Batteries with solid electrolyte multilayers

Abstract

The present invention provides a solid-state secondary battery having multiple layers of solid electrolyte. The solid-state secondary battery disclosed herein is advantageous because it provides improved battery cycling performance combined with excellent power and energy density.

Description

[Technical Field]

[0001] This invention is intended for the field of solid-state secondary batteries. [Background technology]

[0002] In solid-state batteries with electrodes containing lithium or sodium metal, dendrite formation (e.g., Li or Na dendrites) is a major cause of battery failure and shortened battery life. Dendrite formation reduces battery capacity and ultimately leads to complete failure due to short circuits caused by dendrites meeting each other or with the counter electrode. Attempts to solve this problem have focused on improving the stability of the solid electrolyte and modifying the interface between the electrode and the solid electrolyte (e.g., adding a barrier layer). Such improvements have been met with limited success.

[0003] Therefore, improved solid-state batteries incorporating solid electrolytes are needed. [Overview of the project]

[0004] The present invention provides a solid-state secondary battery having a multilayer solid electrolyte. The solid-state secondary battery disclosed herein is advantageous because it exhibits improved battery cycle performance combined with excellent power density and energy density.

[0005] In one embodiment, the present invention provides a secondary battery comprising (a) an anode and a cathode, and (b) a solid electrolyte multilayer disposed between the anode and cathode, comprising (i) a first solid electrolyte and (ii) a second solid electrolyte. The second solid electrolyte is separated from the anode by the first solid electrolyte. That is, the multilayer comprises at least two layers, for example, at least three layers.

[0006] In certain embodiments, the second solid electrolyte is less stable with respect to the anode metal (e.g., lithium or sodium) than the first solid electrolyte. In some embodiments, the first solid electrolyte has a first decomposition energy (E hull), the first local effective modulus (for example, in the case of a solid-state battery), and the first critical modulus (K * ) has a first critical modulus lower than the first local effective modulus, thereby causing the first decomposition energy to have a positive value. In some embodiments, the second solid electrolyte has a second decomposition energy (E hull ), the second local effective modulus (for example, in the case of a solid-state battery), and the second critical modulus (K * The second decomposition energy is negative compared to the first decomposition energy, and the local decomposition of the second solid electrolyte increases the second local effective modulus, causing it to locally exceed the second critical modulus.

[0007] In some embodiments, the solid electrolyte multilayer is subjected to mechanical shrinkage. In certain embodiments, the mechanical shrinkage generates local stresses in the multilayer of about 0.1 GPa to about 250 GPa. In certain embodiments, the battery is subjected to an external pressure of about 0.1 MPa to about 1000 MPa. The pressure may or may be periodically changed during the battery cycle by, for example, a passive response system (e.g., a spring (e.g., having a spring constant determined to apply a specific pressure)) or an active response system (e.g., configured to adjust the pressure in real time (e.g., monitored by a pressure sensor)). In some embodiments, the mechanical shrinkage is caused by warm isostatic pressing (WIP), cold isostatic pressing (CIP), hydraulic cold pressing, or external pressure applied to the battery during assembly (e.g., cold and / or warm isostatic pressing, and / or anisotropic pressing, and / or forming pressure by external pressure of about 0.1 MPa to 1000 MPa and rolling at a temperature of about 25°C to 1000°C).

[0008] In some embodiments, the porosity of the anode, cathode, and / or multilayer is 0% to 25%. In some embodiments, external pressure is provided by mechanical stress from the battery case or pouch cell and / or by a hydraulic press made by a gel or liquid sealed in the environment within the case, cell, or press. In some embodiments, the battery case or pouch cell includes steel, aluminum, polymer, a spring system, an electronic pressurization system with a pressure sensor, and / or a combination thereof.

[0009] In some embodiments, the anode comprises Li or Na metal. In some embodiments, the anode is, for example, silicon, silicon dioxide, Li4Ti5O 12 Li3V2O5, carbon (e.g., amorphous carbon, carbon nanotubes, graphene, carbon nanofibers, fullerenes (e.g., C 60 The anode further comprises a protective layer containing fullerene, hard carbon, or graphite, Au, Ag, Sn, SnO2, or a combination thereof. The particle size of the protective material can be 1 nm to 100 μm. The protective layer can be mixed with Li metal and / or a polymer with a thickness of 0 μm to 500 μm. In some embodiments, the anode further comprises Li, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y, Zr, Nb, Mo, Ag, Cd, In, Sn, Sb, Bi, Cs, Te, or a combination thereof (e.g., as an alloy). In some embodiments, the anode contains Li, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y, Zr, Nb, Mo, Ag, Cd, In, Sn, Sb, Bi, Cs, Te, or combinations thereof in the protective layer. Lithium metal may also be mixed or alloyed with these elements to form a single layer. Mixtures of Li and other metals can form two-dimensional parallel layers or three-dimensional structures. The amount of Li or Na supported in the anode is 0 to 50 mg / cm³. 2It can be set as such. The thickness of Li or Na at the anode can be 0 μm to 1000 μm. 0 μm means that a battery can be made with an anode-free design and that the Li or Na source is the cathode material.

[0010] In certain embodiments, the cathode is 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 0.2 O2 (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-s) O2 (0 ≤ x, y, z, s ≤ 1), Li 1+z Ni x Mn y Co s W (1-x-y-z-s) 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, or LiCo 0.5 Mn 1.5It contains O4. The cathode can be coated with 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, polymer, or carbon. In some embodiments, the cathode contains polymer and / or carbon black, or the first solid electrolyte and / or the second solid electrolyte contains polymer.

[0011] In certain embodiments, the first solid electrolyte is selected from Table 1, or the solid electrolytes in Table 1 where one or more elements are substituted with homologous elements.

Table 1

[0012] The second solid electrolyte may be selected from Table 2, or the solid electrolytes in Table 1 where one or more elements are substituted with homologous elements.

Table 2

[0013] Here, unless otherwise specified, 0 ≦ a, b, d, p, q, w, x, y, z, u, v, w ≦ 1, C is the critical doping amount beyond which the stability of the electrolyte decreases, C can be varied with respect to u, v, w, and 0 ≦ C ≦ 1.

[0014] In some embodiments, the anode contains Na metal. In some embodiments, the first solid electrolyte is selected from Table 3, or from the solid electrolytes of Table 3 in which one or more elements are substituted with homogeneous elements. [Table 3]

[0015] And / or, the second electrolyte is selected from Table 4, or from the solid electrolytes of Table 4 in which one or more elements are substituted with homogeneous elements. [Table 4]

[0016] Here, unless otherwise specified, 0 ≤ p, q, w, x, y, z, u, v, w ≤ 1, C is the critical doping amount beyond which electrolyte stability decreases, C can be varied with respect to u, v, and w, and 0 ≤ C ≤ 1.

[0017] In some embodiments, the anode contains Na, and the anode is graphite, silicon, silicon dioxide, Na4Ti5O 12The protective layer further comprises Na3V2O5, Au, Ag, Sn, SnO2, or carbon, or a combination thereof, and / or the protective layer comprises Na metal or a mixture of Na metal and a polymer with a thickness of 0 μm to 500 μm. The particle size of the protective material can be 1 nm to 100 μm, for example about 1 to 100 nm (for example 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, or 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, or 100nm), for example, approximately 100-1000nm (for example, approximately 100-110nm, 100-125nm, 100-200nm, 200-300nm, 250-500nm, 300-400nm, 400-500nm, 500-600nm, 500-750nm, 600-700nm, 700-800nm, 750-1000nm, 800-900nm, or 900-1000nm, for example, approximately 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 80 0nm, 900nm, or 1000nm), for example, about 1-10μm (for example, about 1-2μm, 1-5nm, 2-3μm, 3-4μm, 4-5μm, 5-10μm, 5-6μm, 6-7μm, 7-8μm, 8-9μm, or 9-10μm, for example, about 1μm, 2μm, 3μm, 4μm, 5μm, 6μm, 7μm, 8μm, 9μm, or 10μm), or for example, about 10-100μm (for example, about 10-20μm, 10-25μm, 10-50μm, 20-30μm, 25-50μm, 30 These are approximately 40μm, 40-50μm, 50-60μm, 50-75μm, 60-70μm, 75-100μm, 70-80μm, 80-90μm, or 90-100μm (for example, about 10μm, 12μm, 13μm, 14μm, 15μm, 16μm, 17μm, 18μm, 19μm, 20μm, 21μm, 22μm, 23μm, 24μm, 25μm, 26μm, 27μm, 28μm, 29μm, 30μm, 40μm, 50μm, 60μm, 70μm, 80μm, 90μm, or 100μm).In some embodiments, the carbon is hard carbon, amorphous carbon, carbon nanotubes, graphene, carbon nanofibers, or fullerenes (e.g., C. 60 ) is included. In some embodiments, the sodium metal in the protective layer is mixed or alloyed with Li, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y, Zr, Nb, Mo, Ag, Cd, In, Sn, Sb, Bi, Cs, Te or combinations thereof. In some embodiments, the cathode is Na w MnO2, Na w CoO2, Na w NiO2, Na w TiO2, Na w VO2, Na w CrO2, Na w FeO2, Na w (Mn x Fe y Co z Ni 1-x-y-z )O2(0≦x,y,z≦1), Na w (M)PO4, Na w (M)P2O7, Na w (M)O2, Na x M y (XO4) z includes. Here, M is a metal element or a combination of metal elements, for example a transition metal element, X is B, S, P, Si, As, Mo, W, or combinations thereof, 0≦x,y,z≦3, 0<w≦1, and O can be partially substituted by F, Cl, Br or I. In some embodiments, the cathode is NaNbO3, NaTaO3, Na2ZrO3, NaNb x Ta 1-x O3(0≦x≦1), yNa2ZrO3-(1-y)NaNb x Ta 1-x O3(0≦x,y≦1), Al2O3, TiO2, ZrO2, AlF3, MgF2, SiO2, ZnS, ZnO, Na4SiO4, Na3PO4, Na3InCl6, Na 1+x Al x Ti 2-xIt includes a coating of (PO4)3 (0 < x < 2), NaMn2O4, NaInO2-NaI, Na6PS5Cl, NaAlO2, or carbon.

[0018] In some embodiments, the battery can be cycled at a current density of 0.001 mA / cm 2 ~100 mA / cm 2 . In some embodiments, the battery, for example, at a cathode loading of 2 mg / cm 2 , after at least 10,000 charge-discharge cycles from 20C rate to 100C rate, has an initial capacity higher than 80 mAh / g and a current density higher than 8 mA / cm 2 and retains at least 80% of its capacity. In certain embodiments, the solid electrolyte multilayer film includes at least two different first solid electrolytes. In some embodiments, the battery cathode material has an output density of at least 10 kW / kg. In some embodiments, the battery cathode material has an energy density of at least 600 Wh / kg.

[0019] In some embodiments, the first solid electrolyte and / or the second solid electrolyte has a core-shell particle structure. In certain embodiments, the core-shell particles have different core conductivities and shell conductivities. In some embodiments, the core conductivity is higher than the shell conductivity. In some embodiments, the core-shell particles have a core composition and a shell composition, and the core composition is different from the shell composition, for example, having different non-stoichiometric weightings of Li or Na. The different core and shell compositions can provide different properties, such as K * , E hull , conductivity, etc., for example, the shell composition may have a smaller K * or a more negative E hull than the core, or, for example, the core conductivity may be higher than the shell conductivity, or any combination thereof.

[0020] In some embodiments, the first solid electrolyte includes a material selected from Table 5 or Table 6, or a material having a formula for a material selected from Table 5 or Table 6, wherein one or more elements are substituted with elements of the same group. [Table 5] [Table 6]

[0021] Furthermore, the second solid electrolyte includes a material selected from Table 7 or Table 8, or a material selected from Table 5 or Table 6, having a formula in which one or more elements are substituted with elements of the same group. [Table 7] JPEG2023548332000010.jpg17137 [Table 8]

[0022] In Tables 5-8, '_{#}' and '_{#±x,y,z,w,l, or m}' represent the non-stoichiometric weighting of the element immediately to the left of '_{#}' or '_{#±x,y,z,w,l, or m}' in the chemical formula of the material, where # can be in the range of #±n. Here, 0≦n≦0.5 and 0≦x,y,z,w,l,m≦#, where # can be ±n and 0≦n≦0.5.

[0023] In some embodiments, the first solid electrolyte includes a material selected from Table 9 or Table 10, or a material having a formula for a material selected from Table 9 or Table 10, wherein one or more elements are substituted with elements of the same group. [Table 9] [Table 10]

[0024] Furthermore, the second solid electrolyte includes a material selected from Table 11 or Table 12, or a material having a formula for a material selected from Table 11 or Table 12, wherein one or more elements are substituted with elements of the same group. [Table 11] [Table 12]

[0025] In Tables 9-12, '_{#}' and '_{#±x,y,z,w,l, or m}' represent the non-stoichiometric weighting of the element immediately to the left of '_{#}' or '_{#±x,y,z,w,l, or m}' in the chemical formula of the material, where # can be in the range of #±n. Here, 0≦n≦0.5 and 0≦x,y,z,w,l,m≦#, where # can be ±n and 0≦n≦0.5.

[0026] In certain embodiments, the first or second solid electrolyte has a core-shell particle structure, and the materials in Table 6, Table 8, Table 10, or Table 12 are present in the shell.

[0027] In some embodiments, the cathode is mixed with a solid electrolyte containing a material selected from Table 13 or Table 14. [Table 13] JPEG2023548332000017.jpg57133 [Table 14] JPEG2023548332000019.jpg57151

[0028] In Tables 13-14, '_{#}' and '_{#±x,y,z,w,l, or m}' represent the non-stoichiometric weighting of the element immediately to the left of '_{#}' or '_{#±x,y,z,w,l, or m}' in the chemical formula of the material, where # can be in the range of #±n. Here, 0≦n≦0.5 and 0≦x,y,z,w,l,m≦#, where # can be ±n and 0≦n≦0.5.

