Negative electrode for a 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

(19) State Intellectual Property Office (12) Invention Patent Application (10) Application Publication Number (43) Application Publication Date (21) Application Number 202480048341.8 (22) Application Date 2024.05.24 (30) Priority Data 63 / 468,648 2023.05.24 US (85) PCT International Application Entering National Phase Date 2026.01.21 (86) PCT International Application Application Data PCT / US2024 / 031039 2024.05.24 (87) PCT International Application Publication Data WO2024 / 243533 EN 2024.11.28 (71) Applicant: Rutgers, Rutgers State University, New Jersey, USA (72) Inventors: G.G. Amatucci, A.B. Harajko, F. Baderway, R. Baylor (74) Patent Agency: Beijing Liande Law Firm, 11361 Patent Attorneys: Huang Dazheng, Zhang Laiguang (51) Int.Cl. H01M 10 / 052 (2006.01) H01M 10 / 0525 (2006.01) H01M 4 / 40 (2006.01) H01M 10 / 056 (2006.01) (54) Invention Title: Negative Electrode for Lithium-ion Batteries (57) Abstract: This invention discloses a battery comprising: a housing; a positive electrode located in the housing; a negative electrode located in the housing, wherein the negative electrode comprises an alloy comprising lithium, magnesium and silver; and an electrolyte located in the housing, the electrolyte being capable of conducting ionic current between the positive and negative electrodes. Claims (2 pages), Description (33 pages), Drawings (48 pages), CN 121548889 A, 2026.02.17, CN 1 21 54 88 89 A. 1. 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, wherein the alloy comprises lithium, magnesium, and silver; and an electrolyte located within the housing, the electrolyte being configured to conduct an ionic current between the positive electrode and the negative electrode. 2. The battery of claim 1, wherein the material of the positive electrode does not include lithium in its atomic structure. 3. The battery of claim 1, wherein the material of the positive electrode includes lithium in its atomic structure. 4. The battery of 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 of 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.7. The battery of claim 1, wherein lithium is added during operation of the battery to form a ternary alloy comprising lithium, magnesium, and silver. 8. The battery of claim 1, wherein lithium of the alloy is formed on the negative electrode during operation of the battery. 9. The battery of claim 1, wherein lithium is deposited on the alloy during operation of the battery. 10. The battery of claim 1, wherein the electrolyte comprises lithium. 11. The battery of claim 1, wherein the negative electrode further comprises graphite. 12. The battery of claim 1, wherein the positive electrode comprises at least one of a metal fluoride, sulfur, or a metal sulfide. 13. The battery of claim 1, wherein the positive electrode comprises at least one of a metal cobalt, nickel, iron, and manganese. 14. The battery of claim 1, wherein the positive electrode comprises iron fluoride or bismuth fluoride. 15. The battery of claim 1, wherein the electrolyte does not include lithium. 16. The battery of claim 1, wherein the electrolyte comprises a fluoride. 17. The battery of claim 1, wherein 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. 17. The battery of claim 16, wherein the d-spacing is approximately 3.9 angstroms. 18. The battery of claim 17, wherein an X-ray diffraction peak corresponding to a d-spacing of approximately 3.1 to 3.5 angstroms is present. 19. The battery of 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-state 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: 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. 24. 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. 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 at least by X-ray diffraction peaks corresponding to a d-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. Claims 2 / 2 Page 3 CN 121548889 A Negative Electrode for Lithium-ion Batteries

[0001] Cross-Reference to Related Applications

[0002] This application claims priority to U.S. Provisional Patent Application 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 negative electrodes for lithium batteries. Background Art

[0004] In known Li-ion batteries, the battery includes a positive electrode and a negative electrode, and the negative electrode includes graphite or some form of carbon. In some known Li-ion batteries, the negative electrode includes a lithium alloy, such as LixSi, LixGe, LixAl, LixSn. In some known batteries, the electrode is plated and stripped of Li metal in each charge and discharge cycle of the battery, respectively. Summary of the Invention

[0005] 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, wherein the negative electrode comprises an alloy, wherein the alloy comprises lithium, magnesium, and silver; and an electrolyte located in the housing, the electrolyte being configured to conduct an ionic current between the positive and negative electrodes.

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

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

[0008] In some embodiments, 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 consistent with Li₂AgMg as determined by XRD.

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

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

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

[0013] In some embodiments, the electrolyte comprises lithium.

[0014] In some embodiments, the negative electrode further comprises graphite.

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

[0016] In some embodiments, the positive electrode comprises at least one of a metal cobalt, nickel, iron, or manganese.

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

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

[0019] In some embodiments, the electrolyte comprises a fluoride.

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

[0021] In some embodiments, the d-spacing is approximately 3.9 Å.

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

[0023] In some embodiments, the battery comprises a lithium-ion battery.

[0024] In some embodiments, the battery comprises a solid-state lithium battery.

[0025] In some embodiments, the electrolyte comprises a solid-state electrolyte.

[0026] In some embodiments, 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 embodiments, the deposition comprises deposition by physical vapor deposition.

[0030] In some embodiments, the deposition comprises depositing a film.

[0031] In some embodiments, the film is deposited by physical vapor deposition.

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

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

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

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

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

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

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

[0039] In some embodiments, 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 embodiments, the ternary alloy is a solid alloy.

[0041] In some embodiments, the ternary alloy is fabricated as a film.

[0042] In some embodiments, the film is deposited by physical vapor deposition.

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

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

[0045] In some embodiments, a lithium-magnesium alloy is deposited on a ternary alloy.

[0046] In some embodiments, a ternary alloy is deposited on the current collector of the battery.

[0047] In some embodiments, a ternary alloy is deposited on the separator of the battery.

[0048] In some embodiments, the battery includes lithium metal. Specification 2 / 33 pages 5 CN 121548889 A

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

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

[0051] In some embodiments, the positive electrode includes sulfur.

[0052] In some embodiments, the positive electrode includes a metal sulfide.

[0053] In some embodiments, the negative electrode further includes graphite.

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

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

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

[0057] In some embodiments, the solid ion conductor comprises lithium fluoride.

[0058] In some embodiments, the battery comprises a fluorine-ion battery.

[0059] In some embodiments, 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 at least 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 embodiments, the structure of the alloy (but not necessarily the stoichiometry of the alloy) is similar to AgLi2Mg. Brief Description of the Drawings

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

[0064] FIG1 is a graph illustrating the results of Li according to Example 1 paired with an NbPO5 electrode according to some embodiments of the invention.

[0065] FIG2 is a graph illustrating the results of Li:Mg according to Example 2 paired with an NbPO5 electrode according to some embodiments of the invention.

[0066] FIG3A is a graph illustrating the results of 7Li:Mg:xAg ternary alloy according to Example 3A paired with an NbPO5 electrode according to some embodiments of the invention.

[0067] FIG3B is a graph showing the results of pairing the 7Li:1Mg:xAg ternary alloy according to Example 3B with an NbPO5 electrode according to some embodiments of the present invention.

[0068] FIG4A is a graph showing the results of pairing the 10Li:1Mg:xAg ternary alloy according to Example 4A with an NbPO5 electrode according to some embodiments of the present invention.

[0069] FIG4B is a graph showing the results of pairing the 10Li:1Mg:xAg ternary alloy according to Example 4B with an NbPO5 electrode according to some embodiments of the present invention.

[0070] FIG5A is a graph showing the results of pairing the 13Li:1Mg:xAg ternary alloy according to Example 5A with an NbPO5 electrode according to some embodiments of the present invention.

