Battery compositions using biogenic anode materials

Abstract

Herein discussed is a method of making an anode, including a) providing rice hull ash (RHA) and treating the RHA with an alkali solution to dissolve silica in the RHA, b) washing the treated RHA with water to remove the dissolved silica and alkali solution to produce silica depleted RHA (SDRHA), c) drying the SDRHA, and d) incorporating the dried SDRHA into the anode. Further discussed is an electrochemical device including an anode, a cathode, and an electrolyte, wherein the anode includes silica depleted rice hull ash (SDRHA), wherein the electrolyte includes at least one sulfonamide solvent and a salt substantially dissolved in the solvent, wherein the sulfonamide solvent has a formula R1-SO2- N-R2R3 wherein Ri is selected from the group consisting of -F, -CF3, -N(CH3)2, and - NCH2CH3, and wherein each of R2 and R3 is selected from the group consisting of -H, -CH3, and -CH2CH3.

Description

Atty. Dkt. No. 142193-0129EM2408PCTBATTERY COMPOSITIONS USING BIOGENIC ANODE MATERIALS CROSS-REFERENCE TO RELATED APPLICATION

[0001] The present application claims the benefit of priority to U. S. Provisional Application No. 63 / 721,174 filed November 15, 2024, the entire contents of which are incorporated herein by reference.TECHNICAL FIELD

[0002] The present disclosure relates generally to battery compositions. More specifically, the present disclosure relates to battery compositions utilizing biogenic anode materials.BACKGROUND

[0003] Lithium-ion batteries (LIBs) can be pivotal for energy storage technologies, powering everything from portable electronics to electric vehicles (EVs) and grid storage solutions.SUMMARY

[0004] At least one aspect of the present disclosure is directed to a method of making an anode. The method can include a) providing rice hull ash (RHA) and treating the RHA with an alkali solution to dissolve silica in the RHA, b) washing the treated RHA with water to remove the dissolved silica and alkali solution to produce silica depleted RHA (SDRHA), c) drying the SDRHA, and d) incorporating the dried SDRHA into the anode. In an embodiment, expansion of the anode during use is no greater than 10% per cycle or no greater than 2% per cycle or no greater than 1% per cycle. In an embodiment, the SDRHA from step b) is treated with an acid and washed again before step c). In an embodiment, pH of the SDRHA from step b) is adjusted before step c). In an embodiment, the SDRHA includes 40-60 wt% of silica and 60-40 wt% of hard carbon. In an embodiment, alkali treatment takes place at a temperature of no greater than 80 °C or no greater than 60 °C or at room temperature. In an embodiment, alkali treatment takes place at a temperature of no less than 600 °C. In an embodiment, at least a portion of the alkali solution and dissolved silica is removed from the treated RHA between step a) and step b).

[0005] Further discussed herein is an electrochemical device that includes an anode, a cathode, and an electrolyte. The anode can include silica depleted rice hull ash (SDRHA). The electrolyte can include at least one sulfonamide solvent and a salt substantially dissolved14908-9576-9715.2Atty. Dkt. No. 142193-0129EM2408PCTin the solvent. The sulfonamide solvent can have a formula R1-SO2-N-R2R3. R1 can be selected from the group consisting of -F, -CF3, -N(CH3)2, and -NCH2CH3. Each of R2 and R3 can be selected from the group consisting of -H, -CH3, and -CH2CH3.

[0006] In an embodiment, the salt is selected from the group consisting of lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), lithium hexafluorophosphate (LiPF6), lithium perchlorate (LiClO4), lithium tetrafluoroborate (LiBF4), lithium triflouromethanesulfonate or lithium tritiate (LiTF), lithium bis(pentafluoroethanesulfonyl)imide (LiBETI), lithium tetracyanoborate (LiB(CN)4), lithium bis(oxalato)borate (LiBOB), lithium difluorooxalatoborate (LiDFOB), sodium bis(fluorosulfonyl)imide (NaFSI), sodium bis(trifluoromethylsulfonyl)imide (NaTFSI), sodium hexafluorophosphate (NaPF6), sodium perchlorate (NaClO4), sodiumtetrafluorob orate (NaBF4), sodium triflouromethanesulfonate or sodium tritiate (NaTF), sodium bis(pentafluoroethanesulfonyl)imide (NaBETI), sodium tetracyanoborate (NaB(CN)4), sodium bis(oxalato)borate (NaBOB), sodium difluorooxalatoborate (NaDFOB), and combinations thereof.

[0007] In an embodiment, the sulfonamide solvent includes N, N-dimethyltrifluoromethanesulfonamide (DMTMSA), N, N-dimethylsulfamoyl fluoride (DMSF), N-ethyl-N-methyl sulfamoyl fluoride (EMSF), N-methyl sulfamoyl fluoride (MSF), bis(2-methoxyethyl)sulfamoyl fluoride (BMSF), diethyl sulfamoyl fluoride (DESF) is, or N-butyl-N, N 0, N 0-trimethylsulfamide (BTMSA). In an embodiment, the electrolyte includes a cosolvent. The cosolvent can include dimethyl sulfoxide (DMSO), Ethyl methyl carbonate (EMC), Dimethyl carbonate (DMC), Diethyl carbonate (DEC), Ethyl Methyl Sulfone (EMS), ethylene glycol diethyl ether (DEE), or fluorinated ether. In an embodiment, the salt is LiFSI. LiFSI can have a molality in the solvent in the range of from 0.5 to 5 or from 0.8 to 3 or from 0.9 to 2. Molality can be defined as moles of solute divided by weight of solvent in kg. In an embodiment, the salt includes NaFSI, NaPF6, LiFSI, LiPF6, or any combination thereof.

