Negative electrode for lithium battery

Abstract

Disclosed herein is a battery including: a case; a positive electrode located in the case; a negative electrode in the case, where the negative electrode includes an alloy, where the alloy includes lithium, magnesium, and silver; and an electrolyte in the housing, the electrolyte being capable of conducting an ionic current between the positive electrode and the negative electrode.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 468,648, filed May 24, 2023, entitled “Negative Electrode for a Battery,” the entire disclosure of which is incorporated herein by reference. Technical Field

[0003] This invention relates to batteries, and more particularly to a negative electrode for lithium batteries. Background Technology

[0004] In known Li-ion batteries, the battery includes a positive electrode and a negative electrode, and the negative electrode comprises graphite or some form of carbon. In some known Li-ion batteries, the negative electrode comprises a lithium alloy, such as Li x Si, Li x Ge, Li x Al, Li x Sn. In some known batteries, the electrodes are coated and stripped of Li metal during each charge and discharge cycle of the battery. Summary of the Invention

[0005] In some embodiments, the present invention provides a battery comprising: a housing; a positive electrode located within the housing; a negative electrode located within the housing, wherein the negative electrode comprises an alloy comprising lithium, magnesium, and silver; and an electrolyte located within the housing, the electrolyte being configured to conduct an ion current between the positive and negative electrodes.

[0006] In some implementations, the material of the positive electrode does not contain lithium in its atomic structure.

[0007] In some implementations, the material of the positive electrode contains lithium in its atomic structure.

[0008] In some implementations, the total weight percentage of lithium, magnesium and silver in the alloy is at least 50% of the total weight of the alloy.

[0009] In some embodiments, the material of the negative electrode has a crystal structure that is consistent with Li2AgMg as determined by XRD.

[0010] In some implementations, the negative electrode material has a crystal structure consistent with AgMg as determined by XRD, wherein lithium is added during battery operation to form an alloy.

[0011] In some implementations, lithium is formed on the negative electrode during battery operation.

[0012] In some implementations, lithium is deposited on the alloy during battery operation.

[0013] In some implementations, the electrolyte includes lithium.

[0014] In some implementations, the negative electrode also includes graphite.

[0015] In some embodiments, the positive electrode comprises at least one of a metal fluoride, sulfur, or a metal sulfide.

[0016] In some implementations, the positive electrode includes at least one of cobalt, nickel, iron, and manganese.

[0017] In some implementations, the positive electrode comprises iron fluoride or bismuth fluoride.

[0018] In some implementations, the electrolyte does not include lithium.

[0019] In some implementations, the electrolyte includes a fluoride.

[0020] In some embodiments, the alloy has a crystal structure represented by X-ray diffraction peaks corresponding to a d-spacing of approximately 3.6 Å to 4.2 Å.

[0021] In some implementations, the d-spacing is approximately 3.9 angstroms.

[0022] In some implementations, there are X-ray diffraction peaks corresponding to a d-spacing of approximately 3.1 to 3.5 angstroms.

[0023] In some implementations, the battery includes a lithium-ion battery.

[0024] In some implementations, the battery includes a solid-state lithium battery.

[0025] In some implementations, the electrolyte includes a solid electrolyte.

[0026] In some implementations, the composition of the alloy varies depending on the thickness of the alloy.

[0027] In some embodiments, the present invention provides a battery comprising: a housing; a positive electrode located in the housing; a negative electrode located in the housing; a current collector located in the housing; a separator located in the housing; an electrolyte located in the housing; and an alloy comprising lithium, magnesium, and silver, wherein the alloy is located on at least one of the negative electrode, the separator, and the current collector.

[0028] In some embodiments, the present invention provides a method comprising: obtaining a housing; arranging a positive electrode in the housing; arranging a negative electrode in the housing; depositing an alloy on the negative electrode, a separator, or a solid electrolyte, wherein the alloy comprises lithium, magnesium, and silver; and arranging an electrolyte in the housing, the electrolyte being configured to conduct current between the positive and negative electrodes.

[0029] In some implementations, deposition includes deposition via physical vapor deposition.

[0030] In some implementations, deposition includes depositing a film.

[0031] In some implementations, films are deposited via physical vapor deposition.

[0032] In some embodiments, the alloy has a crystal structure represented by X-ray diffraction peaks corresponding to a d-spacing of approximately 3.6 Å to 4.2 Å.

[0033] In some embodiments, the present invention provides a battery including electrodes, wherein the electrodes comprise a ternary alloy comprising lithium, magnesium, and silver.

[0034] In some implementations, although the alloy is called a "ternary alloy", it includes one or more other components besides lithium, magnesium and silver.

[0035] In some implementations, the battery is a lithium battery.

[0036] In some implementations, the battery is a lithium-ion battery.

[0037] In some implementations, the electrode is a negative electrode.

[0038] In some implementations, the electrode is a positive electrode.

[0039] In some implementations, the weight percentage of lithium, magnesium, and silver includes at least 50% of the weight of the ternary alloy of the negative electrode.

[0040] In some implementations, the ternary alloy is a solid alloy.

[0041] In some implementations, the ternary alloy is manufactured as a membrane.

[0042] In some implementations, films are deposited via physical vapor deposition.

[0043] In some embodiments, a ternary alloy is deposited on lithium metal. In some embodiments, lithium metal is deposited on a film.

[0044] In some implementations, the ternary alloy is deposited on the lithium-magnesium alloy.

[0045] In some implementations, lithium-magnesium alloys are deposited on ternary alloys.

[0046] In some implementations, ternary alloys are deposited on the current collector of the battery.

[0047] In some implementations, ternary alloys are deposited on the battery separators.

[0048] In some implementations, the battery includes lithium metal.

[0049] In some embodiments, the battery includes a positive electrode. In some embodiments, when installed in a battery, the positive electrode does not include lithium.

[0050] In some embodiments, the positive electrode comprises a metal fluoride. In some embodiments, the metal fluoride comprises iron fluoride. In some embodiments, the metal fluoride comprises bismuth fluoride.

[0051] In some implementations, the positive electrode comprises sulfur.

[0052] In some implementations, the positive electrode comprises a metal sulfide.

[0053] In some implementations, the negative electrode also includes graphite.

[0054] In some implementations, the negative electrode is a solid-state lithium battery.

[0055] In some implementations, the negative electrode is connected to the solid electrolyte of the solid-state battery.

[0056] In some implementations, the surface of the ternary alloy is covered with a solid lithium-ion conductor.

[0057] In some implementations, the solid-state ionic conductor includes lithium fluoride.

[0058] In some implementations, the battery includes a fluorine-ion battery.

[0059] In some implementations, the composition of the alloy varies depending on the thickness of the negative electrode.

[0060] In some embodiments, the ternary alloy has a crystal structure represented by X-ray diffraction peaks corresponding to a d-spacing of approximately 3.6 Å to 4.2 Å.

[0061] In some embodiments, the alloy has a crystal structure represented at least by X-ray diffraction peaks corresponding to a d-spacing of approximately 3.8 Å.

[0062] In some implementations, the alloy’s structure (but not necessarily its stoichiometry) is similar to that of AgLi2Mg. Attached Figure Description

[0063] This section relates to the accompanying drawings, which form part of the disclosed text, and the drawings illustrate some embodiments of the structures, materials, and / or methods of the invention described herein.

[0064] Figure 1 This is a graph illustrating the results of Li according to Example 1 when paired with an NbPO5 electrode, according to some embodiments of the present invention.

[0065] Figure 2 This is a graph illustrating the results of Li:Mg paired with a NbPO5 electrode according to Example 2, based on some embodiments of the present invention.

[0066] Figure 3A This is a graph illustrating the results of pairing a 7Li:Mg:xAg ternary alloy according to Example 3A with a NbPO5 electrode, based on some embodiments of the present invention.

[0067] Figure 3B This is a graph illustrating the results of pairing a 7Li:1Mg:xAg ternary alloy according to Example 3B with a NbPO5 electrode, based on some embodiments of the present invention.

[0068] Figure 4A This is a graph illustrating the results of pairing a 10Li:1Mg:xAg ternary alloy according to Example 4A with a NbPO5 electrode, based on some embodiments of the present invention.

[0069] Figure 4B This is a graph illustrating the results of pairing a 10Li:1Mg:xAg ternary alloy according to Example 4B with a NbPO5 electrode, based on some embodiments of the present invention.

[0070] Figure 5A This is a graph illustrating the results of pairing a 13Li:1Mg:xAg ternary alloy according to Example 5A with a NbPO5 electrode, based on some embodiments of the present invention.

[0071] Figure 5B This is a graph illustrating the results of pairing a 13Li:1Mg:xAg ternary alloy according to Example 5B with a NbPO5 electrode, based on some embodiments of the present invention.

[0072] Figure 6A The graphs are illustrations of results for various electrodes according to embodiment 6A, based on some embodiments of the invention.

[0073] Figure 6B The graphs are diagrams illustrating the results for various electrodes according to Embodiment 6B, based on some embodiments of the invention.

[0074] Figure 7A The graphs are diagrams illustrating the results for various electrodes according to Example 7A, based on some embodiments of the present invention.

[0075] Figure 7B The graphs are diagrams illustrating the results for various electrodes according to Example 7B, based on some embodiments of the present invention.

[0076] Figure 8A The graphs are diagrams illustrating the results for various electrodes according to Example 8A, based on some embodiments of the present invention.

[0077] Figure 8B The graphs are diagrams illustrating the results for various electrodes according to Example 8B, based on some embodiments of the present invention.

[0078] Figure 9A This is a graph illustrating the results for various electrodes according to Example 9A, based on some embodiments of the present invention.

[0079] Figure 9B The graphs are diagrams illustrating the results for various electrodes according to Example 9B, based on some embodiments of the present invention.

[0080] Figure 10A These are graphs illustrating results for various electrodes according to Example 10A, based on some embodiments of the present invention.

[0081] Figure 10B This is a graph illustrating the results for various electrodes according to Example 10B, based on some embodiments of the present invention.

[0082] Figure 11A This is a graph illustrating the results for various electrodes according to Example 11A, based on some embodiments of the present invention.

[0083] Figure 11B These are graphs illustrating the results for various electrodes according to Example 11B, based on some embodiments of the present invention.

[0084] Figure 12A This is a graph illustrating the results for various electrodes according to Example 12A, based on some embodiments of the present invention.

[0085] Figure 12B The graphs are diagrams illustrating results for various electrodes according to Example 12B, based on some embodiments of the present invention.

[0086] Figures 13 to 39 These are graphs illustrating results related to electrode evaluation according to some embodiments of the present invention. Detailed Implementation

[0087] In some embodiments, the present invention provides an alloy structure that offers excellent stability and is beneficial for the stability of Li alloys and Li metal / alloy hybrid negative electrodes.

[0088] In some embodiments, the alloy is referred to as a ternary alloy, comprising at least Li, Mg, and Ag, with or without additional materials. In some embodiments, the ternary alloy is compared to other alloys (especially Li...) x Mg and Li x Alloys of Ag exhibit excellent and unexpected properties. In some embodiments, crystal structures with extremely high amounts of Li and low amounts of Ag are formed, such as in Li7MgAg. 0.125 As in the example. In some embodiments, the crystalline structure is configured as a negative electrode material in the form of a thin film and is used to provide high capacity. In some embodiments, unexpected results allow for the elimination of binders, carbon black, and / or other components used in the manufacture of the negative electrode, further reducing the weight and volume of other components used in the negative electrode and / or the battery.

[0089] In some embodiments, comparative examples of the effectiveness of the method in lithium batteries using two different types of positive electrodes are provided. In some embodiments, comparisons are shown with Li batteries using different structures. x Mg or Li x Improvements to Ag alloys.

[0090] As used in this article, mAh refers to the measured capacity of an electrochemical cell, and mAh / g is a capacity normalized relative to the weight of the active electrode material used in the positive electrode.

[0091] As used herein, a separator refers to a non-electronically conductive material that separates the positive and negative electrodes to prevent electronic contact while maintaining ionic conductivity. The separator is porous, thus allowing ionicly conductive liquid electrolytes to be drawn into the material, or the separator itself is a solid-state ionic conductor of polymeric and / or inorganic compositions.