[0029] In certain embodiments, the solid electrolyte mixed with the cathode comprises one of materials 32-40 from Table 13 or one of materials 37-45 from Table 14.

[0030] In some embodiments, the solid electrolyte mixed with the cathode has a core-shell particle structure.

[0031] In another embodiment, the present invention provides an energy storage method comprising the steps of applying voltage to an anode and a cathode and charging any secondary battery as disclosed herein. In another embodiment, the present invention provides an energy supply method comprising the steps of connecting a load to an anode and a cathode and discharging any secondary battery as disclosed herein.

[0032] definition

[0033] As used herein, the term "approximately" means within ±10% of the value mentioned.

[0034] As used herein with respect to solid electrolytes, the term "stability" refers to the stability of the material against decomposition via reaction with a metal, such as lithium or sodium, at the anode. The stability of solid electrolytes can be determined experimentally. [Brief explanation of the drawing]

[0035] [Figure 1A-1D]Figures 1A to 1D show the battery cycle performance of symmetrical batteries. Figure 1A shows the performance of a symmetrical battery using Li10Ge1P2S12 (LGPS) as the electrolyte, and Figure 1B shows a symmetrical battery using Li5.5PS4.5Cl1.5 (LPSCl) as the electrolyte. Pure lithium metal was used as the electrode, and each half-cycle was performed at 0.25 mA / cm2 for 1 hour at room temperature. For a symmetrical battery with a capacity of 0.25 mAh / cm2, using LPSCl-LGPS-LPSCl as the electrolyte and graphite-coated lithium (Li / G) as the electrode, Figure 1C shows the long cycle (0.25 mA / cm2 at room temperature), and Figure 1D shows the high-rate test (20 mA / cm2, 55°C).

[0036] [Figure 2A-2H] Figures 2A to 2H show chemical probing and SEM images of the solid electrolyte after cycling. Figure 2A shows an optical image of the cross-section of Li / G-LPSCl-LGPS-LPSCl-G / Li after 300 hours of cycling at room temperature and 0.25 mA / cm2. Figure 2B shows the XRD broadening analysis of LGPS after testing of the symmetric battery. The dots represent the broadening of different Bragg peaks after 300 hours of cycling at 0.25 mA / cm2, the angular dependence of strain broadening is shown by the solid line, and the y-intercept represents the degree of size broadening. Figures 2C to 2D show the XPS measurement results of S2p (Figure 2C) and Ge2p (Figure 2D) in the black region after 30 cycles at 55°C and 20 mA / cm2. Figures 2E to 2H show SEM images of different regions on the transition zone of LPSCl (Figure 2E), LGPS (Figure 2F), and LPSCl-LGPS (Figure 2G). The SEM images in Figures 2E, 2F, and 2G were taken from regions (1), (2), and (3), respectively, as shown in Figure 2H.

[0037] [Figure 3A-3I]Figures 3A to 3I show the cycle performance of the multilayer structure. Figure 3A shows the charge-discharge characteristics, Figure 3B shows the capacity retention rate, and Figure 3C shows the Coulomb inefficiency of a battery cycled at 1.5C with cutoff voltages set to 4.2V and 2.5V at 55°C. Figure 3D shows the high-rate discharge characteristics of a graphite-coated Li-LiNi0.8Mn0.1Co0.1O2 (Li / G-NMC811) battery using Li5.5PS4.5Cl1.5Li9.54Si1.74(P0.9Sb0.1)1.44S11.7Cl0.3(LPSCl-LSPS-LPSCl) as the electrolyte. This battery was charged and discharged at the same rate at a temperature of 55°C in an oven with 8% humidity. Figure 3E shows the capacity retention rate, and Figure 3F shows the Coulomb inefficiency of a battery cycled at 15C with cutoff voltages set to 4.35V and 2V at 55°C. Figure 3G shows the charge-discharge characteristics of a battery cycled for more than 10,000 cycles at 20C with voltages set in the range of 2 to 4.35V at 55°C. Figure 3H shows the capacity retention rate, and Figure 3I shows the Coulomb inefficiency of a battery cycled at 20C with cutoff voltages set to 4.35V and 2V at 55°C. All batteries in Figures 3A to 3I use LPSCl-LSPS-LPSCl as the electrolyte, and the NMC811 is not covered with other materials.

[0038] [Figure 4A] Figure 4A shows the battery cycle performance of Li / G-LPSCl-central electrolyte-LPSCl-NMC811 at room temperature and 1C. The central electrolyte includes Li9.54Si1.74(P0.9Sb0.1)1.44S11.7Cl0.3(LSP(Sb)S), Li10Ge1P2S12(LGPS), Li9.54Si1.74P1.44S11.7Cl0.3(LSPS), and Li3YCl6(LYC316). The green curve represents a battery with the structure Li / G-LYC316-LGPS-LPSCl-NMC811, where LYC316 can function as a lithium anode-stable electrolyte.

[0039] [Figure 4B]Figure 4B shows the Ragone plot of the battery in this study compared to previously reported batteries. The reported cycle count and capacity retention rates are labeled in the plot, and the energy density and power density in the figure are calculated based on the mass of the cathode active material.

[0040] [Figure 5] Figure 5 shows the electron conductivity from DC polarization for different electrolytes (Li10Ge1P2S12 (LGPS) and Li5.5PS4.5Cl1.5 (LPSCl)). The electron conductivity was obtained using Ohm's law and the steady-state current value at the endpoint of the curve.

[0041] [Figure 6A-6C] Figures 6A to 6C show SEM images of LPSCl, LGPS, and LSPS particles.

[0042] [Figure 7A-7C] Figures 7A to 7C show an asymmetric battery with Li / G as the anode (lithium capacitive load = 3 mAh / cm²), a stainless steel (SS) current collector as the cathode, and a solid electrolyte as the separator. Lithium was deposited on the surface of the solid electrolyte at 0.25 mA / cm². Different electrochemical behaviors and surface information were observed. In Figure 7A, a short circuit occurred immediately after lithium was deposited on the surface of a pure LPSCl pellet. A metallic color (silver or gray) was observed in the optical image, and small cracks were observed in the SEM image. In Figure 7B, after lithium was deposited on the surface of a pure LGPS pellet, the voltage rose rapidly within a few hours. A desolate color (dark black) was observed in the optical image, and no cracks were observed in the SEM image. In Figure 7C, after sufficient lithium had been deposited on the surface of the LPSCl pellet from which the LGPS had separated, the voltage gradually rose and reached the cutoff voltage. A widespread metallic color (silver or gray) was observed in the optical image, and cracks were observed in the SEM image.

[0043] [Figures 8A-8C]Figures 8A to 8C show the XPS data of the black region (shown in Figure 7B) on the LGPS surface after lithium discharge, along with chemical information for S (Figure 8A), P (Figure 8B), and Ge (Figure 8C).

[0044] [Figures 8D-8F] Figures 8D to 8F show the XPS data of the silver region (shown in Figure 8C) on the LPSCl surface after lithium discharge, along with chemical information for S (Figure 8D), P (Figure 8E), and Cl (Figure 8F).

[0045] [Figure 9A-9B] Figures 9A and 9B show the voltage cycle over time for two symmetrical batteries. Figure 9A shows a symmetrical battery having Li9.54Si1.74(P0.9Sb0.1)1.44S11.7Cl0.3(LSPS) as the electrolyte and graphite-coated lithium (Li / G) as the electrode. Figure 9B shows a symmetrical battery with a configuration of LPSCl-LSPS-LPSCl as the electrolyte and graphite-coated lithium as the electrode, having combinations of Li9.54Si1.74(P0.9Sb0.1)1.44S11.7Cl0.3(LSPS) and Li5.5PS4.5Cl1.5(LPSCl).

[0046] [Figure 10A] Figure 10A shows a high-rate (10 mA / cm²) cycle of a Li10Ge1P2S12 (LGPS) symmetrical battery with Li / G electrodes. The overvoltage starts at 0.6V and rapidly rises to over 1.5V in the first few cycles.

[0047] [Figure 10B] Figure 10B shows a high-rate (15 mA / cm²) cycle of an LGPS symmetric battery with Li / G electrodes. In the first cycle, the overvoltage rose to over 5V.

[0048] [Figure 10C]Figure 10C shows a symmetrical battery using LPSCl as the electrolyte and Li / G as the electrodes, cycled at 0.25 mA / cm². A short circuit occurs during the first two cycles.

[0049] [Figure 11A-11E] Figures 11A to 11E show optical images of the active layer cross-section of the battery. Figure 11A shows an optical image of the Li / G-LPSCl-LGPSCl-G / Li cross-section after 300 hours of cycling at 0.25 mA / cm2 at room temperature, showing another region that has not been resolved. Figure 11B shows an image obtained by post-processing Figure 11A with only black and white colors set. Figure 11C shows an optical image of the same pellet cross-section magnified from Figure 11A. Figure 11D shows an optical image of the Li / G-LPSCl-LGPS-LPSCl-G / Li cross-section after 30 cycles at 20 mA / cm2 at 55°C. Figure 11E shows an image obtained by post-processing Figure 11D with only black and white colors set.

[0050] [Figure 12A-12C] Figures 12A to 12C show XPS measurements of S2p (Figure 12A), P2p (Figure 12), and Ge2p (Figure 12) in the black region of the cross-section of a sandwich pellet after a 300-hour battery cycle at 0.25 mA / cm2.

[0051] [Figures 12D-12F] Figures 12D to 12F show the XPS measurements of S2p (Figure 12D), P2p (Figure 12E), and Ge2p (Figure 12F) in the black region of the cross-section of the sandwich pellet after 30 battery cycles at 20 mA / cm2.

[0052] [Figure 13] Figure 13 shows SEM images of LPSCl, LGPS, and their transition regions before (first row) and after (second row) cycling of the solid electrolytes.

[0053] [Figures 14A-14F]Figures 14A to 14F show the cycle performance of half-cells using pure LGPS or LPSCl as the electrolyte. Figure 14A shows the initial charge-discharge characteristics of a Li-LiCoO2 (Li-LCO) battery using Li5.5PS4.5Cl1.5 (LPSCl) as the electrolyte. Figure 14B shows the initial charge-discharge characteristics when Li10Ge1P2S12 (LGPS) is used as the electrolyte. For LPSCl and LGPS, uncoated LCO and LCO coated with LiNbO3 are applied, respectively. Figures 14C to 14F show the initial charge-discharge characteristics of a graphite-coated Li-LiNi0.8Mn0.1Co0.1O2 (Li / G-NMC811) battery using LPSCl as the electrolyte at (Figure 14C) 0.3C and (Figure 14D) 0.5C, along with the cycle performance at (Figure 14E) 0.3C and (Figure 14F) 0.5C. The NMC811 was not coated with any other materials. In these tests, 1C = 0.43 mA / cm². Current densities in the range of 0.21 mA / cm² to 215 mA / cm², and 1C = 0.43 to 0.8 mA / cm² were also tested. All batteries were tested at room temperature. The composition and materials of the batteries used are summarized in Table 4.

[0054] [Figure 15] Figure 15 shows the cycle of a Li-LCO battery using LPSCl as the electrolyte. The LCO is not coated with any other material.

[0055] [Figures 16A-16F]Figures 16A-16F show the cycle performance of solid electrolyte batteries. Figure 16A shows the high-rate discharge characteristics of a Li-LiNi0.8Mn0.1Co0.1O2 (Li / G-NMC811) battery coated with graphite, using Li5.5PS4.5Cl1.5, LPSCl, Li9.54Si1.74(P0.9Sb0.1)1.44S11.7Cl0.3, LSPS, and LPSCl-LSPS-LPSCl as electrolytes. The battery was initially charged at 0.1C and then discharged at a high rate at room temperature. Figures 16B-16C show the cycle performance of the same battery at 5C (Figure 16B) and 10C (Figure 16C), and in the range of 2.5-4.3V, in an environment without humidity control (55°C). The NMC811 is not coated with any other material. Figure 16D shows the cycle performance of solid-state batteries using multilayer electrolytes with different Li / graphite capacity ratios of 10:1, 5:1, and 2.5:1. Figure 16E shows the cycle performance of solid-state batteries using multilayer electrolytes under different operating pressures of 50-75 MPa, 150 MPa, and 250 MPa. Figure 16F shows the cycle performance of a solid-state battery having a thin multilayer film of Li / G-LPSCl(100 μm)-LSPS(50 μm)-LPSCl(50 μm)-NMC811.

[0056] [Figures 17A-17B] Figures 17A and 17B show the procedure and results of the electrolyte decomposition design. Figure 17A is a schematic flowchart of the calculation procedure. Figure 17B shows the optimal composition, decomposition energy Ehull, and critical modulus K* for LPSCl-Br with minimized K* under the fixed Br requirement (right figure). The left figure shows the values ​​for the original LPSCl without doping or K* minimization.

[0057] [Figures 18A-18C]Figures 18A-18C show the compositional characterization of the core-shell structure in LPSCl-Br particles. Figure 18A shows the SEM-EDX intensity ratio characteristics. The inset shows the line profile scanned from the ion-milled particles. Figures 18B and 18C show the XPS quantification of elemental composition at different ion-milling times. Samples were transported with 15 seconds of air exposure (Figure 18B) and (Figure 18C) in a vacuum transport holder, similar to SEM-EDX.

[0058] [Figures 19A-19F] Figures 19A to 19F show the ultra-long-term cycle performance of SSBs using composition-modified LPSCl-X with a reduced shell critical modulus K*. Figures 19A to 19C show the charge-discharge voltage curves of SSBs using (Figure 19A) LPSCl-F, (Figure 19B) LPSCl-Br, and (Figure 19C) LPSCl-I as the central electrolyte layer. Figures 19D to 19F show the corresponding cycle performance of SSBs using (Figure 19D) LPSCl-F, (Figure 19E) LPSCl-Br, and (Figure 19F) LPSCl-I as the central electrolyte layer. All batteries were cycled at 55°C using LPSCl-X as the central layer sandwiched between LPSCl layers, and using a LiNbO3-coated NMC811 (LNO@811) cathode and a Li-graphite composite anode. The battery configurations are shown at the end of Figures 19D, 19E, and 19F, with the numbers in parentheses corresponding to the numbers in Figure 20C. The batteries in Figures 19A, 19B, 19D, and 19E were cycled in an environmental chamber with 8% humidity control, while the batteries in Figures 19C and 19F were cycled under battery test conditions without humidity control.

