Antimony anodes for solid-state batteries

Abstract

The present technology relates generally to an anode for a solid-state battery, solid- state batteries including the anode, and methods of making the anode. The anode includes antimony having an average particle size of about 1 μm to about 100 μm and a sulfide-based solid-state electrolyte.

Description

Atty. Dkt. No. 118347-0138 (24-024-UPR)ANTIMONY ANODES FOR SOLID-STATE BATTERIESCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of and priority to U.S. Provisional Appl. No. 63 / 713,385, filed October 29, 2024, the contents of which are incorporated herein by reference in its entirety for any and all purposes.GOVERNMENT RIGHTS

[0002] This invention was made with government support under OIA- 1849243 awarded by The National Science Foundation, and 80NSSC23M0189 awarded by The National Aeronautics and Space Administration. The government has certain rights in the invention.TECHNICAL FIELD

[0003] The present technology relates generally to solid-state battery anodes that include antimony as an electroactive material, batteries including these anodes, and methods of making the same.SUMMARY

[0004] In an aspect, which may be combined with any other aspect or embodiment, the present disclosure relates to an anode comprising about 50 wt.% to about 90 wt.% antimony, the antimony having an average particle size of about 1 pm to about 100 pm as measured by scanning electron microscopy; and about 10 wt.% to about 50 wt.% of a first sulfide-based solid-state electrolyte.

[0005] In another aspect, which may be combined with any other aspect or embodiment, the present disclosure relates to a solid-state battery including the anode disclosed herein, a counter electrode, and a solid electrolyte disposed between the anode and the counter electrode, the solid electrolyte comprising a sulfide-based solid-state electrolyte.

[0006] In another aspect, which may be combined with any other aspect or embodiment, the present disclosure relates to a process for forming an anode for a solid-state battery. The process comprises grinding a mixture of antimony, the antimony having an average particle size of about 1 pm to about 100 pm as measured by scanning electron microscopy, and aAtty. Dkt. No. 118347-0138 (24-024-UPR) sulfide-based solid-state electrolyte; and compressing the mixture under a pressure of about 50 MPa to about 500 mPa into a monolithic form.

[0007] Further aspects and embodiments of the present technology are described herein.BRIEF DESCRIPTION OF THE DRAWINGS

[0008] FIG. 1 is an illustration of a solid-state electrochemical cell with an antimony anode and a nickel manganese cobalt cathode.

[0009] FIG. 2 is a graph of X-ray diffraction (XRD) characterization of microscale antimony powder used as an electroactive material in the anode.

[0010] FIGS. 3A and 3B are scanning electron microscopy (SEM) images of nanoscale (FIG. 3 A) and microscale (FIG. 3B) antimony powder used as an electroactive material in the anode.

[0011] FIGS. 4A and 4B are graphs of galvanostatic charge / discharge curves of electrochemical cells with antimony anodes and lithium counter electrodes in a liquid electrolyte of 1 M LiPFe in ethylene carbonate and dimethyl carbonate (EC-DMC) at 50 mA g'1. FIG. 4A includes nanoscale antimony in the anode and FIG. 4B includes microscale antimony in the anode.

[0012] FIGS. 5 A and 5B are graphs of electrochemical impedance spectroscopy (EIS) results of electrochemical cells with antimony anodes and lithium counter electrodes in a liquid electrolyte of 1 M LiPFe in ethylene carbonate and dimethyl carbonate (EC-DMC) at 50 mA g'1at the first, fifth, and tenth cycle. FIG. 5A includes nanoscale antimony in the anode and FIG. 5B includes microscale antimony in the anode.

[0013] FIGS. 6 A and 6B are cross-sectional SEM images of the Antimony electrodes from electrochemical cells with antimony anodes, lithium counter electrodes, and the liquid electrolyte of 1 M LiPFe in EC-DMC after different numbers of galvanostatic cycles. FIG. 6A includes nanoscale antimony in the anode and FIG. 6B includes microscale antimony in the anode.

[0014] FIG. 7 is an illustration of a reaction scheme of the formation of a solid-electrolyte interphase on antimony powder in an anode of an electrochemical cell.Atty. Dkt. No. 118347-0138 (24-024-UPR)

[0015] FIGS. 8A and 8B are graphs of galvanostatic charge / discharge curves of solid-state electrochemical cells with an antimony anode and a lithium indium alloy counter electrode at 50 mA g'1. FIG. 8 A includes nanoscale antimony in the anode and FIG. 8B includes microscale antimony in the anode.

[0016] FIGS. 9A and 9B are SEM images of energy dispersive spectra (EDS) analysis of antimony-solid electrolyte composites. FIG. 9A shows the nanoscale antimony mixed with the solid electrolyte. FIG. 9B shows the microscale antimony mixed with the solid electrolyte.

[0017] FIGS. 10A and 10B are schemes of the antimony-solid electrolyte composite structures. FIG. 10A is an illustration of the nanoscale antimony mixed with the solid electrolyte. FIG. 10B is an illustration of the microscale antimony mixed with the solid electrolyte.

[0018] FIG. 11 is a graph of EIS results of the solid-state electrochemical cell with microscale antimony anode and a lithium indium alloy counter electrode at different cycles.

[0019] FIG. 12 is a graph of rate capability of the solid-state electrochemical cell with microscale antimony anode and a lithium indium alloy counter electrode.

[0020] FIG. 13 is a graph of the cycling performance of the solid-state electrochemical cell with microscale antimony anode and a lithium indium alloy counter electrode.

[0021] FIG. 14 is a graph of XRD results of the lithium nickel manganese cobalt oxide (NMC) cathode material.

[0022] FIGS. 15A and 15B are SEM images of the NMC cathode material at different resolutions.

[0023] FIG. 16 is a graph of galvanostatic charge / discharge curves of solid-state electrochemical cells with antimony anodes and lithium indium alloy counter electrodes at 50 mA g'1.

[0024] FIG. 17 is a graph of rate capability of a solid-state electrochemical cell with an NMC cathode and a lithium indium alloy counter electrode at various current densities.Atty. Dkt. No. 118347-0138 (24-024-UPR)

[0025] FIG. 18 is a graph of the cycling performance of the solid-state electrochemical cell with an NMC cathode and a lithium indium alloy counter electrode at 300 mA g'1.

[0026] FIG. 19 is a graph of galvanostatic charge / discharge curves of the solid-state electrochemical cell with an NMC cathode and a microscale antimony anode at 50 mA g'1.

[0027] FIG. 20 is a graph of rate capability of a solid-state electrochemical cell with an NMC cathode and a microscale antimony anode at various current densities.

[0028] FIG. 21 is a graph of cycling performance of the solid-state electrochemical cell with an NMC cathode and a microscale antimony anode at 300 mA g'1.DETAILED DESCRIPTIONIt is to be appreciated that certain aspects, modes, embodiments, variations, and features of the present methods are described below in various levels of detail in order to provide a substantial understanding of the present technology.Definitions

[0029] Unless defined otherwise, all technical and scientific terms used herein generally have the same meaning as commonly understood by one of ordinary skill in the art to which this technology belongs.

[0030] 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. All methods 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. For example, reference to “a cell” includes aAtty. Dkt. No. 118347-0138 (24-024-UPR) combination of any two or more cells, and the like. Generally, the nomenclature used herein and the laboratory procedures in cell culture, molecular genetics, organic chemistry, analytical chemistry and nucleic acid chemistry and hybridization described below are those well-known and commonly employed in the art.

[0031] 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.%.”

[0032] 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.”

[0033] 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.

[0034] 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.

[0035] 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 its interaction 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, theAtty. Dkt. No. 118347-0138 (24-024-UPR) electrolyte promotes ion cycling between the anode and the cathode. The electrolyte may be a liquid or a solid, as specified herein.

