Rapid cycling of solid-state lithium metal batteries under heavy loads

Abstract

An electrochemical cell (e.g., a solid-state secondary battery) includes a cathode, an anode, and a solid electrolyte disposed between the cathode and the anode. The anode includes an anode material having a plurality of voids. In some embodiments, the cathode includes lithium, and the anode is configured such that lithium metal deposits in the plurality of voids during charging of the electrochemical cell. In some embodiments, the anode includes a constraint-sensitive surface that controls the interplay between lithiation and lithium deposition. The electrochemical cells disclosed herein have the advantages of improved battery cycling performance coupled with excellent power and energy densities.

Description

[Technical Field]

[0001] SUMMARY OF THE INVENTION Embodiments described herein relate to electrochemical cells (e.g., solid-state secondary batteries) that include anode materials having multiple voids, and methods of use and manufacture thereof. [Background technology]

[0002] Lithium (Li) metal anodes are crucial for the development of next-generation high-energy-density batteries due to their high specific capacity (approximately 10 times that of commercially available graphite anodes) and low electrochemical potential. However, due to the inherent properties of lithium metal, lithium anodes present numerous challenges during the charge-discharge process, limiting the practical application of lithium metal secondary batteries. Commercial applications require high-speed cycling with thick cathodes, which requires maintaining the stability of a thick lithium metal layer in the anode, but this is difficult. Harsh cycling conditions, such as high currents and low temperatures, naturally promote uneven lithium deposition and exfoliation, ultimately leading to the formation of lithium dendrites. These dendrites can damage the battery separator, causing short circuits and compromising safety. Furthermore, isolated lithium metal particles form during discharge, reducing the overall cycling performance of the lithium anode. These issues can lead to severe capacity loss and even explosion of lithium metal batteries after extended operation. Summary of the Invention

[0003] Embodiments described herein relate to solid-state secondary batteries with anode materials having multiple voids. During charging of the battery, lithium precipitates in the voids as lithium metal. The voids may be, for example, voids within particles or voids formed between particles due to particle stacking. That is, the anode material may include particles with multiple voids, or multiple voids may exist between particles of the anode material, or both. Lithium may precipitate on the surface of the particles and grow within the voids. Lithium metal may also precipitate underneath the anode film, forming a layer.

[0004] In some embodiments, an electrochemical cell (e.g., a solid-state secondary battery) includes a cathode, an anode, and a solid electrolyte disposed between the cathode and the anode. The anode includes an anode material having a plurality of voids. In some embodiments, the cathode includes lithium, and the anode is configured such that lithium metal deposits in the plurality of voids during charging of the electrochemical cell.

[0005] In some embodiments, the electrochemical cell includes a cathode comprising lithium, an anode comprising an anode material, and a solid electrolyte disposed between the cathode and the anode. In some embodiments, the anode material has a local effective elastic modulus of at least about 0.3 GPa, thereby providing mechanical restraint to the anode. In some embodiments, the anode is configured such that lithium metal deposits on the anode material during charging of the electrochemical cell.

[0006] In some embodiments, the electrochemical cell includes a cathode comprising lithium, an anode comprising an anode material including a plurality of particles, and a solid electrolyte disposed between the cathode and the anode. In some embodiments, the anode is configured such that lithium metal deposits on the anode upon an initial charge of the electrochemical cell. In some embodiments, the deposition of lithium metal causes a volume change of the plurality of particles, the volume change being less than 300% of the original volume of the plurality of particles.

[0007] In some embodiments, a method for storing and releasing electrical energy is provided. The method includes providing a battery including a cathode comprising lithium, an anode comprising an anode material having a plurality of voids, and a solid electrolyte disposed between the anode and the cathode. The method further includes providing electrical energy to the battery during charging, thereby discharging the Li + The process involves transferring ions from the cathode to the anode and depositing them as Li metal in the voids.

[0008] In some embodiments, the method further comprises electrically connecting a load between the anode and the cathode to oxidize and transport Li metal in the voids to the cathode, where it is deposited. + The method includes a step of depositing the metal as ions.

[0009] In some embodiments, Li + Some of the ions react with the surface of the anode material to form a surface layer with the anode material. For example, the electrochemical cell further includes a surface layer on the anode, the surface layer being formed by reaction of the anode material with lithium ions. In some embodiments, the anode material includes nanoscale and / or microscale particles, and the thickness of the surface layer is less than 500 nm, e.g., less than 100 nm. In some embodiments, the volume of the particles after the first charge is less than 300%, e.g., less than 150%, of the original particle volume. In some embodiments, the anode material does not crack or swell (e.g., observable by SEM) during charge or discharge. In some embodiments, the average particle size after 10 charge / discharge cycles is greater than 70% of the original particle size. In some embodiments, the volume of the voids changes by less than 100%, e.g., the anode material is configured such that the volume of a plurality of voids changes by less than 100%, e.g., less than 50%, during charge and discharge. In some embodiments, the particle swelling is less than 300%. In some embodiments, the thickness of the surface layer is less than 500 nm, such as less than 100 nm, hi some embodiments, a portion of the anode material below the surface layer does not undergo lithiation.

[0010] In some embodiments, the battery is subjected to mechanical constraint. For example, the anode material may be sensitive to constraint. In some embodiments, the mechanical constraint is caused by an external pressure of 0.05 to 50 MPa. In some embodiments, the mechanical constraint is caused by the local effective elastic modulus (K eff ) is at least 0.3 GPa.

[0011] In some embodiments, the anode material comprises Si. In some embodiments, the anode material comprises a Si-graphite composite formed from nanoscale and / or microscale Si and graphite particles. In some embodiments, the anode material comprises at least one of Si, a Si alloy, a Si-carbon composite, a Si alloy-carbon composite, Mg metal, a binary Mg alloy, a ternary Mg alloy, a binary Mg alloy-carbon composite optionally containing a solid electrolyte and / or a polymeric binder, or a ternary Mg alloy-carbon composite optionally containing a solid electrolyte and / or a polymeric binder. In some embodiments, at least 10% of the stored electrical energy is stored as lithium metal.

[0012] In some embodiments, a solid-state battery includes a cathode comprising lithium, an anode comprising an anode material having a plurality of voids, and a solid electrolyte disposed between the anode and the cathode, wherein the anode material is mechanically constrained and during charging of the battery, lithium from the cathode is deposited as lithium metal into the plurality of voids.

[0013] In some embodiments, mechanical constraints limit lithiation of the anode material to a surface layer less than 500 nm, e.g., less than 100 nm. In some embodiments, the anode material comprises nanoscale and / or microscale particles, and the surface layer is less than 500 nm thick, e.g., less than 100 nm thick. In some embodiments, the volume of the particles after the first charge is less than 300%, e.g., less than 150%, of the original particle volume. In some embodiments, the anode material does not crack or swell (e.g., observable by SEM) during charge or discharge. In some embodiments, the average particle size after 10 charge / discharge cycles is greater than 70% of the original particle size. In some embodiments, the void volume changes less than 100%, e.g., the anode material is configured so that the volume of a plurality of voids changes less than 100%, e.g., less than 50%, during charging and discharging of the electrochemical cell. In some embodiments, the particle swelling is less than 300%. In some embodiments, the mechanical restraint is provided by an external pressure in the range of about 0.05 MPa to about 50 MPa. In some embodiments, the mechanical restraint is provided by the local effective elastic modulus (K eff ) is at least 0.3 GPa.

[0014] In some embodiments, the anode material is K crit In some embodiments, the anode material includes a material having a capacity over 100 kJ / cm² (referred to as COK) greater than 500 mAh / g / GPa and a COK x V greater than 600 mWh / g / GPa. In some embodiments, the anode material includes Mg metal, or a binary or ternary Mg alloy. In some embodiments, the anode material includes at least one of Si, a Si alloy, a Si-carbon composite, a Si alloy-carbon composite, Mg metal, a binary Mg alloy, a ternary Mg alloy, a binary Mg alloy-carbon composite optionally containing a solid electrolyte and / or a polymeric binder, or a ternary Mg alloy-carbon composite optionally containing a solid electrolyte and / or a polymeric binder. In some embodiments, the anode material includes at least one of LiMg5, Mg7Al1, Mg 149 Li1, Mg 149 Ba1, Mg 149 Ca1, Mg 149 S1, Mg149 Ag1, Mg7B1, Na1Mg 14 B1, or MgPb 2~5 , MgTe 1~2 , MgHg 3~5 , MgAl 1~2 , MgH 1~3 , MgIn5, MgGe 2~5 , MgSi 1~3 , MgSb 0.5~3 , MgSn 1~5 , or MgGa 1~5 , for example, LiMg5, Mg7Al1, Mg 149 Li1, Mg 149 Ba1, Mg 149 Ca1, Mg 149 S1, Mg 149 Ag1, Mg7B1, or Na1Mg 14 includes at least one of B1.

[0015] In some embodiments, the anode material is K crit with a capacity (COK) exceeding 500 mAh / g / GPa and COK×V in the range of 500 - 600 mWh / g / GPa. In some embodiments, the anode material is a Mg alloy represented by the formula Mg x Si 1-x , Mg3Al, Li x Mg 1-x , Mg4Al1Si4, or Li x Mg y Si 1-x-y (1≧x≧0, 0<y<1), a metal-doped Mg represented by the formula Mg x M' y M" 1-x-y (x>0.8, y<0.2, and M' and M" are metal elements), a doped MgO represented by the formula (MgO) 14 Al1Fe1), a doped MgO represented by the formula (MgO) x A y B z O 1-x-y-z (x>0.9, y<0.1, z<0.1, and A and B are elements other than Mg or O), or a binary Mg compound (for example, Mg2P, LiMg5, Mg7Al1, Mg 149 Li1, Mg 149 Ba1, Mg149 Ca1, Mg 149 S1, Mg 149 Ag1, Mg7B1, etc.

[0016] In some embodiments, the anode material is K crit In some embodiments, the anode material comprises a material having a capacity over K (COK) greater than 500 mAh / g / GPa and a COK×V in the range of 300-500 mWh / g / GPa. In some embodiments, the anode material comprises a material having the formula (MgO) x A y B z O 1-x-y-z Doped MgO (e.g., Mg3Al1O4, Li1Mg6B1O7, and K1MgO) is represented by the formula (x>0.7, y<0.3, z<0.3, and A and B are elements other than Mg and O). 14 Ti1O 16 ), formula Mg x Si 1-x Compounds represented by the formula Mg x Si y O 1-x-y or a compound of formula Mg x M' y M" 1-x-y Mg metal alloys (e.g., Mg) represented by the formula (x>0.8, y<0.2, and M' and M" are metals) 14 Al1Fe1, Mg x Al 1-x , Mg 17 Al 12 and its doped compounds, e.g., Mg 16 Al 12 Li1, Mg x Al 1-x , Mg 14 Al1Fe1, Mg 17 Al 12 , and Mg 16 Al 12 doped compounds such as Li1).

[0017] In some embodiments, the anode material comprises Si. In some embodiments, the anode material comprises a Si-graphite composite formed by nanoscale and / or microscale Si and graphite particles. In some embodiments, the anode material is coated on a Li foil on a current collector (e.g., a stainless steel current collector). In some embodiments, the anode material undergoes a self-limiting reaction with lithium under mechanical constraint to form a surface layer. In some embodiments, the anode material comprises nanoscale and / or microscale particles, and the thickness of the surface layer is less than 500 nm, e.g., less than 100 nm. In some embodiments, the anode material does not crack or swell (e.g., observable by SEM) during charge or discharge. In some embodiments, the voids may be from about 1 nm to about 1,000 μm (e.g., 5 nm to 1 μm, 1 to 10 μm, 10 to 100 μm, etc.).

[0018] In some embodiments, the thickness of the surface layer is less than 500 nm, e.g., less than 100 nm. In some embodiments, the anode material comprises particles having a diameter of 1 nm to 100 μm. In some embodiments, the anode material comprises a surface layer or coating that inhibits lithiation. In some embodiments, the battery has a current of about 0.01 to about 200 mA / cm. 2 In some embodiments, the battery has a short-circuit-free current density in the range of about 0.1 to about 200 mg / cm during normal charging and discharging. 2 In some embodiments, the battery has a cathode coating weight of about 1 mAh / cm 2 ~about 20mAh / cm 2 In some embodiments, the battery can be cycled for 1,000 to 20,000 cycles at a charge / discharge time of 1 to 60 minutes or a charge / discharge rate of 0.1 to 30C.

[0019] In some embodiments, the battery has a pouch-type, prismatic, or cylindrical cell shape. In some embodiments, the battery further comprises a protective layer and / or a multilayer of solid electrolyte. In certain embodiments, the protective layer and / or the multilayer of solid electrolyte is deposited, cast, or transferred onto the cathode, anode, or substrate in a layer-by-layer process. In some embodiments, the multilayer comprises n layers of solid electrolyte, where n is 2 or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or more). [Brief explanation of the drawings]

[0020] [Figure 1] FIG. 1 is a schematic diagram of an electrochemical cell including a cathode, an anode, and a solid electrolyte disposed between the cathode and the anode, according to one embodiment.

[0021] [Figure 2] FIG. 2 is a cross-sectional view of an electrochemical cell including a cathode, an anode including an anode material having a plurality of voids, and a solid electrolyte disposed between the cathode and anode, according to one embodiment.

[0022] [Figure 3] FIG. 3 is a cross-sectional view of an electrochemical cell including a cathode, an anode including an anode material having a plurality of voids, and a multi-layer solid electrolyte disposed between the cathode and anode, according to one embodiment.

[0023] [Figure 4] FIG. 4 is a cross-sectional view of an electrochemical cell including a cathode, an anode including an anode material having a plurality of voids, and a solid electrolyte disposed between the cathode and anode, according to one embodiment.

[0024] [Figure 5] FIG. 5 is a simplified flowchart of a method for manufacturing an electrochemical cell including a cathode, an anode, and a solid electrolyte disposed between the cathode and the anode, according to one embodiment.

[0025] [Figure 6] Figures 6(a)-6(e2): Figure 6(a) shows the Li discharge profile at room temperature at a current density of 0.2 mA / cm2 for a Li / G-Li5.5PS4.5Cl1.5 (LPSCl1.5)-Li10GeP2S12 (LGPS)-LPSCl1.5-SiG battery. Figures 6(b1)-6(b3) show FIB-SEM (focused ion beam scanning electron microscope) images of the Si-graphite anode at various discharge states (Figures 6(b1)-6(b3)), corresponding to points 1-3 in Figure 6(a). Figures 6(c1)-6(c3) show SEM-EDS mappings corresponding to the SEM images in Figures 6(c1)-6(c3). In Figures 6(c1)-6(c3), the carbon signal C comes from graphite, oxygen O and nitrogen N come from the reaction of lithium metal with air, and fluorine F comes from the PTFE binder. Figure 6(d) shows the discharge profile of a Li-1M LiPF6 cell in EC / DMC-SiG. Figures 6(e1)-6(e2) show FIB-SEM images of the SiG anode after discharge in the liquid electrolyte battery shown in Figure 6(d).

[0026] [Figure 7]Figures 7(a)-7(f): Figure 7(a) shows a TEM image of a battery that had been charged 500 times. Here, the SiG anode was cut with a FIB. The battery structure was Li-Sig-SEs-NMC83 with a nominal NP ratio of 1.5, and the battery was cycled at 55 °C and 2 C. Figure 7(b) shows an EELS line scan across the line in Figure 7(a). Figure 7(c) shows STEM-EDS mapping of the boxed area in Figure 7(a). Figures 7(d1)-7(d2) show high-resolution TEM images of the Si particles after FIB. Figures 7(e1)–7(e3) show SEM images, including FIB-SEM image (Figure 7(e1)) and EDS mapping (Figures 7(e2–e3)), of the Si-graphite anode in the first discharge state (2.5 V at room temperature, 0.5 C) in a solid electrolyte with a nominal NP ratio of 1.5. No lithium was present beneath the SiG anode. Figure 7(f) shows the XPS of the SiG anode after the cell in Figure 6(a) was fully discharged. The Li / G-SE-SiG was discharged at room temperature with a current density of 0.2 mA / cm. Argon milling was performed for 500 and 1000 seconds at an energy of 0.5 keV.

[0027] [Figure 8]Figures 8(a)–8(d): Figure 8(a) shows a comparison of the capacity retention of monolayer and multilayer SE batteries using SiGe / Li anodes. All batteries had a cathode coating weight of 25 mg / cm2, a current density of 7.4 mA / cm2 (2C rate), and the same overall electrolyte layer thickness. The areal capacities of the batteries after 2000 cycles ranged from 2.8 mAh / cm2 to 2.2 mAh / cm2. Figure 8(b) shows the specific capacity of the three batteries at different C rates, demonstrating that the multilayer electrolyte provides higher capacity than the monolayer electrolyte. All batteries had a cathode coating weight of 25 mg / cm2. Figure 8(c) shows the charge / discharge curves of various multilayer batteries with Si particle sizes of 1 μm and 44 μm. Figure 8(d) shows the charge / discharge curves of multilayer batteries with different cathode coating weights at 0.5 C. The nominal NP ratio was maintained at 1.5 in all batteries. The electrolyte formulas in the figure legends are Li10SnP2S12 (LSnPS), Li10GeP2S12 (LGPS), Li5.5PS4.5Cl1.5 (LSPCl1.5 or Cl1.5), or Li6PS5Cl1.0 (LPSCl1.0 or Cl1.0). All cells were tested at 55°C.

[0028] [Figure 9] Figures 9(a)-9(f): Figure 9(a) shows the charge-discharge curves of a solid-state battery at 5-10C rates, 55°C, and an NMC83 cathode loading of 22 mg / cm2. Here, 1C = 3.2 mA / cm2. Figure 9(b) shows the low-temperature voltage profile of a solid-state battery using Li-SiG as the anode and a cathode loading of 22 mg / cm2. Figures 9(c) and 9(d) show the capacity retention and Coulombic efficiency of the battery operated at 55°C, 6C-6C, and 10C (charge)-2C (discharge). Figure 9(e) shows the capacity and Coulombic efficiency (80% after 1400 cycles) of a battery (NMC83 cathode loading = 15 mg / cm2) operated at 35°C, 5C-5C. Figure 9(f) shows the simulated voltage-capacity dependence of Si at various levels of mechanical constraint. Here, Keff is the effective elastic modulus from 0 to 5 GPa.

[0029] [Figure 10]Figures 10(a1)-10(c2) show FIB-SEM and EDS mapping of silicon / graphite (Si / G) anodes. In Figures 10(a1) and 10(a2), no lithium metal foil was attached to the Si / G film, and no compaction pressure was applied. In Figures 10(b1) and 10(b2), no lithium metal foil was attached to the Si / G film, and compaction pressure was applied. In Figures 10(c1) and 10(c2), lithium metal foil was attached to the Si / G film, and compaction pressure was applied. F comes from the PTFE binder, and Ga comes from the FIB ion source.

[0030] [Figure 11] Figures 11(a)–11(f) show FIB-SEM images and cycle characteristics of liquid and solid electrolyte batteries using SiG anodes. Figures 11(a)–11(b) show FIB-SEM images of the Si / G anode after 5 cycles of a battery with a Si / G-liquid electrolyte-NMC83 (cathode coating weight = 25 mg / cm2). Figure 11(c) shows the charge / discharge curves of a SiG-EC / DMC / 1M LiPF6-NMC83 battery, where the Si was microscale. Figures 11(d)–11(e) show FIB-SEM images of the Si / G anode after 500 cycles of a battery with a Li / SiG-LPSCl-LGPS-LPSCl-NMC83 (cathode coating weight = 25 mg / cm2) and NP ratio of 1.5. Figure 11(f) shows the charge-discharge profile at 55°C and 2C for the same battery used for STEM-EELS in Figure 7(a).