[0059] [Figures 20A-20C]Figures 20A and 20C illustrate the increased capacity and higher rates of LPSCl-I and / or LGPS multilayer batteries. Figure 20A shows the charge-discharge voltage curves at different rates for an LPSCl-I|LGPS battery with the configuration described in (Figure 20A), ending in (3) for its sequence in Figure 20C. Figure 20B shows the cycle performance of three different battery configurations described in Figure 20B, ending in parenthetical numbers for their sequences in Figure 20C: (1) LGPS battery, (2) LGPS battery with LNO coating 811, and (3) LPSCl-I|LGPS battery. C rates from 0.5C to 20C are labeled in addition to the data points. Figure 20C shows a comparison of the initial discharge capacity (blue and purple bars) and average voltage (orange filled dots and white circles) at high and low rates for batteries with different configurations. The electrolyte in parentheses represents the core layer. All batteries, except for (7), (9), and (10), were tested at 55°C without humidity control. For comparison, two types of liquid electrolyte batteries with different particle sizes of LNO@811 ((11) and (12)) were also tested.

[0060] [Figures 21A-21B] Figures 21A and 21B show two examples to illustrate the calculation of K*: an unstable P2S7 / Li interface (Figure 21A) and a stable LiCl / Li interface (Figure 21B).

[0061] [Figures 22A-22D]Figures 22A to 22D show the optimized compositions of LPSCl-X when fixed X is varied as composition I (Figure 22A) and composition F (Figure 22B). K* and decomposition energy correspond to the optimized compositions of LPSCl-F (Figure 22C) and LPSCl-I (Figure 22D). The elemental compositions labeled with dots on the X or Y axis are relative to the values ​​of the original LPSCl-F and LPSCl-I. LPSCl-F is optimized to be deficient in S and P and rich in Li. In the range where F is deficient, Cl may be rich or deficient. LPSCl-I is optimized to be deficient in S and P and rich in Cl and Li. K* is low in both cases, at approximately 10 GPa, and the decomposition energy can be increased to several tens of meV / atom.

[0062] [Figure 23] Figure 23 shows the XRD and optical photographs of LPSCl and LPSCl-X (X=F, Br, I) powders. The LPSCl and LPSCl-Br samples had a pure phase with the F-43m space group, indicated by the dashed line in the XRD reflection, while LPSCl-F and LPSCl-I contained impurities.

[0063] [Figures 24A-24D] Figures 24A to 24D show SEM images of (Figure 24A) LPSCl, (Figure 24B) LPSCl-F, (Figure 24C) LPSCl-Br, and (Figure 24D) LPSCl-I. The particles have similar sizes ranging from a few μm to 30 μm.

[0064] [Figure 25] Figure 25 shows the XPS of LPSCl and LPSCl-X with a 15-second exposure to air during sample transport. The X-axis represents energy (eV), and the Y-axis represents intensity.

[0065] [Figure 26] Figure 26 shows the XPS of LPSCl and LPSCl-X without air exposure during sample transport. The X-axis represents energy (eV), and the Y-axis represents intensity.

[0066] [Figures 27A-27D]Figures 27A to 27D show the XPS quantification of LPSCl-F transported in air for 15 seconds (Figure 27A) and in a vacuum without air exposure (Figure 27B), and LPSCl-I transported in air for 15 seconds (Figure 27C) and in a vacuum without air exposure (Figure 27D).

[0067] [Figures 28A-28C] Figures 28A–28C show the core-shell structure of LPSCl as characterized by SEM-FIB-EDX and XPS. Figure 28A shows the intensity ratios of Li, P, S, and Cl, and the inset shows SEM images of milled and line-scanned particles. Indices greater than 24 correspond to edge points, where S deficiency and Cl abundance are present. The same S deficiency and Cl abundance observed in the range of point indices from 16 to 23 is also located at the edges of cracks in the particles. XPS quantification with milling shows a shell that is S deficiency and Cl rich, by samples transported in both air (Figure 28B) and vacuum (Figure 28C).

[0068] [Figures 29A-29C] Figures 29A to 29C show the XPS analysis of LGPS particles, machine learning-based optimized composition, optimized K*, and predicted resolution energy. Figure 29A shows XPS quantification of LGPS particles (transported in vacuum) at different depths, showing a surface that is Li-rich and S, Ge, and P-deficient. Figure 29B shows machine learning-based optimized compositions with different allowable compositional change rates (compositional change limits) for each element, aiming for a lower K*. The zero point on the X axis corresponds to the original LGPS. Increasing the allowable compositional change optimizes the LGPS to be Li-rich and S, Ge, and P-deficient, which is the same trend observed in the XPS quantification. Figure 29C shows the optimized K* and the predicted resolution energy for the same optimized composition. 0.915 eV is the baseline for Li 0.49 Cl 0.49 P 0.01 S 0.01 for a DFT 0V resolution energy of 0. A relatively small 30% change in composition can reduce K* to less than 15 GPa, along with a relatively large decomposition energy of -100 meV / atom.

[0069] [Figures 30A-30E] Figures 30A to 30E show the XPS analysis and optical photographs of Li-deposited LPSCl (Figure 30A), LPSCl-F (Figure 30B), LPSCl-Br (Figure 30C), LPSCl-I (Figure 30D), and LGPS (Figure 30E). The samples were transported in a vacuum to avoid exposure to air. The XPS analysis suggests that the decomposition was weakest in Li-deposited LPSCl, with the least decrease in S and limited decrease in P, but the decrease in S was stronger in LPSCl-X and LGPS, and the decrease in P was stronger in LPSCl-F and LPSCl-Br. Therefore, the gray and silver color of (A3) Li-deposited LPSCl is mainly due to the Li metal, while the dark gray of (B3) to (D3) Li-deposited LPSCl-X and the black color of (E3) Li-deposited LGPS are mostly due to decomposition.

[0070] [Figure 31] Figure 31 shows a comparison of the cycle performance of Li-G|LPSCl|LNO@811, Li-G|LPSCl|LPSCl-I|GPS|811, and Li-G|LPSCl|LPSCl-I|LNO@811 batteries after 5 cycles at a rate of 0.5C, followed by 20C cycles. In single-electrolyte layer batteries, the 20C capacity rapidly decreases to less than 30mAh / g after 2500 cycles, while multi-layer electrolyte batteries exhibit more robust cycle performance.

[0071] [Figures 32A-32D] Figures 32A to 32D show the Coulomb inefficiency of the 20C rate cycle of Li-G|LPSCl|LPSCl-F|LPSCl|LNO@811 at large scale (Figure 32A) and small scale (Figure 32B), and the Coulomb inefficiency of the 20C rate cycle of Li-G|LPSCl|LPSCl-Br|LPSCl|LNO@811 at large scale (Figure 32C) and small scale (Figure 32D).

[0072] [Figure 33] Figure 33 shows the low-rate cycles of the Li-G|LPSCl|GPS|811 battery.

[0073] [Figures 34A-34B] Figures 34A and 34B show the voltage curves of the battery in Figure 20 (Figure 34A), and a comparison of the LNO@811 liquid electrolyte battery and the solid Li-G|RPSCl|LGPS|LNO@811 battery at different rates (Figure 34B). Multilayer solid-state batteries exhibit far superior rate performance than liquid electrolyte batteries. The 5C, 10C, and 20C rates of the solid-state batteries already demonstrate higher capacities than the 1C, 5C, and 10C rates of the liquid batteries, respectively.

[0074] [Figures 35A-35D] Figures 35A to 35D show the charge-discharge voltage curves for the Li-G|LPSCl|LPSCl-I|LGPS|811 battery at extremely high current densities up to 43 mA / cm² (Figure 35A), and the long-cycle performance at high current densities of 20 mA / cm² and 30 mA / cm² (Figure 35B). In Figure 35B, before cycling the battery 10,000 times at 20 mA / cm², it was first cycled 500 times at 8.6 mA / cm², and then 800 times at 15 mA / cm² (Figure 35C). In Figure 35B, before cycling the battery 10,000 times at 30 mA / cm², it was first cycled at various current densities up to 43 mA / cm². All batteries were cycled at 55°C.

[0075] [Figures 36A-36B] Figures 36A and 36B show the cycle performance of a solid-state battery using a multilayer design with a cathode active material load of 25 mg / cm². The charge-discharge characteristics (Figure 36A) and capacity retention rate (Figure 36B) of the battery cycled at 2C with cutoff voltages set to 4.1V and 2.5V at 55°C are shown. The anode is Li covered with a silicon-graphite mixture (Li / Si-G), with a Si particle size of 1 μm. The cathode is LiNi0.8Mn0.1Co0.1O2 (NMC811, cathode active material load = 25 mg / cm²), and following the LPSCl-LPPS-LPSCl multilayer design, Li5.5PS4.5Cl1.5 (LPSCl) and Li10Ge1P2S12 (LGPS) were used as electrolytes.

[0076] [Figures 37A-37G] Figures 37A to 37G show XPS measurements of pellet cross-sections of cycled batteries using ion milling. Figures 37A to 37C show the results for cycled LPSCl from a Li-G|LPSCl|811 battery operated at 8.6 mA / cm2. Figure 37A shows Li 1s XPS at different milling times, Figure 37B shows Li 1s XPS refinement of a sample milled for 430 seconds, and Figure 37C shows XPS quantification of elemental composition at different ion milling times. Figures 37D to 37G show the results for cycled LPSCl-I from a Li-G|LPSCl|LPSCl-I|LGPS|811 battery operated at 30 mA / cm2. Figure 37D shows Li 1s XPS at different milling times, Figure 37E shows Li 1s XPS refinement of a sample milled for 430 seconds, Figure 37F shows XPS quantification of elemental composition at different ion milling times, and Figure 37G shows S 2p XPS refinement of a sample milled for 430 seconds. [Modes for carrying out the invention]

[0077] The present invention provides a secondary battery comprising a solid electrolyte (SSE) multilayer containing three or more layers, and two or more solid electrolytes having different stabilities. The solid electrolytes may be arranged such that a less stable electrolyte is sandwiched between more stable electrolytes. Local decomposition of the less stable electrolyte can prevent the formation and propagation of cracks in the multilayer and suppress the progression of dendrites.

[0078] Solid electrolytes with high mechanical strength are expected to solve the problem of lithium and sodium dendrites and enable Li and Na anodes. However, in reality, it has been found that lithium penetrates most solid electrolytes even at very low current densities, and the problem remains. The present invention provides a solid-state battery using a multilayer design of a solid electrolyte having a hierarchical structure of interfacial stability to achieve an ultra-high current density without dendrite penetration. A more stable electrolyte ensures interfacial stability in combination with both a high-voltage cathode and a Li or Na metal cathode, and a less stable electrolyte responds to the growth of dendrites with local decomposition and effectively inhibits further growth of dendrites by the kinetic stability introduced by local mechanical contraction. Micron or submicron-sized cracks in ceramic pellets are inevitable in the assembly of batteries that undergo long cycles. The solid electrolyte multilayer of the present invention self-decomposes to fill these cracks and dynamically creates a sufficiently limited "cement" or "concrete" regardless of the path selected by dendrites, thereby maintaining battery performance. It is emphasized that these comparisons and analyses regarding the electrochemical stability at various interfaces are made possible because most of the problems of capacity degradation and internal short circuit caused by Li metal dendrites are prevented through the designed functional decomposition of the present invention. The present invention provides new design principles for electrolytes, interfaces, and devices within the framework of the mechanical contraction theory to enable solid-state batteries with high capacity, stable cycling, high rate, and high current density.

[0079] LiNi 0.8 Mn 0.1 Co 0.1 The cycle performance of a Li metal anode combined with an O2 cathode has been demonstrated to be very stable, with a capacity retention rate of 82% after 10,000 cycles at 20C (70% after 9,300 cycles at 15C). The average Coulombic efficiency for all thousands of cycles is 99.96% at 20C and 100.0009% at 15C, and the maximum power density at the cathode active material level reaches 11.9 kW / kg and the energy density reaches 631 Wh / kg.

[0080] LiNi 0.8 Mn 0.1 Co 0.1 O2 (NMC811) is considered one of the cathode materials with high capacity, high energy density, and high cost efficiency because the composition of expensive Co element is reduced. Li metal is considered the holy grail of anodes for Li-ion batteries due to its high capacity and high energy density. The stable cycling of NMC811 lithium metal batteries is of great significance to the battery industry for electric vehicles. However, the stability of such batteries with most electrolytes, whether liquid or solid, is poor. Li 10±x M 1±y P 2±p S 12±q (M = Ge, Si) is known to be unstable with lithium metal 1 . Usually, in order to insulate the contact between the solid electrolyte and lithium metal, protective layers such as graphite 2 or indium metal 3 are applied. On the other hand, Li - argyrodite Li 6-y PS 5-y Cl 1+y has much higher stability with lithium metal than LGPS 4-6 . Therefore, the present invention provides a very stable battery with a wide space for providing a battery that can employ high-capacity anodes and cathodes and has higher energy density and output density than other batteries.

[0081] Solid electrolyte multilayer

[0082] The secondary battery of the present invention typically comprises an anode, a cathode, and a solid electrolyte multilayer disposed between the anode and the cathode. The solid electrolyte multilayer comprises a first solid electrolyte (e.g., LPSCl) and a second solid electrolyte (e.g., LGPS). The multilayer includes at least one layer of the first solid electrolyte which is more stable with lithium or sodium metal than the second solid electrolyte. The second solid electrolyte is separated from the anode by the first solid electrolyte. The multilayer may also include an 'n' layer of the second solid electrolyte and one or more 'n' layers of the first solid electrolyte (where n is, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.).

