Li2ZrCl6-Li6PS5Cl solid electrolyte pairing for dual solid electrolyte solid batteries

Abstract

The pairing of Li2ZrCl6 (LZC) and Li6PS5Cl (LPSC) solid electrolytes increases the effective electrochemical and chemical stability window of the electrolyte in lithium-based solid-state batteries, and can achieve stable cycling under high-voltage cathodes and metal anodes, with the potential to greatly enhance the energy density of solid-state batteries.

Description

[0001] Cross-reference to related applications

[0002] This application claims the interest in the following jointly pending and jointly assigned applications pursuant to Section 119(e) of 35 USC:

[0003] U.S. Provisional Application Serial No. 63 / 598,827, filed November 14, 2023, by Elias Sebti, Tyler Pennebaker, and Raphaële Clément, entitled “Li2ZrCl6-Li6PS5Cl Solid Electrolyte Pairing for Dual Solid Electrolyte Solid Batteries,” Attorney General’s Case No. G&C 30794.0851 USP1 (UC-2024-868-1); is incorporated herein by reference in its entirety. Technical Field

[0004] This invention relates to the pairing of Li2ZrCl6-Li6PS5Cl solid electrolytes for use in dual solid electrolyte solid batteries. Background Technology

[0005] (Note: This application cites several different publications, as indicated throughout the specification by one or more reference numbers enclosed in square brackets [x]. A list of these different publications, ordered by these reference numbers, can be found in the section entitled “References” below. Each of these publications is incorporated herein by reference.)

[0006] In summary, the limited electrochemical stability window of solid-state electrolytes (SEs) and the implementation of high-voltage cathodes or high-energy-density metal anodes appear to be mutually exclusive, casting doubt on the potential for increased energy density in solid-state batteries (SSBs). No SE composition is known to be stable for both metal anodes and high-voltage oxide cathodes.

[0007] To date, work has primarily focused on paired electrolytes within the same chemical family and possessing comparable electrochemical stability windows (i.e., pairings of two sulfide-based electrolytes), thus limiting their potential use in high-voltage SSBs, as degradation will occur at one or both electrodes. However, in recent years, several groups have reported the combined use of halide and sulfide electrolytes, with mixed results. Wu et al. found that, with the aid of NaCrO2+Na 2.25 Y 0.25 Zr 0.75Na-based SSBs with Cl6 cathode composites and Na3PS4 SE layers have achieved success, showing a record-breaking 89.3% capacity retention over 1000 cycles, as chlorides are stable at high potentials while sulfides passivate the Na-Sn anode.

[21] Other groups have used thin layers of sulfide SEs to prevent contact between chloride SEs and metal anodes, resulting in stable cell cycling due to the passivation behavior of the LPSC / anode interface [2, 14, 16, 12, 13, 15, 26, 27]. However, these studies have not assessed the compatibility of sulfide solid electrolytes and chloride solid electrolytes, which can also affect device-level performance. Indeed, as Samanta et al.

[28] highlighted for various chloride-silver sulfide-germanium ore Li6PS5Cl (LPSC) combinations, chloride-sulfide interfaces are not always chemically compatible. Furthermore, Rosenbach et al. employed a bilayer approach, in which a layer of sulfide SEs was applied to the LiNi... 0.8 Mn 0.1 Co 0.1 The O2:LIC|LIC|LPSC|Li-In cell contains Li3InCl6 (LIC) and LPSC. During cycling, a significant impedance increase was observed at the LIC|LPSC interface, attributed to the reactivity between LIC and LPSC, as observed by InS... - This is partly to prove [4].

[0008] Therefore, there is a need for a chemically (and electrochemically) stable solid-state electrolyte pairing that can be achieved using a high-voltage cathode and a high-energy-density anode. This invention meets this need. Summary of the Invention

[0009] The solid-state electrolyte (SE) pairing of Li₂ZrCl₆-Li₆PS₅Cl (LZC-LPSC) exhibits stable behavior under standard cycling operation in both monolayer and bilayer solid-state batteries (SSBs). LZC is used as the cathode electrolyte material due to its relative stability compared to Li / Li + With a stability of up to 4 V, it can withstand the high oxidation potential in the cathode composite [1, 2]. The LPSC SE layer is placed in contact with the metal anode, thereby preventing the metal anode from being easily reduced by LZC, and by decomposing into ionicly conductive and electronically insulating products (LiCl, Li3P and Li2S), the LPSC SE layer forms a passivation interface for the anode [3]. Therefore, the interfaces at both electrodes are stable, thereby promoting stable cycling of high energy density SSB.

[0010] While maintaining a stable interface with limited resistance growth is crucial for the capacity retention of SSBs, the use of two SEs at the SE / SE interface could introduce resistance growth due to the reactivity of halide and sulfide SEs, thus forming an insulating interfacial phase that restricts Li transphase conduction [4]. However, the LZC-LPSC pair did not decompose until 260 °C and showed stable behavior without large interfacial impedance growth even after heat treatment at 110 °C for 24 hours. This lack of decomposition at the interface is important evidence of a kinetically stable interface with smooth Li transport across the phase boundary. The LZC-LPSC combination also demonstrated stable cycling in both monolayer and bilayer SSBs, which is highly relevant to real-world applications.

[0011] In summary, the LZC-LPSC system is an electrically conductive, scalable, and kinetically stable system that holds great promise for implementation in energy-intensive dual SE SSBs with stable long-term cycling. Attached Figure Description

[0012] This patent or application document contains at least one color drawing. Upon request and payment of the necessary fees, the Patent Office will provide a copy of this patent or patent application publication with one or more color drawings.

[0013] Figure 1: Schematic diagrams of solid electrolytes with single-layer and double-layer configurations.

[0014] Figure 2 Scanning electron microscopy (SEM) images obtained on unmixed solid electrolytes at an accelerating voltage of 2 kV after heat treatment at 300 °C for 12 hours: (a) LZC HT-300, (b) LPSC HT-300, and (c) LPS-HT300. The results show that there is a significant distribution of particle size and shape in all samples.

[0015] Figure 3 (a) XRD patterns of LZC collected after grinding and heat treatment, (b) 6 Li nuclear magnetic resonance (NMR) spectrum, and (c) electrochemical impedance spectroscopy (EIS) spectrum.

[0016] Figure 4Analysis of Oxygen (O) Content in Heat-Treated LZC (LZC HT-300) (a) SEM micrograph of LZC particles coated with platinum (Pt). The probe area is depicted in white. (b) Windowless EDS plot showing the distribution of O in the same probe area that may cover multiple aggregates of LZC particles. Areas containing more or less O than average are depicted in white. An accelerating voltage of 3 kV was used. (c) Weight fractions of various elements obtained from the spectra collected over the entire area shown in (b) indicate that O contamination in the sample is negligible (average O content of 2.9 wt.%). Lithium (Li) was not observed due to the extremely low efficiency and high absorption of X-rays generated in the bonded state of Li. Carbon (C) contamination was evident in the SEM chamber, while silicon (Si) was derived from the substrate, and gallium (Ga) was implanted during the preparation of the cross-section. (d) Variation of average O content in different regions of the sample. The average O content in the O-rich and O-poor regions depicted in Figure (b) differs by no more than 1.2 wt.%, which is within the measurement error range.

[0017] Figure 5 (a) XRD patterns collected by LPSC from the pristine and heat-treated states, and (b) XRD patterns from the heat-treated states. 6 Li NMR spectrum and (c) EIS spectrum.

[0018] Figure 6 Analysis of O content in heat-treated LPSC (LPSC HT-300). (a) SEM micrograph of Pt-coated LPSC particles. Particles are depicted in white. (b) Windowless EDS plot showing the distribution of O in the same LPSC particles. Regions containing more or less O than the average are depicted in white. Accelerating voltage of 3 kV was used. (c) Weight fractions of various elements obtained from the spectra collected over the entire region shown in (b), indicating that O contamination in the sample is negligible (average O content of 1.0 wt.%). A considerable amount of Cl in this sample is undetectable at the low accelerating voltage of 3 kV, and Li was not observed due to the extremely low efficiency and high absorption of Li X-rays in the bonded state. C contamination is evident in the SEM chamber, while Si originates from the substrate, and Ga is implanted during the preparation of the cross-section. (d) Variation of average O content in different regions of the sample. The average O content of the O-rich and O-poor regions depicted in Figure (b) differs by no more than 2.2 wt.%, within the measurement error range.

[0019] Figure 7 (a) XRD patterns of raw and heat-treated LPS. (b) 31 P NMR spectrum and (c) EIS spectrum.