[0071] FIG5B is a graph showing the results of pairing the 13Li:1Mg:xAg ternary alloy according to Example 5B with an NbPO5 electrode according to some embodiments of the present invention.

[0072] FIG6A is a graph illustrating the results for various electrodes according to Embodiment 6A according to some embodiments of the present invention. (Page 3 / 33, CN 121548889 A)

[0073] FIG6B is a graph illustrating the results for various electrodes according to Embodiment 6B according to some embodiments of the present invention.

[0074] FIG7A is a graph illustrating the results for various electrodes according to Embodiment 7A according to some embodiments of the present invention.

[0075] FIG7B is a graph illustrating the results for various electrodes according to Embodiment 7B according to some embodiments of the present invention.

[0076] FIG8A is a graph illustrating the results for various electrodes according to Embodiment 8A according to some embodiments of the present invention.

[0077] Figure 8B is a graph showing the results for various electrodes according to embodiment 8B of the present invention.

[0078] Figure 9A is a graph showing the results for various electrodes according to embodiment 9A of the present invention.

[0079] Figure 9B is a graph showing the results for various electrodes according to embodiment 9B of the present invention.

[0080] Figure 10A is a graph showing the results for various electrodes according to embodiment 10A of the present invention.

[0081] Figure 10B is a graph showing the results for various electrodes according to embodiment 10B of the present invention.

[0082] Figure 11A is a graph showing the results for various electrodes according to embodiment 11A of the present invention.

[0083] Figure 11B is a graph showing the results for various electrodes according to embodiment 11B of the present invention.

[0084] Figure 12A is a graph showing the results for various electrodes according to embodiment 12A of the present invention.

[0085] Figure 12B is a graph illustrating results for various electrodes according to embodiment 12B of the invention.

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

[0087] In some embodiments, the invention provides an alloy structure that provides 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 exhibits superior and unexpected properties relative to other alloys, particularly alloys of LixMg and LixAg. In some embodiments, a crystal structure with extremely high amounts of Li and low amounts of Ag is formed, for example, as in Li7MgAg0.125. In some embodiments, the crystal structure is configured as a negative electrode material in thin film form 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. Specification 4 / 33 pages 7 CN 121548889 A

[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, improvements are shown relative to the use of LixMg or LixAg alloys with different structures.

[0090] As used herein, mAh refers to the measured electrochemical cell capacity, and mAh / g is relative to the positive electrode.The capacity is normalized by the weight of the active electrode material used.

[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, thereby 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, the comparison non-lithium batteries have the following parameters:

[0093] Positive electrode: β Nb0.98Ta0.02PO5

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

[0095] Typical electrode capacity: 1.70mAh

[0096] Positive electrode diameter: 0.79cm = 0.50cm2

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

[0098] Electrolyte volume: 0.050ml

[0099] Voltage: 1.65-2.8V

[0100] Charging: 10mA / g positive

[0101] Discharging: 15mA / g positive

[0102] Separator: One 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, 2×15min, drying at 40°C

[0106] Cu diameter: 12.3mm

[0107] Li / Mg / Ag deposition diameter: 11mm = 0.95cm2

[0108] Baseline Li paired with NbPO5

[0109] Example 1

[0110] As described in Example 1, referring to Figure 1, Li metal was deposited on a 0.95cm2 Cu disk to obtain electrodes of 1.41mAh and 2.16mAh, respectively. These electrodes were also compared with a 150-micron Li metal disk having a capacity of over 15mAh. As outlined in the experiment, two copies of each of the three Li electrodes were fabricated to form an electrochemical cell unit paired with an NbPO5-based positive electrode. As expected, the thick 150-micron Li metal disk cycled very well. However, the large amount of excess Li metal prevents this from becoming a viable path to high-energy-density battery cells. Li metal disks of <5 mAh show significant degradation with cycling, and the worst is observed for the thinner and smallest 1.4 mAh film. As shown in the figure, all battery cells form two copies each and exhibit similar behavior. Without theoretical constraints, it appears that the battery cells fail not due to Li dendrite formation, but rather 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 Pairing with NbPO5 Positive Electrode

[0112] Example 2

[0113] As described in Example 2, referring to Figure 2, Li:Mgx was co-deposited on a 0.95 cm² Cu disk by physical vapor deposition, with the Li:Mg stoichiometric ratio gradually decreasing 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 used to deposit all electrodes, and the amount of Mg was increased to the appropriate stoichiometric ratio as described above. As outlined in the experiment on page 5 / 33 of the specification, CN 121548889 A, two copies of each Li:Mg electrode were fabricated to form an electrochemical cell unit paired with an NbPO5-based positive electrode. As described in Example 1, the deposited Li metal film (100:0, 1.41 mAh) had a high initial capacity but rapidly degraded. The introduction of a small amount of Mg (16:1) resulted in a significant improvement in cycling, but gradually decayed 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, referring to Figure 3A, similar to Example 2, the realization of the Li:Mg alloy resulted in significant stability of the negative Li metal reaction. However, it was observed that this was achieved at the cost of reduced capacity, below the theoretical capacity provided by the Li metal available in the film. This seems 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 because Ag metal has high electronic conductivity and its ability to alloy with Li metal at low voltages. Li:Mg:Ag metal was co-deposited on a 0.95 cm² Cu disk by physical vapor deposition, with Ag gradually increasing. The Li:Mg:Ag stoichiometric ratios were based on a 7Li:1Mg ratio, as indicated in Example 2 as one of the better ratios, and were 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 a high initial capacity but rapidly lost capacity.Effect. The introduction of a small amount of Mg (7:1) resulted in excellent cycling stability, although at a lower capacity. 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 amount of Ag to a ratio of 7:1:0.5 resulted in a capacity increase of 400%, but an increase in capacity decay was observed. In short, the addition of Ag resulted in a significant improvement in the electrochemical performance of the alloy. However, it appears that there is a mechanism at work that is not solely due to the addition of Ag. 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, referring to Figure 3B, it can be seen from the XRD diffraction pattern of the negative electrode used in Example 3A that there is a significant systematic improvement in capacity and cycle life in the presence of a phase similar to "Li2AgMg" in the diffraction pattern, relative to other phases such as LiMgx and AgMg. Surprisingly, such a small amount of Ag induced the stability of this structure, which is usually retained at higher Ag levels. It is unclear whether such a phase has been tested for use in lithium batteries. However, tests have confirmed its remarkable properties.

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

[0121] Example 4A

[0122] Referring to Figure 4A, Example 4A is based on a similar method of co-depositing Li:Mg:Ag metal to improve the electrochemical performance of 7Li:1Mg alloy, which was also developed for the 10Li:1Mg ratio electrode that was considered desirable in Example 2. The 10Li:1Mg:Agx ratio was co-deposited on a 0.95 cm2 Cu disk by physical vapor deposition, with the Ag content gradually increasing 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. Introducing 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 amount of Ag to...A 7:1:0.5 ratio resulted in a capacity increase of >100%, but an increase in capacity decay was observed. The addition of Ag led to a significant improvement in the electrochemical performance of the alloy.

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

[0124] Example 4B

[0125] Referring to FIG4B, as can be seen from the XRD diffraction pattern of the negative electrode used in Example 4A, compared with other phases such as LiMgx, there is a significant systematic improvement in capacity and cycle life in the presence of a phase similar to "Li2AgMg" in the diffraction pattern. The importance of this phase is further confirmed, as first demonstrated in Example 3A.

