Bismuth ferrite (bifeo3) anode for high-capacity and long-cycling lithium-ion batteries

Abstract

Disclosed herein is a battery (e.g., a Li-ion battery) comprising: an anode comprising bismuth ferrite and a binder; a cathode; and an electrolyte comprising a lithium compound and a fluoroethylene carbonate (FEC) additive. Batteries with a bismuth ferrite anode having a carboxymethyl cellulose (CMC) binder and a lithium-containing electrolyte with FEC additive, show a capacity of up to 750 mAh / g at 100 mA / g and high capacity retention, with over 400 mAh / g at 500 mA / g after 1,000 cycles.

Description

BISMUTH FERRITE (BiFeO3) ANODE FOR HIGH-CAPACITY AND LONG-CYCLING LITHIUM-ION BATTERIESCROSS-REFERENCE TO RELATED APPLICATIONS[00011 This application claims the benefit of and priority to U.S. Provisional Appl. No. 63 / 659,490, filed June 13, 2024, the contents of which are incorporated herein by reference in their entirety for any and all purposes.BACKGROUND

[0002] Lithium-ion batteries (LIBs) have found widespread use in electronics, electric tools, and electric vehicles, due to their reasonable energy densities (150-200 W h / kg) and excellent cycling stability. However, with increasing demand for long-range electric vehicles, there is great commercial interest in developing batteries with much higher energy densities (350-500 Wh / kg). Thus, lithium metal batteries and solid-state batteries, rather than LIBs, have received considerable attention from researchers. However, these emerging battery systems suffer from some intrinsic drawbacks that are difficult to address in the near term.10003] For instance, Li metal is prone to dendrite growth, which leads to cell short-circuiting and low Coulombic efficiency. Meanwhile, solid-state electrolytes exhibit a long-standing solid-solid interface problem, which significantly challenges current battery manufacturing technology. Therefore, developing lithium-ion batteries with higher energy densities represents an attractive alternative to lithium metal or solid-state batteries.

[0004] The pursuit of LIBs with high energy densities calls for the development of high- capacity electrode materials, especially anode materials. Graphite is the conventional anode material for LIBs, operating potential (about 0.1 V vs Li / Li+), low cost, and stable cycling life. But graphite has several drawbacks. For instance, it has only a moderate capacity of about 350 mAh / g. Metal oxides provide higher capacities due to the potential to undergo conversion or alloy reactions. Second, the Li-insertion potential in graphite (about 0.1 V vs Li / Li+) is close to that of Li metal plating (about 0 V vs Li / Li+), which leads to safetyconcems, especially under fast-charging or low-temperature conditions. Therefore, it is crucial to develop an alternative anode material with a higher capacity and a higher reaction potential.

[0005] To identify such anode materials, extensive efforts have been focused on alloy materials during the past two decades, such as silicon, tin, aluminum, and antimony. Particularly, silicon- based materials have attracted worldwide attention due to their potential of around 10 times the gravimetric capacity compared to that of the traditional graphite anodes (3578 vs 372 mA h g-1 for graphite). Nonetheless, addressing the significant capacity loss observed during the cycling of the silicon electrodes appears to be a complex challenge. This capacity loss is mainly attributed to the two following distinct factors, which contribute a huge volume expansion (which amount to 270%): (a) the first cause of capacity fading involves the disintegration of silicon grains and the overall architecture of the composite electrode. This leads to a loss of electrical contact with the current collector of the active material, (b) The second factor contributing to capacity fading is the presence of an unstable solid-electrolyte interphase (SEI). This results in continuous degradation of the liquid electrolyte at the surface of the silicon phase. Besides, these alloy materials same as silicon generally suffer from massive volume change (100-300%) and lead to repeated crack and reformation of the SEI, which result in poor cycling stability. To address these issues, sophisticated and complicated methods have to be used, including the preparation of alloy / carbon nanocomposites, the use of new binders / electrolytes, and delicate morphology control. These methods improved the alloy performance to some degree, but they also considerately increase the electrode manufacturing cost. Accordingly, there is intense commercial interest in developing new electrode materials (e.g., anode materials) for LIBs.SUMMARY

[0006] In one aspect, which may be combined with any other aspect or embodiment, the present disclosure relates to a battery, comprising: an anode comprising bismuth ferrite and a binder; a cathode; and an electrolyte comprising a lithium compound and a fluoroethylene carbonate (FEC) additive.

[0007] In some embodiments, the binder comprises a polyvinylidene fluoride (PVDF) or a carboxymethyl cellulose (CMC). In some embodiments, the binder comprises a CMC.

[0008] In some embodiments, the FEC additive is present at a concentration of about 1 wt.% to about 20 wt.%, relative to the total weight of the electrolyte. In some embodiments, the FEC additive is present at a concentration of about 5 wt.% to about 15 wt.%, relative to the total weight of the electrolyte.

[0009] In some embodiments, the lithium compound comprises LiPFe.

[0010] In some embodiments, the cathode comprises LiCoCh.

[0011] In some embodiments, the battery further comprises a separator between the anode and the cathode.

[0012] In some embodiments, the anode further comprises a conductive carbonaceous material. In some embodiments, the conductive carbonaceous material comprises carbon black.

[0013] In some embodiments, the battery has a capacity of greater than or equal to about 650 mAh / g at 100 mA / g. In some embodiments, the battery has a capacity of greater than or equal to about 700 mAh / g at 100 mA / g. In some embodiments, the battery has a capacity of greater than or equal to about 250 mAh / g at 1,000 mA / g.

[0014] In some embodiments, the battery has a capacity retention of greater than or equal to about about 45% after 1,000 cycles. In some embodiments, the capacity retention is greater than or equal to about 50% after 1,000 cycles. In some embodiments, the capacity retention is greater than or equal to about 60% after 1,000 cycles.

[0015] In another aspect, which may be combined with any other aspect or embodiment, the present disclosure relates to a method of manufacturing a batter, the method comprising: preparing an anode by combining bismuth ferrite with a binder; contacting the anode with an electrolyte comprising a lithium compound and a fluoroethylene carbonate (FEC) additive; contacting the electrolyte with a cathode, wherein the electrolyte is between the cathode and the anode.

[0016] In some embodiments, the binder comprises a polyvinylidene fluoride (PVDF) or a carboxymethyl cellulose (CMC). In some embodiments, the binder comprises a carboxymethyl cellulose (CMC).

[0017] In some embodiments, the FEC additive is present at a concentration of 1 wt.% to about 20 wt.%, relative to the total weight of the electrolyte. In some embodiments, the FEC additive is present at a concentration of about 5 wt.% to about 15 wt.%, relative to the total weight of the electrolyte.[0018 j In some embodiments, the lithium compound comprises LiPFe.

[0019] In some embodiments, the cathode comprises LiCoCh.

[0020] In some embodiments, the method further comprises placing a separator between the anode and the cathode.

[0021] In some embodiments, the anode further comprises a conductive carbonaceous material. In some embodiments, the conductive carbonaceous material comprises carbon black.

[0022] Additional aspects and / or embodiments of the invention will be provided, without limitation, in the detailed description of the present technology set forth below. The following detailed description is exemplary and explanatory, but it is not intended to be limiting.BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Various objects, aspects, features, and advantages of the disclosure will become more apparent and better understood by referring to the detailed description taken in conjunction with the accompanying figures.