[0008] In an embodiment, the electrolyte includes at least one selected from the group consisting of N-Ethyl-N-methyl sulfamoyl fluoride (EMSF), dimethoyxethane (DME), Tetrahydrofuran (THF), l,l,2,2-Tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), 1,1,2,2-Tetrafluoroethyl 2,2,2-Trifluoroethyl Ether (TFTFE), 1,2-di ethoxy ethane (DEE), piperidine trifluoromethanesulfonamide (PIP-TMSA), Trifluoroethyl ether(TFE), Trifluoroethyl methyl ether (TMF), N-Butyl-N-24908-9576-9715.2Atty. Dkt. No. 142193-0129EM2408PCTmethylpyrrolidinium (Pyrl4), Trifluorotoluene (PhCF3), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), Dimethyl carbonate (DMC), fluoroethylene carbonate (FEC), fluorinated ethers, and combinations thereof.

[0009] In an embodiment, the electrolyte additionally includes at least one of: fluoroethylene carbonate (FEC), Methyl 2,2,2-trifluoroethyl carbonate (FEMC), 1, 1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), prop- 1-ene- 1,3 -sulfone (PST), propyl propionate (PP), 1,3,6-hexane trinitrile (HTCN), vinylene carbonate (VC), ethylene carbonate (EC), sodium bis(oxalato)borate (NaBOB), lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), sodium difluoro(oxalato)borate (NaDFOB), sodium tetrafluorooxalatophosphate (NaTFOP), lithium tetrafluorooxalatophosphate (LiTFOP), sodium difluorodioxalatophosphate (NaDFOP), lithium difluorodioxalatophosphate (LiDFOP), Dioxathiolane 2,2-dioxide (DTD), tris(trimethylsilyl)phosphite (TMSPi), tris(trimethylsilyl)phosphate (TMSPa), tris(trimethylsilyl)borate (TMSB).

[0010] In an embodiment, the SDRHA includes 40-60 wt% of silica and 60-40 wt% of hard carbon. In an embodiment, the cathode includes a layered oxide, apolyanion, Lithium Nickel Manganese Cobalt Oxide (NMC), Lithium Iron Phosphate (LFP), Lithium-and-Manganese-Rich (LMR), Lithium Manganese Iron Phosphate (LMFP), Lithium Cobalt Oxide (LCO), sodium cobalt oxide (NaCoO2), sodium nickel manganese oxide (NaNiMnCoO2), sodium iron phosphate (Na2FePO4), sodium iron fluorophosphate (Na2FePO4F), sodium vanadium phosphate (NaVPO4), prussian blue analogue, iron based Prussian white (Na2-xFeFe(CN)6), sodium manganese iron phosphate (Na2MnxFei-xPO4), sodium manganese rich (SMR, or manganese rich sodium), sodium manganese oxide (Na2Mn2O4), sodium cobalt oxide (Na2CoO2), sodium iron phosphate-pyrophosphate (NaFPP), or combinations thereof.

[0011] In an embodiment, the device is configured to operate at a voltage of no less than 3.4V, or no less than 3.8V, or no less than 4.0V, or no less than 4.1V, or no less than 4.3V, or no less than 4.5V. In an embodiment, the device is configured to operate at a voltage of up to 4.5 V, or up to 4.3 V, or up to 4.2V, or up to 4.0V, or up to 3.8 V, or up to 3.4V with a coulombic efficiency above 99%. In an embodiment, the device is configured to operate at a temperature in the range of from -30 degrees C to 65 degrees C. In an embodiment, the device is configured to retain at least 80% capacity after 500 cycles, or after 1000 cycles, or after 2000 cycles, or after 5000 cycles at ambient temperature.34908-9576-9715.2Atty. Dkt. No. 142193-0129EM2408PCT

[0012] In an embodiment, no component comprising more than 10 vol% of the solvent has a dielectric constant greater than 50 at 25°C. In an embodiment, the specific capacity ratio of the anode to the specific capacity ratio of the cathode is from 0.9 to 2.0, or from 1.01 to 1.5, or from 1.05 to 1.2. In an embodiment, the device has an initial coulombic efficiency of no less than 80%, or no less than 90%, or no less than 99%.

[0013] In an embodiment, the standard reduction potential of the solvent is no greater than 0 V, or no greater than -0.1 V, or no greater than -0.2 V. In an embodiment, the standard oxidation potential of the solvent is no less than 5.5 V, or no less than 5.75 V, or no less than 6 V. In an embodiment, the device has a maximum electrostatic potential of no less than 1 eV, or no less than 1.1 eV, or no less than 1.2 eV. In an embodiment, the device has a minimum electrostatic potential of no less than -1.4 eV, or no less than -1.3 eV. In an embodiment, the donor number of the solvent is in the range of from 10 kcal / mol to 30 kcal / mol, or from 15 kcal / mol to 20 kcal / mol. In an embodiment, expansion of the anode during use is no greater than 10% per cycle or no greater than 2% per cycle or no greater than 1% per cycle.

[0014] Another aspect of the present disclosure is directed to a method of making an electrochemical device. The method can include providing an anode, a cathode, and an electrolyte. The anode can include silica depleted rice hull ash (SDRHA). The electrolyte can include at least one sulfonamide solvent and a salt substantially dissolved in the solvent. The sulfonamide solvent can have a formula R1-SO2-N-R2R3. R1 can be selected from the group consisting of -F, -CF3, -N(CH3)2, and -NCH2CH3. Each of R2 and R3 can be selected from the group consisting of -H, -CH3, and -CH2CH3.

[0015] Another aspect of the present disclosure is directed to a method of using an electrochemical device. The method can include providing an anode, a cathode, and an electrolyte. The anode can include silica depleted rice hull ash (SDRHA). The electrolyte can include at least one sulfonamide solvent and a salt substantially dissolved in the solvent. The sulfonamide solvent can have a formula R1-SO2-N-R2R3. Ri can be selected from the group consisting of -F, -CF3, -N(CH3)2, and -NCH2CH3. Each of R2 and R3 can be selected from the group consisting of -H, -CH3, and -CH2CH3. In an embodiment, expansion of the anode during use is no greater than 10% per cycle or no greater than 2% per cycle or no greater than 1% per cycle.44908-9576-9715.2Atty. Dkt. No. 142193-0129EM2408PCT

[0016] Those skilled in the art will appreciate that the summary is illustrative only and is not intended to be in any way limiting. Other aspects, inventive features, and advantages of the devices and / or processes described herein, as defined solely by the claims, will become apparent in the detailed description set forth herein and taken in conjunction with the accompanying drawings.DETAILED DESCRIPTION

[0017] Following below are more detailed descriptions of various concepts related to, and implementations of, methods, apparatuses, and systems for battery compositions using biogenic anode materials. The various concepts introduced above and discussed in greater detail below may be implemented in any of a number of ways, as the described concepts are not limited to any particular manner of implementation. Examples of specific implementations and applications are provided primarily for illustrative purposes.