[0031] [Figure 12] Figures 12(a)-12(f) show FIB-SEM images and EDS mapping of the Si / G anode after the first (Figures 12(a)-12(c)) and fifth (Figures 12(d)-12(f)) discharges. The cell had a SiG-LPSCl-LGPS-LPSCl-NMC83 (25 mg / cm) coating mass and an N / P ratio of 1.5. The cell was cycled at room temperature at 0.5 C.

[0032] [Figure 13]Figures 13(a) to 13(f) show XPS, XRD, FIB-SEM images, and EDS mapping of a battery with the structure Si / G-LPSCl-LGPS-LPSCl-NMC83 (coating amount = 25 mg / cm). Figure 13(a) shows the XPS measurement (Li 1s signal) of Si / G with an N / P ratio of 1.5 after the first charge. Figure 13(b) shows the XRD measurement of Si / G with an N / P ratio of 1.5 after the first charge. Figures 13(c) to 13(f) show the FIB-SEM images and EDS mapping of the Si / G anode after charging. The N / P ratio of this battery was 0.3. The battery was cycled at room temperature at 0.5 C.

[0033] [Figure 14] Figures 14(a)-14(g) show the FIB-SEM image (Figure 14(a)) and EDS mapping (Figures 14(b)-14(g)) of a pure Si anode after charging. Figure 14(b) shows all the measured elements (C, N, O, F, and Si). Figure 14(c) shows the F mapping. Figure 14(d) shows the C mapping. Figure 14(e) shows the Si mapping. Figure 14(f) shows the O mapping. Figure 14(g) shows the N mapping. The battery was fabricated with a Si-LPSCl-LGPS-LPSCl-NMC83 (loading = 25 mg / cm2) structure. The NP ratio was 2.5 based on the theoretical capacity of Si and NMC83. The battery was cycled at 0.5 C at room temperature. The C and F signals are from the binder PTFE.

[0034] [Figure 15] Figure 15(a) shows the rate characteristics of cells using different anodes (Si, 75 wt% Si-25 wt% G, and 50 wt% Si-50 wt% G). Figure 15(b) shows the cycling characteristics of Li / Si-SEs-NMC83 (22 mg / cm2 loading) at 6 C-6 C. Figures 15(c)-15(d) show the charge-discharge curves of Li / SiG-SEs-NMC83 (22 mg / cm2 loading) operating at 15(c) 6 C-6 C and 15(d) 10 C-2 C.

[0035] [Figure 16] Figures 16(a)-16(c) show FIB-SEM (Figures 16(a)-16(b)) and EDS mapping (Figure 16(c)) of the SiG anode after discharge at a low operating pressure of 5 MPa. The cell had a structure of Si / G-LPSCl-LGPS-LPSCl-NMC83 (coating amount = 25 mg / cm2) with an NP ratio of 1.5. Cycle testing was performed at room temperature and 0.5 C.

[0036] [Figure 17] Figure 17 shows the cycling performance of a Li-NMC811 solid-state pouch cell (right side of graph) with a Si-G anode protection layer on Li metal. Capacity (mAh / g) (y-axis, left) and coulombic efficiency (%) (y-axis, right) are plotted against the number of cycles (x-axis) over 2000 cycles.

[0037] [Figure 18] Figure 18(a) shows the results of a high-throughput calculation of the voltage (y-axis) and capacity above Kcrit (COK) (x-axis) of the anodic reaction for a Li metal anode when the bandgap is less than 1.5 eV within the plot range. The two dotted lines correspond to y=300 / x and y=600 / x. Figure 18(b) shows the results of a high-throughput calculation of the capacity and capacity above Kcrit of the anodic reaction for a Li metal anode when the bandgap is less than 1.5 eV within the plot range.

[0038] [Figure 19A-C] Figure 19A shows the occurrence of elements in the range of COK > 500 mAh / g / GPa and COK × V > 600 mWh / g / GPa. Figure 19B shows the co-occurrence of two elements in the range of COK > 500 mAh / g / GPa and COK × V > 600 mWh / g / GPa. Figure 19C shows the co-occurrence of three elements in the range of COK > 500 mAh / g / GPa and COK × V > 600 mWh / g / GPa.

[0039] [Figure 20A-C]Figure 20A shows the occurrence of elements when COK > 500 mAh / g / GPa and COK × V is in the range of 500-600 mWh / g / GPa. Figure 20B shows the co-occurrence of two elements when COK > 500 mAh / g / GPa and COK × V is in the range of 500-600 mWh / g / GPa. Figure 20C shows the co-occurrence of three elements when COK > 500 mAh / g / GPa and COK × V is in the range of 500-600 mWh / g / GPa.

[0040] [Figure 21A-C] Figure 21A shows the occurrence of elements when COK > 500 mAh / g / GPa and COK × V is in the range of 400-500 mWh / g / GPa. Figure 21B shows the co-occurrence of two elements when COK > 500 mAh / g / GPa and COK × V is in the range of 400-500 mWh / g / GPa. Figure 21C shows the co-occurrence of three elements when COK > 500 mAh / g / GPa and COK × V is in the range of 400-500 mWh / g / GPa.

[0041] [Figure 22A-D] Figure 22A shows the occurrence of elements when COK > 500 mAh / g / GPa and COK × V ranges from 300 to 400 mWh / g / GPa. Figure 22B shows the co-occurrence of two elements when COK > 500 mAh / g / GPa and COK × V ranges from 300 to 400 mWh / g / GPa. Figure 22C shows the co-occurrence of three elements when COK > 500 mAh / g / GPa and COK × V ranges from 300 to 400 mWh / g / GPa. Figure 22D shows the results of a high-throughput calculation of the anodic reaction voltage (y-axis) versus lithiation composition / Kcrit (x-axis) for a Li metal anode for 59,524 material entries within the plot axes.

[0042] Reference is made throughout the following detailed description to the accompanying drawings, in which like numerals generally refer to like elements unless context dictates otherwise. The illustrative embodiments described in the detailed description, drawings, and claims are not intended to limit the invention. Other embodiments may be utilized, and other changes may be made, without departing from the spirit or scope of the subject matter presented herein. It will be readily understood that the aspects of the present disclosure, as generally described herein and illustrated in the drawings, can be arranged, substituted, combined, and designed in a wide variety of configurations, all of which are expressly considered and made a part of this disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0043] Embodiments described herein relate to an electrochemical cell (e.g., a solid-state secondary battery) that includes a cathode, an anode, and a solid electrolyte disposed between the cathode and the anode. In some embodiments, the anode includes an anode material having a plurality of voids. In some embodiments, the anode is configured such that lithium metal deposits in the plurality of voids during charging of the electrochemical cell. In some embodiments, the anode material has a local effective elastic modulus of at least about 0.3 GPa, thereby mechanically restraining the anode. In some embodiments, the anode is configured such that lithium metal deposits on the anode material during charging of the electrochemical cell. In some embodiments, the anode includes a plurality of particles. In some embodiments, the anode is configured such that lithium metal deposits on the anode upon initial charging of the electrochemical cell. In some embodiments, the deposition of lithium metal results in a volume change of the plurality of particles, the volume change being less than 300% of the original volume of the plurality of particles. In some embodiments, the cathode includes lithium.

[0044] Specifically, embodiments described herein provide a solid-state battery design that exhibits a counterintuitive interaction between two important next-generation anode materials: Li metal and silicon (Si). Rather than behaving as a Si anode with strong Li-Si alloying or lithiation reactions, the solid-state battery of the present embodiments can significantly tune the Li-Si interaction by suppressing lithiation of Si and other materials and instead functioning as a Li metal anode. In this case, the Si matrix promotes uniform, high-speed deposition and exfoliation of Li metal. Other anode materials where this phenomenon can occur are also presented herein. Electrochemical cells of the present disclosure can achieve currents of about 0.01 to about 200 mA / cm without short circuits. 2 (e.g., 19-32mA / cm 2 ) and 0.1 to 200 mg / cm for normal charge / discharge 2 (e.g., 15-25 mg / cm 2 ) commercial-level cathode coating weight, or 1-20mAh / cm 2 (e.g., 1-3mAh / cm 2 According to some embodiments, the electrochemical cells or batteries presented herein may withstand 1,000 to 20,000 charge-discharge cycles (e.g., 1,000 to 2,000 cycles) at charge-discharge rates of 1 to 7 minutes (e.g., 3 to 7 minutes) or 5 to 30 C (e.g., 5 to 10 C).

[0045] Lithium metal and silicon are important battery anode materials with high specific capacity. In particular, lithium (Li) anodes play a crucial role in the development of advanced secondary batteries due to their high specific capacity and low electrochemical potential. However, both lithium metal and silicon anodes suffer from electrochemical problems. The most significant issues with Li anodes are exfoliation and dendrite formation. Exfoliation can occur when the Li replenishment rate exceeds the Li replenishment rate, resulting in the formation of voids at the interface between the Li and solid electrolyte. The accumulation of these voids increases the local current density and ultimately leads to the growth of dendrites on the anode surface. Dendrites are tiny, thorn-like protrusions that pose safety concerns because they can penetrate the battery separator and contact the cathode, causing short circuits and even fires. However, the volume change after lithiation of up to 300% limits the practical use of many types of silicon as anodes in liquid electrolyte batteries. For example, micro-sized silicon particles in a liquid electrolyte can form a thick solid electrolyte interface (SEI). The swelling caused by the lithiation process causes a rapid volume change, which can cause the particles to break down into smaller particles and form a new SEI layer. This process can lead to the formation of small, isolated silicon particles and electrolyte decomposition, which can cause capacity loss and safety issues.

[0046] The embodiments described herein address these challenges, enabling the full potential of Si and Li metal anodes in secondary batteries to be realized while ensuring safety and performance. The electrochemical cells of various embodiments provide a solution that facilitates the use of both lithium and silicon anodes in electrochemical cells that achieve desirable properties such as power, energy, cycle life, and low temperature performance.

[0047] Embodiments of electrochemical cells including the solid electrolytes described herein may have one or more of the following advantages: (1) silicon can act as a support structure for lithium deposition, thereby improving the cycling performance of the battery; (2) lithium metal deposition dominates the electrochemical process at the anode, thereby enabling rapid charging; (3) high areal capacity and robustness with increasing loading; (4) improved energy density, beneficial for various applications (e.g., aerospace applications, electric vehicles, etc.); (5) prevention or reduction of lithium dendrite formation, especially at high current densities (e.g., due to multilayer electrolyte design and dynamic stability); (6) good cycling at low temperatures (e.g., 35°C), which can be advantageous in certain environments; and (7) improved safety of the electrochemical cell, reducing the risk of short circuits due to dendrite formation during operation.

[0048] This study finds that silicon's behavior in solid-state batteries can be dramatically different: for example, materials such as Si, which are typically expected to undergo lithiation during charging when used as an anode material, can instead act as a support structure for lithium deposition.

[0049] In previous liquid or solid-state battery design studies, Si was heavily lithiated and operated as a typical silicon anode, so it was unexpected that Si could function as a scaffold with little lithiation in lithium metal anode applications (see, e.g., Tan, Darren HS, et al. "Carbon-free high-loading silicon anodes enabled by sulfide solid electrolytics." Science 373.6562 (2021): 1494-1499). This significant difference between the electrochemical cells of the embodiments presented herein and conventional batteries is also reflected in the significantly superior rate capabilities of the inventive cells described herein by multiple embodiments.

[0050] Without being bound by theory, the solid-state electrochemical cell environment described herein, unlike liquid electrolyte batteries, is a mechanically constrained system, which first creates thermodynamic metastability for Li deposition on the Si surface. Here, the constraint may be due to the mechanical strength of the individual particles themselves, or it may be applied to neighboring Si particles within a dense solid layer, or a combination thereof. This constraint may add a strain energy barrier to the volume expansion reaction of Si (or similar materials). Furthermore, unlike mechanically soft Ag, which lacks a Li alloy nucleation barrier, Si has a small nucleation barrier for alloying with Li and a large bulk modulus of approximately 100 GPa, which naturally resists the expansion reaction in a mechanically constrained solid environment. These factors combine to create thermodynamic metastability and kinetic stability, creating an energy barrier that prevents deep lithiation of Si, favoring lithium metal deposition. Forming a shallow surface layer of Li-Si alloy without milling may facilitate lithium metal deposition, promoting rapid and uniform lithium metal deposition. Since the yield modulus of lithium metal is only a few MPa, the precipitated lithium can penetrate into the gaps and pores between the Si particles.

[0051] All definitions and definitions used herein are understood to supersede dictionary definitions, definitions in documents incorporated by reference, and / or ordinary meanings of the defined terms.

[0052] As used herein, the singular forms "a," "an," and "the" include the plural referents unless the context clearly dictates otherwise. Thus, for example, "a member" means a single member or combination of members, and "a material" means one or more materials, or a combination thereof.

[0053] In certain embodiments, herein, when a numerical value is preceded by the word "about" or "approximately," it indicates that the value is within a range of ±10%. When a range of values ​​is provided, it is understood that every value between the upper and lower limits of that range (to the tenth of the unit of the lower limit unless the context clearly dictates otherwise), and every other stated or intervening value within that specified range, is included in the disclosure. The upper and lower limits of these smaller ranges, if independently included in the smaller ranges, are also included in the disclosure, except for any explicitly excluded limit in the stated range. When a stated range includes one or both of these limits, ranges excluding one or both of those included limits are also included in the disclosure.

[0054] The term "and / or" as used in this specification and in the embodiments is understood to mean "either or both" of the elements so conjoined, i.e., elements that are sometimes conjunctively present and sometimes disjunctively present. Multiple elements listed with "and / or" should be interpreted similarly, i.e., understood to mean "one or more" of the elements so conjoined. Elements other than the elements specifically identified by the "and / or" clause may optionally be present, whether or not associated with those specifically identified elements. Thus, as a non-limiting example, a reference to "A and / or B," when used in conjunction with open-ended language such as "comprising," may refer in one embodiment to only A (optionally including elements other than B), in another embodiment to only B (optionally including elements other than A), and in yet another embodiment to both A and B (optionally including other elements), etc.

[0055] As used in this specification and in the embodiments, "or" is understood to have the same meaning as "and / or" as defined above. For example, when separating items in a list, "or" or "and / or" is to be interpreted as inclusive, i.e., including at least one and more of the elements or elements in the list, and optionally including additional items not in the list. To the contrary, only explicitly stated terms, such as "only one of" or "exactly one of," or terms such as "consisting of" as used in the embodiments, mean including exactly one element of more than one element or list. In general, the term "or" as used herein will be interpreted as indicating exclusive alternatives (i.e., "either / or, but not both") only when preceded by terms indicating exclusivity, such as "either / or," "one of," "only one of," or "exactly one of." As used in the embodiments, "consisting essentially of" shall have its ordinary meaning as used in the field of patent law.

[0056] In this specification and embodiments, the phrase "at least one" when used in reference to a list of one or more elements is understood to mean at least one element selected from any one or more elements in the list of elements, but does not necessarily include at least one of all elements specifically listed in the list of elements, and does not exclude any combination of the elements in the list. This definition also indicates that elements other than those specifically identified in the list of elements to which the term "at least one" refers may optionally be present, whether related to those specifically identified elements or not. Thus, as a non-limiting example, "at least one of A and B" (or, synonymously, "at least one of A or B," or, synonymously, "at least one of A and / or B") refers, in one embodiment, to at least one (optionally including more than one) A and no B (optionally including elements other than B); in another embodiment, to at least one (optionally including more than one) B and no A (optionally including elements other than A); in yet another embodiment, to at least one (optionally including more than one) A and at least one (optionally including more than one) B (optionally including other elements); etc.

[0057] In the above embodiments and throughout this specification, all transitional phrases such as "comprising," "including," "possessing," "having," "containing," "involving," "holding," and "consisting of" shall be understood to be open-ended, i.e., meaning "including, but not limited to." Only the transitional phrases "consisting of" and "essentially consisting of" shall be closed or semi-closed transitional phrases, respectively, as defined in U.S. Patent Office Manual of Patent Examining Procedure Section 2111.03.

[0058] As used herein and in the embodiments, the term "stability" for a solid electrolyte refers to the stability of the material against decomposition due to reaction with the metal in the anode, such as lithium. The stability of a solid electrolyte can be determined experimentally.

[0059] The term "K" used in this specification and embodimentscrit (COK)" is the lithiation capacity in K crit It refers to the value divided by .

[0060] As used herein and in embodiments, the term "lithiation" of an anode material refers to the penetration of the material with lithium atoms or ions (e.g., by intercalation, insertion, chemical reaction, etc.), as opposed to deposition as lithium metal into voids (e.g., nanoscale and / or microscale voids) of the material (e.g., within or between particles of the material).

[0061] As used herein and in the embodiments, the term "microscale" with respect to anode materials refers to materials having at least one cross-sectional dimension in the range of 1 to 1,000 μm.

[0062] As used herein and in the embodiments, the term "nanoscale" with respect to anode materials refers to materials having at least one cross-sectional dimension in the range of 1 nm to 1,000 nm.

[0063] FIG. 1 is a schematic diagram of an electrochemical cell 100 including, in one embodiment, a cathode 120 (e.g., LCO, LMO, NCA, NMC, LFP, LMNO, and LATP-coated LMNO, NMC83, NMC811, NMC111, NMC532, NMC622, NMC955, etc.), an anode 140 (e.g., particulate Si, SiGe composite, etc.), and a solid electrolyte 130 disposed between the cathode 120 and the anode 140. The electrochemical cell 100 includes the cathode 120 disposed on a cathode current collector 110. The electrochemical cell 100 includes the anode 140 disposed on an anode current collector 150. In some embodiments, the electrochemical cell 100 can be disposed within a housing 160.

[0064] In some embodiments, the electrochemical cell 100 comprises a commercially suitable cathode coating weight of about 0.1 to 200 mg / cm. 2 (For example, about 15 to 25 mg / cm 2 ) for example, about 0.01 to 200 mA / cm2 (For example, about 19 to 32 mA / cm 2 ) and exhibits an improved current density of about 1-20 mAh / cm. 2 (For example, about 1 to 3 mAh / cm 2 ) and can withstand 1,000 to 20,000 charge-discharge cycles (e.g., 1,000 to 2,000 cycles) at, for example, 1 to 7 minutes (e.g., 3 to 7 minutes) or 5 to 30 C (e.g., 5 to 10 C) charge-discharge rates. In some embodiments, electrochemical cell 100 can include materials (e.g., solid electrolyte 130, anode 140, etc.) that are under mechanical constraint. For example, anode 140 is mechanically constrained, which limits lithiation of the anode material to a surface layer of less than about 65 nm. The mechanical restraint may be caused by external pressure, and the external pressure may be, for example, a compression of 5 to 500 MPa (for example, 5 to 10, 10 to 15, 10 to 20, 20 to 30, 25 to 45, 30 to 40, 25 to 50, 35 to 55, 40 to 60, 50 to 75, 50 to 100, 60 to 80, 55 to 70, 65 to 85, 75 to 100). 00, 80 to 90, 80 to 100, 90 to 110, 105 to 120, 100 to 150, 125 to 175, 150 to 200, 175 to 225, 200 to 250, 225 to 275, 250 to 300, 275 to 350, 325 to 375, 350 to 400, 375 to 425, 400 to 450, 425 to 475, 450 to 500 MPa, for example, about 5, 7, 10, 12, 15, 22, 25, 28, 30, 40, 45, 50, 100, 200, 250, 300, 400, 500 MPa. The mechanical constraint can be achieved by, for example, a volumetric constraint combined with a material modulus of at least 0.3 GPa (e.g., at least 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 GPa) to achieve a local effective elastic modulus (K eff) may occur. In some embodiments, the electrochemical cell 100 can include both external pressure and engineered materials to induce a local effective elastic modulus in the material. In some embodiments, the anode 140, cathode 120, and solid electrolyte 130 can form a battery module as a bipolar stack or a parallel stack. In some embodiments, the area of ​​each layer is 0.1 cm 2 ~1m 2 In some embodiments, the mechanical structure can provide a surface layer on anode 140 that is less than 500 nm thick. In some embodiments, lithium metal can be deposited as a surface layer on anode 140, and the mechanical structure can provide a surface layer that is less than 500 nm thick.

