to form a protective layer 2860. That is, multiple examples of the repeating monomer unit "C" can be attached to exposed carbon and / or other atoms, thereby enabling... Figure 30 and Figure 36 The first polymer chain 3010, consisting of multiple units, is formed in a manner shown in the diagram, such as "C"-"C"-"C"-..." etc. The repeating monomer unit "D" may be the same as or different from the repeating monomer unit "C", and thus... Figure 30 and 36The second polymer chain is formed in a manner similar to the first polymer chain by attaching to an additional example of a repeating monomer unit “D”, such as “D”-“D”-“D”-… etc.

[0326] In some aspects, cationic UV resin formulations formed from at least some monomers 3600 may include examples of one or more alicyclic epoxy compounds, any of which may serve as epoxy groups. Alicyclic epoxy compounds tend to have relatively greater reactivity compared to linear alicyclic or aromatic epoxy molecules, such that when any or more of monomers 3600 are used to generate the protective layer 2860, a tight network of polar groups can be formed to produce a relatively brittle polymer-based final product. To reduce undesirable brittleness, some UV cationic resin formulations may be prepared to include polyols (for simplicity, ... Figure 36 (Not shown in the image) as a reactive diluent and performance modifier. In some respects, polyols can act as monomer materials, reacting to form an epoxy-based network. Many different polyols are available compared to single alicyclic epoxy groups, ranging from difunctional and trifunctional diols, polycaprolactone oligomers, and even higher-order dendritic polyols. Selection among a relatively large number of available polyols can help fine-tune the final use properties of protective layer 2860.

[0327] Figure 37 This illustrates the suitability for forming based on some implementation methods. Figure 28 The protective layer of the 2800 battery (2860) is UV-curable monomer (3700). Monomer (3700) can be... Figure 30 An example of monomer "B" and / or monomer "C" may include 1,2-cyclohexanedicarboxylic acid diglycidyl ester (DG-CHDC), 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylic acid ester (ECC), triphenylsulfonium trifluoromethanesulfonate (TPS-TF), diphenylmonium trifluoromethanesulfonate (DPI-TF), diphenylmonium hexafluorophosphate (DPI-HFP), poly[(phenyl glycidyl ether)-co-formaldehyde] (PPGEF) and / or glycidyl 2,2,3,3-tetrafluoropropyl ether (GTFEP).

[0328] In some aspects, the protective layer 2860 may be formed of a variety of polymers (e.g., formed from monomer 3700) that are uniformly mixed together and / or crosslinked (e.g., via ultraviolet light having a UV curing wavelength of 254 nanometers (nm) (UV curing)) to form a three-dimensional (3D) lattice disposed on the anode 2820. The protective layer (e.g., when formed as a 3D lattice) may be formulated according to one or more of the formulations disclosed in Examples 24-28:

[0329] Example 24: UV-curable formulation

[0330]

[0331] Example 25: UV-curable formulation

[0332]

[0333]

[0334] Example 26: UV-curable formulation

[0335]

[0336] Example 27: UV-curable formulation

[0337]

[0338] In some respects, depending on the performance requirements of protective layer 2860, polyethylene glycol (PEG), other polyethers and / or other polyols may be used and / or substituted for any components listed in Examples 23-27. Additionally, variations of Examples 24-27 are possible when the component loading level is adjusted to + / - 3% of the listed levels. Furthermore, in addition to polyoxypropylene diamine (e.g., Except for D-230), all listed components are compatible with UV-catalyzed cationic ROP. In this manner, the first polymer chain 3010 can initiate crosslinking with the second polymer chain 3020 to form carbon-carbon bonds 3026 and generate a 3D lattice disposed on the anode 2820. The 3D lattice can be formed from the various components listed in each example, wherein the components are uniformly mixed together, interconnected with each other, and dispersed throughout the protective layer 2860. That is, the first polymer chain 3010 and the second polymer chain 3020 are exemplary, and additional polymer chains are possible according to the examples. Some examples may also include additional polymer chains crosslinked with each other in addition to one or more of the first polymer chain 3010 or the second polymer chain 3020. In addition, each component listed in any one or more of Examples 21-22 and / or 24-28 may be formed from the corresponding polymer chain.

[0339] That is to say, in Example 26, which represents other examples, there is an average M of 500. n The polyoxyethylene bis(glycidyl ether) (PEG-DEG-500) can be represented as monomer "B" in the first polymer chain 3010, and 1,2-cyclohexanedicarboxylic acid diglycidyl ester (DG-CHDC) can be represented as monomer "C" in the second polymer chain 3010. Monomer "B" can be bonded in 3D to additional examples of monomer "B" and also to one or more examples of monomer "C" to form a 3D lattice. Additional components (for simplicity) Figure 30(Not shown in the image) can be represented as monomer "D", etc. For example, in Example 26, PPGEF (number average molecular weight (Mn) = 345) can be represented as monomer "D" and additional examples of it bonded to itself in 3D, as well as monomer "B" and / or monomer "C" to form a 3D lattice, wherein lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and / or lithium lanthanum zirconium oxide (LLZO) (500 nm particle size) can be depicted as inorganic and / or ionic conductors 3018 and dispersed throughout the protective layer 2860.

[0340] Certain fast-curing alicyclic epoxy monomers, such as those included in Examples 25 and 27 above (e.g., 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate (ECC)), can be incorporated into the protective layer 2860 to achieve higher crosslinking densities, such as Figure 33B At a crosslinking density of 3300B, the groups are rapidly crosslinked together via cationic polymerization, generating a network of polar groups that at least partially retain TFSI. - Anion 2826 is located within the protective layer 2860. Additionally, in some respects, various UV initiators (e.g., onmium hexafluorophosphate (PF6)) may be beneficial for forming the solid electrolyte interfacial phase 2840. - This can replace the photoinitiator disclosed in Examples 24-27. In some other respects, the anion of fluoroantimonyic acid (SbF6) can replace the photoinitiator disclosed in Examples 24-27. - This can replace the photoinitiator disclosed in Examples 24-27. The anion of fluoroantimonic acid (SbF6) - It is soluble in electrolyte 2830 and can be beneficial to use at least some lithium cations (Li). + )2825 alloys at least some regions of the protective layer 2860. In this way, alloying some regions of the protective layer 2860 can consume at least some lithium cations (Li). + )2825, thereby removing consumed lithium cations to prevent them from participating in lithium-lithium metal bonding, thereby forming unwanted dendrites from the anode 2820 toward the cathode 2810.

[0341] Alternatively, in one implementation, once UV curing has been initiated (e.g., by any photoinitiator listed in Examples 24-27), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) can act as a co-initiator, thereby increasing the curing rate. For example, activation of the ROP reaction of the exemplary monomer poly(ethylene glycol) diglycidyl ether (DGEPEG) can be achieved using lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) with a subsequent propagation step. In the activation step, lithium cations (e.g., provided by LiTFSI) attack the carbon-oxygen bonds on one or more epoxy groups of DGEPEG. When this reaction occurs under acidic conditions, the epoxy groups are converted into hydroxyl ions. During the initiation and propagation steps, the hydroxyl ions react with the epoxy groups and other hydroxyl ions via nucleophilic reactions, resulting in chain extension through the formation of COC bonds.

[0342] As an alternative to the previously presented Examples 24-27, the protective layer 2860 can be formulated to include a fluorinated material (e.g., a fluoropolymer, such as glycidyl 2,2,3,3-tetrafluoropropyl ether (GTFEP)) for at least partial grafting onto carbon atom 3014. In this manner, GTFEP can be used as a fluoride ion (F... - The source of 3012 is that it can later dissociate from its corresponding carbon atom to react with lithium cations (Li) via the Woods reaction. + The combination of 28 and 25 produces lithium fluoride (LiF), as discussed elsewhere in this disclosure. Example 28 can be prepared according to the procedure provided in Example 23, comprising the following components:

[0343] Example 28: Fluorinated polymers

[0344]

[0345]

[0346] As shown in Example 28 above, it can be initiated without UV curing because polyoxypropylene diamine (e.g., D-230) is not compatible with UV-catalyzed cationic ROPs. However, in some respects, polyoxypropylene diamine (e.g., D-230) can be replaced with 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate (ECC), thereby making Example 28 UV-curable, similar to Examples 23-27.