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

[0127] Example 5A

[0128] In Example 5A, referring to FIG5A, a similar method of 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:Agx ratio was co-deposited on a 0.95 cm2 Cu disk by physical vapor deposition, with Ag gradually increasing, and the Li:Mg:Ag stoichiometric ratios were 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, 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 a NbPO5-based positive electrode. 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 an almost 100% increase in capacity, but increased capacity decay was observed. In short, the addition of Ag significantly improved the electrochemical performance of the alloy. However, it is also possible that a mechanism beyond the addition of Ag is at least partially at play.

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

[0130] Example 5B

[0131] Compared to Example 5B, referring to FIG5B, as can be seen from the XRD diffraction pattern of the negative electrode used in Example 5A, as the purity of the "Li2AgMg"-like phase in the diffraction pattern increases relative to other phases, there is a significant systematic improvement in cycle life. In fact, the purest sample of 13:1:0.25 results in the best capacity / cycle performance, while other phases show a significant improvement in cycle life.The purity decreases and the presence of harmful LiMgx phase increases, resulting in a systematic deterioration.

[0132] Efficacy of the alloy of the present invention paired with the LiCoO2 positive electrode

[0133] Previous Examples 1 to 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 is provided by the negative electrode of the present invention to be embedded within its crystal structure. This configuration may be very important for future lithium-ion batteries, which have positive electrodes with particularly high energy densities. In most contemporary lithium batteries, the positive electrode has Li present in its crystal structure, and then the Li is removed during the first charge and reacts with the negative electrode. The negative electrode used in today's Li-ion batteries is usually graphite with very low capacity. It is desirable for the Li removed from the positive electrode to be plated in the form of Li metal or reacted with the 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 Li metal that is already present. This is likely mainly due to the harmful 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 current Li batteries to observe the efficacy of Li:Mg:Ag ternary compositions. Specification 7 / 33 pages 10 CN 121548889 A

[0134] Example 6A

[0135] In Example 6A, referring to FIG6A, a positive electrode consisting of LiCoO2 formed as an electrode (15.06 mg / cm2 LiCoO2; 0.495 cm2 = about 1.10 mAh) was placed in an electrochemical cell cell, similar to previous experiments, and the positive electrode was started by charging and then cycled in a 1M LiPF6 EC:DMC electrolyte. The following Li:Mg:Ag negative electrodes were prepared and two copies of each were fabricated to form battery cells paired with LiCoO2 electrodes: 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 (7:2.33:0) to the alloy further improves the 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 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] Efficacy of the alloy of the present invention paired with the LiCoO2 positive electrode

[0137] Example 6B

[0138] Compared to Example 6B, referring to 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 present 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 other phases systematically deteriorate with decreasing purity and the increased presence of harmful LiMgx phases.

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

[0140] Example 7A

[0141] In Example 7A, referring to Figure 7A, the battery cell was manufactured similarly to that of Example 6A, but various controls were explored with respect to the negative electrode to further illustrate the effectiveness of the ternary composition Li:Mg:Ag. The example clearly shows that the three-element composition can result in excellent stability of the ternary composition (7:1:0.125 in this case) in terms of its electrochemical properties.

[0142] Various binary alloys: Comparison with ternary alloys when paired with LiCoO2 positive electrode

[0143] Example 7B

[0144] Referring to Example 7B and FIG7B, as can be seen from 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, there is a significant and clear improvement in cycle life compared to all other compositions showing Bragg reflections associated with the LiMgx phase, pure lithium, and AgxMg phase.

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

[0146] Example 8A

[0147] In Example 8A, referring to FIG8A, the battery cell was manufactured similarly to Example 6A, but various controls were explored with respect to the negative electrode to further illustrate the effectiveness of the ternary composition Li:Mg:Ag. Here, the work focuses on ensuring the robustness of the results of ternary Li:Mg:Ag leading to much better performance than Li:Mg alloys, regardless of the initial stoichiometry of the Li:Mg alloy. In the examples, it can be seen that a variety of 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 is added to induce the production of a ternary composition (7:1:0.125), a very clear and dramatic performance improvement is observed.

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

[0149] Example 8B

[0150] As shown in Example 8B, referring to FIG8B, X-ray diffraction reveals that even with the addition of a very small amount of Ag (7:1:0.125), the performance improvement is significantly enhanced.0.125) also 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 associated with stabilizing this favorable crystal structure by a very small amount of Ag, which has not been previously studied.

[0151] Robustness of the alloy: Increasing the 1Mg:0.125Ag ratio relative to the LiCoO2 positive electrode

[0152] Example 9A

[0153] Referring to Example 9A and Figure 9A, the battery cell was fabricated similarly to Example 6A, but various controls were explored with respect to the negative electrode to further illustrate the effectiveness of the ternary composition Li:Mg:Ag. Here, the work focuses on ensuring the robustness of the ternary Li:Mg:Ag resulting in much better performance than the Li:Mg alloy, regardless of the initial stoichiometry of the Li:Mg:Ag alloy (as opposed to Example 8, which focuses on the Li:Mg alloy). As can be seen in the examples, when paired with LiCoO2, various Li:Mg:Ag alloys (7:1.4:0.175, 7:2.33:0.292, 7:1:0.125) exhibit similarly superior behavior to pure Li metal, with gradually increasing Li content ratios (Mg:0.125Ag, ...

[0154] Alloy robustness: Increasing the 1Mg:0.125Ag ratio relative to the LiCoO2 positive electrode

[0155] Example 9B

[0156] As described in Example 9B, referring to Figure 9B, it can be seen from the XRD diffraction pattern of the negative electrode used in Example 6A that as the purity of the "Li2AgMg"-like phase present in the diffraction pattern increases relative to other phases, there is a significant systematic improvement in cycle life. 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 systematically deteriorate with decreasing purity and the presence of the harmful LiMgx phase. Electrochemical performance is excellent for all compositions that result in the Li2AgMg-type structure.

[0157] Reducing the Li content relative to a 1:0.125 Mg:Ag ratio when paired with a LiCoO2 positive electrode

[0158] Example 10A

[0159] In Example 10A, referring to FIG10A, a battery cell was manufactured similarly to that 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. Here, the work focuses on ensuring the robustness of the ternary Li:Mg:Ag resulting in significantly better performance than Li:Mg alloys, regardless of the initial Li:Mg:Ag alloy.The stoichiometry is as follows (in contrast to Example 8A, which focuses on Li:Mg alloys). In the examples, it can be seen that, when paired with LiCoO2, a variety of Li:Mg:Ag alloys (7:1:0.125, 5:1:0.125, 3:1:0.125) with gradually decreasing Li content exhibit similarly superior behavior compared to pure Li metal, which performs much worse. The optimal composition is approximately a ternary composition (7:1:0.125). However, similarly, if the Li-to-Mg ratio becomes too low (1:1:0.125), performance will be compromised.

[0160] Reducing the Li content relative to a 1:0.125 Mg:Ag ratio when paired with a LiCoO2 positive electrode

[0161] Example 10B

[0162] Referring to Example 10B and Figure 10B, as 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 present 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 systematically deteriorate with decreasing purity and the presence of harmful LiMgx phases.

[0163] Increasing the Ag content relative to the 7Li:1Mg ratio when paired with the LiCoO2 positive electrode

[0164] Example 11A

[0165] In Example 11A, referring to FIG11A, the battery cell was manufactured similarly to that of Example 6A, but various controls were explored with respect to 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 as described on page 9 / 33 of the specification 12 CN 121548889 A, various 7Li:1Mg:Agx alloys (7:1:0, 7:1:0.125, 7:1:0.250) with gradually increasing Ag content exhibit similar excellent 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 Ag ratio relative to Li becomes too high, the performance will be slightly compromised.

