Composite solid electrolyte, device having composite solid electrolyte, and method for producing same

Abstract

The precursor may be provided on the surface of the porous support layer and exposed to a temperature of 1200K or less for a time of 60 seconds or less to sinter the precursor into a porous scaffold. The porous scaffold may include an ion-conducting oxide. A filler may be provided on the surface of the porous scaffold. The filler may have a melting point in the range of 500-1100K. The porous scaffold with the filler may be exposed to a temperature of 1200K or less for ≦50 seconds to melt the filler and form a non-porous composite solid electrolyte layer, the filler infiltrating the porous scaffold. The solid electrolyte layer may be incorporated into a solid-state electrochemical energy device, such as a battery or fuel cell.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of U.S. Provisional Application No. 63 / 265,857, filed December 22, 2021, entitled “High Performance Multilayer Solid Electrolytes,” which is incorporated by reference herein in its entirety.

[0002] (Statement Regarding Federally Sponsored Research) This invention was made with Government support under W911NF2020284 awarded by the United States Army Research Laboratory (ARL). The United States Government has certain rights in this invention.

[0003] The present disclosure relates generally to solid-state structures, and more particularly to composite solid electrolytes for use, for example, in batteries (e.g., solid-state batteries) or solid oxide batteries (e.g., solid oxide fuel cells and / or solid oxide electrolysis cells). [Background technology]

[0004] Solid-state electrolytes (SSEs) formed by ionically conductive ceramics are contemplated for use in next-generation lithium (Li)-ion battery technology, for example to enhance safety and provide higher energy density. To this end, high ionic conductivity (e.g., 10 -3 A series of ceramic SSEs have been developed that exhibit high capacitance (up to 1000 S / cm), wide electrochemical window (e.g., up to 6 V), good chemical stability (e.g., against Li metal), and excellent mechanical properties (e.g., mechanical strength up to 20 GPa). However, problems remain that hinder the adoption of SSEs for all-solid-state batteries. Summary of the Invention [Problem to be solved by the invention]

[0005] First, it is generally not possible for a single composition for SSE to meet all the requirements for efficient operation. For example, LLTO, LiTi2(PO4)3, Li 14Zn(GeO4)4 has low chemical stability with Li metal. Furthermore, sulfides (e.g., Li2S-P2S5, Li2S-P2S5-MS) x ) and hydrides (e.g., LiBH4, LiBH4-LiX (X=Cl, Br, or I)) may have poor compatibility with the cathode materials. Halides (e.g., LiI, spinel Li2ZnI4, and antiperovskite Li3OCl), borates or phosphates (e.g., Li2B4O7, Li3PO4, and Li2O-B2O3-P2O5), and LiPON are generally stable in the 10 -8 ~10 -5 It has a low electrical conductivity of 1.5 S / cm. Garnet Li7La3Zr2O 12 may have interfacial stability issues with certain cathode materials (e.g., LiCoO2), which may result in increased interfacial resistance. The use of coatings has not been effective in fully addressing such issues.

[0006] Furthermore, due to the large energy of ceramic Li-ion conductors, SSEs must be formed as thin films (e.g., tens of microns) to achieve high energy density at the full-cell level. However, such thin-film ceramic SSEs can be difficult to process. Due to the brittleness of most ceramic Li-ion conductors, thin-film SSEs need to be supported on a suitable substrate. Such supports impose significant constraints on electrochemical energy cell configurations, as the supports need to be integrated into the cell assembly process. In addition, materials for supporting the SSEs may be incompatible with some electrochemical energy devices or may result in SSE cracking during conventional sintering due to mismatch in thermal expansion coefficients. [Means for solving the problem]

[0007] Embodiments of the disclosed subject matter may address, among other things, one or more of the problems and shortcomings set forth above.

[0008] Embodiments of the disclosed subject matter system provide a composite solid electrolyte (SSE) for use in electrochemical energy devices such as solid-state batteries or solid oxide fuel cells, as well as methods for its manufacture. In some embodiments, the composite SSE can be a porous scaffold formed on a porous support, such as a porous carbon or metal layer. The porous scaffold can be infiltrated with a low melting glassy ionic conductor to form the composite. In some embodiments, the composite SSE can be formed using a two-step heating process (e.g., heating waves) of short duration (e.g., ≦60 seconds) and limited high temperature (e.g., ≦1200 K). The two-step heating process can avoid cracking of the SSE while still forming a dense, pinhole-free layer (e.g., a non-porous layer). Alternatively or additionally, in some embodiments, the composite SSE can include multiple sublayers of different compositions. In some embodiments, each SSE sublayer can be formed by a heating process (e.g., heating waves) of short duration (e.g., ≦60 seconds) and high sintering temperature (e.g., up to 3000 K). In some embodiments, a limited duration of the heating process can avoid co-diffusion of elements while still forming a dense ceramic structure for the SSE.

[0009] In one or more embodiments, the method can include providing one or more precursors on a first surface of the porous support layer. The method can further include exposing the porous support layer to a first temperature for the first time with the one or more precursors to sinter the one or more precursors to form a porous scaffold. The first temperature can be about 1200 K or less. The first time period can be about 60 seconds or less. The porous scaffold can include an ion-conducting oxide. The method can also include providing one or more fillers on a second surface of the porous scaffold. The one or more fillers can have a melting point in the range of 500 to 1100 K, inclusive. The method can further include subjecting the porous scaffold including the one or more fillers to a second temperature for a second time period to melt the one or more fillers to form a non-porous composite solid electrolyte layer including the one or more fillers infiltrating the porous scaffold. The second temperature can be about 1200 K or less and the second time period can be about 60 seconds or less.

[0010] In one or more embodiments, the electrochemical energy device can include a porous support layer and a non-porous composite solid electrolyte layer. The non-porous composite solid electrolyte layer can be disposed on the porous support layer and can include a porous scaffold and one or more fillers infiltrating the porous scaffold. The porous scaffold can include an ion-conducting oxide. The one or more fillers can have a melting point in the range of 500 to 1100 K, inclusive. At least a portion of the porous support layer can be infiltrated with one or more materials to form an electrode of the electrochemical energy device. In some embodiments, the electrochemical energy device is a solid-state battery.

[0011] Any of the various innovations of the present disclosure can be used in combination or separately. This summary is provided to introduce in a simplified form a selection of concepts that are further described in the detailed description below. This summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter. The foregoing and other objects, features, and advantages of the disclosed technology will become more apparent from the following detailed description, which proceeds with reference to the accompanying drawings. [Brief description of the drawings]