[0347] Figure 38 This illustrates, based on some implementation methods, suitability for use as an additive to adjust... Figure 37Various exemplary non-reactive diluents 3800 are described for dilution levels in UV-curable formulations prepared from UV-curable monomers. In one implementation, the non-reactive diluent may include 1,2-dimethoxyethane (DME) and / or triethylene glycol dimethyl ether (TEGDME). In some aspects, the non-reactive diluent 3800 may be removed from the protective layer 2860 after crosslinking by baking at 100°C. In some other aspects, the non-reactive diluent 3800 may be retained in the protective layer 2860 to enhance lithium cations (Li... + The spread of )2825.

[0348] Figure 39 This illustrates, based on some implementation methods, suitability for use as an additive to adjust... Figure 37 Various exemplary reactive diluents 3900 are used in UV-curable formulations prepared from UV-curable monomers to achieve different dilution levels. In some aspects, the reactive diluent may act as a toughening agent to relieve stress on at least some carbon atoms 3014 (e.g., which may crosslink with each other) within the protective layer 2860, thereby minimizing pinhole formation. Additionally, in some aspects, the non-reactive diluent 3800 and / or the reactive diluent 3900 may be or include materials used as additives in the UV-curable formulation in amounts between 1% and 50% by weight of the formulation, to adjust the viscosity according to the deposition method (e.g., low viscosity for spray coating, compared to high viscosity for slot die or stencil coating methods). In this way, the remaining components are reduced proportionally to the amount of diluent added.

[0349] Figure 40A Graph 4000A shows the relationship between capacity (initial %) and cycle number according to some implementations. Graph 4000A depicts the performance of battery 2800 prepared according to Example 22 relative to Example 21 and an unprotected 40 μm lithium anode (e.g., provided for reference, "Ref."). Example 22 shows a consistently higher capacity retention capability (e.g., initial %) based on the number of operating discharge-charge cycles compared to Example 21 and the unprotected 40 μm lithium anode.

[0350] Figure 40BGraphs showing the relationship between capacity (mAh / g) and cycle number according to some implementations are presented. Graph 4000A depicts the performance of battery 2800 prepared according to Example 22 relative to Example 21 and an unprotected 40μm lithium anode (e.g., provided for reference, "Ref."). Example 22 shows a consistently higher capacity retention capability (e.g., in mAh / g) based on the number of operating discharge-charge cycles compared to Example 21 and the unprotected 40μm lithium anode. Graph 4000A depicts the performance of battery 2800 prepared according to Example 22 relative to Example 21 and an unprotected 40μm lithium anode (e.g., provided for reference, "Ref."). Example 22 shows a consistently higher capacity retention capability (e.g., in initial %) based on the number of operating discharge-charge cycles compared to Example 21 and the unprotected 40μm lithium anode.

[0351] Figure 41A Another graph shows the relationship between capacity (initial %) and cycle number according to some implementations. Graph 4100A depicts the performance of battery 2800 prepared according to Example 28 relative to Example 21 and an unprotected 40 μm lithium anode (e.g., provided for reference, "Ref."). Example 22 shows a consistently higher capacity retention capability (e.g., initial %) according to the number of operating discharge-charge cycles compared to Example 21 and the unprotected 40 μm lithium anode.

[0352] Figure 41B Another graph showing the relationship between capacity (mAh / g) and cycle number according to some implementations is provided. Graph 4100B depicts the performance of battery 2800 prepared according to Example 28 relative to Example 21 and an unprotected 40 μm lithium anode (e.g., provided for reference, “Ref.”). Example 22 shows a consistently higher capacity retention capability (e.g., mAh / g) according to the number of operating discharge-charge cycles compared to Example 21 and the unprotected 40 μm lithium anode.

[0353] Figure 42AAnother exemplary battery 4200A according to some other implementations is shown. Battery 4200A may be an example of other battery configurations disclosed herein. In one implementation, battery 4200A may be implemented as a lithium-sulfur battery and may include a cathode 4210, an anode structure 4222 including an anode 4220 positioned opposite the cathode, a separator 4250 positioned between the anode 4220 and the cathode 4210, and an electrolyte 4230. The anode 4220 may be disposed on and / or coupled to a substrate 4201, for example, a metal current collector formed of nickel (Ni) or aluminum (Al). The cathode 4210 may be disposed on and / or coupled to a substrate 4202, for example, a metal current collector formed of nickel (Ni) or aluminum (Al). In some aspects, the electrolyte 4230 may be formulated by mixing at least two or more solvents, such as those disclosed in Examples 1-20 previously presented. The electrolyte 4230 may be dispersed throughout the cathode 4210 and in contact with the anode 4220. In some respects, the anode 4220 can be a single solid lithium metal foil. In this way, at least some lithium cations (Li) output from the anode 4220... + Lithium cations (Li2825) can participate in dissociation and / or combination reactions during the operating discharge-charge cycle of the 4200A battery. That is, during the discharge cycle of the 4200A battery, lithium cations (Li2825) output from the anode 4220 can participate in dissociation and / or combination reactions. + )4225 can be transported through electrolyte 4230 and remain in its electrochemically advantageous position within cathode 4210 (for simplicity, Figure 42A (Not shown in the image). Then, during the 4200A charging cycle of the battery, after exposure to an external current source, the lithium cations (Li) can be forced to... + )4225 returns to anode 4220.

[0354] Additionally, a solid electrolyte interphase (SEI) layer 4240 may be formed on the anode 4220. In some aspects, a protective layer 4260 may be formed at least partially within and / or on the SEI layer 4240 and facing the cathode 4210. In some aspects, in response to the involvement of lithium cations (Li... + The SEI layer 4240 may be formed on the anode 4220 by one or more compounds in one or more redox reactions with the electrolyte 4230 and one or more solvents. In some implementations, the protective layer 4260 may be at least partially formed of a carbonaceous material including one or more of flat graphene, wrinkled graphene, carbon nanotubes (CNTs), carbon nanotubes (CNO), or non-hollow carbon spherical particles (NHCS), wherein one or more of the carbonaceous materials may be... Figure 9B An example of the carbonaceous structure 956.

[0355] In one implementation, the anode 4220 of the anode structure 4222 can be formed as a solid lithium monolayer, which can output lithium cations (Li₂O₃) during the operating discharge cycle of the lithium-sulfur battery. + SEI layer 4240 may be formed on a solid lithium monolayer, and protective layer 4260 may be formed on SEI layer 4240 and at least partially disposed within said SEI layer in response to the operational discharge-charge cycle of lithium-sulfur battery 4200A. Protective layer 4260 may be an example of other protective layer configurations disclosed herein, including... Figure 28 The protective layer is 2860.

[0356] Alternatively or concurrently, the protective layer 4260 may comprise a polymer backbone 4262 formed of interconnected carbon atoms 4263. In this manner, at least some of the interconnected carbon atoms 4263 may move during the operating discharge-charge cycle of the battery 4200A and define a cooperative segmental mobility (also referred to as “segmental motion”) of the protective layer 4260. Additional polymer chains 4264 may be crosslinked to each other and to at least some of the interconnected carbon atoms 4263 of the polymer backbone 4262. Each of the additional polymer chains 4264 may be formed from interconnected monomer units 4266. In some aspects, a plasticizer 4268 may be dispersed throughout the protective layer 4260 without being covalently bonded to at least some of the interconnected carbon atoms 4263 of the polymer backbone 4262. In some aspects, the plasticizer 4268 may be formed from and / or may comprise one or more of polyethylene glycol (PEG or PEO)-based oligomers, nitrile (e.g., succinate, glutaronitrile, adiponitrile). Alternatively or concurrently, plasticizer 4268 may be formed from a solvent and / or may include a solvent comprising dimethoxyethane (DME), tetrahydrofuran (THF), diethyl ether, dioxolane (DOL), tetraethylene glycol dimethyl ether (TEGDME), toluene, bis(2,2-trifluoroethyl ether) (TEE), fluoroethylene carbonate (FEC), diethyl carbonate (DEC), dimethyl carbonate (DMC), propylene carbonate (PC), and / or ethylene carbonate (EC). Plasticizer 4268 may separate adjacent monomer units of the interconnecting monomer units 4266 of at least some additional polymer chains 4264 (e.g., by means of...). Figure 42B (The spacing 4267). Increasing the spacing between adjacent monomer units can increase the cooperative segmental mobility of at least some additional polymer chains 4264, thereby increasing the ionic conductivity of the protective layer 4260. Furthermore, in some respects, increasing the concentration level of plasticizer 4268 in the protective layer 4260 can increase the passage of lithium cations (Li) through the protective layer 4260. + Conductivity. In some other respects, linear polymer and / or oligomer chains (for simplicity, Figure 42A(Not shown) can be covalently bonded, grafted, and / or crosslinked by crosslinking 4265 to at least some interconnecting carbon atoms 4263 of the polymer backbone 4262. In this way, the linear polymer and / or oligomer chains can increase the cooperative segmental mobility (e.g., maximum cooperative segmental mobility) of the protective layer 4260, which can increase the lithium cation (Li) through the protective layer 4260. + Conductivity. For example, oligomers such as polyoxypropylene diamine (e.g., M-600 can increase the cooperative segmentation mobility of the protective layer 4260 (e.g., maximum cooperative segmentation mobility).