[0024] FIGs. 1A-1H show characterization of bismuth ferrite (BiFeOs) (“BFO”) powders. FIG. 1A shows a X-ray diffraction (“XRD”) pattern. FIG. IB shows a simulated crystal structure. FIG. 1C shows a scanning electron microscopy (“SEM”) image. FIG. ID showsenergy dispersive X-ray spectroscopy (“EDS”) analysis. FIGS. 1E-1H show elemental mapping.

[0025] FIGs. 2A-2D show SEM images of BFO powders at different scales (scale bars: FIG. 2A 500 nm; FIG. 2B 200 nm; FIG. 2C 100 nm; and FIG. 2D 5 pm).

[0026] FIGs. 3A-3F show electrochemical performance of BFO using different binders and electrolytes at a current density of 100 mA / g: FIG. 3A shows a charge / discharge curve using PVDF binder and a regular carbonate electrolyte. FIG. 3B shows cycling performance using PVDF binder and a regular carbonate electrolyte. FIG. 3C shows a charge / discharge curve using PVDF binder and a FEC-added carbonate electrolyte. FIG. 3D shows the cycling performance using PVDF binder and a FEC-added carbonate electrolyte. FIG. 3E shows a charge / discharge curve using CMC binder and a FEC-added carbonate electrolyte. FIG. 3F shows cycling performance using CMC binder and a FEC-added carbonate electrolyte.

[0027] FIG. 4A shows a galvanostatic charge-discharge (“GCD”) curve of BFO@CMC without FEC additive at 100 mA / g current density. FIG. 4B shows BFO half-cell cycling performance of BFO@CMC without FEC additive at 350 mA / g current density. FIG. 4C shows BFO half-cell cycles of BFO@CMC without FEC additive at 100 mA / g current density.

[0028] FIG. 5 shows cyclic voltammograms (CV) of BFO@PVDF and BFO@CMC anodes with and without FEC additive.

[0029] FIGs. 6A-6F show electrochemical performance of Li / BFO within the voltage window of 0.001 - 2.5 V vs. Li+ / Li. FIG. 6A shows rate performance from 100 -1000 mA / g. FIG. 6B shows rate curve from 100 -1000 mA / g. FIG. 6C shows cycling performance at 350 mA / g. FIG. 6D shows CVs at a scan rate of 0.1 mV / s. FIG. 6E shows CVs at various scan rates. FIG. 6F shows Log(I) versus Log(V) plots of six redox peaks in CV curves.

[0030] FIGs. 7A-7F shows top-surface SEM images of BFO@PVDF and BFO@CMC halfcell electrodes acquired before and after cycling. FIG. 7A shows BFO@PVDF electrode before charge / discharge. FIG. 7B shows BFO@PVDF with FEC-added electrode after 10 cycles. FIG. 7C shows BFO@PVDF electrode without FEC additive after 40 cycles. FIG.7D shows BFO@CMC electrode before charge / discharge. FIG. 7E shows BFO@CMC electrode without FEC after 10 cycles. FIG. 7F shows BFO@CMC electrode with FEC after 250 cycles.|0031] FIGs. 8A-8B show in-situ electrochemical impedance spectroscopy (EIS) measurements. FIG. 8A shows EIS measurements for BFO@PVDF electrode before and after 15 cycles with or without 10 % FEC additive, and FIG. 8B shows EIS measurements for BFO@CMC electrode before and after 15 cycles with or without 10 % FEC additive.

[0032] FIG. 9A shows a Nyquist plot for BFO@PVDF with or without 10% FEC. FIG. 9B shows a Nyquist plot for BFO@CMC with or without 10% FEC.

[0033] FIGs. 10A-10C show electrochemical performance of a LiCoCh-BiFeCh full cell. FIG. 10A shows galvanostatic charge / discharge profiles at 100 mA / g. FIG. 10B shows charge / discharge curves at different current densities. FIG. 10C shows rate and cycling performance at different current densities.DETAILED DESCRIPTION

[0034] Before the present disclosure is further described, it is to be understood that the disclosure is not limited to the particular embodiments set forth herein, and it is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.Definitions10035] The following terms are used throughout as defined below.

[0036] As used herein and in the appended claims, singular articles such as “a” and “an” and “the” and similar referents in the context of describing the elements (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. Allmethods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the embodiments and does not pose a limitation on the scope of the claims unless otherwise stated. No language in the specification should be construed as indicating any non-claimed element as essential.

[0037] As used herein, “about” will be understood by persons of ordinary skill in the art and will vary to some extent depending upon the context in which it is used. If there are uses of the term which are not clear to persons of ordinary skill in the art, given the context in which it is used, “about” will mean up to plus or minus 10% of the particular term - for example, “about 10 wt.%” would be understood to mean “9 wt.% to 11 wt.%.” It is to be understood that when “about” precedes a term, the term is to be construed as disclosing “about” the term as well as the term without modification by “about” - for example, “about 10 wt.%” discloses “9 wt.% to 11 wt.%” as well as disclosing “10 wt.%.”100381 The phrase “and / or” as used in the present disclosure will be understood to mean any one of the recited members individually or a combination of any two or more thereof - for example, “A, B, and / or C” would mean “A, B, C, A and B, A and C, B and C, or the combination of A, B, and C.”

[0039] As used herein, the term “anode” refers to the negative electrode of a battery cell that transfers electrons to an external circuit through oxidation during discharging, and receives them from an external circuit and is reduced during charging.

[0040] As used herein, the term “cathode” refers to the positive electrode of a battery cell that receives electrons from an external circuit and is reduced during discharging, and transfers them to an external circuit through oxidation during charging. In the batteries discussed herein with respect to the various exemplary embodiments, the cathode material includes a halogenated compound and / or an electroactive aromatic organic compound as defined above.

[0041] As used herein, the term “electrolyte” refers to a material that provides for ion transport of a battery' cell. An electrolyte acts as a conduit for ion transport through itsinteraction with the anode and the cathode. Upon battery charging, an electrolyte facilitates the movement of ions from the cathode to the anode, whereas upon discharge, the electrolyte facilitates the movement of ions from the anode to the cathode. In rechargeable batteries, the electrolyte promotes ion cycling between the anode and the cathode.

[0042] As will be understood by one skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc. As will also be understood by one skilled in the art all language such as “up to,” “at least,” “greater than,” “less than,” and the like include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member. Thus, for example, a group having 1-3 atoms refers to groups having 1, 2, or 3 atoms. Similarly, a group having 1-5 atoms refers to groups having 1, 2, 3, 4, or 5 atoms, and so forth.Batteries

[0043] The present disclosure discloses a bismuth ferrite (BiFeCh) anode having unexpectedly improved performance over those known in the art. In particular, the BFO anodes of the present disclosure show excellent performance when used with certain binders, electrolytes, and additives. For instance, the use of sodium carboxymethyl cellulose (CMC) binder and fluoroethylene carbonate (FEC) additive imparts much-improved performance compared to previously known cells using BFO anodes. Anodes according to the present disclosure achieve a high capacity of about 750 mAh / g, an excellent rate capability at 1000 mA / g, and stable cycling performance for 1,050 cycles or more. When paired with a LiCoO? cathode, the full cell also demonstrates a promising cell voltage and rate performance.Anodes

[0044] Batteries according to the present disclosure comprise an anode comprising bismuth ferrite, according to the following Formula I:BixFeyOs, where x + y = 2.