[0012] The embodiments will now be described with reference to the accompanying drawings, which are not necessarily drawn to scale. Where applicable, some elements may be simplified or otherwise not shown to help illustrate and explain the underlying features. Like reference numbers refer to like elements throughout the drawings. [Figure 1A-1C] 1A-1C are simplified schematic diagrams of a system that uses a battery formed using a porous support layer in accordance with one or more embodiments of the disclosed subject matter. [Figure 2A] FIG. 2A is a simplified schematic diagram illustrating an embodiment for making a non-porous composite solid electrolyte according to one or more embodiments of the disclosed subject matter. [Figure 2B] FIG. 2B is a simplified schematic diagram illustrating an embodiment for manufacturing a layer assembly of a battery according to one or more embodiments of the disclosed subject matter. [Figure 2C] FIG. 2C is a simplified schematic diagram illustrating an embodiment for manufacturing a layer assembly of a battery according to one or more embodiments of the disclosed subject matter. [Figure 2D] FIG. 2D is a simplified schematic diagram illustrating an embodiment for manufacturing a layer assembly of a battery according to one or more embodiments of the disclosed subject matter. [Diagram 3]FIG. 3 is a process flow diagram for manufacturing a layer assembly of a battery in accordance with one or more embodiments of the disclosed subject matter. [Figure 4A] FIG. 4A is a graph showing an exemplary temperature profile for sintering by thermal shock. [Figure 4B] FIG. 4B depicts a generalized example of a computing environment in which the disclosed technology can be implemented. [Figure 5A-5D] Figure 5A is a digital image of a tantalum-doped Li7La3Zr2O12 (LLZTO) porous scaffold formed on a carbon nanotube (CNT) porous support. Figures 5B-5C are scanning electron microscope (SEM) images of the LLZTO porous scaffold in Figure 5A. Figure 5D is an SEM image of the interface between the LLZTO porous scaffold in Figure 5A and the CNF porous support layer. [Figures 6A-6D] Figure 6A is a digital image of a nonporous composite solid electrolyte formed by infiltrating the LLZTO porous scaffold of Figure 5A with Li3BO3. Figures 6B-6C are SEM images of the LLZTO / LBO composite SSE of Figure 6A. Figure 6D is an SEM image of the interface between the LLZTO / LBO composite SSE of Figure 6A and the CNF porous support layer. [Figure 7A-7D] FIG. 7A is a simplified cross-sectional view of an asymmetric cell for testing the LLZTO / LBO composite SSE; FIG. 7B is a graph showing X-ray diffraction (XRD) analysis of the LLZTO / LBO composite SSE; FIG. 7C is a graph showing the measured ionic conductivity of the LLZTO / LBO composite SSE; and FIG. 7D is a graph showing galvanostatic cycling of the asymmetric cell of FIG. 7A at 0.2 mA / cm2. [Figure 8A-8D] FIG. 8A is a graph showing the calculated electrochemical window for different SSE compositions, FIG. 8B is a graph showing the enlargement of the electrochemical window with multilayer SSEs, and FIGS. 8C-D are SEM images of the cross-section of a fabricated multilayer SSE formed by a thin film of LiBO2 on LLZTO. [Figure 9A-9D]FIG. 9A shows the enlarged electrochemical window of a multilayer SSE formed with NASICON-type Li1.3Al0.3Ti1.7(PO4)3 (LATP) on garnet-type LLZTO, FIG. 9B shows a graph depicting the XRD analysis of the fabricated LATP layer compared to a pure NASICON-type structure, and FIGS. 9C-9D show SEM images of the cross-section of the fabricated multilayer SSE formed by a thin film of LATP on LLZTO. [Figure 10A-10E] FIG. 10A is a graph showing the widening of the electrochemical window for a multilayer SSE formed by LiBO2-Li3PO4 layers formed on pervoskite Li0.33La0.57TiO3 (LLTO); FIGS. 10B-10C are SEM images of cross sections of fabricated multilayer SSEs formed by layers of LiBO2-Li3PO4 and LLTO on a lithium anode; FIG. 10D is an electron micrograph of the interface between the lithium anode and the LiBO2-Li3PO4 film; and FIG. 10E is an SEM image of the interface between the LiBO2-Li3PO4 and LLTO layers. [Figures 11A-11F] 11A-11B are SEM images of cross sections of fabricated multi-layer SSEs formed with Li3PO4 (LPO) on LLZTO; FIG. 11C shows X-ray diffraction analyses of LPO on LLZTO and LiBO2 (LBO) on LLZTO; FIGS. 11D-11E are graphs showing the measured ionic conductivity and activation energy, respectively, of bilayer SSEs formed with LBO on LLZTO; and FIG. 11F is a graph showing resistance versus thickness of the bilayer SSE. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] General Considerations For the purposes of this specification, certain aspects, advantages, and novel features of the embodiments of the present disclosure are described herein. The disclosed methods and systems should not be construed as limiting in any way. Instead, the present disclosure is directed to all novel and non-obvious features and aspects of the various disclosed embodiments, both alone and in various combinations and subcombinations with each other. The methods and systems are not limited to any particular aspects, features, or combinations thereof, and the disclosed embodiments do not require that any one or more particular advantages exist or problems be solved. Techniques from any embodiment or example can be combined with techniques described in any one or more of the other embodiments or examples. In view of the many possible embodiments to which the principles of the disclosed technology may be applied, it should be recognized that the illustrated embodiments are merely illustrative and should not be construed as limiting the scope of the disclosed technology.

[0014] Although some operations of the disclosed methods are described in a particular order for convenient presentation, it should be understood that this method of description encompasses reordering, unless a particular ordering is required by the specific language described below. For example, operations described in sequence may be reordered or performed simultaneously in some cases. Furthermore, for simplicity, the accompanying drawings may not show the various ways in which the disclosed methods may be used in conjunction with other methods. Furthermore, the description may use terms such as "provide" or "achieve" to describe the disclosed methods. These terms are high-level abstractions of the actual operations that are performed. The actual operations that correspond to these terms may vary depending on the specific implementation and are readily discernible by those skilled in the art.

[0015] Disclosure of numerical ranges should be understood to refer to each discrete point within the range, including the endpoints, unless otherwise indicated. Unless otherwise indicated, all numbers expressing amounts of ingredients, molecular weights, percentages, temperatures, times, etc., used in this specification or claims should be understood to be modified by the term "about". Thus, unless otherwise implicitly or explicitly indicated, or unless the context is properly understood by those skilled in the art to have a clearer configuration, the numerical parameters described are approximations that may depend on the desired properties sought and / or the limits of detection under standard testing conditions / methods, as known to those skilled in the art. When directly and explicitly distinguishing the embodiments from the prior art discussed, the embodiment numbers are not approximations unless the word "about" is recited. Whenever "substantially," "approximately," "about," or similar language is expressly used in conjunction with a particular value, a variation of up to 10% of that value is intended, unless expressly stated otherwise.

[0016] Directions and other relative references may be used to facilitate the description of the figures and principles herein, but are not intended to be limiting. For example, certain terms such as "inside," "outside," "up," "down," "top," "bottom," "internal," "external," "left," "right," "front," "rear," "back," and the like may be used. Such terms are used, where applicable, to provide some clarity of description when dealing with relative relationships, particularly with respect to the illustrated embodiments. However, such terms are not intended to imply absolute relationships, positions, and / or orientations. For example, with respect to an object, a "top" portion may become a "bottom" portion by simply flipping the object over. Nevertheless, it is still the same portion, and the object remains the same.

[0017] As used herein, "comprising" means "including," and the singular forms "a" or "an" or "the" include plural references unless the context clearly dictates otherwise. The term "or" refers to a single element or a combination of two or more elements of the referenced alternative elements, unless the context clearly dictates otherwise.

[0018] The various components, parameters, operating conditions, and the like described herein may be alternatives, but these alternatives are not necessarily equivalent and / or will function equally well. Nor is it meant to imply that the options are listed in order of preference, unless otherwise indicated. Any of the groups defined below may be substituted or unsubstituted, unless otherwise indicated.

[0019] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this disclosure belongs.Methods and materials similar or equivalent to those described herein can be used in the practice or testing of this disclosure, but suitable methods and materials are described below.The materials, methods, and examples are illustrative only and are not intended to be limiting.Features of the subject matter of this disclosure will become apparent from the following detailed description and the appended claims.

[0020] Terminology Overview The following is provided to facilitate a description of various aspects of the disclosed subject matter and to guide those of ordinary skill in the art in practicing the disclosed subject matter.

[0021] Heat Wave: Exposing one or more materials to an elevated temperature for a limited time having a duration of about 60 seconds or less to effect melting and / or sintering thereof. In some embodiments, the duration of the elevated temperature is less than 30 seconds, for example, in the range of 3 to 10 seconds. For example, in some embodiments, the duration can be about 5 seconds. In some embodiments, the exposure is for at least 10 minutes prior to the limited period. 3K / sec (e.g., about 10 5 K / sec) to a high temperature and / or after a limited period of time 3 K / sec (e.g., about 10 5 The method may include cooling from a high temperature at a ramp rate of 100 K / sec.

[0022] High temperature: The peak or maximum temperature at the surface of one or more heating elements when excited (e.g., by application of a current pulse) and / or at the surface of the material being heated. In some embodiments, the high temperature is less than 1200 K, e.g., about 1100 K. Alternatively, in some embodiments, the high temperature is in the range of 1200-3000 K. In some embodiments, the temperature of the material being heated (e.g., precursor) can match or substantially match (e.g., within 10%) the temperature of the heating element.

[0023] Nasicon: For example, 0 <x<3であるNa 1+x Zr2Si x P 3-x O 12 A sodium-based superionic conductor having a chemical formula: In some embodiments, Zr, Si, and / or Na in the chemical formula can be replaced by equivalent elements such as V, Sb, or Ta.

[0024] Lithium: For example, Li 2+2x Zinc 1-x A lithium-based superionic conductor with the chemical formula GeO4.