[0357] In some cases, the protective layer 4260 can be configured to operate at the glass transition temperature (T0). g Melting at a lower temperature increases the glass transition temperature, leading to a decrease in the cooperative segmental migration rate of the polymer chains (e.g., maximum cooperative segmental migration rate). Furthermore, this decrease in the cooperative segmental migration rate of the polymer chains (e.g., maximum cooperative segmental migration rate) reduces the amount of lithium cations (Li) passing through the protective layer 4260. + Conductivity. In this way, aspects of this disclosure can enable lithium cations (Li) through the protective layer 4260 to pass through by configuring the glass transition temperature below room temperature (e.g., 18°C-22°C). + Maximize electrical conductivity.

[0358] In some respects, the protective layer 4260 can be prepared by Example 23 according to the formulation provided by Example 29 disclosed below:

[0359] Example 29: Formulations containing plasticizers

[0360]

[0361] In some other implementations, the protective layer 4260 may be formed on the anode as a three-dimensional (3D) polymer lattice (for simplicity, Figure 42A (Not shown in the image), it includes a first polymer chain and a second polymer chain positioned opposite each other. In some aspects, the first polymer chain and the second polymer chain may be respectively... Figure 30 An example of the first polymer chain 3010 and the second polymer chain 3020 in region “A” shown in Figure 3000. In some implementations, each of the first and second polymer chains may include at least temporary chemical bonding to an oxygen anion (O). 2- ), fluoride anion (F) - ) and / or nitrate anions (NO3) - The carbon atom of ). Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) (for simplicity, Figure 42A (Not shown in the image) can be dispersed throughout the 3D polymer lattice to dissociate into lithium cations (Li).+ 4225 and TFSI-anion 4226. In this way, the first and second polymer chains can be crosslinked 4265 to form a 3D polymer lattice with a crosslinking density sufficient to retain TFSI-anion 4226. For example, crosslinking 4265 can be initiated upon exposure to a high-energy environment including ultraviolet (UV) energy and LiTFSI, wherein LiTFSI can be used as a polymerization co-initiator compound.

[0362] In other implementations, the first and second polymer chains can form a 3D polymer lattice through a crosslinking polymerization reaction, which may include ultraviolet (UV) curing at a curing rate. In some aspects, a polymerization co-initiator compound may increase the curing rate. In some cases, the additive is uniformly dispersed throughout the 3D polymer lattice and may include lithium nitrate (LiNO3), inorganic ion-conducting ceramics (including lithium lanthanum zirconium oxide (LLZO), NASICON-type oxides Li), etc. 1+x Al x Ti 2–x (PO4)3 (LATP) or lithium tin phosphide sulfide (LSPS) or nitrogen-oxygen-containing additives. In this way, inorganic ion-conducting ceramics can be uniformly embedded in a 3D polymer lattice and / or uniformly distributed in the protective layer 4260. In some aspects, the protective layer 4260 may include a dry solvent.

[0363] In some alternative or alternative implementations, the protective layer 4260 can trap various types of anions (for simplicity, Figure 42A (Not shown in the image). For example, the protective layer 4260 may be formed of a variety of components, including relatively flexible oligomeric epoxy resin and / or polyol-based compounds, relatively rigid polymeric epoxy resin-based compounds, and / or photoinitiator molecules. In some aspects, at least some of the relatively flexible oligomeric epoxy resin and / or polyol-based compounds can prevent the formation of pinholes in the protective layer 4260. The lithium-containing salt uniformly dispersed throughout the protective layer 4260 can dissociate into lithium (Li+) cations and various types of anions.

[0364] Additionally, in some cases, the protective layer 4260 may be formed on the anode in response to exposure to an ultraviolet (UV) energy source that facilitates UV curing of at least some components of the protective layer 4260. Furthermore, in some aspects, the protective layer 4260 may include a non-reactive diluent, including 1,2-dimethoxyethane (DME), tetrahydrofuran (THF), triethylene glycol dimethyl ether (TEGDME), or 2-methyl-2-oxazoline (MOZ). In some other aspects, the protective layer 4260 may include a reactive diluent, including 1,3-dioxolane (DOL), 3,3-dimethyloxetane (DMO), 2-ethyl-2-oxazoline (EOZ), or ε-caprolactone (CL). In this way, the weight per unit formulation of the protective layer 4260 may be based on the concentration level of the non-reactive or reactive diluent relative to the components of the protective layer 4260. In some aspects, the reactive diluent may reduce the mechanical stress of at least some crosslinking units within the protective layer 4260.

[0365] In some respects, the reactive diluent can be removed from the protective layer 4260. In other respects, the reactive diluent can be retained in the protective layer 4260 after crosslinking at least some of the multiple components (e.g., relatively flexible oligomeric epoxy resin-based compounds and / or polyol-based compounds and / or photoinitiator molecules) 4265 with each other. Retention of the reactive diluent in the protective layer 4260 after crosslinking two or more components can increase the lithium cation (Li... + )4225 diffuses through electrolyte 4230. In one implementation, the relatively rigid polymeric epoxy resin-based compound can be formed from several repeating epoxy monomer units. For example, each repeating epoxy monomer unit is 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate (ECC), which can be crosslinked with additional ECC monomer units to create a network of polar groups (for simplicity, Figure 42A (Not shown in the image). The polar group network can retain at least some of the anions generated during the dissociation of lithium salts.

[0366] Figure 42B This shows the implementation methods. Figure 42A Figure 4200B shows the amplification section “E” of the battery 4200A. In some aspects, the plasticizer 4268 may be crosslinked with additional monomer units (e.g., by crosslinking 3265) and not chemically (e.g., covalently) bonded to the interconnecting carbon atoms 4263 of the polymer backbone 4262. At least some of the crosslinks 4265 of the plasticizer 4268 may expand and / or shrink in volume to impart flexibility to the protective layer 4260. In this way, the protective layer 4260 may expand and / or shrink as needed to accommodate the volume expansion of the anode 4220 caused by the operating discharge-charge cycle of the battery 4200A.

[0367] In one implementation, plasticizer 4268 can influence the cooperative segmentation mobility (e.g., maximum cooperative segmentation mobility) of protective layer 4260. For example, in the absence of plasticizer 4268, the 3D lattice of protective layer 4260 may be relatively rigid due to a high degree of crosslinking 4265, which in turn minimizes the spacing 4267 between adjacent monomer units of interconnecting monomer units 4266. Introducing plasticizer 4268 between adjacent monomer units increases the spacing 4267, which provides more movement volume for additional polymer chains, resulting in additional segmentation movement of protective layer 4260. For example, since plasticizer 4268 is not covalently bonded to the interconnecting carbon atoms 4263 of polymer backbone 4262, the plasticizer may be able to maintain a relatively high degree of migration freedom within the 3D lattice of the protective layer. The relatively high degree of migration freedom of plasticizer 4268 can increase the spacing 4267 between adjacent monomer cells, thereby increasing the flexibility of the protective layer 4260, which may be necessary to accommodate the volume expansion of the anode 4220 associated with the operation of the battery 4200A's discharge-charge cycle.