[0083] Alternatively, the solid multilayer may be arranged in a "sandwich" structure, for example, a structure having one layer of a second solid electrolyte between two layers of one or more first solid electrolytes (e.g., LPSCl-LGPS or LPSCl-LGPS-LPSCl). Or, the multilayer may include an 'n' layer of the second solid electrolyte and one or more 'n' or 'n+1' layers of the first solid electrolyte (where n is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.).

[0084] The second solid electrolyte is less stable to lithium metal or sodium metal than one or more first solid electrolytes. In this arrangement, the first solid electrolyte protects the second solid electrolyte from, for example, large-scale decomposition, while limited local decomposition of the second solid electrolyte inhibits the progression of metal dendrites (see, e.g., Figure 2H). The multilayer may include multiple different first solid electrolytes. In certain embodiments, the solid electrolyte multilayer includes at least two different first solid electrolytes; for example, the solid electrolyte multilayer may include two different solid electrolytes from Table 1 or Table 3.

[0085] The multilayer design is not limited to any particular material. The versatility of the multilayer design is shown in Figure 4A, demonstrating that it can work well with most electrolytes in the middle layer, as long as the second solid electrolyte can exhibit such well-suppressed degradation of Li dendrites under mechanical shrinkage. Such solid electrolytes include, but are not limited to, LGPS, LSPS, and LSP(Sb)S, which also exhibit stable cycling.

[0086] In accordance with this design principle, a wide range of solid electrolytes can be included as one or more first or second solid electrolytes in a multilayer design, provided that they are appropriately arranged relative to each other based on their relative stability. Examples include polymers, gels, sulfides, halogen compounds, oxides, phosphates, and nitrates, as shown in Tables 1-4.

[0087] In one highly promising aspect of the present invention, the stability of the multilayer structure relies on relative chemical and / or electrochemical stability, which is not sensitive to the thickness of the electrolyte layer or the crack density in the microns. This novel strategy of incorporating instability by design differs from conventional wisdom in the field, which involves using solid electrolytes to mechanically prevent Li(or Na) dendrite penetration to improve battery stability (which naturally requires a thick, crack-free electrolyte layer). The inherent flexibility and versatility of the multilayer battery of the present invention allow for easy adaptation to mass production procedures in the battery industry, and enable further optimization of the electrolyte layer thickness and mechanical flexibility in the future without sacrificing safety and performance.

[0088] To quantify the electrochemical stability of the solid electrolyte and its interface in such solid-state batteries (SSBs), a constrained ensemble description was developed. Here, the local effective modulus K eff If sufficient, decomposition accompanied by positive reaction strain can, in principle, be suppressed via metastability (for example, in the case of solid-state batteries). K in GPa units eff This reflects the complex interplay of microstructure, material mechanical strength, and stack pressure of battery devices.

[0089] The inventors of the present invention, K eff The critical threshold elastic modulus K * If greater than, the Gibbs free energy E of the decomposition reaction hull We found that the change from negative to positive suppresses decomposition via metastability. Many sulfide electrolytes are unstable with Li metal at 0V, therefore the interface between the solid electrolyte and Li metal is low K * This is appealing, and the interfacial reaction can be more easily stabilized by mechanical contraction. Importantly, the stress field surrounding the pre-decomposition stage is practically unavoidable, so a lower K * This means that, before it is sufficiently suppressed by metastableness, it generates smaller localized volume expansion and weaker stress fields induced by decomposition. On the other hand, K eff E = 0 GPa is sufficient hull The decomposition can function as an effective supply of "concrete" to repair microcracks that may arise from various stress fields during the cycle, including microcracks that are pre-existing during battery assembly or those induced by localized decomposition itself. Therefore, low K * and sufficient E hull The interfacial reaction can effectively prevent the propagation of cracks and dendrites. Therefore, a continuous local stress field surrounding the pre-decomposition stage, with or without cracks, which is immediately healed by electrochemical decomposition, can provide kinetic stability that further enhances metastability.

[0090] This invention relates to K, a material with over 120,000 types. * and E hull To evaluate this, high-throughput first-principles calculations were used to provide initial quantification for designing functional decompositions, and furthermore, small K at the interface with Li metal. * and sufficient E hull To propose solid electrolyte compositions that are likely to exhibit [a certain characteristic], machine learning is used to extract information (see the method in Example 4). Modifications of the proposed compositions can be implemented through a core-shell strategy, where the shell composition is low K *The core can be advantageously modified according to the predicted composition. For example, the conductivity of the core may be higher than that of the shell. Alternatively or additionally, the shell composition may have a smaller K than the core. * or more negative E hull It may have the following characteristics. The design principles specified herein are also applicable to SSBs having other anode metals, e.g., Na.

[0091] Mechanical contraction

[0092] In some embodiments, the solid electrolyte multilayer is subject to mechanical shrinkage. Mechanical shrinkage of the solid electrolyte can limit the degree of chemical or electrochemical decomposition of the solid electrolyte material by volumetric constraints, as detailed. Local stresses on the order of several GPa up to the mechanical modulus of the solid electrolyte (e.g., about 20 GPa for sulfide solid electrolytes) may arise from mechanical shrinkage. Mechanical shrinkage can be achieved by applying an external pressure of at least 0.1 MPa to several hundred MPa to the battery cell. The level of external pressure required for the battery is determined by the battery material, material processing, and battery assembly method. Mechanical shrinkage may also be provided by forming pressures by cold and / or hot and / or warm isotropic and / or anisotropic pressing and / or rolling with an external pressure on the order of 0.1 MPa to 1000 MPa and a temperature of 25°C to 500°C. Examples of preferred assembly methods include, but are not limited to, warm isotropic pressing (WIP), cold isotropic pressing (CIP), and hydraulic cold pressing of the battery cell or pouch. Mechanical contraction may also be due to an applied pressure of at least 0.1 MPa, for example, at least 20 MPa, or about 0.1 MPa to 40 MPa, where the applied pressure is, for example, about 0.1 MPa to 1 MPa, about 0.1 MPa to 10 MPa, about 1 MPa to 30 MPa, about 20 MPa to 40 MPa, about 30 MPa to 50 MPa, about 40 MPa to 60 MPa, about 50 MPa to 70 MPa, about 60 MPa to 80 MPa, about 70 MPa to 90 MPa, or about 80 MPa to about 100 MPa, about 100 MPa to 200 MPa, about 200 MPa to 400 MPa, about 300 MPa to 500 MPa, about 400 MPa to 600 MPa, about 50 The pressure ranges are 0 MPa to 700 MPa, approximately 600 MPa to 800 MPa, approximately 700 MPa to 900 MPa, or approximately 800 MPa to approximately 1000 MPa, for example, approximately 70 MPa, approximately 75 MPa, approximately 80 MPa, approximately 85 MPa, approximately 90 MPa, approximately 95 MPa, approximately 100 MPa, approximately 150 MPa, approximately 200 MPa, approximately 250 MPa, approximately 300 MPa, approximately 350 MPa, approximately 400 MPa, approximately 450 MPa, approximately 500 MPa, approximately 550 MPa, approximately 600 MPa, approximately 650 MPa, approximately 700 MPa, approximately 750 MPa, approximately 800 MPa, approximately 850 MPa, approximately 900 MPa, approximately 950 MPa, or approximately 1000 MPa.During the manufacturing of the battery, greater mechanical shrinkage may be applied. After providing the forming pressure, the porosity of the anode, cathode, and / or multilayer may be 0% to 15%. In some embodiments, the mechanical shrinkage is such that the local effective modulus is K. * To increase the value and thereby prevent decomposition, or to increase the local stress field generated by the decomposition of the solid electrolyte, K eff to K * It is sufficient to raise the level and thereby stop the decomposition.

[0093] During battery operation, local stress can be maintained by applying an operating stack pressure on the order of 0.1 MPa to 1000 MPa. The operating stack pressure can be applied by mechanical stress from the battery case or pouch cell made of steel, aluminum, plastic, or polymer, and their 3D structure, and / or by hydraulic pressure from a gel or any liquid sealed in the environment surrounding the pouch cell. Furthermore, external pressure may be periodically varied during the battery cycle through a passive response system, such as a spring, or an active response system controlled, such as a pressure sensor or programmed electronic device.

[0094] solid electrolyte

[0095] One or more first solid electrolytes are listed in Tables 1, 3, 5, 6, 9, or 10. 14、17-18、20-21、26-38 The second solid electrolyte may be selected from Table 2, Table 4, Table 7, Table 8, Table 11, or Table 12. 15-16、19、20、22、24-25 They may be selected from the following. Solid electrolytes that are favorable for mixing with the cathode material are listed in Tables 13 and 14. Other solid electrolyte materials that may be suitable include sulfide solid electrolytes, such as Si x P y S z For example, SiP2S 12 Examples include β / γ-PS4. Other solid electrolytes include Ge a P b S c (For example, GeP2S) 12 Germanium solid electrolytes such as Sn d Pe S f (For example, SnP2S) 12 ) and other tin solid electrolytes, iodine solid electrolytes such as P2S8I crystals, glass electrolytes such as alkali metal sulfide-P2S5 electrolytes or alkali metal sulfide-P2S5-alkali metal halide electrolytes, or alkali metal-P g S h-i Alkali metal-P electrolytes such as glass, ceramic, and other electrolytes. g S h-i Examples include electrolytes. Other solid electrolyte materials are known in the art. Solid electrolyte materials may take various forms, such as powders, particles, clay, or solid sheets. An exemplary form is a powder. Advantageously, the solid electrolyte may employ a core-shell particle structure. In particular, the method of the present invention (see, for example, Example 4) may be used to produce a core-shell LPSCl-X (where X is a halide) solid electrolyte having properties suitable for use as a first or second solid electrolyte. LGPS(Li 10 GeP2S 12) may also employ a core-shell particle structure. The solid electrolyte particles such as core-shell particles may have cross-sectional dimensions of about 1 nm to about 30 μm, for example, a diameter, 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, or 100 nm), for example, about 100 to 1000 nm (for example, about 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, or The wavelength may be 1000 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, or 10 μm), or 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, or 30 μm). In a core-shell particle, the shell may account for, for example, about 0.1% to about 99.9% of the particle by volume or mass, such as 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% of the particle.

[0096] Stability may be determined experimentally. For example, a lithium metal symmetric battery made using a solid electrolyte (Li-solid electrolyte-Li) has a current density of <0.5 mA / cm² without a clear voltage rise. 2 If an electrolyte can operate for more than 10 cycles, it can be classified as a first solid electrolyte and stable for its application. For less stable electrolytes (second solid electrolytes), such symmetric batteries will show a clear voltage increase after only a few cycles, e.g., 1 to 3 cycles. Less stable solid electrolytes also show clear changes in composition and structure after contact with or cycling with the lithium metal anode. In some embodiments, the second solid electrolyte responds well to mechanical shrinkage, which is reflected as strain in the solid electrolyte in X-ray diffraction measurements after it has become the central layer of a multilayer solid battery during cycling. This is due to a positive reaction strain of localized decomposition due to shrinkage.

[0097] electrode material

[0098] Electrode materials can be selected to have properties optimized for ion transport. For example, LiNi 0.8 Mn 0.1 Co 0.1 O2 (NMC811) may be preferred due to its high capacity, high energy density, and cost-effectiveness resulting from a reduced composition of expensive Co element. As another example, Li metal possesses high capacity and high energy density. Electrodes for use in solid electrolyte batteries may include metals (e.g., transition metals such as Au), alkali metals (e.g., Li or Na), crystalline compounds such as lithium titanate, or alloys thereof. Other materials for use as electrodes in solid electrolyte batteries are known in the art.

[0099] The electrodes may be solid pieces of material, or they may be deposited on a suitable substrate, such as fluororesin or carbon. For example, liquefied polytetrafluoroethylene (PTFE) has been used as a binder when creating a solution of electrode material for deposition on a substrate. Other binders are known in the art. The electrode material can be used without additives. Alternatively, the electrode material may have additives to enhance its physical and / or ionic conductivity. For example, the electrode material may have additives that modify the surface area exposed to a solid electrolyte such as carbon. Other additives are known in the art. In certain embodiments, the anode comprises Li, for example, Lithium metal. The lithium metal may also be mixed or alloyed with Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y, Zr, Nb, Mo, Ag, Cd, In, Sn, Sb, Bi, Cs, Te, or combinations thereof to form a single layer. Furthermore, mixtures of Li and other metals can form two-dimensional parallel layers or three-dimensional structures. The amount of Li supported at the anode is 0-50 mg / cm³. 2This can be done. The thickness of the Li anode can be 0 μm to 1000 μm. A thickness of 0 μm means that the Li source is the cathode material, and the battery can be fabricated with an anode-free design.

[0100] In some embodiments, the cathode material is, 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 0.2 O2 (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-s) O2(0≦x,y,z,s≦1), Li 1+z Ni x Mn y Co s W (1-x-y-z-s) O2 (0 ≤ x, y, z, w ≤ 1), V2O5, selenium-sulfur compounds, LiCoO2 (LCO), LiFePO4, LiNi 0.5 Mn 1.5 O4, Li2CoPO4F, LiNiPO4, Li2Ni(PO4)F, LiMnF4, LiFeF4, or LiCo 0.5 Mn 1.5 It can contain O4.

[0101] The cathode 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), or poly(vinylidene fluoride-co-trifluoroethylene). The particle size of the cathode material can be 1 nm to 30 μm. The amount of cathode supported is 0.1 to 100 mg / cm³. 2 This can be done. The thickness of the cathode can be 5 μm to 2000 μm. The cathode may be mixed with, for example, the solid electrolyte materials listed in Tables 13 and 14 to provide an increased cathode capacity.

[0102] If the anode contains Na metal, the Na metal can be mixed or alloyed with one or more of the following metals: Li, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y, Zr, Nb, Mo, Ag, Cd, In, Sn, Sb, Bi, Cs, or Te. Mixtures of Na and other metals can form two-dimensional parallel layers or three-dimensional structures. The amount of Na supported in the anode is 0-50 mg / cm³. 2 This can be done. The thickness of the Na in the anode can be 0 μm to 1000 μm. 0 μm means that the battery can be fabricated with an anode-free design, where the Na source is the cathode material.