[0025] Introduction This specification discloses a composite solid structure formed by sintering, which cannot be achieved by conventional sintering techniques due to elemental layer cracking and / or interlayer diffusion. In some embodiments, the composite solid structure can be formed as an ion conductor, for example, to conduct metal ions (e.g., alkali metal ions such as lithium (Li) ions, sodium (Na) ions, potassium (K) ions, and / or alkaline earth metal ions such as magnesium (Mg) or calcium (Ca)) or anions (e.g., oxygen (O) ions). Li A La B M’’ c M’’ D Zr E O F 、Li A La B M’’ c M’’ D Ta E O F Or Li A La B M’ c M’’ D Nb E O F (4 < A < 8.5, 1.5 < B < 4, 0 ≤ c ≤ 2, 0 ≤ D ≤ 2, 0 ≤ E < 2, 10 < F < 13, M’ is a first one selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta, and M’’ is a second one selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta). In some embodiments, one or more layers of the composite solid structure can be formed from a material composition satisfying the chemical formula of Li A La B Zr C Al D M’’’ E O F where 5 < SA < 7.7, 2 < B < 4, 0 < C ≤ 2.5, 0 ≤ D2, and 10 < F < 13), and M’’’ is Nb, Ta, V, W, Mo, or Sb. For example, the composite solid structure is a perovskite-type Li 3x La 2 / 3-xTiO3(LLTO), NASICON type LiTi3(PO4)3, NASICON type Li 1.3 Al 0.3 Ti 1.7 (PO4)3, NASICON type Li 1+x Al x Ge 2-x (PO4)3, garnet type Li7La3Zr2O 12 (LLZO), garnet-type Li7La3Zr 1.4 Ta 0.6 O 12 (LLTZO), LISICON type Li 14 Zn(GeO4)4, thio-LISICON type Li 4-x Ge 1-x P x The insulating layer may include at least one layer having a material composition selected from the group consisting of Li6PS5Cl, Li6PS5Cl, Li6PS5Cl, Li6PS5Cl, Li6PS5Cl, and Li3OCl.

[0026] In some embodiments, the composite solid structure can be formed by sintering a porous scaffold onto a porous support layer. Sintering can involve high temperature heating and / or cooling rates (e.g., ≧10 3This can be achieved by using a high-temperature heating wave (e.g., duration ≦60 seconds) enabled at least in part by a sintering method (e.g., 100 K / sec). Due to the short duration of the applied heating (e.g., a few seconds as opposed to the hours required by conventional sintering), the porous scaffold can be sintered on the porous support layer without cracking. In some embodiments, the filler material can then be melted and infiltrated into the pre-sintered porous scaffold to form a dense layer, e.g., a composite solid electrolyte for an electrochemical energy device (e.g., a battery or fuel cell). Melting can be achieved by using another high-temperature heating wave (e.g., duration ≦60 seconds). In some embodiments, the porous support layer can be converted into an electrode of an electrochemical energy device, e.g., by infiltrating it with a metal (e.g., Li), an electrocatalyst, or a cathode active material. In some embodiments, the material of the porous scaffold can have a melting and / or sintering temperature higher than the melting temperature of the filler material. For example, the material of the porous scaffold may have a melting and / or sintering temperature above 1200 K, while the filler material may have a melting temperature below 1200 K (e.g., a melting point in the range of 500-1100 K).

[0027] For example, FIG. 1A shows a composite solid-state electrolyte (SSE) 106 incorporated into a layer assembly 104 of a battery 102 (e.g., a primary or secondary battery). The battery 102 can include a first electrode 110 and a second electrode 108 on either side of the composite SSE 106 (e.g., having a thickness of 500 μm or less, e.g., in the range of 10-300 μm, such as 10-50 μm). Through the electrodes 108, 110, the battery 102 can be coupled to a node 112 through a suitable electrical circuit, which can be an electrical load for use of charge stored by the battery or a power source to recharge the battery. In some embodiments, the battery 102 can be a Li-ion battery.

[0028] In the illustrated example 100, the composite SSE 106 is formed by a porous scaffold infiltrated with one or more fillers to obtain a dense layer (e.g., non-porous). For example, the porous scaffold can be formed from an ion-conducting ceramic material and / or the filler can be formed from a low melting point ion-conducting glass material (e.g., LiBO3, LiCl, LiBr, LiI, LiF, Li3N, LiBH4, LiBF4). In some embodiments, the porous scaffold, the filler, or both can include elements corresponding to the desired ions to be conducted, among other components. For example, if the battery 102 is a Li-ion battery, the porous scaffold and / or the filler can include Li. The material composition for the composite SSE 106 (e.g., materials for the porous scaffold and / or the infiltrated filler) can be such that the SSE 106 has high ionic conductivity (e.g., ≧1×10 -3 S / cm) and low electronic conductivity (e.g., ≦1×10 -8 S / cm, e.g., ~2×10 -9 For example, the porous scaffold and / or filler may be selected to have a viscosity of at least 1×10 -4 Alternatively or additionally, the porous scaffold and / or filler may have an ionic conductivity of 1×10 -8 It may have an electronic conductivity of 0.1 S / cm or less. In the illustrated example of FIG. 1A, the second electrode 108 is formed from a porous conductive substrate (e.g., porous carbon such as carbon black, or a porous metal layer such as Cu foam, Ti mesh, Ni mesh, etc.) infiltrated with a conductive metal. The porous substrate thus serves as a support for the composite SSE 106 in the layer assembly 104 and serves as an electrode of the battery 102. For example, if the electrode 108 is configured as an anode of the battery 102, the porous substrate can be infiltrated with lithium. Alternatively, if the electrode 108 is configured as a cathode of the battery 102, the porous substrate is infiltrated with a cathode active material. The thickness and porosity of the porous substrate can be tailored to meet the requirements of a particular application (e.g., packing density of the active material). For example, the thickness of the porous substrate can range from 100 μm to 1 mm (inclusive), the porosity can be up to 94% for carbon substrates, and / or the porosity can be up to 90% for metal substrates. In some embodiments, the first electrode 110 can be formed separately from the layer assembly 104 and then bonded thereto to form the battery 102. Alternatively or additionally, in some embodiments, the first electrode 110 can be formed on the layer assembly 104 or integrally with the SSE 106, for example, via the sintering methods disclosed in International Publication No. WO 2020 / 236767, published November 26, 2020, entitled "High Temperature Sintering Systems and Methods."

[0029] Alternatively or additionally, in some embodiments, a composite solid structure may be formed from multiple layers (e.g., two or more) having different material compositions. In some embodiments, a subsequent layer may be sintered on a previously formed layer, for example, via a high-temperature heating wave (e.g., duration 60 seconds or less). Because of the short duration of the applied heating, layers may be formed on top of each other without discernible interlayer diffusion of elements and with clear interfaces between adjacent layers. In some embodiments, the multilayer solid structure is formed as a solid electrolyte for an electrochemical energy device. In some embodiments, the multiple layers may be formed on a support layer, for example, a porous support layer.

[0030] For example, FIG. 1B shows a composite SSE 126 incorporated into a layer assembly 124 of a battery 122 (e.g., a primary or secondary battery). The battery 122 can include a first electrode 110 and a second electrode 108 on either side of a composite SSE having multiple layers 126a-126c. Although three layers 126a-126c are shown in FIG. 1B, two layers or four or more layers are possible according to one or more contemplated embodiments. In some embodiments, each layer 126a-126c in the SSE stack can have a thickness of 1 μm or more, and / or the total thickness of the SSE stack of multiple layers 126a-126c can be 10 μm or more. Through the electrodes 108, 110, the battery 122 can be coupled to a node 112 through an appropriate electrical circuit, which can be an electrical load for use of charge stored by the battery or a power source to recharge the battery. In some embodiments, the battery 122 can be a Li-ion battery.

[0031] In some embodiments, at least some of the layers 126a-126c can have different material compositions, for example, to broaden the electrochemical voltage window of the SSE and / or to enhance the stability of the SSE relative to the adjacent electrodes 108 and / or 110. For example, at least one of the layers 126a-126c can be made of an oxide (e.g., perovskite Li 0.33 La 0.57 TiO3, NASICONLiTi2(PO4)3, LISICON(Li 14 Zn(GeO4)4), garnet Li7La3Zr2O 12 etc.), sulfides (e.g., Li2S-P2S5, Li2S-P2S5-MS x, etc.), hydrides (e.g., LiBH4, LiBH4-LiX, where X is Cl, Br, or I, LiBH4-LiNH2, LiNH2, Li3AlH6, Li2NH, etc.), halides (e.g., LiI, spinel Li2ZnI4, antiperovskite Li3OCl, etc.), or borates or phosphates (e.g., Li2B4O7, Li3PO4, Li2O-B2O3-P2O5, etc.).