[0368] Figure 43 An exemplary battery pack 4300 is shown that can be assembled according to one or more implementations of the subject matter disclosed herein. Exemplary applications of the disclosed battery pack 4300 include providing power for electric vehicles (EVs), portable electronic devices, aerospace applications, and energy storage systems. The battery pack 4300 is shown as including three battery modules 4310, 4320, and 4330. In some aspects, the battery pack 4300 may include other numbers of battery modules assembled with each other. One or more battery modules may be configured in series, such as... Figure 43 As shown, they may be configured to be stacked together. Each of the one or more battery modules may be cuboid in shape or any other three-dimensional (3D) geometry. Each of the battery modules 4310, 4320, and / or 4330 may include one or more lithium-sulfur batteries 4312, each of which may be an example of one or more batteries disclosed herein. The batteries 4312 may be connected to each other, for example, in series, in parallel, or a combination of both. In some implementations, the batteries 4312 may be welded to each other via conductive components 4314 and by means of mechanical welding. In this way, the battery 112 may be prepared to deliver sufficient voltage and power for a desired end-use application (e.g., EV). In some other aspects, the battery 112 may be constructed using an electronically conductive adhesive (for simplicity, Figure 1 Each battery 112 (not shown) is coated with an electronically conductive adhesive (e.g., carbonaceous material) to electrically connect them to each other, and the electronically conductive adhesive can be formed from any carbonaceous material disclosed herein. For example, in some aspects, the electronically conductive adhesive may include carbonaceous materials (e.g., Figure 9BThe aggregates 960 may each have exposed carbon-containing surfaces functionalized with complementary functional groups. In this way, the batteries 4312 can be electrically connected to each other without the conductive component 4314. Removing the conductive component 114 reduces the weight of the battery pack 4300, thereby increasing the energy density of the battery pack 4300 (e.g., measured in milliampere-hours per gram (mAh / g)). In addition, the battery pack 4300 may include additional systems and / or components built into the battery pack 4300 (for simplicity, Figure 1 (Not shown in the image), such as one or more protection units, monitoring units, and sensors.

[0369] Figure 44 This illustrates, based on some implementation methods, what can be used for manufacturing Figure 43 An exemplary battery 4400 of the battery pack 4300. When manufactured in a wound configuration, battery 4400 may be an example of any battery previously disclosed herein, such as... Figure 28 2800 or Figure 42A Battery 4200A. For example, battery 4400 may have a cylindrical shape factor corresponding to the dimensions of an 18650 battery. In some aspects, battery 4400 may have a length between 65.1 mm and 65.3 mm and a circular cross-section between 18.4 mm and 18.6 mm in diameter. In some other aspects, battery 4400 may have a rectangular cross-section and a prismatic shape factor corresponding to the dimensions of a CP3553 battery. For example, battery 4400 may have a height between 56 mm and 58 mm, a length between 34 mm and 36 mm, and a width between 6 mm and 8 mm. Battery 4400 is shown as including a casing 4410 and a core 4420. Generally, the term "core" can refer to designs used for various types of cylindrical rechargeable batteries, including nickel-cadmium (Ni-Cd), nickel-metal hydride (Ni-MH), and lithium-ion (Li-ion) batteries, which are named "core" because their cross-section resembles a rolled-up sponge cake. Shell 4410 may have Figure 44 The longitudinal axis is denoted as AA'. In this way, the core 4420 can be arranged along the longitudinal axis within the housing 4410.

[0370] The core 4420 can be formed into a cross-section having a circular, rectangular, square, triangular, or any other geometric shape. For example... Figure 44As shown, the core 4420 can be formed by cylindrically rolling together various battery components, including an anode 4422, an anode current collector 4402, a first barrier layer 4424, a cathode 4426, and a second barrier layer 4428. Furthermore, the anode 4422, the first barrier layer 4424, the cathode 4426, and the second barrier layer 4428 (collectively referred to as the "internal battery components") can be laminated together. In some aspects, one or more of the first barrier layer 4426 and the second barrier layer 4428 can be... Figure 28 An example of one or more of the protective layer 2860 or the solid electrolyte interphase (SEI) 2840 of the battery 2800. In some other aspects, one or more of the first barrier layer 4426 and the second barrier layer 4428 may be an example of one or more of the protective layer 4260 or the SEI 4240.

[0371] In some respects, the internal battery components can be radially wound around axis AA' to form a core 4420. In some other respects, a center pin (for simplicity, Figure 2 (Not shown) may be attached to the inner edge of the anode 4422, and one or more of the various listed internal battery components may be laminated, radially wound, or coiled around the central pin to form a core 4420. In this way, the core 4420 may be configured such that the anode 4422 and the cathode 4426 are separated by a first barrier layer 4424 and a second barrier layer 4428 to avoid undesirable "short circuit" type conditions within the battery 200.

[0372] The anode 4422, the first barrier layer 4424, the cathode 4426, and the second barrier layer 4428 can each be formed as rectangular sheets, thus having similar or identical physical dimensions. In this way, in some aspects, when formed as sheets, these internal battery components can be aligned with each other during winding, such that no sheet extends longitudinally from the core 4420 parallel to the axis AA'. Alternatively, in some other aspects, the anode 4422 or the cathode 4426 may include tabs 4423 extending longitudinally from the core 4420 parallel to the axis AA', such as... Figure 44 As shown. Typically, battery terminals provide electrical connection between multi-layer current collectors and external target sources, such as the wiring of an electric vehicle (EV). Figure 44 In the configuration of the battery 4400 shown, in some respects, the tab 4423 may be soldered in foil-to-tab form to one or more current collectors before extending beyond (e.g., referred to as "exit") the core 4420 (for convenience, Figure 44(Not shown in the image), thereby enabling the transfer of power to an external load, such as an EV. Alternatively, in some other aspects, after various internal battery components, for example formed as sheets, are co-wound and / or laminated together to form a core 4420, a tab 4423 may be attached to the surface of the cathode 4426 to extend longitudinally along axis AA'. In this way, the tab 4423 can connect the anode 4422 or the cathode 4426 to the negative or positive terminal of the housing 4410, respectively, by, for example, mechanical welding (for simplicity, ...). Figure 2 (Not shown in the image).

[0373] In one or more configurations of the alternatives discussed above, the electrode sheets (anode 4422 or cathode 4426) may be intentionally arranged during the winding process to be misaligned with other internal battery components and / or the first barrier layer 4424 and the second barrier layer 4428, such that portion 4425 may extend longitudinally along the axis AA' of the core 4420. In some respects, a conductive adhesive material, such as glue or any carbonaceous material disclosed herein (for simplicity, Figure 2 (Not shown) can be disposed on and near a portion 4425 disposed within the housing 4410, for example, at the top and bottom of the housing 4410. In this way, the portion 4425 can be electrically connected to the negative and / or positive terminals of the housing 4410, thereby eliminating the need for mechanical soldering methods.

[0374] Generally, some non-lithium-sulfur batteries (e.g., lead-acid, lithium-ion, nickel-manganese-cobalt (NMC), and / or lithium iron phosphate (LFP) batteries) can benefit from increased energy density and reduced cell impedance. Battery discharge-charge cycle performance can be increased by reducing battery weight, which can be achieved by removing or reducing the weight of various inactive components. Such inactive components may include anode connection tabs (e.g., Figure 44 The battery 4400 has a 4423 connector. Battery discharge-charge cycle performance can also be improved by increasing its interaction with an external load (…). Figure 44 The total contact area between the electrical connections (not shown), anode current collector 4402, and / or anode 4422, is increased by means of the anode, which may be formed as a sheet spanning the entire length of anode current collector 4402. Two objectives, such as reducing battery weight by eliminating non-moving parts and increasing the total contact area between the anode and current collector, can be achieved by coating at least a portion of 4425 with a conductive carbon layer formed of an interconnecting graphene material, which may be... Figure 8A An example of carbonaceous particles 800 Figure 9B One or more examples of interconnected aggregates 960 and / or others described elsewhere in this document.

[0375] Anode 4422 may be formed from any suitable material commonly used and / or used as an anode in Li-S cells (e.g., lithium single foil or lithium-containing substrate), and may be an example of any other anode disclosed herein, such as... Figure 28 The anode of the 2800 battery is 2820 or Figure 42A The anode 4220 of the battery 4200A. Furthermore, the anode 4422 may be coupled to an anode current collector 4402 to support, for example, the anode 4422. The cathode 4426 may be an example of any cathode disclosed herein, such as... Figure 22 Cathode 2200, Figure 26A or Figure 26B Cathode 2610, Figure 28 Cathode 2810, Figure 42A The cathode 4426. In some cases, the cathode 4426 may be formed of, coupled to, and / or otherwise comprised of an electrode film 4204, which may be prepared to at least temporarily microscopically define an electroactive material, such as elemental sulfur or other suitable sulfur-containing materials, such as lithium sulfide. For example, in some cases, the electroactive material may be preloaded into the pores of the electrode film 4204 and / or the cathode 4426 to later interact with lithium ions (Li₂O₃) during the operation of the battery 4400 during discharge-charge cycles. + This forms a coordination complex. Furthermore, in some aspects, the electrode film 4404 can be coated (e.g., spray-coated) onto the current collector (for simplicity, Figure 2 (Not shown in the image) For example, on both sides of an aluminum foil, thus providing the desired cathode capacity. Alternatively, in some other respects, the electrode film 4404 serves as a current collector, thereby eliminating the need for a separate cathode current collector coupled to the cathode 4426. In this way, the cathode 4426 can be a stand-alone cathode.