[0020] Figure 8Analysis of O content in heat-treated LPS (LPS HT-300). (a) SEM micrograph of Pt-coated LPS particles. Particles are depicted in white. (b) Windowless EDS plot showing the distribution of O in the same LPS particles. Regions containing more or less O than the average are depicted in white. An accelerating voltage of 3 kV was used. (c) Weight fractions of various elements obtained from the spectra collected over the entire region shown in (b), indicating that O contamination in the sample is negligible (average O content of 3.5 wt.%). Li was not observed due to the extremely low efficiency and high absorption of X-rays generated in the bonded state of Li. C contamination was evident in the SEM chamber, while Si was derived from the substrate and Ga was implanted during the preparation of the cross-section. (d) Variation of average O content in different regions of the sample. The average O content in O-rich and O-poor regions (as shown in Figure (b)) differed by no more than 5 wt.%.

[0021] Figure 9 Results of synchrotron XRD under in-situ heating experiments. Diffraction patterns as a function of temperature were obtained for a) LZC+LPS and b) LZC+LPSC mixed samples. Patterns were acquired during the temperature ramp from room temperature to 300 °C and during the subsequent temperature hold at 300 °C. c) R-values ​​were obtained from sequential refinement of the LZC+LPSC diffraction pattern during in-situ experiments using a two-phase (LZC and LPSC) model. wp Value. R wp The value begins to increase from approximately 260°C, indicating sample degradation. Due to the low crystallinity of the sample, the LZC+LPS spectrum cannot be refined.

[0022] Figure 10 Analysis of LZC and LPS samples annealed for 24 hours at various temperatures (e.g., HT-110 represents treatment at 110 °C) and mixed tablets. (a) XRD patterns obtained on all samples. Degradation observed in HT-300 samples is marked with * for LiCl and * for Li x Zr y The P2S6 phase is marked with °. (b) was obtained on the same sample. 6 Li and (c) 31 P ss-NMR spectra. The unmixed spectrum in Figure (a) is the sum of two spectra, each of which was obtained on a single phase without mixing. 31Low-intensity, unidentified signals in the P spectrum are indicated by circles (°). (d) Zr 3d XPS spectra obtained from the mixing and pressing of pristine Li2ZrCl6 with HT-110, HT-150 and HT-300. (e) Raman spectra collected at various points on LZC-LPS HT-300 samples and annealed unmixed LPS. The spectra of ZrS2 and ZrS3 were digitized according to the reports: ZrS2 data from Mañas-Valero et al.

[29] , and ZrS3 data from Jin et al.

[30] .

[0023] Figure 11 Analysis of LZC and LPSC samples annealed for 24 hours at various temperatures (e.g., HT-110 represents treatment at 110 °C) and mixed tablets. (a) XRD patterns obtained on all samples. Degradation observed in HT-300 samples is marked with * for LiCl and * for Li x Zr y The P2S6 phase is marked with °. (b) was obtained on the same sample. 6 Li and (c) 31 P ss-NMR spectra. The unmixed spectrum in Figure (b) is the sum of two spectra, where each spectrum was obtained on a single phase without mixing. (d) Zr3d XPS spectra obtained from mixed pellets of pristine Li2ZrCl6 and HT-110, HT-150 and HT-300. (e) Raman spectra collected at various points on LZC-LPSC HT-300 samples and annealed unmixed LPSC. The spectra of ZrS2 and ZrS3 were digitized according to the reports: ZrS2 data from Mañas-Valero et al.

[29] , and ZrS3 data from Jin et al.

[30] .

[0024] Figure 12 Analysis of annealed LZC and small-particle LPSC samples, as well as mixed tablets, after heat treatment (e.g., HT-110 represents treatment at 110 °C) for 24 hours. (a) XRD patterns obtained on all samples. Degradation observed in HT-300 is marked with * for LiCl and * for Li x Zr y The P2S6 phase is marked with °. (b) was obtained on the same sample. 6 Li and (c) 31 P ss NMR spectra. The “unmixed” spectrum in Figure (b) is the sum of two spectra collected from pure LZC and pure LPSC (after annealing), scaled to match a 1:1 molar ratio.

[0025] Figure 13EIS Nyquist plots of samples prepared with LPSC and LZC before and after heat treatment at 110 °C (HT-110) for 24 hours under an applied pressure of 70 MPa. All spectra were obtained at an applied pressure of 70 MPa and an excitation voltage of 30 mV. These spectra were collected on (a) bilayer presses prepared from pristine LPSC and pristine LZC, (b) bilayer presses prepared from LPSC and LZC respectively annealed at 300 °C for 12 hours (labeled "HT-300"), and (c) pristine LZC sample (unannealed).

[0026] Figure 14 Regarding the LZC-LPSC HT-25 sample 6 Li VT-NMR. All spectra were obtained at 18.8 T and a rotation speed of 30 kHz. In these spectra, the LPSC resonance was fixed at 1.3 ppm to avoid ppm drift from the heating effect of the gasket coil.

[0027] Figure 15 Galvanostatic cycling profiles of (a) monolayer and (b) bilayer solid-state cells using LZC and LPSC. After the first cycle at C / 10, comparisons are made at C / 3 between 4 and 2.5 V for Li / Li. + (c) Capacity was plotted as a function of cycle number to track capacity retention. The cathode was made of 40 wt% LFP, 57 wt% LZC, and 3 wt% VGCF. Fluctuations in cell capacity were due to laboratory (diurnal) temperature variations.

[0028] For electrochemical performance evaluation, the cells were cycled at 50 MPa at room temperature with Li0.5In as the counter electrode. Capacity utilization and cell cycling were evaluated using a Neware Instrument cycler (https: / / newarebattery.com, incorporated herein by reference), starting with a 0.1C initiation cycle followed by a longer cycle at 0.3C. All cells were cycled at room temperature, as evidenced by capacity fluctuations due to time-of-day temperature variations.

[0029] Figures 16A-16B A flowchart illustrating a method for manufacturing a solid-state electrode, electrode, or battery is shown.

[0030] Figure 17 : A schematic diagram of an exemplary cold pressing apparatus that can be used to manufacture the tablet layers described herein.

[0031] Figure 18 : A schematic diagram of a bench vise that can be used during an exemplary hot pressing process according to one or more embodiments. Obtained from Figure 1 of

[25] .

[0032] Figure 19 Anode-free battery according to one or more embodiments.

[0033] Figure 20 Example battery heating and operation circuit. Detailed Implementation

[0034] In the following description of preferred embodiments, reference is made to the accompanying drawings, which form a part therein, and specific embodiments in which the invention may be practiced are illustrated by way of illustration. It should be understood that other embodiments may be utilized and structural changes may be made without departing from the scope of the invention.

[0035] Technical Specifications

[0036] Exemplary solid electrolyte configuration

[0037] Figure 1 illustrates an exemplary configuration of a solid electrolyte in a lithium solid-state battery. The battery includes: a composite cathode layer comprising Li₂ZrCl₆ (LZC), wherein LZC is the cathode electrolyte; and a solid electrolyte layer comprising Li₆PS₅Cl (LPSC). In a monolayer system, the composite cathode layer and the solid electrolyte layer are in direct contact. In a bilayer system, the composite cathode layer and the solid electrolyte layer are coupled via the cathode electrolyte layer.

[0038] Figure 1A A single-layer configuration is shown, in which a solid electrolyte layer is located between the composite cathode layer and the anode of the battery. Figure 1B A dual-layer configuration is shown, which includes a solid electrolyte layer in contact with a separate cathode electrolyte layer containing LZC, wherein the cathode electrolyte layer is located between the solid electrolyte layer and the composite cathode layer.

[0039] like Figure 1A and 1B As shown, the cathode electrolyte layer and the composite cathode layer each include a first plurality of particles containing LZC, and the solid electrolyte layer includes a second plurality of particles containing LPSC. The average particle size and particle size distribution of the particles enable physical contact between the first plurality of particles and the second plurality of particles to promote lithium transport between LPSC and LZC, while suppressing harmful reactivity between LZC and the LPSC during normal battery operation.

[0040] In one or more embodiments, the cathode electrolyte layer and / or composite cathode layer each include a first plurality of particles comprising LZC and having a first diameter D1 in the range of 10 nm ≤ D1 ≤ 2 micrometers. The solid electrolyte layer includes a second plurality of particles comprising LPSC and having a second diameter D2 in the range of 10 nm ≤ D2 ≤ 10 micrometers.

[0041] In one or more embodiments, the cathode electrolyte layer and / or composite cathode layer each comprise ball-milled particles containing LZC. In another embodiment, the cathode electrolyte layer and / or composite cathode layer each comprise particles containing LZC having the same or equivalent size distribution, disorder, crystallinity, and conductivity characteristics as particles formed by ball milling LZC-containing powder. In some embodiments, the LZC is a crystal with defects and / or disorder, and has a conductivity greater than 0.1 mS / cm.