[0166] Increasing the Ag content relative to the 7Li:1Mg ratio when paired with a LiCoO2 positive electrode

[0167] Example 11B

[0168] Referring to Figure 11B, similar to Example 8B, X-ray diffraction 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]

[0170] Increased areal capacity to 3 mAh / cm2 when paired with LiCoO2 positive electrode

[0170] Example 12A

[0171] Referring to Example 12A and Figure 12A, the battery cell was manufactured similarly to Example 6A, but two batteries were manufactured in which the amount of LiCoO2 positive electrode utilized in the electrochemical battery cell was gradually increased, ranging from 1.2 mAh / cm2 to 3.0 mAh / cm2. 3.0 mAh / cm2 is the target value for most commercial applications and confirms the unique ability of the ternary alloy to maintain stable cycling of the Li coating. The results show that the alloy is very effective in supporting stable cycling at these areal capacities.

[0172] Increased areal capacity to 3 mAh / cm2 when paired with LiCoO2 positive electrode

[0173] Example 12B

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

[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-pitch is approximately 4.6 angstroms. 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 angstroms to 5.0 angstroms. In some embodiments, the d-pitch is approximately 3.1 angstroms to 5.0 angstroms. In some embodiments, the d-pitch is approximately 3.2 angstroms to 5.0 angstroms. In some embodiments, the d-pitch is approximately 3.3 angstroms to 5.0 angstroms. In some embodiments, the d-pitch is approximately 3.4 angstroms to 5.0 angstroms. In some embodiments,The d-pitch is approximately 3.5 angstroms to 5.0 angstroms. In some embodiments, the d-pitch is approximately 3.6 angstroms to 5.0 angstroms. In some embodiments, the d-pitch is approximately 3.7 angstroms to 5.0 angstroms. In some embodiments, the d-pitch is approximately 3.8 angstroms to 5.0 angstroms. In some embodiments, the d-pitch is approximately 3.9 angstroms to 5.0 angstroms. In some embodiments, the d-pitch is approximately 4.0 angstroms to 5.0 angstroms. In some embodiments, the d-pitch is approximately 4.1 angstroms to 5.0 angstroms. In some embodiments, the d-pitch is approximately 4.2 angstroms to 5.0 angstroms. 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 Å to 5.0 Å. In some embodiments, the d-pitch is approximately 4.8 Å to 5.0 Å. In some embodiments, the d-pitch is approximately 4.9 Å to 5.0 Å.

[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 Å to 4.9 Å. In some embodiments, the d-pitch is approximately 4.4 Å to 4.9 Å. In some embodiments, the d-pitch is approximately 4.5 Å to 4.9 Å. In some embodiments, the d-pitch is approximately 4.6 Å to 4.9 Å. In some embodiments, the d-pitch is approximately 4.7 Å to 4.9 Å. In some embodiments, the d-pitch is approximately 4.8 Å to 4.9 Å.

[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...The spacing 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 Å to 4.8 Å. In some embodiments, the d-pitch is approximately 4.4 Å to 4.8 Å. In some embodiments, the d-pitch is approximately 4.5 Å to 4.8 Å. In some embodiments, the d-pitch is approximately 4.6 Å to 4.8 Å. In some embodiments, the d-pitch is approximately 4.7 Å to 4.8 Å.

[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 Å to 4.7 Å. In some embodiments, the d-pitch is approximately 4.4 Å to 4.7 Å. In some embodiments, the d-pitch is approximately 4.5 Å to 4.7 Å. In some embodiments, the d-pitch is approximately 4.6 Å to 4.7 Å.

[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. Specification 11 / 33 pages 14 CN 121548889 A 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 Å to 4.6 Å. In some embodiments, the d-pitch is approximately 4.4 Å to 4.6 Å. In some embodiments, the d-pitch is approximately 4.5 Å to 4.6 Å.

[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 embodiments, the d-pitch is approximately 4.3 Å to 4.5 Å. In some embodiments, the d-pitch is approximately 4.4 angstroms to 4.5 angstroms.

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

[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 angstroms to 4.2 angstroms. In some embodiments, the d-pitch is approximately 4.1 angstroms to 4.2 angstroms.

[0185] In some embodiments, the d-pitch is approximately 3.0 angstroms to 4.1 angstroms. In some embodiments, the d-pitch is approximately 3.1 angstroms to 4.1 angstroms. In some embodiments, the d-pitch is approximately 3.2 angstroms to 4.1 angstroms. In some embodiments, the d-pitch is approximately 3.3 angstroms to 4.1 angstroms. In some embodiments, the d-pitch is approximately 3.4 angstroms to 4.1 angstroms. In some embodiments, the d-pitch is approximately 3.5 angstroms to 4.1 angstroms. In some embodiments, the d-pitch is approximately 3.6 angstroms to 4.1 angstroms. (See page 12 / 33 of the specification, CN 121548889 A)In some embodiments, the d-pitch is approximately 3.7 angstroms to 4.1 angstroms. In some embodiments, the d-pitch is approximately 3.8 angstroms to 4.1 angstroms. In some embodiments, the d-pitch is approximately 3.9 angstroms to 4.1 angstroms. In some embodiments, the d-pitch is approximately 4.0 angstroms to 4.1 angstroms.

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

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

[0192] In some embodiments, the d-pitch is approximately 3.0 Å to 3.4 Å. 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] Hereinafter, we present further embodiments of the invention.

[0196] Experiment:

[0197] Electrode preparation and button cell assembly: Specification 13 / 33 pages 16 CN 121548889 A

[0198] Thin films of Li metal and combinations of Li, Mg and Ag metals were deposited by 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 cm2) was used as the deposition substrate, wherein the deposited film area was 0.95 cm2. A positive electrode Nb0.99Ta0.1PO5 (NTPO) was used as the Li-free intercalated positive electrode, which was prepared using 70 wt% NTPO, 10 wt% carbon and 20 wt% PVdF-HFP polymer binder. Using lithium cobalt(III) oxide (LiCoO2, LCO) to containThe Li-intercalated positive electrode was prepared using 80 wt% LCO, 8 wt% carbon, and 12 wt% PVdF-HFP polymer binder (15.06 mg / cm2, 0.495 cm2). Two positive electrode disks were dried overnight at 120°C under vacuum. A coin cell was prepared under argon atmosphere with water and oxygen content below 0.1 ppm. A single-layer Celgard separator (25 μm) was used in the coin 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. The coin cell constructed using a PVD thin-film negative electrode and an LCO positive electrode was charged to 4.2 V with a constant current C / 10, then charged to the current cutoff C / 40 with a constant voltage, and then discharged to 2.75 V with a constant current C / 10. Alternatively, a button cell constructed using a positive electrode NTPO was discharged to 1.65V at 15mA / g and then charged to 2.8V at 10mA / g. The charge and discharge capacity of the cycle was 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 (ex-situ XRD) at a scan rate of 0.6185 degrees / minute 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 resulting XRD patterns were used to understand the phase differences between the deposited compositions and were processed using EVA and TOPAZ Rietveld refinement procedures. In-situ XRD analysis was performed using a self-developed battery cell, with the negative electrode Li:Mg:Ag thin film deposit located on a porous Cu mesh substrate (Li 0.0072 / scan, 2.45 degrees / min).