[0036] 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.The Present Technology

[0037] Disclosed herein are anodes for solid-state lithium-ion batteries that include antimony. Also disclosed herein are solid-state electrochemical cells including these anodes, solid-state lithium-ion batteries including these anodes, and methods of forming these anodes and electrochemical cells. The antimony anodes have unexpectedly improved performance over those known in the art. In particular, solid-state electrochemical cells with these antimony anodes provide longer cycling stability than electrochemical cells with antimony anodes with liquid electrolytes. For instance, anodes according to the present disclosure achieve a high capacity of about 660 mAh g-1, and a cycling stability of 70% capacity retention over 1000 cycles.

[0038] In an aspect, the anode includes antimony that acts as an electroactive material. The antimony may be substantially evenly dispersed or evenly dispersed in the anode. As used herein, substantially evenly dispersed means the average particle density is maintained across different regions of the anode within a range of ± 50%, 40%, 30%, 20%, 10%, 5%, or 1%.

[0039] The solid-state electrolyte may be present in the anode as a particulate matter having an average particle size as measured by scanning electron microscopy imaging of about 50Atty. Dkt. No. 118347-0138 (24-024-UPR) nm to about 500 pm. In some embodiments, the anode may include antimony with nanoscale particle sizes, including about 50 nm to about 1 pm, including about 100 nm to about 500 nm. In some embodiments, the anode may include antimony with microscale particle sizes, including about 1 pm to about 100 pm, including about 1 pm to about 90 pm, about 1 pm to about 80 pm, about 1 pm to about 50 pm, or about 10 pm to about 50 pm.

[0040] The antimony may be amorphous or crystalline. The antimony may have a crystalline or polycrystalline structure. For example, the antimony may have rhombohedral crystal structure.

[0041] The antimony may be present in the anode in an amount, relative to the total weight of the anode, of about 20 wt.% to about 95 wt.%, about 30 wt.% to about 95 wt.%, about 40 wt.% to about 90 wt.%, about 50 wt.% to about 90 wt.%, about 60 wt.% to about 80 wt.%, about 65 wt.% to about 75 wt.%, or about 61 wt.%, about 62 wt.%, about 63 wt.%, about 64 wt.%, about 65 wt.%, about 66 wt.%, about 67 wt.%, about 68 wt.%, about 69 wt.%, about 70 wt.%, about 71 wt.%, about 72 wt.%, about 73 wt.%, about 74 wt.%, about 75 wt.%, about 76 wt.%, about 77 wt.%, about 78 wt.%, about 79 wt.%, about 80 wt.%, or any range including and / or in-between any two of these values.

[0042] The antimony mass loading in the anode may be about 0.1 mg cm’2to about5 mg cm’2(e.g., about 0.1 mg cm’2to about 4 mg cm’2, about 0.1 mg cm’2to about 3 mg cm’2, about 0.1 mg cm’2to about 2 mg cm’2, about 0.5 mg cm’2to about 2 mg cm’2, or about 1 mg cm’2to about 2 mg cm’2).

[0043] The anode further includes a sulfide-based solid-state electrolyte. The solid-state electrolyte may provide ion conductivity and reduce interfacial resistance between the anode and the solid-state electrolyte used in the electrochemical cell. The sulfide-based solid-state electrolyte may be the same material or a different material than the one used as the solid- state electrolyte in the electrochemical cell.

[0044] The sulfide-based solid-state electrolyte may include an argyrodite solid electrolyte, a thio-LISICON solid electrolyte, any other suitable sulfide-based solid-state electrolyte, or a combination of any two or more thereof. Argyrodite-type solid electrolytes may have a chemical formula of LiePSsX where X is Cl, Br, I, or a combination of two or more thereof. Thio-LISICON solid electrolytes may have a formula of Li4-xMi-yMy'S4 where M is Si, Ge, or a combination thereof, and M' is P, Al, Zn, Ga, or a combination of any two or moreAtty. Dkt. No. 118347-0138 (24-024-UPR) thereof. Examples of sulfide-based solid-state electrolytes include, but are not limited to, lithium phosphorus sulfur chloride, lithium phosphorus sulfur fluoride, lithium phosphorus sulfur bromide, lithium phosphorus sulfur iodide, lithium germanium phosphorus sulfide, lithium zinc germanium oxide, lithium tin phosphorus sulfide, lithium silicon phosphorus sulfide, lithium silicon aluminum sulfide, lithium sulfide, phosphorus sulfide, lithium phosphorus sulfide, silicon sulfide, lithium orthosilicate, or a combination of any two or more thereof.

[0045] The solid-state electrolyte may be present in the anode as a particulate matter having an average particle size as measured by scanning electron microscopy imaging of about 1 pm to about 100 pm, including about 1 pm to about 90 pm, about 1 pm to about 80 pm, about 1 pm to about 70 pm, about 1 pm to about 60 pm, or about 1 pm to about 50 pm.

[0046] The solid-state electrolyte may be present in the anode in an amount, relative to the total weight of the anode, of about 1 wt.% to about 70 wt.%, about 1 wt.% to about 60 wt.%, about 1 wt.% to about 50 wt.%, about 2 wt.% to about 50 wt.%, about 5 wt.% to about 50 wt.%, about 10 wt.% to about 50 wt.%, about 20 wt.% to about 40 wt.%, or about 21 wt.%, about 22 wt.%, about 23 wt.%, about 24 wt.%, about 25 wt.%, about 26 wt.%, about 27 wt.%, about 28 wt.%, about 29 wt.%, about 30 wt.%, about 31 wt.%, about 32 wt.%, about 33 wt.%, about 34 wt.%, about 35 wt.%, about 36 wt.%, about 37 wt.%, about 38 wt.%, about 39 wt.%, about 40 wt.%, or any range including and / or in-between any two of these values.

[0047] The anode may include a conductive carbon. The conductive carbon may include carbon black (e.g., Ketjen black, acetylene carbon black, or Super P), graphite, graphite, hard carbon, amorphous carbon, soft carbon, mesocarbon microbeads (MCMB), mesoporous carbon, carbon nanotubes, carbon nanofibers, graphene, or a mixture of any two or more thereof. The conductive carbon may be present in the anode in an amount, relative to the total weight of the anode, of about 1 wt.% to about 50 wt.%, about 5 wt.% to about 40 wt.%, about 10 wt.% to about 30 wt.%, about 15 wt.% to about 25 wt.%, or about 10 wt.%.

[0048] The anode may further include a binder. The binder may support volume changes in the cathode during battery cycling. The binder may be poly(vinylidene fluoride) (PVDF), carboxymethyl cellulose (CMC), polyacrylic acid (PAA), poly(tetrafluoroethylene) (PTFE), styrene-butadiene rubber (SBR), or a mixture of any two or more thereof. The binder may be present in the anode in an amount, relative to the total weight of the anode, of about 1 wt.% toAtty. Dkt. No. 118347-0138 (24-024-UPR) about 40 wt.%, about 2 wt.% to about 30 wt.%, about 5 wt.% to about 20 wt.%, about 5 wt.% to about 15 wt.%, or about 5 wt.%.

[0049] The anode may, in any embodiment herein, further include lithium.

[0050] In another aspect, an electrochemical cell is provided that includes the anode of any embodiment disclosed herein. The electrochemical cell further includes a counter electrode. The electrochemical cell may also include a solid-state electrolyte between the counter electrode and the anode. The electrochemical cell may be a rechargeable lithium-ion battery.