[0045] In some embodiments, x is greater than or equal to 0.50, greater than or equal to 0.55, greater than or equal to 0.60, greater than or equal to 0.65, greater than or equal to 0.70, greater than or equal to 0.75, greater than or equal to 0.80, greater than or equal to 0.85, greater than or equal to 0.90, greater than or equal to 0.95, greater than or equal to 0.96, greater than or equal to 0.97, greater than or equal to 0.98, greater than or equal to 0.99, greater than or equal to 1.0, greater than or equal to 1.01, greater than or equal to 1.02, greater than or equal to 1.03, greater than or equal to 1.04, greater than or equal to 1.05, greater than or equal to 1.10, greater than or equal to 1.15, greater than or equal to 1.20, greater than or equal to 1.25, greater than or equal to 1.30, greater than or equal to 1.35, greater than or equal to 1.40, greater than or equal to 1.45, greater than or equal to 1.50, or any range or value including and / or in between any two of these values.

[0046] In some embodiments, x is less than or equal to 1.50, less than or equal to 1.45, less than or equal to 1.40, less than or equal to 1.35, less than or equal to 1.30, less than or equal to 1.25, less than or equal to 1.20, less than or equal to 1.15, less than or equal to 1.10, less than or equal to 1.05, less than or equal to 1.04, less than or equal to 1.03, less than or equal to 1.02, less than or equal to 1.01, less than or equal to 1.0, less than or equal to 0.99, less than or equal to 0.98, less than or equal to 0.97, less than or equal to 0.96, less than or equal to 0.95, less than or equal to 0.90, less than or equal to 0.85, less than or equal to 0.80, less than or equal to 0.75, less than or equal to 0.70, less than or equal to 0.65, less than or equal to 0.60, less than or equal to 0.55, less than or equal to 0.50 , or any range or value including and / or in between any two of these values.(0047] In some embodiments, x is from 0.5 to 1.5, from 0.6 to 1.4, from 0.7 to 1.3, from 0.75 to 1.25, from 0.8 to 1.2, from 0.9 to 1.1, from 0.95 to 1.05, or any range or value including and / or in between any two of these values.

[0048] In some embodiments, y is greater than or equal to 0.50, greater than or equal to 0.55, greater than or equal to 0.60, greater than or equal to 0.65, greater than or equal to 0.70, greater than or equal to 0.75, greater than or equal to 0.80, greater than or equal to 0.85, greater than or equal to 0.90, greater than or equal to 0.95, greater than or equal to 0.96, greater than or equal to 0.97, greater than or equal to 0.98, greater than or equal to 0.99, greater than or equal to 1.0, greater than or equal to 1.01, greater than or equal to 1.02, greater than or equal to 1.03, greater than or equal to 1.04, greater than or equal to 1.05, greater than or equal to 1.10, greater than or equal to 1.15, greater than or equal to 1.20, greater than or equal to 1.25, greater than or equal to 1.30, greater than or equal to 1.35, greater than or equal to 1.40, greater than or equal to 1.45, greater than or equal to 1.50, or any range or value including and / or in between any two of these values.

[0049] In some embodiments, y is less than or equal to 1.50, less than or equal to 1.45, less than or equal to 1.40, less than or equal to 1.35, less than or equal to 1.30, less than or equal to 1.25, less than or equal to 1.20, less than or equal to 1.15, less than or equal to 1.10, less than or equal to 1.05, less than or equal to 1.04, less than or equal to 1.03, less than or equal to 1.02, less than or equal to 1.01, less than or equal to 1.0, less than or equal to 0.99, less than or equal to 0.98, less than or equal to 0.97, less than or equal to 0.96, less than or equal to 0.95, less than or equal to 0.90, less than or equal to 0.85, less than or equal to 0.80, less than or equal to 0.75, less than or equal to 0.70, less than or equal to 0.65, less than or equal to 0.60, less than or equal to 0.55, less than or equal to 0.50 , or any range or value including and / or in between any two of these values.

[0050] In some embodiments, y is from 0.5 to 1.5, from 0.6 to 1.4, from 0.7 to 1.3, from 0.75 to 1.25, from 0.8 to 1.2, from 0.9 to 1.1, from 0.95 to 1.05, or any range or value including and / or in between any two of these values.

[0051] In some embodiments, the anode further comprises a conductive carbonaceous material. In some embodiments, the conductive carbonaceous material comprises graphene, graphene oxide, graphite, carbon black, carbon nanotubes, or any combination thereof.

[0052] In some embodiments, the anode comprises a conductive carbonaceous material at a concentration, relative to the total weight of the anode, of greater than or equal to about 1 wt.%, greater than or equal to about 2 wt.%, greater than or equal to about 3 wt.%, greater than or equal to about 4 wt.%, greater than or equal to about 5 wt.%, greater than or equal to about 6 wt.%, greater than or equal to about 7 wt.%, greater than or equal to about 8 wt.%, greater than or equal to about 9 wt.%, greater than or equal to about 10 wt.%, greater than or equal to about 11 wt.%, greater than or equal to about 12 wt.%, greater than or equal to about 13 wt.%, greater than or equal to about 14 wt.%, greater than or equal to about 15 wt.%, greater than or equal to about 16 wt.%, greater than or equal to about 17 wt.%, greater than or equal to about 18 wt.%, greater than or equal to about 19 wt.%, greater than or equal to about 20 wt.%, greater than or equal to about 21 wt.%, greater than or equal to about 22 wt.%, greater than or equal to about 23 wt.%, greater than or equal to about 24 wt.%, greater than or equal to about 25 wt.%, greater than or equal to about 26 wt.%, greater than or equal to about 27 wt.%, greater than or equal to about 28 wt.%, greater than or equal to about 29 wt.%, greater than or equal to about 30 wt.%, greater than or equal to about 35 wt.%, or any range or value including and / or in between any two of these values.

[0053] In some embodiments, the anode comprises a conductive carbonaceous material at a concentration, relative to the total weight of the anode, of less than or equal to about 35 wt.%, less than or equal to about 30 wt.%, less than or equal to about 29 wt.%, less than or equal to about 28 wt.%, less than or equal to about 27 wt.%, less than or equal to about 26 wt.%, less than or equal to about 25 wt.%, less than or equal to about 24 wt.%, less than or equal to about 23 wt.%, less than or equal to about 22 wt.%, less than or equal to about 21 wt.%, less than or equal to about 20 wt.%, less than or equal to about 19 wt.%, less than or equal to about 18 wt.%, less than or equal to about 17 wt.%, less than or equal to about 16 wt.%, less than or equal to about 15 wt.%, less than or equal to about 14 wt.%, less than or equal to about 13 wt.%, less than or equal to about 12 wt.%, less than or equal to about 11 wt.%, less than or equal to about 10 wt.%, less than or equal to about 9 wt.%, less than or equal to about8 wt.%, less than or equal to about 7 wt.%, less than or equal to about 6 wt.%, less than or equal to about 5 wt.%, less than or equal to about 4 wt.%, less than or equal to about 3 wt.%, less than or equal to about 2 wt.%, less than or equal to about 1 wt.%, or any range or value including and / or in between any two of these values.

[0054] In some embodiments, the anode comprises a conductive carbonaceous material at a concentration, relative to the total weight of the anode, of about 1 wt.% to about 30 wt.%, about 5 wt.% to about 28 wt.%, about 10 wt.% to about 25 wt.%, about 15 wt.% to about 20 wt.%, or any range or value therein between, or any range or value including and / or in between any two of these values.Binders

[0055] In batteries according to the present disclosure, the anode comprises a binder. The binder may be any suitable material for maintaining the structural integrity of the anode, ensuring proper adhesion, and ensuring efficient electron and ion transport during charge and discharge cycles. In some embodiments, the binder comprises polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC) e.g., sodium carboxym ethylcellulose), styrenebutadiene rubber (SBR), or any combination thereof. In some embodiments, the binder comprises a PVDF or a CMC. In some embodiments, the binder comprises a CMC.