[0065] In some embodiments, the housing 160 can be pouch-shaped, such as an aluminum pouch, a mica pouch, a polymer pouch, or the like. In some embodiments, the housing 160 can be a prismatic cell. The housing 160 can be formed of a strong, rigid, and heat-resistant material. In some embodiments, the housing 160 comprises iron, iron alloys, aluminum, aluminum alloys, titanium alloys, stainless steel, carbon steel, galvanized steel, carbon compounds and their alloys, plastic, carbon or glass fiber-filled plastic, polymer, other suitable materials, or combinations thereof. In some embodiments, the housing 160 can be coated with a corrosion-resistant or flame-retardant material (e.g., Teflon, nylon, aluminum oxide, titanium oxide, corrosion-resistant and / or flame-retardant paint, etc.). In some embodiments, the housing 160 is configured to be lightweight and occupy a minimal volume relative to the volume of the electrochemical cell 100 to maintain power / volume efficiency.

[0066] In some embodiments, anode 140 includes an anode material (not shown). In some embodiments, the anode material is one from which Li can be deposited during charging under conditions induced by the cell design without the majority of the material being lithiated. Such materials, when used as anodes in other batteries, would function as anode materials by lithiation, for example, by insertion or intercalation.

[0067] In some embodiments, the anode material may have a plurality of voids (not shown in FIG. 1 ). The voids may be due, for example, to gaps between microscale or nanoscale particles. Alternatively, or in addition, the voids may be, for example, pores or other interstices within the particles forming the anode material. For example, in some embodiments, the anode material may include porous particles. In some embodiments, the anode material may further include a plurality of voids between the porous particles. In some embodiments, the anode material may include non-porous particles and may include a plurality of voids due to the spaces between the non-porous particles. The voids, in some embodiments, allow Li to pass through during charging. + Li can be accepted in the form of ions being precipitated in the voids as Li metal. The cross-sectional dimensions of the voids can be from several nm (e.g., 5 to 10 nm) to several tens of μm (e.g., 10, 20, 30, 40, or 50 μm), for example, 5 nm to 50 μm, 5 nm to 100 nm (e.g., 5 to 50, 25 to 60, 45 to 80, or 75 to 100 nm), 100 nm to 1 μm (e.g., 100 to 200, 150 to 450), , 200-300, 250-600, 400-500, 500-750, 600-800, 700-900, 900-1,000 nm), 1 μm to 50 μm (e.g., 1-10, 5-10, 7-15, 12-20, 15-20, 15-30, 20-30, 25-50, 30-40, 35-45, 40-50 μm). In some embodiments, the cross-sectional dimension of each of the plurality of voids is in the range of about 5 nm to about 50 nm.

[0068] In some embodiments, the anode material has a high surface area, e.g., a high ratio of surface area to volume and / or mass. The anode material can be in a variety of forms, such as a powder, particles, clay, or solid sheet. One example of a form is a powder. In some embodiments, the anode material comprises a plurality of particles having diameters ranging from about 1 μm to about 100 μm.

[0069] After application of molding pressure (e.g., mechanical pressure during initial charging and discharging of electrochemical cell 100), in some embodiments, the plurality of voids in anode 140 may have a volume of about 0% to about 99% of the volume of anode 140, e.g., 10-15%, 10-20%, 15-30%, 25-50%, 30-40%, 35-50%, 40-50%, 50-75%, 40-60%, 55-80%, 65-90%, 60-80%, 75-90%, 80-90%, 85-95%, or 90-99%.

[0070] In some embodiments, the anode material is under mechanical constraint. In some embodiments, the mechanical constraint is provided by at least one of an anode material having a local effective elastic modulus of at least about 0.3 GPa or an external pressure applied to the electrochemical cell in a range of about 0.05 MPa to about 50 MPa. That is, in some embodiments, the anode 140 is mechanically constrained by an anode material having a local effective elastic modulus of at least about 0.3 GPa or by an external pressure applied to the electrochemical cell 100 in a range of about 0.05 MPa to about 50 MPa. In some embodiments, the anode material includes at least one of Si or a Si-graphite composite.

[0071] In some embodiments, the anode material can be Si. The Si can be, for example, pure silicon or silicon mixed with other materials, such as silicon mixed with graphite (composite materials, e.g., Si-graphite composites formed from microscale and / or nanoscale Si and graphite particles, i.e., SiG). Other suitable anode materials are also investigated in this disclosure (see Figures 12(a)-16(c)). In some embodiments, suitable anode materials include K crit The capacity (COK) is greater than 500mAh / g / GPa, and (K crit × V) (COK × V) is greater than 600 mWh / g / GPa, such as Mg metal or binary or ternary alloys of Mg (e.g., LiMg5, Mg7Al1, Mg 149 Li1, Mg 149 Ba1, Mg 149 Ca1, Mg 149 S1, (Mg 149 Ag1, Mg7B1, or Na1Mg 14 B1), where the capacity is calculated from the theoretical lithiation composition of the material, and V is Li + is the average lithiation voltage of the anode 140 relative to K / Li, crit is the critical elastic modulus that can suppress the chemical reaction between the Li metal and the material. crit Capacities above K reflect the sensitivity of the material to the lithiation capacity being suppressed by mechanical constraints and converted into the lithium deposition capacity of interest. crit The capacity (COK) is greater than 500mAh / g / GPa, and (K crit × V) (COK × V) is in the range of 500 to 600 mWh / g / GPa, for example, a material of the formula Mg x Si 1-x , Mg3Al, Li x Mg 1-x , Mg4Al1Si4, Li x Mg y Si 1-x-y Mg alloy, formula Mg x M' y M" 1-x-y(x>0.8, y<0.2) (e.g. Mg 14 Al1Fe1) metal doped Mg, formula (MgO) x A y B z O 1-x-y-z (x>0.9) doped MgO, binary Mg compounds (e.g., Mg2P), etc. Other suitable materials include K crit Materials with a COK greater than 500 mAh / g / GPa and a COK × V in the range of 300 to 500 mWh / g / GPa, such as those of the formula (MgO) x A y B z O 1-x-y-z Doped MgO (e.g., Mg3Al1O4, Li1Mg6B1O7, K1Mg 14 Ti1O 16 ), formula Mg x Si 1-x Compound of formula Mg x Si y O 1-x-y or compounds of the formula Mg x M' y M" 1-x-y Mg metal alloys (e.g., Mg x Al 1-x , e.g. Mg 17 Al 12 , and its doped compounds, such as Mg 16 Al 12 Li1). Suitable materials may be those that undergo a self-limiting reaction with lithium under mechanical constraint to form a surface layer (e.g., 65 nm or less, e.g., about 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5 nm, e.g., 5-10 nm, 8-15 nm, 10-20 nm, 15-25 nm, 20-40 nm, 30-60 nm, 45-55 nm, 50-60 nm, 55-65 nm). In some embodiments, the anode material may be formed from particles, and the particles may have a diameter of 1-100 μm.

[0072] In some embodiments, the anode material included in anode 140 may include a coating (e.g., a coating on particles comprising the material), a surface layer, a coating that inhibits bulk lithiation, etc. This may be a surface layer that occurs, for example, upon lithiation, as described herein. Alternatively, the surface layer may be included separately, for example, by a coating, for example, by self-assembly on or from the anode material (e.g., using solution or vapor processes, atomic layer deposition, chemical vapor deposition, electroless plating, polymer grafting, etc.).

[0073] In some embodiments, the anode material may exhibit no or minimal change in volume or shape as a result of operation of electrochemical cell 100. For example, the anode material may not crack or swell (e.g., observable by SEM) during charging or discharging. The volume of the anode material (e.g., particles) after the first charge may be less than 300% of the original particle volume. For example, the volume of the particles after the first charge is 100-300% of the original volume (e.g., 100-110%, 100-120%, 100-125%, 110-140%, 115-135%, 125-135%, 125-150%, 140-150%, 150-200%, 150-250%, 150-300%, 200-250%, 200-300%, 250-300%, etc., e.g., about 100%, 105%, 110%, 115%, 125%, 135%, 140%, 150%, 150%, 150%, 160%, 165%, 170%, 175%, 180%, 185%, 190%, 200%, 210%, 215%, 220%, 230%, 240%, 250%, 260%, 270%, 280%, 290%, 300%, 310%, 320%, 330%, 340%, 350%, 360%, 370%, 380%, 390%, 400%, 410%, 420%, 430%, 440%, 450%, 460%, 470%, 480%, 490%, 500%, 510%, 520%, 530%, 540%, 550%, 560%, 570%, 580%, 590%, 600%, 610%, 620%, 630%, 640%, 650%, 660%, 670%, 680%, 690%, 700 %, 120%, 125%, 130%, 135%, 140%, 145%, 150%, 165%, 170%, 175%, 180%, 185%, 190%, 195%, 200%, 205%, 210%, 215%, 220%, 225%, 230%, 235%, 240%, 245%, 250%, 255%, 260%, 265%, 270%, 275%, 280%, 285%, 290%, 295%, 299%).

[0074] In some embodiments, the volume of the particles after the first charge may be at least about 100%, at least about 105%, at least about 110%, at least about 115%, at least about 120%, at least about 125%, at least about 130%, at least about 135%, at least about 140%, at least about 145%, at least about 150%, at least about 165%, at least about 170%, at least about 175%, at least about 180%, at least about 185%, at least about 190%, at least about 195%, at least about 200%, at least about 205%, at least about 210%, at least about 215%, at least about 220%, at least about 225%, at least about 230%, at least about 235%, at least about 240%, at least about 245%, or at least about 250% of the original volume. In some embodiments, the volume of the particles after the first charge can be about 300% or less, about 295% or less, about 290% or less, about 285% or less, about 280% or less, about 275% or less, about 270% or less, about 265% or less, about 260% or less, about 255% or less, about 250% or less, about 240% or less, about 230% or less, about 220% or less, about 210% or less, or about 200% or less of its original volume. Combinations of the above volume percentages are also possible (e.g., volume percentages of at least about 150% and about 300% or less, and at least about 150% and about 200% or less), including all values ​​and ranges therebetween.

[0075] Alternatively, or in addition, the average particle size of the anode material after 10 charge-discharge cycles may be greater than 70% of the original particle size (e.g., 70 to 115% of the original particle size, e.g., 70 to 75%, 70 to 80%, 80 to 100%, 75 to 85%, 80 to 90%, 85 to 95%, 85 to 100%, 90 to 100%, 90 to 110%, 95 to 110%, 95 to 105%, 100 to 110%, or 105 to 115%, e.g., about 70%, 75%, 80%, 85%, 90%, 95%, 100%, 105%, 110%, or 115% of the original particle size). In some embodiments, the volume of the plurality of voids may change less than 100% (e.g., 1-100%, 1-50%, 1-10%, 5-15%, 1-25%, 20-40%, 30-40%, 25-50%, 40-50%, 50-100%, or less than 1%) during charging and / or discharging of the battery. In some embodiments, the particles may swell less than 300% (e.g., 1-50%, 1-10%, 5-15%, 1-25%, 20-40%, 30-40%, 25-50%, 40-50%, 50-100%, 50-150%, 50-200%, 50-250%, 50-300%, or less than 1%) during charging and / or discharging of the electrochemical cell 100.

[0076] In some embodiments, the anode 140 can be deposited on a suitable substrate, such as a fluoropolymer or carbon. For example, a polytetrafluoroethylene (PTFE) solution can be used as a binder when preparing an electrode material solution for deposition on a substrate. Other binders known in the art can be used in some embodiments. The anode materials described herein can be used without additives. Alternatively, the anode material can include additives to improve its physical and / or ion-conducting properties. For example, the anode material can include additives to change the surface area exposed to a solid electrolyte, such as carbon. Other additives known in the art can be used in some embodiments. A mixture of Li and other metal(s) can form 2D parallel layers or a 3D structure. In some embodiments, the amount of Li loaded in the anode 140 can be 0 to 50 mg / cm. 2 It can be said that:

[0077] In some embodiments, cathode 120 includes a cathode material (e.g., a material containing lithium). The cathode material can be selected to have optimal properties for ion transport. For example, cathode 120 can be a LiNi 0.1 ... 0.8 Mn 0.1 Co 0.1 O2 (NMC811). In some embodiments, electrochemical cell 100 can also be constructed using other suitable cathode materials known in the art for use as electrodes in solid electrolyte batteries.

[0078] In some embodiments, the cathode 120 may be, for example, LiNi 0.8 Mn 0.1 Co 0.1 O2(NMC811), LiNi 0.33 Mn 0.33 Co 0.33 O2(NMC111), LiNi 0.5 Mn 0.3 Co 0.2O2(NMC532), LiNi 0.6 Mn 0.2 Co 0.2 O2(NMC622), LiNi 0.9 Mn 0.05 Co 0.05 O2 (NMC955), LiNi x Mn y Co (1-x-y) O2(0≦x, y≦1), LiNi x Co y Al (1-x-y) O2(0≦x,y≦1), LiMn2O4, LiMnO2, LiNiO2, Li 1+z Ni x Mn y Co (1-x-y-z) O2(0≦x,y,z≦1), Li 1+z Ni x Mn y Co w Al (1-x-y-z-w) O2(0≦x,y,z,w≦1), Li 1+z Ni x Mn y Co w W (1-x-y-z-w) O2 (0≦x, y, z, w≦1), V2O5, selenium, sulfur, selenium-sulfur compounds, LiCoO2 (LCO), LiFePO4, LiNi 0.5 Mn 1.5 O4, Li2CoPO4F, LiNiPO4, Li2Ni(PO4)F, LiMnF4, LiFeF4, LiCo 0.5 Mn 1.5 The cathode can contain LiNbO3, LiTaO3, Li2ZrO3, LiNb X Ta 1-X O3(0≦x≦1), yLi2ZrO3-(1-y)LiNb X Ta 1-x O3(0≦x,y≦1), Al2O3, TiO2, ZrO2, AlF3, MgF2, SiO2, ZnS, ZnO, Li4SiO4, Li3PO4, Li3InCl6, Li 1+x Al x Ti 2-x(PO4)3 (0 < x < 2), LiMn2O4, LiInO2-LiI, Li6PS5Cl, LiAlO2, polymers, and carbon can be coated. In some embodiments, the cathode 120 can include a polymer and / or carbon black. In some embodiments, the cathode 120 can include a first electrolyte including a polymer and / or a second solid electrolyte.

[0079] In some embodiments, the cathode 120 may be a solid piece of material or may be formed on a suitable substrate, such as a fluoropolymer or carbon. For example, when preparing a cathode material solution for film formation on a substrate, a polytetrafluoroethylene (PTFE) solution can be used as a binder. Other binders are also known in the art. In some embodiments, the cathode material can be used without additives. Alternatively, the cathode material may have additives for improving its physical properties and / or ion conduction properties. For example, the cathode material may have an additive such as carbon that changes the surface area exposed to the solid electrolyte. In some embodiments, other additives known in the art can also be applied.

[0080] In some embodiments, the cathode 120 can be mixed with a polymer and / or carbon. Examples of polymers include polyethylene oxide, polyvinylidene fluoride, poly(vinylidene fluoride-co-hexafluoropropylene), poly(ethyl methacrylate), poly(vinylidene fluoride-co-trifluoroethylene), and the like. The particle size of the cathode material can be from about 1 nm to about 30 μm. In some embodiments, the coating amount of the cathode 120 is about 0.1 mg / cm 2 ~ about 100 mg / cm 2 and can be. In some embodiments, the thickness of the cathode 120 can be from about 5 μm to about 2,000 μm. The cathode 120 can improve the cathode capacity by mixing with the solid electrolyte material described herein.

[0081] Other cathode materials with promising high capacity and energy density, such as selenium and sulfur, also show significantly better cycling performance in multilayer designs than in single-layer designs.

[0082] In some embodiments, cathode 120 can be blended with a polymer and carbon black, and solid electrolyte 130 can be blended with a polymer. Examples of polymers include, but are not limited to, polyethylene oxide, polyvinylidene fluoride, poly(vinylidene fluoride-co-hexafluoropropylene), poly(ethyl methacrylate), poly(vinylidene fluoride-co-trifluoroethylene), other suitable polymers, or suitable combinations thereof. In some embodiments, solid electrolyte 130 has a thickness of about 5 μm to about 1,000 μm. In some embodiments, cathode 120 has a thickness of about 5 μm to about 2,000 μm.

[0083] In some embodiments, the solid-state electrolyte (SSE) 130 may include an inorganic solid electrolyte, such as, for example, a crystalline or glassy inorganic lattice with high ionic conductivity, and may contain ions (e.g., Li + ions) can diffuse through the lattice. SSE130 may be, for example, an oxide, phosphate, or sulfide of lithium (e.g., LGPS, LiSiPS, LiPS, Li 5.5 PS 4.5 Cl 1.5 (LSPCl 1.5 ), Li6PS5Cl 1.0 (LPSCl 1.0 ), other suitable electrolyte materials, or combinations thereof). Examples of solid electrolyte materials are listed below.

[0084] Other suitable solid electrolyte materials include sulfide solid electrolytes (e.g., Si x P y S z , SiP2S 12 Other solid electrolytes include germanium solid electrolytes (e.g., Ge a P b Sc , or GeP2S 12 ), tin solid electrolyte (e.g., Sn d P e S f , or SnP2S 12 ), iodine solid electrolyte (e.g., P2S8I crystal), glass electrolyte (e.g., alkali metal sulfide-P2S5 electrolyte, or alkali metal sulfide-P2S5-alkali metal halide electrolyte), or glass ceramic electrolyte (e.g., alkali metal-P g S h-I Examples of suitable solid electrolyte materials include, but are not limited to, solid electrolytes (e.g., cellulose, cellulose acetate, cellulose esters, cellulose acylates, cellulose ester ...