[0103] Na cathode material is Na w MnO2, Na w CoO2, Na w NiO2, Na w TiO2, Na w VO2, Na w CrO2, Na w FeO2, Na w (Mn x Fe y Co z Ni 1-x-y-z )O2(0≦x,y,z≦1), Na w(M)PO4, Na w (M)P2O7, Na w (M)O2, Na x M y (XO4) z (Here, M includes, but is not limited to, metal elements such as transition metals, and can be one metal element or a combination of metal elements. X represents B, S, P, Si, As, Mo, W, 0 ≤ x, y, z ≤ 3, 0 < w ≤ 1, and O can be partially substituted with F, Cl, Br, I.) can be used.

[0104] Cathode materials such as selenium and sulfur, which can be expected to have high capacity and high energy density, also show much better cycle performance in multilayer designs than in monolayer designs.

[0105] In certain embodiments, the cathode can be mixed with a polymer and carbon black, and the solid electrolyte can be mixed with a polymer. Examples of polymers can include polyethylene oxide, polyvinylidene fluoride, poly(vinylidene fluoride - co - hexafluoropropylene), poly(ethyl methacrylate), or poly(vinylidene fluoride - co - trifluoroethylene). The thickness of the solid electrolyte layer is 5 - 1000 μm. The thickness of the cathode can be 5 - 2000 μm. The cathode, anode, and solid electrolyte can use bipolar or parallel laminations to form a battery module. The area of each layer is 0.1 cm 2 ~1 m 2 can be used.

[0106] Coating of the electrode

[0107] In some cases, the electrode material may further include a coating on its surface to function as an interfacial layer between the base electrode material and the solid electrolyte. In particular, the coating is configured to improve the interfacial stability between the electrode such as the cathode and the solid electrolyte for excellent cycle performance. For example, the electrode materials for the electrodes of the present invention include LiNbO3, LiTaO3, Li2ZrO3, LiNb X Ta1-X O3 (0 ≦ x ≦ 1), yLi2ZrO3-(1-y)LiNb X Ta 1-x O3 (0 ≦ x, y ≦ 1), Al2O3, TiO2, ZrO 2、 AlF3, MgF2, SiO2, ZnS, ZnO, Li4SiO4Li3PO4, Li3InCl 6、 Li 1+x Al x Ti 2-x (PO4)3 (0 < x < 2), LiMn2O4, LiInO2-LiI, Li6PS5Cl, LiAlO2, and carbon, particularly including but not limited to LiNbO3.

[0108] The anode containing Li is silicon, silicon dioxide, Li4Ti5O 12 , Li3V^2O5, Au, Ag, Sn, SnO2, carbon (e.g., amorphous carbon, carbon nanotubes, graphene, carbon nanofibers, fullerenes (e.g., C 60 It should be noted that in the original text, there seems to be a formatting issue in "Li4SiO4Li3PO4" which might be a typo. Also, in the translation of "Li3V2O5", the "^" is added to indicate a possible superscript error in the original text. If this is not a correct interpretation, please provide more context or clarify the original text.The protective layer may include hard carbon or graphite, or a combination thereof. The particle size of the protective layer can be 1 nm to 100 μm, for example, about 1 to 100 nm (for example, 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, or 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, or 100 nm), for example, approximately 100-1000 nm (for example, approximately 100-110 nm, 100-125 nm, 100-200 nm, 200-300 nm, 250-500 nm, 300-400 nm, 400-500 nm, 500-600 nm, 500-750 nm, 600-700 nm, 700-800 nm, 750-1000 nm, 800-900 nm, or 900-1000 nm, for example, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900nm or around 1000nm), for example, about 1-10μm (for example, about 1-2μm, 1-5nm, 2-3μm, 3-4μm, 4-5μm, 5-10μm, 5-6μm, 6-7μm, 7-8μm, 8-9μm, or 9-10μm, for example, about 1μm, 2μm, 3μm, 4μm, 5μm, 6μm, 7μm, 8μm, 9μm, or 10μm), or for example, about 10-100μm (for example, about 10-20μm, 10-25μm, 10-50μm, 20-30μm, 25-50μm, 30-40μm) The thickness can be 40-50 μm, 50-60 μm, 50-75 μm, 60-70 μm, 75-100 μm, 70-80 μm, 80-90 μm, or 90-100 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). The protective layer can be mixed with Li metal and / or polymer with a thickness of 0 μm to 500 μm.The lithium metal layer can be protected by a layer formed of one or more elements of Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y, Zr, Nb, Mo, Ag, Cd, In, Sn, Sb, Bi, Cs, or Te. The lithium metal layer can be alloyed with one or more elements of Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y, Zr, Nb, Mo, Ag, Cd, In, Sn, Sb, Bi, Cs, or Te.

[0109] In certain embodiments, the solid electrolyte multilayer is silicon, Li4Ti5O 12 , Li3V2O5, silicon dioxide, carbon (e.g., amorphous carbon, carbon nanotubes, graphene, carbon nanofibers, fullerenes (e.g., C 60The anode and / or cathode are separated by a protective layer containing hard carbon, or graphite (for example, as a graphite coating on the electrode), Au, Ag, Sn, SnO2, or a combination thereof. The particle size of the protective material can be 1 nm to 100 μm, for example, about 1 to 100 nm (for example, 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, or 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, or 10 0nm), for example, approximately 100-1000nm (for example, approximately 100-110nm, 100-125nm, 100-200nm, 200-300nm, 250-500nm, 300-400nm, 400-500nm, 500-600nm, 500-750nm, 600-700nm, 700-800nm, 750-1000nm, 800-900nm, or 900-1000nm, for example, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, (approximately 900 nm or 1000 nm), for example, about 1-10 μm (for example, about 1-2 μm, 1-5 nm, 2-3 μm, 3-4 μm, 4-5 μm, 5-10 μm, 5-6 μm, 6-7 μm, 7-8 μm, 8-9 μm, or 9-10 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 10-100 μm (for example, about 10-20 μm, 10-25 μm, 10-50 μm, 20-30 μm, 25-50 μm, 30-40 μm) The thickness can be 40-50 μm, 50-60 μm, 50-75 μm, 60-70 μm, 75-100 μm, 70-80 μm, 80-90 μm, or 90-100 μm (for example, approximately 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).

[0110] In batteries using sodium, the sodium metal is silicon, silicon dioxide, or Na4Ti5O 12 Na3V2O5, carbon (hard carbon, amorphous carbon, carbon nanotube, graphene, carbon nanofiber, fullerene (e.g., C) 60A protective layer may include hard carbon or graphite, Au, Ag, Sn, SnO2, or a combination thereof. The particle size of the protective material can be 1 nm to 100 μm, for example, about 1 to 100 nm (for example, 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, or 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, or 10 0nm), for example, approximately 100-1000nm (for example, approximately 100-110nm, 100-125nm, 100-200nm, 200-300nm, 250-500nm, 300-400nm, 400-500nm, 500-600nm, 500-750nm, 600-700nm, 700-800nm, 750-1000nm, 800-900nm, or 900-1000nm, for example, approximately 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm) , 900nm, or 1000nm), for example, about 1-10μm (for example, about 1-2μm, 1-5nm, 2-3μm, 3-4μm, 4-5μm, 5-10μm, 5-6μm, 6-7μm, 7-8μm, 8-9μm, or 9-10μm, for example, about 1μm, 2μm, 3μm, 4μm, 5μm, 6μm, 7μm, 8μm, 9μm, or 10μm), or for example, about 10-100μm (for example, about 10-20μm, 10-25μm, 10-50μm, 20-30μm, 25-50μm, 30-40μm) The thickness can be 40-50 μm, 50-60 μm, 50-75 μm, 60-70 μm, 75-100 μm, 70-80 μm, 80-90 μm, or 90-100 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). The protective layer can be a mixture of Na metal and / or polymer in thickness from 0 μm to 500 μm.The Na metal layer can be protected by a layer formed of one or more elements of Li, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y, Zr, Nb, Mo, Ag, Cd, In, Sn, Sb, Bi, Cs, or Te. The protective layer can include sodium metal alloyed with one or more elements of Li, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y, Zr, Nb, Mo, Ag, Cd, In, Sn, Sb, Bi, Cs, or Te.

[0111] The Na cathode can be NaNbO3, NaTaO3, Na2ZrO3, NaNb x Ta 1-x O3 (0 ≤ x ≤ 1), yNa2ZrO3-(1-y)NaNb X Ta 1-X O3 (0 ≤ x,y ≤ 1), Al2O3, TiO2, ZrO2, AlF3, MgF2, SiO2, ZnS, ZnO, Na4SiO4, Na3PO4, Na3InCl6, Na 1+x Al x Ti 2-x (PO4)3 (0 < x < 2), NaMn2O4, NaInO2-NaI, Na6PS5Cl, NaAlO2, and can be coated with carbon.

[0112] Indium may be used to coat the electrode.

[0113] In some embodiments, the coating of the electrode can include polyethylene oxide, polyvinylidene fluoride, poly(vinylidene fluoride-co-hexafluoropropylene), poly(ethyl methacrylate), or poly(vinylidene fluoride-co-trifluoroethylene).

[0114] Battery performance

[0115] In some embodiments, the battery is, for example, 2 mg / cm 2With a cathode load of 80mAh / g and 8mA / cm², after at least 10,000 charge-discharge cycles at a rate of 20C to 100C. 2 It maintains at least 80% of its capacity, along with a higher current density. In some embodiments, the battery has a current density of 0.001 mA / cm². 2 ~100mA / cm 2 It can be cycled at a current density of . In some embodiments, the battery cathode material has a power density of at least 10 kW / kg. In some embodiments, the battery cathode material has an energy density of at least 600 Wh / kg (e.g., 631 Wh / kg). The battery of the present invention may have an average Coulomb efficiency of 99.96% or more at 20C and 100.00% at 15C over all thousands of cycles, along with a maximum power density reaching 11.9 kW / kg and an energy density up to 631 Wh / kg at the cathode active material level. The battery of the present invention has low Coulomb inefficiency, e.g., 10 -4 ~10 -3 It may have a Coulomb inefficiency of the order of . [Examples]

[0116] Overview of the Method - Examples 1-3

[0117] Li 5.5 PS 4.5 Cl 1.5 (LPSCl) was prepared by high-energy ball milling followed by post-annealing. Stoichiometric amounts of Li2S (purity over 99.9%, Alfa Aesar), P2S5 (S purity over 99%, Sigma Aldrich), and LiCl (purity over 99%, Alfa Aesar) powders were milled for 16 hours in a planetary mill PM200 (Retsch GmbH, Germany) under a protective argon atmosphere. The ball-milled powder was then transferred to a quartz tube and annealed at 500°C for 1 hour at 5°C·min. -1 and 1℃·min -1 Heating was performed using the specified heating and cooling rates.

[0118] Li 9.54Si 1.74 (P 0.9 S 0.1 ) 1.44 S 11.7 Cl 0.3 (LSPS) was prepared using the same method. Li2S (purity over 99.9%, Alfa Aesar), SiS2 (purity over 99%, American Elements), P2S5 (purity over 99%, Sigma Aldrich), Sb2S5 (Sigma Aldrich), and LiCl (purity over 99%, Alfa Aesar) were used and milled for 40 hours (LSPS). A spinning speed of 375 rpm was used. 5℃·min -1 The powder was heated at 460°C for 8 hours, using the heating rate and the natural cooling rate. All heat treatments were performed under the protection of an Ar gas flow.

[0119] A 25 μm thick, 1 / 4-inch diameter Li foil was covered with a 3 / 8-inch diameter graphite film with a weight ratio of graphite (BTR, China) to PTFE of 95:5. The volume ratio of Li to graphite was 2.5:1. The cathode layer consisted of 30 wt% solid electrolyte and 70 wt% LiCoO2 (Sigma Aldrich) or LiNi 0.8 Mn 0.1 Co 0.1 O2 (XTC, China) 2 mg / cm³ 2 It was prepared by mixing in the specified loading amounts. 140 mg of Li was used as the electrolyte. 10 Ge1P2S 12 (MSE Supplies LLC) or LPSCl was used. The composite electrolyte consisted of 30 mg of LPSCl and 110 mg of LGPS (or LSPS). The anode-solid electrolyte-cathode for half-cells, or the anode-electrolyte-cathode for symmetrical cells, were pressed together at 467 MPa in a homemade pressurized cell and maintained at 250 MPa during testing. All batteries were assembled in an argon-atmosphere glove box, and constant-current battery cycle tests were performed on an ArbinBT2000 workstation.

[0120] Example 1

[0121] Electrodes made of pure lithium metal, electrolyte made of Li 10 Ge1P2S 12 A symmetrical battery using (LGPS) can fail immediately due to voltage sparks, as shown in Figure 1A. On the other hand, Li in such a symmetrical battery 5.5 PS 4.5 Cl 1.5 (LPSCl) can operate for more than 150 hours before a short circuit occurs. Figures 1A and 1B show the rise in overvoltage (decomposition of electrolyte) and the sharp drop in voltage (short circuit). 5-7 These two typical failure phenomena actually manifest. In addition to the difference in stability with Li metal, the two electrolytes actually exhibit physical and (electro)chemical properties, including ionic conductivity, electronic conductivity, particle size, and mechanical modulus, as shown in Figures 5, 6 and Table 15. 3、4、7、8 They look very similar. [Table 15]

[0122] * All measurements are based on cold pressing without heat treatment. ** The order of magnitude of the electronic conductivity measured in this study is consistent with that reported in the literature. *** Particle size is measured from SEM images. **** The modulus of elasticity is derived from past research results.