[0092] According to the embodiments described below, a comparison with non-lithium batteries has the following parameters:

[0093] Positive electrode: β Nb 0.98 Ta 0.02 PO5

[0094] Positive electrode composition: 70% active material, 20% Pvdf / HFP, 10% SP

[0095] Typical electrode capacity: 1.70mAh

[0096] Positive electrode diameter: 0.79cm = 0.50cm 2

[0097] Electrolyte: LiPF6 EC:DMC (baseline, no additives)

[0098] Electrolyte volume: 0.050 ml

[0099] Voltage: 1.65-2.8V

[0100] Charging: 10mA / g positive

[0101] Discharge: 15mA / g positive

[0102] Separator: a single Celgard sheet, approximately 25 micrometers thick

[0103] Negative electrode deposition:

[0104] Substrate: Cu 110, purity 99.9%, oxygen 0.04%, trace Ag

[0105] Substrate pretreatment: Acetone, 2 × 15 min, drying at 40 °C

[0106] Cu diameter: 12.3mm

[0107] Li / Mg / Ag deposition diameter: 11 mm = 0.95 cm 2

[0108] Baseline Li paired with NbPO5

[0109] Example 1

[0110] As described in Example 1, refer to Figure 1 Li metal was deposited on a 0.95 cm layer. 2Electrodes with capacities of 1.41 mAh and 2.16 mAh were obtained on Cu disks, respectively. These electrodes were also compared with 150 μm Li metal disks with capacities exceeding 15 mAh. As outlined in the experiments, two copies of each of the three Li electrodes were fabricated to form electrochemical cell units paired with NbPO5-based positive electrodes. As expected, the thick 150 μm Li metal disks cycled very well. However, the large excess of Li metal prevented this from becoming a viable path to high-energy-density cell units. Li metal disks with capacities <5 mAh showed significant degradation with cycling, and the situation was worst for the thinner and smallest 1.4 mAh film. As shown in the figure, two copies of each cell unit were formed and showed similar behavior. Without being bound by theory, it appears that the cell units fail not due to Li dendrite formation, but due to Li consumption via harmful reactions with the electrolyte. Therefore, the Li electrode with the least Li metal reserve fails the fastest. The data illustrate the need for a negative electrode with significantly increased stability.

[0111] Baseline LiMg paired with NbPO5 positive electrode

[0112] Example 2

[0113] As described in Example 2, refer to Figure 2 Li:Mg was deposited via physical vapor deposition x Co-deposited at 0.95cm 2 On the Cu disk, the Li:Mg stoichiometric ratio gradually decreased to 100:0, 16:1, 13:1, 10:1, 7:1, and 5:1. To properly compare all electrodes, 1.6 g of Li metal was deposited on all electrodes, and the amount of Mg was increased to the appropriate stoichiometric ratio as described above. As outlined in the experiments, two copies of each Li:Mg electrode were fabricated to form electrochemical cell units paired with NbPO5-based positive electrodes. As described in Example 1, the deposited Li metal film (100:0, 1.41 mAh) exhibited high initial capacity but rapidly degraded. The introduction of a small amount of Mg (16:1) resulted in a significant improvement in cycling, but this gradually diminished after approximately 25 cycles. However, the 7:1 sample resulted in excellent cycling stability, albeit at lower capacities. This trend of excellent cycling stability but gradually decreasing capacity continued with increasing Mg content. Ratios from 7:1 to 10:1 showed the optimal combination of cycling stability and capacity.

[0114] 7Li:Mg:xAg ternary alloy paired with NbPO5 positive electrode

[0115] Example 3A

[0116] Compared to Example 3A, Reference Figure 3ASimilar to Example 2, the realization of the Li:Mg alloy resulted in significant stabilization of the negative Li metal reaction. However, this was observed to be achieved at the cost of reduced capacity, below the theoretical capacity provided by the Li metal available in the film. This appears to be due to transport limitations. In an attempt to increase the achievable capacity, a small amount of Ag metal was introduced into the composition, due to Ag metal's high electronic conductivity and its ability to alloy with Li metal at low voltages. The Li:Mg:Ag metal was co-deposited in a 0.95 cm⁻¹ film by physical vapor deposition. 2 On the Cu disk, Ag was gradually added, with Li:Mg:Ag stoichiometric ratios based on a 7Li:1Mg ratio, as indicated in Example 2 as one of the better ratios, at 100:0:0, 7:1:0, 7:1:0.125, 7:1:0.500, and 7:1:1.00. To properly compare all electrodes, 1.6 g of Li metal was used to deposit all electrodes, with the amounts of Mg and Ag increased to the appropriate stoichiometric ratios as described above. As outlined in the experiments, two copies of each Li:Mg:Ag electrode were fabricated to form electrochemical cell units paired with NbPO5-based positive electrodes. As described in Example 1, the deposited Li metal film (100:0, 1.41 mAh) exhibited high initial capacity but rapidly degraded. The introduction of a small amount of Mg (7:1) resulted in excellent cycling stability, albeit at lower capacities. Adding a very small amount of Ag at a ratio of 7:1:0.125 resulted in a capacity increase of almost 50% while maintaining capacity retention. Increasing the Ag content to a ratio of 7:1:0.5 resulted in a 400% increase in capacity, but increased capacity decay was observed. In short, the addition of Ag significantly improved the electrochemical properties of the alloy. However, it appears that a mechanism beyond just Ag addition is at play. Therefore, the alloy was examined by X-ray diffraction.

[0117] 7Li:1Mg:xAg ternary alloy paired with NbPO5 positive electrode

[0118] Example 3B

[0119] As shown in Example 3B, refer to Figure 3B As can be seen from the XRD diffraction pattern of the negative electrode used in Example 3A, compared to other phases such as LiMg x The presence of a "Li₂AgMg"-like phase, observed in the diffraction pattern, along with AgMg, resulted in a significant systematic improvement in capacity and cycle life. Surprisingly, even small amounts of Ag induced stability in this structure, which is typically preserved at higher Ag concentrations. It is unclear whether this phase has been tested for use in lithium-ion batteries. However, testing has confirmed its remarkable properties.

[0120] 10Li:1Mg:xAg ternary alloy paired with NbPO5 positive electrode

[0121] Example 4A

[0122] refer to Figure 4A Example 4A describes a similar method based on co-deposition of Li:Mg:Ag metal to improve the electrochemical performance of a 7Li:1Mg alloy. This method was also developed for the 10Li:1Mg ratio electrode considered desirable in Example 2. The 10Li:1Mg:Ag metal was deposited via physical vapor deposition. x The ratio of co-deposited at 0.95cm 2 On the Cu disk, the Ag content was gradually increased to 100:0:0, 10:1:0, 10:1:0.125, 10:1:0.250, and 10:1:0.500. To properly compare all electrodes, 1.6 g of Li metal was used to deposit all electrodes, and the amounts of Mg and Ag were increased to the appropriate stoichiometric ratios as described above. As outlined in the experiments, two copies of each Li:Mg:Ag electrode were fabricated to form electrochemical cell units paired with NbPO5-based positive electrodes. As described in Example 1, the deposited Li metal film (100:0, 1.41 mAh) exhibited high initial capacity but rapidly degraded. The introduction of a small amount of Mg (10:1) resulted in excellent cycling stability, albeit at lower capacities. Similarly, adding a very small amount of Ag at a ratio of 7:1:0.125 resulted in a capacity increase of almost 30% to 40% while maintaining capacity retention. Increasing the Ag content to a ratio of 7:1:0.5 resulted in a capacity increase of >100%, but increased capacity decay was observed. The addition of Ag significantly improved the electrochemical properties of the alloy.

[0123] 10Li:1Mg:xAg ternary alloy paired with NbPO5 positive electrode

[0124] Example 4B

[0125] Compared to Example 4B, Reference Figure 4B As can be seen from the XRD diffraction pattern of the negative electrode used in Example 4A, compared to other phases such as LiMg x The presence of a phase resembling "Li2AgMg" in the diffraction pattern resulted in a significant systematic improvement in capacity and cycle life. This further confirmed the importance of this phase, as first demonstrated in Example 3A.

[0126] 13Li:1Mg:xAg ternary alloy paired with NbPO5 positive electrode

[0127] Example 5A

[0128] In Example 5A, reference Figure 5AA similar method, co-depositing Li:Mg:Ag metal to improve the electrochemical performance of 7Li:1Mg and 10Li:1Mg alloys, was also developed for the 13Li:1Mg ratio electrode considered desirable in Example 2. The 13:1:Ag metal was deposited via physical vapor deposition. x The ratio of co-deposited at 0.95cm 2 On the Cu disk, Ag was gradually added, with Li:Mg:Ag stoichiometric ratios of 100:0:0, 13:1:0, 13:1:0.125, and 13:1:0.250. To properly compare all electrodes, 1.6 g of Li metal was used to deposit all electrodes, with the amounts of Mg and Ag increased to the appropriate stoichiometric ratios as described above. As outlined in the experiments, two copies of each Li:Mg:Ag electrode were fabricated to form electrochemical cell units paired with NbPO5-based positive electrodes. As described in Example 1, the deposited Li metal film (100:0, 1.41 mAh) exhibited high initial capacity but rapidly degraded. The introduction of a small amount of Mg (13:1) resulted in significantly improved cycling stability, albeit at lower capacities. Similarly, the addition of a very small amount of Ag at a ratio of 7:1:0.250 resulted in a near 100% increase in capacity, but increased capacity decay was observed. In summary, the addition of Ag led to a significant improvement in the electrochemical performance of the alloy. However, there may also be a mechanism that works at least partially, rather than simply adding Ag.

[0129] 13Li:1Mg:xAg ternary alloy paired with NbPO5 positive electrode

[0130] Example 5B

[0131] Compared to Example 5B, Reference Figure 5B As can be seen from the XRD diffraction pattern of the negative electrode used in Example 5A, there is a significant systematic improvement in cycle life as the purity of the "Li2AgMg"-like phase in the diffraction pattern increases relative to other phases. In fact, the purest sample at 13:1:0.25 results in the best capacity / cycle performance, while other phases show a significant improvement in cycle life with decreasing purity and the presence of harmful LiMg. x The presence of phases increases, leading to a systematic deterioration.

[0132] The effectiveness of pairing the alloy of this invention with the LiCoO2 positive electrode

[0133] Previous Examples 1 through 5B utilized a positive electrode (based on NbPO5) that did not contain Li in its structure. Therefore, during the first discharge of the battery, all Li was supplied by the negative electrode of this invention to be embedded within its crystal structure. This configuration could be very important for future lithium-ion batteries, which will have positive electrodes with particularly high energy densities. In most contemporary lithium-ion batteries, the positive electrode contains Li present in its crystal structure, which is then removed during the first charge and reacts with the negative electrode. The negative electrode used in today's Li-ion batteries is typically graphite with extremely low capacity. It is desirable that the Li removed from the positive electrode be plated in Li metallic form or reacted with an alloy to provide excellent energy density for the battery. However, in most cases, this results in very poor cycle efficiency, even when placed on a small amount of already present Li metallic. This is likely primarily due to the detrimental reaction between the newly plated Li and the electrolyte. Based on the very positive results we observed with the non-lithiated positive electrode, we investigated the use of lithium-containing layered compounds in today's Li batteries to observe the efficacy of Li:Mg:Ag ternary compositions.

[0134] Example 6A

[0135] In Example 6A, reference Figure 6A The positive electrode (15.06 mg / cm³) is composed of LiCoO₂ forming the electrode. 2 LiCoO2; 0.495cm 2 A 1.10 mAh (approximately) electrode was placed in an electrochemical cell, similar to previous experiments, with the positive electrode initially charged and then cycled in a 1 M LiPF6 EC:DMC electrolyte. The following Li:Mg:Ag negative electrodes were prepared and two copies of each were fabricated to form cell units paired with a LiCoO2 electrode: 0:0:0, 7:0:0, 7:2.33:0, 7:0.538:0.067, 7:1:0.125, and 7:1:0.50. It can be seen that the absence of any Li at the negative electrode (Cu) results in very poor performance, with only a slight improvement compared to the pure Li film. Adding Mg to the alloy (7:2.33:0) further improves cycle stability, but the 7:1:0.125 alloy with a very small amount of Ag results in a very clear improvement in cycle stability of >100%, and the capacity is also improved relative to the pure Li film, and by 50% compared to the binary Li:Mg alloy. This also confirms the excellent properties of the alloy when paired with a pre-lithiated positive electrode compound.

[0136] The effectiveness of pairing the alloy of this invention with the LiCoO2 positive electrode

[0137] Example 6B

[0138] Compared to Example 6B, Reference Figure 6B As can be seen from the XRD diffraction pattern of the negative electrode used in Example 6, there is a significant systematic improvement in cycle life as the purity of the "Li2AgMg"-like phase in the diffraction pattern increases relative to other phases. In fact, the purest sample (7:1:0.125) results in the best cycle performance, while other phases show a significant improvement in cycle life with decreasing purity and the presence of harmful LiMg. x The presence of phases increases, leading to a systematic deterioration.

[0139] Various binary alloys: A comparison with ternary alloys when paired with LiCoO2 positive electrodes

[0140] Example 7A

[0141] In Example 7A, reference Figure 7A The battery cells were fabricated similarly to those in Example 6A, but various controls were explored with respect to the negative electrode to further illustrate the efficacy of the ternary composition Li:Mg:Ag. The examples clearly demonstrate that the three-element composition can result in a ternary (in this case, 7:1:0.125) exhibiting excellent stability in its electrochemical properties.