[0085] In some embodiments, the solid electrolyte 130 can be deposited or cast onto a suitable substrate, such as a polyester (PET) film, cathode, anode, or other solid electrolyte layer. For example, nitrile rubber (NBR), acrylate rubber (ABR), and polyisobutene (PIB) have been used as binders to prepare solutions of electrolyte materials for deposition onto substrates. Other binders are known in the art. The solid electrolyte 130 can be mixed with a solvent (e.g., p-xylene, isobutyl isobutyrate, or a mixture thereof, such as anhydrous p-xylene and isobutyl isobutyrate (1:1 vol / vol)) and a binder (e.g., a polymer, an arylate polymer, e.g., 0.5% to 5 wt%) to prepare a slurry for layer formation. In some embodiments, the solid electrolyte 130 can include multiple electrolyte layers that can be deposited, cast, or transferred layer-by-layer onto a substrate. The multiple electrolyte layers may include n layers of solid electrolyte (where n is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.).

[0086] In some embodiments, the solid electrolyte 130 is a core-shell particle, such as a core-shell LPSCl-X (X is a halide) or LGPS (Li 10 GeP2S12 ), examples of which are described in WO 2019 / 104181, WO 2020 / 112843, and WO 2022 / 094412, each of which is incorporated herein by reference in its entirety. 10 GeP2S 12 The solid electrolyte particles, for example, core-shell particles, may have a cross-sectional dimension, for example, a diameter, of about 1 nm to about 30 μm, for example, about 1 to 100 nm (for example, about 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm), for example, about 100 to 1,000 nm (for example, about 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1, 000 nm), for example, about 1 to 10 μm (for example, about 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm), for example, about 10 to 30 μm (for example, about 10 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm, 30 μm). In core-shell particles, the shell may account for about 0.1% to about 99.9% of the particle, for example, about 1-10%, about 10-20%, about 20-30%, about 25-50%, about 40-60%, about 50-75%, about 60-80%, about 75-90%, or about 80-99% by volume or mass. Stability can be determined experimentally.

[0087] In some embodiments, the solid electrolyte 130 of the electrochemical cell 100 can include multiple layers of solid-state electrolytes (SSEs), such as two, three, or more layers, and two or more solid electrolytes with different stabilities. The solid electrolytes can be arranged such that a less stable electrolyte is sandwiched between more stable electrolytes. In the SSE multilayers, localized decomposition of the less stable electrolytes can inhibit the formation or propagation of cracks in the multilayers and inhibit the propagation of dendrites.

[0088] In some embodiments, the solid electrolyte 130 (e.g., a multilayer of solid electrolyte) may be mechanically constrained. Mechanical constraining of the solid electrolyte 130 can limit the extent of chemical or electrochemical decomposition of the solid electrolyte material through volumetric constraint. Local stresses ranging from several GPa to the mechanical modulus of the solid electrolyte 130 can be generated by mechanical constraining. This mechanical constraining can be achieved by applying an external pressure of at least 0.1 MPa to several hundred MPa to the electrochemical cell 100. The level of external pressure applied to the battery is determined by the battery materials, material processing, and battery assembly method. Mechanical constraining can be provided by external pressures ranging from 0.1 MPa to 1,000 MPa and forming pressures associated with cold and / or hot and / or warm isotropic and / or anisotropic pressing and / or rolling at temperatures between 25°C and 500°C. Suitable assembly methods include, but are not limited to, warm isostatic pressing (WIP), cold isostatic pressing (CIP), and hydraulic cold pressing of the electrochemical cell 100 or the housing 160 (e.g., pouch-type).The mechanical restraint is at least 0.05 MPa, for example, at least 0.1 MPa, 0.5 MPa or more, 1 MPa or more, 5 MPa or more, 10 MPa or more, 15 MPa or more, 20 MPa or more, for example, about 0.05 MPa to about 50 MPa, about 0.05 MPa to about 0.1 MPa, about 0.075 MPa to about 0.15 MPa, about 0.1 MPa to about 1 MPa, about 0.1 MPa to about 10 MPa, about 1 MPa to about 30 MPa, about 20 MPa to about 40 MPa, about 30 MPa to about 50 MPa, about 40 MPa to about 60 MPa, about 50 MPa to about 70 MPa, about 60 MPa to about 80 MPa, about 70 MPa to about 90 MPa, about 80 MPa to about 100 MPa, about 100 MPa to about 200 MPa, about 200 MPa to about 400 MPa, about This can occur by applying a pressure of 300 MPa to about 500 MPa, about 400 MPa to about 600 MPa, about 500 MPa to about 700 MPa, about 600 MPa to about 800 MPa, about 700 MPa to about 900 MPa, or about 800 MPa to about 1,000 MPa, for example, about 70 MPa, about 75 MPa, about 80 MPa, about 85 MPa, about 90 MPa, about 95 MPa, about 100 MPa, about 150 MPa, about 200 MPa, about 250 MPa, about 300 MPa, about 350 MPa, about 400 MPa, about 450 MPa, about 500 MPa, about 550 MPa, about 600 MPa, about 650 MPa, about 700 MPa, about 750 MPa, about 800 MPa, about 850 MPa, about 900 MPa, about 950 MPa, or about 1,000 MPa. Greater mechanical restraint may also be applied during battery fabrication. After applying molding pressure, the porosity of cathode 120 and / or solid electrolyte 130 (e.g., a multilayer of solid electrolyte) may be about 0% to about 50%, about 5% to about 50%, about 10% to about 50%, about 20% to about 50%, or about 30% to about 50% by volume. In some embodiments, the mechanical constraint reduces the local effective elastic modulus, K. crit Either it is sufficient to raise the temperature above K, thereby preventing decomposition, or the local stress field caused by the decomposition of the solid electrolyte eff K crit This prevents decomposition.

[0089] In some embodiments, when electrochemical cell 100 is operating, local stress can be maintained by applying an operating stack pressure on the order of 0 MPa to 1,000 MPa (e.g., in the range of about 1 MPa to about 50 MPa). The operating stack pressure can be applied by mechanical stress from the housing 160 (e.g., a steel, aluminum, plastic, or polymer battery case or pouch-type cell, and their 3D structures) and / or hydraulic pressure from a gel or any liquid enclosed in the environment surrounding the pouch-type cell. The external pressure can be cyclically varied during battery cycling by a passive response system, such as a spring, or an active response system controlled by, for example, a pressure sensor and a programmed electronic device. Alternatively, local stress can be maintained without applying an operating stack pressure.

[0090] In some embodiments, anode current collector 150 may be a thin metal sheet, such as a conductive metal sheet (aluminum, copper, stainless steel, etc.). In some embodiments, layers of other materials may be present between anode current collector 150 and anode 140. In addition to the anode materials described herein, anode 140 may include lithium metal. In some embodiments, anode current collector 150 may further include a lithium metal foil disposed on anode current collector 150. In some embodiments, lithium metal may be mixed or alloyed with Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Ga, Ge, As, Rb, Sr, Y, Zr, Nb, Mo, Ag, Cd, In, Sn, Sb, Bi, Cs, Te, or a combination thereof to form a single layer. In some embodiments, anode current collector 150 may include copper, aluminum, nickel, titanium, or any combination thereof.

[0091] In some embodiments, the cathode current collector 110 may be a thin metal sheet (e.g., aluminum, copper, or carbon-based foil). In some embodiments, the cathode current collector 110 may comprise aluminum, stainless steel, or other suitable current collector material.

[0092] FIG. 2 is a cross-sectional view of an electrochemical cell 200 according to one embodiment. Electrochemical cell 200, according to an embodiment, comprises an anode 240 disposed on an anode current collector 250, a cathode 220 disposed on a cathode current collector 210, and a solid electrolyte 230 disposed between the cathode 220 and the anode 240. In some embodiments, electrochemical cell 200 may be the same as or substantially similar to electrochemical cell 100 described above with reference to FIG. 1. In some embodiments, anode 240, which includes anode material and is disposed on anode current collector 250, cathode 220 disposed on cathode current collector 210, and solid electrolyte 230 disposed between cathode 220 and anode 240, may be the same as or substantially similar to anode 140, anode current collector 150, cathode 120, cathode current collector 110, and solid electrolyte 130, respectively, described with reference to FIG. 1. In some embodiments, the electrochemical cell 200 may be placed under mechanical restraint (P), as described above with respect to FIG.

[0093] In some embodiments, the anode 240 includes particles 242 (e.g., porous or non-porous). In some embodiments, the anode 240 may include a plurality of voids 244 present between the particles 242. In some embodiments, the particle size of particles 242 may be from about 1 μm to about 100 μm (inclusive), for example, about 1-10 μm (e.g., about 1-2 μm, 1-5 μm, 2-3 μm, 3-4 μm, 4-5 μm, 5-10 μm, 5-6 μm, 6-7 μm, 7-8 μm, 8-9 μm, 9-10 μm, for example, about 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm), or, for example, about 10-100 μm (e.g., about 10-20 μm, 10-25 μm, 10-50 μm, 20-30 μm). μm, 25 to 50 μm, 30 to 40 μm, 40 to 50 μm, 50 to 60 μm, 50 to 75 μm, 60 to 70 μm, 75 to 100 μm, 70 to 80 μm, 80 to 90 μm, 90 to 100 μm, for example, about 10 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm).

[0094] In some embodiments, the particle diameter of the particles 242 may be from 1 nm to 1,000 nm (inclusive), for example, about 1 to 100 nm (e.g., about 1 to 10 nm, 1 to 25 nm, 10 to 20 nm, 20 to 30 nm, 25 to 50 nm, 30 to 40 nm, 40 to 50 nm, 50 to 60 nm, 50 to 75 nm, 60 to 70 nm, 70 to 80 nm, 75 to 100 nm, 80 to 90 nm, 90 to 100 nm, for example, about 1 nm, 5 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm). m), for example, about 100 to 1,000 nm (for example, about 100 to 110 nm, 100 to 125 nm, 100 to 200 nm, 200 to 300 nm, 250 to 500 nm, 300 to 400 nm, 400 to 500 nm, 500 to 600 nm, 500 to 750 nm, 600 to 700 nm, 700 to 800 nm, 750 to 1,000 nm, 800 to 900 nm, 900 to 1,000 nm, for example, about 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1,000 nm).

[0095] In some embodiments, a plurality of voids 244 may be formed between the particles 242. In some embodiments, the voids 244 may be formed by gaps between the particles 242, e.g., microscale or nanoscale particles. Alternatively, or in addition, the voids 244 may be, for example, pores or other interstices present within the particles 242 forming the anode material. In some embodiments, the particles 242 may be porous and / or the plurality of voids 244 may be formed between the particles 242. In some embodiments, the anode material may further include a plurality of voids between the porous particles. In some embodiments, the anode material may include non-porous particles, but the anode material may include a plurality of voids 244 caused by spaces between the non-porous particles. The voids 244 may, in some embodiments, allow Li to escape during charging. +The voids 244 can receive Li in the form of ions that precipitate in the voids as Li metal. The cross-sectional dimensions of the voids 244 may be from several nm (e.g., 5 to 10 nm) to several tens of μm (e.g., 10, 20, 30, 40, 50 μm), for example, 5 nm to 50 μm, 5 nm to 100 nm (e.g., 5 to 50, 25 to 60, 45 to 80, 75 to 100 nm), for example, 100 nm to 1 μm (e.g., 100 to 200, 150 to 450, 200-300, 250-600, 400-500, 500-750, 600-800, 700-900, 900-1000 nm), or for example, 1 μm to 50 μm (e.g., 1-10, 5-10, 7-15, 12-20, 15-20, 15-30, 20-30, 25-50, 30-40, 35-45, 40-50 μm). In some embodiments, the cross-sectional dimension of each of the plurality of voids 244 is in the range of about 5 nm to about 50 nm.

[0096] After application of molding pressure, in some embodiments, the voids 244 of the anode 240 may be 0% to 99% of the volume of the anode 140, such as 10-15%, 10-20%, 15-30%, 25-50%, 30-40%, 35-50%, 40-50%, 50-75%, 40-60%, 55-80%, 65-90%, 60-80%, 75-90%, 80-90%, 85-95%, or 90-99%. In some embodiments, the voids 244 of the anode 240 may be at least about 3%, at least about 5%, at least about 7%, at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, or at least about 95% of the volume of the anode 140.

[0097] FIG. 3 is a cross-sectional view of an electrochemical cell 300 in one embodiment. The electrochemical cell 300 includes an anode 340 disposed on an anode current collector 350, a cathode 320 disposed on a cathode current collector 310, and a solid electrolyte 330 disposed between the cathode 320 and the anode 340. In some embodiments, the solid electrolyte 330 may include multiple layers of solid electrolytes (SSEs) having different stabilities (i.e., at least two of the layers 332, 334, and 336 described herein). The multiple layers of solid electrolytes may be arranged such that a less stable electrolyte layer is sandwiched between more stable electrolyte layers. Localized decomposition of the less stable electrolyte in the SSE multilayer can inhibit the formation or propagation of cracks in the multilayer and inhibit dendrite propagation.

[0098] In some embodiments, electrochemical cell 300 can be the same as or substantially similar to electrochemical cell 100 described above with reference to Figure 1. In some embodiments, anode 340, which includes an anode material and is disposed on anode current collector 350, cathode 320, which is disposed on cathode current collector 310, and solid electrolyte 330, which is disposed between cathode 320 and anode 340, can be the same as or substantially similar to anode 140, 240, anode current collector 150, 250, cathode 120, 220, cathode current collector 110, 210, and solid electrolyte 130, 230, respectively, described with reference to Figures 1 and 2. In some embodiments, electrochemical cell 300 can be placed under mechanical restraint (P), as described above with reference to Figure 1.

[0099] In some embodiments, the solid multilayer 330 may include a first solid electrolyte 332 (e.g., LPSCl), a second solid electrolyte 334 (e.g., LGPS, LSnPS, etc.), and optionally a third solid electrolyte 336 (e.g., LPSCl). In some embodiments, the first solid electrolyte 332 is more stable with respect to lithium metal than the second solid electrolyte 334. The second solid electrolyte 334 may be separated from the anode 340 by the first solid electrolyte 332. In some embodiments, the multilayer 330 may include n layers of the second solid electrolyte 334 and n layers of one or more first solid electrolytes 332 (where n is, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.).

[0100] The solid multilayer 330 may alternatively be, for example, a "sandwich" structure, such as one layer of the second solid electrolyte 334 sandwiched between two layers of the first solid electrolyte 332 (e.g., LPSCl-LGPS or LPSCl-LGPS-LPSCl). Alternatively, the multilayer may include n layers of the second solid electrolyte 334 and n or n+1 layers of one or more first solid electrolytes 332 (where n is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.).

[0101] In some embodiments, the second solid electrolyte 334 may be less stable to lithium metal than the one or more first solid electrolyte layers 332 and 336. In this arrangement, the first solid electrolyte layer 332 can protect the second solid electrolyte layer 334, for example, from large-scale decomposition, while simultaneously limiting localized decomposition of the second solid electrolyte 334 and inhibiting the development of metal dendrites. The multilayer 330, in some embodiments, may include multiple different first solid electrolytes 332. For example, at least two different first solid electrolytes 332, e.g., a multilayer of solid electrolytes, may include two different solid electrolytes selected from the suitable solid electrolytes listed below.

[0102] The multilayer design is not limited to a specific material, and various electrolytes can be used in the center layer, provided that the second solid electrolyte 334 and / or the third solid electrolyte 336 are sufficiently inhibited from decomposing into Li dendrites under mechanical constraint. Such solid electrolytes include, but are not limited to, LGPS, LSPS, and LSP(Sb)S, which also exhibit stable cycling characteristics.

[0103] Following this design principle, one or more of the first solid electrolyte 332 or second electrolyte 334 can include a wide range of solid electrolytes, such as polymers, gels, or sulfides, halides, oxides, phosphates, nitrates, etc., as long as they are appropriately positioned relative to one another within the multilayer electrolyte 330 according to their relative stability.

[0104] The stability of the multilayer solid electrolyte 330 is due to its relative chemical and / or electrochemical stability, which is unaffected by the thickness of the electrolyte layer or the micron-level crack density. This strategy of designing instability differs from the conventional approach in the field, which is to improve electrochemical cell stability by mechanically blocking Li dendrite penetration using a solid electrolyte. This conventional approach typically involves using a thick, crack-free electrolyte layer. The inherent flexibility and versatility of the multilayer solid electrolyte 330 included in the electrochemical cell 300 described herein facilitates its compatibility with mass production processes in the battery industry and allows for further optimization of the thickness and mechanical flexibility of the electrolyte 330 layer in the future without sacrificing safety or performance.

[0105] A constrained ensemble description has been developed to quantify the electrochemical stability of solid electrolytes and their interfaces in solid-state batteries (SSBs). In this description, decomposition with positive reaction strain is characterized by a local effective elastic modulus (e.g., the elastic modulus with application to solid-state batteries) K eff is sufficient, it can in principle be suppressed by metastability. effreflects the complex interplay of microstructure, mechanical strength of the material, and stack pressure of the battery device.

[0106] The multiple electrolyte layers 330 can be cast layer-by-layer directly onto the anode 340 and / or cathode 320. Alternatively, the electrolyte 330 can be cast layer-by-layer onto a separate substrate and then transferred to the anode 340 and / or cathode 320 by pressure (e.g., using a press such as a calendar press, hydraulic press, or isostatic press).

[0107] In certain embodiments, the solid electrolyte (i.e., first solid electrolyte 332 and / or second solid electrolyte 334 and / or third solid electrolyte 336) can be selected from any suitable Li-containing solid electrolyte. For example, in some embodiments, first solid electrolyte 332 can be selected from Li6PS5Cl, Li 6±y PS 5±y Cl 1±y , Li 5.5 PS 4.5 Cl 1.5 , Li 5.5±y PS 4.5±y Cl 1.5±y , Li 6±y PS 5±y Br 1±y , Li 6±y PS 5±y I 1±y , Li 6±y PS 5±y F 1±y , Li6PS5Cl 1-x F x (0≦x≦C), Li 6±y PS 5±y (Cl 1-x F x ) 1±y (0≦x≦C), Li 6±y PS 5±y (Cl 1-x Br x ) 1±y (0≦x≦C), Li 6±y PS 5±y (Cl 1-x I x ) 1±y (0≦x≦C), Li 6±y PS5±y (Br u I v F w Cl 1-u-v-w ) 1±y Li x P y S z (Br u I v F w Cl 1-u-v-w ) p (0≦u,v,w≦C,0≦x,y,z,p≦7)、Li7P2S8I、Li3PS4、Li 3±x P 1±y S 4±z 、54Li3PS4-46LiI、xLi3PS4-(1-x)LiI、Li 9.6 P3S 12 、Li3ClO、Li3BrO、Li3Br x Cl 1-x O、Li7La3Zr2O 12 、The 6.75 The3Zr 1.75 Ta 0.5 O 12 、The 6.75±x The 3±y Zr 1.75±z Ta 0.5±u O 12±v 、The 6.25 Al 0.25 The3Zr2O 12 、The 6.25±x Al 0.25±y The 3±z Zr 2±u O 12±v 、The 6.3 The3Zr 1.65 W 0.35 O 12 、The 6.3±x The 3±y Zr 1.65±z W 0.35±u O 12±v 、The 6.5 The3Zr 1.5 Nb 0.5 O 12 、The 6.5±x The 3±y Zr 1.5±z Nb 0.5±u O 12±v 、Thex PO y N z (0 <x=2y+3z-5≦3)、Li 6.4 Ga 0.2 La3Zr2O 12 , Li 6.4±x Ga 0.2±y La 3±u Zr 2±v O 12±w , Li3PO4, Li3YCl6, Li3YBr6, Li3InCl6, Li3InBr6, Li3ErCl6, Li3ErBr6, Li3ScCl6, Li3ScBr6, Li3(Y x In y Sc 1-x-y )(F u Br v Cl 1-u-v ) 6, or any material in this group in which one or more elements are replaced by a uniform element. Unless otherwise specified, 0≦a, b, d, p, q, w, x, y, z, u, v, w≦1. C is the critical doping content beyond which the stability of the electrolyte decreases. C can vary depending on u, v, and w, and 0≦C≦1.