[0018] The dominance of lithium-ion batteries can be attributed to high energy density, long cycle life, and relatively low self-discharge rates. These batteries can utilize graphite anodes or incorporate silicon into anode materials. Silicon-graphite anodes can offer substantial improvements in energy density but also present significant challenges, such as mechanical degradation and poor coulombic efficiency. Some strategies to develop high-performance silicon-based anodes for next-generation batteries can focus on managing volume expansion and enhancing efficiency. These advancements have the potential to move the industry closer to making silicon-dominant anodes commercially viable for a wide range of applications, such as electric vehicles and consumer electronics.

[0019] There is a need and interest to develop improved energy storage devices. The present disclosure is directed to battery compositions that enable the use of biogenic silicon materials in anodes and that enhance battery performances, such as operating voltages and battery capacities after many cycles.

[0020] Overview. In recent years, silica (SiO2) has emerged as a promising material for use in anodes for lithium-ion batteries due to its high theoretical capacity for lithium storage, significantly higher than traditional graphite-based anodes. Silicon (Si, the reduced form of silica) can theoretically store 3579 mAh / g, much higher than graphite's 372 mAh / g. However, despite its potential, silicon-based anodes can face significant challenges that limit their practical use, particularly mechanical degradation and poor coulombic efficiency as detailed below.54908-9576-9715.2Atty. Dkt. No. 142193-0129EM2408PCT

[0021] Mechanical Degradation due to Volume Expansion: One of the biggest obstacles in using silica or silicon anodes is the extreme volume expansion that occurs during lithiation (e.g., when lithium ions enter the material during battery charging). Silicon, when alloying with lithium, can expand up to 300%. This large expansion and contraction during charge / discharge cycles can lead to mechanical stress, cracking, and pulverization of the silicon structure. As a result, the can anode lose its structural integrity, leading to poor cycle life and a rapid decline in battery capacity.

[0022] Poor Coulombic Efficiency: Coulombic efficiency, which refers to the ratio of the charge output to the charge input in each cycle, can be crucial for long-lasting batteries. Silicon-based anodes can exhibit low initial coulombic efficiency (e.g., below 50%) because a significant portion of the lithium can be consumed to form a solid electrolyte interphase (SEI) layer on the anode surface during the first few cycles. This SEI layer can stabilize the surface but can be continually destroyed and reformed due to the volume changes in silicon, leading to lithium loss and lower efficiency over time.

[0023] A first strategy to overcome these issues can include (1) Lower Silica Content Mixed with Graphite. This approach can include blending silica with graphite to leverage the benefits of both materials. By using a lower content of silica, the anode can benefit from its higher capacity without suffering from extreme mechanical degradation. Graphite, with its stable cycling performance, can mitigate the volume expansion problem by acting as a buffer material. This hybrid material can show improved cycle stability and better overall performance, though it can come with a trade-off in terms of energy density, as the capacity can be diluted by the graphite content.

[0024] A second strategy to overcome these issues can include (2) Nano-Structuring and Coating, Some of the most advanced solutions can involve nano-engineering the silica or silicon particles. Silicon can be encapsulated in materials like graphite or carbon at the nanoscale to help manage volume expansion. Another approach is Graphite Coating. By coating silicon or silica nanoparticles with a layer of graphite, a protective barrier can be created that prevents direct exposure of the silicon to the electrolyte, thereby reducing SEI formation and preserving lithium. The graphite can also help to distribute the stress from expansion more evenly, reducing cracking and mechanical degradation. Additionally, nanoscale engineering can reduce the size of silica or silicon particles to the nanoscale that allows for better accommodation of volume changes. Nanoscale particles can expand more uniformly and can be less prone to cracking than bulk silicon. Furthermore, smaller particles64908-9576-9715.2Atty. Dkt. No. 142193-0129EM2408PCTcan have shorter diffusion paths for lithium ions, which can improve reaction kinetics and enhance battery performance. For example, silicon-dominant anode materials can replace graphite with a composite that uses nano-structured silicon particles. This methodology can enhance energy density while maintaining stability during cycling. Similarly, a silicon-carbon composite can reduce the mechanical degradation and improve the lifetime of lithium-ion batteries.

[0025] A third strategy to overcome these issues can include (3) Advanced Binders and Electrolytes. Another strategy to address mechanical degradation can include using advanced binders and optimized electrolytes. Binders can hold the anode material together, and polymers can stretch and accommodate the expansion of silicon. Electrolytes can be engineered to form more stable SEI layers that can tolerate volume changes, reduce capacity¬ fade, and improve coulombic efficiency.

[0026] The anode material (e.g., carbon and silicon, silicon carbide, SiC) can be derived from biogenic sources, such as sugarcane bagasse or agricultural residues. These materials for anodes can be renewable and inexpensive, which are applicable in lithium-ion batteries or sodium-ion batteries. For example, biogenic SiO2 can be converted to silicon (Si) through a reduction process. As an example, rice husk ash (RHA) can be used for obtaining such biogenic materials. Unlike the strategies discussed above, the anodes made from RHA are less costly and less complicated to produce.