[0051] FIG. 1 is an illustration of a solid-state electrochemical cell 100 with an antimony anode 110 and a nickel manganese cobalt cathode 120. The electrochemical cell 100 includes a sulfide-based solid-state electrolyte 130 between the anode 110 and the cathode 120.

[0052] The counter electrode may be a cathode. The cathode may include a cathode active material. Illustrative cathode active materials include, but are not limited to, lithium cobalt oxide (LiCoCh), lithium nickel oxide (LiNiCh), lithium manganese cobalt oxide (e.g., LiCoo.5Mm.5O4, LiCoMnO4), lithium manganese oxide (LiMn2O4), lithium nickel manganese cobalt oxide(e.g., LiNio.8Mno.1Coo.1O2, LiNio.6Mno.2Coo.2O2, LiMm / 3Coi / 3Nii / 3O2), lithium manganese nickel oxide (LiMno.5Nio.5O2), lithium nickel cobalt aluminum oxide (LiNiCoAlO2), lithium iron phosphate (LiFePO4), or a combination of any two or more thereof. The active material may be evenly dispersed in the cathode. The active material may be present in an amount, relative to the total weight of the cathode, of about 25 wt.% to about 95 wt.% (e.g., about 25 wt.% to about 85 wt.% sulfur, about 30 wt.% to about 80 wt.%, about 50 wt.% to about 80 wt.%, about 50 wt.% to about 80 wt.%, or any range including and / or inbetween any two of these values).

[0053] The cathode may further include a binder. The binder may be poly(vinylidene fluoride) (PVDF), carboxymethyl cellulose (CMC), polyacrylic acid (PAA), poly(tetrafluoroethylene) (PTFE), styrene-butadiene rubber (SBR), or a mixture of any two or more thereof. The binder may be present in an amount, relative to the total weight of the cathode, of about 0 wt.% to about 20 wt.% (e.g., about 5 wt.% to about 20 wt.%, about 5 wt.% to about 15 wt.%, about 10 wt.%, or any range including and / or in-between any two of these values).Atty. Dkt. No. 118347-0138 (24-024-UPR)

[0054] The cathode may further include a conductive carbon. The conductive carbon may include carbon black (e.g., Ketjen black, acetylene carbon black, or Super P), graphite, hard carbon, amorphous carbon, soft carbon, mesocarbon microbeads (MCMB), mesoporous carbon, carbon nanotubes, carbon nanofibers, graphene, or a mixture of any two or more thereof. The conductive carbon may be present in an amount, relative to the total weight of the cathode, of about 0 wt.% to about 50 wt.% (e.g., about 5 wt.%, about 40 wt.%, about 10 wt.% to about 30 wt.%, about 15 wt.% to about 25 wt.%, about 20 wt.%, or any range including and / or in-between any two of these values).

[0055] The cathode may further include a sulfide-based solid-state electrolyte. The solid- state electrolyte may provide ion conductivity and reduce interfacial resistance between the cathode and the solid-state electrolyte used in the electrochemical cell. The sulfide-based solid-state electrolyte may be the same material or a different material than the one used as the solid-state electrolyte in the electrochemical cell.

[0056] The sulfide-based solid-state electrolyte may include an argyrodite solid electrolyte, a thio-LISICON solid electrolyte, any other suitable sulfide-based solid-state electrolyte, or a combination of any two or more thereof. Argyrodite-type solid electrolytes may have a chemical formula of LiePSsX where X is Cl, Br, I, or a combination of two or more thereof. Thio-LISICON solid electrolytes may have a formula of Li4-xMi-yMy'S4 where M is Si, Ge, or a combination thereof, and M' is P, Al, Zn, Ga, or a combination of any two or more thereof. Examples of sulfide-based solid-state electrolytes include, but are not limited to, lithium phosphorus sulfur chloride, lithium phosphorus sulfur fluoride, lithium phosphorus sulfur bromide, lithium phosphorus sulfur iodide, lithium germanium phosphorus sulfide, lithium zinc germanium oxide, lithium tin phosphorus sulfide, lithium silicon phosphorus sulfide, lithium silicon aluminum sulfide, lithium sulfide, phosphorus sulfide, lithium phosphorus sulfide, silicon sulfide, lithium orthosilicate, or a combination of any two or more thereof.

[0057] The counter electrode may include lithium metal or a lithium metal alloy, e.g., where the electrochemical cell is a half-cell. For example, the lithium metal alloy may be lithium indium.

[0058] The electrochemical cell includes a solid-state electrolyte. The solid-state electrolyte may be a sulfide-based solid-state electrolyte. The sulfide-based solid-stateAtty. Dkt. No. 118347-0138 (24-024-UPR) electrolyte may be the same as or different from the sulfide-based solid-state electrolyte in the anode.

[0059] The sulfide-based solid-state electrolyte may include an argyrodite solid electrolyte, a thio-LISICON solid electrolyte, any other suitable sulfide-based solid-state electrolyte, or a combination of any two or more thereof. Argyrodite-type solid electrolytes may have a chemical formula of LiePSsX where X is Cl, Br, I, or a combination of two or more thereof. Thio-LISICON solid electrolytes may have a formula of Li4-xMi-yMy'S4 where M is Si, Ge, or a combination thereof, and M' is P, Al, Zn, Ga, or a combination of any two or more thereof. Examples of sulfide-based solid-state electrolytes include, but are not limited to, lithium phosphorus sulfur chloride, lithium phosphorus sulfur fluoride, lithium phosphorus sulfur bromide, lithium phosphorus sulfur iodide, lithium germanium phosphorus sulfide, lithium zinc germanium oxide, lithium tin phosphorus sulfide, lithium silicon phosphorus sulfide, lithium silicon aluminum sulfide, lithium sulfide, phosphorus sulfide, lithium phosphorus sulfide, silicon sulfide, lithium orthosilicate, or a combination of any two or more thereof.

[0060] The sulfide-based solid-state may have a monolithic shape (e.g., a pellet). The monolithic shape may be formed by compressing a powder (e.g., compressing at a pressure of about 40 MPa to about 500 MPa, or about 50 MPa to about 400 MPa, or about 50 MPa to about 300 MPa).

[0061] In another aspect, a method of forming the anode is provided. The method includes grinding a mixture of antimony and a solid-state electrolyte and compressing the mixture into a monolithic form. The solid-state electrolyte may be a sulfide-based solid-state electrolyte. The antimony may have an average particle size of about 1 pm to about 100 pm as measured by scanning electron microscopy.

[0062] Grinding the mixture of antimony and a solid-state electrolyte may include using a mortar and pestle, planetary ball milling, high energy ball milling, or another grind milling process to grind antimony powder with solid-state electrolyte powder.

[0063] The antimony powder may have an average particle size, as measured by scanning electron microscopy imaging, of about 1 pm to about 100 pm, including about 1 pm to about 90 pm, about 1 pm to about 80 pm, about 1 pm to about 70 pm, about 1 pm to about 60 pm, or about 1 pm to about 50 pm.Atty. Dkt. No. 118347-0138 (24-024-UPR)

[0064] The antimony powder may be amorphous or crystalline. The antimony powder may have a crystalline or polycrystalline structure. For example, the antimony may have rhomb ohedral crystal structure.