[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 (2keV). (Specific sputtering schemes will be added later).

[0206] Results:

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

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

[0209] Using a Li-free intercalation compound as the positive electrode in the Li-ion battery configuration allows for Li in the negative electrode to be...The removal of the coating was used for direct evaluation, where the impact of harmful reactions occurring via Li plating was limited. These harmful reactions included the interaction between Li metal and the electrolyte, and, most importantly, masked 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 was 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). Furthermore, this configuration may be relevant to realizing future high-energy-density battery configurations characterized by high-energy-density, non-lithiated positive electrodes (such as sulfur or metal fluoride composites).

[0210] As shown in Figure 13, a baseline-deposited Li metal film (containing the same amount of Li metal (1.48 mAh / cm²) as most of the lithium-containing alloy films studied herein) and a Li metal disk (150 μm Li metal, >15.79 mAh / cm²) were evaluated when paired with an NTPO positive electrode. As expected, the high-capacity Li metal disk exhibited better cycle stability than the lower-capacity Li films of 2.27 mAh / cm² and 1.48 mAh / cm², due to the excess Li metal reserve and the 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 a high-energy-density battery cell, considering both energy density and safety. Therefore, these electrodes must be improved to enhance stability in order to utilize the high energy density capability of Li metal.

[0211] Figure 13 shows the discharge and charge areal capacity (mAh / cm2) of the Li metal film when paired with NTPO (a) and the specific capacity (mAh / g NTPO) of the Li metal film benchmark when paired with NTPO battery cells (b), both observed up to 50 cycles. The Li metal film benchmarks used include negative electrodes with a given calculated areal capacity of >15.79 mAh / cm2 (red), 2.27 mAh / cm2 (green), and 1.48 mAh / cm2 (blue).

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

[0213] To evaluate the effect on performance, Mg was incorporated into the Li film deposition composition. As shown in Figure 14, co-deposited Li:Mg alloys were studied when paired with the positive electrode NTPO at normalized stoichiometric ratios of 1:0, 16:1, 13:1, 10:1, 7:1, and 5:1, where the discharge capacity was observed up to 50 cycles. Here, compared with all other Li:Mg compositions shown, the normalized Li:Mg alloys showed the best performance.The reference film exhibited high initial capacity but failed rapidly. The introduction of a small amount of Mg (16Li:1Mg) improved this initial performance while still maintaining a 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 theoretical available capacity) is likely due to transport limitations.

[0214] To address this challenge and increase the achievable capacity, Ag metal was introduced into the alloy due to its high electronic conductivity, large atomic size, and its ability to form alloys with Li metal at low voltages, as well as the possibility of forming extended solid solutions. Utilizing the previously identified beneficial 7:1 Li:Mg ratio, Ag was added to the composition in gradually increasing stoichiometric ratios (Li:Mg:Ag = 7:1:0.125, 7:1:0.25, 7:1:0.5, and 7:1:1). As shown in Figure 15, the addition of 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% relative 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 the 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 shows the discharge and charge areal capacity (mAh / cm2) of the Li:Mg film when paired with NTPO (a) and the specific capacity (mAh / g NTPO) 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: 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 shows the discharge and charge areal capacity (mAh / cm2) of the ternary Li:Mg:Ag film when paired with NTPO (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 cycle was observed to 50. The Li:Mg:Ag thin 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 performance of the Ag-doped compositions, X-ray diffraction was used to understand and identify the potential key action phases in these compositions. As shown in Figure 35, the XRD patterns of the Li:Mg:Ag compositions are characterized by the formation of strong Bragg reflections associated with the Li2AgMg and AgMg intermetallic phases, wherein the compositions lacking the Ag component, 7:0:0 and 7:1:0, are characterized only by pure Li or Li0.9Mg0.1 phases, respectively. 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 shows the XRD patterns of Li:Mg:Ag thin film negative electrode compositions comprising the following ratios: 7:1:0.125, 7:1:0.25, 7:1:0.5, and 7:1:1, as well as normalized Li metal films and a 7:1 Li:Mg baseline.

[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 showed performance improvements relative to a pure Li baseline containing the same normalized Li content (Table 1). Here, these compositions are further evaluated using similar Ag addition ratios utilized in the 7:1 Li:Mg optimization. As shown in Figure 17, the introduction of Mg into the Li film (10:1) resulted 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) resulted in 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 resulted in significant increases in capacity (for 10:1:0.5, the increase was >100%), however, as previously observed, this was also accompanied by an increased capacity decay. Given this improvement in performance, XRD was again used to identify the potential key active phase. As shown in Figure 18, 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 shows the discharge and charge capacity (mAh / cm2) of the ternary Li:Mg:Ag film paired with NTPO (A) and the specific discharge capacity (mAh / g NTBO) of the Li:Mg:Ag film 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: 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 shows the XRD patterns of Li:Mg:Ag thin-film negative electrode compositions comprising the following ratios: 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) relative to pure Li and the 13:1 Li:Mg composition revealed a very significant capacity improvement. However, similar to the observations of the previously discussed 10:1 Li:Mg, the capacity increase with the addition of Ag was accompanied by an increase in capacity decay. Additionally, as shown in Figure 20, 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 shows the discharge and charge areal capacity (mAh / cm2) (A) of the ternary Li:Mg:Ag film paired with NTPO and the specific capacity (mAh / g NTBO) (B) of the Li:Mg:Ag film 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: 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 shows the XRD patterns of thin-film negative electrode compositions comprising the following Li:Mg:Ag ratios: 13:1:0.25 (green), 13:1:0.125 (red), 13:1:0 (blue), and a normalized Li metal film reference (black). Specification 16 / 33 pages 19 CN 121548889 A

[0226] In summary, through the evaluation of Li:Mg:Ag thin-film deposits, ratios of 7:1:0, 10:1:0, and 13:1:0 were found to be suitable for...Adding Mg to pure Li compositions resulted in superior cycle 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 excellent cycle 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 the 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 have revealed potential solid solution formation induced by the formation of the Li₂AgMg phase, where 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 lattice parameter of AgMg. However, despite the potential for solid solution formation found in these ternary compositions, a larger relative ratio of Li:Mg and Mg:Ag may be detrimental. Therefore, based on the initial optimization when paired with NTPO, the 7:1:0.125 Li:Mg:Ag ratio was initially considered alone to provide the greatest benefit among all the compositions observed in this paper, based on its superior cycling stability and moderate capacity recovery compared to Li films alone and the 7:1 Li:Mg composition. The ability of the 7:1:0.125 composition to pair with LCO is further explored in the following sections. Specification 17 / 33 pages 20 CN 121548889 A

[0227]

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

[0229] Table 2. Maximum Li extraction (mAh / cm2) of Li:Mg:Ag composition Specification 18 / 33 pages 21 CN 121548889 A

[0230]

[0231] Table 2. Maximum lithium extraction in terms of areal capacity (mAh / cm2) during cycling of thin film Li:Mg:Ag composition when paired with NTPO. The cycles in which maximum lithium extraction was observed are shown in the right column.