[0142] Various binary alloys: A comparison with ternary alloys when paired with LiCoO2 positive electrodes

[0143] Example 7B

[0144] Referring to Example 7B and Figure 7B As can be seen in the XRD diffraction pattern of the negative electrode used in Example 7A, with the formation of a phase similar to "Li2AgMg" present in the diffraction pattern of the composition 7:1:0.125, relative to the phase shown in LiMg... x Phase, pure lithium and Ag x All other compositions with Mg-related Bragg reflection show a significant and clear improvement in cycle life.

[0145] Li equivalent cyclic sample paired with LiCoO2 positive electrode

[0146] Example 8A

[0147] In Example 8A, reference Figure 8ASimilar to Example 6A, battery cells were fabricated, but various controls were explored with respect to the negative electrode to further illustrate the efficacy of the ternary composition Li:Mg:Ag. Here, the work focuses on ensuring the robustness of the results, where ternary Li:Mg:Ag leads to significantly better performance than Li:Mg alloys, regardless of the initial stoichiometry of the Li:Mg alloy. In the examples, it can be seen that various Li:Mg alloys (7:0.7:0, 7:1:0, 7:0.538:0) exhibit similar behavior to pure L metal alone when paired with LiCoO2. However, when a small amount of Ag was added to induce the fabrication of the ternary composition (7:1:0.125), a very clear and dramatic performance improvement was observed.

[0148] Li equivalent cyclic sample paired with LiCoO2 positive electrode

[0149] Example 8B

[0150] As shown in Example 8B, refer to Figure 8B X-ray diffraction revealed that even the addition of very small amounts of Ag (7:1:0.125) unexpectedly stabilized the crystal structure associated with Li₂MgAg, but with an increase in lattice parameters. Here, as in all other compositions, the improvement in electrochemical properties is linked to the stabilization of this favorable crystal structure by very small amounts of Ag, which has not been previously investigated.

[0151] The robustness of the alloy: The ratio of 1Mg:0.125Ag is increased relative to the LiCoO2 positive electrode.

[0152] Example 9A

[0153] Referring to Example 9A and Figure 9A Similar to Example 6A, battery cells were fabricated, but various controls were explored with respect to the negative electrode to further illustrate the efficacy of the ternary Li:Mg:Ag composition. Here, the work focuses on ensuring the robustness of ternary Li:Mg:Ag resulting in significantly better performance than Li:Mg alloys, regardless of the initial stoichiometry of the Li:Mg:Ag alloy (as opposed to Example 8, which focused on Li:Mg alloys). In the examples, it can be seen that, when paired with LiCoO2, various Li:Mg:Ag alloys (7:1.4:0.175, 7:2.33:0.292, 7:1:0.125) with gradually increasing Li content ratios exhibit similar superior behavior compared to pure Li metal, which performs much worse. The optimal composition is approximately the ternary composition (7:1:0.125). However, if the ratio of (Mg:0.125Ag) to Li becomes too high (7:7:0.875), performance will be compromised.

[0154] The robustness of the alloy: The ratio of 1Mg:0.125Ag is increased relative to the LiCoO2 positive electrode.

[0155] Example 9B

[0156] As described in Example 9B, refer to Figure 9B As can be seen from the XRD diffraction pattern of the negative electrode used in Example 6A, there is a significant systematic improvement in cycle life as the purity of the "Li₂AgMg"-like phase in the diffraction pattern increases relative to other phases. In fact, the purest samples of 7:1:0.125 and 7:2.33:0.292 result in the best cycle performance, while other phases show a significant improvement in cycle life with decreasing purity and the presence of harmful LiMg. x The presence of a phase systematically worsens the performance. For all compositions leading to the Li₂AgMg type structure, the electrochemical performance is excellent.

[0157] When paired with a LiCoO2 positive electrode, the Li content relative to a 1:0.125 Mg:Ag ratio is reduced.

[0158] Example 10A

[0159] In Example 10A, reference Figure 10A Similar to Example 6A, battery cells were fabricated, but various controls were explored with respect to the negative electrode to further illustrate the efficacy of the ternary Li:Mg:Ag composition. Here, the work focuses on ensuring the robustness of ternary Li:Mg:Ag resulting in significantly better performance than Li:Mg alloys, regardless of the initial stoichiometry of the Li:Mg:Ag alloy (as opposed to Example 8A, which focused on Li:Mg alloys). In the examples, it can be seen that, when paired with LiCoO2, various Li:Mg:Ag alloys (7:1:0.125, 5:1:0.125, 3:1:0.125) with gradually decreasing Li content exhibit similar superior behavior compared to pure Li metal, which performs much worse. The optimal composition is approximately the ternary composition (7:1:0.125). However, again, if the Li-to-Mg ratio becomes too low (1:1:0.125), performance will be compromised.

[0160] When paired with a LiCoO2 positive electrode, the Li content relative to a 1:0.125 Mg:Ag ratio is reduced.

[0161] Example 10B

[0162] Referring to Example 10B and Figure 10BAs can be seen from the XRD diffraction pattern of the negative electrode used in Example 10A, there is a significant systematic improvement in cycle life as the purity of the "Li₂AgMg"-like phase in the diffraction pattern increases relative to other phases. In fact, the purest sample of 7:1:0.125 results in the best cycle performance, while 5:1:0.125 and 3:1:0.125 show improved cycle life with decreasing purity and the presence of harmful LiMg. x The system deteriorates systematically due to the existence of the phase.

[0163] When paired with a LiCoO2 positive electrode, the Ag content relative to the 7Li:1Mg ratio is increased.

[0164] Example 11A

[0165] In Example 11A, reference Figure 11A Similar to Example 6A, battery cells were fabricated, but various controls were explored for the negative electrode to further illustrate the effectiveness of the ternary composition Li:Mg:Ag. In the examples, it can be seen that, when paired with LiCoO2, various 7Li:1Mg:Ag compositions with gradually increasing Ag content perform significantly better than pure Li metal. x Alloys (7:1:0, 7:1:0.125, 7:1:0.250) exhibit similar excellent behavior. The optimal composition is approximately the ternary composition (7:1:0.125). However, if the Ag-to-Li ratio becomes too high, the performance will be slightly compromised.

[0166] When paired with a LiCoO2 positive electrode, the Ag content relative to the 7Li:1Mg ratio is increased.

[0167] Example 11B

[0168] refer to Figure 11B Similar to Example 8B, X-ray diffraction in Example 11B revealed that even the addition of a very small amount of Ag in (7:1:0.125) unexpectedly stabilized the crystal structure associated with Li₂AgMg. Here, as in all other ternary compositions investigated, the improvement in electrochemical properties is associated with the stabilization of this favorable crystal structure by a very small amount of Ag, as can be seen in Example 11A.

[0169] When paired with a LiCoO2 positive electrode, the areal capacity is increased to 3 mAh / cm². 2

[0170] Example 12A

[0171] Referring to Example 12A and Figure 12ASimilar to Example 6A, two batteries were manufactured, in which the amount of LiCoO2 positive electrode used in the electrochemical battery cell gradually increased, ranging from 1.2 mAh / cm³. 2 Up to 3.0mAh / cm 2 3.0mAh / cm 2 These are target values ​​for most commercial applications, and the ternary alloy demonstrates a unique ability to maintain stable cycling of Li plating. The results show that the alloy is highly effective in supporting stable cycling at these areal capacities.

[0172] When paired with a LiCoO2 positive electrode, the areal capacity is increased to 3 mAh / cm². 2

[0173] Example 12B

[0174] In Example 12B, reference Figure 12B XRD revealed that all negative electrodes used in Example 12A, except for pure Li metal, had a Li2AgMg structure.

[0175] In some embodiments, the ternary alloy has a crystal structure represented at least by X-ray diffraction peaks corresponding to a d-spacing of approximately 3.0 Å. In some embodiments, the d-spacing is approximately 3.1 Å. In some embodiments, the d-spacing is approximately 3.2 Å. In some embodiments, the d-spacing is approximately 3.3 Å. In some embodiments, the d-spacing is approximately 3.4 Å. In some embodiments, the d-spacing is approximately 3.5 Å. In some embodiments, the d-spacing is approximately 3.6 Å. In some embodiments, the d-spacing is approximately 3.7 Å. In some embodiments, the d-spacing is approximately 3.8 Å. In some embodiments, the d-spacing is approximately 3.9 Å. In some embodiments, the d-spacing is approximately 4.0 Å. In some embodiments, the d-spacing is approximately 4.1 Å. In some embodiments, the d-spacing is approximately 4.2 Å. In some embodiments, the d-spacing is approximately 4.3 Å. In some embodiments, the d-spacing is approximately 4.4 Å. In some embodiments, the d-spacing is approximately 4.5 Å. In some embodiments, the d-spacing is approximately 4.6 Å. In some embodiments, the d-pitch is approximately 4.7 angstroms. In some embodiments, the d-pitch is approximately 4.8 angstroms. In some embodiments, the d-pitch is approximately 4.9 angstroms. In some embodiments, the d-pitch is approximately 5.0 angstroms.

[0176] In some embodiments, the d-pitch is approximately 3.0 Å to 5.0 Å. In some embodiments, the d-pitch is approximately 3.1 Å to 5.0 Å. In some embodiments, the d-pitch is approximately 3.2 Å to 5.0 Å. In some embodiments, the d-pitch is approximately 3.3 Å to 5.0 Å. In some embodiments, the d-pitch is approximately 3.4 Å to 5.0 Å. In some embodiments, the d-pitch is approximately 3.5 Å to 5.0 Å. In some embodiments, the d-pitch is approximately 3.6 Å to 5.0 Å. In some embodiments, the d-pitch is approximately 3.7 Å to 5.0 Å. In some embodiments, the d-pitch is approximately 3.8 Å to 5.0 Å. In some embodiments, the d-pitch is approximately 3.9 Å to 5.0 Å. In some embodiments, the d-pitch is approximately 4.0 Å to 5.0 Å. In some embodiments, the d-pitch is approximately 4.1 Å to 5.0 Å. In some embodiments, the d-pitch is approximately 4.2 Å to 5.0 Å. In some embodiments, the d-pitch is approximately 4.3 angstroms to 5.0 angstroms. In some embodiments, the d-pitch is approximately 4.4 angstroms to 5.0 angstroms. In some embodiments, the d-pitch is approximately 4.5 angstroms to 5.0 angstroms. In some embodiments, the d-pitch is approximately 4.6 angstroms to 5.0 angstroms. In some embodiments, the d-pitch is approximately 4.7 angstroms to 5.0 angstroms. In some embodiments, the d-pitch is approximately 4.8 angstroms to 5.0 angstroms. In some embodiments, the d-pitch is approximately 4.9 angstroms to 5.0 angstroms.

[0177] In some embodiments, the d-pitch is approximately 3.0 Å to 4.9 Å. In some embodiments, the d-pitch is approximately 3.1 Å to 4.9 Å. In some embodiments, the d-pitch is approximately 3.2 Å to 4.9 Å. In some embodiments, the d-pitch is approximately 3.3 Å to 4.9 Å. In some embodiments, the d-pitch is approximately 3.4 Å to 4.9 Å. In some embodiments, the d-pitch is approximately 3.5 Å to 4.9 Å. In some embodiments, the d-pitch is approximately 3.6 Å to 4.9 Å. In some embodiments, the d-pitch is approximately 3.7 Å to 4.9 Å. In some embodiments, the d-pitch is approximately 3.8 Å to 4.9 Å. In some embodiments, the d-pitch is approximately 3.9 Å to 4.9 Å. In some embodiments, the d-pitch is approximately 4.0 Å to 4.9 Å. In some embodiments, the d-pitch is approximately 4.1 Å to 4.9 Å. In some embodiments, the d-pitch is approximately 4.2 Å to 4.9 Å. In some embodiments, the d-pitch is approximately 4.3 angstroms to 4.9 angstroms. In some embodiments, the d-pitch is approximately 4.4 angstroms to 4.9 angstroms. In some embodiments, the d-pitch is approximately 4.5 angstroms to 4.9 angstroms. In some embodiments, the d-pitch is approximately 4.6 angstroms to 4.9 angstroms. In some embodiments, the d-pitch is approximately 4.7 angstroms to 4.9 angstroms. In some embodiments, the d-pitch is approximately 4.8 angstroms to 4.9 angstroms.