[0065] The sulfide-based solid-state electrolyte powder may include an argyrodite solid electrolyte, a thio-LISICON solid electrolyte, any other suitable sulfide-based solid-state electrolyte, or a combination of any two or more thereof. Argyrodite-type solid electrolytes may have a chemical formula of LiePSsX where X is Cl, Br, I, or a combination of two or more thereof. Thio-LISICON solid electrolytes may have a formula of Li4-xMi-yMy'S4 where M is Si, Ge, or a combination thereof, and M' is P, Al, Zn, Ga, or a combination of any two or more thereof. Examples of sulfide-based solid-state electrolytes include, but are not limited to, lithium phosphorus sulfur chloride, lithium phosphorus sulfur fluoride, lithium phosphorus sulfur bromide, lithium phosphorus sulfur iodide, lithium germanium phosphorus sulfide, lithium zinc germanium oxide, lithium tin phosphorus sulfide, lithium silicon phosphorus sulfide, lithium silicon aluminum sulfide, lithium sulfide, phosphorus sulfide, lithium phosphorus sulfide, silicon sulfide, lithium orthosilicate, or a combination of any two or more thereof.

[0066] The solid-state electrolyte may have an average particle size, as measured by scanning electron microscopy imaging, of about 1 pm to about 100 pm, including about 1 pm to about 90 pm, about 1 pm to about 80 pm, about 1 pm to about 70 pm, about 1 pm to about 60 pm, or about 1 pm to about 50 pm.

[0067] The antimony powder may be present in the mixture in an amount, relative to the total weight of the anode, of about 20 wt.% to about 95 wt.%, about 30 wt.% to about 95 wt.%, about 40 wt.% to about 90 wt.%, about 50 wt.% to about 90 wt.%, about 60 wt.% to about 80 wt.%, about 65 wt.% to about 75 wt.%, or about 61 wt.%, about 62 wt.%, about 63 wt.%, about 64 wt.%, about 65 wt.%, about 66 wt.%, about 67 wt.%, about 68 wt.%, about 69 wt.%, about 70 wt.%, about 71 wt.%, about 72 wt.%, about 73 wt.%, about 74 wt.%, about 75 wt.%, about 76 wt.%, about 77 wt.%, about 78 wt.%, about 79 wt.%, about 80 wt.%, or any range including and / or in-between any two of these values.

[0068] The solid-state electrolyte powder may be present in the mixture in an amount, relative to the total weight of the anode, of about 1 wt.% to about 70 wt.%, about 1 wt.% to about 60 wt.%, about 1 wt.% to about 50 wt.%, about 2 wt.% to about 50 wt.%, about 5 wt.%Atty. Dkt. No. 118347-0138 (24-024-UPR) to about 50 wt.%, about 10 wt.% to about 50 wt.%, about 20 wt.% to about 40 wt.%, or about21 wt.%, about 22 wt.%, about 23 wt.%, about 24 wt.%, about 25 wt.%, about 26 wt.%, about27 wt.%, about 28 wt.%, about 29 wt.%, about 30 wt.%, about 31 wt.%, about 32 wt.%, about33 wt.%, about 34 wt.%, about 35 wt.%, about 36 wt.%, about 37 wt.%, about 38 wt.%, about39 wt.%, about 40 wt.%, or any range including and / or in-between any two of these values.

[0069] The weight ratio (w / w) of antimony powder and solid-state electrolyte that is formed into a mixture may be about 1 : 1, 1 :2 to about 2: 1, about 3 : 1 to about 1 :3, about 1 :4 to about 4:1, about 1 :5 to about 5: 1, about 1 :6 to about 6: 1, about 1 :7 to about 7: 1, about 1 :8 to about 8:1, about 1 :9 to about 9: 1, about 1 : 10 to about 10: 1, about 2:3 to about 3:2, about 2:5 to about 5:2, about 2:7 to about 7:2, about 2:9 to about 9:2, about 3:4 to about 4:3, about 3:5 to about 5:3, about 3:7 to about 7:3, about 3:8 to about 8:3, about 3: 10 to about 10:3, about 4:5 to about 5:4, about 4:7 to about 7:4, about 4:9 to about 9:4, about 5:6 to about 6:5, about 5:7 to about 7:5, about 5:8 to about 8:5, about 5:9 to about 9:5, about 6:7 to about 7:6, 8:9 to about 9:8, or any range including and / or in-between any two of these values. For example, the weight ratio of antimony powder and solid-state electrolyte may be about 6:3 to about 8: 1, about 6:2 to about 8:2, or about 7:2.

[0070] Compressing the mixture may be conducted at a pressure of about 50 MPa to about 500 MPa (e.g., about 50 MPa to about 400 MPa, about 50 MPa to about 300 MPa, about 100 MPa to about 300 MPa, or about 200 MPa to about 300 MPa).EXAMPLES

[0071] The present technology is further illustrated by the following Examples, which should not be construed as limiting in any way. The examples herein are provided to illustrate advantages of the present technology and to further assist a person of ordinary skill in the art with preparing or using the compositions and systems of the present technology. The examples should in no way be construed as limiting the scope of the present technology, as defined by the appended claims. The examples can include or incorporate any of the variations, aspects, or embodiments of the present technology described above. The variations, aspects, or embodiments described above may also further each include or incorporate the variations of any or all other variations, aspects, or embodiments of the present technology. The following Examples demonstrate the preparation, characterization,Atty. Dkt. No. 118347-0138 (24-024-UPR) and use of illustrative antimony electrodes. In these examples, antimony composite materials were fabricated and investigated as anodes for batteries.Example 1: Preparation of Chemicals and Materials

[0072] Two types of antimony were investigated as anode materials. The nanoscale antimony had a particle size of 100 nm to 500 nm as measured by scanning electron microscopy (SEM). The microscale antimony had a particle size of about 60 pm to about 100 pm as measured by SEM. The microscale antimony (Sb) powder (100 mesh, 99.5% trace metals basis) and lithium nickel manganese cobalt oxide (NMC, 98 %) were purchased from Sigma Aldrich. The LiePSsCl solid-state electrolyte (SSE) was purchased from the MTI corporation.

[0073] The antimony nanoparticles were synthesized by a chemical reduction method. In a typical synthesis, 0.1 g of PVP (K-30) was dissolved in 10 mL of water, followed by the addition of 0.03 g of NaBEU and stirred for 10 minutes until complete dissolution. The solution was transferred into a two-neck flask, which was further purged with nitrogen gas to create an inert atmosphere. In a separate glass vial, 0.05 g of SbCh was dissolved in 3 mL of ethanol under inert atmosphere, which was dropwise added to the above NaBEL solution by syringe with constant stirring. The resulting mixture was stirred for two hours. The antimony nanoparticles were centrifuged and washed four times with water and ethanol, followed by drying at 80 °C in a vacuum oven.

[0074] FIG. 2 is a graph of X-ray diffraction (XRD) characterization of microscale antimony powder used as an electroactive material in the anode. As shown in FIG. 2, both the microscale and nanoscale antimony samples exhibited high purity, with all the XRD peaks well assigned to the standard antimony peak card (JCPDF card # 00-0050562).

[0075] FIGS. 3A and 3B are SEM images of nanoscale (FIG. 3A) and microscale (FIG. 3B) antimony powder used as an electroactive material in the anode. The particle size and morphology of the nanoscale and microscale antimony powder were analyzed. As shown in FIG. 3A, the as-synthesized nanoscale antimony sample had a somewhat spherical morphology with a particle size of about 100 nm to about 500 nm. In comparison, the microscale antimony had a bulk structure with a relatively irregular morphology. The average particle size was about 60 pm to about 100 pm (FIG. 3B).Atty. Dkt. No. 118347-0138 (24-024-UPR)Example 2: Preparation of Electrochemical Cells with Liquid Electrolyte

[0076] Coin cell electrochemical cells with liquid electrolytes were prepared. A uniform slurry was prepared by grinding antimony powders (nanoscale or microscale), carbon black, and PVDF binder in an 8: 1 : 1 mass ratio. The obtained slurry was cast onto copper foil and dried at 70 °C for 10 hours in a vacuum oven. The electrode was cut into circular shape (1 cm in diameter) with an average mass loading of 2 mg cm'2. 2032 type coin cells were assembled in a glove box, where the counter / reference electrode was a lithium metal chip, the working electrode was the microscale antimony or the nanoscale antimony, the electrolyte was 1 M LiPFe / EC-DMC, and the separator was a Celgard polymer separator.Example 3: Battery Testing of Electrochemical Cells with Liquid Electrolyte

[0077] Battery performance was tested on a Landt tester (CT3002AU) at room temperature. Electrochemical impedance spectra (EIS) results were obtained on a Biologic SP-150 Potentiostat. 2032-type coin cells of LillSb half cells were assembled as described in Example 2. The anode was a pure Li metal chip, the cathode was the microscale or nanoscale antimony electrode, and the liquid electrolyte is 1 M LiPFe / EC-DMC (1 : 1 volume ratio, EC: ethylene carbonate; DMC: dimethyl carbonate).