[0042] Figure 1 further illustrates the battery including a current collector (e.g., a metal) on top of a composite cathode layer and below an anode layer. In the illustrated embodiment, the composite cathode layer further includes LZC mixed with a cathode active material and a carbon conductive additive. In one or more embodiments, the cathode active material comprises a lithium transition metal compound, and the anode layer comprises a lithium alloy or lithium metal. Exemplary lithium transition metal compounds include, but are not limited to, lithium transition metal oxides, lithium transition metal fluorides, or lithium transition metal polyanionic compounds.

[0043] First Example: Evaluation of the Stability of LZC-LPSC

[0044] a. LZC preparation

[0045] LZC was synthesized by mechanochemical synthesis (3 hours at 550 rpm) from LiCl and ZrCl4 in a 2:1 molar ratio, containing 10 wt% excess ZrCl4 to compensate for its preferential adhesion to the grinding media. X-ray diffraction (XRD) patterns of the ground material were obtained. Figure 3 (a) and 6 Li NMR spectroscopy ( Figure 3 (b) confirms that it is a P with a small amount of LiCl impurities. The nature of m1 polymorphs [5]. The 0.167 mS cm⁻¹ was measured using EIS. -1 The lithium-ion conductivity is 0.431. Activation energy of 0.008 eV ( Figure 3 (c)).

[0046] Samples intended for chemical reactivity testing were annealed under vacuum in sealed ampoules at 300°C for 12 hours. The heat treatment preserved the LZC crystal structure and resulted in the absorption of LiCl by LZC, as observed in its XRD patterns and... 6 The disappearance of the Li NMR spectrum proves ( Figure 3 (a) and 3(b)). After annealing at 300 °C, as observed by scanning electron microscopy (SEM), the particles appear to have a wide size range from approximately 10 nm to 2 μm. Figure 2(a) The ionic conductivity of annealed LZC decreased to 5.26. mS cm -1 Furthermore, the activation energy increases to 0.495. 0.009 eV ( Figure 2 (c) Given that the chemical stability of chloride and sulfide solid electrolytes has been found to be sensitively dependent on the O content of impurities, windowless EDS was used to probe the O content of LZC samples annealed to 300 °C. This technique allows for high-resolution analysis of light elements. Here, an airless workflow was employed to minimize sample contamination, with sample transfer utilizing a SemiLab shuttle. First, solid electrolyte powder was deposited onto a Pt / Pd-coated Si wafer within an Ar-filled glove box. Then, a protective Pt layer was deposited on top of the particles. Cross-section preparation was performed using a focused ion beam (FIB). Grooves were milled to clean the cross-sectional surface, and the cross-section was further polished with a lower current beam. To increase the resolution of the EDS plot, the sample volume from which X-rays were generated was minimized and kept as small as possible or on the order of the particle size. For this purpose, a low accelerating voltage of 3 kV was used, limiting the probe depth to less than about 1 μm, which could potentially cover multiple aggregated particles of LZC. The low accelerating voltage used for O analysis means that the X-ray K-lines of most other elements are only weakly excited or not excited at all, and the resulting EDS spectra cannot be used for conventional EDS quantification. The results of this analysis are shown in... Figure 4 The data indicates minimal O contamination in the sample (average O content of 2.9 wt.%) and minimal variation in O content throughout the sample (the difference in O content between O-rich and O-poor areas does not exceed 1.2 wt.%, which is within the measurement error range). Therefore, it can be safely assumed that O plays a minimal role in the stability of the LZC electrolyte.

[0047] b. LPSC preparation

[0048] LPSC was purchased from a commercial supplier. Its XRD pattern and... 31 P NMR spectroscopy ( Figure 5 (a) and 5(b)) confirmed its F The crystal structure is 3m, which is very consistent with previous reports [6]. Its ionic conductivity and activation energy are 2.19 mS / cm. -1 and 0.362 0.007 eV ( Figure 5 (c)).

[0049] Samples intended for chemical reactivity testing were annealed in sealed ampoules under vacuum at 300°C for 12 hours. The heat treatment preserved the LPSC crystal structure, as evidenced by the retention and identical reflections in the XRD patterns. 31The results of P NMR spectroscopy ( Figure 5 (a) and 5(b)). After heat treatment, as observed by SEM, the particles appear to have a wide range of sizes, from approximately 10 nm to 10 micrometers. Figure 2 (b) The ionic conductivity and activation energy of annealed LPSC increased to 2.60 mS cm⁻¹. -1 and 0.395 0.006 eV ( Figure 4 (c) The O content of LPSC samples annealed to 300 °C was probed using windowless EDS (similar sample preparation to that used for LZC), with a low accelerating voltage of 3 kV, thus limiting the probe depth to less than approximately 1 μm. The probe volume was approximately within the size of a single LPSC particle, such as... Figure 6 As shown in (a). This is shown in... Figure 6 The windowless EDS results in (b)-(d) indicate minimal O contamination in the sample (average O content of 1.0 wt.%) and minimal variation in O content throughout the sample (the difference in O content between O-rich and O-poor areas does not exceed 2.2 wt.%, which is within the measurement error range). Therefore, it can be safely assumed that O plays a minimal role in the stability of LPSC electrolytes.

[0050] c. Li3PS4 (LPS) preparation

[0051] Li3PS4 was purchased from a commercial supplier. Its XRD pattern and... 31 P NMR spectroscopy ( Figure 7 (a) and 7(b)) confirmed its Pnma crystal structure, which is very consistent with previous reports [7, 8]. Its ionic conductivity and activation energy are 7.26 Ω·cm. mScm -1 and 0.392 0.005 eV ( Figure 7 (c)).

[0052] Samples intended for chemical reactivity testing were annealed under vacuum in sealed ampoules at 300°C for 12 hours. The heat treatment resulted in a slight decrease in crystallinity. Figure 7 (a) and 31 Separation in P NMR spectrum The fraction of type PS4 tetrahedrons increases ( Figure 7 (b) The peak at 86.5 ppm) [9]. After heat treatment, as observed by SEM, the particles appear to have a wide range of sizes, from about 10 nm to 2 micrometers. Figure 2 (c) After annealing, the ionic conductivity decreased to 5.47. mS cm -1 Furthermore, the activation energy increases to 0.421. 0.012 eV ( Figure 7 (c) The O content of LPS samples annealed to 300 °C was probed using windowless EDS (similar sample preparation to that used for LZC), with a low accelerating voltage of 3 kV, thus limiting the probe depth to less than approximately 1 μm. The probe volume was approximately within the size of a single LPS particle, such as... Figure 8 As shown in (a). This is shown in... Figure 8 The windowless EDS results in (b)-(d) indicate minimal O contamination in the sample (average O content of 3.5 wt.%) and minimal variation in O content throughout the sample (difference in O content between O-rich and O-poor areas not exceeding 5.0 wt.%). Therefore, it can be safely assumed that O plays a minimal role in the stability of the LPS electrolyte.

[0053] d. Heat treatment process

[0054] As described above, prior to the mixed heat treatment test, LZC, LPSC, and LPS were individually annealed at 300°C under vacuum for 12 hours to avoid the evolution of individual phases during the reactivity test.

[0055] To test the reactivity between SEs, the powder was ground in a mortar with a pestle for 20 minutes to produce a homogeneous mixture, and then pressed into pellets to generate the maximum contact surface area between the phases. The contact area between LZC and LPS(C) in these pellets was significantly greater than that present in SSB because the contact area was confined to a 2D plane within the cell (at the cathode composite-SE layer interface in a single-layer cell or at the interface between SEs in a bilayer configuration), thereby accelerating the formation of decomposition products.

[0056] This exploration focuses on the LZC-LPSC pairing, with the LZC-LPS pairing used as a control to highlight the impressive stability of the LZC-LPSC system. As an initial test of chemical compatibility, milled LZC was mixed with pristine LPS(C) at a 1:1 molar ratio and examined using synchrotron X-ray diffraction (XRD) during in-situ heating. The experiment involved a gradual temperature ramp from room temperature to 300 °C, followed by a hold at 300 °C. Figure 9 The results presented indicate that although the LZC-LPS mixture begins to degrade at about 90°C, it is stable up to about 260°C.

[0057] To further understand the degradation mechanism of these mixtures, LZC and LPS(C), both pre-annealed at 300°C for 12 hours, were mixed in a 1:1 molar ratio and exposed to heat treatment at 25°C, 70°C, 110°C, 150°C, and 300°C for 24 hours. Prior to heat treatment, tablets were sealed under vacuum in dry quartz ampoules. The mixed-phase heat-treated sample (HT-) was labeled according to its exposure temperature (i.e., HT-110 was treated at 110°C for 24 hours).