[0056] In some embodiments, the binder is present at a concentration, relative to the total weight of the anode, of greater than or equal to about 1 wt.%, greater than or equal to about 2 wt.%, greater than or equal to about 3 wt.%, greater than or equal to about 4 wt.%, greater than or equal to about 5 wt.%, greater than or equal to about 6 wt.%, greater than or equal to about 7 wt.%, greater than or equal to about 8 wt.%, greater than or equal to about 9 wt.%, greater than or equal to about 10 wt.%, greater than or equal to about 11 wt.%, greater than or equal to about 12 wt.%, greater than or equal to about 13 wt.%, greater than or equal to about 14 wt.%, greater than or equal to about 15 wt.%, greater than or equal to about 16 wt.%, greater than or equal to about 17 wt.%, greater than or equal to about 18 wt.%, greater than or equal to about 19 wt.%, greater than or equal to about 20 wt.%, or any range or value including and / or in between any two of these values.

[0057] In some embodiments, the binder is present at a concentration, relative to the total weight of the anode, of less than or equal to about 20 wt.%, less than or equal to about 19 wt.%, less than or equal to about 18 wt.%, less than or equal to about 17 wt.%, less than or equal to about 16 wt.%, less than or equal to about 15 wt.%, less than or equal to about 14 wt.%, less than or equal to about 13 wt.%, less than or equal to about 12 wt.%, less than or equal to about 11 wt.%, less than or equal to about 10 wt.%, less than or equal to about 9 wt.%, less than or equal to about 8 wt.%, less than or equal to about 7 wt.%, less than or equal to about 6 wt.%, less than or equal to about 5 wt.%, less than or equal to about 4 wt.%, less than or equal to about 3 wt.%, less than or equal to about 2 wt.%, less than or equal to about 1 wt.%, or any range or value including and / or in between any two of these values.Electrolytes

[0058] In some embodiments, a battery according to the present disclosure comprises any suitable electrolyte for introducing Li+ions into the battery. In some embodiments, the electrolyte comprises lithium hexafluorophosphate (LiPFe) lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium perchlorate (LiCIC ), lithium nitrate (LiNCh), or any combination thereof. The electrolyte may comprise additional components, including plasticizers, solvents (e.g., SO2, 1,3-dioxolane (DOL), 1,2-dimethy oxy ethane (DME), ethylene carbonate (EC), diethyl carbonate (DEC), or dimethyl sulfoxide (DMSO), or a combination thereof). In some embodiments, the electrolyte comprises LiPFe (e.g., about 1 M) in EC:DEC (1 : 1)Additives

[0059] In some embodiments, the electrolyte or electrode materials further comprise one or more additives. For instance, in some embodiments, a battery according to the present disclosure comprises an additive in the electrolyte and / or the electrode (anode, cathode) materials. In some embodiments, the one or more additives comprise(s), by way of nonlimiting example, fluoroethylene carbonate (FEC; CAS No. 114435-02-8) vinylene carbonate, ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), propylene carbonate (PC), dipropyl carbonate (DPC), or any combination thereof.

[0060] In some embodiments, the additive is present in the electrolyte at a concentration, relative to the total weight of the electrolyte, of greater than or equal to about 1 wt.%, greater than or equal to about 2 wt.%, greater than or equal to about 3 wt.%, greater than or equal to about 4 wt.%, greater than or equal to about 5 wt.%, greater than or equal to about 6 wt.%, greater than or equal to about 7 wt.%, greater than or equal to about 8 wt.%, greater than or equal to about 9 wt.%, greater than or equal to about 10 wt.%, greater than or equal to about 11 wt.%, greater than or equal to about 12 wt.%, greater than or equal to about 13 wt.%, greater than or equal to about 14 wt.%, greater than or equal to about 15 wt.%, greater than or equal to about 16 wt.%, greater than or equal to about 17 wt.%, greater than or equal to about 18 wt.%, greater than or equal to about 19 wt.%, greater than or equal to about 20 wt.%, or any range or value including and / or in between any two of these values.[00611 In some embodiments, the additive is present in the electrolyte at a concentration, relative to the total weight of the electrolyte, of less than or equal to about 20 wt.%, less than or equal to about 19 wt.%, less than or equal to about 18 wt.%, less than or equal to about 17 wt.%, less than or equal to about 16 wt.%, less than or equal to about 15 wt.%, less than or equal to about 14 wt.%, less than or equal to about 13 wt.%, less than or equal to about 12 wt.%, less than or equal to about 11 wt.%, less than or equal to about 10 wt.%, less than or equal to about 9 wt.%, less than or equal to about 8 wt.%, less than or equal to about 7 wt.%, less than or equal to about 6 wt.%, less than or equal to about 5 wt.%, less than or equal to about 4 wt.%, less than or equal to about 3 wt.%, less than or equal to about 2 wt.%, less thanor equal to about 1 wt.%, or any range or value including and / or in between any two of these values.

[0062] In some embodiments, the additive is present in the electrolyte at a concentration, relative to the total weight of the electrolyte, of about 1 wt.% to about 20 wt.%, about 5 wt.% to about 15 wt.%, about 8 wt.% to about 12 wt.%, or any range or value therein between, or any range or value including and / or in between any two of these values.

[0063] In some embodiment, the electrolyte comprises FEC at a concentration, by weight relative to the total weight of the electrolyte, of about 1 wt.% to about 20 wt.%, about 5 wt.% to about 15 wt.%, about 8 wt.% to about 12 wt.%, or about 10 wt.%Cathodes

[0064] In some embodiments, a battery according to the present disclosure comprises a cathode comprising lithium, sodium, potassium, magnesium, calcium, vanadium, aluminum, zinc, silicon, graphite, graphene, porous carbon, activated carbon, silicon compound, a metal oxide, or combinations thereof. In some embodiments, the cathode comprises a non-metal oxide. In some embodiments, the cathode comprises, by way of non-limiting example, a non- metal oxide such as silicon, a form of silicon, graphite, graphene, porous carbon, activated carbon, or any combination thereof. In some embodiments, the cathode comprises a metal oxide. In some embodiments, the cathode comprises LiCoCh, Li4TisOi2, LisVCh, LiMnBCh, LiVo.5Tio.5S2, Li3V2O5, Li3+xV2O5, LisMoCU, LisW2O7, or any combination thereof. In some embodiments, the cathode comprises LiCoCh.Separators

[0065] In some embodiments, a battery according to the present disclosure comprises a separator. The separator may comprise any suitable material for maintaining electrical isolation of the cathode and anode in a battery (e.g., a Li-ion battery), while also facilitating ion (e.g., Li+ion) transport between the cathode and the anode. In some embodiments, the separator comprises a membrane comprising a porous carbon, a polyethylene, a polypropylene (e.g., CELGARD® 2400), a poly vinylidene fluoride (PVDF), a polytetrafluoroethylene (PTFE), a cellulose, a ceramic, a glass fiber, or a combinationthereof. In some embodiments, the membrane material comprises a polypropylene (e.g., CELGARD® 2400).Battery Performance

[0066] In some embodiments, batteries according to the present disclosure have high capacity. In some embodiments, a battery according to the present disclosure has a capacity of greater than or equal to about 400 mAh / g, greater than or equal to about 425 mAh / g, greater than or equal to about 450 mAh / g, greater than or equal to about 475 mAh / g, greater than or equal to about 500 mAh / g, greater than or equal to about 525 mAh / g, greater than or equal to about 550 mAh / g, greater than or equal to about 575 mAh / g, greater than or equal to about 600 mAh / g, greater than or equal to about 625 mAh / g, greater than or equal to about 650 mAh / g, greater than or equal to about 675 mAh / g, greater than or equal to about 700 mAh / g, greater than or equal to about 725 mAh / g, greater than or equal to about 750 mAh / g, or any range or value including and / or in between any two of these values. In some embodiments, the capacity is measured at about 100 mA / g, about 150 mA / g, about 200 mA / g, about 250 mA / g, about 300 mA / g, about 350 mA / g, about 400 mA / g, about 450 mA / g, about 500 mA / g, about 550 mA / g, about 600 mA / g, about 700 mA / g, about 800 mA / g, about 900 mA / g, or about 1000 mA / g, or any range or value including and / or in between any two of these values.