[0078] FIGS. 4A and 4B are graphs of galvanostatic charge / discharge (GCD) curves of electrochemical cells with antimony anodes and lithium counter electrodes in a liquid electrolyte of 1 M LiPFe in ethylene carbonate and dimethyl carbonate (EC -DMC) at 50 mA g'1. FIG. 4A includes nanoscale antimony in the anode and FIG. 4B includes microscale antimony in the anode.

[0079] As shown in FIG. 4A, the GCD curves of nanoscale antimony showed an initial charge capacity of about 600 mAh g'1, which was higher than the microscale antimony electrode (520 mAh g'1, FIG. 4B). The higher capacity demonstrated by the nanoscale antimony may have resulted from its smaller particle size, which shortens the Li+diffusion pathway inside the metal alloy and thus increases the capacity. In the following cycles, the nanoscale antimony electrode showed a stable charge / discharge process, with GCD curves overlapping each other. By contrast, the microscale antimony electrode suffered from a continuous capacity fade with cycling, which may be related to its ultra larger particle size and volume change.Atty. Dkt. No. 118347-0138 (24-024-UPR)

[0080] FIGS. 5 A and 5B are graphs of electrochemical impedance spectroscopy (EIS) results of electrochemical cells with antimony anodes and lithium counter electrodes in a liquid electrolyte of 1 M LiPFe in ethylene carbonate and dimethyl carbonate (EC-DMC) at 50 mA g'1at the first, fifth, and tenth cycle. FIG. 5A includes nanoscale antimony in the anode and FIG. 5B includes microscale antimony in the anode.

[0081] EIS analysis measures electrical resistance of the battery electrode. As shown in FIGS. 5A and 5B, the overall EIS responses included a suppressed semi-circle and a linear slope, which may be attributed to the charge-transfer resistance (Ret) and ion diffusion process. The Ret is an indicator of the solid-electrolyte interphase (SEI) formation on the alloy electrode surface.

[0082] The EIS responses of the nanoscale antimony electrode were nearly identical to each other at the 1stand 5thcycle (FIG. 5A), and there was little change at the 10thcycle. This suggests that the SEI formation did not undergo a significant change during the cycling. In contrast, the microscale antimony electrode had a continuous increase in the size of the semicircle (FIG. 5B), suggesting that the charge-transfer resistance may get larger with cycling. This indicates that the SEI layers on the microscale antimony electrode surface may become thicker with cycling. Therefore, the ion conduction in the microscale antimony may be less than that of nanoscale antimony with cycling, leading to its lower capacity and faster capacity fading.

[0083] FIGS. 6 A and 6B are cross-sectional SEM images of the antimony electrodes from electrochemical cells with antimony anodes, lithium counter electrodes, and the liquid electrolyte of 1 M LiPFe in EC-DMC after different numbers of galvanostatic cycles. FIG. 6A includes nanoscale antimony in the anode and FIG. 6B includes microscale antimony in the anode.

[0084] Cross-sectional SEM analysis of the cycled antimony electrodes in the liquid electrolytes was conducted to investigate volume expansion and electrode pulverization with cycling. As shown in FIG. 6A, the thickness of the nanoscale antimony electrode increased from 15.2 pm to 18.7 pm after 10 charge / discharge cycles, which corresponded to a small expansion rate of 23%. In contrast, the microscale antimony electrode increased from 26.1 pm to 45.3 pm after 10 cycles (FIG. 6B), which corresponded to a larger expansion rate of 73%. Careful examination suggested that the microscale antimony electrode also sufferedAtty. Dkt. No. 118347-0138 (24-024-UPR) from particle pulverization and structural disintegration, with more cracks and larger voids observed after 10 cycles. These SEM results provide additional evidence of the capacity fading in microscale antimony electrodes.

[0085] Without being bound by any theory, FIG. 7 is an illustration of a reaction scheme of the formation of a solid-electrolyte interphase (SEI) on antimony powder in an anode of an electrochemical cell. The scheme illustrates the relationship between the volume change and the SEI formation. During the initial discharge process, Li+ions may enter the antimony material lattice and form a LisSb alloy. Due to the decomposition of the salts and solvents, the Lis Sb alloy surface may be deposited and covered by the SEI layers. SEI layers typically comprise both organic and inorganic components, and may not be robust enough to accommodate large volume change. Upon charging, volume shrinkage may cause these SEI layers to break down, loosely attaching to the antimony metal surface. In the following cycles, there may be another round of SEI reformation and breakage cycle, which, after multiple cycles, may lead to a thick SEI layer that may impede Li+ion insertion.

[0086] In general, nanoscale materials may buffer the volume change and thus lead to a more stable Li+(de)insertion process. However, the microscale antimony electrode faces a larger volume change and material disintegration / pulverization issue, resulting in the observed impedance increment, electrode detachment, and capacity fading.Example 4: Preparation of Electrochemical Cells with Solid Electrolyte

[0087] Antimony anodes for solid-state electrochemical cells were prepared. Antimony powders (nanoscale or microscale) were ground with LiePSsCl solid-state electrolyte (SSE) with a mortar and pestle for 20 minutes in a mass ratio of 7:3. The anode active mass loading was about 1.5 mg cm'2.

[0088] To make solid-state LilnllSb half cells, the SSE pellet (90 mg) was prepared by pressing 90 mg of SSE powder into a monolith using a hydraulic press under 50 MPa. Then, a composite of antimony and SSE powders was disposed on one side of the SSE pellet, and then the combination was pressed with the hydraulic press under 250 MPa for 15 minutes to form a monolith. The counter / reference electrode was a lithium-indium alloy, which has a redox potential of about 0.6 V vs. Li+ / Li. The indium thickness was 200 pm, and 2 pieces of indium metal foil were punched to a diameter of 1 / 4 inch for use. A small piece of lithium metal was cut and sandwiched between two indium metal pieces, providing a lithium-indiumAtty. Dkt. No. 118347-0138 (24-024-UPR) alloy with a mass ratio of 1 :38 (molar ratio: Lisin?). This Li-In alloy was attached to the SSE pellet opposite the working electrode with a moderate pressure. The solid-state battery was transferred into a custom battery case, and the half cells were tested with a predetermined approximate stack pressure of 50 MPa. The InLilINMC half cells were assembled in a similar way. Regarding the SbIINMC full cell, the composite of antimony and SSE and the composites of NMC and SSE were spread on each side of the SSE pellets, and the negative / positive capacity ratio was about 1 :1.Example 5: Battery Testing of Electrochemical Cells with Solid Electrolyte

[0089] Solid-state batteries were assembled according to Example 4. Battery performance was tested on a Landt tester (CT3002AU) at room temperature. Electrochemical impedance spectra (EIS) results were obtained on a Biologic SP-150 Potentiostat.