[0108] In some embodiments, the second solid electrolyte 334 is Li 10 GeP2S 12 , Li 10±x Ge 1±y P 2±p S 12±q , Li 10±x Ge 1±y (P p Sb 2-p )S 12±q , Li 10 SiP2S 12 , Li 10±x Si 1±y P 2±p S 12±q , Li 10 SnP2S 12 , Li 10±x Sn 1±y P 2±p S 12±q , Li 10±x Sn 1±y (P p Sb2-p )S 12±q 、Li 6±y P (1-x) Sb x S 5±y (Br u l v F w Cl 1-u-v-w ) 1±y (x≧C,0≦u,v,w≦1)、Li 6±y P (1-x) Sb x S 5±y (Br u l v F w Cl 1-u-v-w ) 1±y (u,v,w≧C,0≦x≦1),Li 3±x P 1±y S 4±z ,Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 ,Li 10±x Si 1±y P 2±p S 12±q Cl w ,Li 9.54 Si 1.74 (P x Sb 1-x ) 1.44 S 11.7 Cl 0.3 ,Li 10±x Si 1±y (P x Sb 1-x ) 2±p S 12±q Cl w ,Li 10±x Si 1±y (P x Sb 1-x ) 2±p S 12±q (F u Br v I w Cl 1-u-v-w)z ,Li 10±x (Si a Sn b Ge 1-a-b ) 1±y (P x Sb 1-x ) 2±p (S dYes 1-d ) 12±q (F u Br v l w Cl 1-u-v-w)z ,Li 3.2 P 0.8 Sn 0.2 S4,Li 3.2±x P 0.8±y Sn 0.2±z S 4±u ,Li7P3S 11 ,75Li2S-25P2S5,(x)Li2S-(1-x)P2S5,Li7Ge3PS 12 ,Li 1.5 AI 0.5 You 1.5 (PO4)3,Li 7+x G e3+y P 1+z S 12+u ,Li6PS5Cl 1-x F x (x≧C),Li 6±y P.S. 5±y (Cl 1-x F x ) 1±y (x≧C),Li 6±y P.S. 5±y (Cl 1-x Br x ) 1±y (x≧C),Li 6±y P.S. 5±y (Cl 1-x l x ) 1±y (x≧C),Li 6±y P.S. 5±y (Br u l v F w Cl 1-u-v-w ) 1±y (u,v,w≧C),Li x P y S z (Br u l v F w Cl 1-u-v-w ) p (u,v,w≧C,0≦x,y,z,p≦7),nLiX-xACl 3-The doping agent may be selected from the group consisting of (1-x)GaF3 (n=2, 3, 4, X=Cl, Br, A=La, In), nLiCl-LiOH-GaF3 (n=2, 3, 4), nLiX-GaF3 (X=Cl, Br, n=2, 3, 4), or any material in this group in which one or more elements are replaced with a uniform element. Unless otherwise specified, 0≦a, b, d, p, q, w, x, y, z, u, v, w≦1. C is the critical doping content, beyond which the electrolyte stability decreases. C can vary with u, v, and w, and 0≦C≦1.

[0109] In some embodiments, the first solid electrolyte layer 332 and / or the second solid electrolyte layer 334 may have a core-shell particle structure. In certain embodiments, the core and shell particles may have different core and shell conductivity. In some embodiments, the core may have a higher conductivity than the shell. In some embodiments, the core and shell particles have a core composition and a shell composition, and the core composition may differ from the shell composition, for example, by a non-stoichiometric weight ratio of Li. The difference in the core and shell composition may allow for, for example, a difference in the K crit , E hull For example, the shell composition may be higher in K than the core. crit is small or E hull may be negatively large, or for example, the conductivity of the core may be higher than the conductivity of the shell, or any combination thereof.

[0110] In some embodiments, the first solid electrolyte 332 and / or the second solid electrolyte 334 may be selected from the group consisting of Li_{0.3}Cl_{0.6}Er_{0.1}, Li_{0.3}Cl_{0.6}Y_{0.1}, Li_{0.3}Cl_{0.6}Sc_{0.1}, Li_{0.291}O_{0.5}Zr_{0.083}La_{0.125}, Li_{0.271}O_{0.508}Ga_{0.008}Zr_{0.084}La_{0.127}, Li_{0.265}O_{0.510}Al_{0.010}Zr_{0.085}La _{0.127}, Li_{0.276}O_{0.510}Zr_{0.063}Nb_{0.021}La_{0.127}, L i_{0.270}O_{0.515}Zr_{0.070}La_{0.128}W_{0.015}, Li_{0.400-x}B _{0.000-y}O_{0.000-z}AI_{3.503+w}Si_{0.133-I}S_{0.465-m}, Li_{0.3+x}CI_{0.6-y}Sc_{0.1-z}, Li_{0.3+x}CI_{0.6-y}Er_{0.1-z}, Li_ {0.3+x}CI_{0.6-y}Er_{0.1-z}, Li_{0.3+x}CI_{0.6-y}Y_{0.1-z}, Li_{0.444+x}S_{0.444-y}Sn_{0.111-z}, Li_{0.44+x}P_{0.08-y}S_{0.3 6-z}CI_{0.12-w}, Li_{0.270+x}O_{0.515-y}Zr_{0.070-z}La_{0.128 +w}W_{0.015-l}, Li_{0.265+x}O_{0.510-y}Al_{0.010-z}Zr_{0.085+w}La_{0.127+l}, Li_{0.291+x}O_{0.5-y}Zr_{0.083-z}La_{0.125-w}, Li_{0.276+x}O_{0.510-y}Zr_{0.063+z}Nb_{0.021-w}La_{0.127+l} and Li_{0.166+x}B_{0.166-y}O_{0.5-z}Al_{0.125+w}Cl_{0.041+l}, or any material in which one or more elements of this group are replaced by an element of the same group number.where "_{#}" and "_{#±x, y, z, w, l, or m}" represent non-stoichiometric weighting of the elements immediately to the left of "_{#}" or "_{#±x, y, z, w, l, or m}" in the chemical formula of the material, and # can be in the range #±n, where 0≦n≦0.5, and 0≦x, y, z, w, l, m≦#, and # can be ±n, 0≦n≦0.5.

[0111] In some embodiments, the second solid electrolyte 334 is Li_{0.6}O_{0.2}Cl_{0.2}, Li_{0.6}O_{0.2}Br_{0.2}, Li_{0.3}Br_{0.6}Er_{0.1}, Li_{0.3}Br_{0.6}Y_{0.1}, Li_{0.3}Sc_{0.1}Br_{0.6}, Li_{0.3}Br_{0.6}In_{0.1}, Li_{0.375}O_{0.5}P_{0.125}, Li_{0.3}CI_{0.6}In_{0.1}, Li_{0.166}B_{0.166}O_{0.5}Al_{0.125}Cl_{0.041}, Li_{0.444}S_{0.444}Sn_{0.111}, Li_{0.416}Si_{0.106}S_{0.363}I_{0.113}, Li_{0.428}P_{0.142}S_{0.428}, Li_{0.485}P_{0.029}S_{0.367}Ge_{0.044}I_{0.073}, Li_{0.433}S_{0.452}As_{0.018}Sn_{0.094}, Li_{0.325}B_{0.181}S_{0.377}I_{0.115}, Li_{0.475}Si_{0.026}P_{0.048}S_{0.374}Br_{0.074}, Li_{0.461}O_{0.076}P_{0.076}S_{0.307}CI_{0.076}, Li_{0.400}B_{0.000}O_{0.000}AI_{3.503}Si_{0.133}S_{0.465}, Li_{0.461}P_{0.076}S_{0.384}I_{0.076}, Li_{0.44}P_{0.08}S_{0.36}CI_{0.108}Br_{0.012}, Li_{0.44}P_{0.08}S_{0.36}Cl_{0.108}I_{0.012}, Li_{0.44}P_{0.08}S_{0.36}Cl_{0.12}, Li_{0.388}P_{0.111}S_{0.444}I_{0.055}, Li_{0.6+x}O_{0.2+y}Br_{0.2-z}, Li_{0.6-x}O_{0.2-y}Cl_{0.2+z}, Li_{0.3+x}Br_{0.6-y}In_{0.1-z}, Li_{0.3+x}Br_{0.6-y}Y_{0.1-z}, Li_{0.3+x}Br_{0.6-y}Er_{0.1-z},Li_{0.416+x}Si_{0.106+y}S_{0.363-z}I_{0.113-w},Li_{0.3+x}Sc_{0.1-y}Br_{0.6-z},Li_{0.166+x}B_{0.166-y}O_{0.5-z}AI_{0.125+w}Cl_{0.041+1},Li_{0.375+x}O_{0.5-y}P_{0.125-z},Li_{0.485+x}P_{0.029-y}S_{0.367-z}Ge_{0.044+w}I_{0.073-1},Li_{0.5+x}P_{0.071-y}S_{0.428-z},Li_{0.461+x}P_{0.076-y}S_{0.384-z}I_{0.076-w},Li_{0.433+x}S_{0.452-y}As_{0.018-z}Sn_{0.094-w},Li_{0.481+x}P_{0.074-y}S_{0.407-z}Cl_{0.037-w},Li_{0.461+x}O_{0.076+y}P_{0.076-z}S_{0.307-w}Cl_{0.076-1},Li_{0.475+x}Si_{0.026+y}P_{0.048-z}S_{0.374-w}Br_{0.074-1},Li_{0.461+x}P_{0.076-y}S_{0.384-z}Br_{0.076+w},Li_{0.461+x}P_{0.076-y}S_{0.384-z}Cl_{0.076-w},Li_{0.44+x}P_{0.08-y}S_{0.36-z}CI_{0.108-w}Br_{0.012+1},Li_{0.44+x}P_{0.08-y}S_{0.36-z}CI_{0.108-w}I_{0.012+1},Li_{0.428+x}P_{0.142-y}S_{0.428-z},Li_{0.423+x}AI_{0.038+y}P_{0.076-z}S_{0.461-w},Li_{0.4+x}Si_{0.04+y}P_{0.08-z}S_{0.48-w},Li_{0.4+x}Si_{0.04+y}P_{0.08-z}S_{0.48-w},Li_{0.44+x}F_{0.032-y}P_{0.08-z}S_{0.36-w}Cl_{0.088-1},Li_{0.4+x}P_{0.08-y}S_{0.48-z}Sn_{0.04+w},Li_{0.4 + x}P_{0.08 - y}S_{0.48 - z}Sn_{0.04 + w}, Li_{0.385 + x}Si_{0.070 + y}P_{0.058 - z}S_{0.473 - w}Cl_{0.012 - 1}, Li_{0.388 + x}P_{0.111 + y}S_{0.444 - z}I_{0.055 + w}, Li_{0.385 + x}Si_{0.070 + y}P_{0.052 - z}S_{0.473 - w}Cl_{0.012 - 1}Sb_{0.005 - m}, Li_{0.310 + x}P_{0.152 + y}S_{0.537 - z}, Li_{0.375 + x}P_{0.125 + y}S_{0.5 - z}, Li_{0.308 + x}P_{0.153 + y}S_{0.536 - z}I_{0.001 - w}, Li_{0.333 + x}P_{0.142 + y}S_{0.523 - z}, Li_{0.333 + x}P_{0.142 + y}S_{0.523 - z}, Li_{0.333 + x}P_{0.142 + y}S_{0.523 - z}, Li_{(continued on next page) 0.3 + x}P_{0.138 + y}S_{0.509 - z}Mn_{0.004 - w}I_{0.014 + l}, Li_{0.2 + x}P_{0.173 + y}S_{0.565 - z}, Li_{0.390 + x}P_{0.121 + y}S_{0.487 - z}, Li_{0.337 + x}P_{0.139 + y}S_{(continued on next page) 0.522 - z}Mo_{0.000 + w}, Li_{0.390 + x}P_{0. + y}S_{0.487 - z}Sn_{0.024 + w}, Li_{0.004 + x}Li_{0.373 + y}B_{0.001 - z}P_{0.124 + w}S_{0.496 - 1}, Li_{0.393 + x}P_{0.090 + y}S_{0.484 - z}Ge_{0.030 + w}, Li_{0.4 + x}P_{0.08 + y}S_{0.48 - z}Ge_{0.04 + w}, Li_{0.304 + x}P_{0.043 + y}S_{0.521 - z}Ge_{0.130 + w}, Li_{0.325 - x}B_{0.181 + y}S_{0.377 + z}I_{0.115 - w}, and Li_{0.081 + x}O_{0.648 - y}Al_{0.027 + z}P _{0.162 - w}Ti_{0.081-1}, or any material in which one or more elements of this group are replaced with elements of the same group number, where "#" and "#±x,y,z,w,l,m}" represent the non-stoichiometric weighting of the elements immediately to the left of "#" or "#±x,y,z,w,l,m}" in the chemical formula of the material, and # can be in the range #±n, where 0≦n≦0.5, and 0≦x,y,z,w,l,m≦#, and # can be ±n, 0≦n≦0.5.

[0112] In some embodiments, Li_{0.375}O_{0.5}P_{0.125},Li_{0.3}Br_{0.6}Er_{0.1},Li_{0.166}B_{0.166}O_{0.5}Al_{0.125}Cl_{0.041},Li_{ 0.081}O_{0.648}Al_{0.027}P_{0.162}Ti_{0.081},Li_{0.3}Cl_{0.6}Er_{0.1},Li_{0.3}Cl_{0.6}Y_{0.1},Li_{0.3}Cl_{0.6}Sc_{0.1}. 265}O_{0.510}Al_{0.010}Zr_{0.085}La_{0.127},Li_{0.271}O_{0.508}Ga_{0.008}Zr_{0.084}La_{0.127},Li_{0.276}O_{0.510}Zr_{0.063}Nb _{0.021}La_{0.127},Li_{0.270}O_{0.515}Zr_{0.070}La_{0.128}W_{0.015},Li_{0.291}O_{0.5}Zr_{0.083}La_{0.125},Li_{0.3}Br_{0.6}In {0.1},Li_{0.3}Sc_{0.1}Br_{0.6},Li_{0.3}Br_{0.6}Y_{0.1},Li_{0.260}P_{0.173}S_{0.565},Li_{0.304}P_{0.043}S_{0.521}Ge_{0.130},Li _{0.310}P_{0.152}S_{0.537},Li_{0.308}P_{0.153}S_{0.536}I_{0.001},Li_{0.333}P_{0.142}S_{0.523},Li_{0.333}P_{0.142}S_{0.523} _{0.333}P_{0.142}S_{0.523},Li_{0.325}B_{0.181}S_{0.377}I_{0.115},Li_{0.337}P_{0.139}S_{0.522}Mo_{0.000},Li_{0.333}P_{0.138}S_{0.509}Mn_{0.004}I_{0.014},Li_{0.375}P_{0.125}S_{0.5},H_{0.004}Li_{0.373}B_{0.001}P_{0.124}S_{0.496},Li_{0.390}P_{0.121}S_{0.487},Li_{0.385}Si_{0.070}P_{0.052}S_{0.473}Cl_{0.012}Sb_{0.005},Li_{0.390}P_{0.097}S_{0.487}Sn_{0.024},Li_{0.385}Si_{0.070}P _{0.058}S_{0.473}Cl_{0.012},Li_{0.393}P_{0.090}S_{0.484}Ge_{0.030},Li_{0.4}Si_{0.04}P_{0.08}S_{0.48},Li_{0.4}Si_{0.04}P_{0.08}}S_{0.48},Li_{0.4}P_{0.08}S_{0.48}Ge_{0.04},Li_{0.388}P_{0.111}S_{0.444}I_{0.055},Li_{0.400}B_{0.000}O_{0.000}Al_{3.503}Si_{0.003} .133}S_{0.465},Li_{0.4}P_{0.08}S_{0.48}Sn_{0.04},Li_{0.4}P_{0.08}S_{0.48}Sn_{0.04},Li_{0.423}Al_{0.038}P_{0.076}S_{0.461} {0.433}S_{0.452}As_{0.018}Sn_{0.094},Li_{0.444}S_{0.444}Sn_{0.111},Li_{0.44}P_{0.08}S_{0.36}Cl_{0.108}I_{0.012},Li_{0.428}P_{ 0.142}S_{0.428},Li_{0.44}P_{0.08}S_{0.36}Cl_{0.12},Li_{0.44}F_{0.032}P_{0.08}S_{0.36}Cl_{0.088},Li_{0.44}P_{0.08}S_{0.36}Cl_{ 0.108}Br_{0.012},Li_{0.461}O_{0.076}P_{0.076}S_{0.307}Cl_{0.076},Li_{0.416}Si_{0.106}S_{0.363}I_{0.113},Li_{0.6}O_{0.2}Cl_{0.2},Li_{0.461}P_{0.076}S_{0.384}I_{0.076},Li_{0.461}P_{0.076}S_{0.384}Cl_{0.076},Li_{0.461}P_{0.076}S_{0.384}Br_{0.076},Li_{0.481}P_{0.074}S_{0.407}Cl_{0.037},Li_{0.475}Si_{0.026}P_{0.048}S_{0.374}Br_{0.074},Li_{0.6}O_{0.2}Br_{0.2},Li_{0.485}P_{0.029}S_{0.367}Ge_{0.044}I_{0.073},Li_{0.5}P_{0.071}S_{0.428},Li_{0.3+x}Cl_{0.6-y}Er_{0.1-z},Li_{0.3+x}Cl_{0.6-y}Y_{0.1-z},Li_{0.081+x}O_{0.648-y}Al_{0.027+z}P_{0.162-w}Ti_{0.081-l},Li_{0.3+x}Cl_{0.6-y}Sc_{0.1-z},Li_{0.3+x}Br_{0.6-y}Er_{0.1-z},Li_{0.265+x}O_{0.510-y}Al_{0.010-z}Zr_{0.085+w}La_{0.127+l},Li_{0.271+x}O_{0.508-y}Ga_{0.008-z}Zr_{0.084+w}La_{0.127+l},Li_{0.276+x}O_{0.510-y}Zr_{0.063+z}Nb_{0.021-w}La_{0.127+l},Li_{0.166+x}B_{0.166-y}O_{0.5-z}Al_{0.125+w}Cl_{0.041+l},Li_{0.291+x}O_{0.5-y}Zr_{0.083-z}La_{0.125-w},Li_{0.270+x}O_{0.515-y}Zr_{0.070-z}La_{0.128+w}W_{0.015-l},Li_{0.400-x}B_{0.000-y}O_{0.000-z}Al_{3.503+w}Si_{0.133-l}S_{0.465-m},Li_{0.3+x}Cl_{0.6-y}In_{0.1-z},Li_{0.3+x}Sc_{0.1-y}Br_{0.6-z},Li_{0.3+x}Br_{0.6-y}Y_{0.1-z},Li_{0.3+x}Br_{0.6-y}In_{0.1-z},Li_{0.325-x}B_{0.181+y}S_{0.377+z}I_{0.115-w},Li_{0.260+x}P_{0.173+y}S_{0.565-z},Li_{0.375+x}P_{0.125+y}S_{0.5-z},Li_{0.304+x}P_{0.043+y}S_{0.521-z}Ge_{0.130+w},Li_{0.310+x}P_{0.152+y}S_{0.537-z},Li_{0.333+x}P_{0.142+y}S_{ 0.523-z},Li_{0.333+x}P_{0.142+y}S_{0.523-z},Li_{0.333+x}P_{0.142+y}S_{0.523-z},Li_{0.375+x}O_{0.5-y}P_{0.125-z},Li_{0.308+x}P _{0.153+y}S_{0.536-z}I_{0.001-w},Li_{0.333+x}P_{0.138+y}S_{0.509-z}Mn_{0.004-w}I_{0.014+l},Li_{0.337+x}P_{0.139+y}S_{0.522-z}}Mo_{0.000+w},Li_{0.6-x}O_{0.2-y}Cl_{0.2+z},Li_{0.388+x}P_{0.111+y}S_{0.444-z}I_{0.055+w},H_{0.004+x}Li_{0.373+y}B_{0.001-z}P _{0.124+w}S_{0.496-l},Li_{0.461+x}O_{0.076+y}P_{0.076-z}S_{0.307-w}Cl_{0.076-l},Li_{0.390+x}P_{0.097+y}S_{0.487-z}Sn_{0.024+x} w},Li_{0.393+x}P_{0.090+y}S_{0.484-z}Ge_{0.030+w},Li_{0.6+x}O_{0.2+y}Br_{0.2-z},Li_{0.390+x}P_{0.121+y}S_{0.487-z},Li_{0.4+x} P_{0.08+y}S_{0.48-z}Ge_{0.04+w},Li_{0.385+x}Si_{0.070+y}P_{0.052-z}S_{0.473-w}Cl_{0.012-l}Sb_{0.005-m},Li_{0.385+x}Si_{0.070+y} +y}P_{0.058-z}S_{0.473-w}Cl_{0.012-l},Li_{0.416+x}Si_{0.106+y}S_{0.363-z}I_{0.113-w},Li_{0.461+x}P_{0.076-y}S_{0.384-z}Br_{0.384-z}.076+w},Li_{0.4+x}Si_{0.04+y}P_{0.08-z}S_{0.48-w},Li_{0.4+x}Si_{0.04+y}P_{0.08-z}S_{0.48-w},Li_{0.4+x}P_{0.08-y}S_{0.48-z}Sn_{0.04+w},Li_{0.4+x}P_{0.08-y}S_{0.48-z}Sn_{0.04+w},Li_{0.428+x}P_{0.142-y}S_{0.428-z},Li_{0.423+x}Al_{0.038+y}P_{0.076-z}S_{0.461-w},Li_{0.444+x}S_{0.444-y}Sn_{0.111-z},Li_{0.433+x}S_{0.452-y}As_{0.018-z}Sn_{0.094-w},Li_{0.485+x}P_{0.029-y}S_{0.367-z}Ge_{0.044+w}I_{0.073-l},Li_{0.44+x}P_{0.08-y}S_{0.36-z}Cl_{0.108-w}I_{0.012+l},Li_{0.44+x}P_{0.08-y}S_{0.36-z}Cl_{0.108-w}Br_{0.012+l},Li_{0.44+x}P_{0.08-y}S_{0.36-z}Cl_{0.12-w},Li_{0.44+x}F_{0.032-y}P_{0.08-z}S_{0.36-w}Cl_{0.088-l},Li_{0.475+x}Si_{0.026+y}P_{0.048-z}S_{0.374-w}Br_{0.074-l},Li_{0.461+x}P_{0.076-y}S_{0.384-z}Cl_{0.076-w},Li_{0.461+x}P_{0.076-y}S_{0.384-z}I_{0.076-w},Li_{0.481+x}P_{0.074-y}S_{0.407-z}Cl_{0.037-w},Li_{0.5+x}P_{0.071-y}S_{0.428-z}, or any material in which one or more elements of this group are replaced with elements of the same group number, where "#" and "#±x,y,z,w,l,m}" represent the non-stoichiometric weighting of the elements immediately to the left of "#" or "#±x,y,z,w,l,m}" in the material's chemical formula, and # can be in the range #±n, where 0≦n≦0.5, and 0≦x,y,z,w,l,m≦#, and # can be ±n, 0≦n≦0.5.