[0067] In some embodiments, batteries according to the present disclosure have a high capacity retention. In some embodiments, a battery according to the present disclosure has a capacity retention of greater than or equal to about 40%, greater than or equal to about 45%, greater than or equal to about 50%, greater than or equal to about 55%, greater than or equal to about 60%, greater than or equal to about 65%, greater than or equal to about 70%, greater than or equal to about 75%, greater than or equal to about 80%, greater than or equal to about 85%, or any range or value including and / or in between any two of these values. In some embodiments, the capacity retention is measured after about 1, about 2, about 3, about 4, about 5, about 10, about 15, about 20, about 25, about 30, about 35, about 40, about 45, about 50, about 55, about 60, about 70, about 80, about 90, about 100, about 150, about 200, about 250, about 300, about 350, about 400, about 450, about 500, about 600, about 700, about 800,about 900, or about 1,000 charge-discharge cycles, at about 100 mA / g, about 150 mA / g, about 200 mA / g, about 250 mA / g, about 300 mA / g, about 350 mA / g, about 400 mA / g, about 450 mA / g, about 500 mA / g, about 550 mA / g, about 600 mA / g, about 700 mA / g, about 800 mA / g, about 900 mA / g, or about 1000 mA / g.

[0068] Reference will now be made in detail to some specific examples demonstrating the technology of the disclosure. While various experimental examples are described herein, it will be understood that it is not intended to limit the present technology to the described embodiments.EXAMPLESExample 1. Preparation and Structural / Morphological Analysis of BFO PowdersMaterials Synthesis(0069] BFO powder was synthesized via a solid-state route, followed by a thermal annealing process. Stoichiometric amounts of precursors Fe20s and Bi2Os (Sigma-Aldrich 99.97 % purity) were measured, with 15 wt.% excess of Bi2Os to balance the loss of Bi during calcination. The oxides were mixed to homogeneity in isopropanol using a high-energy planetary ball-mill with zirconia balls (Across International, PQ-N04 Planetary Ball Mill) running at 45 Hz (2700 rpm) for 8 hours. The resulting material was heated on a hot plate at 100 °C for 8 hours to remove the solvent. The dried mixture was then annealed in a muffle furnace (Carbolite, HTF1700) at a rate of 5°C / minute up to a temperature of 875°C, then held for 10 hours. The resulting annealed BFO powder was then ground and stored until further use.Structural Analysis

[0070] Structural analysis of the synthesized BFO powder was performed utilizing an X-ray diffractometer (Rigaku Smart Lab) with a Cu Ka source (X =1.5408 A) from 20° to 80°, at a scan rate of 2° per minute. Scanning electron microscopy (SEM) and energy dispersive X- ray spectroscopy (EDS) were carried out using a JEOL JSM 648oLV) to characterize morphology and chemical composition, respectively.[00711 Referring to FIG. 1, the as-prepared BFO appears as yellow-colored fine powders. As shown in FIG. 1A, X-ray diffraction (XRD) analysis revealed XRD patterns that were well indexed to the standard BiFeOs compound (JCPDS No. 086-1518, space group R3c) but exhibited a very low intensity peak (*) at 28°. The structure is approximated by the illustration shown in FIG. IB, which shows the rhombohedral BFO crystal structure, where both Fe3+and Bi3+ions are six-coordinated to oxygen atoms. Due to the presence of heavy Fe and Bi ions, the BFO material exhibits a high crystal density of 8.29 g / cm3, which is much higher than graphite and thus beneficial for volumetric energy density.

[0072] BFO morphology and structure were further examined by SEM. As shown in FIG. 1C, the BFO exhibits quasi-spherical morphology, where the particle size ranges from 50 nm to 300 nm. FIG. 2 shows additional SEM images at different scales. The EDS spectra shown in FIG. ID reveals the presence of only Fe, Bi, and O, with a Bi:Fe atomic ratio of approximately 1 :1. FIGS. IE - 1H show elemental maps, where Fe, Bi, and O are homogeneously distributed throughout the sample.Example 2. Preparation and Characterization of Electrochemical Cells With BFO AnodesCell Fabrication|0073[ To perform electrochemical testing, the anode was prepared by mixing 70% (w / w) of the active material, BFO, 20% (w / w) Super P carbon black as a conducting agent, and 10% (w / w) binder (PVDF or CMC). The prepared slurry was spread on a copper foil (thickness 9 pm), utilizing a doctor blade (MTI Corp.). The coated foil was then dried overnight at 60°C. Anodes (10-mm diameter) were then obtained from the foil, then were further dried at 60°Cunder vacuum for two hours in an inert atmosphere glove box (MBRAUN, USA). For assembling CR2032 coin-type half-cells, Li foil was used as counter electrode, and polypropylene ethylene as a separator. To compare the electrochemical performance, polyvinylidene fluoride (PVDF) binder with N-methyl-2-pyrrolidone (NMP) and the CMC binder with distilled water were utilized in different cells. For the electrolyte, 1 M LiPFe in 1 : 1 ethylene carbonate (EC): diethyl carbonate (DEC) was used, with and without 10% fluoroethylene carbonate (FEC) additive. The influence of electrolyte additives on the electrochemical performance of BFO was investigated for both PVDF- and CMC -based electrodes.Electrical Characterization

[0074] All electrochemical performance were carried out by applying a Li half-cell and fullcell versus LiCoCh as a cathode in the voltage range of 0.001-2.5 V versus Li+ / Li, if not mentioned otherwise. Cyclic voltammetry (CV) analysis was performed using various scan rates from 0.1-1 mV / s. Galvanostatic charge-discharge (GCD) measurements were performed at a current of 50 mA / g (1C = 770 mA / g), where theoretical capacity was estimated according to both conversion and alloying reactions mechanism. The total number of Li ions involved in the electrochemical reaction was measured as nine electron transfer per formula unit - six from conversion reaction, three from alloying reaction. All the electrochemical estimations were performing using a Landt battery tester. Cyclic voltammetry was performed using Biologic Science Instruments with the EC-Lab program.Performance of BFO Anodes Using Different Binders and Electrolytes

[0075] BFO anodes have been reported for LIBs. However, their performance has proven unsatisfactory, due to low mass loading, low capacity, or poor cycling stability. Testing conditions and performances of BFO anodes known in the art are summarized in Table 1.Table 1. Comparison of BFO-based Anode Materials

[0076] Consistent with the data summarized in Table 1, poly(vinylidene) fluoride (PVDF) binder cannot effectively buffer the electrode volume change. Additionally, previous BFO anodes have used conventional carbonate electrolytes without any additives, preventing formation of a stable solid-electrolyte interphase (SEI).