[0123] To focus on the most significant difference between the two electrolytes, their stability against lithium metal, lithium was discharged in LGPS or LPSCl in asymmetric batteries (see, for example, Figures 7 and 8). The surface of LGPS turned black (see, for example, Figure 7B), while the surface of LPSCl showed no significant color change (see, for example, Figures 7A and 7C). XPS showed resistance to Li2S and reduced Ge in LGPS. σ+While other components exhibit severe decomposition, LPSCl shows almost no decomposition peaks (see Figures 8A-8F). In Figure 1C, a symmetrical battery with a Li metal anode is assembled using a multilayer electrolyte design of LPSCl-LGPS-LPSCl, where the order of the electrolyte names represents the order of the materials in the battery, and the total thickness of the electrolyte layer is maintained throughout the paper unless otherwise specified. The outer layers of the two LPSCl layers are in direct contact with the lithium metal, which is protected by graphite to further (electro)chemically protect the interface. This electrolyte combination exhibits stable cycle performance of over 300 hours, which is superior to any battery using a single electrolyte in our tests. As shown in Figure 9, LGPS is used with Li 9.54 Si 1.74 (P 0.9 S 0.1 ) 1.44 S 11.7 Cl 0.3 The same performance can be achieved by substituting (LSPS).

[0124] Figure 1D shows 20 mA / cm². 2 This shows the cycle performance of a symmetrical battery. The battery operates for 30 cycles without any significant short-circuit signals. The charge-discharge curve shows a low overvoltage of -0.5V, with a slight upward trend in the last few cycles. This is similar to what was previously observed with a graphite-protected Li metal anode. 2 However, no short circuits were observed even at this ultra-high current density, indicating that this multilayer structure has the stability to prevent penetration of lithium dendrites. Previously, the inventors demonstrated that protection of the graphite layer allows a Li / graphite-LGPS-graphite / Li symmetrical battery to reach 10 mA / cm². 2 It was reported that testing was possible up to that point. However, as shown in Figure 10, the overvoltage was much higher (10 mA / cm²). 2 At 1.5V, this high overvoltage prevents sustained operation over long cycles or operation at higher current densities. Here, the LPSCl layer stabilizes the primary interface with the Li / graphite layer, lowering the overall overvoltage and enabling actual cycling at high current densities.

[0125] On the other hand, as shown in Figures 2A-2B, 0.25 mA / cm 2 After operating a symmetrical battery for 300 hours, a clear black region appears in the cross-sectional optical image of the electrolyte pellet. A similar pattern is observed at 20 mA / cm². 2 This is also observed in the battery after 30 cycles (Figures 11A-11E). This is the same color as seen under an optical microscope as the decomposition caused by lithium discharged onto the LGPS surface (see Figures 7B and 8A-8C). However, the black areas are only observed in limited areas from the cross-sectional view. As identified by XPS, the decomposition is at either a slow rate (Figure 12) or a high rate (see Figures 2C-2D and 12), and involves moderately reduced Ge without any extremely low Ge content in the Li-Ge alloy. In Figures 2E-2H, SEM images were taken from three regions—LPSCl, the LGPS layer, and their transition regions—from the same symmetrical battery after 300 hours of cycling. The LPSCl showed clear cracks after cycling (Figure 2E), progressing from a state with no observable cracks before cycling (Figure 13). In contrast, the LGPS layer showed no cracks even after cycling (Figure 2F). Furthermore, compared to the LGPS before cycling (Figure 13), many morphological details on the cross-section in the post-cycled sample are obscured, as if masked by the "cement" or "concrete" layer (Figure 2F). This suggests that localized decomposition occurs during cycling and may play a significant role here in preventing crack formation.

[0126] Previously, it was predicted that at the interface between LGPS and Li metal without mechanical shrinkage, for example, at an interface immersed in a liquid electrolyte cell environment, Li-Ge alloys should be the standard decomposition product. 2 However, in the all-solid-state battery designed by the inventors, calculations predict that the decrease in Ge is suppressed under test conditions with sufficient localized mechanical contraction, and this has been observed in XPS, electronically isolating the decomposition. 2Recently, such mechanical shrinkage has been found to further provide kinetic stability to effectively suppress the propagation of LGPS decomposition through ionic passivation when exceeding the voltage (quasi-) stability window by far, enabling the stabilization of LGPS up to 10V. 9 Here, mechanical shrinkage is likely to inhibit the further propagation of the decomposition interface between LGPS and Li dendrites at 0V by such ionic and electronic passivation. Therefore, this well-constrained decomposition functions as a self-degrading "cement" or "concrete" that fills all micron- or submicron-sized cracks that pre-existed during battery assembly or occurred during battery cycling, enabling high-current density cycling without short circuits caused by Li dendrite penetration.

[0127] Example 2

[0128] To demonstrate the uniqueness and practicality of the multilayer design, batteries with a single-layer electrolyte design having a lithium metal anode and a high-voltage cathode of NMC811 were fabricated using various electrolytes. The configuration of the solid-state battery with the multilayer design showed significantly improved battery performance for the combination of the NMC811 cathode and the Li metal anode. (Figs. 3, Fig. 15). The discharge capacity at 10C of the multilayer electrolyte design (LPSCl-LSPS-LPSCl) was 127 mAh / g after slow charging at 0.1C with a low cut-off voltage of 1.0V at room temperature, which is larger than the capacities of the single-layer designs using the LPSCl (87.9 mAh / g) or LSPS (80.6 mAh / g) electrolyte (Fig. 16A).

[0129] At high temperatures (55°C) and low cycle rates, this solid-state battery exhibits a capacity of 155.7 mAh / g at 1.5C. After 600 cycles, the battery shows almost no degradation and retains 97.7% of its capacity (Figures 3A and 3B), demonstrating superior cycle performance compared to many other batteries currently reported. This indicates that the interface between the cathode material (NMC811) and the solid electrolyte (LPSCl) is highly stable. Compared to NMC811 liquid batteries, the mechanical contraction environment should play a crucial role in preventing degradation of NMC811, LPSCl, and their interface. 9 As shown in Figure 3D, at high rates, the battery exhibited discharge capacities of 144.1 mAh / g at 5C charge and 5C discharge, 114.4 mAh / g at 10C, 102.2 mAh / g at 15C, and 81.0 mAh / g at 20C. After 1000 cycles at 5C, the solid battery showed a capacity retention rate of 77.8% and could be cycled back to 153.0 mAh / g at 0.1C after 1000 long cycles (Figure 16B). This means that such batteries can be reused for stationary energy storage system applications after use in electric vehicles. Furthermore, the battery at 10C showed a capacity retention rate of 85.7% after 3000 cycles (Figure 16C). Furthermore, the Li / G capacity ratio in the anode composite can be further increased to 10:1, corresponding to an anode capacity of approximately 2000 mAh / g, indicating significant room for further engineering of the battery energy density (Figure 16D). Moreover, the present invention demonstrates that the operating stack pressure can be easily reduced to 50-75 MPa without sacrificing the electrochemical performance of the design (Figure 16E). Another very promising aspect of the present invention is that the stability of the multilayer structure derives from a combination of designed (electro)chemical stability and instability, and is not sensitive to the thickness of the electrolyte layer and the micron crack density during initial battery assembly, thus allowing for further reduction of the electrolyte layer thickness (Figure 16F).

[0130] Example 3

[0131] To further demonstrate the stability of the multilayer battery of the present invention against Li dendrites under extreme cycling conditions, Li is used as the electrolyte. 5.5 PS 4.5 Cl 1.5 Li 9.54 Si 1.74 (P 0.9 S 0.1 ) 1.44 S 11.7 Cl 0.3 Li-LiNi coated with graphite using (LPSCl-LSPS-LPSCl) 0.8 Mn 0.1 Co 0.1 O2(Li / G-NMC811) batteries were cycled to 10,000 cycles at 15C and 20C. At 15C, the batteries showed capacity retention of 90% after 3,000 cycles and 70% after 9,300 cycles (Figure 3E), with a Coulomb inefficiency of 10 -4 ~10 -5 This shows an order of magnitude (Figure 3F). At a high rate of 20C, the charge-discharge characteristics (Figure 3G) show very limited shape change even after long cycles, the capacity retention rate is high at 82% (Figure 3H), and the Coulomb inefficiency is 10 -3 ~10 -4 The order of magnitude is (Figure 3I). Note that the average Coulomb inefficiency for battery cycling at 20C is 0.04%, i.e., the Coulomb efficiency is 99.96%, and the average Coulomb efficiency at 15C is -0.0009%, i.e., the Coulomb efficiency is 100.0009%. The Coulomb efficiency with long cycles does not indicate any harmful side reactions occurring in the system. Side reactions have not been reported from lithium metal battery systems, and have been rarely reported in other lithium-ion batteries, regardless of whether the electrolyte is solid or liquid. 10 The energy density and power density in this invention are significantly higher than those reported to date (Figure 4B). 6,11-13 The small negative sign in the efficiency at 15C indicates that a small amount of lithium was replenished from the lithium metal anode. This is an advantage of lithium metal anodes over anode-free batteries, as even a very thin layer of lithium metal can be beneficial to cycle performance. 6 .

[0132] Conversely, and consistent with the results of symmetrical battery tests, the Li-LPSCl-LCO battery exhibits a small irreversible capacity in the first cycle (see Figure 14). Similar to the cathode material, the stability of LPSCl and lithium metal allows it to be maintained for at least 50 cycles without significant capacity degradation (see Figure 15). In contrast, the reaction at the primary interface between LGPS and the lithium metal layer results in a large irreversible capacity (see, for example, Figure 14B).

[0133] Figure 14C shows a graphite-protected lithium as the anode. 2 The charge-discharge curves of an LPSCl battery with an uncoated NMC811 cathode are shown. Here, 30 wt% LPSCl is well mixed with NMC811 in the cathode layer. The battery exhibits good cycle performance at a low cycle rate during the first 60 cycles (Figure 14E). This indicates good interfacial stability between LPSCl and NMC811. The rapid capacity drop after 60 cycles is due to dendrites penetrating cracks, as discussed in Figure 2. At higher current densities (0.5C), the battery with the Li / G-LPSCl-NMC811 structure shows a micro-short signal very early in the cycle (see Figure 14D), which leads to a decrease in cycle performance (see Figure 14F). The battery composition and materials used are summarized in Table 16. [Table 16]

[0134] Example 4

[0135] The solid electrolyte design strategy of the present invention is Li argyrodite electrolyte Li 5.5 PS 4.5 Cl 1.5 This was experimentally demonstrated by doping the original electrolyte material of (LPSCl) with both LPSCl and doped LPSCl-X, e.g., Li 5.5 PS 4.5 Cl 1.5-y X y(Here, X is F, Br, or I, with y=0.4 for F and y=0.15 for Br and I.) is synthesized by solid-state reaction, and then, using Li metal protected with graphite as the anode, NMC811 (LiNi in this embodiment) is synthesized. 0.83 Mn 0.06 Co 0.11 Using O2) single crystal particles as the cathode, a multilayer electrolyte was constructed according to the inventors' recent approach, and an SSB was assembled (see Method). By replacing the central layer of LPSCl with LPSCl-X and making compositional changes derived by computer design, the battery of the present invention achieves 8.6 mA / cm². 2 It exhibits ultra-long cycle performance exceeding 25,000 cycles at high current densities (or 20C rate). Furthermore, for the NMC811, high capacity SSB with various interfaces between the cathode and electrolyte particles, and between multiple electrolyte layers, has been demonstrated, reaching 197 mAh / g at a 0.5C rate and approximately 180 mAh / g at a 1.5C rate. Such batteries of the present invention can also exhibit very different capacities at a 20C rate, namely an impressive 120 mAh / g compared to a good 90 mAh / g (where 1C = 150 mAh / g or 0.43 mA / cm²). 2 (That is.)

[0136] Figure 17A shows lower K * This document presents a computer design procedure for new compositions with the following characteristics: Using material information for composition, energy, and volume obtained from first-principles density functional theory (DFT)-based simulations, the hull energy E at 0V is calculated for 124,497 different materials. hull , and the critical modulus K at the interface with Li metal * The following was calculated (see Method for details of the calculation). Macroscopic properties (composition, energy) and target value (E hull , K * By applying machine learning to the model of ), we determined the relationship from discrete data points in a high-dimensional parameter space generated by high-throughput computation. Furthermore, we extrapolated this relationship to a continuous composition space and, taking an arbitrary composition as input, obtained a smaller K * We performed composition optimization for this purpose.

[0137] Figure 17B shows the K of LPSCl-Br. * This shows a machine learning prediction of the compositional changes necessary to minimize K. Compared to the original LPSCl composition, the compositional change results in K without doping with new elements (y=0.00). * By minimizing K, * The pressure can already be reduced from 25.1 GPa to 8.4 GPa. Here, the LPSCl composition was optimized to be deficient in S and P, and rich in Cl and Li. Furthermore, Br was doped in compositions (y) from 0 to 0.2, and K * Minimizing E hull The K factor increases from 0 meV / atom to 30-75 meV / atom (still much lower than the original LPSCl's 500 meV / atom), and the composition of other elements changes slightly. Note that the 0 eV reference state of the decomposition energy with Li metal in machine learning was consistent with the DFT results based on LiCl stable at 0 V (see Methods below and Figure 21). Similar compositional trends were also predicted for LPSCl-I and LPSCl-F (Figure 22). Therefore, based on the images, such compositions doped with F, Br, and I are low K * And, enough E to stabilize the Li metal anode. hull It is highly likely that this indicates...

[0138] The core-shell LPSCl-X electrolyte was synthesized by a solid-state reaction (see method below), and its X-ray diffraction (XRD), optical photographs, and scanning electron microscope (SEM) images can be seen in Figures 23 and 24. LPSCl-X exhibited the same F-43m space group as its parent LPSCl and showed similar particle sizes. The core-shell structure was discovered in LPSCl-Br by energy-dispersive spectroscopy (EDX) using SEM and X-ray photoelectron spectroscopy (XPS) from cross-sections of ion-beam-milled particles (Figure 18). Therefore, the EDX line profile in Figure 18A indicates that the LPSCl-Br shell is deficient in P and S, and rich in Cl and Br.