[0178] In some embodiments, the d-pitch is approximately 3.0 Å to 4.8 Å. In some embodiments, the d-pitch is approximately 3.1 Å to 4.8 Å. In some embodiments, the d-pitch is approximately 3.2 Å to 4.8 Å. In some embodiments, the d-pitch is approximately 3.3 Å to 4.8 Å. In some embodiments, the d-pitch is approximately 3.4 Å to 4.8 Å. In some embodiments, the d-pitch is approximately 3.5 Å to 4.8 Å. In some embodiments, the d-pitch is approximately 3.6 Å to 4.8 Å. In some embodiments, the d-pitch is approximately 3.7 Å to 4.8 Å. In some embodiments, the d-pitch is approximately 3.8 Å to 4.8 Å. In some embodiments, the d-pitch is approximately 3.9 Å to 4.8 Å. In some embodiments, the d-pitch is approximately 4.0 Å to 4.8 Å. In some embodiments, the d-pitch is approximately 4.1 Å to 4.8 Å. In some embodiments, the d-pitch is approximately 4.2 Å to 4.8 Å. In some embodiments, the d-pitch is approximately 4.3 angstroms to 4.8 angstroms. In some embodiments, the d-pitch is approximately 4.4 angstroms to 4.8 angstroms. In some embodiments, the d-pitch is approximately 4.5 angstroms to 4.8 angstroms. In some embodiments, the d-pitch is approximately 4.6 angstroms to 4.8 angstroms. In some embodiments, the d-pitch is approximately 4.7 angstroms to 4.8 angstroms.

[0179] In some embodiments, the d-pitch is approximately 3.0 Å to 4.7 Å. In some embodiments, the d-pitch is approximately 3.1 Å to 4.7 Å. In some embodiments, the d-pitch is approximately 3.2 Å to 4.7 Å. In some embodiments, the d-pitch is approximately 3.3 Å to 4.7 Å. In some embodiments, the d-pitch is approximately 3.4 Å to 4.7 Å. In some embodiments, the d-pitch is approximately 3.5 Å to 4.7 Å. In some embodiments, the d-pitch is approximately 3.6 Å to 4.7 Å. In some embodiments, the d-pitch is approximately 3.7 Å to 4.7 Å. In some embodiments, the d-pitch is approximately 3.8 Å to 4.7 Å. In some embodiments, the d-pitch is approximately 3.9 Å to 4.7 Å. In some embodiments, the d-pitch is approximately 4.0 Å to 4.7 Å. In some embodiments, the d-pitch is approximately 4.1 Å to 4.7 Å. In some embodiments, the d-pitch is approximately 4.2 Å to 4.7 Å. In some embodiments, the d-pitch is approximately 4.3 angstroms to 4.7 angstroms. In some embodiments, the d-pitch is approximately 4.4 angstroms to 4.7 angstroms. In some embodiments, the d-pitch is approximately 4.5 angstroms to 4.7 angstroms. In some embodiments, the d-pitch is approximately 4.6 angstroms to 4.7 angstroms.

[0180] In some embodiments, the d-pitch is approximately 3.0 Å to 4.6 Å. In some embodiments, the d-pitch is approximately 3.1 Å to 4.6 Å. In some embodiments, the d-pitch is approximately 3.2 Å to 4.6 Å. In some embodiments, the d-pitch is approximately 3.3 Å to 4.6 Å. In some embodiments, the d-pitch is approximately 3.4 Å to 4.6 Å. In some embodiments, the d-pitch is approximately 3.5 Å to 4.6 Å. In some embodiments, the d-pitch is approximately 3.6 Å to 4.6 Å. In some embodiments, the d-pitch is approximately 3.7 Å to 4.6 Å. In some embodiments, the d-pitch is approximately 3.8 Å to 4.6 Å. In some embodiments, the d-pitch is approximately 3.9 Å to 4.6 Å. In some embodiments, the d-pitch is approximately 4.0 Å to 4.6 Å. In some embodiments, the d-pitch is approximately 4.1 Å to 4.6 Å. In some embodiments, the d-pitch is approximately 4.2 Å to 4.6 Å. In some embodiments, the d-pitch is approximately 4.3 angstroms to 4.6 angstroms. In some embodiments, the d-pitch is approximately 4.4 angstroms to 4.6 angstroms. In some embodiments, the d-pitch is approximately 4.5 angstroms to 4.6 angstroms.

[0181] In some embodiments, the d-pitch is approximately 3.0 Å to 4.5 Å. In some embodiments, the d-pitch is approximately 3.1 Å to 4.5 Å. In some embodiments, the d-pitch is approximately 3.2 Å to 4.5 Å. In some embodiments, the d-pitch is approximately 3.3 Å to 4.5 Å. In some embodiments, the d-pitch is approximately 3.4 Å to 4.5 Å. In some embodiments, the d-pitch is approximately 3.5 Å to 4.5 Å. In some embodiments, the d-pitch is approximately 3.6 Å to 4.5 Å. In some embodiments, the d-pitch is approximately 3.7 Å to 4.5 Å. In some embodiments, the d-pitch is approximately 3.8 Å to 4.5 Å. In some embodiments, the d-pitch is approximately 3.9 Å to 4.5 Å. In some embodiments, the d-pitch is approximately 4.0 Å to 4.5 Å. In some embodiments, the d-pitch is approximately 4.1 Å to 4.5 Å. In some embodiments, the d-pitch is approximately 4.2 Å to 4.5 Å. In some implementations, the d-pitch is approximately 4.3 to 4.5 angstroms. In some implementations, the d-pitch is approximately 4.4 to 4.5 angstroms.

[0182] In some embodiments, the d-pitch is approximately 3.0 Å to 4.4 Å. In some embodiments, the d-pitch is approximately 3.1 Å to 4.4 Å. In some embodiments, the d-pitch is approximately 3.2 Å to 4.4 Å. In some embodiments, the d-pitch is approximately 3.3 Å to 4.4 Å. In some embodiments, the d-pitch is approximately 3.4 Å to 4.4 Å. In some embodiments, the d-pitch is approximately 3.5 Å to 4.4 Å. In some embodiments, the d-pitch is approximately 3.6 Å to 4.4 Å. In some embodiments, the d-pitch is approximately 3.7 Å to 4.4 Å. In some embodiments, the d-pitch is approximately 3.8 Å to 4.4 Å. In some embodiments, the d-pitch is approximately 3.9 Å to 4.4 Å. In some embodiments, the d-pitch is approximately 4.0 Å to 4.4 Å. In some embodiments, the d-pitch is approximately 4.1 Å to 4.4 Å. In some embodiments, the d-pitch is approximately 4.2 Å to 4.4 Å. In some implementations, the d-spacing is approximately 4.3 to 4.4 angstroms.

[0183] In some embodiments, the d-pitch is approximately 3.0 Å to 4.3 Å. In some embodiments, the d-pitch is approximately 3.1 Å to 4.3 Å. In some embodiments, the d-pitch is approximately 3.2 Å to 4.3 Å. In some embodiments, the d-pitch is approximately 3.3 Å to 4.3 Å. In some embodiments, the d-pitch is approximately 3.4 Å to 4.3 Å. In some embodiments, the d-pitch is approximately 3.5 Å to 4.3 Å. In some embodiments, the d-pitch is approximately 3.6 Å to 4.3 Å. In some embodiments, the d-pitch is approximately 3.7 Å to 4.3 Å. In some embodiments, the d-pitch is approximately 3.8 Å to 4.3 Å. In some embodiments, the d-pitch is approximately 3.9 Å to 4.3 Å. In some embodiments, the d-pitch is approximately 4.0 Å to 4.3 Å. In some embodiments, the d-pitch is approximately 4.1 Å to 4.3 Å. In some embodiments, the d-pitch is approximately 4.2 Å to 4.3 Å.

[0184] In some embodiments, the d-pitch is approximately 3.0 Å to 4.2 Å. In some embodiments, the d-pitch is approximately 3.1 Å to 4.2 Å. In some embodiments, the d-pitch is approximately 3.2 Å to 4.2 Å. In some embodiments, the d-pitch is approximately 3.3 Å to 4.2 Å. In some embodiments, the d-pitch is approximately 3.4 Å to 4.2 Å. In some embodiments, the d-pitch is approximately 3.5 Å to 4.2 Å. In some embodiments, the d-pitch is approximately 3.6 Å to 4.2 Å. In some embodiments, the d-pitch is approximately 3.7 Å to 4.2 Å. In some embodiments, the d-pitch is approximately 3.8 Å to 4.2 Å. In some embodiments, the d-pitch is approximately 3.9 Å to 4.2 Å. In some embodiments, the d-pitch is approximately 4.0 Å to 4.2 Å. In some embodiments, the d-pitch is approximately 4.1 Å to 4.2 Å.

[0185] In some embodiments, the d-pitch is approximately 3.0 Å to 4.1 Å. In some embodiments, the d-pitch is approximately 3.1 Å to 4.1 Å. In some embodiments, the d-pitch is approximately 3.2 Å to 4.1 Å. In some embodiments, the d-pitch is approximately 3.3 Å to 4.1 Å. In some embodiments, the d-pitch is approximately 3.4 Å to 4.1 Å. In some embodiments, the d-pitch is approximately 3.5 Å to 4.1 Å. In some embodiments, the d-pitch is approximately 3.6 Å to 4.1 Å. In some embodiments, the d-pitch is approximately 3.7 Å to 4.1 Å. In some embodiments, the d-pitch is approximately 3.8 Å to 4.1 Å. In some embodiments, the d-pitch is approximately 3.9 Å to 4.1 Å. In some embodiments, the d-pitch is approximately 4.0 Å to 4.1 Å.

[0186] In some embodiments, the d-pitch is approximately 3.0 Å to 4.0 Å. In some embodiments, the d-pitch is approximately 3.1 Å to 4.0 Å. In some embodiments, the d-pitch is approximately 3.2 Å to 4.0 Å. In some embodiments, the d-pitch is approximately 3.3 Å to 4.0 Å. In some embodiments, the d-pitch is approximately 3.4 Å to 4.0 Å. In some embodiments, the d-pitch is approximately 3.5 Å to 4.0 Å. In some embodiments, the d-pitch is approximately 3.6 Å to 4.0 Å. In some embodiments, the d-pitch is approximately 3.7 Å to 4.0 Å. In some embodiments, the d-pitch is approximately 3.8 Å to 4.0 Å. In some embodiments, the d-pitch is approximately 3.9 Å to 4.0 Å.

[0187] In some embodiments, the d-pitch is approximately 3.0 Å to 3.9 Å. In some embodiments, the d-pitch is approximately 3.1 Å to 3.9 Å. In some embodiments, the d-pitch is approximately 3.2 Å to 3.9 Å. In some embodiments, the d-pitch is approximately 3.3 Å to 3.9 Å. In some embodiments, the d-pitch is approximately 3.4 Å to 3.9 Å. In some embodiments, the d-pitch is approximately 3.5 Å to 3.9 Å. In some embodiments, the d-pitch is approximately 3.6 Å to 3.9 Å. In some embodiments, the d-pitch is approximately 3.7 Å to 3.9 Å. In some embodiments, the d-pitch is approximately 3.8 Å to 3.9 Å.

[0188] In some embodiments, the d-pitch is approximately 3.0 Å to 3.8 Å. In some embodiments, the d-pitch is approximately 3.1 Å to 3.8 Å. In some embodiments, the d-pitch is approximately 3.2 Å to 3.8 Å. In some embodiments, the d-pitch is approximately 3.3 Å to 3.8 Å. In some embodiments, the d-pitch is approximately 3.4 Å to 3.8 Å. In some embodiments, the d-pitch is approximately 3.5 Å to 3.8 Å. In some embodiments, the d-pitch is approximately 3.6 Å to 3.8 Å. In some embodiments, the d-pitch is approximately 3.7 Å to 3.8 Å.

[0189] In some embodiments, the d-pitch is approximately 3.0 Å to 3.7 Å. In some embodiments, the d-pitch is approximately 3.1 Å to 3.7 Å. In some embodiments, the d-pitch is approximately 3.2 Å to 3.7 Å. In some embodiments, the d-pitch is approximately 3.3 Å to 3.7 Å. In some embodiments, the d-pitch is approximately 3.4 Å to 3.7 Å. In some embodiments, the d-pitch is approximately 3.5 Å to 3.7 Å. In some embodiments, the d-pitch is approximately 3.6 Å to 3.7 Å.

[0190] In some embodiments, the d-pitch is approximately 3.0 angstroms to 3.6 angstroms. In some embodiments, the d-pitch is approximately 3.1 angstroms to 3.6 angstroms. In some embodiments, the d-pitch is approximately 3.2 angstroms to 3.6 angstroms. In some embodiments, the d-pitch is approximately 3.3 angstroms to 3.6 angstroms. In some embodiments, the d-pitch is approximately 3.4 angstroms to 3.6 angstroms. In some embodiments, the d-pitch is approximately 3.5 angstroms to 3.6 angstroms.

[0191] In some embodiments, the d-pitch is approximately 3.0 angstroms to 3.5 angstroms. In some embodiments, the d-pitch is approximately 3.1 angstroms to 3.5 angstroms. In some embodiments, the d-pitch is approximately 3.2 angstroms to 3.5 angstroms. In some embodiments, the d-pitch is approximately 3.3 angstroms to 3.5 angstroms. In some embodiments, the d-pitch is approximately 3.4 angstroms to 3.5 angstroms.