[0090] FIGS. 8A and 8B are graphs of galvanostatic charge / discharge curves of solid-state electrochemical cells with an antimony anode and a lithium indium alloy counter electrode at 50 mA g'1. FIG. 8 A includes nanoscale antimony in the anode and FIG. 8B includes microscale antimony in the anode. In contrast to the results with a liquid electrolyte, the solid-state electrochemical cells with microscale antimony electrodes demonstrated a higher capacity and more stable cycling than nanoscale antimony electrodes.

[0091] Both the nanoscale antimony and microscale antimony electrodes were tested in the solid-state battery configuration, wherein the Li-indium (Liln) alloy served as the counter and reference electrode. The current density as 50 mA g’1, and the reaction potential as shifted to the Li+ / Li couple. As shown in in FIG. 8A, the nanoscale antimony electrode showed a discharge and charge capacity of about 800 and 350 mAh g’1, respectively, leading to a lower initial Coulombic efficiency of about 44%. In the following cycles, the capacity did not activate or increase, and it remained lower at about 350 mAh g'1. This performance was less than that in the liquid electrolyte.

[0092] Surprisingly, the microscale antimony electrode in the solid-state electrochemical cell demonstrated highly stable GCD curves. The initial charge and discharge capacities were 611 mAh g'1and 692 mAh g’1, respectively, leading to a higher Coulombic efficiency of 88.4%. Subsequently, there was a subtle activation process, and the charge capacity increased to about 660 mAh g’1, corresponding to a full capacity utilization of antimony. Moreover, the Coulombic efficiency stabilized at 99.93%, in the following cycles, indicatingAty. Dkt. No. 118347-0138 (24-024-UPR) high reaction reversibility. The microscale antimony performance in the solid electrolyte was better than that in the liquid electrolyte, and better than that of nanoscale antimony in the solid electrolyte.

[0093] FIGS. 9A and 9B are SEM images of energy dispersive spectra (EDS) analysis of antimony-solid electrolyte composites. FIG. 9A shows the nanoscale antimony mixed with the solid electrolyte. FIG. 9B shows the microscale antimony mixed with the solid electrolyte. To understand the performance disparity, SEM and EDS analysis was conducted on the composites of antimony and SSE. As shown in FIG. 9 A, the nanoscale antimony particles were fully encapsulated in the SSE matrix, since the P, S, and Cl elements were predominant in the antimony / SSE composite, and much less antimony signal was detected as a result. By contrast, the composite of microscale antimony had a different elemental distribution. As shown in FIG. 9B, the antimony element was well mixed with the sulfur element, and there existed connections between different antimony metal particles. Based on these observations, the electron / ion conduction pathway in the antimony / SSE composite may be different for the nanoscale antimony and microscale antimony materials.

[0094] Without being bound by any theory, FIGS. 10A and 10B are schemes of the proposed antimony-solid electrolyte composite structures. FIG. 10A is an illustration of the nanoscale antimony mixed with the solid electrolyte. FIG. 10B is an illustration of the microscale antimony mixed with the solid electrolyte. Without being bound by any theory, the particle size may play a role in the electrode-electrolyte microstructure and thus the solid battery performance. It is noted that the pristine LiePSsCl SSE was a microscale material (10-20 pm), which is larger than the nanoscale antimony but much smaller than the microscale antimony metals. Besides, the sulfide SSE was mechanically soft and ductile, which may deform its shape during the electrode preparation process.

[0095] Specifically, when the antimony powders were ground with SSEs, these soft SSEs may spread themselves and cover the Sb surface. In the case of nanoscale antimony, the antimony metals were much smaller than the SSEs, therefore, partial antimony metals may be fully encapsulated or buried inside the SSE matrix. These incorporated antimony nanomaterials may have excellent ion conduction but may lose electron conduction (FIG. 10 A), thus impeding the electrode redox reactions. Consequently, the nanoscale antimony electrode exhibited lower capacity utilization in solid-state electrolytes. In contrast, the microscale antimony metals (about 60 pm to about 100 pm) were larger than the SSEAtty. Dkt. No. 118347-0138 (24-024-UPR) materials (about 10 to about 20 pm), which may reverse the electrode / electrolyte distribution scenario. As proposed in FIG. 10B, the relatively smaller SSE may not fully encapsulate the microscale antimony metals; instead, they may uniformly attach to the microscale antimony surface, providing excellent ion conduction. Furthermore, these larger antimony particles may connect with each other during the electrode grinding process, establishing electron percolation pathways. Consequently, the microscale antimony electrode may have a higher capacity utilization.

[0096] FIG. 11 is a graph of EIS results of the solid-state electrochemical cell with microscale antimony anode and a lithium indium alloy counter electrode at different cycles. EIS analysis of the microscale antimony electrode in the solid-state battery was performed to understand its stable cycling performance. As shown in FIG. 11, the microscale antimony battery showed a negligible change in the charge-transfer resistance, which is different from the microscale antimony electrode in the liquid electrolyte. The comparison here suggests that no substantial side reactions or SEI built-up took place in the solid electrolyte with microscale antimony.

[0097] FIG. 12 is a graph of rate capability of the solid-state electrochemical cell with microscale antimony anode and a lithium indium alloy counter electrode. The rate capability test provided reaction kinetics and reversibility information. Current densities ranging from 50 mA g'1to 3000 mA g'1were tested. As shown in FIG. 12, the capacity as 658, 659, 636, 580, 536, 502, 440, and 392 mAh g'1at the current density of 50, 100, 300, 600, 800, 1000, 1500, and 2000 mA g’1, respectively. Even at a higher current rate of 3000 mA g'1(~4.5 C), the microscale antimony electrode still delivered a reversible capacity of about 325 mAh g’1, which corresponded to approximately 50% capacity utilization. This indicated that the microscale antimony electrode has the potential to be a high-rate and fast-charging battery electrode. When the current density restored to 50 mA g’1, 100% of capacity was recovered. The high-rate capability illustrated excellent reaction reversibility with fast kinetics of the (de)alloy reaction with microscale antimony anode.

[0098] FIG. 13 is a graph of the cycling performance of the solid-state electrochemical cell with microscale antimony anode and a lithium indium alloy counter electrode. Besides the high-rate performance, the microscale antimony electrode also exhibited a promising cycling performance. When tested at a current density of 1000 mA g’1, the charge capacity fadedAtty. Dkt. No. 118347-0138 (24-024-UPR) from 495 mAh g'1to about 350 mAh g'1over 1000 cycles, corresponding to a high capacity retention of 70% (FIG. 13) with an average Coulombic efficiency of about 100%.

[0099] FIG. 14 is a graph of XRD results of the lithium nickel manganese cobalt oxide (NMC) cathode material. To further explore the commercial viability of the microscale antimony anode, a full cell that utilized a commercial lithium nickel manganese cobalt oxide (NMC) as the cathode was tested. XRD analysis was used to verify the phase purity of NMC. As shown in FIG. 14, the NMC material showed its characteristic diffraction peaks at 18.7, 36.6, 38.3, 44.5, 48.6, 58.8, 64.8 and 68.3°, which may be attributed to the diffraction planes of (003), (101), (012), (104), (015), (107), (018), (110) and (113) respectively. The results match well with a phase-pure NMC.

[0100] FIGS. 15A and 15B are SEM images of the NMC cathode material at different resolutions. The SEM analysis of NMC showed well-defined large spherical particles with a size distribution ranging from 5 pm to 10 pm. Close examination of individual spheres indicated that each sphere was made of small crystals arranged in a 3D configuration to form a spherical shape as shown in FIGS. 15A and 15B.