[0139] Figure 2B shows the XPS quantification of elemental composition at different ion milling depths, and also shows a core-shell composition trend consistent with EDX, with information on Li deficiency within the shell. Note that both the SEM-EDX samples in Figure 18A and the XPS samples in Figure 18B were exposed to air for a short time during sample transport. Figure 18C shows the XPS results for samples without air exposure. The shell region is now well defined and limited to the particle surface, but the same core-shell composition trend is still maintained, except for Li. Similar trends are observed for LPSCl-F and LPSCl-I (Figure 27), and the original XPS data are shown in Figures 25 and 26. Changes in shell composition, especially in those without air contamination, are K * This is consistent with the trend predicted from the minimization of (Figures 21B and 22), and the stable surface during synthesis is K * <K s eff Therefore, the relatively low surface tension should satisfy the critical modulus K of the surface through the composition gradient. * The surface effective modulus K can be minimized. s eff This suggests that it may also play that role.

[0140] Note that EDX and XPS analysis of the original LPSCl without Br doping also shows a core-shell structure with a shell region rich in Li and Cl and deficient in S (Figure 28). * After minimization, a much lower E is suggested by machine learning predictions at y=0.00. hull For the value (Figure 17B, right panel), the shell composition of LPSCl is considered to be more stable with the Li metal than the core, which is why the high E was predicted based on the core composition. hull Nevertheless, this may explain previous experiments showing that the LPSCl of the Li aldirodite electrolyte can cycle in direct contact with Li metal (Figure 17B, left). The inventors of this invention believe that Li 10 GeP2S 12 The typical sulfide electrolyte of (LGPS) also exhibits a Li-rich and S-deficient shell, and the predicted compositional trend is low K at approximately 15 GPa. *While suitable for, relatively high E hull This is maintained (Figure 29), and it should be noted that this is consistent with previous DFTs and experimental findings that LGPS is less stable with Li metal.

[0141] To test these different stabilities predicted above for LPSCl and doped LPSCl-X, the inventors deposited Li metal onto the electrolyte by discharge in the assembly of a symmetrical battery having a multilayer structure of Li metal, then graphite (G), then LPSCl, then LGPS, then the electrolyte of interest (LPSCl or LPSCl-X), i.e., LiG|LPSCl|LGPS|electrolyte. The thin graphite layer added between the Li metal and LPSCl is to improve interfacial stability during the initial battery assembly. Figure 30 shows an XPS and visual comparison between the Li-deposited intrinsic LPSCl, LPSCl-X, and LGPS. The XPS analysis shows that the decomposition is weakest in the Li-deposited LPSCl and stronger in LPSCl-X and LGPS, which is consistent with the above predictions. Therefore, the inventors successfully synthesized the suggested compositions for the core-shell LPSCl-X particles and the shells of LPSCl particles, and K * and E hull Because the value is low, the stability of LPSC with respect to Li metal becomes higher, E hull Because the critical modulus (K) is relatively high, the stability of LPSCl-X with respect to Li metal is lower, making it more like LGPS. However, the decomposition of LPSCl-X at 0V is designed to have a critical modulus (K). * Because of its low ) ratio, it is more likely to be stabilized more quickly by mechanical contraction than LGPS.

[0142] Furthermore, the inventors fabricated an SSB assembly of Li-G|LPSCl|LNO@NMC811 using NMC811 single crystal particles (or simply 811) coated with LiNbO3(LNO) embedded in LPSCl. This battery exhibited a high discharge capacity of 191 mAh / g at a 0.5C rate, but rapidly decayed at high-rate cycles (Figure 31). Therefore, an additional layer of LPSCl-X was inserted to separate the original single-layer LPSCl layer into two layers each at the anode and cathode, creating a new battery assembly of Li-G|LPSCl|LPSCl-X|LPSCl|LNO@811, hereafter referred to as an LPSCl-X battery. In Figure 19, all LPSCl-X (X=F,Br,I) batteries initially underwent 5 cycles at a 0.5C rate, and then at a 20C rate (8.6 mA / cm²). 2 ) is cycled and tested. Voltage and capacitance are high Coulomb efficiency (mainly 10 in Figure 32). -4 from 10 -3 LPSCl-F batteries and LPSCl-Br batteries exhibit very slow decay over 25,000 cycles (Figures 20A, 20B, 20D, and 20E) with low Coulomb inefficiencies of the order of magnitude. On the other hand, LPSCl-I batteries show high initial capacity but decay relatively quickly at 10,000 cycles (Figures 20C and 20F), which is likely also influenced by the level of uncontrolled humidity during the test conditions.

[0143] The initial 0.5C capacities of LPSCl-F and LPSCl-Br batteries are 148mAh / g and 136mAh / g, respectively, while that of LPSCl-I is 178mAh / g. At 20C, the LPSCl-F battery exhibits an initial discharge capacity of 88mAh / g, quickly peaking at 95mAh / g after 750 cycles, and showing a significant retention rate of 93% to 81.5mAh / g after 10,000 cycles and 83% to 73.2mAh / g after 20,000 cycles. For LPSCl-Br batteries, the initial capacity was 89mAh / g, the peak capacity was 93mAh / g at the 7th cycle, the retention rate after 10,000 cycles was 78% (69mAh / g), and the retention rate after 16,000 cycles was 77%. For LPSCl-I batteries, the initial capacity was 124mAh / g, the peak capacity was 128mAh / g at the 3rd cycle, and the retention rate after 10,000 cycles was 79% (98.2mAh / g). The performance of multilayer electrolyte batteries shows a significant improvement compared to batteries with a single LPSCl electrolyte layer (Figure 31).

[0144] Furthermore, the inventors introduce LGPS into a multilayer battery configuration. First, they assemble three batteries: Li-G|LPSCl|LPSCl-I|LGPS|811, called the LPSCl-I|LGPS|811 battery; Li-G|LPSCl|LGPS|811, called the LGPS|811 battery; and Li-G|LPSCl|LGPS|LNO@811, called the LGPS|LNO@811 battery. Figure 20A shows the voltage curves of the LPSCl-I|LGPS|811 battery at different rates, resulting in an impressive capacity of 128mAh / g at a 20C rate. Figure 20B shows the cycle performance of the three batteries at different rates, from low rate to high rate and back to low rate. At a 0.5C rate, all three batteries exhibit a high discharge capacity of approximately 200mAh / g. The LGPS|LNO@811 battery operated for 150 cycles with a capacity retention rate of 98.9%, while the other two batteries operated for 5 cycles before increasing the rate. Note that the inventors also tested other LGPS|811 batteries with capacities ranging from 177mAh / g to 182mAh / g (Figure 33) that operated for 500 cycles at 1.5C.

[0145] The inventors note that LGPS|811 and LPSCl-I|LGPS|811 batteries, which use uncoated bare NMC811, behave differently from LGPS|LNO@811 batteries, which use LNO-coated NMC811, when the rate is increased. At a rate of 20C, the LGPS|LNO@811 battery exhibits a capacity of only 90mAh / g, while the LGPS|811 battery reaches 120mAh / g and stabilizes at 111mAh / g after 400 cycles. The LPSCl-I|LGPS|811 battery reaches a maximum of 128mAh / g, and after 2500 cycles at a rate of 20C, the battery is returned to a slower rate of 0.5C and cycled, achieving a capacity of 198mAh / g after 50 cycles. Note that all three batteries recover their low-rate capacity after high-rate cycling.

[0146] However, bare 811 batteries exhibit a significant capacity drop early in high-rate cycle tests, followed by a slow increase until the capacity stabilizes. This phenomenon is rarely observed in 811s coated with LNO. Therefore, the LNO@811-LGPS interface plays a crucial role in its high-rate behavior. Further development of coating materials and electrolyte substrates for in-situ coating through interface decomposition during battery cycling is important for SSBs to exhibit both flat cycle performance and high-rate capacities exceeding 120 mAh / g.

[0147] The inventors further tested SSBs with different multilayer combinations, and their initial discharge capacity and average voltage are shown in Figure 4C ((1)~(10)), and their voltage characteristics are shown in Figure 34. This includes the three batteries discussed in Figure 20A / 20B ((1)(2)(3)) and the three batteries discussed in Figure 19 ((7)(9)(10)). At a 0.5C rate, all batteries with LGPS in the cathode region ((1)~(4) in Figure 4C) showed capacities higher than 190 mAh / g, indicating that LGPS is good for low-rate capacities, whether bare or coated 811. On the other hand, LPSCl in the cathode ((6)~(10)) reduces the capacity to less than 180 mAh / g, except for the all-LPSCl battery ((5)) with the fewest primary interfaces between layers. However, this battery exhibits poor cycles (Figure 31).

[0148] At 20C rates, both bare 811-LGPS ((1)(3)(4)) and bare 811-LPSCl ((6)) batteries can reach capacities exceeding 100 mAh / g, suggesting that the interface between bare 811 and sulfide electrolytes may generally be favorable for high-rate capacities. While LNO@811-LPSCl ((5)(7)) batteries exhibit high capacities exceeding 100 mAh / g, LNO@811-LGPS ((2)) batteries show a low capacity of 90 mAh / g, suggesting that the LNO coating on 811 may be more compatible with LPSCl than LGPS at high rates. Other types of bare 811 with higher tap density and particle size exhibit lower high-rate capacities than those with smaller particle size 811 ((1) and (6) respectively) when using LGPS ((4)) and LPSCl ((8)) as cathode substrates. This suggests that the Li diffusion rate in 811 is a significant factor limiting capacity at 20C rates. However, all of these SSBs exhibit much better high-rate performance than the liquid electrolyte LNO@811 battery (Figure 34B). This suggests that there is little capacity at 20C due to large polarization ((11)(12)).

[0149] At extremely high rates exceeding 20C, a bare 811-LGPS-LPSCl-I((3)) battery exhibits a current density of 43mA / cm² (100C rate, current density 43mA / cm²) as shown in Figure 35A. 2 ) from 120mAh / g (40C rate, 17.2mA / cm²) 2 It exhibits a high capacity of 20mA / cm². 2 and 30mA / cm 2 At this high current density, the battery can cycle stably for over 10,000 cycles (Figure 35B). The two batteries in Figure 35B were cycled with different histories prior to the 10,000-cycle long cycle. 20 mA / cm 2 The battery initially draws 8.6mA / cm². 2 Then run 500 cycles, then 15mA / cm 2 It was run for 800 cycles (Figure 35C). 30mA / cm 2 The battery initially draws 43mA / cm². 2 The system cycled at various current densities up to (Figure 35D).

[0150] The cycle performance of a multilayer solid-state battery (Li / Si-G|LPSCl-LGPS-LPSCl|NMC811) is shown in Figures 36A and 36B. Figure 36A shows the charge-discharge characteristics at different C rates, and Figure 36B shows the capacity retention of a battery cycled at 2C with cutoff voltages set to 4.1V and 2.5V at 55°C. Over 80% of the capacity was maintained even after 700 cycles. The anode was a silicon-graphite mixture covering Li (Li / Si-G). Here, the particle size of Si = 1 μm, and the cathode was LiNi 0.8 Mn 0.1 Co 0.1 O2(NMC811, cathode active material load = 25 mg / cm³) 2 ) and according to the LPSCl-LGPS-LPSCl multilayer design, Li is used as the electrolyte. 5.5 PS 4.5 Cl 1.5 (LPSCl) and Li 10 Ge1P2S 12 (LGPS) was used.

[0151] 8.6 mA / cm² 2Figures 37A-37C show the results of XPS measurements of cycled battery pellet cross-sections, accompanied by ion milling results for cycled LPSCl from a Li-G|LPSCl|811 battery operating at 30 mA / cm². Figure 37A shows Li 1s XPS at different milling times, Figure 37B shows Li 1s XPS refinement of a sample milled for 430 seconds, and Figure 37C shows XPS quantification of elemental composition at different ion milling times. 2 Figures 37D-37G show the results of XPS measurements of cycled battery pellet cross-sections, accompanied by ion milling results for cycled LPSCl-I from a Li-G|LPSCl|LPSCl-I|LGPS|811 battery operating in LGPS. Figure 37D shows Li 1s XPS at different milling times, Figure 37E shows Li 1s XPS refinement of a sample milled for 430 seconds, Figure 37F shows XPS quantification of elemental composition at different ion milling times, and Figure 37G shows S 2p XPS refinement of a sample milled for 430 seconds.

[0152] Materials and methods

[0153] DFT Binary Calculation: Pseudo-Aspect A x B 1-x Unconstrained (K eff =0GPa)E hull (or decomposition energy) was calculated by constructing a phase diagram using the Python Materials Genomics library. RXN (x, 0 GPa). All G RXN (x, 0GPa) is E in machine learning. hull It is used as input. For different compositions of x, both the pseudophase volume (V) and the reaction strain (ε) are different, G RXN (x,K eff ) can be calculated using the following formula.

number

[0154] When all pseudophases of x composition have a resolution energy of 0, K* is critical K eff That is the case.

number

[0155] If ε(x) ≤ 0, then ε(x) is defined as 0, and K * E becomes infinite. In situations where the material is inherently stable with respect to Li, hull and K * Both of these are zero by definition. The novel method presented here is built on our computing platform and, together with a new machine learning model, extends the ability of constrained ensemble prediction to the design of (in)stability in materials.