[0113] In some embodiments, the cathode 320 may be Li_{0.385}Si_{0.070}P_{0.058}S_{0.473}Cl_{0.012}, Li_{0.393}P_{0.090}S_{0.484}Ge_{0.030}, Li_{0.4}Si_{0.04}P_{0.08}S_{0.48}, Li_{0.4}Si_{0.04}P_{0.08}S_{0.48}, Li_{0.4}P_{0.08}S_{0.48}Ge_{0.04}, Li_{0.388}P_{ 0.111}S_{0.444}I_{0.055}, Li_{0.400}B_{0.000}O_{0.000}Al_{3.503}Si_{0.133}S_{0.465}, Li_{0.4}P_{0.08}S_{0.48}Sn_{0.04}, and Li_{0.4}P_{0.08}S_{0.48}Sn_{0.04}, or any material in which one or more elements of this group are replaced by an element of the same group number. where "_{#}" and "_{#±x,y,z,w,l,m}" represent the non-stoichiometric weighting of the elements immediately to the left of "_{#}" or "_{#±x,y,z,w,l,m}" in the chemical formula of the material, and # can be in the range #±n, where 0≦n≦0.5, and 0≦x,y,z,w,l,m≦#, and # can be ±n, 0≦n≦0.5.

[0114] In some embodiments, the cathode 320 may be selected from the group consisting of Li_{0.4+x}P_{0.08+y}S_{0.48-z}Ge_{0.04+w}, Li_{0.385+x}Si_{0.070+y}P_{0.052-z}S_{0.473-w}Cl_{0.012-l}Sb_{0.005-m}, Li_{0.385+x}Si_{0.070+y}P_{0.058-z}S_{0.473-w}Cl_{0.012-l}, Li_{0.416+x}Si_{0.106+y}S_{0.363-z}I_{0.113-w}, Li_{0.461+x}P_{0.076-y} The solid electrolyte 330 may be mixed with a material selected from S_{0.384-z}Br_{0.076+w}, Li_{0.4+x}Si_{0.04+y}P_{0.08-z}S_{0.48-w}, Li_{0.4+x}Si_{0.04+y}P_{0.08-z}S_{0.48-w}, Li_{0.4+x}P_{0.08-y}S_{0.48-z}Sn_{0.04+w}, Li_{0.4+x}P_{0.08-y}S_{0.48-z}Sn_{0.04+w}, or any material in which one or more elements of this group are replaced with elements of the same group number. where "_{#}" and "_{#±x,y,z,w,l,m}" represent the non-stoichiometric weighting of the elements immediately to the left of "_{#}" or "_{#±x,y,z,w,l,m}" in the chemical formula of the material, and # can be in the range #±n, where 0≦n≦0.5, and 0≦x,y,z,w,l,m≦#, and # can be ±n, 0≦n≦0.5.

[0115] In some embodiments, the solid electrolyte 330 can be mixed with the cathode 320 and / or the solid electrolyte 330 can have a core-shell particle structure.

[0116] 4 is a cross-sectional view of an electrochemical cell 400 according to embodiments. The electrochemical cell 400 includes an anode 440 disposed on an anode current collector 450, a cathode 420 disposed on a cathode current collector 410, and a solid electrolyte 430 disposed between the cathode 420 and the anode 440. In some embodiments, the solid electrolyte 430 can include multiple layers of a solid electrolyte (SSE) (e.g., as described with respect to the solid electrolyte 330). In some embodiments, the solid electrolyte 430 can have a first side and a second side opposite the first side. In some embodiments, the first side of the solid electrolyte 430 can be coated with a first coating 422 (e.g., a protective material) and / or the second side of the solid electrolyte 430 can be coated with a second coating 446. In some embodiments, the first coating 422 may be disposed between the cathode 420 and the solid electrolyte 430, and / or the second coating 446 may be disposed between the anode 440 and the solid electrolyte 430. In some embodiments, the electrochemical cell 400 may further include a third coating 448 disposed between the anode 440 and the anode current collector 450.

[0117] In some embodiments, electrochemical cell 400 can be the same as or substantially similar to electrochemical cells 100, 200, 300 described above with reference to Figures 1, 2, and 3. In some embodiments, anode 440, which includes an anode material and is disposed on anode current collector 450, cathode 420, which is disposed on cathode current collector 410, and solid electrolyte 430, which is disposed between cathode 420 and anode 440, can be the same as or substantially similar to anode 140, 240, 340, anode current collector 150, 250, 350, cathode 120, 220, 320, cathode current collector 110, 210, 310, and solid electrolyte 130, 230, 330, respectively, described with reference to Figures 1, 2, and 3. In some embodiments, electrochemical cell 400 can be placed under mechanical restraint (P), as described above with reference to Figure 1.

[0118] In some embodiments, the coatings 422 and / or 446 can act as an interfacial layer between the base electrode material and the solid electrolyte 430. In particular, the coatings 422 and 446 can be configured to improve the interfacial stability between the electrode (e.g., the cathode 420) and the solid electrolyte 430 and achieve excellent cycle performance. For example, the coating 422 or the cathode 420 can be LiNbO3, LiTaO3, Li2ZrO3, LiNb X Ta 1-X O3 (0 ≦ x ≦ 1), yLi2ZrO3-(1-y)LiNb X Ta 1-x O3 (0 ≦ x, y ≦ 1), Al2O3, TiO2, ZrO2, AlF3, MgF2, SiO2, ZnS, ZnO, Li4SiO4, Li3PO4, Li3InCl6, Li 1+x Al x Ti 2-x (PO4)3 (0 < x < 2), LiMn2O4, LiInO2-LiI, Li6PS5Cl, LiAlO2, and may include carbon, but are not limited thereto. In some embodiments, the coating 422 includes LiNbO3.

[0119] In some embodiments, the solid electrolyte 430 can be separated from the anode material and / or the cathode material by the coatings 446 and 422, respectively, which include Li4Ti5O 12 , Li3V2O5, silicon dioxide, carbon (e.g., amorphous carbon, carbon nanotubes, graphene, carbon nanofibers, fullerenes (e.g., C 60 ), hard carbon, graphite (e.g., as a graphite coating on the electrode), Au, Ag, Sn, SnO2, or combinations thereof.

[0120] In some embodiments, coatings 422, 446, and / or 448 may include particles. In some embodiments, the particle size of the coating is about 1 nm to about 100 μm, e.g., about 1-100 nm (e.g., about 1-10 nm, 1-25 nm, 10-20 nm, 20-30 nm, 25-50 nm, 30-40 nm, 40-50 nm, 50-60 nm, 50-75 nm, 60-70 nm, 70-80 nm, 75-100 nm, 80-90 nm, 90-100 nm, e.g., about 1 nm, 5 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 150 nm, 160 nm, 170 nm, 180 nm, 190 nm, 210 nm, 220 nm, 230 nm, 240 nm, 250 nm, 260 nm, 270 nm, 280 nm, 290 nm, 300 nm, 310 nm, 320 nm, 330 nm, 340 nm, 350 nm, 360 nm, 370 nm, 380 nm, 390 nm, 400 nm, 410 nm, 420 nm, 430 nm, 440 nm, 450 nm, 460 nm, 470 nm, 480 nm, 490 nm, 500 nm, 510 nm, 520 nm, 530 nm, 540 nm, 550 nm, 560 nm, 570 nm, 580 nm, 590 nm 0 nm, 100 nm), for example, about 100 to 1,000 nm (for example, about 100 to 110 nm, 100 to 125 nm, 100 to 200 nm, 200 to 300 nm, 250 to 500 nm, 300 to 400 nm, 400 to 500 nm, 500 to 600 nm, 500 to 750 nm, 600 to 700 nm, 700 to 800 nm, 750 to 1,000 nm, 800 to 900 nm, 900 to 1,000 nm, for example, about 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm m, 800 nm, 900 nm, 1,000 nm), for example, about 1 to 10 μm (for example, about 1 to 2 μm, 1 to 5 μm, 2 to 3 μm, 3 to 4 μm, 4 to 5 μm, 5 to 10 μm, 5 to 6 μm, 6 to 7 μm, 7 to 8 μm, 8 to 9 μm, or 9 to 10 μm (for example, about 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, or 10 μm), or, for example, about 10 to 100 μm (for example, about 10 to 20 μm, 10 to 25 μm, 10 to 50 μm, 20 to 30 μm, 25 to 50 μm, 3 The thickness may be 0 to 40 μm, 40 to 50 μm, 50 to 60 μm, 50 to 75 μm, 60 to 70 μm, 75 to 100 μm, 70 to 80 μm, 80 to 90 μm, or 90 to 100 μm, for example, about 10 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, or 100 μm.

[0121] In some embodiments, coatings 422, 446, and / or 448 may include indium. In some embodiments, coatings 422, 446, and / or 448 may include polyethylene oxide, polyvinylidene fluoride, poly(vinylidene fluoride-co-hexafluoropropylene), poly(ethyl methacrylate), or poly(vinylidene fluoride-co-trifluoroethylene).

[0122] In some embodiments, coatings 422, 446, and / or 448 (e.g., protective layers) can be blended with Li metal and / or a polymer to a thickness of about 0 μm to about 500 μm. In some embodiments, the lithium metal layer can be protected by a layer formed of one or more of the following elements: Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Ga, Ge, As, Rb, Sr, Y, Zr, Nb, Mo, Ag, Cd, In, Sn, Sb, Bi, Cs, Te. In some embodiments, the lithium metal layer can be alloyed with one or more of the following elements: Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Ga, Ge, As, Rb, Sr, Y, Zr, Nb, Mo, Ag, Cd, In, Sn, Sb, Bi, Cs, Te. In some embodiments, the lithium metal layer can be protected by a compound of H, Li, B, C, N, O, F, Na, Mg, Al, Si, P, S, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Ga, Ge, As, Se, Br, Rb, Sr, Y, Zr, Nb, Mo, Ag, Cd, In, Sn, Sb, Te, I, Cs, Ba, Pt, Au, Hg, Tl, Pb, Bi, Po, At, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu. In some embodiments, the third coating 448 can include a lithium layer disposed on the anode current collector 450, which can be configured to provide additional lithium metal for lithiation in the anode 440.

[0123] 5 shows a schematic flow chart of a method 10 for fabricating an electrochemical cell including a cathode, an anode, and a solid electrolyte disposed between the cathode and the anode, according to one embodiment. Although described with respect to electrochemical cell 100 and its components, method 10 is equally applicable to any electrochemical cell, including any of the embodiments described herein. All such embodiments are contemplated and considered within the scope of the present disclosure.

[0124] Method 10 includes, in step 12, disposing cathode 110 on cathode current collector 110. In some embodiments, the cathode material included in cathode 110 includes lithium. Method 10 may optionally include, in step 14, disposing a first coating on cathode 110. In some embodiments, this coating may be the same as or substantially similar to coating 422 described with respect to FIG. 4. Method 10 further includes, in step 16, disposing anode 140 on anode current collector 150. In some embodiments, the anode material forming anode 140 includes a plurality of voids defined therein. These voids may, in some embodiments, be the same as or substantially similar to voids 244 described with respect to FIG. 2. Method 10 may optionally include, in step 18, disposing a second coating (e.g., similar to coating 446 described above) on anode 140. In some embodiments, method 10 includes disposing solid electrolyte 130 between cathode 110 and anode 140 to form electrochemical cell 100. In some embodiments, the formed electrochemical cell may be the same as or substantially similar to electrochemical cells 100, 200, 300, and 400 described above with respect to FIGS. 1-4 . In some embodiments, method 10 may further include, in step 24, compressing electrochemical cell 100 at a predetermined pressure. This pressure may create a mechanical constraint on the electrochemical cell that is the same as or substantially similar to the mechanical constraint described above with respect to FIGS. 1 and 2 . Method 10 may further include, in step 26, charging electrochemical cell 100. In some embodiments, charging may deposit lithium metal in the voids of anode 140. Method 10 may further include, in step 28, discharging electrochemical cell 100. In some embodiments, discharging may oxidize the lithium metal deposited in the voids.

[0125] In some embodiments, a method for storing (e.g., step 26) and releasing (e.g., step 24) electrical energy includes converting Li into Li by applying a voltage to the solid-state electrochemical cell or battery of some embodiments described herein. + This involves storing electrical energy as chemical energy by transporting Li as ions from the cathode to the anode, where it is deposited (e.g., plated) into the voids as Li metal. Upon discharge, Li metal is converted to Li + and migrates back to the cathode.

[0126] To release (discharge) the stored chemical energy as electrical energy, a load is electrically connected between the anode and cathode, and Li + Ions are allowed to migrate from the anode through the solid electrolyte to the cathode. In some embodiments, the bulk (e.g., less than about 500 nm (e.g., less than 400 nm, less than 300 nm, less than 200 nm, less than 100 nm, less than 65 nm) of the material from the surface) does not accept Li (e.g., lithiation does not proceed).

[0127] The methods described herein may include repeating the above cycle multiple times, for example, 1,000 or more times, for example, 1,000 to 20,000 times (e.g., 1,000 to 1,500 times, 1,250 to 1,750 times, 1,500 to 2,000 times, 1,500 to 2,500 times, 2,000 to 3,000 times, 2,500 to 5,000 times, 5,000 to 10,000 times, 5,000 to 15,000 times, 10,000 to 20,000 times, or 15,000 to 20,000 times).

[0128] The method of storing and releasing electrical energy is, for example, in the first charge / discharge cycle, first Li + This may include reacting some of the ions to form a surface layer on the anode material, or the anode material may already have a surface layer.

[0129] The methods described herein can include actively applying external pressure (e.g., by pressing) during cycling. In some embodiments, at least 10% (e.g., at least 15%, 20%, 25%, 30%, 40%, 50%, 60%, 70%, 75%, 80%, 85%, 90%, e.g., about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 100%, 101%, 102%, 103%, 104%, 105%, 106%, 107%, 108%, 109%, 110%, 111%, 112%, 113%, 114%, 115%, 116%, 117%, 118%, 119%, 120%, 121%, 122%, 123%, 124%, 125%, 126%, 127%, 128%, 129%, 130%, 131%, 132%, 133%, 134%, 135%, 136%, 137%, 138%, 139%, 140%, 141%, 142%, 143%, 144%, 145%, 146%, 147%, 148%, 149%, 150%, 151%, 152%, 153%, 154%, 155%, 156%, 157%, 158%, 159%, 160%, 161%, 162%, 163%, 164%, 165%, 166%, 167%, 168%, %, 98%, 99%, e.g., 10-15%, 10-20%, 15-30%, 25-50%, 40-60%, 50-75%, 65-80%, 75-99%, 70-90%, 80-90%, 90-95%, 93-97%, 95-99.99%, e.g., greater than 99%, e.g., 99.01% to 99.99%) is stored as lithium metal (e.g., within the voids), i.e., at least 10% of the stored electrical energy is not stored as lithiated anode material, but rather as lithium deposited within the voids.