[0077] To investigate the effects of binder and electrolyte effect on the BFO anode performance, various binders and electrolyte combinations were tested in coin cells: (1) PVDF binder plus a conventional carbonate electrolyte of 1 M LiPFe / EC-DMC; (2) PVDF binder plus a carbonate electrolyte with fluoroethylene carbonate (FEC) additives, IM LiPFe / EC-DMC+10% FEC; and (3) sodium carboxymethyl cellulose (CMC) binder plus a carbonate electrolyte with FEC additive, 1 M LiPFe / EC-DMC+10% FEC.1H. Xia et al., Electrochemical Properties of BiFeOi Thin Films Prepared by Pulsed Laser Deposition, 2 FUNCT. MATER. LETT. 163-67 (2009).2L. Shihai et al., BiFeO 3 as Electrode Material for Lithium Batteries, 14 J. NEW MATER. ELECTROCHEM. SYSTEMS 141-46 (2011).3M. Dwan & S.B. Majumder, Investigations on the Multifunctionality of Bismuth Iron Oxide, 72 TRANS. IND. INST. METALS 2061-72 (2019).4M. Dewan et al., Electrophoretically Deposited Bismuth Iron Oxide as Dual Role Anode Material for Both Lithium and Sodium-Ion Batteries, 27 MATER. TODAY COMMUN. 102358 (Sep. 2020).(0078] Referring to FIG. 3A and FIG. 3B, the BFO electrode shows a charge capacity of about 600 mAh / g in the first cycle, but it quickly decreases to 266 mAh / g in 40 cycles. The average Coulombic efficiency is 94%. This performance is quite similar to that reported for previous BFO anodes. (See, e.g., H.F. Andersen et al., Silicon-Carbon Composite Anodes from Inustrial Battery Grade Silicon, 9 Set. REPORTS 1-9 (2019).) Without being bound to any particular theory, it is hypothesized that the unsatisfactory performance of BFO anodes stems from the use of poorly-suited binders and electrolytes. For instance, it is hypothesized that the PVDF binder fails to prevent large volume changes in BFO anodes and cannot maintain close contact of BFO particles, which is important to maintaining good electrical conductivity.[0079 j The present inventors prepared BFO-based cells using a CMC binder with FEC additive, which surprisingly enables better performance for BFO-based anodes. Referring to FIG. 3C and FIG. 3D, when FEC additives are added to the electrolyte, the BFO@PVDF electrode shows a similar capacity but slightly improved cycling performance. After 40 cycles, the charge capacity and average Coulombic efficiency are 331 mAh / g and 95%, respectively, which are higher than observed for the pristine electrolyte.(0080] Referring now to FIGS. 4A - 4C, BFO@CMC electrodes, without FEC additive, showed average Coulombic efficiency of 97.07%. Generally, FEC additive enhances the stability and elasticity of solid electrolyte interphase (SEI) of BFO anode with lithium. When CMC binders and FEC additive are used together, the BFO electrode demonstrates unexpectedly improved performance, with more stable charge / discharge curves, a higher charge capacity of about750 mAh / g (FIG. 3E), and better cycling stability (FIG. 3F). After 100 cycles, the capacity retention is still as high as 90%, and the average Coulombic efficiency is 98%.[00811 Referring to FIG. 5, cyclic voltammetry (CV) experiments reveal that BFO@CMC with 10% FEC is very stable, even after 250 cycles. Meanwhile, the CV profile of the PVDF- (with or without FEC additive) and CMC-based electrodes (without FEC additive) show a clear decrease in stability, even after 15 cycles. Thus, the cycling performance at 500mA / g current rates is surprisingly stable at more than 1050 cycles, which far surpasses the stability observed for previous BFO-based anodes.

[0082] Besides having high capacity and stable performance, the BFO anodes according to the present disclosure also demonstrate excellent rate performance and a long-term cycling properties. Referring to FIG. 6A, the charge capacity is 751, 712, 646, 573, and 443 mAh / g at 100, 200, 350, 500, and 800 mA / g, respectively. Even at 1000 mA / g, the charge capacity is still maintained at 344 mAh / g, which is close to the capacity observed for graphite. When the current density is restored to 100 mA / g, the charge capacity recovers to 584 mAh / g, which corresponds to a recovery ratio of about 78%. FIG. 6B shows the charge / discharge curves at corresponding current density. FIG. 6C displays the cycling performance at 350 mAg, where after 50 cycles, the capacity slowly fades from 651 to 541 mAh / g, corresponding to a high-capacity retention of 80%. The average Coulombic efficiency was 98%.

[0083] Cyclic voltammetry (CV) analysis was performed to further investigate the Li- insertion mechanism in BFO. FIG. 6D shows the CV curves at 0.1 mV / s, which overlap well after the first cycle and suggest high reaction reversibility. There are three pairs of reduction / oxidation peaks at 0.59 / 0.95 V, 0.75 / 1.84 V, and 1.33 / 2.32 V, respectively, indicating a stepwise reaction mechanism. Without being bound to any particular theory, it is hypothesized that in the first discharge, the BiFeOs material will undergo a conversion reaction and transform to Bi and Fe metals. Then Bi metals will react with Li+ions to form LixBi alloys. During the charge process, the LixBi alloys will become Bi metal. Then, the Bi and Fe metal will react with Li2O to form Bi2Os and Fe2Os. The proposed conversion-alloy reaction mechanism can be expressed in the following equations.Discharging BiFeCh + 6Li++ 6e Bi + Fe + 3Li2O; E = 1.33 V (Eq. 1) Bi + Li++e ^ LiBi; E = 0.75 V (Eq. 2)LiBi + 2Li++ 2e Li3Bi; E = 0.59 V (Eq. 3)ChargingLi3Bi - 3Li+- 3e Bi; E = 0.95 V (Eq. 4)2Bi - 6e + 3Li2O Bi2O3+ 6Li+; E = 1.84 V (Eq. 5)2Fe - 6e + 3Li2O Fe2O3+ 6Li+; E = 2.32 V (Eq. 6)

[0084] Referring to FIG. 6E, to investigate the reaction kinetics, CV measurements were tested at various scanning rates. It is hypothesized that the current of the redox reaction is related to the scanning rate by the equation of i=ayb, where a and b are adjustable variables. In general, the b value ranges from 0.5 to 1. If b equals to 0.5, the reaction is a diffusion- controlled process. If b equals to 1.0, it implies a complete capacitive process. (See, e.g., D. Wang et al., Flexible Additive Free FhVsOs nanowire Membrane as Cathode for Sodium Ion Batteries, 18 PHYS. CHEM. CHEM. PHYS. 12074-79 (2016).) As shown in FIG. 6F, the b values for Ol / Rl, O2 / R2, and O3 / R3 are found to be 0.71 / 0.83. 0.82 / 0.83, 0.84 / 0.86 respectively. This indicates that the Li-insertion in BFO is a mixed process, with some capacity from capacitive insertion, which may explain the excellent rate capability. It is found that the peak currents in oxidation for all the scan rates have been found to be increased and shifted towards high potentials, which is consistent with the stability of the BFO@CMC anode having FEC additive in the electrolyte.Example 3. Structural and Morphological Characterization of BFO Electrodes After Cycling

[0085] To illustrate the nature of heterogeneous mechanical degradation and failure of PVDF binder, BFO@PVDF electrodes (with FEC additive) were analyzed by SEM after cycling. FIG. 7A and FIG. 7B show top views of a BFO@PVDF electrode before (FIG. 7A) and after (FIG. 7B) 10 cycles. No cracks are evident before charge / discharge, but cracks wereobserved after 10 cycles. For a BFO@PVDF electrode without FEC additive, holes and cracks were observed on the electrode after 40 cycles (see FIG. 7C).