[0032] In some embodiments, each layer 126a-126c of the SSE can be formed by sequential high temperature sintering, for example, by applying a high temperature heating wave to a precursor disposed on an underlying layer (e.g., a support or a pre-sintered SSE layer). For example, each layer 126a-126c of the SSE can be made with a controlled degree of densification (e.g., porous or dense) due to the tunability of the heating wave technique. In the illustrated example 120 of FIG. 1B, the bottom SSE layer 126c is formed on a second electrode 108 formed of a porous and conductive substrate (e.g., porous carbon such as carbon black, or a porous metal layer such as Cu foam, Ti mesh, Ni mesh, etc.) infiltrated with a conductive metal. The porous substrate thus serves as a support for the SSE layers 126a-126c in the layer assembly 124 and serves as an electrode of the battery 102. In some embodiments, the first electrode 110 can be formed separately from the layer assembly 124 and then bonded thereto to form the battery 102. Alternatively or additionally, in some embodiments, the first electrode 110 can be formed integrally with the layer assembly 124 or with the SSE layer 126a, for example, by the sintering methods disclosed in the above-incorporated International Publication No. WO 2020 / 236767.

[0033] In some embodiments, the infiltrated porous scaffold of FIG. 1A and the multi-layered embodiment of FIG. 1B can be combined together to form a composite solid structure, e.g., a filler-infiltrated porous scaffold formed on a porous support layer, and one or more additional layers of different material compositions formed on the porous scaffold. For example, FIG. 1C shows a composite SSE 136 incorporated into a layer assembly 134 of a battery 132 (e.g., a primary or secondary battery). As with other examples described above, the battery 132 (e.g., a Li-ion battery) can include a first electrode 110 and a second electrode 108 on either side of the composite SSE that connects the battery 132 to a node 112. Here, however, the composite SSE is formed by a filler-infiltrated porous scaffold layer 106 and multiple additional layers 126a-b on top of the layer 106. Although two layers 126a-b are shown in FIG. 1C, one layer or more than two layers are possible according to one or more contemplated embodiments.

[0034] Although certain material compositions are mentioned above and elsewhere herein, embodiments of the disclosed subject matter are not limited thereto. Rather, other material compositions are possible according to one or more contemplated embodiments, for example, to accommodate different ion conduction, to provide different performance metrics (e.g., higher ionic conductivity and / or lower electronic conductivity), to provide different manufacturing limitations (e.g., different melting points and / or sintering temperatures), to provide different mechanical properties (e.g., mechanical strength), or for any other reason.

[0035] Solid electrolyte formed using a porous support layer FIG. 2A illustrates a two-step heating wave process 200 for forming a composite SSE. First, a porous support layer 202 is provided. In some embodiments, the porous support layer 202 is formed from a conductive material, such as carbon or metal. For example, in some embodiments, the porous support layer 202 can be formed from conductive carbon particles or structures, such as a matrix of carbon nanotubes (CNTs). Alternatively, in some embodiments, the porous support layer 202 can be formed of a metal mesh or foam, such as a Cu foam, Ti mesh, or Ni mesh. At 204, one or more precursors can be provided on the porous support layer by known deposition techniques, such as, but not limited to, spray coating, blade coating, printing, or tape transfer. This results in a precursor layer 206 on the porous support layer 202, which can then be sintered at 208 by applying a high temperature heating wave to integrally form a porous scaffold 210 on the porous support layer 202. For example, the porous scaffold 210 can be formed from a material that conducts metal ions or anions, as described in detail above and elsewhere herein.

[0036] In some embodiments, the high temperature heating wave is at a temperature below that typically used to sinter the precursor into a dense (e.g., non-porous) film. For example, conventional sintering may use a temperature above 1400K to sinter a layer of LLZTO, while the heating wave of 208 may use less than 1200K, such as about 1100K. In addition, the high temperature heating wave has a duration substantially shorter than that typically used in sintering. For example, conventional sintering may require several hours or at least several minutes, while the heating wave of 208 is performed for a duration of less than 30 seconds, such as about 5 seconds. In some embodiments, to accommodate the different thermal expansion coefficients between the porous support layer and the precursor, the degree of sintering was controlled to maintain the porous morphology of the scaffold 210 with limited shrinkage but sufficient neck growth for continuous Li-ion conduction pathways. Due to the limited size change of the porous SSE during short sintering, the formation of cracks can be avoided or at least reduced.

[0037] The porous scaffold 210 is then infiltrated 212 with one or more fillers to obtain a dense non-porous layer 214 as a composite SSE on the porous support layer 202. In some embodiments, the filler infiltration 212 can include depositing one or more fillers (or precursors thereof) on the porous scaffold 210 and then applying another high temperature heating wave. Deposition of the filler material on the porous scaffold 210 can be done by any known deposition technique, such as, but not limited to, spray coating, blade coating, and vapor deposition. In some embodiments, the filler material is a glassy material (e.g., LBO) with a low melting point (e.g., a melting point in the range of 500-1100 K). For example, the filler material can be formed from a material that conducts metal ions or anions, as described in detail above and elsewhere herein.

[0038] The high temperature heating wave for infiltration 212 can be similar to that for sintering 208, for example, at a temperature below 1200 K (e.g., ∼1100 K) and a duration of less than 30 seconds (e.g., ∼5 seconds). Alternatively, the high temperature heating wave for infiltration 212 can be different from that for sintering 208, for example, at a lower temperature (e.g., based on the lower melting point of the selected filler material) and / or a different duration (e.g., less than 60 seconds). In some embodiments, the infiltration 212 is such that the filler material completely penetrates the thickness of the porous scaffold 210 to form a uniformly dense layer 214 extending, for example, from the interface with the porous support layer 202 to the exposed top surface of layer 214. Alternatively, in some embodiments, the infiltration 212 can be such that the filler material penetrates to a depth of at least 0.5 μm from the exposed top surface of layer 214.

[0039] Electrode layer formed from a porous support layer Because the support layer 202 is porous, in some embodiments, the support layer 202 can be used as a host for anode or cathode materials to serve as electrodes in a full cell assembly, in addition to supporting a composite SSE during and after fabrication. For example, FIG. 2B shows a process 220 for fabrication of a layer assembly in which the porous support layer forms the anode. In the illustrated example, an SSE layer 222 is preformed on the porous support layer 202. In some embodiments, the SSE layer 222 can be a composite SSE, for example, formed by the process 200 of FIG. 2A and / or incorporating multiple layers of different SSE materials (e.g., as shown in FIGS. 1B-1C). Alternatively, in some embodiments, the SSE layer 222 can be a single layer SSE formed directly on the surface of the support layer 202, for example, via sintering (e.g., similar to the formation of layer 126c of FIG. 1B), or can be formed separately and provided on the support layer surface (e.g., via any conventional technique, such as printing, spraying, tape transfer, etc.). At 224 , the SSE layer 222 can be provided (eg, by lamination) with the cathode 230 on the SSE layer 222 such that the cathode 230 is disposed between the porous support layer 202 and the cathode 230 .

[0040] In the illustrated example, the cathode 230 can be formed by a cathode support substrate 226 infiltrated with a cathode active material 228. In some embodiments, the cathode support substrate 226 can be a porous substrate formed of a conductive material. For example, the cathode support substrate 226 can be formed of a porous carbon, such as a matrix of carbon black particles (e.g., 5-10 wt%). In some embodiments, the cathode active material 228 can have a composition including lithium and another metal. Alternatively, in some embodiments, the cathode can be and / or include a liquid electrolyte, for example, as disclosed in Cheng et al., “Ionic Liquid-Containing Cathode-Enhanced Ceramic Solid Electrolyte,” iScience, March 2022, 25(3), 103896, which is incorporated herein by reference. Other configurations and compositions for the cathode 230 are also possible in accordance with one or more contemplated embodiments.