[0027] Method of Making Biogenic Anode Materials. Rice hull ash (RHA) can include silica and hard carbon. RHA can be produced from rice hulls that are burned in a furnace or incinerator at a temperature of 600-800 °C. This heat treatment (e.g., pyrolysis) can produce hard carbon in RHA. In an embodiment, RHA is processed to produce carbon and silica as biogenic materials for battery anodes. In an embodiment, RHA is washed / activated with potassium hydroxide (KOH) or sodium hydroxide (NaOH) to activate carbon (e.g., alkali treatment or alkali washing of RHA). KOH or NaOH can act as an activating agent that increases the surface area and porosity of the carbon by creating pores in the carbon structure. This makes the material more suitable for applications like energy storage. In an embodiment, washing RH / X with KOH helps remove impurities such as silica and other unwanted materials from the ash, leaving behind hard carbon at a higher content in the product. This product is silica depleted rice hull ash (SDRHA). In various embodiments, silica depleted rice hull ash (SDRHA) is obtained from RHA, which includes, for example,74908-9576-9715.2Atty. Dkt. No. 142193-0129EM2408PCT45-60 wt% silica and 55-40 wt% carbon. Because of the molecular weight difference, the SDRHA composition translates into a very high-volume fraction of hard carbon.

[0028] In various embodiments, chemical activation with KOH or NaOH washing improves the electrical conductivity of the resulting carbon material, making it suitable for electrochemical applications. In various embodiments, the washing process also alters the structure of the carbon, creating a disordered carbon matrix that is characteristic of hard carbon, useful in applications like sodium-ion batteries. In an embodiment, washing RHA with an alkali solution does not completely remove silica. However, this treatment step can play a role in altering the structure of the silica and enhancing the extraction of carbon.

[0029] In an embodiment, KOH treatment reacts with silica (SiO2) in the RHA, but it does not remove silica entirely. In an embodiment, KOH treatment causes dissolution of some of the silica, which outcome depends on the temperature, concentration of KOH, and treatment time. In various embodiments, KOH reacts with silica to form potassium silicate (K2SiO3), which is then dissolved in water and washed away, reducing the silica content in the ash. In some embodiments, additional silica removal is performed using acid treatment (e.g., with HC1).

[0030] In various embodiments, the alkali treatment and washing of RHA produces SDRHA, which includes 40 wt%-60 wt% silica with the remainder being hard carbon. In various embodiments, the alkali treatment and washing and acid treatment of RHA produces SDRHA, which includes 40 wt%-60 wt% silica with the remainder being hard carbon. Silica and hard carbon are mixed at a very fine scale in the SDRHA. In various embodiments, the thus produced SDRHA is suitable for making biogenic anodes. Hard carbon produced from RHA can be applicable in sodium-ion batteries and sometimes lithium-ion batteries because of its ability to store energy efficiently. The high surface area and porosity from KOH activation improve the capacity for ion storage. In addition, such activated hard carbon is also applicable in supercapacitors due to its high surface area, which allows for rapid charge and discharge cycles.

[0031] In an embodiment, RHA includes more than 80 wt% or 90 wt% of silica, but after alkali treatment / washing, the silica content is no more than 60 wt% or no more than 50 wt% or no more than 40 wt%, which means the carbon content is no less than 70 vol% or no less than than 80 vol% or no less than 90 vol%. Such carbon content in the SDRHA can limit expansion of silica during use as a battery anode. In various embodiments, expansion of this84908-9576-9715.2Atty. Dkt. No. 142193-0129EM2408PCTanode is no greater than 10% or no greater than 2% or no greater than 1% per cycle, making it mechanically stable and robust.

[0032] In an embodiment, RHA is washed with potassium hydroxide or sodium hydroxide solution and then washed with water (or steam) to produce SDRHA In various embodiments, alkali treatment / washing is performed at room temperature or at a temperature of no greater than 80 °C or no greater than 60 °C. In an embodiment, alkali treatment takes place at a temperature of no less than 600 °C. Water or steam is then used to wash away the alkali solution. In some embodiments, the pH of the remaining product is adjusted. The produced SDRHA is dried at a temperature of no greater than 100 °C or no greater than 250 °C or no greater than 600 °C. The dried SDRHA can then be used to make anodes.

[0033] Battery Compositions. An electrolyte that includes a solvent that includes N, N-dimethyltrifluoromethane-sulfonamide (DMTMSA, i.e., C3H6F3NO2S) orDimethyl sulfamoyl fluoride (DMSF, i.e., FSO2NC2H6) can enable the use of biogenic anode materials (e.g., SDRHA and the alike) in batteries and mitigates many associated challenges.

[0034] In an embodiment, a method of making an anode includes a) providing rice hull ash (RHA) and treating the RHA with an alkali solution to dissolve silica in the RHA, b) washing the treated RHA with water to remove the dissolved silica and alkali solution to produce silica depleted RHA (SDRHA), c) drying the SDRHA, and d) incorporating the dried SDRHA into the anode. In an embodiment, expansion of the anode during use is no greater than 10% per cycle or no greater than 2% per cycle or no greater than 1% per cycle. In an embodiment, the SDRHA from step b) is treated with an acid and washed again before step c). In an embodiment, pH of the SDRHA from step b) is adjusted before step c). In an embodiment, the SDRHA includes 40-60 wt% of silica and 60-40 wt% of hard carbon. In an embodiment, alkali treatment takes place at a temperature of no greater than 80 °C or no greater than 60 °C or at room temperature. In an embodiment, alkali treatment takes place at a temperature of no less than 600 °C. In an embodiment, at least a portion of the alkali solution and dissolved silica is removed from the treated RHA between step a) and step b).

[0035] Further discussed herein is an electrochemical device that includes an anode, a cathode, and an electrolyte. The anode can include silica depleted rice hull ash (SDRHA). The electrolyte can include at least one sulfonamide solvent and a salt substantially dissolved in the solvent. The sulfonamide solvent can have a formula R1-SO2-N-R2R3. Ri can be94908-9576-9715.2Atty. Dkt. No. 142193-0129EM2408PCTselected from the group consisting of -F, -CF3, -N(CH3)2, and -NCH2CH3. Each of R2 and R3 can be selected from the group consisting of -H, -CEE, and -CH2CH3.