[0232] Table 3. Lattice parameters and phase percentages of Li:Mg:Ag composition Specification 19 / 33 pages 22 CN 121548889 A

[0233]

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

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

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

[0237] Given the success of the 7:1 Li:Mg structure in stabilizing pure Li metal anodes in the previous section, and the addition of Ag to significantly improve capacity and cycling stability, especially 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 its 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. Thus, by utilizing the observations on initial irreversible capacity loss and capacity decay during cycling in CN 121548889 A on pages 20 / 33 of the specification, we achieved a more realistic understanding of the functionality of the beneficial thin-film compositions in a more commercially relevant cell configuration. In this commercially relevant cell configuration, we introduced additional Li:Mg:Ag compositions to further understand and individually consider the benefits achieved by the 7:1:0.125 compositions identified in the previous section, but within the phase window of (7+x:1:0.125) versus (7-x:1:0.125) as previously studied, where all compositions utilized contain a fixed Li content (Table 1).

[0238] As observed in the previous section, the Li ratio within the 1:0.125 Mg:Ag system significantly affects cycling performance and achievable capacity when paired with NTPO. Further investigation into the role of Li in 1:0.125 Mg:Ag systems (including additional ratios of 5:1:0.125, 3:1:0.125, and 1:1:0.125) revealed a decline in electrochemical performance as the Li:Mg and Li:Ag ratios approached 1:1 (Figure 21). As shown, compared to the beneficial 7:1:0.125 composition (2.28% loss), a slightly higher irreversible capacity loss was observed as the relative Li content decreased 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 a significantly earlier onset of detrimental capacity decay (Figure 21, Table 4), where all compositions contained a fixed normalized Li content (Table 1). Therefore, there are detrimental ratios for Li:Mg and Li:Ag that degrade performance, with the latter, at extreme levels (1:1:0.125), even relative to the poorly performing Li metal benchmark (1:0:0), showing a significant performance degradation.The capacity retention rate is significantly reduced. Therefore, there exists an ideal Li:Mg and Li:Ag ratio, which forms 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 film compositions showed that the unique binary:ternary ratio within the film 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 has the lowest amount of ternary phase and the lowest ternary:binary ratio in the group. Compositions 5:1:0.125 and 3:1:0.125 show improved electrochemical performance, possibly due to a relative increase in ternary phase (79.50%, 69.87% vs. 43.57%) compared to the 1:1:0.125 composition. The electrochemical differences between these improved compositions may be due to the relative percentage of the binary phase, with the slightly better-performing 3:1:0.125 composition characterized by a relatively higher ternary:binary ratio, similar to the ternary:binary ratio of 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 allow for more favorable containment of excess Li⁺ brought in via LCO.

[0240] Figure 21 shows the discharge capacity (mAh / cm²) observed in the ternary Li:Mg:Ag composition paired with LCO as a percentage of cycles (up to cycle 65). 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. Specification 21 / 33 pages 24 CN 121548889 A

[0241]

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

[0243]

[0244] Table 5. Lattice parameters and compositional 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 shows the compositions including 7:1:0.125 (yellow), 5:1:0.125 (red), 3:1:0.125 (blue), 1:1:0.125, and Li metal reference 1:0:0. (Specification)Page 22 / 33, page 25, CN 121548889, A. XRD patterns of Li:Mg:Ag compositions with a ratio of 0.125 (green) and Li metal reference 1:0:0 (black).

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

[0247] As observed in the previous section, 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 were investigated. As shown in Figure 23, adding a small amount of Ag to the 7:1 Li:Mg composition (to reach 7:1:0.125) resulted in a significant improvement in capacity retention during cycling and a reduction in first-cycle loss, a trend also observed in the previous section when paired with NTPO. However, increasing the relative Ag content above 0.125 resulted in a significant decrease in performance and a corresponding increase in irreversible capacity loss (Figure 23, Table 5). Therefore, similar to the trend observed in the previous sections, making the Li:Ag and Ag:Mg ratio close to 1:1 proves detrimental relative to the composition 7:1:0.125. As shown in Table 5, the above trend can be further supported by analyzing the corresponding Li2AgMg and AgMg lattice parameters, where increasing the corresponding Ag:Mg ratio leads to an increase in the AgMg lattice but a decrease in the Li2AgMg lattice. In addition, 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 23 shows the discharge capacity (mAh / cm2) of the ternary Li:Mg:Ag paired with LCO according to the number of cycles (up to cycle 65). 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 comprising 7:1:0.5, 7:1:0.25, 7:1:0.125 and Li metal reference 1:0:0. Instruction manual, pages 23 / 33, 26, CN 121548889 A

[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 shows the compositions including 7:1:0.5 (red), 7:1:0.25 (green), 7:1:0.125 (yellow), and 7:1:0 (blue).XRD patterns of Li:Mg:Ag compositions with a Li metal reference of 1:0:0 (black) and Li metal reference of 1:0:0 (black).

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

[0255] In view of the significant effects observed between the relative ratios of Li:Mg, Li:Ag and Mg:Ag explored above, the relative percentage of fixed 1Mg:0.125Ag in the normalized Li composition was changed. 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 in 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 shows the discharge capacity (mAh / cm2) of ternary Li:Mg:Ag paired with LCO according to the number of cycles (up to cycle 65). The Li:Mg:Ag thin film negative electrode compositions shown here include the following ratios: 7:2.233:0.292 (red), 7:1.4:0.175 (blue), 7:1:0.125 (yellow), and normalized Li metal reference 1:0:0 (black), wherein all Li-containing compositions contain the same amount of Li. Specification 24 / 33 pages 27 CN 121548889 A

[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 compositional 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 shows 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).

[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 is warranted to understand the robustness of the compositional range. As shown in the figureAs shown, the binary combinations of Li:Mg (including 7:7, 7:2.33, 7:1, and 7:07) fail to meet the performance requirements of the 7:1:0.125 composition, with the near-1:1 Li:Mg composition exhibiting the worst performance (Figure 27, Table 10). Furthermore, the binary combinations of Mg:Ag were evaluated, and compositions with relatively low Ag concentrations relative to Mg concentrations (0:7:1, 0:3:1, 0:1:0.125) 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 0:1:1 ratio) showed improved capacity retention up to cycle 65, similar to the beneficial 7:1:0.125 composition, but with a decrease in initial capacity and a reduction in the AgMg lattice parameter. 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 cycling performance similar to that of Mg alone (0:1:1), where no significant performance benefit was observed as the relative Mg:Ag ratio increased. The lattice parameter of the binary 0:1:0.125 composition is not similar to that 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 performance decreases with the addition of Ag up to a 0:1:1 composition relative to Mg alone (0:1:0), and that 7:1:0.125 shows improved performance relative to its binary counterpart (0:1:0.125), this suggests that only a specific range of AgMg phases is beneficial for supporting capacity retention.

[0267] Figure 27 shows the discharge capacity (mAh / cm2) of ternary Li:Mg:Ag paired with LCO according to the number of cycles (up to cycle 65). The Li:Mg:Ag thin film negative electrode composition shown here comprises 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 normalized Li metal reference 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 shows the discharge capacity (mAh / cm2) observed in ternary Li:Mg:Ag paired with LCO according to the number of cycles (up to cycle 65). The Li:Mg:Ag thin film negative electrode compositions shown here 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 shows the XRD patterns of Li:Mg:Ag compositions comprising 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 a normalized Li metal reference of 7:0:0 (black).

[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 the specification of 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. Pages 27 / 33 of CN 121548889 A.

[0276] Figure 30 shows 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 a normalized Li metal reference of 7:0:0 (black).