[0041] In the illustrated example, the anode 234 can be formed by infiltrating the porous support layer 202 with Li at 232 (e.g., for use in a lithium ion battery). The integrated layer assembly 236 can then be used as a battery, e.g., after appropriate packaging. In some embodiments, the Li can be infiltrated at 232 in a limited manner, e.g., to confine the infiltration to the porous support layer 202. Alternatively or additionally, the Li can be infiltrated throughout the layer assembly 236. In such cases, the cathode 230 can be previously delithiated.

[0042] FIG. 2C illustrates another process 240 for the manufacture of a layer assembly in which a porous support layer forms an anode. In the illustrated example, a cathode 230 is provided first. As described above, the cathode 230 can be formed by a porous cathode support layer 226 infiltrated with a cathode active material 228. At 242, one or more precursors 244 for the SSE layer can be provided on the cathode 230 via any known deposition technique (e.g., spray coating, blade coating, printing, vapor deposition, etc.). At 246, the precursors 244 can be subjected to sintering to convert the precursors 244 into an SSE layer 248. In some embodiments, the precursor layer 244, the sintered layer 246, and the SSE layer 248 can be similar to the precursor layer 206, the sintered layer 208, and the porous scaffold 210 of FIG. 2A, respectively. In such embodiments, the porous scaffold can be further infiltrated with a filler to obtain a substantially non-porous SSE layer 248, for example, in a manner similar to that described above with respect to FIG. 2A. Alternatively, in some embodiments, the SSE precursor may be directly formed into a substantially non-porous layer, for example, by application of a suitable sustained heat wave. For example, the heat wave for sintering 246 may be at a temperature in the range of 1200-3000 K for a duration of 60 seconds or less (e.g., 10-20 seconds).

[0043] In the illustrated example of Figure 2C, a porous support layer 202 may then be provided on the SSE layer 248, for example by lamination. In some embodiments, the porous support layer 202 may be formed of conductive carbon or metal, for example, as described above with respect to Figures 2A-2B. After providing the porous support layer 202, the anode 234 may be formed in a manner similar to that described above with respect to Figure 2B, for example by Li infiltration at 232, resulting in a layer assembly having an SSE layer 248 disposed between the anode 234 and the cathode 230.

[0044] 2D illustrates another process 260 for the manufacture of a layer assembly in which a porous support layer forms an anode. In the illustrated example, the cathode 230 and SSE layer 248 can be formed in a manner similar to that described above with respect to FIG. 2C. At 262, a metal layer can be provided (e.g., by lamination, contact with a metal melt, evaporation, sputtering, etc.) on the SSE 248 to function as the anode 264. In some embodiments, the metal layer can be solid Li. Alternatively, in some embodiments, the metal layer can be formed as a porous layer (e.g., Cu foam, Ni foam, Ti mesh, etc.), for example, as a host for infiltration of Li.

[0045] Although the above examples have focused on converting the porous support layer to an anode electrode, embodiments of the disclosed subject matter are not so limited. Indeed, in some embodiments, the porous support layer can be converted to a cathode instead by appropriate selection of the infiltrating material composition (e.g., cathode active material) and / or the composition of the support layer (e.g., carbon black or metal foam / mesh).

[0046] Manufacturing method using a porous support layer FIG. 3 illustrates a method 300 for manufacturing a layer assembly having a composite SSE and a porous support layer. The method 300 begins at an initial step 302 and can proceed to a process step 304, where a porous support layer can be provided. For example, the porous support layer can include a porous matrix of a conductive material (e.g., a carbon-based material such as carbon nanotubes, metal foam, metal mesh, etc.). The method 300 can proceed to a process step 306, where one or more precursors for forming the SSE are provided on a first surface of the porous support layer. The providing of the process step 306 can use any known deposition technique, such as, but not limited to, spray coating, printing, blade coating, and vapor deposition. Alternatively or additionally, the precursor can be provided in a powder form, and the providing of the process step 306 can include, for example, ball milling and / or calcination. In some embodiments, the precursor is, for example, an ionically conductive oxide having a melting point higher than the first temperature (e.g., 1200 K).

[0047] The method 300 can proceed to process step 308, where the precursor (and porous support layer) is exposed to one or more first high temperature heating waves to convert the precursor into a sintered porous scaffold. In some embodiments, the first high temperature heating wave is performed for a limited duration with a peak temperature less than the first temperature. For example, the duration of the first heating wave can be limited to 10 seconds or less (e.g., ∼5 seconds) and the temperature of the first heating wave can be ∼1100 K. The first heating wave can be performed via Joule heating or any other heating modality capable of generating high temperatures of limited duration.

[0048] Method 300 can proceed to process step 310, where one or more filler materials (or precursors thereof) are provided on the porous scaffold. In some embodiments, the filler materials can be disposed on an exposed surface of the porous scaffold opposite the porous support layer, and providing in process step 306 can use any known deposition technique, such as, but not limited to, spray coating, printing, blade coating, and vapor deposition. Alternatively or additionally, the filler materials can be provided in powder form, and providing in process step 310 can include, for example, ball milling and / or calcination. In some embodiments, the filler materials are, for example, glassy materials having a melting point below the first temperature (e.g., in the range of 500-1100 K).

[0049] Method 300 can proceed to process step 312, where one or more infill materials (and the porous scaffold and porous support layer) are exposed to one or more second high temperature heating waves to melt the infill materials and allow the melt to infiltrate the porous scaffold, thereby forming a substantially non-porous SSE layer. In some embodiments, the infiltration is sufficient to completely fill the porous scaffold. Alternatively, in some embodiments, the infill material infiltrates to a depth of at least 0.5 μm from the exposed surface of the porous scaffold. In some embodiments, the second high temperature heating wave is performed for a limited duration at a peak temperature higher than the melting point of the infill material. For example, the duration of the second heating wave can be limited to 10 seconds or less (e.g., ∼5 seconds) and the temperature of the first heating wave can be ∼1100 K. The first heating wave can be performed via Joule heating, or any other heating modality capable of generating high temperatures of limited duration.

[0050] The method 300 can proceed to a decision step 314, where it is determined whether an additional SSE layer is desired, e.g., to provide an additional layer that modifies the electrochemical window of the composite SSE and / or protects the SSE layer from degradation via contact with one of the electrodes. If an additional layer is desired for the composite SSE, the method 300 can proceed from the decision step 314 to a treatment step 316, where an additional precursor can be disposed on an exposed surface of the previously formed layer (e.g., the surface of the previously formed layer opposite the porous support layer). The provision of the treatment step 316 can use any known deposition technique, such as, but not limited to, spray coating, printing, blade coating, and vapor deposition. Alternatively or additionally, the precursor can be provided in powder form, and the provision of the treatment step 316 can include, for example, ball milling and / or calcination. In some embodiments, the precursor is, for example, an ionically conductive oxide having a melting point higher than the first temperature.

[0051] The method 300 then proceeds to process step 318, where the precursor (and preformed SSE layer and porous support layer) are exposed to one or more third high temperature heating waves to convert the precursor into a sintered SSE layer. In some embodiments, the third high temperature heating wave is performed for a limited duration at a peak temperature higher than the first temperature. For example, the duration of the third heating wave can be limited to 60 seconds or less (e.g., 10-20 seconds) and the temperature of the third heating wave can be in the range of 1200-3000 K. The third heating wave can be performed via Joule heating or any other heating modality capable of generating high temperatures of limited duration. In some embodiments, the composition of the newly sintered SSE layer can be different from the previously formed SSE layer. After the third heating wave, the method 300 can return to the determining step 314.

[0052] If no additional SSE layer is desired in determining step 314, method 300 may proceed to process step 320, where at least a portion of the porous support layer is converted to a first electrode (e.g., one of the anode and cathode of a battery). In some embodiments, the converting of process step 320 may include infiltrating the porous support layer with Li metal to form an anode or infiltrating the porous support layer with a cathode active material to form a cathode. Method 300 may proceed to process step 322, where a second electrode (e.g., the other of the anode and cathode of a battery) is provided on a side of the composite SSE opposite the porous support layer. In some embodiments, providing process step 322 may include disposing (e.g., via lamination) an electrode layer (e.g., a cathode support with cathode active material for a cathode, or a Li metal layer or Li-infiltrated porous metal for an anode) on the composite SSE. Alternatively or additionally, in some embodiments, the anode and / or cathode may be integrally formed on the respective surfaces of the SSE, for example, by sintering a layer directly onto the SSE (e.g., as described in International Publication No. WO 2020 / 236767, published November 26, 2020, entitled "High Temperature Sintering Systems and Methods," incorporated herein by reference).