[0036] In an embodiment, the salt is selected from the group consisting of lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), lithium hexafluorophosphate (LiPF6), lithium perchlorate (LiClO4), lithium tetrafluoroborate (LiBF4), lithium triflouromethanesulfonate or lithium tritiate (LiTF), lithium bis(pentafluoroethanesulfonyl)imide (LiBETI), lithium tetracyanoborate (LiB(CN)4), lithium bis(oxalato)borate (LiBOB), lithium difluorooxalatoborate (LiDFOB), sodium bis(fluorosulfonyl)imide (NaFSI), sodium bis(trifluoromethylsulfonyl)imide (NaTFSI), sodium hexafluorophosphate (NaPF6), sodium perchlorate (NaClO4), sodiumtetrafluorob orate (NaBF4), sodium triflouromethanesulfonate or sodium tritiate (NaTF), sodium bis(pentafluoroethanesulfonyl)imide (NaBETI), sodium tetracyanoborate (NaB(CN)4), sodium bis(oxalato)borate (NaBOB), sodium difluorooxalatoborate (NaDFOB), and combinations thereof.

[0037] In an embodiment, the sulfonamide solvent includes N, N-dimethyltrifluoromethanesulfonamide (DMTMSA), N, N-dimethylsulfamoyl fluoride (DMSF), N-ethyl-N-methyl sulfamoyl fluoride (EMSF), N-methyl sulfamoyl fluoride (MSF), bis(2-methoxyethyl)sulfamoyl fluoride (BMSF), diethyl sulfamoyl fluoride (DESF) is, or N-butyl-N, N 0, N 0-trimethylsulfamide (BTMSA). In an embodiment, the electrolyte includes a cosolvent. The cosolvent can include dimethyl sulfoxide (DMSO), Ethyl methyl carbonate (EMC), Dimethyl carbonate (DMC), Diethyl carbonate (DEC), Ethyl Methyl Sulfone (EMS), ethylene glycol diethyl ether (DEE), or fluorinated ether. In an embodiment, the salt is LiFSI. LiFSI can have a molality in the solvent in the range of from 0.5 to 5 or from 0.8 to 3 or from 0.9 to 2. Molality can be defined as moles of solute divided by weight of solvent in kg. In an embodiment, the salt includes NaFSI, NaPF6, LiFSI, LiPF6, or any combination thereof.

[0038] In an embodiment, the electrolyte includes at least one selected from the group consisting of N-Ethyl-N-methyl sulfamoyl fluoride (EMSF), dimethoyxethane (DME), Tetrahydrofuran (THF), l,l,2,2-Tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), 1,1,2,2-Tetrafluoroethyl 2,2,2-Trifluoroethyl Ether (TFTFE), 1,2-di ethoxy ethane (DEE), piperidine trifluoromethanesulfonamide (PIP-TMSA), Trifluoroethyl ether(TFE), Trifluoroethyl methyl ether (TMF), N-Butyl-N-methylpyrrolidinium (Pyrl4), Trifluorotoluene (PhCF3), ethyl methyl carbonate (EMC),104908-9576-9715.2Atty. Dkt. No. 142193-0129EM2408PCTdiethyl carbonate (DEC), Dimethyl carbonate (DMC), fluoroethylene carbonate (FEC), fluorinated ethers, and combinations thereof.

[0039] In an embodiment, the electrolyte additionally includes at least one of: fluoroethylene carbonate (FEC), Methyl 2,2,2-trifluoroethyl carbonate (FEMC), 1, 1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), prop-l-ene-l,3-sultone (PST), propyl propionate (PP), 1,3,6-hexane trinitrile (HTCN), vinylene carbonate (VC), ethylene carbonate (EC), sodium bis(oxalato)borate (NaBOB), lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), sodium difluoro(oxalato)borate (NaDFOB), sodium tetrafluorooxalatophosphate (NaTFOP), lithium tetrafluorooxalatophosphate (LiTFOP), sodium difluorodi oxalatophosphate (NaDFOP), lithium difluorodi oxalatophosphate (LiDFOP), Dioxathiolane 2,2-dioxide (DTD), tris(trimethylsilyl)phosphite (TMSPi), tris(trimethylsilyl)phosphate (TMSPa), tris(trimethylsilyl)borate (TMSB).

[0040] In an embodiment, the SDRHA includes 40-60 wt% of silica and 60-40 wt% of hard carbon. In an embodiment, the cathode includes a layered oxide, apolyanion, Lithium Nickel Manganese Cobalt Oxide (NMC), Lithium Iron Phosphate (LFP), Lithium-and-Manganese-Rich (LMR), Lithium Manganese Iron Phosphate (LMFP), Lithium Cobalt Oxide (LCO), sodium cobalt oxide (NaCoO2), sodium nickel manganese oxide (NaNiMnCoO2), sodium iron phosphate (Na2FePO4), sodium iron fluorophosphate (Na2FePO4F), sodium vanadium phosphate (NaVPO4), prussian blue analogue, iron based Prussian white (Na2-xFeFe(CN)6), sodium manganese iron phosphate (Na2MnxFei-xPO4), sodium manganese rich (SMR, or manganese rich sodium), sodium manganese oxide (Na2Mn2O4), sodium cobalt oxide (Na2CoC>2), sodium iron phosphate-pyrophosphate (NaFPP), or combinations thereof.

[0041] In an embodiment, the device is configured to operate at a voltage of no less than 3.4V, or no less than 3.8V, or no less than 4.0V, or no less than 4. IV, or no less than 4.3V, or no less than 4.5V. In an embodiment, the device is configured to operate at a voltage of up to 4.5 V, or up to 4.3 V, or up to 4.2V, or up to 4.0V, or up to 3.8 V, or up to 3.4V with a coulombic efficiency above 99%. In an embodiment, the device is configured to operate at a temperature in the range of from -30°C to 65°C. In an embodiment, the device is configured to retain at least 80% capacity after 500 cycles, or after 1000 cycles, or after 2000 cycles, or after 5000 cycles at ambient temperature.114908-9576-9715.2Atty. Dkt. No. 142193-0129EM2408PCT

[0042] In an embodiment, no component comprising more than 10 vol% of the solvent has a dielectric constant greater than 50 at 25°C. In an embodiment, the specific capacity ratio of the anode to the specific capacity ratio of the cathode is from 0.9 to 2.0, or from 1.01 to 1.5, or from 1.05 to 1.2. In an embodiment, the device has an initial coulombic efficiency of no less than 80%, or no less than 90%, or no less than 99%.