[0376] Electrode film 4404 may be composed of multiple carbonaceous aggregates (for simplicity, Figure 2 (Not shown) Formed, for example, non-hollow carbon spherical (NHCS) particles bonded together. Each NHCS particle can be... Figure 22 The first and third section particles 2212, Figure 22 Particles 2222 in the second and third sections Figure 8A An example of carbonaceous particles, such as 800. At least some NHCS particles can aggregate together and thus collectively form tubular NHCS particle aggregates, which can be Figure 9BAn example of aggregate 960. In this way, one or more of the carbonaceous aggregates and / or other carbon-based materials described in this disclosure may aggregate together to collectively define an electrode film 204 having pores (e.g., micropores, mesopores, and / or macropore channels) of various sizes and / or principal dimensions. The carbonaceous aggregates and / or materials used to form the electrode film 4404 may have exposed surfaces decorated with silicon and / or silicon-containing materials. In one or more specific examples, electroactive materials may constitute between 60 wt% and 90 wt% of the electrode film 4404.

[0377] Electrolytes (for simplicity, Figure 44 (Not shown) can be uniformly dispersed in at least the entire cathode 4426 and in contact with the anode 4422, thereby providing a suitable solution for lithium-ion (Li) batteries. + The electrolyte is an ion-conducting material. It can be any example of an electrolyte disclosed in this disclosure, such as electrolyte 130, electrolyte 230, etc., formulated according to the examples 1-20 presented above. In some cases, the electrolyte can be a liquid-phase electrolyte or a gel-phase electrolyte and can be added after forming the core 4420. In this configuration, in some aspects, the first barrier layer 4424 and the second barrier layer 4428 can serve as separators. For example, the first barrier layer 4424 and the second barrier layer 4428 can be formed of different materials from each other, such that one barrier layer can serve as a separator while the other barrier layer can serve as a non-aqueous electrolyte membrane. In some other cases, each of the first barrier layer 4424 and the second barrier layer 4428 can serve as a separator and a non-aqueous electrolyte membrane. Additionally, in some other aspects, the battery 4400 can be... Figure 26B An example of battery 2600B. In this way, battery 4400 may therefore include solid electrolyte 2630 incorporated into battery 4400 during the formation of core 4420.

[0378] Figure 45A This shows the implementation methods in... Figure 44 A top view of a cross-section of an exemplary cathode 4500A within the core 4420 of the battery 4400. The cathode 4500A may be an example of one or more cathodes disclosed in this disclosure, such as... Figure 22 Cathode 2200, Figure 29 Cathode 2900, Figure 42A Cathode 4210 or Figure 44 The cathode 4426. The cathode 4500A may include a current collector 4510, a top-side electrode film 4520A coated on a first surface of the current collector 4510, and a bottom-side electrode film 4530A coated on a second surface opposite to the first surface of the current collector 4510. When surrounding... Figure 2When wound around axis AA', the top electrode film 4520A may face outward, for example away from axis AA' and towards the casing 4410 of battery 4400, and the bottom electrode film 4530A may face inward, for example towards axis AA' and away from the casing 4410 of battery 4400. In this way, the top electrode film 4520 may be subjected to tensile stress when wound around axis AA' to form core 4240. The tensile stress may stretch the top electrode film 4520 from the opposite direction, and thereby may undesirably propagate pre-existing cracks in the top electrode film 4520. In some aspects, the propagation of pre-existing cracks may cause at least a portion of the top electrode film 4520 to delaminate from the current collector 4510. Simultaneously with the stretching of the top electrode film 4520, the bottom electrode film 4530 may be subjected to compressive stress corresponding to the tensile stress of the top electrode film 4520. In some aspects, the compressive stress may cause buckling delamination of the bottom film 4530 from the current collector 4510.

[0379] To address the undesirable delamination described above, one or both of the top-side electrode film 4520A and / or the bottom-side electrode film 4530A may be formed from interconnecting aggregates 4532. In some aspects, one or more of the aggregates 4532 may be an example of any carbonaceous aggregate, agglomerate, and / or material disclosed in this disclosure, such as... Figure 22 Particle 2212 in Zone 1-3 Figure 22 Particles 2222 in the second and third zones Figure 8A Carbonaceous particles 800, etc. In one implementation, at least some aggregates 4532 may be non-hollow carbon spherical (NHCS) particles as previously described, said particles may aggregate together to form tubular NHCS particle aggregates, which may be... Figure 9B An example of aggregate 960. The described carbonaceous material can be produced by sp... 2 Hybridization and / or sp 3 Wrinkles and / or flexural regions formed by hybrid carbon atoms ( Figure 45A (Not shown) to be adjacent to each other. During the curling process, carbon atoms in such flexed regions can have a relatively high level of mobility relative to conventional two-dimensional (2D) graphene-based materials or conventional carbonaceous structures (e.g., carbon nano-onions (CNO)). In this way, the use of such relatively flexible carbonaceous materials characterized by flexed regions can limit or eliminate unwanted crack-induced delamination of the top electrode film 4520A and / or buckling-related delamination of the bottom electrode film 4530A. In this way, both the top electrode film 4520A and the bottom electrode film 4530A can remain attached to the current collector 4510 during the curling process without unwanted transfer to, for example, Figure 44On the first barrier layer 4424 and the second barrier layer 4428, this could potentially lead to an internal short circuit. The relatively flexible and robust mechanical structure provided by the aggregate 4532 also provides electrical conductivity, thereby allowing the production of a core 4420 with the desired energy density value.

[0380] Figure 45B A side view of an exemplary unwound cathode 4500B according to some implementations is shown. Cathode 4500B may be... Figure 44 Cathode 4426 and / or Figure 45A An example of the cathode 4500A and / or any other cathode disclosed in this disclosure. Figure 45B In the illustrated configuration, cathode 4500B may include current collector 4510, electrode film 4520B laminated on one side of current collector 4510, and electrode film 4530B laminated on the opposite side of current collector 4510. Electrode films 4520B and 4530B may be examples of a top-side electrode film 4520A and a bottom-side electrode film 4530A, respectively, and may also be formed from interconnecting aggregates 4532. In this way, when around axis AA' (for simplicity, Figure 45B When rolled up (not shown), membrane 4520B can form Figure 45A The top-side electrode film 4520A, and the film 4530B can be formed Figure 45A The bottom-side electrode film is 4530A. In Figure 45B In the process, the top-side electrode film 4520A and the bottom-side electrode film 4530A may have thicknesses denoted as "H1" and "H2", respectively. In some cases, thickness H1 and thickness H2 are the same. Furthermore, the thickness may be between 10 micrometers (μm) and 250 μm.

[0381] At least some interconnecting aggregates 4522 may have a shape that is relatively uniform with respect to each other. In some cases, the uniform shape may be spherical, elliptical, or other well-defined three-dimensional (3D) shapes that can be arranged in a closely packed orientation, for example, without gaps formed between adjacent examples of interconnecting aggregates 4532. In some other cases, the uniform shape may have pores 4524 formed and uniformly distributed between at least some interconnecting aggregates 4532. In this way, at least some pores 4524 may interconnect with each other to form one or more channels (for simplicity, ...). Figure 45B (Not shown in the image). Solvents, such as liquid substances, used to generate cathode 4500B may be exposed to the surrounding atmosphere, thereby drying and / or evaporating through channels during the slurry drying process of the top-side electrode film 4520B and the bottom-side electrode film 4530B. For example, channels may provide a defined path for the solvent to escape from cathode 4500B during slurry drying, thereby reducing or eliminating the development of uncontrolled drying-induced cracks between adjacent examples of interconnecting aggregates 4532.

[0382] Furthermore, the uniform distribution of pores 4524 corresponds to the uniform distribution of channels, allowing solvent to escape uniformly from the top-side electrode film 4520B and the bottom-side electrode film 4530B without creating drying-induced cracks between adjacent examples of interconnecting aggregates 4532. In some aspects, the top-side electrode film 4520B and the bottom-side electrode film 4530B can each be formed as a conductive matrix, wherein the formation of undesirable cracks or fractures within the matrix may compromise the structural conductivity of the cathode 4500B, resulting in a lower specific capacity value. The cathode 4500B can be produced with the desired structural conductivity having a relatively high areal loading for electroactive materials such as elemental sulfur, thanks to the more robust mechanical structure provided by various configurations of the interconnecting aggregates 4532. Additionally, at least some of the interconnecting aggregates 4532 can have flexural regions that increase flexibility relative to conventional carbonaceous materials. In this way, the cathode 4500B can be rolled up during the formation of the core 4420 without being subjected to tensile and / or compressive stresses sufficient to cause crack propagation and / or delamination, respectively.