[0277] E. High areal capacity 7:1:0.125 composition film

[0278] Given that the 7:1:0.125 composition is normalized to close to 1The 0.4 mAh / cm2 was successful, and higher areal capacity deposits were evaluated to explore the practical stability of this ternary composition and the potentially beneficial Li2AgMg phase in the commercially available 2 to 3 mAh / cm2 areal capacity range. Here, the 7:1:0.125 composition has been doubled (>2 mAh / cm2) and still achieved stable performance when paired with LCO (Figure 31, Table 11). In addition, this higher capacity composition can allow for additional solid solution formation, based on a slight decrease in the Li2AgMg lattice parameter compared to the 1.1 mAh / cm2 7:1:0.125 composition. Both the single and doubled 7:1:0.125 compositions exhibited similar ratios of ternary:binary phase percentages, with the single 7:1:0.125 composition exhibiting a larger percentage of Li metal phase.

[0279] Figure 31 shows the discharge capacity (mAh / cm2) observed in the ternary Li:Mg:Ag paired with LCO as a percentage of cycles (up to cycle 65). The Li:Mg:Ag thin film negative electrode compositions shown herein comprise 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 comprising 7:1:0.125, doubled deposit 7:1:0.15, and normalized Li metal reference 7:0:0. Specification 28 / 33 pages 31 CN 121548889 A

[0282]

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

[0284] Figure 32 shows the XRD patterns of Li:Mg:Ag compositions including double-thickness compositions 7:1:0.125 (>2 mAh / cm2) (red) and 7:1:0.125 (1.1 mAh / cm2) (yellow) and normalized Li metal reference 7:0:0 (1.1 mAh / cm2) (black).

[0285] Figure 33 shows 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). Performance is evaluated based on second discharge capacity (mAh / cm2).

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

[0287] As shown in the previous section, the ternary composition 7:1:0.125 is not only superior to pure Li, but more importantly, superior to Li:A binary combination of Mg and Ag:Mg components. This property is attributed to the presence and distribution of beneficial Li2AgMg and AgMg phases throughout the film. The homogeneity of these phases and elements across the entire thickness of the deposited film remains questionable. As shown in Figure 34, the homogeneity of the co-deposited 7:1:0.125 sample was evaluated using XPS depth analysis, where the BE signals from the Ag and Mg components remained unshifted across the entire depth of the analyzed film (up to approximately 7500 nm at a total sputtering time of approximately 15000 s, or a computation rate of 0.5 nm / sec) relative to the binding energy (BE) observed towards the surface of the film and its adjacent substrate regions. The BE observed for Ag (~368.8 eV) showed a slight blue shift relative to the baseline Ag signal observed for pure Ag metal (~368.2 eV, Figure 36) and those Ag signals (~368.2 eV) documented in the literature. The observed BE (~1303 eV) for Mg is consistent with the baseline Mg signal (~1303.1 eV, Fig. 36) observed for pure Mg metal and those 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 relatively stabilizing with increasing depth. After additional sputtering, a shift of 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. As shown in Fig. 35, the atomic percentages of Li, Mg, and Ag components remained relatively constant throughout the film after a total of ~5000 seconds. In summary, apart from a slight increase in Li concentration on the surface possibly due to reactions with glovebox contaminants, the elemental distribution of these elements remained relatively constant with depth, indicating that the distribution of ternary and binary phases is relatively uniform throughout the material's depth.

[0288] Additionally, as shown in Figure 36, XPS depth analysis was also performed on the co-deposited binary film (0:1:1). The BE of the Ag and Mg components was observed from the surface to the substrate adjacent to the substrate (pages 29 / 33 of the specification, CN 121548889 A) (total sputtering time approximately 6180 seconds, or approximately 3090 nm at a calculation 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 seconds of sputtering. This is consistent with the 7:1:0.125 ternary composition.The signal observed in the material (1303.4 eV) showed a blue shift compared to this Mg BE (1303.6 eV).

[0289] Figure 34 shows XPS depth analysis of the co-deposited 7:1:0.125 film composition, 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 shows the atomic percentage distribution of the Li1s, Mg1s, and Ag3d signals observed in the 7:1:0.125 composition during sputtering.

[0291] Figure 36 shows XPS depth analysis of the co-deposited 0:1:1 film composition, including Mg1s (a) and Ag3d (b) signals, where the baseline Mg and dg signals are 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 using a dual-salt fluorine organic (FOS)-based electrolyte that has previously demonstrated stable Li metal coating. As shown in Figure 37, for both the 7:1:0.125 and 7:0:0 compositions, the use of the FOS-based electrolyte composition significantly improved capacity retention and cycling performance relative to its performance with the standard commercial electrolyte 1M LiPF6 EC / DMC. In addition, 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 shows the discharge capacity (mAh / cm2) observed in the Li:Mg:Ag film when paired with an LCO battery cell (up to 200 cycles). 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 LiPF6 EC / DMC (yellow (7:1:0.125), black (7:0:0)) and the optimized composition 1M LiTFSI 0.4M LDFOB 90 / 10 FOS / 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 (pages 30 / 33, CN 121548889 A) and optimized electrolyte 1M LiTFSI 0.4M LDFOB 90 / 10 FOS / FEC.

[0297] 4. Ex-situ XRD evaluation of the transformation of MgAg to Li2AgMg upon 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 the Li ion configuration is paired with LCO, where Li is added to the negative electrode. Since the binary phase is structurally related to the ternary phase, there is a question: does the binary phase transform into a ternary structure upon lithiation? The binary Ag:Mg film was lithied to Lix = 4.42 and removed for examination by ex-situ XRD. As shown in Figure 38, lithiation of the binary Mg:Ag composition (0:1:1) resulted in the formation of the ternary Li2AgMg phase, as indicated by the appearance of the superstructure (1,1,1) Li2AgMg Bragg reflection and (331) reflection. Rietveld analysis of these spectra revealed that the lattice parameters of gMg and Li2AgMg were 3.311 Å and 6.638 Å, respectively, consistent with the ICDD standard. In summary, the XRD data clearly support the direct transformation of the AgMg binary to the Li2AgMg ternary phase upon electrochemical lithiation.

[0299] Figure 38 shows the ex-situ XRD evaluation of the binary composition 0:1:1 (blue) and the electrochemically lithiated binary composition 4.42:1:1 (red).

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

[0301] Lithiation of the ternary composition 7:1:0.125 to an addition of Lix=4.42 (as performed for the aforementioned 0:1:1 study) revealed the formation of a similar ternary phase, but in greater quantities. The presence of ternary Li2AgMg and binary MgAg components at the maximum lithiation level of the Li-ion battery cell configuration indicates that both components can 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 shows the out-of-situ XRD evaluation of the ternary composition 7:1:0.125 (blue) and the electrochemically lithiated 11.42:1:0.125 (red) composition.

[0303] The present invention includes the following embodiments:

[0304] Embodiment 1. A battery, comprising:

[0305] a casing;

[0306] a positive electrode located in the casing;

[0307] a negative electrode located in the casing,

[0308] wherein the negative electrode comprises an alloy,

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

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

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

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

[0313] Embodiment 4. The battery according to Embodiment 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] Embodiment 5. The battery according to Embodiment 1, wherein the material of the negative electrode has a crystal structure consistent with Li2AgMg as determined by XRD.

[0315] Embodiment 6. The battery according to Embodiment 1, wherein the material of the negative electrode has a crystal structure consistent with AgMg as determined by XRD, 34 CN 121548889 A, Pages 31 / 33 of Specification

[0316] wherein lithium is added during battery operation to form a ternary alloy comprising lithium, magnesium and silver.

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

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

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

[0320] Embodiment 10. The battery according to Embodiment 1, wherein the negative electrode further comprises graphite.