[0058] For the LZC-LPS system, the 90°C initial reaction temperature observed by in-situ heated synchrotron XRD was confirmed by analysis of the heat-treated mixed tablets. XRD analysis of the mixed tablets ( Figure 10 (a) The presence of LiCl in samples treated at 110 °C and above indicates degradation of the original LZC and LPS phases, with additional Li associated with the Li2MP2S6 (M=V, Mn, Fe, Co, Ni and Zn) compounds reported by Sundaramoorthy et al.

[31] . x Zr y The P2S6 phase was present in the HT-300 sample. It was obtained from pristine and heat-treated LZC-LPS mixed tablets. 6 Li and 31 P ss-NMR spectra such as Figure 10 As shown in (b) and 10(c). In Figure 10 In (c), for the HT-110 sample, 6 The Li LPS resonance begins to broaden, and at 1.37 ppm, distributions are observed. -LPS has another small broad resonance, which is at 89.1 ppm. 31 The P resonance response increased, indicating the degradation of the LPS phase. After 24 hours at 300°C, some LZC remained, while LPS had completely decomposed, producing LiCl and Li. x Zr y P2S6, which is very consistent with the XRD results. Although LZC 6 The Li resonance did not show significant evolution at 150℃, but Figure 10 The Zr3d XPS pattern shown in (d) points to the formation of ZrS2 and ZrS3 substances, indicating that LZC is reacting with LPS. Figure 10 The Raman spectra shown in (e) confirm the presence of S8 and P2S6 in the degraded sample during heat treatment at 300 °C. 4- and ZrS x substance.

[0059] Earlier in-situ heated synchrotron XRD results indicated that the LZC-LPSC combination was very stable at temperatures up to approximately 260°C, a finding that was further confirmed by analysis of the heat-treated mixed tablets. Figure 11 (a) shows the XRD results obtained on pristine LZC and LPSC, as well as on mixed tablets. Only after heat treatment at 300 °C did the tablets show any signs of degradation, with the formation of LiCl and LiCl similar to the LZC-LPS system. x Zr y P2S6 phase. In Figure 11 In (b) and 11(c), for all samples heat-treated at or below 150 °C, the samples obtained on the LZC-LPSC samples... 6 Li and 31 The P SS-NMR spectrum showed no signs of evolution. Heat treatment at 300℃ completely decomposed the LPSC, leaving... -Li3PS4, Li x Zr y P2S6 and LiCl. Figure 11 (d) shows that the Zr 3d XPS further confirms the stability of the LZC-LPSC combination up to 150 °C, as the HT-150 sample retains the original LZC signal. In the HT-300 sample, LZC, ZrS2, ZrS3, and PS4... 3- and P2S6 4- Some were detected by Raman spectroscopy (see...) Figure 11 (e) confirms that a reaction between LZC and LPSC occurred during the heat treatment.

[0060] Neither of the two SE pairings tested here is thermodynamically stable; however, when the powders are mixed, compressed into tablets, and heated together, the LPSC-LZC pairing remains unreacted up to approximately 260 °C, while the LPS-LZC pairing reacts at approximately 90 °C. The higher chemical compatibility of the LPSC-LZC pairing is expected to translate into higher (electro)chemical stability when the dual electrolytes are cycled in SSBs. Although dual electrolyte chemistry plays a crucial role in reactivity (thermodynamic factors), the finite kinetics of the decomposition reaction are also important in stabilizing the LZC-LPSC pairing. Although the SEs of interest have fairly different particle sizes (see...), Figure 2 (a), 2(b), 2(c)), but the inventors noted that particle size did not appear to play a major role in the stability of the LZC-LPSC system. In fact, further testing using LPSC particles of approximately 1 μm size (as specified by the supplier) yielded results similar to those obtained using larger LPSC particles (>1 μm), such as... Figure 12As shown. No reactivity was observed in the HT-150 sample; degradation was only observed after heat treatment at 300°C.

[0061] Second embodiment: Evaluation of the conductivity properties of LZC-LPSC

[0062] Analysis of bilayer tablets

[0063] In a custom Ti / PEEK / Ti plunger cell, bilayer tablets were pressed using sequential layer densification with LPSC (first pressed at 350 MPa) followed by LZC (pressed at 175 MPa). Two types of dense bilayer tablets were formed using a milled or pristine phase and an annealed phase (denoted as HT-300), with relative densities of 94% and 96%, respectively. First, we compared the total conductivity and activation energy of LZC / LPSC and LZC HT-300 / LPSC HT-300 tablets at room temperature to determine the effect of annealing at 300 °C. Then, we investigated the effect of heat treatment at 110 °C for 24 hours under an applied pressure of 70 MPa (simulating industrial-related hot pressing) on ​​the total conductivity and activation energy of the LZC HT-300 / LPSC HT-300 bilayer tablets at room temperature. Figure 13 EIS data obtained from LPSC / LZC pellets were fitted using a parallel constant phase element (CPE) and a resistor connected in series with the CPE (blocking electrode behavior) to simulate conduction through the material bulk, indicating that even at low temperatures (limited to EIS systems at -30°C), the interfacial components cannot separate from the bulk.

[0064] We observed that the total conductivity decreased from 0.304 mS / cm for the LZC / LPSC bilayer tablet. -1 Significantly reduced to 1.30 μS cm⁻¹ for LZC HT-300 / LPSC HT-300 bilayer tablets. -1 ( Figure 13 (a) This reduction is attributed to the significant decrease in the electrical conductivity of the LZC component during crystallization, as the conductivity of this component alone decreased from 0.167 mS / cm after annealing at 300°C for 24 hours. -1 Reduced to 0.526 μS cm -1 ,like Figure 13 As shown in (b), the activation energy is 0.417 kJ / LPSC bilayer. The voltage was increased from 0.008 eV to 0.561 eV in the LZCHT-300 / LPSC HT-300 bilayer. 0.015 eV. For LZC HT-300 / LPSC HT-300 tablets, this activation energy is greater than any activation energy of the HT-300 phase alone (LZC HT-300: 0.495 eV). 0.009 eV; LPSC HT-300: 0.395 The value of 0.006 eV indicates that the activation barrier associated with interface transport is significant.

[0065] After heat treatment at 70 MPa and 110 °C for 24 hours, the electrical conductivity of the LPSC HT-300 / LZC HT-300 bilayer decreased from 1.30 μS / cm. -1 Increased to 1.52 μS cm -1 ( Figure 13 (c) , consistent with the increase in relative density (96% to 100%). Activation energy increases from 0.561 The .015 eV decreased to 0.493. 0.008 eV, which is very close to the value obtained for pure LZC HT-300 (0.495 eV). 0.009 eV). This indicates that the interfacial activation energy is small and significantly reduced compared to before heat treatment at 110 °C.

[0066] These results led the inventors to believe that hot calendering of thin SE films could be a feasible and scalable method to form conductive bilayer SE assemblies from LZC and LPSC for incorporation into SSBs. The pressure, speed, and temperature of the calender should be selected to limit the potential decrease in reactivity or conductivity of individual phases.

[0067] Third embodiment: NMR characterization

[0068] exist Figure 14 The variable temperature (VT) of the HT-25 sample shown (the two phases were previously annealed separately at 300°C, mixed, and heat-treated at 25°C for 24 hours) 6 Li NMR showed signs of Li chemical exchange between the two phases.

[0069] In NMR, as sample temperature increases and the rate of chemical exchange between different local environments increases, the resonances corresponding to the sites in the exchange become slightly closer together, broaden, and eventually merge at their weighted average positions when they reach a crossover point [10,11]. Therefore, in the hybrid LZC-LPSC system... 6 Li VT-NMR can provide insights into the electrical conductivity of the interface between two phases by observing the chemical exchange of Li.

[0070] For the HT-25 sample, at a low temperature of 308 K, the asymmetric tails of the LZC (-1.1 ppm) and LPSC (1.3 ppm) signals pointed towards each other, indicating a small degree of exchange. When the sample temperature was further increased to 341 K, each signal gradually broadened and shifted towards the other, thus confirming that the interface between the phases allowed interphase Li hopping.

[0071] Despite the large particle size of each individual phase (all pre-heat-treated) and the low densification pressure (measured on powder derived from densified HT-25 tablets, ground with a pestle in a mortar, and densified by hand while filling the rotor), the detection of Li jumps across the phase boundaries confirmed high conductivity at the interfaces between the phases.