[0086] As demonstrated in FIG. 7D, Similar investigations on BFO@CMC electrodes show that BFO@CMC electrodes have no cracks before cycling. Further FIG. 7E shows that the BFO@CMC electrode without FEC additive after 10 cycles also has no cracks. FIG. 4F shows the SEM image of BFO@CMC electrode with FEC additive after 250 cycles. Even after 250 cycles, the electrode is a thin, dense film with no cracks.

[0087] Referring again to FIG. 7E and FIG. 7F, CMC binder can provide adhesion to maintain the mechanical integrity of the electrode, while PVDF binder (FIGS. 7A - 7C) is unable to adhere the electrode materials on the current collector, permitting formation of inter-particle cracks, which in turn contributes significantly to the severe capacity loss observed for the BFO@PVDF electrodes. So even though PVDF binder is considered to show good binding on active materials / current collectors, reasonable electrochemical stability, and good wettability toward polar electrolyte solutions for facile Li ion transport, PVDF binder is unable to endure large volume changes due to its insufficient mechanical strength, forming vertical channels (cracks) after cycling. However, when CMC is the binder, no cracks are observed after cycling, though some swelling response is observed at higher cycle numbers. The lack of crack formation for BFO@CMC electrodes may increase battery life, improve storage performance, and improve overall electrochemical performance.Example 4. Analysis of SEI Formation

[0088] Solid-electrolyte interface (SEI) formation on the BiFeCh anode before and after cycling has been tested with in-situ electrochemical impedance spectroscopy (EIS). It is well known that the SEI is a surface layer that allows ions to move freely and isolates electron flow. Referring to FIG. 8A and FIG 8B, it was observed that the resistance values of cells using CMC binders with 10% FEC additive in the electrolyte vary considerably with cell voltage. Mainly, the resistance of SEI (ASEI) increases significantly with lithiation and decreases reversibly in the subsequent delithiation process in a narrow voltage range between 1.0 V and 0.5 V. In the change of the solution resistance (As) during the first lithiation process, the SEI forms in two voltage regions: a first region generally occurring above 0.5 V,which is less conductive; and a second region below 0.5 V, which is highly conductive. The ionic conductivity of the first region is greatly affected by the solvents and salts of the electrolyte. We observed that the ’sri increases more significantly for PVDF binder than for CMC binder.

[0089] The EIS analysis provides some insight into volume expansion of the BFO electrodes. Generally, EIS is used to analyze the underlying reaction kinetics and the impedance of electrodes. FIG. 9 shows Nyquist plots for BFO@PVDF with or without 10% FEC (FIG. 9A) and BFO@CMC with or without 10% FEC (FIG. 9B). In the initial cycles for the coin cells with PVDF binder with and without FEC additive in the electrolyte, there is a small semicircle related to SEI-derived resistance, but a clear decrease for the second semi-circle that relates to charge transfer resistance. This is explained by the volume expansion of BFO, causing the electrode to be pressurized by a spring inside the coin cell. This results in a better electrical contact between the active material / binder system and current collector, leading to a decrease of interphase electronic contact resistance. However, at higher cycle numbers, the series resistance starts to increase, indicating that the ionic conductivity of the electrolyte or the electrical conductivity through electrodes and / or current collector decreases.Additionally, the SEI-related semi-circle increases gradually, which is possibly caused by the blocking of electrolyte channels, arising due to microstructural changes in the electrode. It is possible that this phenomenon arises from electrochemical fusion of BFO particles or decomposition of the electrolyte. The interphase contacts and charge transfer resistance remain stable but after the higher cycling, the SEI resistance grows dramatically, which indicates an inhibited transport of lithium ions through the electrodes.

[0090] When CMC is used as the binder, with and without FEC additive, the charge transfer resistance is relatively low compared to that observed for BFO@PVDF electrodes, suggesting faster diffusion of Li+ions. At higher cycle numbers, a resonance is observed between solution resistance and the charge transfer resistance, which improves specific capacity and capacity retention. The interfacial parameters calculated by this analysis are shown in Table 2 (Rs= solution resistance; Ret = charge transfer resistance; Zw= Warburg impedance).Table 2. EIS Fitting Results of BFO@PVDF and BFO@CMC With or Without FECExample 5. Cell Performance

[0091] To further evaluate the BFO performance, a full electrochemical cell was assembled using a LiCoCh cathode and a BFO anode, where the N / P mass ratio (N: negative, P: positive) was 1.1 : 1. Referring to FIG. 10A, the full cell exhibits a charge / discharge capacity of 694 / 378 mAh / g in the first cycle, which corresponds to a low initial Coulombic efficiency of 55%. The irreversible capacity loss would be expected to originate from the BFO anode side, which consumes Li+ions and forms SEI layers. However, over the following 8 cycles, the discharge capacity increases to about 450 mAh / g, and the Coulombic efficiency is increased to 98%, indicating a reversible insertion process. The average discharge voltage is 2.5 V, which is reasonable for full cell applications.

[0092] FIG. 10B shows the rate performance the full cell. At current densities of 100, 200, 350, 500, 800, and 1000 mA / g, the discharge capacities are 423, 386, 332, 282, 205 and 163 mAh / g, respectively. This performance is consistent with that observed for the BFO halfcells. FIG. IOC shows the rate and cycling data for the full cell. As shown, after the 1000 mA / g rate test, the capacity can be restored to about 428 mAh / g at 100 mA / g. Moreover, the Coulombic efficiency is as high as 97-98% at different current densities. After the rate test, the full cell capacity fades from 428 mAh / g to 311 mAh / g over the next 57 cycles, which should result from the Li+ion loss in each cycle, because the Coulombic efficiency is less than 100%.

[0093] The present technology is not to be limited in terms of the particular aspects described in this application, which are intended as single illustrations of individual aspects of the present technology. Many modifications and variations of this present technology can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. Functionally equivalent methods and apparatuses within the scope of the present technology, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. Such modifications and variations are intended to fall within the scope of the present technology. It is to be understood that this present technology is not limited to particular methods, reagents, compounds compositions or biological systems, which can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0094] The methods illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed herein. Thus, for example, the terms “comprising”, “including,” containing”, etc. shall be read expansively and without limitation. Additionally, the terms and expressions employed herein have been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof. It is recognized that various modifications are possible within the scope of the disclosure claimed. Thus, it should be understood that although the present disclosure has been specifically disclosed by preferred embodiments and optional features, modification and variation of the disclosure embodied therein herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this disclosure.

[0095] The disclosure has been described broadly and generically herein. Each of the narrower species and subgeneric groupings falling within the generic disclosure also form part of the methods. This includes the generic description of the methods with a proviso or negative limitation removing any subject matter from the genus, regardless of whether or not the excised material is specifically recited herein. The present technology is not to be limited in terms of the particular embodiments described in this application, which are intended as single illustrations of individual aspects of the present technology. Many modifications and variations of this present technology can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. Functionally equivalent methods and apparatuses within the scope of the present technology, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. Such modifications and variations are intended to fall within the scope of the present technology. It is to be understood that this present technology is not limited to particular methods, reagents, compounds compositions or biological systems, which can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0096] One skilled in the art readily appreciates that the present disclosure is well adapted to carry out the objects and obtain the ends and advantages mentioned, as well as those inherent therein. Modifications therein and other uses will occur to those skilled in the art. These modifications are encompassed within the spirit of the disclosure and are defined by the scope of the claims, which set forth non-limiting embodiments of the disclosure.