[0053] Although shown separately, it is contemplated that various processing steps may occur simultaneously or iteratively. Additionally, certain processing steps shown as occurring after others may actually occur beforehand. Although steps 304-322 of method 300 have been described as being performed once, in some embodiments, multiple iterations of certain processing steps may be used before proceeding to the next decision or processing step. Additionally, although steps 304-322 of method 300 are shown and described separately, in some embodiments, the processing steps may be combined and performed together (concurrently or sequentially). Additionally, while FIG. 3 shows a particular order of steps 304-322, embodiments of the disclosed subject matter are not limited thereto. Indeed, in certain embodiments, the steps may occur in a different order than those shown, or simultaneously with other steps. In some embodiments, method 300 may comprise only some of steps 304-322 of FIG. 3B.

[0054] high temperature heating wave In any of the disclosed examples, a heating source (e.g., one or more joule heating elements) can subject the SSE precursor to a brief high temperature heating wave to form a sintered structure and / or can subject the filler material to a brief high temperature heating wave to melt the material for infiltration into the porous SSE scaffold. For example, FIG. 4A shows an exemplary wave 400 for a high temperature heating wave. In some embodiments, the heating wave 400 is a high temperature T H to and / or high temperature T H from low temperature T, e.g., room temperature (e.g., 20-25°C) or high temperature (e.g., <500K, e.g., 100-200°C) L For example, the heating wave 400 can provide a rapid transition to / from the sintering point T H (eg, at least 500K) or thereabouts, and may include a short dwell time t1 (eg, ≦60 seconds).

[0055] In some embodiments, the residence time t1 may be 10 seconds or less (e.g., 3 to 10 seconds, e.g., ∼5 seconds) and / or the high temperature T Hmay be 1200 K or less (e.g., ∼1100 K), for example, when a heating wave is used to form a porous scaffold and / or melt the filler material. In some embodiments, the residence time t1 may be 30 seconds or less (e.g., 10-20 seconds) and / or a high temperature T H For example, when sintering to form a non-porous SSE layer directly from a precursor, the heating wave 400 may be at least 1200 K (e.g., 1200-3000 K). In some embodiments, the heating wave 400 may be at a high temperature T H to and / or high temperature T L For example, the heating wave 400 may include a rapid transition from a rapid heating ramp R H (For example, ≥ 10 3 K / sec, e.g. 10 4 ~10 5 K / sec) and / or rapid cooling ramp R C (For example, ≥ 10 3 K / sec, e.g. 10 4 ~10 6 K / sec).

[0056] In some embodiments, the high temperature heating wave can be provided by Joule heating, microwave heating, laser heating, electron beam heating, spark discharge heating, or any other heating mechanism capable of providing the sintering temperature, heating rate, and / or cooling rate. For example, systems and methods for providing high temperature heating waves can be similar to those disclosed in International Publication No. WO2020 / 236767, published on November 26, 2020, entitled "High Temperature Sintering System and Method," and International Publication No. WO2022 / 204494, published on September 29, 2022, entitled "High Temperature Sintering Furnace System and Method," both of which are incorporated herein by reference. For example, the controller can control the power source to apply a time-limited current to the Joule heating element, which causes the heating element to rapidly rise to a high temperature, dwell at the high temperature for a predetermined time, and then rapidly cool from the high temperature.

[0057] In some embodiments, the high temperature heating wave can be terminated by carrying the sintered structure out of the heating zone and / or by deactivating, deenergizing, or other terminating the operation of the heating elements. Alternatively or additionally, in some embodiments, cooling at the end of the heating wave can be achieved using one or more passive cooling features (e.g., a heat sink thermally coupled to the heating elements and / or the sintered structure, etc.), one or more active cooling features (e.g., a fluid flow directed at the sintered structure and / or heater, a fluid flow through a heat sink thermally coupled thereto, etc.), or any combination thereof.

[0058] Computer implementation 4B depicts a generalized example of a suitable computing environment 431 in which the innovations described above, such as, but not limited to, aspects of the method 300 and / or a controller of a heating or sintering system (e.g., a furnace), may be implemented. The computing environment 431 is not intended to suggest any limitation as to scope of use or functionality, as the innovations may be implemented in a variety of general-purpose or special-purpose computing systems. For example, the computing environment 431 may be any of a variety of computing devices (e.g., a desktop computer, a laptop computer, a server computer, a tablet computer, etc.).

[0059] Referring to FIG. 4B, the computing environment 431 includes one or more processing units 435, 437 and memory 439, 441. In FIG. 4B, this basic configuration 451 is included within the dashed line. The processing units 435, 437 execute computer-executable instructions. The processing units may be a central processing unit (CPU), a processor in an application specific integrated circuit (ASIC), or any other type of processor (e.g., hardware processor, graphics processing unit (GPU), virtual processor, etc.). In a multi-processing system, multiple processing units execute computer-executable instructions to increase processing power. For example, FIG. 4B shows a central processing unit 435 and a graphics processing unit or co-processing unit 437. The tangible memory 439, 441 may be volatile memory (e.g., registers, cache, RAM), non-volatile memory (e.g., ROM, EEPROM, flash memory, etc.), or some combination of the two accessible by the processing units. The memories 439, 441 store software 433 in the form of computer-executable instructions suitable for execution by a processing unit(s) that implements one or more innovations described herein.

[0060] A computing system may have additional features. For example, computing environment 431 includes storage 461, one or more input devices 471, one or more output devices 481, and one or more communication connections 491. An interconnection mechanism (not shown), such as a bus, controller, or network, interconnects the components of computing environment 431. Typically, operating system software (not shown) provides an operating environment for other software executing in computing environment 431 and coordinates the activities of the components of computing environment 431.

[0061] Tangible storage 461 may be removable or non-removable and includes magnetic disks, magnetic tapes or cassettes, CD-ROMs, DVDs, or any other medium that can be used to store information in a non-transitory manner and that can be accessed within computing environment 431. Storage 461 may store instructions for software 433 that implements one or more innovations described herein.

[0062] The input device(s) 471 may be a touch input device such as a keyboard, a mouse, a pen, or a trackball, a voice input device, a scanning device, or another device that provides input to the computing environment 431. The output device 471 may be a display, a printer, speakers, a CD-writer, or another device that provides output from the computing environment 431.

[0063] The communication connection(s) 491 enable communication over a communication medium to another computing entity. The communication medium conveys information such as computer-executable instructions, audio or video input or output, or other data in a modulated data signal. A modulated data signal is a signal that has one or more of its characteristics set or changed in such a manner as to encode information in the signal. By way of example, and not limitation, the communication medium may be electrical, optical, radio frequency (RF), or another carrier.

[0064] Any of the disclosed methods may be implemented as computer-executable instructions stored on one or more computer-readable storage media (e.g., one or more optical media disks, volatile memory components (such as DRAM or SRAM), or non-volatile memory components (such as flash memory or hard drives)) and executed on a computer (e.g., any commercially available computer, including a smartphone or other mobile device that includes computing hardware). The term computer-readable storage medium does not include communication connections such as signals and carrier waves. Any computer-executable instructions for implementing the disclosed techniques, as well as any data created and used during the implementation of the disclosed embodiments, may be stored on one or more computer-readable storage media. The computer-executable instructions may be, for example, a dedicated software application or part of a software application accessed or downloaded via a web browser or other software application (such as a remote computing application). Such software may be executed, for example, on a single local computer (e.g., any suitable commercially available computer) or in a networked environment using one or more networked computers (e.g., via the Internet, a wide area network, a local area network, a client-server network (such as a cloud computing network), or any other such network).

[0065] For clarity, only selected aspects of the software-based implementation are described. Other details that are well known in the art are omitted. For example, it should be understood that the disclosed technology is not limited to any particular computer language or program. For example, aspects of the disclosed technology may be implemented in any language, including C++, Java TM, Python, and / or any other suitable computer language. Similarly, the disclosed technology is not limited to any particular computer or hardware type. Particular details of suitable computers and hardware are well known and need not be described in detail in this disclosure.