[0072] Fourth Implementation Example: Evaluation of Cyclic Behavior

[0073] Dual-SE SSBs are assembled in single-layer and double-layer configurations, featuring a Li-In anode and a cathode composite material composed of an LZC cathode electrolyte, LiFePO4 (LFP) cathode active material, and vapor-grown carbon fiber (VGCF) conductive additive. In the single-layer cell, the LPSC SE layer is placed in direct contact with the composite cathode. In the double-layer cell, a thin buffer layer of LZC is placed between the LPSC SE layer and the cathode composite material to prevent contact between the easily oxidized sulfide SE and LFP. Figure 15 (c) provides diagrams of two cell architectures.

[0074] Both cell types exhibited similar first-cycle capacities at a C / 10 current rate of approximately 100 mAh g. -1 There is almost no overpotential (see Figure 15 (a) and 15 (b)).

[0075] In the second cycle, after increasing the rate to C / 3, the cell overpotential increased and the discharge capacity decreased to approximately 75 mAh g. -1 .

[0076] After 140 cycles, the discharge capacities of single-layer and double-layer cells were 56.8 and 69.6 mAh g, respectively. -1 The faster capacity decay observed for the single-layer configuration is due to sulfide SE oxidation caused by the contact between the LPSC layer and the cathode composite, highlighting the long-term cycling benefits of preventing contact between the CAM and SE layers through the LZC buffer layer.

[0077] The stable cycling performance of the LZC / LPSC bilayer cell suggests that SE pairing could be a viable option for further bilayer SSB development. However, even during the initial C / 10 cycles, the cell capacity relative to the theoretical capacity of the LFP (170 mAh g) remains low. -1 The low level indicates a need for further optimization of the cell structure to achieve greater cathode utilization.

[0078] In summary, the experimental results presented in this paper confirm that:

[0079] 1. LZC-LPSC pairing is a highly conductive and stable solid-state electrolyte pairing with great potential for realizing energy-dense solid-state batteries. Although LZC-LPSC is not thermodynamically stable in terms of decomposition, its large particle size makes it kinetically stable, maintaining the bulk structure and conductivity of both components even when exposed to high temperatures.

[0080] 2. LZC-LPSC forms a nearly 100% dense bilayer tablet through cold pressing, highlighting the promising mechanical properties of this pairing.

[0081] 3. Even under cold or low-pressure conditions, the LZC-LPSC phase boundary exhibits high conductivity to Li.

[0082] 4. Cells assembled with LZC-LPSC solid electrolyte pairings exhibited stable cycling behavior of more than 150 cycles at room temperature.

[0083] Fifth Example: Particle Size Analysis

[0084] Rough estimates of the particle size distribution of LZC, LPSC, and LPS solid electrolytes annealed to 300 °C were obtained using a GeminiSEM560 scanning electron microscope (SEM), an accelerating voltage of 2 kV, an electron current of 50–100 pA, and an SE2 Everhart-Thornley detector. Zeiss SmartSEM software was used for SEM image acquisition and microscope operation.

[0085] Exemplary process steps for manufacturing a solid electrolyte that can be used in lithium-ion batteries.

[0086] Figure 16A A method for preparing a solid electrolyte in combination with a cathode electrolyte is shown, comprising the following steps.

[0087] Box 1600 indicates obtaining a first powder containing LZC and a second powder containing LPSC. The first powder can be manufactured by ball milling or an equivalent method.

[0088] Box 1602 indicates densifying the first powder to form a first tablet layer or densifying the second powder to form a second tablet layer - that is, densifying the first (second) powder to form a first (second) tablet layer.

[0089] Box 1604 indicates that a second (first) powder is deposited on a first (second) tablet layer and the second (first) powder on the first (second) tablet layer is densified to form a second (first) tablet layer.

[0090] In one embodiment, densification includes cold pressing. Figure 17 The cold pressing process is shown, in which pressure is applied using a hydraulic press at room temperature.

[0091] In one embodiment, cold pressing at room temperature includes applying a pressure of at least 350 MPa to the second powder for at least 1 minute to form a second tablet layer; and applying a pressure of at least 175 MPa to the first powder containing LZC for at least 1 minute while the first powder is on top of the second tablet layer.

[0092] In one or more embodiments, the densification includes or further includes hot pressing or hot rolling (calendering) to form a tighter interfacial contact between the tablet layers. Figure 18 The hot pressing process is illustrated, in which the sample is pre-cold-pressed in a cell, the sample cell is then clamped in a vise (e.g., at 70 MPa), and the sample cell is then placed in an environmental chamber at 110°C for 24 hours.

[0093] References [21-23] describe exemplary processes for cold pressing and hot pressing in solid electrolytes described herein. Reference

[23] describes an exemplary hot rolling process for densification of solid-state batteries.

[0094] Box 1606 represents a solid electrolyte and a cathode electrolyte formed by the process, wherein a first sheet layer and a second sheet layer form a double layer, or wherein the first sheet layer is a solid electrolyte as part of a densified composite cathode configured as a single layer.

[0095] Box 1608 indicates an optional combination of the electrolyte with the battery's electrodes. In one embodiment, this combination includes pressing a first sheet layer to the cathode and pressing a second sheet layer to the anode.

[0096] Figure 16B A method for manufacturing a solid electrolyte in combination with a cathode electrolyte is shown according to another embodiment.

[0097] Box 1610 represents combining LZC powder containing LZC compound with a first binder in an LZC solution;

[0098] Box 1612 represents combining LPSC powder containing LPSC compound with a second binder in an LPSC solution;

[0099] Box 1614 represents drying the solution to form an LZC layer and an LPSC layer; and

[0100] Box 1616 represents making the LZC layer contact the LPSC layer.

[0101] Illustrative embodiments of the present invention include, but are not limited to, the following (also referring to Figures 1-20).

[0102] 1. A device structure 100, 200 for use in lithium-ion solid-state batteries, comprising:

[0103] Composite cathode layer 102, the composite cathode layer comprising an LZC compound containing at least lithium, zirconium, and chlorine, optionally fluorine, and / or oxygen. Figure 1A and 1B LZC in the context of cathode electrolytes; and

[0104] Solid electrolyte layers 104 and 106, wherein the solid electrolyte layers contain LPSC compounds ( Figure 1A and 1B The LPSC compound contains at least lithium, phosphorus, sulfur, and chlorine (optionally oxygen and fluorine), and the LPSC compound is arranged in a sulforaphite-germanium structure.

[0105] The composite cathode layer and the solid electrolyte layer are in direct contact or coupled via the cathode electrolyte layer 108.

[0106] 2. The device structure according to claim 1, wherein the LZC compound has a trigonal crystal structure (P-3m1) or a monoclinic crystal structure (C2 / m).

[0107] 3. The device structure according to claim 1 or 2, wherein the LZC compound comprises Li2ZrCl6 and the LPSC compound comprises Li6PS5Cl.

[0108] 4. The device structure according to any one of claims 1 to 3, wherein:

[0109] The LZC compound includes Li 2-x ZrCl 6-x (0≤x≤2) or Li2Zr 1-x Cl 6-4x (0≤x≤1) or a variant thereof in which at least one of Li, Zr, or Cl is replaced by another element; and

[0110] The LPSC compound includes Li 6-x PS 5-x Cl 1+x (0≤x≤1).

[0111] 5. The device structure according to any one of clauses 1 to 4, wherein the composite cathode layer comprises the LZC compound mixed with cathode active material 116 and carbon conductive additive 118.

[0112] 6. The device structure according to any one of clauses 1 to 5, wherein the electrochemical cell includes the solid electrolyte layer in contact with the anode and located between the anode and the composite cathode layer (see, for example...). Figure 15c) wherein the chemical composition of the LZC compound and the LPSC compound results in a capacity retention of at least 87% after 100 cycles, wherein each cycle includes the cell 110 under C / 3 conditions (charging for more than 3 hours and discharging for more than 3 hours) or at a slower rate of charging and discharging.

[0113] 7. Figure 1B An example of a device structure according to any one of clauses 1 to 5 is shown, further comprising:

[0114] Double-layered, comprising:

[0115] The cathode electrolyte layer 108 containing LZC compound, and

[0116] The solid electrolyte layer 106 containing LPSC compounds,

[0117] The cathode electrolyte layer 108 is located between the solid electrolyte layer 106 and the composite cathode layer 102.

[0118] 8. The device structure according to Clause 7, wherein when the electrochemical cell comprises a double layer located between and in contact with the anode and the composite cathode layer, the chemical composition of the LZC compound and the LPSC compound results in a capacity retention of at least 97% after 125 cycles, wherein each cycle comprises the cell 202 under C / 3 conditions (charging for more than 3 hours and discharging for more than 3 hours) or at a slower rate of charging and discharging.

[0119] 9. The device structure according to any one of Clauses 1 to 9, wherein the tablet mixture of LZC compound and LPSC compound is characterized at a temperature of at least 200 degrees Celsius as being electrochemically stable by measurement and free from decomposition, degradation or reaction products associated with the reaction of LZC compound and LPSC compound, wherein said measurement includes at least one of X-ray diffraction measurement, X-ray photoelectron spectroscopy (XPS), solid-state nuclear magnetic resonance (NMR) spectroscopy or Raman spectroscopy.