[0383] Additionally, in some aspects, at least some interconnected agglomerates 4522 may have different diameters relative to each other. For example, the diameter of a given agglomerate may be determined based on the thickness (e.g., H1 and / or H2) of the film containing said agglomerates (e.g., top-side electrode film 4520B and / or bottom-side electrode film 4530B). In some aspects, relatively large agglomerates within film 4520B may be generated during the manufacturing process to have a size proportional to the thickness of top-side electrode film 4520B. For example, the size of a relatively large agglomerate 4522 may be one-fifth the thickness of film 4520B (“…”). 1 / 5”). Relatively small agglomerates 4522 may be generated during the manufacturing process to a size that is a fraction of the size of relatively large agglomerates. In some cases, the size of the relatively small agglomerates 4522 may be one-third the size of the relatively large agglomerates (“ 5”). 1 / 3”). In this way, the size ratio between relatively small aggregates and relatively large aggregates can be between 1:1 and 1:3.3.

[0384] Size differences between at least some of the interconnecting aggregates 4532 can help increase the packing density level of the aggregates within a defined volume. For example, relatively small aggregates can at least partially fill some of the pores 4524 between adjacent examples of interconnecting aggregates. In this way, the cathode 4500B can be produced as having an increased level of electroactive material (e.g., elemental sulfur) infiltrating the channels formed between aggregates of various sizes relative to conventional cathode constructions, which can be packed together at an increased density level, resulting in an increase in the specific capacity of the cathode 4500B. In addition, an approximate size ratio of 1:1 to 1:3.3 can result in relatively fewer connection points in each of the top-side electrode film 4520B and the bottom-side electrode film 4530B. Since stress concentration tends to accumulate at the connection points between the individual aggregates, fewer connection points in each of the top-side electrode film 4520B and the bottom-side electrode film 4530B can reduce the overall stress concentration level of the interconnecting aggregates 4532, especially in aggregates located away from the current collector 4510. In this way, the cathode 4500B can undergo increased flexural stress throughout the winding process without cracking or delamination, to form the core 4420.

[0385] Additionally, in some aspects, the cathode 4500B may have a cathode electroactive material embedded within each of the top-side electrode film 4520B and the bottom-side electrode film 4530B (for simplicity, Figure 3 (Not shown in the image). For example, the electroactive material may be infiltrated into various pores 4524 dispersed in at least some interconnect aggregates 4522. In some other aspects, each of the interconnect aggregates 4532 may include secondary particles (for simplicity, Figure 3 (not shown), wherein at least some of them can contact each other to jointly form a second porous structure having a second plurality of pores, the second plurality of pores being defined by the void space between adjacent secondary particles. The second plurality of pores (for simplicity, Figure 3 (not shown in the image) can be interconnected to provide one or more channels (for simplicity, Figure 3 (Not shown) is used for solvent escape. Therefore, the solvent can evaporate along these additional channels. These additional porosities can correspondingly reduce the tortuosity within the top-side electrode film 4520B and / or the bottom-side electrode film 4530B, thereby at least preventing the formation of drying-induced cracks in the cathode 4500B.

[0386] Figure 46 This shows the implementation methods. Figure 45B A micrograph of an exemplary electrode film 4600 of the cathode 4500B. The electrode film 4600 may be an example of a top-side electrode film 4520B and / or a bottom-side and / or 4530B, depicting at least some interconnected aggregates 4522 and pores 4524. Figure 46As shown, each interconnecting aggregate 4522 may be porous. In this way, in some cases, at least some interconnecting aggregates 4522 may comprise overlapping secondary carbonaceous particles (for simplicity, Figure 4 The second pore (not shown in the image) is generated (for simplicity, Figure 4 (Not shown in the text). Figure 46 The average size of the pores 4524 shown can be larger than the average size of the second pores. The second plurality of pores can be large enough to allow lithium ions (Li...) to pass through. + Ions and electrolytes can wet interconnected aggregates 4522 and reach the cathode electroactive material confined within multiple secondary particles.

[0387] Figure 47 This illustrates, based on some implementation methods, what can be used for manufacturing Figure 45A and Figure 45B Exemplary aggregates 4700 of the top-side electrode film 4520B and / or the bottom-side electrode film 4530B. Aggregate 4700 may be an example of one of the interconnecting aggregates 4532, shown as including porous particles 4710, a carbon layer 4720, and a functional layer 4730. Aggregate 4700 may have a spherical, elliptical, or other well-defined three-dimensional (3D) shape. In some cases, the shape of aggregate 4700 may facilitate interlocking with additional examples positioning aggregate 4700. That is, multiple examples of aggregate 4700 may be seamlessly interconnected to form any electrode disclosed in this disclosure. For example, in some aspects, aggregate 4700 may be deposited (e.g., spray-coated) onto... Figure 45A and Figure 45B On the current collector 4510. In some implementations, the agglomerate 4700 may have a diameter between 2 μm and 50 μm. In this way, multiple examples of agglomerates can be interconnected to, for example, form Figure 45B The top-side electrode film 4520B and / or the bottom-side electrode film 4530B. Additionally, due to the close-packed nature of the various examples of agglomerates 4700, the tortuosity of the top-side electrode film 4520B and / or the bottom-side electrode film 4530B may be relatively lower compared to conventional carbonaceous films. This low tortuosity can, in turn, provide a relatively direct pathway for the evaporation of solvents during the drying process used in battery manufacturing (for simplicity, Figure 47 (Not shown in the image). Additionally, the top electrode film 4520B and / or the bottom electrode film 4530B can withstand lower drying stress during the drying process due to their low torsion. In this way, lower drying stress can correspondingly prevent the formation of unwanted drying-induced cracks in the top electrode film 4520B and / or the bottom electrode film 4530B.

[0388] In some respects, particles 4710 can form aggregates of multiple interconnected secondary particles 4712. Furthermore, each secondary particle 4712 can form an aggregate of multiple primary particles (for simplicity, ...). Figure 5 (Not shown in the image). Each primary particle can be... Figure 8A An example of carbonaceous particles 800 Figure 9B Examples of interconnected aggregates 960 and / or similar entities described elsewhere herein. Each primary particle may include multiple grapheneized surfaces (e.g., exposed surfaces of graphene nanosheets adjacent to each other), comprising multiple carbon atoms. These carbon atoms may be covalently bonded to carbon atoms of adjacent primary particles (e.g., via sp...). 2 - Hybrid bond or sp 3 -Hybridized bonds) to co-form secondary particles 4712. In some cases, such as Figure 5 As shown, particle 4710 may be formed from a plurality of interconnected secondary particles 4712. A second plurality of pores 4714 may be defined by void spaces formed between adjacent secondary particles 4712. In some aspects, the secondary particles 4712 may overlap each other and create at least some void spaces between adjacent secondary particles 4712. Additionally, in some aspects, the second plurality of pores 4714 may be uniformly distributed throughout particle 4710. Alternatively, in some other aspects, the second plurality of pores 4714 may be aggregated in one or more regions within particle 4710. For example, the average size of the second plurality of pores 4714 may be smaller than [missing information]. Figure 46 The average size of the pores 4524. In addition to the second plurality of pores 4714, each secondary particle 4712 may have one or more peripheral pores 4716 located at or near the particle periphery, the size and / or location of which may be defined by, for example, a carbon dioxide etching process. Alternatively, other suitable processing techniques may be used to produce the peripheral pores 4716 and the particles 4710. For example, the particles 4710 may be formed by spray drying and / or by an atomization process and by other suitable solution-based methods.