[0097] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.

[0098] All references, articles, publications, patents, patent publications, and patent applications cited herein are incorporated by reference in their entireties for all purposes.

[0099] However, mention of any reference, article, publication, patent, patent publication, and patent application cited herein is not, and should not be taken as, an acknowledgment orany form of suggestion that they constitute valid prior art or form part of the common general knowledge in any country in the world.

[0100] The present technology may include, but is not limited to, the features and combinations of features recited in the following lettered paragraphs, it being understood that the following paragraphs should not be interpreted as limiting the scope of the claims as appended hereto or mandating that all such features must necessarily be included in such claims:A. A battery, comprising: an anode comprising bismuth ferrite and a binder; a cathode; and an electrolyte comprising a lithium compound and a fluoroethylene carbonate (FEC) additive.B. The battery of Paragraph A, wherein the binder comprises a polyvinylidene fluoride(PVDF) or a carboxymethyl cellulose (CMC).C. The battery of Paragraph A or Paragraph B, wherein the binder comprises a CMC.D. The battery of any one of Paragraphs A-C, wherein the FEC additive is present at a concentration of about 1 wt.% to about 20 wt.%, relative to the total weight of the electrolyte.E. The battery of any one of Paragraphs A-D, wherein the FEC additive is present at a concentration of about 5 wt.% to about 15 wt.%, relative to the total weight of the electrolyte.F. The battery of any one of Paragraphs A-E, wherein the lithium compound comprisesLiPF6.G. The battery of any one of Paragraphs A-F, wherein the cathode comprises LiCoCh.H. The battery of any one of Paragraphs A-G, further comprising a separator between the anode and the cathode.I. The battery of any one of Paragraphs A-H, wherein the anode further comprises a conductive carbonaceous material.J. The battery of Paragraph I, wherein the conductive carbonaceous material comprises carbon black.K. The battery of any one of Paragraphs A- J, wherein the battery has a capacity of greater than or equal to about 650 mAh / g at 100 mA / g.L. The battery of Paragraph K, wherein the battery has a capacity of greater than or equal to about 700 mAh / g at 100 mA / g.M. The battery of any one of Paragraphs A-L, wherein the battery has a capacity of greater than or equal to about 250 mAh / g at 1,000 mA / g.N. The battery of any one of Paragraphs A-M, wherein the battery has a capacity retention of greater than or equal to about 45% after 1,000 cycles.O. The battery of Paragraph N, wherein the capacity retention is greater than or equal to about 50% after 1,000 cycles.P. The battery of Paragraph N or O, wherein the capacity retention is greater than or equal to about 60% after 1,000 cycles.Q. A method of manufacturing a battery, the method comprising: preparing an anode by combining bismuth ferrite with a binder; contacting the anode with an electrolyte comprising a lithium compound and a fluoroethylene carbonate (FEC) additive; contacting the electrolyte with a cathode, wherein the electrolyte is between the cathode and the anode.R. The method of Paragraph Q, wherein the binder comprises a poly vinylidene fluoride(PVDF) or a carboxymethyl cellulose (CMC).S. The method of Paragraph Q or Paragraph R, wherein the binder comprises a carboxymethyl cellulose (CMC).T. The method of any one of Paragraphs Q-S, wherein the FEC additive is present at a concentration of 1 wt.% to about 20 wt.%, relative to the total weight of the electrolyte.U. The method of any one of Paragraphs Q-T, wherein the FEC additive is present at a concentration of about 5 wt.% to about 15 wt.%, relative to the total weight of the electrolyte.V. The method of any one of Paragraphs Q-U, wherein the lithium compound comprisesLiPF6.W. The method of any one of Paragraphs Q-V, wherein the cathode comprises LiCoCh.X. The method of any one of Paragraphs Q-W, further comprising placing a separator between the anode and the cathode.Y. The method of any one of Paragraphs Q-X, wherein the anode further comprises a conductive carbonaceous material.Z. The method of Paragraph Y, wherein the conductive carbonaceous material comprises carbon black.[01011 Other embodiments are set forth in the following claims, along with the full scope of equivalents to which such claims are entitled.

Claims

WHAT IS CLAIMED IS:

1. A battery, comprising: an anode comprising bismuth ferrite and a binder; a cathode; and an electrolyte comprising a lithium compound and a fluoroethylene carbonate (FEC) additive.

2. The battery of claim 1, wherein the binder comprises a polyvinylidene fluoride (PVDF) or a carboxymethyl cellulose (CMC).

3. The battery of claim 1, wherein the binder comprises a CMC.

4. The battery of claim 1, wherein the FEC additive is present at a concentration of about 1 wt.% to about 20 wt.%, relative to the total weight of the electrolyte.

5. The battery of claim 1, wherein the FEC additive is present at a concentration of about 5 wt.% to about 15 wt.%, relative to the total weight of the electrolyte.

6. The battery of claim 1, wherein the lithium compound comprises LiPFe.

7. The battery of claim 1, wherein the cathode comprises LiCoCh.

8. The battery of claim 1, further comprising a separator between the anode and the cathode.

9. The battery of claim 1, wherein the anode further comprises a conductive carbonaceous material.

10. The battery of claim 9, wherein the conductive carbonaceous material comprises carbon black.

11. The battery of claim 1, wherein the battery has a capacity of greater than or equal to about 650 mAh / g at 100 mA / g.

12. The battery of claim 11, wherein the battery has a capacity of greater than or equal to about 700 mAh / g at 100 mA / g.

13. The battery of claim 1, wherein the battery has a capacity of greater than or equal to about 250 mAh / g at 1,000 mA / g.

14. The battery of any one of the preceding claims, wherein the battery has a capacity retention of greater than or equal to about 45% after 1,000 cycles.

15. The battery of claim 14, wherein the capacity retention is greater than or equal to about50% after 1,000 cycles.

16. The battery of claim 14, wherein the capacity retention is greater than or equal to about60% after 1,000 cycles.

17. A method of manufacturing a battery, the method comprising: preparing an anode by combining bismuth ferrite with a binder; contacting the anode with an electrolyte comprising a lithium compound and a fluoroethylene carbonate (FEC) additive; contacting the electrolyte with a cathode, wherein the electrolyte is between the cathode and the anode.

18. The method of claim 17, wherein the binder comprises a polyvinylidene fluoride (PVDF) or a carboxymethyl cellulose (CMC).

19. The method of claim 17, wherein the binder comprises a carboxymethyl cellulose(CMC).

20. The method of claim 17, wherein the FEC additive is present at a concentration of 1 wt.% to about 20 wt.%, relative to the total weight of the electrolyte.

21. The method of claim 17, wherein the FEC additive is present at a concentration of about5 wt.% to about 15 wt.%, relative to the total weight of the electrolyte.

22. The method of claim 17, wherein the lithium compound comprises LiPFe.

23. The method of claim 17, wherein the cathode comprises LiCoCh.

24. The method of claim 17, further comprising placing a separator between the anode and the cathode.

25. The method of any one of claims 17-24, wherein the anode further comprises a conductive carbonaceous material.

26. The method of claim 25, wherein the conductive carbonaceous material comprises carbon black.

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