[0120] 10. The device structure according to any one of clauses 1 to 9, wherein the tableting mixture of the LZC compound and the LPSC compound does not contain Li at a temperature of at least 200 degrees Celsius. x Zr y P2S6 -Li3PS4, ZrS2, LiCl, ZrS3, PS4 3- or P2S6 4- part.

[0121] 11. The apparatus structure according to any one of claims 1 to 10, wherein,

[0122] The cathode electrolyte layer 108 and the composite cathode layer 102 each include a first plurality of particles 112 containing the LZC compound.

[0123] The solid electrolyte layer includes a second plurality of particles 114 containing the LPSC compound, and

[0124] The average particle size (e.g., diameter or maximum diameter) and particle size distribution of the particles enable physical contact between the first plurality of particles and the second plurality of particles to facilitate lithium transport between the LPSC compound and the LZC compound, while suppressing harmful reactivity between the LZC compound and the LPSC compound during normal battery operation.

[0125] 12. The apparatus structure according to any one of clauses 1 to 11, wherein:

[0126] The cathode electrolyte layer and / or the composite cathode layer each comprise a first plurality of particles, the first plurality of particles containing the LZC compound and having a first diameter D1 in the range of 10 nm ≤ D1 ≤ 2 micrometers, and

[0127] The solid electrolyte layer includes a second plurality of particles, the second plurality of particles containing the LPSC compound and having a second diameter D2 in the range of 10 nm ≤ D2 ≤ 10 micrometers.

[0128] 13. The device structure according to any one of clauses 1 to 12, wherein the cathode electrolyte layer and / or the composite cathode layer comprises ball-milled particles 112 containing the LZC compound.

[0129] 14. The device structure according to any one of clauses 1 to 13, wherein the cathode electrolyte layer and / or the composite cathode layer comprises particles 112 containing the LZC compound, the particles 112 having the same or equivalent size distribution, disorder, crystallinity and conductivity characteristics as particles formed by ball milling powder containing the LZC compound.

[0130] 15. The device structure according to any one of clauses 1 to 14, wherein the LZC compound is a crystal with defects and / or disorder and has an electrical conductivity greater than 0.1 mS / cm.

[0131] 16. A lithium-ion solid-state battery 110, comprising a device structure according to any one of claims 1 to 6 and 8 to 15, wherein:

[0132] The battery includes a composite cathode layer and an anode 116;

[0133] The solid electrolyte layer is a single electrolyte layer 104 located between the composite cathode layer and the anode 116.

[0134] 17. A lithium-ion solid-state battery 110,202, comprising a device structure according to any one of claims 1 to 16, wherein:

[0135] The battery includes a composite cathode layer and an anode 116;

[0136] The composite cathode layer includes LZC compound particles 112 mixed with cathode active material particles 116 and carbon conductive additive particles 118.

[0137] The cathode electrolyte layer 108 contacts the composite cathode layer and the solid electrolyte layer 106; and

[0138] The solid electrolyte layer 106 is located between the anode 116 and the cathode electrolyte layer 102.

[0139] 18. A lithium-ion solid-state battery system 2000, comprising a device structure according to any one of claims 1 to 17:

[0140] Electrochemical cells 110, 202, which include solid electrolyte layers 106, 104 located between an anode 116 and a composite cathode layer 102;

[0141] A heating element 2004 coupled to the battery cell is used to heat the battery cell to a desired temperature; and

[0142] Circuit 2006 is configured to charge the electrochemical cell at a desired temperature T of at least 70 degrees Celsius (upper limit 250°C, such as room temperature ≤ T ≤ 250°C).

[0143] 19. A lithium-ion solid-state battery system comprising the device structure according to any one of claims 1 to 18, said lithium-ion solid-state battery system comprising:

[0144] Electrochemical cells 110, 202, comprising solid electrolyte layers 104, 106 located between an anode 116 and a composite cathode layer 102; and

[0145] Circuits 1500,2004 are configured or operable to charge and / or operate an electrochemical cell at an elevated voltage (e.g., above 3.4 V) applied across the anode and composite cathode layers, said elevated voltage being greater than the voltage applied in the electrochemical cell comprising a solid electrolyte layer, said electrochemical cell containing either an LPSC compound but not an LZC compound, or containing an LZC compound but not an LPSC compound.

[0146] 20. The battery according to any one of Clauses 15 to 19, wherein the cathode active material 102 comprises a lithium transition metal compound or sulfur, and / or the anode 116 comprises a lithium alloy or lithium metal.

[0147] 21. The battery according to Clause 20, wherein the lithium transition metal compound comprises lithium transition metal oxide, lithium transition metal fluoride, lithium transition metal polyanionic compound, lithium transition metal fluoride or lithium transition metal sulfide.

[0148] 22. The device structure according to any one of clauses 1 to 22, wherein the solid electrolyte layers 106, 104, the composite cathode layer 102 and the cathode electrolyte layer 108 each comprise a pressed layer or a densified layer or a layer cast from a solution.

[0149] 23. An anode-free battery 1900, comprising a device structure according to any one of claims 1 to 14, the anode-free battery comprising a solid electrolyte layer located between a composite cathode layer and a current collector, such that lithium extracted from the composite cathode layer during initial charging of the battery is directly plated onto the current collector 1902 to form an anode.

[0150] 24. A method for preparing a solid electrolyte in contact with a cathode electrolyte, comprising:

[0151] A first layer containing an LZC compound containing at least lithium, zirconium, and chlorine is brought into contact with a second layer containing an LPSC compound containing at least lithium, phosphorus, sulfur, and chlorine, the LPSC compound being arranged in a sulfogermanium ore structure.

[0152] 25. The method described in accordance with Clause 24 further includes:

[0153] The LZC powder containing the LZC compound is combined with a first binder in an LZC solution;

[0154] The LPSC powder containing the LPSC compound is combined with a second binder in an LPSC solution;

[0155] The solution was dried to form an LZC layer and an LPSC layer; and

[0156] Make the LZC layer contact the LPSC layer.

[0157] 26. The method according to Clause 24, wherein the method comprises:

[0158] Obtain an LZC tablet layer containing the LZC compound; deposit LPSC powder containing the LPSC compound onto the LZC tablet layer; and densify the LPSC powder on the LZC tablet layer, or

[0159] LZC powder containing the LZC compound is deposited on the LPSC tablet layer, and the LZC powder on the LPSC tablet layer is densified.

[0160] 27. The method according to Clause 26, wherein the densification includes cold pressing.

[0161] 28. The method according to Clause 27, wherein cold pressing at room temperature comprises:

[0162] Apply pressure (e.g., but not limited to at least 350 MPa, for at least 1 minute) to the LPSC powder to form the LPSC tablet layer; and

[0163] When the LZC powder is on top of the LPSC tablet layer, pressure is applied to the LZC powder (e.g., but not limited to at least 175 MPa, for at least 1 minute).

[0164] 29. The method according to any one of Clauses 24 to 28, wherein densification or casting further comprises hot pressing or hot rolling (calendering) to form a closer interfacial contact between the sheet layers.

[0165] 30. The method according to any one of clauses 24 to 29, further comprising:

[0166] Pressing a first layer, including a first pressing layer, onto the cathode, or casting a first layer, including a casting layer, onto the cathode; and

[0167] The second layer, including the second pressing layer, is pressed onto the anode, or the second layer, including the casting layer, is cast onto the anode.

[0168] 31. The method according to any one of clauses 24 to 30, wherein the first layer and the second layer form a double layer, or wherein the first layer comprises an LZC compound, a cathode active material, and a carbon conductive additive in a monolayer configuration.

[0169] 32. The method according to any one of clauses 24 to 31, wherein the first layer is formed from LZC powder comprising an LZC compound, the LZC powder comprising particles formed by ball milling or having the same or equivalent size distribution, disorder, crystallinity and electrical conductivity characteristics as particles formed by ball milling of powder comprising the LZC compound.

[0170] 33. The method according to any one of clauses 24 to 32, wherein,

[0171] The first layer is formed of LZC powder, and the second layer is formed of LPSC powder.

[0172] The LZC powder is deposited on the cathode when the first layer is formed before the second layer is formed; or

[0173] The LPSC powder is deposited on the anode while the second layer is formed before the first layer is formed.

[0174] 34. The method according to any one of clauses 24 to 33, performed in an oxygen-free and moisture-free chamber or environment.

[0175] 35. The method according to Clause 34, wherein the chamber or environment contains an inert gas (e.g., Ar).