[0043] In an embodiment, the standard reduction potential of the solvent is no greater than 0 V, or no greater than -0.1 V, or no greater than -0.2 V. In an embodiment, the standard oxidation potential of the solvent is no less than 5.5 V, or no less than 5.75 V, or no less than 6 V. In an embodiment, the device has a maximum electrostatic potential of no less than 1 eV, or no less than 1.1 eV, or no less than 1.2 eV. In an embodiment, the device has a minimum electrostatic potential of no less than -1.4 eV, or no less than -1.3 eV. In an embodiment, the donor number of the solvent is in the range of from 10 kcal / mol to 30 kcal / mol, or from 15 kcal / mol to 20 kcal / mol. In an embodiment, expansion of the anode during use is no greater than 10% per cycle or no greater than 2% per cycle or no greater than 1% per cycle.

[0044] Further discussed herein is a method of making an electrochemical device. The method can include providing an anode, a cathode, and an electrolyte. The anode can include silica depleted rice hull ash (SDRHA). The electrolyte can include at least one sulfonamide solvent and a salt substantially dissolved in the solvent. The sulfonamide solvent can have a formula R1-SO2-N-R2R3. Ri can be selected from the group consisting of -F, -CF3, -N(CH3)2, and -NCH2CH3. Each of R2 and R3 can be selected from the group consisting of -H, -CH3, and -CH2CH3.

[0045] Also discussed herein is a method of using an electrochemical device. The method can include providing an anode, a cathode, and an electrolyte. The anode can include silica depleted rice hull ash (SDRHA). The electrolyte can include at least one sulfonamide solvent and a salt substantially dissolved in the solvent. The sulfonamide solvent can have a formula R1-SO2-N-R2R3. Ri can be selected from the group consisting of -F, -CF3, -N(CH3)2, and -NCH2CH3,. Each of R2 and R3 can be selected from the group consisting of -H, -CH3, and -CH2CH3. In an embodiment, expansion of the anode during use is no greater than 10% per cycle or no greater than 2% per cycle or no greater than 1% per cycle.

[0046] A challenge with using SDRHA as an anode or any biogenic anode material is the poor coulombic efficiency. DMTMSA and DMSF can create more stable, ultra-thin solid124908-9576-9715.2Atty. Dkt. No. 142193-0129EM2408PCTelectrolyte interface (SEI) layers between the electrolyte and the anode. DMTMSA- and DMSF -based electrolytes can mitigate the growth rate of these SEI layers, which both mitigates the impedance growth and the loss of lithium ions, which are key to maintaining capacity. As such, these electrolytes can result in much higher capacity retention with cycles (e.g., a higher coulombic efficiency) when using biogenic anode materials.

[0047] Having now described some illustrative implementations, it is apparent that the foregoing is illustrative and not limiting, having been presented by way of example. In particular, although many of the examples presented herein involve specific combinations of method acts or system elements, those acts and those elements may be combined in other ways to accomplish the same objectives. Acts, elements and features discussed in connection with one implementation are not intended to be excluded from a similar role in other implementations or implementations.

[0048] The phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. The use of “including” “comprising” “having” “containing” “involving” “characterized by” “characterized in that” and variations thereof herein, is meant to encompass the items listed thereafter, equivalents thereof, and additional items, as well as alternate implementations consisting of the items listed thereafter exclusively. In one implementation, the systems and methods described herein consist of one, each combination of more than one, or all of the described elements, acts, or components.

[0049] While various inventive embodiments have been described and illustrated herein, those of ordinary skill in the art will readily envision a variety of other means and / or structures for performing the function and / or obtaining the results and / or one or more of the advantages described herein, and each of such variations and / or modifications is deemed to be within the scope of the inventive embodiments described herein. More generally, those skilled in the art will readily appreciate that all parameters, dimensions, materials, and configurations described herein are meant to be exemplary and that the actual parameters, dimensions, materials, and / or configurations will depend upon the specific application or applications for which the inventive teachings is / are used. Those skilled in the art will recognize or be able to ascertain, using no more than routine experimentation, many equivalents to the specific inventive embodiments described herein. It is, therefore, to be understood that the foregoing embodiments are presented by way of example only and that, within the scope of the appended claims and equivalents thereto, inventive embodiments may be practiced otherwise than as specifically described and claimed. Inventive embodiments of134908-9576-9715.2Atty. Dkt. No. 142193-0129EM2408PCTthe present disclosure are directed to each individual feature, system, article, material, kit, and / or method described herein. In addition, any combination of two or more such features, systems, articles, materials, kits, and / or methods, if such features, systems, articles, materials, kits, and / or methods are not mutually inconsistent, is included within the inventive scope of the present disclosure.

[0050] Also, various inventive concepts may be embodied as one or more methods, of which an example has been provided. The acts performed as part of the method may be ordered in any suitable way. Accordingly, embodiments may be constructed in which acts are performed in an order different than illustrated, which may include performing some acts simultaneously, even though shown as sequential acts in illustrative embodiments.

[0051] All definitions, as defined and used herein, should be understood to control over dictionary definitions, definitions in documents incorporated by reference, and / or ordinary meanings of the defined terms.

[0052] The indefinite articles “a” and “an,” as used herein in the specification and in the claims, unless clearly indicated to the contrary, should be understood to mean “at least one.”

[0053] The phrase “and / or” as used herein in the specification and in the claims, should be understood to mean “either or both” of the elements so conjoined, i.e., elements that are conjunctively present in some cases and disjunctively present in other cases. Multiple elements listed with “and / or” should be construed in the same fashion, i.e., “one or more” of the elements so conjoined. Other elements may optionally be present other than the elements specifically identified by the “and / or” clause, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, a reference to “A and / or B”, when used in conjunction with open-ended language such as “comprising” can refer, in one embodiment, to A only (optionally including elements other than B); in another embodiment, to B only (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements).