[0389] Additionally, in some aspects, the carbon layer 4720 can conformally coat the exposed surface of the particles 4710 and at least partially immobilize the secondary particles 4712 to retain them within the particles 4710. The carbon layer 4720 can be prepared to avoid hindering the formation of ions such as lithium ions (Li ions) associated with battery discharge-charge operation cycles. + The transport of carbon layers 4720. In some respects, carbon layer 4720 can be formed from monolithic and 3D amorphous carbon-containing growths and / or structures. Furthermore, carbon layer 4720 can be composed of multiple layers of graphene, graphite, fullerene, carbon nanotubes, and / or carbon onions. interconnectionExample formation. The carbon layer 4720 serves to bind the contents of the agglomerate 4700 together, thereby increasing the mechanical robustness of the agglomerate 4700 relative to conventional carbonaceous materials (e.g., CNO). In this way, the agglomerate 4700 is also relatively more resistant to internal collapse relative to conventional carbonaceous materials, which may be caused by slurry casting and subsequent spray drying processes. The increased structural stiffness, hardness, and / or toughness of the agglomerate can facilitate the inclusion of electroactive materials with higher areal loading levels within the agglomerate 4700. In this way, the energy density of any currently disclosed core configuration incorporating the agglomerate 4700 can be relatively higher than, for example, the energy density of a battery using conventional cathode materials.

[0390] Additionally, the aggregate 4700 may further have a functional layer 4730 deposited on top of the carbon layer 4720. The functional layer 4730 may be coated along the outer edge of the carbon layer 4720, such that at least some of the second plurality of pores 4714 can be opened by the addition of the functional layer 4730. In some implementations, the functional layer 4730 may have a thickness of less than approximately 300 nm. In some implementations, the functional layer 4730 may be an ion-conducting layer configured to enhance the ion conductivity of the aggregate 4700. In some cases, the functional layer 4730 may contain one or more functional groups, one or more polar and ion-conducting additives, or combinations thereof. Examples of one or more polar and ion-conducting additives include lithium lanthanum zirconium oxide (LLZO), lithium phosphorus oxynitride (LIPON), or combinations thereof. Examples of one or more functional groups include amine groups, oxygen-containing groups, sulfur-containing groups, or any combination thereof.

[0391] Figure 48A This illustrates, based on some implementation methods, what can be used for manufacturing Figure 47 A micrograph of an exemplary secondary particle 4800A of the aggregate 4700. The secondary particle 4800A may be... Figure 47 An example of secondary particle 4712. As shown, secondary particle 4800A can be formed from primary particles 4802A, at least some of which may have carbon atoms covalently bonded to each other, for example, between adjacent secondary particles 4800A. In this way, in some aspects, secondary particle 4800A can be as follows: Figure 48A The chain or string-like structure shown. Alternatively, in some other aspects, the secondary particles 4800A can be formed into other 3D shapes, including multiple interconnected instances of primary particles 4802A, which may include graphite, graphene flakes, spherical fullerenes, carbon nanotubes, carbon nanotubes (CNO), and / or amorphous carbon. Each of the primary particles 4802A may have a diameter between about 50 nm and 100 nm and include nanoscale pores, each of which may have a diameter between 0 nm and about 25 nm. In this way, the electroactive material (for simplicity, Figure 48A(Not shown) can be microscopically confined within at least some nanoscale pores. For example, the electroactive material can constitute between 60 wt% and 90 wt% of the top-side electrode film 4520B and / or the bottom-side electrode film 4530B. The electroactive material can be elemental sulfur and / or other suitable sulfur-containing materials, such as lithium sulfide.

[0392] Figure 48B This illustrates, based on some implementation methods, what can be used for manufacturing Figure 47 A micrograph of another exemplary secondary particle 4800B of the aggregate 4700. Similar to secondary particle 4800A, secondary particle 4800B may comprise a plurality of primary particles 4802B covalently bonded together to form secondary particle 4800B. As shown, secondary particle 4800B may have a shape containing one or more branches, rather than a string or chain as shown in 4800A. In this way, the surface area of ​​secondary particle 4800B may be relatively larger than that of secondary particle 4800A. Therefore, the electroactive material residing within the multiple nanoscale pores of secondary particle 4800B can be relatively more exposed to the wetted Li+ ions and electrolyte during battery operation, thereby accelerating the desired electrochemical reactions of the battery.

[0393] Figure 49A and Figure 49BA flowchart illustrating an exemplary operation 4900 for manufacturing a cathode for a lithium-sulfur battery core, according to several implementations, is shown. In various implementations, operation 4900 may be performed in one or more reactors, which may include a thermal reactor chamber, a plasma reactor, a spray dryer, an atomizer, or any other suitable chemical processing apparatus. In some implementations, operation 4900 may be used to manufacture a cathode having 60 wt% and 90 wt% elemental sulfur or sulfur-containing electroactive material embedded in an electrode film formed by depositing multiple agglomerates on a current collector, each of which comprises multiple primary particles covalently bonded together to form multiple secondary particles, the multiple secondary particles being bonded together by a carbon layer, for example, as disclosed elsewhere in this disclosure. In some aspects, operation 4900 begins at block 4902, feeding multiple primary particles into a thermal reactor. Operation 4900 continues at block 4904, agglomerating the multiple primary particles into multiple secondary particles. Operation 4900 continues at box 4906, introducing one or more pores into a plurality of secondary particles. Operation 700 continues at box 4908, mixing the plurality of secondary particles with a first binder in a first solvent. Operation 4900 continues at box 4910, agglomerating the plurality of secondary particles into a plurality of aggregates, wherein the first binder is coated on each of the plurality of aggregates. Operation 4900 continues at box 4912, carbonizing the plurality of aggregates. Operation 4900 continues at box 4914, injecting sulfur into a plurality of nanoscale pores in each of the plurality of aggregates. Operation 4900 continues at box 4916, preparing a slurry comprising the plurality of aggregates and a second binder in a second solvent. Operation 4900 continues at box 4918, casting the slurry in film form onto a current collector surface. Operation 4900 continues at box 4920, removing the second solvent from the cast slurry.

[0394] In some implementations, the plurality of primary particles may include graphite, graphene sheets, spherical fullerenes, carbon nanotubes, carbon nanotubes (CNO), amorphous carbon, or any combination thereof. In some implementations, the plurality of primary particles may have a diameter between approximately 50 nm and 100 nm. In various implementations, each of the plurality of primary particles may have a plurality of nanoscale pores. The plurality of nanoscale pores may have a diameter between 0 nm and approximately 25 nm. In various implementations, the electroactive material may be confined within at least some of the plurality of nanoscale pores. In some cases, the electroactive material may be elemental sulfur. In other cases, the electroactive material may be other suitable sulfur-containing materials, such as lithium sulfide.

[0395] In some implementations, the first binder may include a polymeric material that can bond adjacent carbonaceous materials (e.g., graphene nanosheets) together as shown in the reference during the carbonization of multiple agglomerates in block 4912. Figure 47The one or more carbon layers. For example, the first adhesive may be polyacrylonitrile (PAN), bitumen, formaldehyde-based resin, or any combination thereof.

[0396] In various implementations, the aggregates may have spherical, elliptical, or other well-defined three-dimensional shapes, which, when cast onto a current collector, are adapted to leave gaps between adjacent aggregates. In some implementations, each of the aggregates may have a diameter between approximately 2 μm and approximately 50 μm.

[0397] Figure 49C A flowchart illustrating another exemplary operation for manufacturing a cathode for a winding core used in lithium-sulfur batteries, according to some implementations, is shown. In various implementations, [the following is possible:] Figure 7 In box 4912 of A, multiple aggregates are carbonized before operation 4930 is performed. In other implementations, operation 730 can be combined with... Figure 7 In block 4916 of B, a slurry comprising multiple agglomerates and a second binder is prepared simultaneously in a second solvent. For example, operation 730 begins at block 4932, coating each of the multiple agglomerates along the outer edge with a functional layer without clogging the multiple pores of each of the multiple agglomerates. In some implementations, the functional layer has a thickness of less than about 300 nm. In some implementations, the functional layer may be an ion-conducting layer. In some cases, functional layer 4730 may contain one or more functional groups, one or more polar and ion-conducting additives, or combinations thereof. Examples of one or more polar and ion-conducting additives include lithium lanthanum zirconium oxide (LLZO), lithium phosphorus oxynitride (LIPON), or combinations thereof. Examples of one or more functional groups include amine groups, oxygen-containing groups, sulfur-containing groups, or any combination thereof.

[0398] Figure 50A A flowchart illustrating exemplary operations for manufacturing a core for a lithium-sulfur battery, according to several other implementations, is shown. In various implementations, operation 5000 can be performed using any suitable winding machine or by hand to manufacture the core for the lithium-sulfur battery. In some implementations, operation 5000 can be used to wind a laminate containing an anode sheet, a first barrier layer, a cathode sheet, and a second barrier layer into a core having various cross-sectional shapes. In various implementations, operation 5000 begins at block 5002, stacking the first barrier layer on top of the anode sheet. Operation 5000 continues at block 5004, stacking the cathode sheet on top of the first barrier layer. Operation continues at block 5006, stacking the second barrier layer on top of the cathode sheet. Operation continues at block 5008, winding the laminate into a core. Operation continues at block 5010, inserting the core into a metal casing. Operation continues at block 5012, sealing the metal casing to obtain the core for the lithium-sulfur battery.