[0176] 36. The device structure or battery according to any one of Clauses 1 to 23, which is manufactured using the method according to any one of Clauses 24 to 34.

[0177] 37. The battery according to any one of Clauses 15 to 20, wherein the solid electrolyte layer forms a passivation interface against the anode by decomposing into ionicly conductive and electronically insulating products (LiCl, Li3P and Li2S).

[0178] 38. The apparatus, method, system or battery according to any one of clauses 1 to 37, wherein the selection of the chemical composition of the LZC compound and the LPSC compound refers to the selection of elements (i.e., lithium, zirconium, etc.) and the stoichiometry / relative amounts of those elements in the compound.

[0179] 39. The apparatus, method, system, or battery according to Clause 38, wherein the stability of the cathode electrolyte in contact with the high-voltage cathode depends on the anions. In one embodiment, chlorine (Cl) is chosen because of its relatively high electronegativity and the likelihood that it will give up electrons (be oxidized) upon contact with the cathode. Replacing chlorine (Cl) with fluorine (F) or oxygen (O) can further increase the high-voltage stability of this cathode electrolyte.

[0180] 40. The apparatus, method, system, or battery according to Clause 38, wherein the solid electrolyte is selected as Li6PS5Cl because it is stable relative to a low-voltage anode. It does not contain any elements that are easily reduced (absorbing electrons when in contact with the anode).

[0181] 41. The apparatus, method, system or battery according to any one of clauses 1 to 40, wherein the LZC compound and / or the LPSC compound further comprises at least one of O, F, Si, Ge, Sn, Se or Y.

[0182] 42. The apparatus configuration according to any one of the clauses, wherein the LZC compound and the LPSC compound each have an oxygen content of less than 5 wt.%, as measured in LZC and LPSC samples using a process comprising:

[0183] The LZC (LPSC) sample was prepared using the following steps:

[0184] Particles of the LZC compound (LPSC) were deposited onto a Pt / Pd-coated Si wafer inside an Ar-filled glove box, and a protective Pt layer was deposited on top of the particles.

[0185] Grooves were milled into the Pt layer using a focused ion beam (FIB) to expose the cross-section of the particles; and

[0186] Polish the cross section using, for example, a lower current beam;

[0187] Performing energy dispersive X-ray spectroscopy (EDS) includes:

[0188] The electron beam is accelerated to the cross-section at an accelerating voltage of less than 3 kV, limiting the detection depth to less than 1 μm below the cross-section; and

[0189] The oxygen content is determined based on the analysis of X-rays emitted from the LZC (LPSC) sample in response to the electron beam.

[0190] 43. The apparatus structure according to any one of clauses 1 to 42, wherein the LZC compound and the LPSC compound each have an oxygen content below a threshold (e.g., less than 10 wt.% oxygen).

[0191] 44. The apparatus structure according to any one of clauses 1 to 43, which is manufactured and processed in an inert and moisture-free atmosphere containing less than 10 ppm water and less than 10 ppm oxygen.

[0192] 45. The device structure according to any one of clauses 1 to 44, wherein the combination of the LZC compound and the LPSC compound is chemically and electrochemically stable for the operating conditions of the electrochemical cell comprising the device structure.

[0193] 46. ​​The apparatus structure according to any one of the clauses, wherein the LZC compound and the LPSC compound have a different composition from Li2ZrCl6-Li6PS5Cl.

[0194] Advantages and improvements

[0195] The realization of Li2ZrCl6-Li6PS5Cl (LZC-LPSC) SE pairing in a single SSB offers the opportunity to achieve higher energy densities than today's conventional lithium-ion batteries, along with significant safety advantages due to the replacement of flammable organic electrolytes. Energy density and safety are two of the most important metrics for battery development, particularly for consumer products with sufficiently small dimensions to power mobile devices such as smartphones and electric vehicles. Therefore, any battery technology capable of enhancing either of these metrics has a significant commercial advantage.

[0196] In summary, the limited electrochemical stability window of solid-state electrolytes (SES) appears to be mutually exclusive with the implementation of high-voltage cathodes or high-energy-density metal anodes, casting doubt on the potential for increased energy density in SSBs. To date, no SE composition is known to be stable for both metal anodes and high-voltage oxide cathodes.

[0197] However, this disclosure has demonstrated that appropriate combinations of different SEs within a single SSB can withstand the electrochemical environments on both sides of the battery. By implementing an antioxidant cathode electrolyte and a reduction-resistant SE layer, the dual-SE approach utilizes the different electrochemical stability windows of the two electrolytes to maximize the stability of the SE interface at the cathode and anode, thereby enabling stable high-voltage cycling over a wide potential range. Alternatively, a bilayer architecture can be implemented in which a thin layer of cathode electrolyte is introduced between the SE layer and the cathode composite material, thereby preventing any possible contact between the cathode active material and the easily oxidized SE layer. The observed compatibility of the LZC-LPSC system indicates that SSBs combining oxide cathodes and metal anodes with >4V can cycle stably [2, 13, 15, 5, 17].

[0198] This disclosure also presents data comparing the stability of two solid electrolyte combinations (LZC and LPSC, and LZC and LPS) at different temperatures. First, a simple alternative method was used to test the (electro)chemical stability of the SE pair of interest under normal SSB operating conditions, i.e., chemical stability under various heat treatment conditions from 25°C to 300°C. The basic assumption here is that SE pairs that are more stable under normal SSB operating conditions should also be stable at higher heat treatment temperatures.

[0199] The inventors’ research has confirmed that the phase boundaries between SE materials are highly conductive to Li ions, and that the materials have the potential for further improvement when densified together under cold or hot pressing conditions.

[0200] While the data presented in this paper demonstrate that the LZC-LPSC SE pairing exhibits stable behavior under standard cycling in monolayer and bilayer SSBs assembled with LiFePO4 as the cathode active material and Li-In as the anode, these properties are expected to transfer to other cathode active materials and anodes. Studies of additional cathode and anode materials with this pairing are expected to confirm the potential for stable interfaces with high-voltage cathodes and high-capacity anodes. Overall, the LZC-LPSC system is a conductive, scalable, and kinetically stable system, and holds great promise for implementation in energy-intensive dual SESSBs with stable long-term cycling.

[0201] Furthermore, both LZC and LPSC are deformable, which greatly facilitates their processing and enables the fabrication of all cells via cold pressing, reducing manufacturing costs compared to SSB, which incorporates hard oxide (SE) materials. While cold pressing is the cheapest manufacturing option, we also demonstrated that the high chemical stability of LZC and LPSC up to 260°C allows them to be hot-pressed together to form a near 100% dense layer, thus facilitating lithium conduction across the interface. Finally, both LZC and LPSC are composed of elements abundant on Earth with robust supply networks, meaning that the procurement of their synthetic precursor materials is less affected by market fluctuations. Both classes of materials (halides and sulfides) have also been fabricated using scalable wet synthesis procedures, facilitating their respective production [18, 14, 19].

[0202] References

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[0235] in conclusion

[0236] This is a description of preferred embodiments of the invention. The foregoing description of one or more embodiments of the invention is presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise forms disclosed. Many modifications and variations are possible in accordance with the above teachings. The scope of the invention is intended to be limited not by this detailed description, but by the appended claims.

Claims

1. A device structure that can be used in lithium-ion solid-state batteries, comprising: A composite cathode layer comprising an LZC compound containing at least lithium, zirconium, and chlorine, wherein the LZC compound is a cathode electrolyte; as well as A solid electrolyte layer comprising an LPSC compound containing at least lithium, phosphorus, sulfur, and chlorine, the LPSC compound being arranged in a sulforaphite-germanium structure, and... in: The composite cathode layer and the solid electrolyte layer are in direct contact or coupled through the cathode electrolyte layer; as well as For the operating conditions of an electrochemical cell including the device structure described above, the combination of the LZC compound and the LPSC compound is chemically and electrochemically stable.

2. The device structure according to claim 1, wherein the LZC compound has a trigonal crystal structure (P-3m1) or a monoclinic crystal structure (C2 / m).

3. The device structure according to claim 1, wherein the LZC compound comprises Li2ZrCl6 and the LPSC compound comprises Li6PS5Cl.

4. The device structure according to claim 1, wherein: The LZC compound includes Li 2-x ZrCl 6-x (0≤x≤2) or Li2Zr 1-x Cl 6-4x (0≤x≤1) or a variant thereof that replaces at least one of Li, Zr or Cl with another element; as well as The LPSC compound includes Li 6-x PS 5-x Cl 1+x (0≤x≤1).

5. The device structure according to claim 1, wherein the composite cathode layer comprises the LZC compound mixed with the cathode active material and the carbon conductive additive.