[0054] As used herein in the specification and in the claims, “or” should be understood to have the same meaning as “and / or” as defined above. For example, when separating items in a list, “or” or “and / or” shall be interpreted as being inclusive, i.e., the inclusion of at least one, but also including more than one of a number or list of elements, and, optionally, additional unlisted items. Only terms clearly indicated to the contrary, such144908-9576-9715.2Atty. Dkt. No. 142193-0129EM2408PCTas “only one of’ or “exactly one of,” or, when used in the claims, “consisting of,” will refer to the inclusion of exactly one element of a number or list of elements. In general, the term “or” as used herein shall only be interpreted as indicating exclusive alternatives (i.e., “one or the other but not both”) when preceded by terms of exclusivity, such as “either” “one of’ “only one of’ or “exactly one of’. “Consisting essentially of’ when used in the claims, shall have its ordinary meaning as used in the field of patent law.

[0055] As used herein in the specification and in the claims, the phrase “at least one,” in reference to a list of one or more elements, should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements. This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase “at least one” refers, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, “at least one of A and B” (or, equivalently, “at least one of A or B,” or, equivalently “at least one of A and / or B”) can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements).

[0056] Where technical features in the drawings, detailed description or any claim are followed by reference signs, the reference signs have been included to increase the intelligibility of the drawings, detailed description, and claims. Accordingly, neither the reference signs nor their absence have any limiting effect on the scope of any claim elements.

[0057] The systems and methods described herein may be embodied in other specific forms without departing from the characteristics thereof. The foregoing implementations are illustrative rather than limiting of the described systems and methods. Scope of the systems and methods described herein is thus indicated by the appended claims, rather than the foregoing description, and changes that come within the meaning and range of equivalency of the claims are embraced therein.154908-9576-9715.2

Claims

Atty. Dkt. No. 142193-0129EM2408PCTWHAT IS CLAIMED IS:

1. A method of making an anode, comprising:a) providing rice hull ash (RHA) and treating the RHA with an alkali solution to dissolve silica in the RHA;b) washing the treated RHA with water to remove the dissolved silica and alkali solution to produce silica depleted RHA (SDRHA);c) drying the SDRHA; andd) incorporating the dried SDRHA into the anode.

2. The method of claim 1, wherein expansion of the anode during use is no greater than 10% per cycle or no greater than 2% per cycle or no greater than 1% per cycle.

3. The method of claim 1, wherein the SDRHA from step b) is treated with an acid and washed again before step c).

4. The method of claim 1, wherein pH of the SDRHA from step b) is adjusted before step c).

5. The method of claim 1, wherein the SDRHA includes 40-60 wt% of silica and 60-40 wt% of hard carbon.

6. The method of claim 1, wherein alkali treatment takes place at a temperature of no greater than 80°C or no greater than 60°C or at room temperature, or wherein alkali treatment takes place at a temperature of no less than 600 °C..

7. The method of claim 1, wherein at least a portion of the alkali solution and dissolved silica is removed from the treated RHA between step a) and step b).

8. An electrochemical device comprising:an anode, a cathode, and an electrolyte;wherein the anode comprises silica depleted rice hull ash (SDRHA);wherein the electrolyte comprises at least one sulfonamide solvent and a salt substantially dissolved in the solvent;164908-9576-9715.2Atty. Dkt. No. 142193-0129EM2408PCTwherein the sulfonamide solvent has a formula R1-SO2-N-R2R3;wherein Ri is selected from the group consisting of -F, -CF3, -N(CH3)2, and -NCH2CH3; andwherein each of R2 and R3 is selected from the group consisting of -H, -CH3, and -CH2CH3.

9. The device of claim 8, wherein the salt is selected from the group consisting of lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), lithium hexafluorophosphate (LiPF6), lithium perchlorate (LiClO4), lithium tetrafluoroborate (LiBF4), lithium triflouromethanesulfonate or lithium tritiate (LiTF), lithium bis(pentafluoroethanesulfonyl)imide (LiBETI), lithium tetracyanoborate (LiB(CN)4), lithium bis(oxalato)borate (LiBOB), lithium difluorooxalatoborate (LiDFOB), sodium bis(fluorosulfonyl)imide (NaFSI), sodium bis(trifluoromethylsulfonyl)imide (NaTFSI), sodium hexafluorophosphate (NaPF6), sodium perchlorate (NaClO4), sodiumtetrafluorob orate (NaBF4), sodium triflouromethanesulfonate or sodium tritiate (NaTF), sodium bis(pentafluoroethanesulfonyl)imide (NaBETI), sodium tetracyanoborate (NaB(CN)4), sodium bis(oxalato)borate (NaBOB), sodium difluorooxalatoborate (NaDFOB), and combinations thereof.

10. The device of claim 8, wherein the salt is LiFSI and wherein LiFSI has a molality in the solvent in the range of from 0.5 to 5 or from 0.8 to 3 or from 0.9 to 2, wherein molality is moles of solute divided by weight of solvent in kg.

11. The device of claim 8, wherein the salt comprises NaFSI, NaPF6, LiFSI, LiPF6, or any combination thereof.

12. The device of claim 8, wherein the sulfonamide solvent comprises N, N-dimethyltrifluoromethanesulfonamide (DMTMSA), N, N-dimethylsulfamoyl fluoride (DMSF), N-ethyl-N-methyl sulfamoyl fluoride (EMSF), N-methyl sulfamoyl fluoride (MSF), bis(2-methoxyethyl)sulfamoyl fluoride (BMSF), diethyl sulfamoyl fluoride (DESF) is, or N-butyl-N, N 0, N 0-trimethylsulfamide (BTMSA).

13. The device of claim 8, wherein the electrolyte comprises a cosolvent, wherein the cosolvent comprises dimethyl sulfoxide (DMSO), Ethyl methyl carbonate (EMC), Dimethyl 174908-9576-9715.2Atty. Dkt. No. 142193-0129EM2408PCTcarbonate (DMC), Diethyl carbonate (DEC), Ethyl Methyl Sulfone (EMS), ethylene glycol diethyl ether (DEE), or fluorinated ether.