[0101] FIG. 16 is a graph of galvanostatic charge / discharge curves of solid-state LilnlINMC electrochemical cells with antimony anodes and lithium indium alloy counter electrodes at 50 mA g'1. As shown in FIG. 16, the initial charge capacity was about 230 mAh g’1, which may partially result from the oxidative decomposition of the sulfide electrolyte. In the following cycles, the charge / discharge process stabilized, with a reversible capacity of about 125 mAh g’1, which is a reasonable value for the NMC cathode in the solid-state battery context.

[0102] FIG. 17 is a graph of rate capability of a solid-state electrochemical cell with an NMC cathode and a lithium indium alloy counter electrode at various current densities.

[0103] The rate performance of NMC was performed at various current densities of 50, 100, 200, 300 and 500 mA g’1, and exhibited corresponding capacities of 125, 99, 72, 57 and 36 mAh g’1, respectively. The NMC cathode half-cell showed less stable rate performance as compared to the microscale antimony half-cell. Without being bound by any theory, this may result from the semiconductive nature of the metal oxide, whereas antimony is a pure metal with a much higher electronic conductivity.Atty. Dkt. No. 118347-0138 (24-024-UPR)

[0104] FIG. 18 is a graph of the cycling performance of the solid-state electrochemical cell with an NMC cathode and a lithium indium alloy counter electrode at 300 mA g'1. The NMC cathode exhibited a stable cycling performance. As shown in FIG. 18, there was no obvious capacity fading after 200 cycles, which indicated reaction reversibility. Therefore, the NMC may be used as a long-cycling cathode to make SbIINMC full cells.

[0105] FIG. 19 is a graph of galvanostatic charge / discharge curves of the solid-state SbIINMC full cell with an NMC cathode and a microscale antimony anode at 50 mA g'1. The full cell has an N / P ratio of about 1 : 1. Microscale antimony was used in the anode. As shown in FIG. 19, the SbIINMC full cell showed a high capacity of about 700 mAh g'1(based on the antimony mass) during the charge process, which was close to the theoretical capacity of antimony (660 mAh g'1). However, this capacity was not fully reversible, and the discharge capacity decreased to 428 mAh g'1. This corresponded to a moderate Coulombic efficiency of about 61%, which likely resulted from the sulfide electrolyte oxidization on the NMC cathode side. During the subsequent cycles, the GCD curves overlapped well, and the capacity stabilized at about 400 mAh g’1, suggesting a reversible reaction process. The average voltage was about 2.8 V.

[0106] FIG. 20 is a graph of rate capability of a solid-state electrochemical cell with an NMC cathode and a microscale antimony anode at various current densities. This solid-state SbIINMC full cell showed promising rate performance. The discharge capacity was 428, 371, 346, 297 and 233 mAh g'1at the current densities of 50, 100, 200, 300 and 500 mA g’1, respectively.

[0107] FIG. 21 is a graph of cycling performance of the solid-state electrochemical cell with an NMC cathode and a microscale antimony anode at 300 mA g'1. This solid-state full cell demonstrated an impressive cycling performance. When cycled at 300 mA g’1, there was no obvious capacity fading after 2000 cycles, indicating a nearly 100% capacity retention. Meanwhile, the Coulombic efficiency was close to 100% as well, suggesting a highly reversible insertion process. Such stability illustrates the potential of this SbIINMC full cell in practical applications.EQUIVALENTS

[0108] While certain embodiments have been illustrated and described, a person with ordinary skill in the art, after reading the foregoing specification, can effect changes,Atty. Dkt. No. 118347-0138 (24-024-UPR) substitutions of equivalents and other types of alterations to the compounds of the present technology or salts, compositions, derivatives, and mixtures as set forth herein. Each aspect and embodiment described above can also have included or incorporated therewith such variations or aspects as disclosed in regard to any or all of the other aspects and embodiments.

[0109] The present technology is also not to be limited in terms of the particular aspects described herein, 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 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 appended claims. It is to be understood that this present technology is not limited to particular methods, reagents, compounds, compositions, labeled compounds 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 aspects only, and is not intended to be limiting. Thus, it is intended that the specification be considered as exemplary only with the breadth, scope and spirit of the present technology indicated only by the appended claims, definitions therein and any equivalents thereof.

[0110] The embodiments, 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, but it is recognized that various modifications are possible within the scope of the claimed technology. Additionally, the phrase “consisting essentially of’ will be understood to include those elements specifically recited and those additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase “consisting of’ excludes any element not specified.[OHl] 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 therebyAtty. Dkt. No. 118347-0138 (24-024-UPR) described in terms of any individual member or subgroup of members of the Markush group. Each of the narrower species and subgeneric groupings falling within the generic disclosure also form part of the invention. This includes the generic description of the invention 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.

[0112] 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.

[0113] All publications, patent applications, issued patents, and other documents (for examplejournals, articles and / or textbooks) referred to in this specification are herein incorporated by reference as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated by reference in its entirety. Definitions that are contained in text incorporated by reference are excluded to the extent that they contradict definitions in this disclosure.

[0114] 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. An anode comprising: about 50 wt.% to about 90 wt.% antimony, the antimony having an average particle size of about 1 pm to about 100 pm as measured by scanning electron microscopy; and about 10 wt.% to about 50 wt.% of a first sulfide-based solid-state electrolyte.Atty. Dkt. No. 118347-0138 (24-024-UPR)B. The anode of Paragraph A, wherein the antimony has an average particle size of about 1 pm to about 50 pm as measured by scanning electron microscopy.C. The anode of Paragraph A or Paragraph B, wherein the first sulfide-based solid-state electrolyte comprises lithium phosphorus sulfur chloride, lithium phosphorus sulfur fluoride, lithium phosphorus sulfur bromide, lithium phosphorus sulfur iodide, lithium germanium phosphorus sulfide, lithium zinc germanium oxide, lithium tin phosphorus sulfide, lithium silicon phosphorus sulfide, lithium silicon aluminum sulfide, lithium sulfide, phosphorus sulfide, lithium phosphorus sulfide, silicon sulfide, lithium orthosilicate, or a combination of any two or more thereof.D. The anode of Paragraph A or Paragraph B, wherein the first sulfide-based solid-state electrolyte comprises LiePSsX, where X is F, Cl, Br, I, or a combination of two or more thereof.E. The anode of any one of Paragraphs A-D, wherein the first sulfide-based solid-state electrolyte has an average particle size of about 1 pm to about 50 pm as measured by scanning electron microscopy.F. The anode of any one of Paragraphs A-E, wherein an antimony mass loading is about 1 mg cm'2to about 2 mg cm'2.G. The anode of any one of Paragraphs A-F, wherein the antimony and first sulfide-based solid-state electrolyte are present as a composite formed by grinding together antimony and the first sulfide-based solid-state electrolyte.H. A solid-state battery comprising the anode of any one of Paragraphs A-E; a counter electrode; and a solid electrolyte disposed between the anode and the counter electrode, the solid electrolyte comprising a second sulfide-based solid-state electrolyte.I. The solid-state battery of Paragraph H, wherein the second sulfide-based solid-state electrolyte comprises lithium phosphorus sulfur chloride, lithium phosphorus sulfur fluoride, lithium phosphorus sulfur bromide, lithium phosphorus sulfur iodide, lithium germanium phosphorus sulfide, lithium zinc germanium oxide, lithium tin phosphorusAtty. Dkt. No. 118347-0138 (24-024-UPR) sulfide, lithium silicon phosphorus sulfide, lithium silicon aluminum sulfide, lithium sulfide, phosphorus sulfide, lithium phosphorus sulfide, silicon sulfide, lithium orthosilicate, or a combination of any two or more thereof.J. The solid-state battery of Paragraph H, wherein the second sulfide-based solid-state electrolyte comprises LiePSsX, where X is F, Cl, Br, I, or a combination of two or more thereof.K. The solid-state battery of Paragraph H, wherein the second sulfide-based solid-state electrolyte is the same as the first sulfide-based solid-state electrolyte.L. The solid-state battery of any one of Paragraphs H-K, wherein the counter electrode comprises lithium metal.M. The solid-state battery of any one of Paragraphs H-K, wherein the counter electrode is a cathode.N. The solid-state battery of Paragraph M, wherein the cathode comprises lithium cobalt oxide, lithium nickel oxide, lithium nickel cobalt oxide, lithium manganese oxide, lithium nickel manganese cobalt oxide, lithium manganese nickel oxide, lithium nickel manganese cobalt aluminum oxide, lithium iron phosphate, or a combination of any two or more thereof.O. A process for forming an anode for a solid-state battery, the process comprising: grinding a mixture of antimony, the antimony having an average particle size of about 1 pm to about 100 pm as measured by scanning electron microscopy, and a sulfide-based solid-state electrolyte; and compressing the mixture under a pressure of about 50 MPa to about 500 MPa into a monolithic form.P. The process of Paragraph O, wherein the mixture comprises about 50 wt.% to about 90 wt.% antimony and about 10 wt.% to about 50 wt.% of the sulfide-based solid-state electrolyte.Q. The process of Paragraph O or Paragraph P, wherein compressing the mixture comprises the pressure of about 200 MPa to about 300 MPa.Atty. Dkt. No. 118347-0138 (24-024-UPR)R. The process of any one of Paragraphs O-Q, wherein the sulfide-based solid-state electrolyte comprises lithium phosphorus sulfur chloride, lithium phosphorus sulfur fluoride, lithium phosphorus sulfur bromide, lithium phosphorus sulfur iodide, lithium germanium phosphorus sulfide, lithium zinc germanium oxide, lithium tin phosphorus sulfide, lithium silicon phosphorus sulfide, lithium silicon aluminum sulfide, lithium sulfide, phosphorus sulfide, lithium phosphorus sulfide, silicon sulfide, lithium orthosilicate, or a combination of any two or more thereof.S. The process of any one of Paragraphs O-R, wherein the sulfide-based solid-state electrolyte comprises LiePSsX, where X is F, Cl, Br, I, or a combination of two or more thereof.T. The process of any one of Paragraphs O-S, wherein the sulfide-based solid-state electrolyte has an average particle size of about 1 pm to about 50 pm as measured by scanning electron microscopy.