[0130] [Example] <Methods> The following methods apply to Examples 1 to 5. <Materials and batteries> Li 5.5 PS 4.5 Cl 1.5 (LPSCl) was prepared by high-energy ball milling followed by annealing. Stoichiometric amounts of Li2S (99.9% purity, Alfa Aesar), P2S5 (99% purity, Sigma-Aldrich), and LiCl (99% purity, Alfa Aesar) were milled in a planetary mill PM200 (Retsch GmbH, Germany) under an Ar protective atmosphere for 16 h, and then sintered at 550 °C in a quartz tube.

[0131] A lithium foil with a diameter of 0.63 cm and a thickness of 25 μm was covered with a silicon-graphite composite film (SiG) with a diameter of 0.79 cm. The weight ratio of the SiG was 47.6%:47.6%:4.8% silicon (1 μm size, Skyspring Nanomaterials, Inc.), graphite (BTR, China), and PTFE. The cathode layer consisted of a 30 wt% solid electrolyte, LiNi coated with single-crystal LiNbO3. 0.83 Mn 0.1 Co 0.07 In addition to 70 wt% O2 (particle size 1-5 μm, MSE Supplies), 3 wt% PTFE was mixed, and the coating amount of the active substance was 10-60 mg / cm. 2 The monolayer design consisted of 120 mg of LPSCl as the electrolyte. 1.0 or LPSCl 1.5 In the multilayer design, 20 mg of LPSCl 1.5 and 100 mg of LGPS (or LSnPS). 1.5 -LGPS-LPSCl 1.5 The entire battery, with its NMC83 structure, was pressurized to 400 MPa in a homemade pressure cell and maintained at 50 MPa during testing. The nominal NP ratio was controlled between 0.3 and 1.5 and calculated based on the theoretical capacities of Si (3,000 mAh / g) and NMC83 (200 mAh / g). All batteries were assembled in an argon-atmosphere glove box, and the humidity of the battery test environment was controlled in a Memmert hpp110. Battery testing was performed at 0°C, 35°C, or 55°C using Arbin equipment. During high-rate cycling, the cutoff voltages were set at 2.5V to 4.1V and 2.0V to 4.35V. Liquid electrolyte cells were fabricated using Li or SiG as the anode and EC / DMC (v:v = 1:1) containing 1M LiPF6 as the electrolyte.

[0132] The anode protection layer and three solid electrolyte layers were cast sequentially onto lithium-coated copper foil (5 μm). To prepare the anode protection layer slurry, 50 wt% silicon powder (1 μm), 50 wt% graphite powder, and 2.5 wt% acrylate-based polymer binder were mixed with anhydrous p-xylene and isobutyl isobutyrate (1:1 vol / vol) using a planetary centrifugal mixer (Thinky Corporation). Milling balls were added to the resulting mixture to form a homogeneous slurry, which was then cast using a doctor blade and dried at room temperature. The next one, two, or three solid electrolyte layers were made of Li6PS5Cl, Li 10 SnP2S 12 , Li6PS5Cl, and their slurries were prepared in a similar manner, using additional solvent to adjust viscosity. The amount of polymer binder varied from 0.5 to 5 wt%. Each new layer was cast on top of the previous layer after drying at room temperature for approximately 2 minutes. After coating the fourth layer, the film was transferred to a dynamic vacuum oven and completely dried at 60 °C for 12 hours. The dried multilayer film was cut to a specific size of 35 mm x 28 mm using a pneumatic punch machine for the fabrication of pouch-type cells. Using a similar casting method, one, two, or more solid electrolytes were cast onto a cathode or polyester (PET) film. In some experiments, the electrolyte was cast onto the PET, and then the electrolyte layer was transferred to the cathode or anode by applying calendar pressure or hydrostatic pressure. Pouch-type cell batteries consisted of an anode, cathode, and multilayer film. These sheets were stacked and packed into a laminate bag. The cells were densified by pressing at 350 MPa and 70 °C.

[0133] <xps> XPS is a Thermo Scientific K-Alpha + The measurement was performed using a spot size of 400 μm. A vacuum transfer module was used to transport the sample from the glove box to the XPS chamber. The sample was prevented from coming into contact with the atmosphere during transport and measurement of the XPS sample. Argon ion milling was performed for 500 to 1,000 seconds with an energy of 0.5 keV and a current of approximately 0.6 μA.

[0134] <fib-sems> Cross-sectional observations were performed using a focused ion beam scanning electron microscope (FIB-SEM) with an FEI Helios 660. The raw material and the cycle-treated pellets were transported from an argon-filled glove box in sealed plastic bags. The samples were exposed to air for 1-2 minutes during transport. Pt pretreatment and Ga + Milling was performed to prepare clean cross-section areas at different current values. SEM-EDX observations were performed using the internal EDAX tool and detector. Cells for FIB-SEM observations were tested at room temperature.

[0135] <eels> The lithiated layer of the anode material was processed by FIB to a thickness suitable for electron energy loss spectroscopy (EELS). The thickness was confirmed to be 65 nm by both FIB-SEM and TEM. In TEM, the convergence angle was 30 mrad, the collection angle was 43 mrad, and the ln(I t The thickness is calculated based on I / I = approximately 0.54, where I t and I0 are the total spectrum integral and the zero-loss integral, respectively. This thickness provides a sufficient signal for lithium detection. (Scanning) TEM, HRTEM, and EELS were measured using an ARM200 at a voltage of 200 kV.

[0136] Example 1: Initial investigation Figure 6(a) shows the specific capacity at room temperature of a solid-state asymmetric battery composed of Li / graphite (G)-solid electrolyte (Ses)-SiG, where SiG is a composite layer consisting of micro-sized Si and graphite particles. The discharge capacity, i.e., the ratio of Li / G to SiG, + The transfer of lithium exceeds 5,600 mAh / g, calculated based on the Si coating mass, far exceeding the theoretical capacity of 3,000 mAh / g. At discharges of approximately 5,000 mAh / g, signs of short circuiting are observed, indicating lithium penetration. The discharge curve shows a sharp drop at the end of discharge when Li is depleted on the Li / G side. Focused ion beam scanning electron microscopy (FIB-SEM) images and energy dispersive spectroscopy (EDS) mapping were acquired (Figure 6(b1)) at three different discharge conditions to reveal the anode morphology and chemical composition. Before discharge, the pristine anode exhibits pores between the Si particles (Figure 6(b1)). Upon discharge toward 0 V, neither cracking of the Si particles nor obvious swelling of the Si particles is observed (Figures 6(b2) and 6(b3)). At -0.2 V, significant lithium deposition was already observed between the Si particles (Figure 6(b3)), and its morphology and oxygen signal confirmed the presence of lithium metal (Figures 6(c1)–6(c3)). This is because lithium metal is the most reactive component in the composite with respect to atmospheric oxygen and nitrogen. To further support the conclusion that the oxygen EDS signal is primarily from lithium metal, Figures 10(a1)–(c2) show cross-sections of pristine SiG composites with and without a lithium metal anode foil directly beneath the SiG layer. In these cross-sections, the dominant oxygen and nitrogen signals originate solely from the added lithium metal foil. Furthermore, considering that at a very low discharge current density of 0.2 mA / cm2, almost no polarization occurred and most of the capacity was below 0 V, these results suggest that significant lithium deposition occurred on the SiG, and the composite functioned as a lithium metal anode rather than a silicon anode.

[0137] In contrast to the surprising behavior in the solid-state batteries described above, in the liquid electrolyte battery, Si microparticles exhibited a voltage drop of 0.5 V and 0.3 V (VS Li / Li + ) shows a normal plateau, which corresponds to the two lithium alloy reactions (Fig. 6(d)), with a total capacity of approximately 1,800 mAh / g. Furthermore, SEM observations show a morphology that is quite different from the crushed Si that is common in Si anodes in liquid electrolyte batteries (Figs. 6(e1)-6(e2)). Furthermore, LiNi 0.83 Mn 0.06 Co 0.11 When an O2(NMC83) cathode is combined with a SiG anode in a liquid electrolyte battery, crushing of the Si particles is again observed after only five cycles (Figs. 11(a) and 11(b)). This indicates damage caused by volume expansion due to lithiation. This phenomenon is accompanied by a deterioration in cycling performance (Fig. 11(c)), with only 30% capacity remaining after five cycles. Unlike the Si particles in the liquid electrolyte battery, in the solid-state battery the Si particles remain intact. The entire solid-state battery is constructed with SiG covering a thin layer of Li metal (25 μm) on the anode, with a loading of 25 mg / cm. 2 The cathode was fabricated using NMC83. The nominal anode-to-cathode (NP) ratio was 1.5, hypothetically calculated based on the capacities of Si (3000 mAh / g) and NMC83 (200 mAh / g). The lithium metal layer beneath the SiGe composite layer provides an additional lithium source, improving the battery's cycling performance. The multilayer electrolyte configuration also provides cycling stability against Li dendrites. FIB-SEM images of Si particles after 500 cycles (Figures 11(d)-(f)) showed no cracks, fractures, or irregular edges. If no fractures are observed in solid-state batteries (Figures 6(b) and 11(d)-(f)), it is possible that Si lithiation is largely limited and capacity is primarily provided by the precipitation and exfoliation of lithium metal. To test this hypothesis, we performed a more direct observation of the lithium distribution in the anode, as described herein.

[0138] Example 2: Spectroscopic analysis of the anode Li, being a light element, cannot be detected by EDS, but it can be detected by electron energy loss spectroscopy (EELS) and X-ray photoelectron spectroscopy (XPS). First, we combined EELS line scans with EDS mapping from scanning transmission electron microscopy (STEM) to clarify the lithium distribution in the SiG composite anode (Figs. 7(a)–7(c)). Figure 7(a) shows a dark-field STEM image of the SiG anode from a battery stopped at a state of charge of 4.1 V after 500 cycles (Fig. 11(f)). The SiG anode portion was milled to a depth of 65 nm using FIB. Scanning from the outside of the Si particle to the bulk (Fig. 7(a)), the EELS Li K-edge (Fig. 7(b)) reveals that Li is present only in the outer regions of the Si particles. The absence of Li inside the Si particles indicates that most of the Si was not lithiated during the battery cycling test. Therefore, even if Li-Si alloying does occur, it is thought to be limited to a surface layer less than 65 nm thick, as shown in the region where the Si-L and Li-K EELS signals coexist in Figure 7(b).

[0139] STEM-EDS mapping was also performed on the same sample (Figure 7). The oxygen and nitrogen signals exhibited distributions consistent with the Li element detected by EELS and were all present on the exterior of the Si particles. High-resolution TEM images (Figures 7(d1)-7(d2)) reveal lattice fringes of the (111) plane, with a measured d-spacing of 3.1 Å. This is in good agreement with the initial Si crystalline phase (Kim, H., Seo, M., Park, MH & Cho, J. A Critical size of silicon nano-anodes for lithium rechargeable batteries. Angew. Chemie - Int. Ed. 49, 2146-2149 (2010)). Furthermore, the microscale Si particles maintain their intact morphology without cracks after cycling in the charged state (Figure 7(c), STEM) and upon discharge (Figure 7(c) and Figures 12(a)-12(f), SEM). Furthermore, the entire battery exhibits clearly separated EDS signals from oxygen (representing Li), carbon (derived from graphite), and Si (Figures 7(c), 7(e2)–7(e3), and Figures 12(c)–12(f)). This is consistent with the results from the asymmetric battery (see Figures 6(c1)–6(c3)). These results further support the finding that the primary source of electrochemical capacity in the various solid-state battery configurations tested is lithium deposition on the Si surface, rather than Si lithiation. Thus, the anode is actually a lithium metal anode, not a silicon anode. It should be noted that in the initial assembly of the battery shown in Figures 6(a)–6(e2), Figures 7(e1)–7(e3), and Figures 12(a)–12(f), there is no lithium below the SiG layer, and therefore all observed lithium metal is deposited from the other electrode side (Li / G or NMC83). In particular, at a nominal NP ratio of 1.5 calculated based on the Si and NMC capacities, the Si-Li alloying capacity is in principle sufficient to accommodate all the lithium from the cathode, which is different from the surprising result observed here, where there is almost no Si capacity.

[0140] XPS also shows a lithium metal signal from the SiG anode side after the first charge of the NMC-SES-SiG solid-state battery (Fig. 13(a)). This result further supports the deposition of lithium metal upon cathode charging, since no lithium layer was formed on the initial anode side. XRD measurements on the same anode clearly showed the initial Si phase, rather than the lithiated alloy phase (Fig. 9(b)). Figure 7(f) shows the XPS measurement results around the Si peak energy for a Li-Ses-SiG solid-state battery with a discharge capacity of over 5,000 mAh / g, after all lithium had been stripped from the Li anode and deposited on the SiG side. Li-Si-O appears to be present on the Si surface. However, after 500 seconds of argon ion milling at low energy (0.5 keV and 0.6 μA, SiO2 etching rate ∼0.52 Å / s) (Chang, HY et al. X-ray Photoelectron Spectroscopy Equipped with Gas Cluster Ion Beams for Evaluation of the Sputtering Behavior of Various Nanomaterials. ACS Appl. Nano Mater. 5, 4260-4268 (2022); Kyoung, YK et al. Electronic structures of SiO2 thin films via Ar gas cluster ion beam soupering. Surf. Interface Anal. 46, 58-61 (2014)), the Li-Si-O signal diminishes, and Si, Li-Si, and Si-O signals appear. After 1,500 seconds of milling, the Li-Si-O and Li-Si signals disappear, leaving only the Si and Si-O peaks. This indicates that only a surface layer of Si particles with a thickness of less than 60 nm exists, and the interior is still the initial Si phase, which is consistent with the STEM-EELS and XRD results.

[0141] Furthermore, when the nominal NP ratio was decreased to 0.3, lithium deposition beneath the entire SiG layer was more pronounced (Figures 13(e) and 13(f)) compared with the case where the nominal NP ratio was 1.5 (Figures 9(c) and 13(d)). This is because the porous regions between the Si particles in the SiG anode layer with NP = 0.3 were not large enough for lithium deposition. Lithium deposition was also observed on pure Si anodes without graphite, but in principle, Si should have sufficient capacity to be lithiated by alloying (Figures 14(a)–14(g)). Therefore, the solid-state battery described here converts the behavior of silicon from that expected for a silicon anode to that of a lithium metal anode. Instead of lithiating Si through the conventional alloying and milling process, Si is confirmed to function solely as a scaffold to host the deposition and exfoliation of Li metal in the voids between Si particles as the primary capacity source.

[0142] Example 3: Battery performance Here, lithium dendrites can be problematic, especially at high current densities, since lithium deposition and delamination account for a large portion of the anode capacity. In addition to the design of multilayer electrolytes that prevent Li dendrite penetration through dynamic stability (Ye, L. & Li, X. A dynamic stability design strategy for lithium metal solid state batteries. Nature 593, 218-222 (2021)), computational dynamic stability (Wang, Y., Ye, L., Chen, X. & Li, X. A Two-Parameter Space to Tune Solid Electrolytes for Lithium Dendrite Constriction. J. Am. Chem. Soc. 2, 886-897 (2022); Fitzhugh, W., Chen, X., Wang, Y., Ye, L. & Li, X. Solid-electrolyte-interphase design in constrained ensemble for solid state batteries. Energy Environ. Sci. 14, 4574-4583 (2021)) has been further quantified and designed to facilitate the selection, design, and synthesis of advanced electrolyte materials in experiments. These efforts have resulted in a reduction of 8.6 to 43 mA / cm 2 This corresponds to an extremely high rate of 20C to 80C, and all of the current densities were 2 mg / cm. 2 Therefore, high C rates can be achieved at low cathode loadings at high current densities, whereas commercially reasonable cathode loadings (>15 mg / cm) are not. 2 ), an important question was whether the C-rate could be lowered (but still be sufficient for fast charging, e.g., 2C-10C).

[0143] FIG. 8(a) shows a Li metal anode solid state battery described herein with a Li-Sig-SEs-NMC83 configuration at a cathode loading of 25 mg / cm 2 A properly designed multilayer electrolyte configuration in combination with a Li-SiG anode according to embodiments described herein provides a cycling performance of 7.4 mA / cm 2 At high current densities of 1C and 2C, the multilayer design exhibits 80% capacity retention after 1,000 or 2,000 cycles. In contrast, the monolayer electrolyte configuration, with the same total electrolyte layer thickness, exhibits much poorer cycling performance, lasting less than 500 cycles at the same cathode loading and rate. Figure 8(b) further shows that at 1C to 2C rates, the multilayer design exhibits much higher capacity than the monolayer design, with good cycling performance of approximately 2-3 mAh / cm. 2 We show that an areal capacity of 10 ... 2 and areal capacity up to 7mAh / cm 2 It shows high robustness even when the temperature reaches 0°C (see Fig. 8(d)).

[0144] Two prerequisites are essential for fast charging of alkali metal-based batteries: fast electrochemical reaction rate and prevention of lithium dendrite formation. Fast charging is difficult in conventional Si-based batteries because the Li-Si alloying reaction is relatively slow and typically involves Si milling. However, in the solid-state batteries described herein, lithium metal deposition dominates the electrochemical process in the anode. This mechanism not only avoids the problems caused by Si swelling but also provides a faster reaction pathway for fast cycling because Li exfoliation and deposition are faster than Li-Si alloying. Fast charging is enabled by the faster lithium exfoliation and deposition than Li-Si alloying, and the suppression of dendrite formation by the multilayer solid electrolyte described herein. Figure 9(a) shows the fast charging capability of a SiGe composite anode using a high NMC83 loading in the cathode. A capacity of more than 157 mAh / g can be delivered at a 5C fast charge and 1C normal discharge. Even at a 6C rapid charge / discharge rate, the capacity is greater than 110mAh / g. The discharge capacity of the solid-state battery at 0°C is 154mAh / g (Figure 9(b)).

[0145] Figure 15(a) shows a comparison of the rate performance of different anodes. The 50 wt%Si-50 wt%G composite shows the highest value at low rate, while pure Si appears to have a slight advantage at high rate. However, the SiG composite has a lower capacity than the commercial grade of 22 mg / cm. 2 The application amount is 1 to 2.3mAh / cm 2 The Li-SiG anode exhibits a high areal capacity of 1000 mA / cm and superior cycling performance (80% capacity retention after 1,500 cycles, see Figure 9(c)) compared to pure Si (80% capacity retention after 1,000 cycles, see Figure 15(b)). The Li-SiG anode battery also maintains 75% capacity retention after more than 2,000 cycles at 6C charge and 6C discharge, and 75% capacity retention after 1,200 cycles at 10C charge and 2C discharge (Figure 9(d)). The charge and discharge profiles are shown in Figures 15(c) and 15(d). The current densities at 6C and 10C are 19.5 mA / cm, respectively. 2 and 32.7mA / cm 2 It is important to note that the electrochemical cell described here performs well at high cycle rates even at temperatures as low as 35°C (see Figure 9e).