[0399] The first and second barrier layers may contain the same material and both serve as typical separators. In some other respects, the first and second barrier layers may contain different materials for specific purposes. For example, one barrier layer may serve as a typical separator, while the other may serve as a non-aqueous electrolyte membrane. Each of the first and second barrier layers may serve as a separator and a non-aqueous electrolyte membrane. The core may have a cross-section that is circular, rectangular, square, triangular, or any other geometry.

[0400] Figure 50B A flowchart illustrating another exemplary operation 5020 for manufacturing a wound Li-S battery according to some implementations is shown. In various implementations, operation 5020 may be... Figure 50A In box 5010, the core is inserted into the metal casing and then executed. In other implementations, operation 5020 can be combined with... Figure 50A One or more processes of exemplary operation 5000 are performed simultaneously. For example, operation 5020 begins at block 5022, adding an electrolyte to the core. In some implementations, the electrolyte may be a solid electrolyte, a polymer electrolyte, or other suitable non-aqueous electrolyte, which may be sandwiched within the laminate and subjected to winding. In other implementations, the electrolyte may be aqueous and may be added to the laminate before or after the winding process.

[0401] Figure 50C A flowchart illustrating another exemplary operation 5030 for manufacturing a winding core for lithium-sulfur batteries, according to some implementations, is shown. In various implementations, operation 5030 may be... Figure 8B The operation is performed after the electrolyte is added to the core in box 5022. In other implementations, operation 5030 can be combined with... Figure 50A One or more processes of exemplary operation 5000 are performed simultaneously. For example, operation 5030 begins at block 5032, soldering multiple batteries to one or more battery modules. Operation 5030 continues at block 5034, assembling the one or more battery modules into one or more battery packs.

[0402] Figure 51 The diagram illustrates a lithium-sulfur battery 5100 according to some implementations. The lithium-sulfur battery 5100 may be an example of one or more batteries and / or battery configurations disclosed herein, such as... Figure 1 100 batteries Figure 2 200 batteries Figure 28 2800 and / or Figure 42AThe battery 4200A. All aspects of this disclosure recognize that increased energy density (e.g., specific capacity) and reduced cell impedance are desirable characteristics in electrochemical cells. For example, replacing certain inactive cell components (e.g., anode tabs) with conductive materials can reduce the overall weight of the battery while also increasing the contact area between the anode current collector and the internal container surface of the cell, resulting in rapid current flow and / or power delivery. Removing the anode tabs, resulting in a "tabless" lithium-sulfur battery 5100, can also improve battery reliability because conventional anode tabs can be spot-welded to the cell container. Spot-welded areas are prone to overheating, thus accelerating battery degradation under normal and / or high-intensity use conditions. Carbonaceous materials 5160, for example... Figure 47 Particle 4710, Figure 8A Carbonaceous particles 800 and / or Figure 9B Multiple examples of aggregates 960 may be interconnected and positioned between the conductive components of the lithium-sulfur battery 5100 and the anode container 5122 to replace conventional anode tabs welded to the battery canister. In some cases, various components of the carbonaceous material 5160 may be coated onto the entire bottom-facing surface of the core 5190. Furthermore, certain components may be selected to be included in the carbonaceous material 5160 to increase its flexibility and / or elasticity. In this way, the carbonaceous material 5160 can be produced as a relatively compressible and responsive contact area compared to conventional adhesives and / or conductive anode adhesives.

[0403] Compared to spot welding or contact welding, and some conductive epoxy resin materials filled with metal sheets, the use of carbonaceous material 5160 can lead to a lithium-sulfur battery 5100 with an electrical load (for simplicity, Figure 51 The contact resistance between (not shown) is low. In some aspects, the carbonaceous material 5160 may be formed from a first carbon component and a second carbon component. The first carbon component and the second carbon component are combined into a homogeneous mixture (for simplicity, Figure 51 (Not shown in the image) The carbonaceous material 5160 can be formed as an adhesive layer by cross-linking the carbon atoms in each of the first and second carbon components. In this way, a dual-purpose region and / or layer capable of both conductivity and adhesion can be created and realized within the lithium-sulfur battery 5100. Furthermore, in some aspects, the carbonaceous material 5160 can be formed by combining various carbon allotropes with each other (for simplicity, ...). Figure 51 (Not shown in the image).

[0404] At least some carbon allotropes of carbonaceous material 5160 may include surfaces functionalized with amine-containing groups. These carbon allotropes may be blended with other carbon allotropes, which may be functionalized with epoxy groups and / or thermal crosslinking agents. In some implementations, the thermal crosslinking agent may be any suitable thermal crosslinking agent and / or crosslinking compound, fraction, radical initiator, and / or high-energy environment disclosed herein. Any carbon allotropes may be controlled in terms of density, porosity, and thermal conductivity to provide desired physical, chemical, and / or mechanical properties and / or characteristics. In this way, carbonaceous material 5160 may have increased mechanical robustness, flexibility, and electronic conductivity compared to conventional viscous and / or conductive materials.

[0405] In some aspects, the lithium-sulfur battery 5100 may include a core 5190, which may be formed as one or more cell types, such as 18650, 26650, and / or 21700 cells. The core 5190 of the lithium-sulfur battery 5100 may include an anode 5122 (e.g., formed without an anode tab), a solid electrolyte interphase (SEI) 5104 formed on the anode 5102, a protective layer 5110, a cathode 5140, and a separator 5130 located between the cathode 5140 and the anode 5102. In one implementation, the anode 5122 may be formed from a single solid layer of metallic lithium with a thickness between 60 micrometers (μm) and 85 μm. Furthermore, the protective layer 5110 may have a thickness between 2 μm and 5 μm and may act as a natural insulator, preventing internal short circuits within the lithium-sulfur battery 5100 by blocking adhesive materials (e.g., carbonaceous material 5160) from penetrating into the separator 5130. Furthermore, in some aspects, the separator 5130 may be configured such that the porosity at the edge of the core 5190 (e.g., near the cathode cap 5180 or anode container 5122) differs from the porosity of the separator 5130 adjacent to the central region of the anode 5102 and / or cathode 5140. In one implementa...

Claims

1. A lithium-sulfur battery comprising: a cap circumferentially welded to a cylindrical housing; a cylindrical jellyroll comprising: an anode comprising one or more of lithium or lithium-containing alloys; and a cathode comprising one or more structured layers of agglomerates of carbonaceous particles disposed on opposite sides of a cathode current collector; a negative terminal disposed along a length of the cylindrical housing and longitudinally welded to the anode current collector, wherein the negative terminal is partially exposed outside the housing; and a positive terminal comprising a mandrel, longitudinally welded to the cathode current collector, and separated from the housing by an insulator, wherein the agglomerates of carbonaceous particles in the one or more structured layers disposed on the cathode current collector have substantially similar sizes and are characterized by an average agglomerate size, and the average size of the agglomerates in the one or more structured layers disposed on a side of the cathode current collector facing the housing is greater than the average size of the agglomerates in the one or more structured layers disposed on a side of the cathode current collector facing the mandrel.

2. The lithium-sulfur battery of claim 1, further comprising a separator disposed between the anode and the cathode.

3. The lithium-sulfur battery of claim 2, wherein the separator comprises a ceramic-containing material.

4. The lithium-sulfur battery of claim 1, wherein the negative terminal is formed of nickel.

5. The lithium-sulfur battery of claim 1, wherein the anode further comprises an anode protection layer disposed on the anode and configured to protect the anode from lithium corrosion.

6. The lithium-sulfur battery of claim 5, wherein the anode protection layer comprises one or more of: a polymer network comprising one or more layers of carbonaceous material grafted with fluorinated polymers crosslinked to each other, carbonaceous material, or fluorinated poly(meth)acrylate.

7. The lithium-sulfur battery of claim 1, wherein a cathode loading associated with the cathode is at least 7 mg / cm 2 .

8. The lithium-sulfur battery of claim 1, wherein a ratio of the reversible capacity of the anode (mAh) to the reversible capacity of the cathode (N / P ratio) is between 2 and 4.

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