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

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

[0323] Embodiment 13. The battery of Embodiment 1, wherein the positive electrode comprises iron fluoride or bismuth fluoride.

[0324] Embodiment 14. The battery of Embodiment 1, wherein the electrolyte does not include lithium.

[0325] Embodiment 15. The battery of Embodiment 1, wherein the electrolyte comprises fluoride.

[0326] Embodiment 16. The battery of Embodiment 1, wherein 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.

[0327] Embodiment 17. The battery of Embodiment 16, wherein the d-spacing is approximately 3.9 Å.

[0328] Embodiment 18. The battery of Embodiment 17, wherein X-ray diffraction peaks corresponding to a d-spacing of approximately 3.1 Å to 3.5 Å are present.

[0329] Embodiment 19. The battery according to Embodiment 1, wherein the battery comprises a lithium-ion battery.

[0330] Embodiment 20. The battery according to Embodiment 1, wherein the battery comprises a solid-state lithium battery.

[0331] Embodiment 21. The battery according to Embodiment 1, wherein the electrolyte comprises a solid-state electrolyte.

[0332] Embodiment 22. The battery according to Embodiment 1, wherein the composition of the alloy varies according to the thickness of the alloy.

[0333] Embodiment 23. A battery comprising:

[0334] a housing;

[0335] a positive electrode located in the housing;

[0336] a negative electrode located in the housing;

[0337] a current collector located in the housing;

[0338] a separator located in the housing;

[0339] an electrolyte located in the housing; and

[0340] an alloy, wherein the alloy comprises lithium, magnesium, and silver,

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

[0342] Embodiment 24. A method comprising:

[0343] obtaining a housing;

[0344] arranging a positive electrode in the housing;

[0345] arranging a negative electrode in the housing;

[0346] depositing an alloy on the negative electrode, a separator, or a solid electrolyte,

[0347] wherein the alloy comprises lithium, magnesium, and silver; and

[0348] arranging an electrolyte in the housing, the electrolyte being configured to conduct current between the positive and negative electrodes.

[0349] Embodiment 25. The method of embodiment 24, wherein deposition comprises deposition by physical vapor deposition. Specification 32 / 33 pages 35 CN 121548889 A

[0350] Embodiment 26. The method of embodiment 24, wherein deposition comprises depositing a film.

[0351] Embodiment 27. The method of embodiment 26, wherein deposition comprises depositing a film by physical vapor deposition.

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

[0353] Embodiment 29. The method of Embodiment 24, wherein the positive electrode does not include lithium.

[0354] Embodiment 30. The method of Embodiment 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] Embodiment 31. The method of Embodiment 24, wherein the electrolyte includes lithium.

[0356] Embodiment 32. The method of Embodiment 24, wherein the negative electrode further includes graphite.

[0357] Embodiment 33. The method of Embodiment 24, wherein the positive electrode includes iron fluoride or bismuth fluoride.

[0358] Embodiment 34. The method of Embodiment 24, wherein the electrolyte does not include lithium.

[0359] Embodiment 35.The method according to embodiment 24, wherein the electrolyte comprises a fluoride.

[0360] Embodiment 36. The method according to embodiment 24, wherein the electrolyte does not include lithium. Instruction manual page 33 / 33, page 36, CN 121548889 A, Figure 1; Instruction manual figure 1 / 48, page 37, CN 121548889 A, Figure 2; Instruction manual figure 2 / 48, page 38, CN 121548889 A, Figure 3A; Instruction manual figure 3 / 48, page 39, CN 121548889 A, Figure 3B; Instruction manual figure 4 / 48, page 40, CN 121548889 A, Figure 4A; Instruction manual figure 5 / 48, page 41, CN 121548889 A, Figure 4B; Instruction manual figure 6 / 48, page 42, CN 121548889 A, Figure 5A; Instruction manual figure 7 / 48, page 43, CN 121548889 A, Figure 5B; Instruction manual figure 8 / 48, page 44, CN 121548889 A, Figure 6A; Instruction manual figure 9 / 48, page 45, CN 121548889 A Figure 6B: Instruction manual illustration, page 10 / 48, number 46, CN 121548889 A; Figure 7A: Instruction manual illustration, page 11 / 48, number 47, CN 121548889 A; Figure 7B: Instruction manual illustration, page 12 / 48, number 48, CN 121548889 A; Figure 8A: Instruction manual illustration, page 13 / 48, number 49, CN 121548889 A; Figure 8B: Instruction manual illustration, page 14 / 48, number 50, CN 121548889 A; Figure 9A: Instruction manual illustration, page 15 / 48, number 51, CN 121548889 A; Figure 9B: Instruction manual illustration, page 16 / 48, number 52, CN 121548889 A; Figure 10A: Instruction manual illustration, page 17 / 48, number 53, CN 121548889 A; Figure 10B: Instruction manual illustration, page 18 / 48, number 54, CN 121548889 A; Figure 11A Instruction manual illustrations, page 19 / 48, figure 55, CN 121548889 A, figure 11B; Instruction manual illustrations, page 20 / 48, figure 56, CN 121548889 A, figure 12A; Instruction manual illustrations, page 21 / 48, figure 57, CN 121548889 A, figure 12B; Instruction manual illustrations, page 22 / 48, figure 58, CN 121548889 A, figure 13; Instruction manual illustrations, page 23 / 48, figure 59, CN.Figure 14 of the instruction manual, page 24 / 48, CN 121548889 A; Figure 15 of the instruction manual, page 25 / 48, CN 121548889 A; Figure 16 of the instruction manual, page 26 / 48, CN 121548889 A; Figure 17 of the instruction manual, page 27 / 48, CN 121548889 A; Figure 18 of the instruction manual, page 28 / 48, CN 121548889 A; Figure 19 of the instruction manual, page 29 / 48, CN 121548889 A; Figure 20 of the instruction manual, page 30 / 48, CN 121548889 A; Figure 21 of the instruction manual, page 31 / 48, CN 121548889 A; Figure 22 of the instruction manual, page 32 / 48, CN 121548889 A Figure 23 Appendix to the Instruction Manual, Page 33 / 48, 69 CN 121548889 A Figure 24 Appendix to the Instruction Manual, Page 34 / 48, 70 CN 121548889 A Figure 25 Appendix to the Instruction Manual, Page 35 / 48, 71 CN 121548889 A Figure 26 Appendix to the Instruction Manual, Page 36 / 48, 72 CN 121548889 A Figure 27 Figure 28 Appendix to the Instruction Manual, Page 37 / 48, 73 CN 121548889 A Figure 29 Appendix to the Instruction Manual, Page 38 / 48, 74 CN 121548889 A Figure 30 Appendix to the Instruction Manual, Page 39 / 48, 75 CN 121548889 A Figure 31 Appendix to the Instruction Manual, Page 40 / 48, 76 CN 121548889 A Figure 32 Appendix to the Instruction Manual, Page 41 / 48, 77 CN 121548889 A Figure 33 Instruction manual figures 42 / 48, page 78, CN 121548889 A, Figure 34; Instruction manual figures 43 / 48, page 79, CN 121548889 A, Figure 35; Instruction manual figures 44 / 48, page 80, CN 121548889 A, Figure 36; Instruction manual figures 45 / 48, page 81, CN 121548889 A, Figure 37; Instruction manual figures 46 / 48, page 82, CN 121548889 A, Figure 38; Instruction manual figures 47 / 48, page 83, CN 121548889 A, Figure 39; Instruction manual figures 48 / 48, page 84.CN 121548889 A

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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