[0066] It should also be appreciated that any functionality described herein may be performed, at least in part, by one or more hardware logic components instead of software. For example, and without limitation, exemplary types of hardware logic components that may be used include field programmable gate arrays (FPGAs), program specific integrated circuits (ASICs), program specific standard products (ASSPs), systems on a chip (SOCs), complex programmable logic devices (CPLDs), etc.

[0067] Additionally, any of the software-based embodiments (e.g., including computer-executable instructions for causing a computer to perform any of the disclosed methods) can be uploaded, downloaded, or remotely accessed via suitable communication means. Such suitable communication means include, for example, the Internet, the World Wide Web, an intranet, a software application, cable (including fiber optic cable), magnetic communication, electromagnetic communication (including radio frequency, microwave, and infrared communication), electronic communication, or other such communication means. In any of the above examples and embodiments, the provision of requests (e.g., data requests), instructions (e.g., data signals), commands (e.g., control signals), or any other communication between systems, components, devices, etc. can be by generation and transmission of appropriate electrical signals via wired or wireless connections.

[0068] Example of fabrication and experimental results Porous scaffolds infiltrated with filler Using a carbon nanotube (CNT) support, Li7La3Zr2TaO12 A dense composite SSE was formed by forming a porous LLZTO (LLZTO) scaffold and then infiltrating the scaffold with molten Li3BO3 (LBO) glass. In particular, a two-step fabrication process was used. First, a porous LLZTO film was formed on the CNT support by sintering the LLZTO precursor at 1100 K for only 5 seconds. This short heating wave formed a LLZTO porous scaffold on the CNT support, as shown in Figure 5A, with a substantially crack-free morphology. The enlarged images in Figures 5B-5C further show that the LLZTO scaffold has a continuous porous microstructure, due in part to the precise control of the sintering time and temperature. Furthermore, as shown in Figure 5D, the LLZTO porous scaffold has a seamless interface with the CNT support. In the second step of the fabrication process, the LBO glass is placed on the porous LLZTO film and exposed to another short heating wave, specifically 1100 K, for only 5 seconds. This second short heating wave is sufficient to melt the LBO, thereby allowing it to infiltrate and fill the pores of the LLZTO scaffold to achieve a dense composite SSE layer, as shown in Figure 6A. As shown in Figures 6B-6C, the CNT-supported LBO / LLZTO composite SSE film exhibits a dense structure. A dense interface between the CNT support and the dense composite SSE layer was maintained, as shown in Figure 6D.

[0069] As shown in FIG. 7B, the composite SSE on the CNT support exhibits the desired phases consistent with the standard diffraction pattern of LLZTO. To test the electrochemical properties, an asymmetric test cell 700, FIG. 7A, was fabricated. In particular, the test cell 700 includes an electrode 702 formed from Li and an adjacent composite SSE layer 704 (LLZTO / LBO) supported on a porous support layer 706 (CNT). A Li melt 708 was also provided at the end of the porous support layer 706 opposite the Li electrode 702. This asymmetric test cell 700 was used to evaluate the electrical conductivity of the composite SSE and its galvanostatic cycling performance. As shown in FIG. 7C-7D, the composite SSE was measured using a galvanostatic charge of 7×10 -5 High Li-ion conductivity of 0.2mA / cm 2 It provides stable charge / discharge curves with a low overvoltage of 7mV at 1000V.

[0070] multilayer structure To provide a composite SSE that has an extended electrochemical voltage window and can remain stable against electrode materials (e.g., cathode and Li metal anode), a multilayer structure was formed. The multilayer structure was achieved by using continuous ink printing followed by application of a high temperature wave (e.g., at temperatures between 1200 and 3000 K for durations of 30 s or less). Calculations were performed on the garnet LLZTO and Li 3x La 2 / 3-x It has been shown that TiO3 (LLTO) has either a relatively low oxidation potential or a high reduction potential, limiting its electrochemical stability with the cathode or Li metal anode. To identify the addition of an SSE layer that can be used to improve performance, NASICON-type Li 1.3 Al 0.3 Ti 1.7 P3O 12 (LATP), Li7La3Zr2O 12 The electrochemical windows were calculated for several other materials, including (LLZO), LiCoO2, LiBO2, and Li3PO4. The results of the calculations are summarized in Figure 8A. These materials can have better stability at high or low voltages when incorporated into a multilayer structure design, as shown in Figure 8B.

[0071] In the fabricated case, multilayer composite SSEs were formed from LiBO2 and LLZTO. In particular, LiBO2 precursor powder was placed on the LLZTO film and sintered by a short heating wave using a Joule heating element. The LiBO2 / LLZTO SSEs remained about 0.5 mm from the Joule heating element throughout the heating wave, thereby reducing the heat loss during sintering and shortening the sintering time. When the sintering temperature reached ~1073 K, the LiBO2 powder melted into a liquid state and spread on the LLZTO surface, forming a dense and uniform interface with LLZTO, as shown in Figure 8C. Such an interface may help to reduce the interfacial resistance. Even at a thickness of about 3 μm, the sintered LiBO2 thin film retained a clear interface with LLZTO, as shown in Figure 8D. No interlayer element co-diffusion was observed, suggesting that element diffusion was effectively inhibited by the heating wave method. With conventional sintering, retaining high ionic conductivity of multilayer garnet SSEs with NASICON (e.g., NASICON and garnet) or glass (e.g., glass and garnet) can be a challenge, as sintering for longer durations can lead to Li loss, which reduces the ionic conductivity. In contrast, the use of short heating waves to sinter each SSE layer can avoid or at least reduce Li loss, thereby maintaining the ionic conductivity of the resulting multilayer composite SSE. Indeed, multilayer SSEs formed by LiBO2 and LLZTO exhibited ionic conductivities of 3 mS / cm, which is one of the highest values ​​reported for garnet bulk.

[0072] In another example, garnet has a high ionic conductivity of ~1 mS / cm and excellent stability with Li metal, but a relatively oxidation potential of ~3 V, limiting its ability to pair with higher voltage cathode materials. Furthermore, due to chemical instability with the cathode material at high sintering temperatures (e.g., >773 K), garnet could not be co-sintered with certain cathodes, such as LiCoO2, which could lead to poor interfacial contact and / or increased interfacial resistance. To broaden the electrochemical window of the garnet SSE, NASICON can be used as a thin buffer layer between the garnet and the cathode material, as shown in Figure 9A. For example, LATP features a high ionic conductivity of ~1 mS / cm and is calculated to have a high anode potential of 4.31 V. This can broaden the oxidation potential of garnet for pairing with LiCoO2 cathodes.

[0073] As mentioned above, conventional sintering can suffer from challenges due to Li loss and elemental interlayer co-diffusion, leading to reduced ionic conductivity and poor battery performance. Therefore, it can be difficult to fabricate multilayer SSEs with LATP and LLZTO using conventional techniques. In contrast, we used a solution-based technique together with a high-temperature heating wave of limited duration to successfully sinter the LATP thin film on the LLZTO pellet with a tight interface, as shown in Figure 6C. In particular, the LATP precursor ink was directly printed on the LLZTO pellet, followed by sintering for about 5 seconds. When the sintering temperature reached ~1473 K, the LATP precursor reacted and densified within ~5 seconds, forming a continuous and dense coating layer on the LLZTO surface. Due to the short sintering time, Li loss was effectively suppressed, producing a LATP thin film with a pure NASICON-type structure at the desired high ionic conductivity, as shown in Figure 9B. As shown in Figure 9C, the thickness of the LATP coating layer is ~10 μm, which is much thinner than that of the LLZTO pellet (~400 μm), and thus helps to achieve high gravimetric energy density. As suggested by Figures 9D-9E, a tight interface between the layers was maintained (indicating reduced interfacial resistance) and no interlayer co-diffusion was observed. This multilayer film formed from LATP and LLZTO allows the LLZTO to be co-sintered with the LiCoO2 cathode for full-cell assembly.