[0115] Other embodiments are set forth in the following claims, along with the full scope of equivalents to which such claims are entitled.

Claims

Atty. Dkt. No. 118347-0138 (24-024-UPR)WHAT IS CLAIMED IS:

1. An anode comprising: about 50 wt.% to about 90 wt.% antimony, the antimony having an average particle size of about 1 pm to about 100 pm as measured by scanning electron microscopy; and about 10 wt.% to about 50 wt.% of a first sulfide-based solid-state electrolyte.

2. The anode of claim 1, wherein the antimony has an average particle size of about 1 pm to about 50 pm as measured by scanning electron microscopy.

3. The anode of claim 1, wherein the first sulfide-based solid-state electrolyte comprises lithium phosphorus sulfur chloride, lithium phosphorus sulfur fluoride, lithium phosphorus sulfur bromide, lithium phosphorus sulfur iodide, lithium germanium phosphorus sulfide, lithium zinc germanium oxide, lithium tin phosphorus sulfide, lithium silicon phosphorus sulfide, lithium silicon aluminum sulfide, lithium sulfide, phosphorus sulfide, lithium phosphorus sulfide, silicon sulfide, lithium orthosilicate, or a combination of any two or more thereof.

4. The anode of claim 1, wherein the first sulfide-based solid-state electrolyte comprisesLiePSsX, where X is F, Cl, Br, I, or a combination of two or more thereof.

5. The anode of claim 1, wherein the first sulfide-based solid-state electrolyte has an average particle size of about 1 pm to about 50 pm as measured by scanning electron microscopy.

6. The anode of claim 1, wherein an antimony mass loading is about 1 mg cm'2to about2 mg cm'2.

7. The anode of claim 1, wherein the antimony and first sulfide-based solid-state electrolyte are present as a composite formed by grinding together antimony and the first sulfide- based solid-state electrolyte.

8. A solid-state battery comprising the anode of claim 1; a counter electrode; andAtty. Dkt. No. 118347-0138 (24-024-UPR) a solid electrolyte disposed between the anode and the counter electrode, the solid electrolyte comprising a second sulfide-based solid-state electrolyte.

9. The solid-state battery of claim 8, wherein the second sulfide-based solid-state electrolyte comprises lithium phosphorus sulfur chloride, lithium phosphorus sulfur fluoride, lithium phosphorus sulfur bromide, lithium phosphorus sulfur iodide, lithium germanium phosphorus sulfide, lithium zinc germanium oxide, lithium tin phosphorus sulfide, lithium silicon phosphorus sulfide, lithium silicon aluminum sulfide, lithium sulfide, phosphorus sulfide, lithium phosphorus sulfide, silicon sulfide, lithium orthosilicate, or a combination of any two or more thereof.

10. The solid-state battery of claim 8, wherein the second sulfide-based solid-state electrolyte comprises LiePSsX, where X is F, Cl, Br, I, or a combination of two or more thereof.

11. The solid-state battery of claim 8, wherein the second sulfide-based solid-state electrolyte is the same as the first sulfide-based solid-state electrolyte.

12. The solid-state battery of claim 8, wherein the counter electrode comprises lithium metal.

13. The solid-state battery of claim 8, wherein the counter electrode is a cathode.

14. The solid-state battery of claim 13, wherein the cathode comprises lithium cobalt oxide, lithium nickel oxide, lithium nickel cobalt oxide, lithium manganese oxide, lithium nickel manganese cobalt oxide, lithium manganese nickel oxide, lithium nickel manganese cobalt aluminum oxide, lithium iron phosphate, or a combination of any two or more thereof.

15. A process for forming an anode for a solid-state battery, the process comprising: grinding a mixture of antimony, the antimony having an average particle size of about 1 pm to about 100 pm as measured by scanning electron microscopy, and a sulfide-based solid-state electrolyte; and compressing the mixture under a pressure of about 50 MPa to about 500 MPa into a monolithic form.Atty. Dkt. No. 118347-0138 (24-024-UPR)16. The process of claim 15, wherein the mixture comprises about 50 wt.% to about 90 wt.% antimony and about 10 wt.% to about 50 wt.% of the sulfide-based solid-state electrolyte.

17. The process of claim 15, wherein compressing the mixture comprises the pressure of about 200 MPa to about 300 MPa.

18. The process of claim 15, wherein the sulfide-based solid-state electrolyte comprises lithium phosphorus sulfur chloride, lithium phosphorus sulfur fluoride, lithium phosphorus sulfur bromide, lithium phosphorus sulfur iodide, lithium germanium phosphorus sulfide, lithium zinc germanium oxide, lithium tin phosphorus sulfide, lithium silicon phosphorus sulfide, lithium silicon aluminum sulfide, lithium sulfide, phosphorus sulfide, lithium phosphorus sulfide, silicon sulfide, lithium orthosilicate, or a combination of any two or more thereof.

19. The process of claim 15, wherein the sulfide-based solid-state electrolyte comprisesLiePSsX, where X is F, Cl, Br, I, or a combination of two or more thereof.

20. The process of claim 15, wherein the sulfide-based solid-state electrolyte has an average particle size of about 1 pm to about 50 pm as measured by scanning electron microscopy.

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