[0192] In some embodiments, the d-pitch is approximately 3.0 angstroms to 3.4 angstroms. In some embodiments, the d-pitch is approximately 3.1 angstroms to 3.4 angstroms. In some embodiments, the d-pitch is approximately 3.2 angstroms to 3.4 angstroms. In some embodiments, the d-pitch is approximately 3.3 angstroms to 3.4 angstroms.

[0193] In some embodiments, the d-pitch is approximately 3.0 angstroms to 3.3 angstroms. In some embodiments, the d-pitch is approximately 3.1 angstroms to 3.3 angstroms. In some embodiments, the d-pitch is approximately 3.2 angstroms to 3.3 angstroms.

[0194] In some embodiments, the d-pitch is approximately 3.0 angstroms to 3.2 angstroms. In some embodiments, the d-pitch is approximately 3.1 angstroms to 3.2 angstroms. In some embodiments, the d-pitch is approximately 3.0 angstroms to 3.1 angstroms.

[0195] Below, we present further embodiments of the present invention.

[0196] experiment:

[0197] Electrode fabrication and coin cell assembly:

[0198] Thin films of Li metal and combinations of Li, Mg, and Ag metals were deposited using physical vapor deposition (PVD) via thermal evaporation to achieve selected stoichiometric ratios. Unless otherwise stated, the composition is the nominal composition determined prior to deposition, as all components were utilized during the deposition process. For all Li-co-deposited deposits, the lithium content was normalized to 1.4 mAh. A 5 mil copper substrate (1.21 cm⁻¹) was used. 2 ( ) is used as a deposition substrate, wherein the deposited film has an area of ​​0.95 cm². 2 Using the positive electrode Nb 0.99 Ta 0.1 PO5 (NTPO) was used as a Li-free intercalation positive electrode, prepared by using 70 wt% NTPO, 10 wt% carbon, and 20 wt% PVdF-HFP polymer binder. Lithium cobalt (III) oxide (LiCoO2, LCO) was used as a Li-containing intercalation positive electrode, prepared by using 80 wt% LCO, 8 wt% carbon, and 12 wt% PVdF-HFP polymer binder (15.06 mg / cm³). 2 0.495cm 2 Two positive electrode disks were dried overnight at 120°C under vacuum. Button cells were prepared under argon atmosphere with water and oxygen content below 0.1 ppm. A single-layer Celgard separator (25 μm) was used in the button cell construction, and the cells were wetted with 50 μl of the standard electrolyte 1M LiPF6 EC / DMC.

[0199] Electrochemical characterization:

[0200] Electrochemical tests were performed using a bio-logic galvano / potentiostat. A coin cell constructed using a PVD thin-film negative electrode and an LCO positive electrode was charged to 4.2V with a constant current C / 10, then charged to current cutoff C / 40 with a constant voltage, and then discharged to 2.75V with a constant current C / 10. Alternatively, a coin cell constructed using an NTPO positive electrode was discharged to 1.65V at 15mA / g and then charged to 2.8V at 10mA / g. Cyclic charge and discharge capacities were evaluated for both experiments.

[0201] Physical characterization:

[0202] X-ray diffraction:

[0203] The negative electrode Li:Mg:Ag thin film deposit on a glass slide was characterized by X-ray diffraction (in-situ XRD) at a scan rate of 0.6185 degrees / min using a Bruker D8 diffractometer (Cu ka, wavelength = 1.54056 Å). The negative electrode Li:Mg:Ag thin film deposit was sealed using Kapton® to limit environmental contamination and oxidation. The generated XRD patterns were used to understand the phase differences between the deposited compositions and were processed using EVA and TOPAZ Rietveld refinement programs. In-situ XRD analysis was performed using a self-developed cell unit, where the negative electrode Li:Mg:Ag thin film deposit is located on a porous Cu mesh substrate (Li... 0.0072 / scan, 2.45 degrees / minute).

[0204] X-ray photoelectron spectroscopy:

[0205] Phase distribution and chemical characterization as a function of depth were evaluated using X-ray photoelectron spectroscopy (XPS, K-alpha, Thermo Scientific). Potential surface charging effects were eliminated using an electron neutralization gun. The subsurface film region was revealed using argon sputtering (2 keV). (Specific sputtering schemes will be added later).

[0206] result:

[0207] Optimization of Li:Mg:Ag negative electrode when paired with NTPO

[0208] Li ion configuration: Baseline Li reference when paired with NTPO

[0209] Using a Li-free intercalation compound as the positive electrode in a Li-ion battery configuration allows for direct evaluation of Li removal from the negative electrode, with limited impact from detrimental reactions occurring via Li plating. These detrimental reactions include Li metal-electrolyte interactions, and, most importantly, mask the inefficiencies associated with abundant Li reserves in half-cell configurations using Li metal as the negative electrode. Here, a previously developed NTPO positive electrode with negligible initial cycle loss and excellent cycle stability is used, with the capacity used in excess relative to the thin-film negative electrode to ensure complete delithiation of the alloy, to evaluate and develop optimized alloy compositions for Li metal stabilization (as detailed in the experimental section). 9 Additionally, this configuration may be related to achieving future high-energy-density battery configurations, characterized by high energy density and non-lithiated positive electrodes (such as sulfur or metal fluoride composites).

[0210] like Figure 13 As shown, the baseline-deposited Li metal film (which contains the same amount of Li metal (1.48 mAh / cm³) as most of the lithium-containing alloy films studied in this paper) is compared. 2 And a Li metal disk (150μm Li metal, >15.79mAh / cm²) 2 The performance was evaluated when paired with an NTPO positive electrode. As expected, the high-capacity Li metal disk exhibited better cycle stability than the lower-capacity 2.27 mAh / cm³. 2 and 1.48mAh / cm 2 The improved cycling stability of the Li thin film is due to the excess Li metal reserve and its ability to absorb Li consumption caused by electrolyte interactions. However, despite the improved performance, it is practically impossible to incorporate a large amount of excess Li metal to achieve high-energy-density battery cells, considering both energy density and safety. Therefore, to utilize the high energy density capability of Li metal, these electrodes must be improved to enhance stability.

[0211] Figure 13 The discharge and charge areal capacities (mAh / cm²) of the Li metal film when paired with NTPO are shown. 2 (a) and the specific capacity (mAh / g NTPO) of the Li metal thin film benchmark when paired with NTPO battery cells (b), were both observed up to 50 cycles. The Li metal thin film benchmark used included >15.79 mAh / cm² of the given calculated area capacity. 2 (Red), 2.27mAh / cm 2 (Green) and 1.48mAh / cm 2 (Blue) Negative electrode.

[0212] a. Improvement of Li thin films using Mg and Ag alloys

[0213] To evaluate the impact on performance, Mg was incorporated into the Li thin film deposition composition. For example... Figure 14 As shown, co-deposited Li:Mg alloys were studied with normalized stoichiometric ratios of 1:0, 16:1, 13:1, 10:1, 7:1, and 5:1 when paired with a positive electrode NTPO, with discharge capacity observed up to 50 cycles. Here, the normalized Li metal reference film exhibited high initial capacity compared to all other Li:Mg compositions shown, but failed rapidly. Introducing a small amount of Mg (16Li:1Mg) improved this initial performance while still maintaining high initial capacity; however, capacity decay was still observed after approximately 25 cycles. Alternatively, increasing the Mg content by further reducing the ratio to 10:1, 7:1, and 5:1 reduced the initial capacity but significantly improved the cycling stability of all the aforementioned compositions, with an ideal combination of Li metal stability and capacity reduction observed for ratios from 7:1 to 10:1. This observed capacity reduction (below the available theoretical capacity) is likely due to transport limitations.

[0214] To address this challenge and increase achievable capacities, Ag metal was introduced into the alloy due to its high electronic conductivity, large atomic size, ability to form alloys with Li metal at low voltages, and the potential for forming extended solid solutions. Utilizing the previously identified advantageous 7:1 Li:Mg ratio, Ag was added to the composition in gradually increasing stoichiometric ratios (Li:Mg:Ag ratios of 7:1:0.125, 7:1:0.25, 7:1:0.5, and 7:1:1). Figure 15 As shown, adding a small amount of Ag at a ratio of 7:1:0.125 resulted in excellent cycling performance and capacity retention, with a capacity increase of almost 50% compared to the same composition lacking Ag (7:1:0). Further increasing the relative silver content to 7:1:0.25, 7:1:0.5, and 7:1:1 significantly improved capacity (an increase of almost 400% for 7:1:0.5), however, at the cost of faster capacity decay. In summary, a significant improvement in cycling stability was observed by adding a small amount of Mg (7:1) to the pure Li composition at the expense of areal capacity; however, the resulting capacity reduction was significantly mitigated by adding a small amount of Ag (7:1:0.125) to the alloy composition.

[0215] Figure 14 The discharge and charge areal capacities (mAh / cm²) of the Li:Mg film when paired with NTPO are shown. 2(a) and (b) the specific capacity (mAh / g NTBO) of the Li:Mg:Ag thin film when paired with an NTPO battery cell, both observed up to 50 cycles. The Li:Mg:Ag thin film negative electrode compositions shown here comprise the following ratios: 16:1:0 (blue), 13:1:0 (red), 10:1:0 (black), 7:1:0 (yellow), 5:1:0 (green), and a normalized Li metal film reference (light blue), wherein all Li-containing compositions contain the same amount of Li.

[0216] Figure 15 The discharge and charge areal capacities (mAh / cm²) of the ternary Li:Mg:Ag film paired with NTPO are shown. 2 (A) and the specific capacity (mAh / g NTPO) of the Li:Mg:Ag film when paired with an NTPO Li-ion battery cell (B), both observed up to 50 cycles. The Li:Mg:Ag film negative electrode compositions shown here comprise the following ratios: 7:1:0.125 (green), 7:1:0.25 (blue), 7:1:0.5 (red), and 7:1:1 (black), as well as a normalized Li metal film (light blue) and a 7:1 Li:Mg reference (yellow), wherein all Li-containing compositions contain the same amount of Li.

[0217] Given the substantial improvement in the properties of Ag-doped compositions, X-ray diffraction is used to identify and characterize the potential key active phases in these compositions. For example... Figure 35 As shown, the XRD patterns of the Li:Mg:Ag compositions are characterized by strong Bragg reflections associated with the Li₂AgMg and AgMg intermetallic phases. The compositions lacking the Ag component, 7:0:0 and 7:1:0, are characterized by pure Li or Li₂, respectively. 0.9 Mg 0.1 Therefore, the performance improvements observed for the 7:1:0.125 and 7:1 compositions are likely due to the formation of Li2AgMg and AgMg phases, with the Li2AgMg phase achieved through a very small amount of Ag. Additional details regarding the phases and composition of the films will be discussed in subsequent sections.

[0218] Figure 16 XRD patterns of Li:Mg:Ag thin film negative electrode compositions comprising the following ratios are shown: 7:1:0.125, 7:1:0.25, 7:1:0.5 and 7:1:1, as well as normalized Li metal film and 7:1 Li:Mg reference.

[0219] b. Evaluation of Li:Mg:Ag compositions using excess Li.

[0220] As shown in the previous sections, the 10:1 and 13:1 Li:Mg compositions exhibited improved performance relative to a pure Li baseline containing the same normalized Li content (Table 1). Here, these compositions are further evaluated using a similar Ag addition ratio utilized in the 7:1 Li:Mg optimization. Figure 17 As shown, the introduction of Mg into the Li film (10:1) results in a significant improvement in cycling performance compared to the pure Li film, at the cost of reduced capacity (a trend also observed for the 7:1 Li:Mg film). Here, the addition of a small amount of Ag (10:1:0.125) leads to a significant increase in capacity of 30% to 40%, while maintaining a moderate capacity retention. Further increasing the Ag content to 10:1:0.25 and 10:1:0.5 results in significant increases in capacity (for 10:1:0.5, the increase is >100%); however, as previously observed, this is also accompanied by an increased capacity decay. Given this improvement in performance, XRD is again used to identify the potential key participating phase. Figure 18 As shown, the addition of a small amount of Ag (10:1:0.125) to the 10:1 Li:Mg composition resulted in the formation of a significant amount of the Li2AgMg phase, which, according to the previous section, was observed in the high-performance 7:1:0.125 composition.

[0221] Figure 17 The discharge and charge capacities (mAh / cm³) of the ternary Li:Mg:Ag film paired with NTPO are shown. 2 (A) and (B) the specific discharge capacity (mAh / g NTBO) of the Li:Mg:Ag film when paired with an NTPO battery cell, both observed up to 50 cycles. The Li:Mg:Ag film negative electrode compositions shown here comprise the following ratios: 10:1:0.125 (green), 10:1:0.25 (blue), and 10:1:0.5 (red), as well as normalized Li metal film (black) and 10:1:0 (yellow) Li:Mg references, wherein all Li-containing compositions contain the same amount of Li.