14. The device of claim 8, wherein the electrolyte comprises at least one selected from the group consisting of N-Ethyl-N-methyl sulfamoyl fluoride (EMSF), dimethoyxethane (DME), Tetrahydrofuran (THF), l,l,2,2-Tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), 1,1,2,2-Tetrafluoroethyl 2,2,2-Trifluoroethyl Ether (TFTFE), 1,2-di ethoxy ethane (DEE), piperidine trifluoromethanesulfonamide (PIP-TMSA), Trifluoroethyl ether(TFE), Trifluoroethyl methyl ether (TMF), N-Butyl-N-methylpyrrolidinium (Pyrl4), Trifluorotoluene (PhCF3), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), Dimethyl carbonate (DMC), fluoroethylene carbonate (FEC), fluorinated ethers, and combinations thereof.

15. The device of claim 8, wherein the electrolyte additionally comprises at least one of: fluoroethylene carbonate (FEC), Methyl 2,2,2-trifluoroethyl carbonate (FEMC), 1, 1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), prop-l-ene-l,3-sultone (PST), propyl propionate (PP), 1,3,6-hexane trinitrile (HTCN), vinylene carbonate (VC), ethylene carbonate (EC), sodium bis(oxalato)borate (NaBOB), lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), sodium difluoro(oxalato)borate (NaDFOB), sodium tetrafluorooxalatophosphate (NaTFOP), lithium tetrafluorooxalatophosphate (LiTFOP), sodium difluorodi oxalatophosphate (NaDFOP), lithium difluorodi oxalatophosphate (LiDFOP), Dioxathiolane 2,2-dioxide (DTD), tris(trimethylsilyl)phosphite (TMSPi), tris(trimethylsilyl)phosphate (TMSPa), tris(trimethylsilyl)borate (TMSB).

16. The device of claim 8, wherein the SDRHA includes 40-60 wt% of silica and 60-40 wt% of hard carbon.

17. The device of claim 8, wherein the cathode comprises a layered oxide, apolyanion, Lithium Nickel Manganese Cobalt Oxide (NMC), Lithium Iron Phosphate (LFP), Lithium-and-Manganese-Rich (LMR), Lithium Manganese Iron Phosphate (LMFP), Lithium Cobalt Oxide (LCO), sodium cobalt oxide (NaCoO2), sodium nickel manganese oxide (NaNiMnCoO2), sodium iron phosphate (Na2FePO4), sodium iron fluorophosphate (Na2FePO4F), sodium vanadium phosphate (NaVPO4), prussian blue analogue, iron based Prussian white (Na2-xFeFe(CN)6), sodium manganese iron phosphate (Na2MnxFei-xPO4),184908-9576-9715.2Atty. Dkt. No. 142193-0129EM2408PCTsodium manganese rich (SMR, or manganese rich sodium), sodium manganese oxide (Na2Mn2C>4), sodium cobalt oxide (Na2CoC>2), sodium iron phosphate-pyrophosphate (NaFPP), or combinations thereof.

18. The device of claim 8 configured to operate at a temperature in the range of from -30°C to 65°C.

19. The device of claim 8 configured to operate at a voltage of no less than 3.4 V, or no less than 3.8V, or no less than 4.0V, or no less than 4. IV, or no less than 4.3V, or no less than 4.5V.

20. The device of claim 8 configured to operate at a voltage of up to 4.5 V, or up to 4.3 V, or up to 4.2V, or up to 4.0V, or up to 3.8V, or up to 3.4V with a coulombic efficiency above 99%.

21. The device of claim 8 configured to retain at least 80% capacity after 500 cycles, or after 1000 cycles, or after 2000 cycles, or after 5000 cycles at ambient temperature.

22. The device of claim 8, wherein no component comprising more than 10 vol% of the solvent has a dielectric constant greater than 50 at 25°C.

23. The device of claim 8, wherein the specific capacity ratio of the anode to the specific capacity ratio of the cathode is from 0.9 to 2.0, or from 1.01 to 1.5, or from 1.05 to 1.2.

24. The device of claim 8 having an initial coulombic efficiency of no less than 80%, or no less than 90%, or no less than 99%.

25. The device of claim 8, wherein the standard reduction potential of the solvent is no greater than 0 V, or no greater than -0.1 V, or no greater than -0.2 V; or wherein the standard oxidation potential of the solvent is no less than 5.5 V, or no less than 5.75 V, or no less than 6 V.194908-9576-9715.2Atty. Dkt. No. 142193-0129EM2408PCT26. The device of claim 8, wherein the device has a maximum electrostatic potential of no less than 1 eV, or no less than 1.1 eV, or no less than 1.2 eV; or wherein the device has a minimum electrostatic potential of no less than -1.4 eV, or no less than -1.3 eV.

27. The device of claim 8, wherein the donor number of the solvent is in the range of from 10 kcal / mol to 30 kcal / mol, or from 15 kcal / mol to 20 kcal / mol.

28. The device of claim 8, wherein expansion of the anode during use is no greater than 10% per cycle or no greater than 2% per cycle or no greater than 1% per cycle.

29. A method of making an electrochemical device, the method comprising:providing an anode, a cathode, and an electrolyte;wherein the anode includes silica depleted rice hull ash (SDRHA);wherein the electrolyte comprises at least one sulfonamide solvent and a salt substantially dissolved in the solvent;wherein the sulfonamide solvent has a formula R1-SO2-N-R2R3;wherein Ri is selected from the group consisting of -F, -CF3, -N(CH3)2, and - NCH2CH3; andwherein each of R2 and R3 is selected from the group consisting of -H, -CH3, and -CH2CH3.

30. A method of using an electrochemical device, the method comprising:providing an anode, a cathode, and an electrolyte;wherein the anode includes silica depleted rice hull ash (SDRHA);wherein the electrolyte comprises at least one sulfonamide solvent and a salt substantially dissolved in the solvent;wherein the sulfonamide solvent has a formula R1-SO2-N-R2R3;wherein Ri is selected from the group consisting of -F, -CF3, -N(CH3)2, and - NCH2CH3; andwherein each of R2 and R3 is selected from the group consisting of -H, -CH3, and -CH2CH3.

31. The method of claim 30, wherein expansion of the anode during use is no greater than 10% per cycle or no greater than 2% per cycle or no greater than 1% per cycle.204908-9576-9715.2