[0146] Example 4: Effect of pressure To investigate the role of mechanical constraint in the effects discovered here, we calculated the Si anode properties under different levels of mechanical constraint. Figure 9(f) shows the results for different levels of mechanical constraint (K) from 0 to 5 GPa. eff ) shows the voltage and capacity dependence of a Si anode under This was predicted by constrained ensemble thermodynamic calculations (Fitzhugh et al., Energy Environ. Sci. 14, 4574-4583 (2021), Fitzhugh, W., Ye, L. & Li, X. The effects of mechanical constriction on the operation of sulfide-based solid state batteries. J. Mater. Chem. A 7, 23604-23627 (2019), and Wu, F., Fitzhugh, W., Ye, L., Ning, J. & Li, X. Advanced sulfide solid electrolytic by core-shell structural design. Nat. Commun. 9, 1-11 (2018)), (Wang, Y., Ye, L., Chen, X. & Li, X. A Two-Parameter Space to Tune Solid Electrolytes for Lithium Dendrite Constriction. J. Am. Chem. Soc. 2, 886-897 (2022)). That is, Si undergoes volume expansion when alloyed with lithium under zero or low mechanical constraint, but the strain energy associated with the expansion can resist the alloying reaction under strong mechanical constraint. K eff The simulated capacity of Si at ≈5 GPa is already small (164 mAh / g) above 0 V, very close to the capacity measured above 0 V in Figure 6(a). Note that 5 GPa is not the external pressure. This means that the Li-Si alloying reaction and the associated grinding at the Si particle surface result in a local effective modulus exceeding 5 GPa. As a result of this high local effective modulus, lithium deposition is favorable, and lithium deposition may be observed even in SiG anodes operating at external pressures as low as 5 MPa in solid-state batteries (see Figures 16(a)–(c)). All these results suggest that this knowledge may be widely applicable to the future design of solid-state and liquid electrolyte batteries with excellent rate capabilities. Advanced designs may allow the limited adoption of Si and other materials suitable for Li metal anode applications at various scales.

[0147] Example 5: Solid Pouch Cell Figure 17 shows the cycle characteristics of a pouch-type cell with a Si-G anode protection layer on Li metal. The electrolyte was prepared using a slurry casting method. The solid electrolyte was mixed with a solvent and a binder to prepare a slurry. Anhydrous p-xylene and isobutyl isobutyrate (1:1 vol / vol) were used as the solvent, and an arylate-type polymer was used as the binder. The solid electrolyte consisted of Li6PS5Cl, Li 10 SnP2S 12 The solid-state pouch cell was subjected to a cycle test at a high rate of 5C, and the initial capacity was approximately 125 mAh / g, and the capacity retention rate after 2000 cycles was approximately 90%.

[0148] Example 6: Computational investigation of other suitable materials To explore what other material types may be applicable as anodes in accordance with embodiments described herein, the theoretical Li-ion lithiation capacity of the material is divided by the critical elastic modulus of the material, including Li metal. This index indicates the extent to which the lithiation capacity of the material is constrained by mechanical constraints and converted into a target lithium deposition capacity. The results of these calculations are shown in Figures 18(a)-18(b). Figure 18(a) shows the voltage (y-axis) vs. K of the anodic reaction for a Li metal anode. crit Figure 18(b) shows the results of high-throughput calculations of the capacity over K (COK) (x-axis) for the anodic reaction with a Li metal anode. crit Figures 19(a), 20(a), 21(a), and 22(a) show the occurrence of elements in the ranges COK > 500 mAh / g / GPa and COK × V > 600 mWh / g / GPa. Figures 19(b), 20(b), 21(b), and 22(b) show the co-occurrence of two elements in the corresponding ranges COK and COK × V. Figures 19(c), 20(c), 21(c), and 22(c) show the co-occurrence of three elements in the corresponding ranges COK and COK × V. Figure 22(d) shows the voltage (y-axis) of the anodic reaction versus lithiation composition / K for a Li metal anode for 59,524 material entries within the plot axes. crit The results of high-throughput calculations are shown on the x-axis. + is the average lithiation voltage of the material relative to K / Li, crit is the critical elastic modulus that can suppress the lithiation reaction between Li metal and the material. The inset shows the elemental distribution of 11,568 material entries in the region between the dashed line in Fig. 22(d) and the boundary where the lithiation energy per unit lithium per constraint is maximized.

[0149] Various concepts may be embodied as one or more methods, of which at least one example is provided. Tasks included within some of the methods may be performed in any suitable order. Thus, embodiments may be constructed that perform tasks in an order different from that shown in the specification. This may include performing some actions simultaneously even though an example embodiment shows them as being performed sequentially. In other words, it should be understood that such features are not necessarily limited to a particular order of tasks, but rather, tasks may be performed serially, asynchronously, simultaneously, in parallel, simultaneously, synchronously, etc., across any number of threads, processes, services, servers, etc., in a manner consistent with this disclosure. Thus, some of these features may be mutually inconsistent in that they cannot exist simultaneously in a single embodiment. Similarly, some features may be applicable to one aspect of the invention but not to other aspects.

[0150] Additionally, the present disclosure may include other innovations not currently described. Applicant reserves all rights with respect to such innovations, including the right to file additional applications, continuations, continuations-in-part, divisional applications, and / or the like that embody such innovations. Accordingly, it should be understood that any aspects of the present disclosure, including advantages, embodiments, examples, functions, features, logic, operation, organization, structure, topology, and the like, are not intended to limit the present disclosure, which may be defined as limitations on embodiments or equivalents thereof. Depending on the particular needs and / or characteristics of individual and / or business users, database configurations and / or relational models, data types, data transmission and / or network configurations, syntactic structures, and the like, various embodiments of the technology disclosed herein may be implemented in a manner that allows for high flexibility and customization, as described herein.

[0151] While specific embodiments of the present disclosure have been outlined above, many alternatives, modifications, and variations will be apparent to those skilled in the art. Accordingly, the embodiments described herein are intended to be illustrative, and not limiting. Various changes may be made without departing from the concept and scope of the present disclosure. While the methods and steps described above indicate certain events occurring in a particular order, those skilled in the art, having the benefit of this disclosure, will understand that the order of certain steps can be changed and that such changes are included in variations of the present disclosure. Furthermore, certain steps may be performed simultaneously in a parallel process, where possible, or sequentially, as described above. While embodiments have been specifically shown and described, it will be understood that various changes in form and detail are possible.< / eels> < / xps>

Claims

1. 1. An electrochemical cell comprising: a cathode comprising lithium; an anode comprising an anode material having a plurality of voids; a solid electrolyte disposed between the cathode and the anode; The anode is configured such that lithium metal is deposited in the plurality of voids during charging of the electrochemical cell.

2. 10. The electrochemical cell of claim 1, The electrochemical cell, wherein each of the plurality of voids has a cross-sectional dimension in the range of about 5 nm to about 100 μm.

3. 3. The electrochemical cell according to claim 1 or claim 2, the anode material comprises a plurality of particles; The electrochemical cell, wherein each of the plurality of particles has a diameter in the range of about 1 μm to about 100 μm.

4. The electrochemical cell according to any one of claims 1 to 3, The electrochemical cell, wherein the anode material is configured such that the plurality of voids undergoes a volumetric change of less than 100% during charging and discharging of the electrochemical cell.

5. The electrochemical cell according to any one of claims 1 to 4, an electrochemical cell, wherein the anode material comprises at least one of Si, a Si alloy, a Si-carbon composite, a Si alloy-carbon composite, Mg metal, a binary Mg alloy, a ternary Mg alloy, a binary Mg alloy-carbon composite optionally containing a solid electrolyte and / or a polymeric binder, and a ternary Mg alloy-carbon composite optionally containing a solid electrolyte and / or a polymeric binder.

6. The electrochemical cell according to any one of claims 1 to 5, An electrochemical cell wherein the anode material is under mechanical constraint, the anode material being constraint-sensitive.

7. 7. The electrochemical cell of claim 6, a surface layer on the anode, the surface layer being formed by reaction of the anode material with lithium ions; The electrochemical cell, wherein the mechanical restraint results in a thickness of the surface layer of less than 500 nm.

8. 8. The electrochemical cell of claim 6 or claim 7, The electrochemical cell, wherein the mechanical constraint results from at least one of the anode material having a local effective elastic modulus of about 0.3 GPa or greater, or an external pressure in the range of about 0.05 MPa to about 50 MPa exerted on the electrochemical cell.

9. 1. An electrochemical cell comprising: a cathode comprising lithium; an anode comprising an anode material; a solid electrolyte disposed between the cathode and the anode; the anode material having a local effective elastic modulus of at least about 0.3 GPa such that the anode is under mechanical constraint; An electrochemical cell wherein the anode is configured such that lithium metal is deposited on the anode material during charging of the electrochemical cell.

10. 10. The electrochemical cell of claim 9, An electrochemical cell, wherein the anode material comprises at least one of Si, a Si-carbon composite, Mg metal, a binary Mg alloy, or a ternary Mg alloy.

11. 11. The electrochemical cell of claim 9 or claim 10, The anode material is K ｃｒｉｔ The capacity (COK) is greater than 500 mAh / g / GPa, and ｃｒｉｔ x V) (COK x V) is greater than 600 mWh / g / GPa.

12. 12. The electrochemical cell of claim 11, an electrochemical cell, wherein the anode material comprises at least one of Si, a Si alloy, a Si-carbon composite, a Si alloy-carbon composite, Mg metal, a binary Mg alloy, a ternary Mg alloy, a binary Mg alloy-carbon composite optionally containing a solid electrolyte and / or a polymeric binder, and a ternary Mg alloy carbon composite optionally containing a solid electrolyte and / or a polymeric binder.

13. 13. The electrochemical cell of claim 12, The anode material is LiMg ５ , Mg ７ Al １ , Mg １４９ Li １ , Mg １４９ Ba １ , Mg １４９ Ca １ , Mg １４９ S １ , Mg １４９ Ag １ , Mg ７ B １ , MgPb ２～５ , MgTe １～２ , MgHg ３～５ , MgAl １～２ , MgH １～３ , MgIn ５ , MgGe ２～５ , MgSi １～３ , MgSb ０．５～３ , MgSn １～５ , MgGa １～５ , Na １ Mg １４ B １ , an electrochemical cell comprising at least one of:

14. 10. The electrochemical cell of claim 9, The anode material is K ｃｒｉｔ The capacity (COK) is greater than 500 mAh / g / GPa, and ｃｒｉｔ x V) (COK x V) is 500 to 600 mWh / g / GPa.

15. 10. The electrochemical cell of claim 9, The anode material is K ｃｒｉｔ Electrochemical cells comprising materials having a capacity over 100 kJ / g / GPa (COK) greater than 500 mAh / g / GPa and a COK x V between 300 and 500 mWh / g / GPa.

16. 1. An electrochemical cell comprising: a cathode comprising lithium; an anode comprising an anode material, the anode material comprising a plurality of particles; a solid electrolyte disposed between the cathode and the anode; the anode is configured such that upon an initial charge of the electrochemical cell, lithium metal is deposited on the anode, and the deposition of the lithium metal reduces the volume of the plurality of particles to less than 300% of the original volume of the plurality of particles.

17. 17. The electrochemical cell of claim 16, an electrochemical cell, wherein the anode material comprises at least one of Si, a Si alloy, a Si-carbon composite, a Si alloy-carbon composite, Mg metal, a binary Mg alloy, a ternary Mg alloy, a binary Mg alloy-carbon composite optionally containing a solid electrolyte and / or a polymeric binder, and a ternary Mg alloy carbon composite optionally containing a solid electrolyte and / or a polymeric binder.

18. 18. The electrochemical cell of claim 16 or claim 17, The electrochemical cell, wherein each of the plurality of particles has a diameter in the range of about 1 μm to about 100 μm.

19. 19. The electrochemical cell according to any one of claims 1 to 18, the anode material has a plurality of voids; The electrochemical cell, wherein the anode material is configured such that the volume of the plurality of voids changes by less than 50% during charging and discharging of the electrochemical cell.

20. 20. The electrochemical cell according to claim 1, the anode material is mechanically constrained; the mechanical restraint causes the lithium metal to deposit as a surface layer on the anode; The electrochemical cell, wherein the thickness of the surface layer is less than 500 nm.

21. 1. A method for discharging electrical energy, comprising: a) providing a battery, said battery comprising: i) a cathode comprising Li; ii) an anode comprising an anode material having a plurality of voids; and iii) providing a solid electrolyte disposed between the anode and the cathode; and b) providing electrical energy to the battery to ＋ transferring ions from the cathode to the anode and depositing them as Li metal in the plurality of voids during charging. A method comprising:

22. 22. The method of claim 21, wherein a load is electrically connected between the anode and the cathode such that, during discharge, Li metal in the plurality of voids is oxidized and transported to the cathode, where Li ＋ The method further comprising the step of depositing as ions.

23. 22. The method of claim 21, wherein the Li ＋ A method in which a portion of the ions react with the surface of the anode material to form a surface layer with the anode material.

24. 24. The method of claim 23, wherein the surface layer has a thickness of less than 500 nm.

25. 24. The method of claim 23, wherein the anode material comprises microscale and / or nanoscale particles and the thickness of the surface layer is less than 500 nm.

26. 22. The method of claim 21, wherein the volume of the particles after the first charge is less than 300% of the original particle volume.

27. 22. The method of claim 21, wherein the average particle size after 10 charge-discharge cycles is greater than 70% of the original particle size.

28. 22. The method of claim 21, wherein the anode material does not crack or swell during charging or discharging.

29. 24. The method of claim 23, wherein a portion of the anode material below the surface layer does not undergo lithiation.

30. 22. The method of claim 21, wherein the battery is under mechanical restraint.

31. 31. The method of claim 30, wherein the mechanical restraint is provided by an external pressure of 0.05 to 50 MPa.

32. 31. The method of claim 30, wherein the mechanical constraint is a local effective elastic modulus (K ｅｆｆ ) is at least 0.3 GPa.

33. 22. The method of claim 21, wherein the anode material comprises Si.

34. 34. The method of claim 33, wherein the anode material comprises a Si-graphite composite material formed from nanoscale and / or microscale Si and graphite particles.

35. 22. The method of claim 21, wherein at least 10% of the stored electrical energy is stored as lithium metal.

36. A solid-state battery, a) a cathode comprising Li; b) an anode comprising an anode material having a plurality of voids; c) a solid electrolyte disposed between the anode and the cathode; The anode material is under mechanical constraint and during charging of the solid-state battery, Li from the cathode is ＋ ions precipitate as Li metal in the plurality of voids.

37. 37. The battery of claim 36, wherein the mechanical constraint limits lithiation of the anode material to a surface layer of less than 500 nm.

38. 37. The battery of claim 36, wherein the mechanical restraint is provided by an external pressure of 0.05 to 50 MPa.

39. 37. The battery of claim 36, wherein the mechanical constraint is greater than the local effective elastic modulus (K ｅｆｆ ) is at least 0.3 GPa.

40. 37. The battery of claim 36, wherein the anode material is K ｃｒｉｔ The capacity (COK) is greater than 500 mAh / g / GPa, and ｃｒｉｔ x V) (COK x V) is greater than 600 mWh / g / GPa.

41. 37. The battery of claim 36, wherein the anode material comprises Mg metal or a binary or ternary alloy of Mg.

42. 42. The battery of claim 41, wherein the anode material is LiMg ５ , Mg ７ Al １ , Mg １４９ Li １ , Mg １４９ Ba １ , Mg １４９ Ca １ , Mg １４９ S １ , Mg １４９ Ag １ , Mg ７ B １ , Na １ Mg １４ B １ , or MgPb ２～５ , MgTe １～２ , MgHg ３～５ , MgAl １～２ , MgH １～３ , MgIn ５ , MgGe ２～５ , MgSi １～３ , MgSb ０．５～３ , MgSn １～５ , MgGa １～５ A battery comprising at least one of:

43. 37. The battery of claim 36, wherein the anode material is K ｃｒｉｔ The capacity (COK) is greater than 500 mAh / g / GPa, and ｃｒｉｔ x V) (COK x V) is in the range of 500 to 600 mWh / g / GPa.

44. 37. The battery of claim 36, The anode material has the formula Mg ｘ Si １－ｘ , Mg ３ Al, Li ｘ Mg １－ｘ , Mg ４ Al １ Si ４ , Li ｘ Mg ｙ Si １－ｘ－ｙ wherein 1≧x≧0 and 0<y<1; or the formula Mg ｘ M' ｙ M" １－ｘ－ｙ metal-doped Mg, wherein x>0.8 and y<0.2, and M′ and M″ are metals; or formula (MgO) ｘ A ｙ B ｚ O １－ｘ－ｙ－ｚ 1. A battery comprising doped MgO or a binary Mg compound of the formula: wherein x>0.9 and y<0.1 and z<0.1, and A and B are elements other than Mg and O.

45. 37. The battery of claim 36, wherein the anode material is K ｃｒｉｔ 1. A battery comprising a material having a capacity (COK) greater than 500 mAh / g / GPa and a COK×V in the range of 300-500 mWh / g / GPa.

46. 37. The battery of claim 36, wherein the anode material comprises: Formula (MgO) ｘ A ｙ B ｚ O １－ｘ－ｙ－ｚ doped MgO of the formula: wherein x>0.7 and y<0.3 and z<0.3, and A and B are elements other than Mg or O; Formula Mg ｘ Si １－ｘ The compound Formula Mg ｘ Si ｙ O １－ｘ－ｙ or a compound of Formula Mg ｘ M' ｙ M" １－ｘ－ｙ Mg metal alloy of the formula: wherein x>0.8 and y<0.2, and M' and M" are metals. Including batteries.

47. 37. The battery of claim 36, wherein the anode material comprises Si.

48. 48. The battery of claim 47, wherein the anode material comprises a Si-graphite composite material formed from nanoscale and / or microscale Si and graphite.

49. 37. The battery of claim 36, wherein the anode material is coated on a Li foil on a current collector.

50. 37. The battery of claim 36, wherein the anode material undergoes a self-limiting reaction with lithium under mechanical restraint to form a surface layer.

51. 51. The battery of claim 50, wherein the surface layer has a thickness of less than 500 nm.

52. 51. The battery of claim 50, the anode material comprises microscale and / or nanoscale particles; The battery, wherein the thickness of the surface layer is less than 500 nm.

53. 37. The battery of claim 36, A battery in which the particle volume after the first charge is less than 300% of the original particle volume.

54. 37. The battery of claim 36, A battery in which the average particle size after 10 charge-discharge cycles is greater than 70% of the original particle size.

55. 37. The battery of claim 36, A battery wherein the anode material does not crack or swell during charging or discharging.

56. 37. The battery of claim 36, The battery, wherein each void in the plurality of voids has a cross-sectional dimension in the range of 1 nm to 1000 μm.

57. 37. The battery of claim 36, The battery wherein the anode material comprises particles having a diameter of 1 nm to 100 μm.

58. 37. The battery of claim 36, a battery wherein the anode material has a surface layer or coating that inhibits lithiation.

59. 37. The battery according to claim 36, wherein the current is 0.01 to 200 mA / cm ２ A battery having a current density of

60. 37. The battery according to claim 36, wherein the content of the electrolyte is 0.1 to 200 mg / cm ２ a cathode coating amount of

61. 37. The battery of claim 36, having a capacity of 1 to 20 mAh / cm ２ A battery having an areal capacity of

62. 37. The battery of claim 36, A battery capable of 1,000 to 20,000 charge / discharge cycles at 1 to 60 minutes or 0.1 to 30C rates.

63. 37. The battery of claim 36, having a pouch-type, prismatic-type, or cylindrical cell shape.

64. 37. The battery of claim 36, further comprising a protective layer and / or multiple layers of solid electrolyte.

65. 65. The battery of claim 64, The battery, wherein the protective layer and / or multilayer is deposited, cast, or transferred onto the cathode, the anode, or a substrate in a layer-by-layer process.

66. 65. The battery of claim 64, wherein the multilayer comprises n layers of solid electrolyte, n > 2.

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