[0222] Figure 18 XRD patterns of Li:Mg:Ag thin film negative electrode compositions with the following ratios are shown: 10:1:0.5 (red), 10:1:0.25 (blue), 10:1:0.125 (green) and 10:1:0 (yellow), as well as normalized Li metal film and 10:1 Li:Mg reference (black).

[0223] Similarly, optimization of the beneficial 13:1 Li:Mg composition (as indicated above) with the addition of Ag (13:1:0.25) compared to pure Li and the 13:1 Li:Mg composition revealed a very significant capacity improvement. However, similar to the observations previously discussed with the 10:1 Li:Mg composition, the capacity increase was accompanied by an increase in capacity decay with the addition of Ag. Additionally, as... Figure 20 As shown, the addition of Ag (13:1:0.125, 13:1:0.25) to the 13:1 composition resulted in the formation of the same Li2AgMg and AgMg intermetallic phases as previously observed.

[0224] Figure 19 The discharge and charge areal capacities (mAh / cm²) of the ternary Li:Mg:Ag film paired with NTPO are shown. 2 (A) and the specific capacity (mAh / g NTBO) of the Li:Mg:Ag film when paired with an NTPO battery cell (B), both observed up to 50 cycles. The Li:Mg:Ag film negative electrode compositions shown here comprise the following ratios: 13:1:0.125 (red), 13:1:0.25 (green), and normalized Li metal film (black) and 13:1:0 Li:Mg reference (blue), wherein all Li-containing compositions contain the same amount of Li.

[0225] Figure 20 XRD patterns of thin-film negative electrode compositions comprising the following Li:Mg:Ag ratios are shown: 13:1:0.25 (green), 13:1:0.125 (red), 13:1:0 (blue), and normalized Li metal film reference (black).

[0226] In summary, evaluation of Li:Mg:Ag thin film deposits showed that adding Mg to pure Li compositions at ratios of 7:1:0, 10:1:0, and 13:1:0 all resulted in superior cycling stability compared to Li metal alone, although capacity was significantly reduced (Table 2). Adding very small amounts of Ag to these compositions significantly improved the capacity of these alloys while maintaining the excellent cycling stability of the Li ion configuration when paired with NTPO. However, compositions with higher relative Li content (especially the 13:1:0.125 and 13:1:0.25 compositions) experienced earlier capacity decay. Based on initial XRD analysis, stabilization was induced by transformation to Li₂AgMg and AgMg intermetallic alloy phases, which have not yet been investigated for use in Li batteries. As shown in Table 3, initial results revealed potential solid solution formation induced by the formation of the Li₂AgMg phase. Increasing the relative lithium content of the Li:Mg:Ag film from 7 Li to 13 Li in the 1:0.125 Ag:Mg and 1:0.25 Ag:Mg systems resulted in a gradual decrease in the lattice parameter of the Li₂AgMg phase and a gradual increase in the AgMg lattice parameter. However, despite the potential solid solution formation observed in these ternary compositions, a larger relative ratio of Li:Mg to Mg:Ag may be detrimental. Therefore, based on initial optimization with NTPO pairing, a 7:1:0.125 Li:Mg:Ag ratio was initially considered alone to provide the greatest benefit among all compositions observed in this study, based on its superior cycling stability and moderate capacity recovery compared to Li films alone and the 7:1 Li:Mg composition. The capabilities of the 7:1:0.125 composition when paired with LCO are further explored in the following sections.

[0227]

[0228] Table 1. Li:Mg:Ag composition ratios used in electrochemical evaluation and XRD analysis, along with ratios normalized for Li content.

[0229] Table 2. Maximum Li extraction (mAh / cm³) of Li:Mg:Ag compositions 2 )

[0230]

[0231] Table 2. Areal capacity (mAh / cm²) of thin-film Li:Mg:Ag compositions paired with NTPO during cycling 2 The maximum lithium extracted. The cycle in which the maximum lithium extraction was observed is shown in the right column.

[0232] Table 3. Lattice parameters and phase percentages of Li:Mg:Ag compositions

[0233]

[0234] Table 3. Lattice parameters and compositional percentages of Li2AgMg and AgMg phases present in Li:Mg:Ag thin film compositions including 7:1:0.125, 7:1:0.25, 7:1:0.5, 7:1:1, 10:1:0.125, 10:1:0.25, 10:1:0.5, 13:1:0.125, and 13:1:0.25.

[0235] 1. Evaluation of the Li:Mg:Ag negative electrode when paired with LCO

[0236] A. Effect of Li ratio in a 1:0.125 Mg:Ag system

[0237] Given the success of the 7:1 Li:Mg structure in stabilizing pure Li metal anodes in previous sections, and the significant improvement in capacity and cycling stability achieved by adding Ag, particularly in the 7:1:0.125 composition, a similar analysis is now applied using Li-containing intercalation compounds. Here, instead of removing the Li content from the thin-film negative alloy electrode for intercalation into the NTPO cathode, we remove Li from the Li-containing intercalation compound LCO for reaction or deposition onto the negative thin-film electrode. This allows us to gain a more realistic understanding of the functionality of the beneficial thin-film composition in a more commercially relevant cell configuration by observing initial irreversible capacity loss and capacity decay during cycling. In this commercially relevant cell configuration, we introduce an additional Li:Mg:Ag composition to further understand and individually consider the benefits achieved by the 7:1:0.125 composition identified in previous sections, but in accordance with previous studies (7... +x :1:0.125) Comparison (7 -x Within a phase window of 1:0.125, all compositions used contain a fixed Li content (Table 1).

[0238] As observed in previous sections, the Li ratio in the 1:0.125 Mg:Ag system significantly affects cycling performance and achievable capacity when paired with NTPO. Further exploration of the role of Li in the 1:0.125 Mg:Ag system (including additional ratios of 5:1:0.125, 3:1:0.125, and 1:1:0.125) reveals that electrochemical performance decreases as the Li:Mg and Li:Ag ratios approach 1:1. Figure 21As shown in the figure, compared to the beneficial 7:1:0.125 composition (2.28% loss), with decreasing relative Li content to 5:1:0.125 (2.81% loss), 3:1:0.125 (2.73% loss), and 1:1:0.125 (13.79% loss), in addition to significantly earlier-onset detrimental capacity decay, a slightly higher irreversible capacity loss was observed. Figure 21 (Table 4), where all compositions contain a fixed normalized Li content (Table 1). Therefore, there is a detrimental Li:Mg and Li:Ag ratio that degrades performance, with significant performance degradation even relative to the poorly performing Li metal baseline (1:0:0) at extremes (1:1:0.125). Therefore, there exists an ideal Li:Mg and Li:Ag ratio that provides a beneficial basis for Li plating and morphological evolution during cycling, achieving high discharge capacity retention and low irreversible loss.

[0239] XRD characterization of the above membrane compositions showed that the unique binary:ternary ratio within the membrane can contribute to greater capacity retention (and not necessarily just high ternary phase purity). As shown in Table 5, the poor-performing composition 1:1:0.125 incorporated the lowest amount of ternary phase and had the lowest ternary:binary ratio in the group. Compositions 5:1:0.125 and 3:1:0.125 showed improved electrochemical performance, likely due to a relative increase in ternary phase compared to the 1:1:0.125 composition (79.50%, 69.87% vs. 43.57%). The electrochemical differences between these improved compositions are likely due to the relative percentage of binary phase, with the slightly better-performing 3:1:0.125 composition characterized by a relatively higher ternary:binary ratio, similar to the best-performing 7:1:0.125 composition (where the electrochemical difference may be related to Li₂AgMg lattice expansion). Therefore, when paired with LCO, a unique range of ternary:binary phase percentages may be required to provide greater capacity retention and cycling performance, as these components can more favorablely accommodate excess Li introduced via LCO. + .

[0240] Figure 21 The following figures show the discharge capacity (mAh / cm³) observed in the ternary Li:Mg:Ag compound paired with LCO, based on the number of cycles (up to cycle 65). 2 The Li:Mg:Ag thin-film negative electrode compositions shown herein comprise the following ratios: 7:1:0.125 (yellow), 5:1:0.125 (red), 3:1:0.125 (blue), 1:1:0.125 (green), and a normalized Li metal reference of 1:0:0 (black), wherein all Li-containing compositions contain the same amount of Li.

[0241]

[0242] Table 4. First-cycle % irreversible loss of Li:Mg:Ag compositions including 7:1:0.125, 5:1:0.125, 3:1:0.125, 1:1:0.125 and Li metal-based 1:0:0.

[0243]

[0244] Table 5. Lattice parameters and composition percentages of Li2AgMg and AgMg phases present in Li:Mg:Ag thin film compositions including 7:1:0.125, 5:1:0.125, 3:1:0.125, 1:1:0.125 and Li metal reference 1:0:0.

[0245] Figure 22 The XRD patterns of Li:Mg:Ag compositions including 7:1:0.125 (yellow), 5:1:0.125 (red), 3:1:0.125 (blue), 1:1:0.125 (green) and Li metal reference 1:0:0 (black) are shown.

[0246] B. Effect of Ag ratio in the 7:1 Li:Mg system

[0247] As observed in previous sections, the Ag ratio in the 7:1 Li:Mg system significantly affects cycling performance and achievable capacity when paired with NTPO. Here, modifications to the Ag ratio in the 7:1 Li:Mg system are investigated. Figure 23 As shown, adding a small amount of Ag (to achieve a 7:1:0.125 ratio) to the 7:1 Li:Mg composition resulted in a significant improvement in capacity retention during cycling and a reduction in initial cycle loss, a trend also observed in previous sections when paired with NTPO. However, increasing the relative Ag content above 0.125 led to a significant decrease in performance and a corresponding increase in irreversible capacity loss. Figure 23 (Table 5). Therefore, similar to the trend observed in previous sections, bringing the Li:Ag and Ag:Mg ratios closer to 1:1 proves detrimental relative to the composition 7:1:0.125. As shown in Table 5, this trend is further supported by analysis of the corresponding Li₂AgMg and AgMg lattice parameters, where increasing the corresponding Ag:Mg ratio leads to an increase in the AgMg lattice size but a decrease in the Li₂AgMg lattice size. Furthermore, as the Ag:Mg ratio approaches 1, the corresponding percentage of the ternary phase decreases, a trend opposite to that observed for the AgMg phase.

[0248] Figure 23The following figures show the discharge capacity (mAh / cm³) observed in the ternary Li:Mg:Ag compound paired with LCO, based on the number of cycles (up to cycle 65). 2 The Li:Mg:Ag thin-film negative electrode compositions shown herein comprise the following ratios: 7:1:0.125 (yellow), 7:1:0.25 (green), 7:1:0.5 (red), 7:1:0 (blue), and a normalized Li metal reference of 1:0:0 (black), wherein all Li-containing compositions contain the same amount of Li.

[0249]

[0250] Table 6. First-cycle % irreversible loss of Li:Mg:Ag compositions including 7:1:0.5, 7:1:0.25, 7:1:0.125 and Li metal-based 1:0:0.

[0251]

[0252] Table 7. Lattice parameters and composition percentages of Li2AgMg and AgMg phases present in Li:Mg:Ag thin film compositions including 7:1:0.5, 7:1:0.25 and 7:1:0.125.

[0253] Figure 24 The XRD patterns of Li:Mg:Ag compositions including 7:1:0.5 (red), 7:1:0.25 (green), 7:1:0.125 (yellow), 7:1:0 (blue) and Li metal reference 1:0:0 (black) are shown.

[0254] C. Effect of Mg:Ag ratio relative to the percentage of Li

[0255] Given the significant effects observed between the relative ratios of Li:Mg, Li:Ag, and Mg:Ag explored above, the fixed relative percentage of 1Mg:0.125Ag within the normalized Li composition was altered. Increasing the relative Mg:Ag content to 1.40:0.175 and 2.233:0.292 (increases of 40% and 120%, respectively) resulted in a slightly larger irreversible capacity loss during the first cycle; however, cycling performance was observed to be similar to that of the 7:1:0.125 composition, suggesting that the Ag:Mg component plays a synergistic role in establishing an environment favorable for Li incorporation, possibly in the form of an alloy continuum or the final Li metal coating. Figure 25 (Table 7).

[0256] Figure 25 The following figures show the discharge capacity (mAh / cm³) observed in the ternary Li:Mg:Ag compound paired with LCO, based on the number of cycles (up to cycle 65).2 The Li:Mg:Ag thin-film negative electrode compositions shown herein comprise the following ratios: 7:2.233:0.292 (red), 7:1.4:0.175 (blue), 7:1:0.125 (yellow), and a normalized Li metal reference of 1:0:0 (black), wherein all Li-containing compositions contain the same amount of Li.