[0156] Machine Learning: The composition, energy, and volume of 124497 types of materials are determined by the hull energy (E) at the interface between the material and the Li metal. hull ) and K * For high-throughput calculation of the value, it is queried from the Materials Project. Macroscopic properties (composition, energy, volume) and target value (E hull , K * Machine learning is applied to model the relationship between (X,y) and (x1,x2,...,x). The machine learning model in this study is based on a decision tree. A decision tree consists of hierarchical computation (decision) nodes. The input data to the decision tree is (X,y)=({x1,x2,...,x n The form is},y), where x i'x' is a feature vector, and 'y' is the target value. Decision trees can perform both regression and classification tasks, depending on whether the property of the target variable y is continuous or a finite class. Starting with the input feature vector, each node in the decision tree applies a conditional statement to the feature vector's value and moves to the next node based on the truth value of that conditional statement. Optimizing the tree involves selecting both a criterion feature and a threshold for each node that best partitions the set of items overall. Instead of measuring error, better metrics such as cross-entropy or the Gini exponent are commonly used to measure the goodness of the choice of criteria and data partitioning. The input feature vector X consists of a 10⁴-dimensional composition vector. Specifically, K of 0V * For better learning results, the output also includes x from 0 to 0.9 in the input. The target y is K * It is selected as and becomes the decomposition energy under different conditions. K at 0V * Regarding this, the target y is K in the corresponding x. * The Extremely Randomized Tree model, an ensemble model of individual decision trees, is used. In such a model, a large number of N trees are initialized simultaneously (N=30 in this setting). Each tree in the ensemble is supplied with training data sampled from the training set. A random subset of candidate features is used, and a threshold is randomly drawn from each candidate feature. The best of these randomly generated thresholds is selected as the partitioning rule. Using the trained model along with the target feature y, the composition with the optimal y is found by grid search. The optimization with fixed F / Br / I in Figures 17B and 22 involves a 50% relative composition change constraint for each element to avoid the disappearance of specific elements. Since most compounds are unstable with respect to Li metal, the data for the hull energy of 0 is insufficient in the training set, and the reference for the hull energy of 0 predicted by machine learning needs to be calibrated by DFT. LiCl shows in the DFT binary calculation that its decomposition energy with Li metal is -0eV (Figure 21), and Li 0.49 Cl 0.49 S 0.01 P0.01 This indicates that the predicted decomposition energy is 0.915 eV. Therefore, in Figures 17B, 22, and 29, the decomposition energy shifts down by 0.915 eV.

[0157] Material synthesis: Li 5.5 PS 4.5 Cl 1.5 Li 5.5 PS 4.5 Cl 1.1 F 0.4 Li 5.5 PS 4.5 Cl 1.45 Br 0.15 and Li 5.5 PS 4.5 Cl 1.45 I 0.15 The precursors were prepared by ball milling and solid-state reaction. Stoichiometric amounts of Li2S (99.9% purity, Alfa Aesar), P2S5 (99% purity, Sigma Aldrich), LiF (over 99% purity, Sigma Aldrich), LiBr (over 99% purity, Sigma Aldrich), LiI (over 99% purity, Sigma Aldrich), and LiCl (over 99% purity, Alfa Aesar) were weighed and milled for 16 hours under argon protection. The precursors were transferred to a quartz tube and annealed at 550°C for 1 hour in an argon stream with a heating rate of 5°C / min and a cooling rate of 1°C / min. I purchased the LGPS (325 mesh) from MSE.

[0158] Scanning electron microscopy-focused ion beam-energy dispersive spectroscopy (SEM-FIB-EDX): SEM-FIB-EDX was performed on an FEI Helios 660. Solid electrolyte powder was dispersed on carbon tape and mounted on an SEM stub. The sample was sealed in a plastic box within a glove box containing less than 0.1% O2 and H2O. To avoid exposure to air, the sample was quickly transferred to the SEM in ~15 seconds. The high voltage was 10kV and the magnification was 10,000x. The solid electrolyte particles were etched with a focused ion beam, and an EDX line scan was performed on the cross-section of the etched particles.

[0159] X-ray photoelectron spectroscopy (XPS): XPS was performed using a Thermo Scientific K-Alpha+ with a beam size of 400 μm. Samples were mounted in standard XPS sample holders and sealed in plastic bags. The samples were then transferred to a vacuum environment with approximately 15 seconds of exposure to air. Other samples were mounted in sample holders with vacuum transport modules to completely avoid air exposure. + Ion milling was performed with an ionic energy of 1000 eV and in monatomic mode, and is estimated to have milled Ta2O5 with a bulk modulus of ~140 GPa at 0.26 nm / second. Measured spectra were used for quantification. All XPS results were fitted by peak differentiation and simulation via Avantage.

[0160] X-ray diffraction (XRD): XRD data was obtained using a Rigaku Miniflex 6G. Powder samples were sealed with Kapton film in an argon-filled glove box to prevent air contamination.

[0161] Electrochemistry: A lithium metal solid-state battery with a structure of Li / graphite-LPSCl-center layer-(separation layer)-cathode substrate was fabricated. A 25 μm lithium metal was covered with a graphite thin film and used as the anode. The graphite layer was made by mixing 95 wt% graphite (BTR, China) and 5 wt% PTFE, with a lithium-to-graphite capacity ratio of 2.5:1. 40 mg of LPSCl and 100 mg of center layer powder were applied as the electrolyte. If the center layer differs from that in the cathode substrate, 60 mg of a separation layer of the same electrolyte powder as the cathode substrate is added. LiNbO3 was coated at 1.9 wt% on NMC811 (MSE Supplies) according to previously reported information (Reference 17). NMC811 with large particle size was obtained from XTC in China. To function as a cathode, 70 wt% (LNO@)811 was mixed with 30 wt% LPSCl, and 3% PTFE was added to form the cathode membrane. The cathode loading amount was 2 mg / cm³. 2The battery was initially pressurized to 460 MPa, and a stack pressure of 250 MPa was maintained by the pressurized cell. The battery was cycled at 55°C in an environmental chamber controlled to maintain humidity below 10% within a Memmert hpp110, using either an Arbin battery test station (data log rate: 10 points / sec), or a Solartron 1400 cell test system (data log rate: 10 points / sec) or a LANHE battery test system (data log rate: 1 point / sec) at 55°C. [Table 17]

[0162] In Figure 20B, the (3) Li-G|LPSCl|LPSCl-I|LGPS|811 battery is cycled from 2.5V to 4.25V, starting from a low rate, then a high rate, and then back to a low rate. The subsequent 0.5C cycle is from 2.5V to 4.13V.

[0163] A liquid battery was assembled using Li metal as the anode, glass fiber as the separator, and 1M LiPF6 as the electrolyte in EC / DMC (volume ratio 1:1). 2 mg / cm³ 2 Cathode films with the same active material load were coated in a ratio of NMC811:carbon:PTFE = 85:10:5.

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[0165] Other embodiments are described in the claims.

Claims

1. It is a secondary battery, an anode comprising Li metal, Cathode and, The system comprises a solid electrolyte multilayer disposed between the anode and the cathode, The aforementioned solid electrolyte multilayer is i) A first layer containing a first solid electrolyte, ii) comprising a second layer containing a second solid electrolyte, The second layer is separated from the anode by the first layer, A secondary battery in which the first solid electrolyte and the second solid electrolyte are sulfide solid electrolytes.

2. A secondary battery according to claim 1, wherein the second solid electrolyte has lower stability with respect to the anode metal than one or more of the first solid electrolytes.

3. A secondary battery according to claim 1, The aforementioned solid electrolyte multilayer is under mechanical contraction in a secondary battery.

4. A secondary battery according to claim 3, The mechanical shrinkage exerted on the solid electrolyte multilayer is approximately 0.1 GPa to approximately 250 GPa in this secondary battery.

5. A secondary battery according to claim 4, The aforementioned battery is a secondary battery subjected to an external pressure of approximately 0.1 MPa to approximately 1000 MPa.

6. A secondary battery according to claim 1, A secondary battery in which the porosity of at least one of the anode, the cathode, or the solid electrolyte multilayer is 0% to 25%.

7. A secondary battery according to claim 1, Further comprising a battery case or pouch cell, A secondary battery in which the battery case or pouch cell includes at least one of steel, aluminum, or polymer, or includes at least one of a spring system or an electronic pressurization system having a pressure sensor.

8. A secondary battery according to claim 1, The anode is Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y, Zr, Nb, Mo, Ag, Cd, In, Sn, Sb, Bi, Cs, Te, or a combination thereof, or Li ４ Ti ５ O １２ Li ３ V ２ O ５ A secondary battery, or one that further incorporates carbon.

9. A secondary battery according to claim 1, A secondary battery wherein the anode further comprises a protective layer comprising silicon, silicon dioxide, Li₄Ti₅O₁₂, Li₃V₂O₅, carbon, Au, Ag, Sn, SnO₂, or a combination thereof.

10. A secondary battery according to claim 1, A secondary battery, wherein the anode further comprises a protective layer comprising Li, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y, Zr, Nb, Mo, Ag, Cd, In, Sn, Sb, Bi, Cs, Te, or a combination thereof.

11. A secondary battery according to claim 1, The anode further comprises a protective layer having a particle size of approximately 1 nm to 100 μm, wherein the secondary battery.

12. A secondary battery according to claim 8, The carbon in the secondary battery includes graphite, hard carbon, amorphous carbon, carbon nanotubes, graphene, carbon nanofibers, or fullerene.

13. A secondary battery according to claim 1, The cathode is LiNi ０．８ Mn ０．１ Co ０．１ O ２ (NMC811), LiNi ０．３３ Mn ０．３３ Co ０．３３ O ２ (NMC111), LiNi ０．５ Mn ０．３ Co ０．２ O ２ (NMC532), LiNi ０．６ Mn ０．２ Co ０．２ O ２ (NMC622), LiNi ０．９ Mn ０．０５ Co ０．０５ O ２ (NMC955), LiNi ｘ Mn ｙ Co （１－ｘ－ｙ） O ２ (0 ≤ x, y ≤ 1), LiNi ｘ Co ｙ Al （１－ｘ－ｙ） O ２ (0 ≤ x, y ≤ 1), LiMn ２ O ４、 LiMnO ２ , LiNiO ２、 Li １＋ｚ Ni ｘ Mn ｙ Co （１－ｘ－ｙ－ｚ） O ２ (0 ≤ x, y, z ≤ 1), Li １＋ｚ Ni ｘ Mn ｙ Co ｗ Al （１－ｘ－ｙ－ｚ－ｓ） O ２ (0 ≤ x, y, z, s ≤ 1), Li １＋ｚ Ni ｘ Mn ｙ Co ｓ W （１－ｘ－ｙ－ｚ－ｓ） O ２ (0 ≤ x, y, z, w ≤ 1), V ２ O ５ , selenium, sulfur, selenium-sulfur compounds, LiCoO ２ (LCO), LiFePO ４ , LiNi ０．５ Mn １．５ O ４ , Li ２ CoPO ４ F, LiNiPO ４、 Li ２ Ni(PO ４ ) F, LiMnF ４、 LiFeF ４、 Or LiCo ０．５ Mn １．５ O ４ Rechargeable batteries, including those mentioned above.

14. A secondary battery according to claim 1, The cathode comprises a polymer or carbon black, and is a secondary battery.

15. A secondary battery according to claim 1, A secondary battery in which at least one of the first solid electrolyte or the second solid electrolyte includes a polymer.

16. A secondary battery according to claim 1, A secondary battery in which the first solid electrolyte is selected from Table 1, or the second solid electrolyte is selected from Table 2. Table 1 Table 2 Here, unless otherwise specified, 0 ≤ a, b, d, p, q, w, x, y, z, u, v, w ≤ 1, C is the critical doping amount beyond which the stability of the electrolyte decreases, C can be varied with respect to u, v, w, and 0 ≤ C ≤ 1.

17. A secondary battery according to Claim 1, wherein the secondary battery retains at least 80% of its capacity after at least 10,000 charge-discharge cycles from a 20C rate to a 100C rate.

18. A secondary battery according to claim 1, The aforementioned secondary battery is a secondary battery that can be cycled at current densities from 0.001 mA / cm² to 100 mA / cm².

19. A secondary battery according to claim 1, The solid electrolyte multilayer comprises at least two different first solid electrolytes, and is a secondary battery.

20. A secondary battery according to claim 1, The battery cathode material is a secondary battery having a power density of at least 10 kW / kg.

21. A secondary battery according to claim 1, The battery cathode material has an energy density of at least 600 Wh / kg, and is a secondary battery.

22. A secondary battery according to any one of claims 1 to 21, A secondary battery wherein at least one of the first solid electrolyte or the second solid electrolyte has a core-shell particle structure.

23. A secondary battery according to claim 1, The first solid electrolyte includes a material selected from Table 6, or a material having a formula for a material selected from Table 6, in which one or more elements are substituted with elements of the same group, or A secondary battery comprising a second solid electrolyte which is a material selected from Table 7 or Table 8, or a material having a formula for a material selected from Table 7 or Table 8, in which one or more elements are substituted with elements of the same group. Table 6 Table 7 Table 8 Here, '_{#}' and '_{#±x, y, z, w, l, or m}' represent the nonstoichiometric weighting of the element immediately to the left of '_{#}' or '_{#±x, y, z, w, l, or m}' in the chemical formula of the material. # is within the range of #±n, 0 ≤ n ≤ 0.5, 0 ≤ x, y, z, w, l, m ≤ #, # is within the range of ±n, and 0 ≤ n ≤ 0.

5.

24. A secondary battery according to claim 23, The first solid electrolyte or the second solid electrolyte has a core-shell particle structure, The materials in Table 6 or Table 8 are secondary batteries present in the shell.

25. A secondary battery according to claim 1, A secondary battery in which the cathode is mixed with a solid electrolyte containing a material selected from Table 13 or Table 14. Table 13 Table 14 Here, '_{#}' and '_{#±x, y, z, w, l, or m}' represent the nonstoichiometric weighting of the element immediately to the left of '_{#}' or '_{#±x, y, z, w, l, or m}' in the chemical formula of the material. # is within the range of #±n, 0 ≤ n ≤ 0.5, 0 ≤ x, y, z, w, l, m ≤ #, # is within the range of ±n, and 0 ≤ n ≤ 0.

5.

26. A secondary battery according to claim 25, A secondary battery wherein the solid electrolyte mixed with the cathode comprises one of the materials 32 to 40 in Table 13, or one of the materials 37 to 45 in Table 14.

27. A secondary battery according to claim 25 or claim 26, A secondary battery wherein at least one of the first solid electrolyte or the second solid electrolyte has a core-shell particle structure.

28. The steps include applying a voltage across the anode and the cathode, An energy storage method comprising the step of charging a secondary battery according to any one of claims 1 to 27.

29. The steps include connecting a load to the anode and the cathode, An energy supply method comprising the step of discharging a secondary battery according to any one of claims 1 to 27.

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