6. The device structure according to claim 5, wherein when the electrochemical cell includes the solid electrolyte layer in contact with the anode and located between the anode and the composite cathode layer, the chemical composition of the LZC compound and the LPSC compound results in a capacity retention of at least 87% after 100 cycles, wherein each cycle includes the cell being charged and discharged at C / 3 conditions (charging for more than 3 hours and discharging for more than 3 hours) or at a slower rate.

7. The device structure according to claim 1, further comprising: Double-layered, comprising: A cathode electrolyte layer containing LZC compounds, and The solid electrolyte layer containing LPSC compounds, The cathode electrolyte layer is located between the solid electrolyte layer and the composite cathode layer.

8. The device structure according to claim 7, wherein when the electrochemical cell comprises the double layer located between and in contact with the anode and the composite cathode layer, the chemical composition of the LZC compound and the LPSC compound such that the capacity retention is at least 97% after 125 cycles, wherein each cycle comprises the cell being charged and discharged at C / 3 conditions (charging for more than 3 hours and discharging for more than 3 hours) or at a slower rate.

9. The device structure according to claim 1, wherein the tablet mixture of the LZC compound and the LPSC compound is characterized at a temperature of at least 200 degrees Celsius as being electrochemically stable by measurement and free from decomposition, degradation, or reaction products associated with the reaction of the LZC compound and the LPSC compound, wherein the measurement includes at least one of X-ray diffraction measurement, X-ray photoelectron spectroscopy (XPS), solid-state nuclear magnetic resonance (NMR) spectroscopy, or Raman spectroscopy.

10. The device structure according to claim 1, wherein the tableting mixture of the LZC compound and the LPSC compound does not contain Li at a temperature of at least 200 degrees Celsius. x Zr y P2S6 -Li3PS4, ZrS2, LiCl, ZrS3, PS4 3- or P2S6 4- part.

11. The device structure according to claim 1, wherein: The cathode electrolyte layer and the composite cathode layer each include a first plurality of particles containing the LZC compound. The solid electrolyte layer includes a second plurality of particles containing the LPSC compound, and The average particle size and particle size distribution of the particles enable physical contact between the first plurality of particles and the second plurality of particles to promote lithium transport between the LPSC compound and the LZC compound, while suppressing harmful reactivity between the LZC compound and the LPSC compound during normal battery operation.

12. The device structure according to claim 1, wherein: The cathode electrolyte layer and / or the composite cathode layer each comprise a first plurality of particles, the first plurality of particles containing the LZC compound and having a first diameter D1 in the range of 10 nm ≤ D1 ≤ 2 micrometers, and The solid electrolyte layer includes a second plurality of particles, the second plurality of particles containing the LPSC compound and having a second diameter D2 in the range of 10 nm ≤ D2 ≤ 10 micrometers.

13. The device structure according to claim 1, wherein the cathode electrolyte layer and / or the composite cathode layer comprises ball-milled particles containing the LZC compound.

14. The device structure according to claim 1, wherein the cathode electrolyte layer and / or the composite cathode layer comprises particles containing the LZC compound, the particles having the same or equivalent size distribution, disorder, crystallinity and conductivity characteristics as particles formed by ball milling powder containing the LZC compound.

15. The device structure according to claim 1, wherein the LZC compound is a crystal with defects and / or disorder, and has an electrical conductivity greater than 0.1 mS / cm.

16. A lithium-ion solid-state battery, comprising the device structure according to claim 5, wherein: The battery includes the composite cathode layer and the anode; The solid electrolyte layer is a single electrolyte layer located between the composite cathode layer and the anode.

17. A lithium-ion solid-state battery, comprising the device structure according to claim 1, wherein: The battery includes the composite cathode layer and the anode; The composite cathode layer comprises particles of the LZC compound mixed with particles of cathode active material and particles of carbon conductive additive. The cathode electrolyte layer contacts the composite cathode layer and the solid electrolyte layer; and The solid electrolyte layer is located between the anode and the cathode electrolyte layers.

18. A lithium-ion solid-state battery system, comprising the device structure according to claim 1: An electrochemical cell, the electrochemical cell comprising a solid electrolyte layer located between an anode and the composite cathode layer; A heating element coupled to the battery cell for heating the battery cell to a desired temperature; and A circuit configured to charge the electrochemical cell at temperatures up to at least 70 degrees Celsius.

19. A lithium-ion solid-state battery system comprising the device structure according to claim 1, wherein the lithium-ion solid-state battery system comprises: An electrochemical cell, the electrochemical cell comprising a solid electrolyte layer located between an anode and the composite cathode layer; as well as A circuit configured to charge and / or operate the electrochemical cell at an increased voltage applied across the anode and the composite cathode layer, the increased voltage being greater than a voltage applied to the electrochemical cell comprising a solid electrolyte layer, a cathode electrolyte, and a composite cathode layer, the electrochemical cell containing an LPSC compound but not an LZC compound, or containing an LZC compound but not an LPSC compound.

20. The battery of claim 19, wherein the cathode active material comprises a lithium transition metal compound or sulfur, and / or the anode comprises a lithium alloy or lithium metal.

21. The battery according to claim 20, wherein the lithium transition metal compound comprises lithium transition metal oxide, lithium transition metal fluoride, lithium transition metal polyanionic compound, lithium transition metal fluoride, or lithium transition metal sulfide.

22. The device structure according to claim 1, wherein the solid electrolyte layer, the composite cathode layer and the cathode electrolyte layer each comprise a pressed layer or a densified layer or a layer cast from a solution.

23. An anode-free battery, comprising the device structure according to claim 1, wherein the anode-free battery includes the solid electrolyte layer located between the composite cathode layer and the current collector, such that lithium extracted from the composite cathode layer during the initial charging of the battery is directly plated onto the current collector to form an anode.

24. A method for preparing a solid electrolyte in contact with a cathode electrolyte, comprising: A first layer comprising an LZC compound containing at least lithium, zirconium, and chlorine is brought into contact with a second layer comprising an LPSC compound containing at least lithium, phosphorus, sulfur, and chlorine, the LPSC compound being arranged in a sulfogermanium ore structure.

25. The method of claim 24, further comprising: The LZC powder containing the LZC compound is combined with a first binder in an LZC solution; The LPSC powder containing the LPSC compound is combined with a second binder in an LPSC solution; The solution was dried to form an LZC layer and an LPSC layer; and Make the LZC layer contact the LPSC layer.

26. The method of claim 24, wherein the method comprises: Obtain an LZC tablet layer containing the LZC compound; deposit LPSC powder containing the LPSC compound onto the LZC tablet layer; And densify the LPSC powder on the LZC tablet layer, or LZC powder containing the LZC compound is deposited on the LPSC tablet layer, and the LZC powder on the LPSC tablet layer is densified.

27. The method of claim 26, wherein the densification comprises cold pressing.

28. The method of claim 27, wherein cold pressing at room temperature comprises: Pressure is applied to the LPSC powder to form the LPSC tablet layer; as well as Pressure is applied to the LZC powder when it is on top of the LPSC tablet layer.

29. The method of claim 24, wherein the contact further comprises hot pressing or hot rolling (calendering) to form a tighter interfacial contact between the tablet layers.

30. The method of claim 24, wherein the contact further comprises: The first layer, including the first pressing layer, is pressed onto the cathode, or the first layer, including the casting layer, is cast onto the cathode; as well as The second layer, including the second pressing layer, is pressed onto the anode, or the second layer, including the casting layer, is cast onto the anode.

31. The method of claim 24, wherein the first layer and the second layer form a double layer, or wherein the first layer comprises the LZC compound, the cathode active material and the carbon conductive additive, and the first layer is configured as a single layer.

32. The method of claim 24, wherein the first layer is formed of LZC powder comprising the LZC compound, the LZC powder comprising particles formed by ball milling or having the same or equivalent size distribution, disorder, crystallinity and electrical conductivity characteristics as particles formed by ball milling the powder comprising the LZC compound.

33. The method according to claim 24, wherein: The first layer is formed of LZC powder, and the second layer is formed of LPSC powder. The LZC powder is deposited on the cathode when the first layer is formed before the second layer is formed; or The LPSC powder is deposited on the anode while the second layer is formed before the first layer is formed.

34. The method of claim 24, wherein the method is performed in an oxygen-free and moisture-free chamber or environment.

35. The method of claim 33, wherein the chamber or environment contains an inert gas (e.g., Ar).

36. The device structure or battery according to claim 1, which is manufactured using the method of claim 24.

37. A battery comprising the electrochemical cell of claim 1, the battery comprising a solid electrolyte layer between the composite cathode layer and the anode, wherein the solid electrolyte layer forms a passivated interface against the anode by decomposing into ionicly conductive and electronically insulating products (including at least one of LiCl, Li3P or Li2S).

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