[0257]

[0258] Table 8. First-cycle % irreversible loss of Li:Mg:Ag compositions including 7:2.233:0.292, 7:1.40:0.175, 7:1:0.125 and Li metal reference 1:0:0.

[0259]

[0260] Table 9. Lattice parameters and composition percentages of Li2AgMg and AgMg phases present in Li:Mg:Ag thin film compositions including 7:2.233:0.292, 7:1.40:0.175, and 7:1:0.125.

[0261] Figure 26 The XRD patterns of Li:Mg:Ag compositions including 7:2.233:0.292 (red), 7:1.40:0.175 (blue), 7:1:0.125 (yellow) and Li metal reference 1:0:0 (black) are shown.

[0262] D. Further evaluation of binary Li:Mg and Mg:Ag compositions

[0263] Given the success of the 7:1-2.33:0.125-0.292 film compositions in establishing low irreversible loss and good cycling stability, further exploration of binary Li:Mg and Mg:Ag compositions was undertaken to understand the robustness of the compositional range. As shown in the figure, binary Li:Mg combinations (including 7:7, 7:2.33, 7:1, and 7:07) failed to meet the performance requirements of the 7:1:0.125 compositions, with compositions closer to 1:1 Li:Mg exhibiting the worst performance. Figure 27 (Table 10). Furthermore, binary Mg:Ag combinations were evaluated, and compositions with relatively low Ag concentrations (0:7:1, 0:3:1, 0:1:0.125) relative to Mg concentrations exhibited poor performance compared to Li metal alone, the beneficial 7:1:0.125 composition, and the binary Li:Mg compositions evaluated above. Figure 28(Table 11). Adding Li to the 0:1:0.125 binary composition (to reach 7:1:0.125) resulted in an increase in the AgMg binary phase and a decrease in the AgMg lattice parameter to 3.336 Å (compared to 3.278 Å) (Table 12).

[0264] Further increasing the Ag content in the Mg:Ag binary composition (to a ratio of 0:1:1) showed improved overall capacity retention up to cycle 65, similar to the beneficial 7:1:0.125 composition, but the initial capacity decreased and the AgMg lattice parameter decreased. This raises questions about whether the AgMg binary phase transforms into the ternary Li₂AgMg.

[0265] In summary, removing Li from the 7:1:0.125 composition revealed similar cycling performance to Mg alone (0:1:1), with no significant performance benefit observed as the relative Mg:Ag ratio increased. The lattice parameters of the binary 0:1:0.125 composition are not close to those of the 7:1:0.125 composition. Instead, the AgMg phase lattice of the 7:1:0.125 composition is close to that of the 0:7:1 phase (3.336 Å vs. 3.306 Å, respectively). Therefore, in addition to the specific range of AgMg phase percentages discussed above, a given range of lattice parameters (≥3.336 Å) can indicate favorable ternary and binary phase interactions that can support high performance.

[0266] Given that the performance decreases with the addition of Ag up to 0:1:1 relative to Mg alone (0:1:0), and that the performance of 7:1:0.125 is improved relative to its binary counterpart (0:1:0.125), this suggests that only the presence of a specific range of AgMg phases is beneficial for supporting capacity retention.

[0267] Figure 27 The following figures show the discharge capacity (mAh / cm³) observed in the ternary Li:Mg:Ag compound when paired with LCO, based on the number of cycles (up to cycle 65). 2 The Li:Mg:Ag thin-film negative electrode compositions shown herein comprise the following ratios: 7:7:0 (green), 7:2.33:0 (blue), 7:1:0 (red), 7:0.7:0 (light blue), 7:0.538:0 (pink), 7:1:0.125 (yellow), and a normalized Li metal reference of 7:0:0 (black), wherein all Li-containing compositions contain the same amount of Li.

[0268]

[0269] Table 10. First-cycle % irreversible loss of Li:Mg:Ag compositions including 7:7:0, 7:2.33:0, 7:1:0, 7:0.7:0, 7:1:0.125 and normalized Li metal reference 7:0:0.

[0270] Figure 28 The following figures show the discharge capacity (mAh / cm³) observed in the ternary Li:Mg:Ag compound paired with LCO, based on the number of cycles (up to cycle 65). 2 The Li:Mg:Ag thin-film negative electrode compositions shown herein comprise the following ratios: 0:7:1 (red), 0:3:1 (green), 0:1:1 (light blue), 0:1:0.125 (pink), 0:1:0 (blue), 7:1:0.125 (yellow), and a normalized Li metal reference of 7:0:0 (black), wherein all Li-containing compositions contain the same amount of Li.

[0271] Figure 29 The XRD patterns of Li:Mg:Ag compositions including 7:7:0 (green), 7:1:0 (red), 7:0.7:0 (light blue), 7:0.538:0 (pink), 7:2.33:0 (dark blue), 7:1:0.125 (yellow) and normalized Li metal reference 7:0:0 (black) are shown.

[0272]

[0273] Table 11. First-cycle % irreversible loss of Li:Mg:Ag compositions including 0:7:1, 0:3:1, 0:1:1, 0:1:0.125, 0:1:0, 7:1:0.125 and normalized Li metal reference 7:0:0.

[0274]

[0275] Table 12. Lattice parameters and composition percentages of Li2AgMg and AgMg phases present in Li:Mg:Ag thin film compositions including 0:7:1, 0:3:1, 0:1:1, 0:1:0.125 and 7:1:0.125.

[0276] Figure 30 The XRD patterns of Li:Mg:Ag compositions including 0:7:1 (red), 0:3:1 (green), 0:1:1 (light blue), 0:1:0.125 (pink), 7:1:0.125 (yellow), 0:1:0 (dark blue), and normalized Li metal reference 7:0:0 (black) are shown.

[0277] E. High areal capacity 7:1:0.125 composite membrane

[0278] Given that the 7:1:0.125 composition is normalized to approximately 1.4 mAh / cm³ 2 Success was achieved, and evaluations were conducted on deposits with higher areal capacity to explore the commercially viable 2 to 3 mAh / cm³ potential of this ternary composition and the potentially beneficial Li₂AgMg phase. 2 Practical stability within the area capacity range. Here, the 7:1:0.125 composition has been doubled (>2mAh / cm³). 2 ), and still achieved stable performance when paired with LCO ( Figure 31 (Table 11). Furthermore, this higher capacity composition allows for the formation of additional solid solutions, based on the 1.1 mAh / cm³... 2 Compared to the 7:1:0.125 composition, the Li₂AgMg lattice parameter is slightly lower. Both the single-part and double-part 7:1:0.125 compositions exhibit similar ratios of ternary:binary phase percentages, with the single-part 7:1:0.125 composition exhibiting a larger percentage of the Li metallic phase.

[0279] Figure 31 The following figures show the discharge capacity (mAh / cm³) observed in the ternary Li:Mg:Ag compound paired with LCO, based on the number of cycles (up to cycle 65). 2 The Li:Mg:Ag thin-film negative electrode composition shown herein comprises the following ratios: 7:1:0.125, doubled thickness 7:1:0.125, and normalized Li metal reference 7:0:0, wherein all Li-containing compositions contain the same amount of Li.

[0280]

[0281] Table 13. First-cycle % irreversible loss of Li:Mg:Ag compositions including 7:1:0.125, doubled deposits 7:1:0.15, and normalized Li metal baseline 7:0:0.

[0282]

[0283] Table 14. Lattice parameters and composition percentages of Li2AgMg and AgMg phases present in Li:Mg:Ag thin film compositions including 7:1:0.125 and doubled 7:1:0.125.

[0284] Figure 32 The diagram shows a double-thickness composition 7:1:0.125 (>2mAh / cm). 2 (Red) and 7:1:0.125 (1.1mAh / cm) 2 (yellow) and normalized Li metal reference 7:0:0 (1.1 mAh / cm³) 2XRD pattern of (black) Li:Mg:Ag composition.

[0285] Figure 33 A schematic diagram depicting the Li₂AgMg phase purity (a) of all ternary compositions and their corresponding performance when paired with NTPO (b) and LCO (c) is shown. This is based on the second discharge capacity (mAh / cm²). 2 To evaluate performance.

[0286] 2. In-depth evaluation of the high-performance 7:1:0.125 composition

[0287] As shown in the previous sections, the ternary composition 7:1:0.125 is not only superior to pure Li, but more importantly, to binary compositions of Li:Mg and Ag:Mg components. This performance is attributed to the presence and distribution of beneficial Li₂AgMg and AgMg phases throughout the film. However, the homogeneity of these phases and elements across the entire thickness of the deposited film remains questionable. Figure 34 As shown, XPS depth analysis was used to evaluate the homogeneity of the co-deposited 7:1:0.125 sample, where the binding energy (BE) from both the Ag and Mg components remained undisplaced across the entire depth of the analyzed film (up to approximately 7500 nm at a computation rate of 0.5 nm / sec) relative to the surface of the film and its adjacent substrate region. The BE observed for Ag (~368.8 eV) was significantly higher than the baseline Ag signal observed for pure Ag metal (~368.2 eV). Figure 36 The observed BE (~368.2 eV) for Mg and the Ag signals recorded in the literature show a slight blue shift. The BE observed for Mg (~1303 eV) is similar to the baseline Mg signal observed for pure Mg metal (~1303.1 eV). Figure 36 This is consistent with the Mg signals (~1303 eV) recorded in the literature. Unlike the observed Ag and Mg signals, the initial Li1s BE was shown to exhibit a sustained redshift in the first ~500 seconds, while the signal tended to stabilize with increasing depth. After additional sputtering, a shift of the BE toward the Li metal (55 eV) was observed. This change in the Li1s signal is likely due to surface contaminants containing foreign carbon and other elements found at relatively high Li1s binding energies. Figure 35 As shown, after a total of ~5000 seconds, the atomic percentages of Li, Mg, and Ag components remained relatively constant throughout the film. In summary, apart from a slight increase in Li concentration on the surface, possibly due to reaction with glovebox contaminants, the elemental distribution of these elements remained relatively constant with depth, indicating that the distribution of ternary and binary phases was relatively uniform throughout the material's depth.

[0288] In addition, such as Figure 36 As shown, XPS depth analysis was also performed on the co-deposited binary film (0:1:1). The basis emissions (BEs) of the Ag and Mg components were observed from the surface to the adjacent region of the substrate (total sputtering time approximately 6180 s, or approximately 3090 nm at a computation rate of 0.5 nm / sec). As shown, the Ag3d BE revealed with increasing depth is consistent, appearing to have a red shift compared to those observed with increasing depth for the 7:1:0.125 composition (368.5 eV vs. 368.8 eV, respectively). However, a relative blue shift of the Mg1s signal was observed compared to the baseline Mg BE, due to the presence of potential surface oxides, where a consistent red-shifted BE was observed after approximately 1110 s of sputtering. This Mg BE (1303.6 eV) shows a blue shift compared to the signal observed (1303.4 eV) in the 7:1:0.125 ternary composition.

[0289] Figure 34 XPS depth analysis of the co-deposited 7:1:0.125 film composition is shown, including Li1s (a), Mg1s (b), and Ag3d (c) signals. The blue arrows indicate the direction of the signals as the total sputtering time progresses.

[0290] Figure 35 The atomic percentage distribution of Li1s, Mg1s, and Ag3d signals observed in the 7:1:0.125 composition during sputtering is shown.

[0291] Figure 36 XPS depth analysis of the co-deposited 0:1:1 thin film composition is shown, including Mg1s (a) and Ag3d (b) signals, with the baseline Mg and dg signals shown in Figures (c) and (d), respectively. The blue arrows indicate the direction of the signals as the total sputtering time progresses.

[0292] 3. Improvement of 7:1:0.125 film performance using optimized FOS-based electrolyte.

[0293] The performance of the 7:1:0.125 composition paired with LCO was further improved by utilizing a previously demonstrated stable Li metal-coated dual-salt fluorine organic (FOS) electrolyte. For example... Figure 37 As shown, for both the 7:1:0.125 and 7:0:0 compositions, the use of FOS-based electrolyte compositions significantly improved capacity retention and cycling performance compared to their performance with the standard commercial electrolyte 1M LiPF6 EC / DMC. Furthermore, as shown in Table 15, a significant improvement in irreversible loss during the first cycle was also observed for both the 7:1:0.125 and 7:0:0 compositions when using the optimized FOS-based electrolyte.

[0294] Figure 37 The discharge capacity (mAh / cm³) observed when the Li:Mg:Ag thin film was paired with an LCO battery cell is shown. 2 (up to cycle 200). The Li:Mg:Ag thin film negative electrode compositions shown here comprise the following ratios: 7:1:0.125 and 7:0:0, wherein all Li-containing compositions contain the same amount of Li. The above thin film compositions are shown using the standard electrolyte 1M LiPF6EC / DMC (yellow (7:1:0.125), black (7:0:0)) and the optimized composition 1M LiTFSI 0.4M LDFOB 90 / 10FOS / FEC (red (7:1:0.125), gray (7:0:0)).

[0295]

[0296] Table 15. % Irreversible loss in the first cycle of Li:Mg:Ag compositions 7:1:0.125 and 7:0:0 when paired with LCO using standard commercial electrolyte 1M LiPF6 EC / DMC and optimized electrolyte 1M LiTFSI 0.4M LDFOB 90 / 10 FOS / FEC.

[0297] 4. Ex-situ XRD evaluation of the MgAg to Li2AgMg transformation during lithiation.

[0298] As shown in the figure, the binary MgAg and Li₂AgMg phases are structurally and functionally related, as physical XRD analysis has revealed that a certain amount of the binary phase contributes to electrochemical performance, especially when Li ions are paired with LCO, with Li added to the negative electrode. Since the binary phase is structurally related to the ternary phase, a question arises: does the binary structure transform into a ternary structure upon lithiation? The binary Ag:Mg film was lithiated to Lix = 4.42 and then removed for examination via out-of-situ XRD. Figure 38 As shown, lithiation of the binary Mg:Ag composition (0:1:1) leads to the formation of the ternary Li₂AgMg phase, as indicated by the presence of Bragg reflections and (331) reflections in the superstructure (1,1,1)Li₂AgMg. Rietveld analysis of these spectra revealed lattice parameters of Mg and Li₂AgMg of 3.311 Å and 6.638 Å, respectively, consistent with ICDD standards. In conclusion, the XRD data clearly support the direct transformation of the AgMg binary into the Li₂AgMg ternary phase upon electrochemical lithiation.

[0299] Figure 38 Ex-situ XRD evaluations of the binary composition 0:1:1 (blue) and the electrochemically lithiated binary composition 4.42:1:1 (red) are shown.

[0300] 5. Structural evolution of the 7:1:0.125 ternary structure during electrochemical lithiation: ex-situ XRD

[0301] Lithiation of the ternary composition 7:1:0.125 to an additive Lix of 4.42 (as performed for the aforementioned 0:1:1 study) revealed the formation of a similar ternary phase, but in greater quantity. The presence of both ternary Li₂AgMg and binary MgAg components at the maximum lithiation level in the Li-ion battery cell configuration indicates that both components contribute to electrochemical performance. Small size changes in the ternary phase were observed, and no two-phase development occurred during lithiation. Rietveld analysis of these spectra revealed that the Li, AgMg, and Li₂AgMg components of the original unlithiated 7:1:0.125 composition (3.492 Å, 3,328 Å, and 6.658 Å, respectively) were similar to those of the lithiated 11.42:1:0.125 composition (3.492 Å, 3,329 Å, and 6.658 Å, respectively).

[0302] Figure 39 Ex-situ XRD evaluations of the ternary composition 7:1:0.125 (blue) and the electrochemically lithiated 11.42:1:0.125 (red) composition are shown.

[0303] The present invention includes the following embodiments:

[0304] Implementation Scheme 1. A battery, comprising:

[0305] case;

[0306] The positive electrode is located inside the casing;

[0307] The negative electrode is located inside the casing.

[0308] The negative electrode includes an alloy.

[0309] The alloy includes lithium, magnesium, and silver; and

[0310] The electrolyte, located in the shell, is configured to conduct ionic current between the positive and negative electrodes.

[0311] Implementation Scheme 2. The battery according to Implementation Scheme 1, wherein the material of the positive electrode does not contain lithium in its atomic structure.

[0312] Implementation Scheme 3. The battery according to Implementation Scheme 1, wherein the material of the positive electrode includes lithium in its atomic structure.

[0313] Implementation Scheme 4. The battery according to Implementation Scheme 1, wherein the total weight percentage of lithium, magnesium and silver in the alloy is at least 50% of the total weight of the alloy.

[0314] Implementation Scheme 5. The battery according to Implementation Scheme 1, wherein the material of the negative electrode has a crystal structure consistent with Li2AgMg as determined by XRD.

[0315] Implementation Scheme 6. The battery according to Implementation Scheme 1, wherein the material of the negative electrode has a crystal structure consistent with AgMg as determined by XRD.

[0316] Lithium is added during battery operation to form a ternary alloy consisting of lithium, magnesium, and silver.

[0317] Implementation Scheme 7. The battery according to Implementation Scheme 1, wherein lithium is formed on the negative electrode during battery operation.

[0318] Implementation Scheme 8. The battery according to Implementation Scheme 1, wherein lithium is deposited on the alloy during battery operation.

[0319] Implementation Scheme 9. The battery according to Implementation Scheme 1, wherein the electrolyte comprises lithium.

[0320] Implementation Scheme 10. The battery according to Implementation Scheme 1, wherein the negative electrode further includes graphite.

[0321] Implementation Scheme 11. The battery according to Implementation Scheme 1, wherein the positive electrode comprises at least one of metal fluoride, sulfur, or metal sulfide.

[0322] Implementation Scheme 12. The battery according to Implementation Scheme 1, wherein the positive electrode comprises at least one of cobalt, nickel, iron, and manganese.

[0323] Implementation Scheme 13. The battery according to Implementation Scheme 1, wherein the positive electrode comprises iron fluoride or bismuth fluoride.

[0324] Implementation Scheme 14. The battery according to Implementation Scheme 1, wherein the electrolyte does not include lithium.

[0325] Implementation Scheme 15. The battery according to Implementation Scheme 1, wherein the electrolyte includes a fluoride.

[0326] Implementation Scheme 16. The battery according to Implementation Scheme 1, wherein the alloy has a crystal structure represented by at least X-ray diffraction peaks corresponding to a d-spacing of approximately 3.6 Å to 4.2 Å.

[0327] Implementation Scheme 17. The battery according to Implementation Scheme 16, wherein the d-pitch is approximately 3.9 angstroms.

[0328] Implementation Scheme 18. The cell according to Implementation Scheme 17, wherein there are X-ray diffraction peaks corresponding to a d-spacing of approximately 3.1 Å to 3.5 Å.

[0329] Implementation Scheme 19. The battery according to Implementation Scheme 1, wherein the battery includes a lithium-ion battery.

[0330] Implementation Scheme 20. The battery according to Implementation Scheme 1, wherein the battery includes a solid-state lithium battery.

[0331] Implementation Scheme 21. The battery according to Implementation Scheme 1, wherein the electrolyte includes a solid electrolyte.

[0332] Implementation Scheme 22. The battery according to Implementation Scheme 1, wherein the composition of the alloy varies depending on the thickness of the alloy.

[0333] Implementation Scheme 23. A battery, comprising:

[0334] case;

[0335] The positive electrode is located inside the casing;

[0336] The negative electrode is located inside the casing;

[0337] The current collector is located inside the casing;

[0338] A partition, located within the casing;

[0339] Electrolytes, which are located in the shell; and

[0340] Alloys, including lithium, magnesium, and silver,

[0341] The alloy is located on at least one of the negative electrode, separator, and current collector.

[0342] Implementation Scheme 24. A method comprising:

[0343] Obtain the shell;

[0344] The positive electrode is arranged in the housing;

[0345] The negative electrode is arranged in the housing;

[0346] Depositing alloys on negative electrodes, separators, or solid electrolytes.

[0347] The alloys include lithium, magnesium, and silver; and

[0348] An electrolyte is arranged in the shell and configured to conduct current between the positive and negative electrodes.

[0349] Implementation Scheme 25. The method according to Implementation Scheme 24, wherein deposition includes deposition via physical vapor deposition.

[0350] Implementation Scheme 26. The method according to Implementation Scheme 24, wherein deposition includes depositing a film.

[0351] Implementation Scheme 27. The method according to Implementation Scheme 26, wherein deposition includes depositing a film by physical vapor deposition.

[0352] Implementation Scheme 28. The method according to Implementation Scheme 24, wherein the alloy has a crystal structure represented by at least X-ray diffraction peaks corresponding to a d-spacing of approximately 3.6 Å to 4.2 Å.

[0353] Implementation Scheme 29. The method according to Implementation Scheme 24, wherein the positive electrode does not include lithium.

[0354] Implementation Scheme 30. The method according to Implementation Scheme 24, wherein the total weight percentage of lithium, magnesium and silver in the alloy is at least 50% of the total weight of the alloy.

[0355] Implementation Scheme 31. The method according to Implementation Scheme 24, wherein the electrolyte comprises lithium.

[0356] Implementation Scheme 32. The method according to Implementation Scheme 24, wherein the negative electrode further includes graphite.

[0357] Implementation Scheme 33. The method according to Implementation Scheme 24, wherein the positive electrode comprises iron fluoride or bismuth fluoride.

[0358] Implementation Scheme 34. The method according to Implementation Scheme 24, wherein the electrolyte does not include lithium.

[0359] Implementation Scheme 35. The method according to Implementation Scheme 24, wherein the electrolyte includes a fluoride.

[0360] Implementation Scheme 36. The method according to Implementation Scheme 24, wherein the electrolyte does not include lithium.

Claims

1. A battery, comprising: case; The positive electrode is located within the housing; The negative electrode is located within the housing. The negative electrode comprises an alloy. The alloy comprises lithium, magnesium, and silver; and An electrolyte, located within the housing, is configured to conduct ionic current between the positive electrode and the negative electrode.

2. The battery according to claim 1, wherein the material of the positive electrode does not contain lithium in its atomic structure.

3. The battery according to claim 1, wherein the material of the positive electrode contains lithium in its atomic structure.

4. The battery according to claim 1, wherein the total weight percentage of lithium, magnesium and silver in the alloy is at least 50% of the total weight of the alloy.

5. The battery according to claim 1, wherein the material of the negative electrode has a crystal structure consistent with Li2AgMg as determined by XRD.

6. The battery according to claim 1, wherein the material of the negative electrode has a crystal structure consistent with AgMg as determined by XRD. Lithium is added during the operation of the battery to form a ternary alloy comprising lithium, magnesium, and silver.

7. The battery of claim 1, wherein lithium of the alloy is formed on the negative electrode during operation of the battery.

8. The battery of claim 1, wherein lithium is deposited on the alloy during operation of the battery.

9. The battery of claim 1, wherein the electrolyte comprises lithium.

10. The battery of claim 1, wherein the negative electrode further comprises graphite.

11. The battery according to claim 1, wherein the positive electrode comprises at least one of a metal fluoride, sulfur, or a metal sulfide.

12. The battery according to claim 1, wherein the positive electrode comprises at least one of cobalt, nickel, iron, and manganese.

13. The battery according to claim 1, wherein the positive electrode comprises iron fluoride or bismuth fluoride.

14. The battery of claim 1, wherein the electrolyte does not include lithium.

15. The battery of claim 1, wherein the electrolyte comprises a fluoride.

16. The battery of claim 1, wherein the alloy has a crystal structure represented by X-ray diffraction peaks corresponding to a spacing of approximately 3.6 Å to 4.2 Å.

17. The battery of claim 16, wherein the d-pitch is approximately 3.9 angstroms.

18. The battery of claim 17, wherein there are X-ray diffraction peaks corresponding to a d-spacing of approximately 3.1 Å to 3.5 Å.

19. The battery according to claim 1, wherein the battery comprises a lithium-ion battery.

20. The battery of claim 1, wherein the battery comprises a solid-state lithium battery.

21. The battery of claim 1, wherein the electrolyte comprises a solid electrolyte.

22. The battery of claim 1, wherein the composition of the alloy varies according to the thickness of the alloy.

23. A battery, comprising: case; The positive electrode is located within the housing; The negative electrode is located within the housing; A current collector, located within the housing; A partition, located within the housing; Electrolyte, which is located in the shell; and Alloy, wherein the alloy comprises lithium, magnesium and silver, The alloy is located on at least one of the negative electrode, the separator, and the current collector.

24. A method comprising: Obtain the shell; The positive electrode is arranged in the housing; The negative electrode is arranged in the housing; Depositing an alloy on the negative electrode, separator, or solid electrolyte. The alloy comprises lithium, magnesium, and silver; as well as An electrolyte is disposed in the housing and is configured to conduct current between the positive electrode and the negative electrode.

25. The method of claim 24, wherein the deposition comprises deposition by physical vapor deposition.

26. The method of claim 24, wherein the deposition comprises a deposited film.

27. The method of claim 26, wherein the deposition comprises depositing the film by physical vapor deposition.

28. The method of claim 24, wherein the alloy has a crystal structure represented by X-ray diffraction peaks corresponding to a spacing of approximately 3.6 Å to 4.2 Å.

29. The method of claim 24, wherein the positive electrode does not include lithium.

30. The method of claim 24, wherein the total weight percentage of lithium, magnesium and silver in the alloy is at least 50% of the total weight of the alloy.

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