[0074] In another example, we fabricated a multilayer SSE of LiBO2-Li3PO4 and perovskite-type LLTO, which reduced the reduction potential of LLTO to 0.69 V and effectively improved the chemical stability of LLTO with Li metal anode. LLTO is attractive for solid-state battery applications in terms of its high ionic conductivity, but it is prone to decomposition when in contact with Li metal. A glass SSE, especially LiBO2-Li3PO4, was selected to provide a protective film as part of the SSE, as shown in Figure 10A. The glass SSE exhibits excellent chemical stability against Li metal, so it can insulate LLTO from the Li metal anode. To protect LLTO, Ti 4+ When it comes into contact with Li metal, Ti 3+Since the coating layer needs to be very dense without pinholes, it is difficult to achieve such a layer in conventional sintering due to elemental co-diffusion and ceramic cracking. In contrast, the use of high-temperature heating waves of limited duration can effectively form a multi-layer SSE with this pinhole-free protective layer.

[0075] As shown in Figures 10B-10E, the LiBO2-Li3PO4 film was melted at high temperature to form a dense structure without cracks or pinholes. After immersion in molten Li-Sn alloy at 423K, the molten Li metal fully wets the LiBO2-Li3PO4 surface without any reaction, forming an integrated uniform interface, as shown in Figure 10D, further enhancing the density of LiBO2-Li3PO4. Thereby, the LiBO2-Li3PO4 film prevents the direct approach between the LLTO layer and the Li layer, and inhibits the LLTO from being reduced by the molten Li.

[0076] In another embodiment, a composite SSE was formed by layers of Li3PO4 and LLZTO. As shown in FIG. 11A, a glass Li3PO4 protective layer was melted onto the LLZTO pellets using a sintering temperature of ∼1773 K for a short time (e.g., 3 seconds). The thickness of the resulting Li3PO4 film was ∼5 μm. With higher sintering temperatures, the Li3PO4 thin film can adopt a crystalline structure with coalesced fine grains, which helps to enhance ionic conductivity. As shown in FIG. 11B, a compact, uniform and clear interlayer interface is generated, and it can be seen that the co-diffusion between the device layers is well suppressed. As shown in FIG. 11C, Li3PO4 exhibited a pure phase structure, suggesting that the short sintering time effectively suppresses lithium loss during sintering.

[0077] Figure 11C shows similar results obtained for glassy LiBO2 on LLZTO (LBO) through a similar fabrication process. Also, as shown in Figures 11D-11E, the ionic conductivity of LLZTOOOA was 0.3 mS / cm and the activation energy was ~0.23 eV. The interface resistance of the bilayer LiBO2-LLZTO is comparable to the highest reported ionic conductivity of LiBO2 (e.g., 10 -5 ~10 -8 S / cm) to 24 Ω cm 2 The actual interface resistance was estimated to be 24 Ω cm due to the thin LiBO2 coating layer, as shown in Figure 11F. 2 It must be much lower.

[0078] Further examples of the disclosed technology In view of the above implementations of the disclosed subject matter, the present application discloses additional examples in the appendices listed below. It should be noted that any feature of the appendices alone, or two or more features of the appendices taken in combination, and optionally combined with one or more features of one or more additional appendices, are also included within the scope of the disclosure of the present application.

[0079] Appendix 1. (a) providing one or more precursors on a first surface of a porous support layer; (b) exposing the one or more precursors to the porous support layer at a first temperature for a first time period to sinter the one or more precursors to form a porous scaffold, the first temperature being less than or equal to about 1200 K and the first time period being less than or equal to about 60 seconds, the porous scaffold comprising an ion-conducting oxide; (c) providing one or more fillers on the second surface of the porous scaffold having a melting point in the range of 500 to 1100 K, inclusive; (d) exposing the porous scaffolding having the one or more fillers to a second temperature for a second time period to melt the one or more fillers and form a non-porous composite solid electrolyte layer having the one or more fillers infiltrating the porous scaffolding, wherein the second temperature is less than or equal to about 1200 K and the second time period is less than or equal to about 60 seconds.

[0080] Appendix 2. the second temperature is about the same as or less than the first temperature; The first temperature is about 1100 K; The method according to any section or example herein, particularly Appendix 1, wherein the second temperature is about 1100K; or any combination of the above.

[0081] Appendix 3. the second time period is about the same as or less than the first time period; The first time period is about 5 seconds; the second time is about 5 seconds; or The method of any section or example herein, in particular the method of any one of Appendices 1-2, which is any combination of the above.

[0082] Appendix 4. The method according to any of the sections or examples herein, particularly any one of Appendices 1-3, wherein the composite solid electrolyte layer conducts alkali metal ions, alkaline earth metal ions, anions, or any combination thereof.

[0083] Appendix 5. 5. The method of any one of claims 1 to 4, wherein the composite solid electrolyte layer conducts lithium ions, sodium ions, potassium ions, magnesium ions, calcium ions, oxygen ions, or any combination thereof.

[0084] Appendix 6. The method according to any of the sections or examples herein, particularly any one of Appendices 1 to 5, wherein the porous support layer comprises carbon or metal.

[0085] Appendix 7. The method according to any of the sections or examples herein, particularly any one of Appendices 1 to 6, wherein the porous support layer comprises a matrix of carbon nanofibers.

[0086] Appendix 8. The method according to any of the sections or examples herein, particularly any one of Appendices 1 to 6, wherein the porous support layer comprises a metal mesh.

[0087] Appendix 9. The method according to any of the clauses or examples herein, particularly any one of Appendices 1 to 8, wherein the melting in (d) is such that the one or more fillers penetrate into the porous scaffold to a depth of 0.5 μm or more from the second surface of the porous scaffold.

[0088] Appendix 10. The method according to any of the paragraphs or examples herein, particularly any one of Appendices 1 to 9, wherein the one or more fillers comprise a glassy, ​​ionically conductive material.

[0089] Appendix 11. The method according to any of the sections or examples herein, particularly any one of Appendices 1 to 10, wherein the one or more fillers comprise Li3BO3, LiCl, LiBr, LiI, LiF, Li3N, LiBH4, LiBF4, or any combination of the foregoing.

[0090] Appendix 12. Li A La B M' c M'' D Zr E O F , Li A La B M'' c M'' D Ta E O F , or Li A La B M' c M'' D Nb E O F ; Where 4 < A < 8.5, 1.5 < B < 4, 0 ≤ C ≤ 2, 0 ≤ D ≤ 2, 0 ≤ E < 2, and 10 < F < 13, and M’ is a first one selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta, and M’ is a second one selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta, the method described in any item or example of this specification, in particular, any one item of Appendices 1 to 11.

[0091] Appendix 13. The ion-conductive oxide of the porous scaffold is Li A La B M’ c M’’ D Zr E O F 、Li A La B M’’ c M’’ D Ta E O F 、or Li A La B M’ C M’’ D Nb E O F and includes a compound having the formula of Where 4 < A < 8.5, 1.5 < B < 4, 0 ≤ C ≤ 2, 0 ≤ D ≤ 2, 0 ≤ E < 2, and 10 < F < 13, M’ is a first one selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta, M’’ is a second one selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta, the method described in any item or example of this specification, in particular, any one item of Appendices 1 to 11.

[0092] Appendix 14. The ion-conductive oxide of the porous scaffold is perovskite-type Li 0.33 La 0.57 TiO3, NASICON-type Li 1.3 Al 0.3 Ti 1.7(PO4)3, NASICON type LiTi2(PO4)3, NASICON type Li 1+x Al x Ge 2-x (PO4)3, garnet type Li7La3Zr2O 12 (LLZO), tantalum-doped Li7La3Zr2TaO 12 (LLTZO), LISICON type Li 14 Zn(GeO4)4, or any combination thereof, wherein x is a number.

[0093] Appendix 15. The ionically conductive oxide is tantalum-doped Li7La3Zr2TaO 12 (LLTZO) and the one or more fillers are Li3BO3.

[0094] Appendix 16. The method of any section or example herein, particularly any one of Appendices 1 to 15, further comprising, after (d), forming one or more additional solid electrolyte layers on the composite solid electrolyte layer by sintering the one or more additional precursors at a third temperature for a third time, wherein the third time is about 60 seconds or less.

[0095] Appendix 17. The method according to any of the sections or examples herein, particularly appendix 16, wherein the one or more additional solid electrolyte layers have a material composition different from a material composition of the composite solid electrolyte layer.

[0096] Appendix 18. the third temperature is greater than or equal to the first temperature; the third time is greater than or equal to the first time; The third temperature is in the range of 1000 to 1500 K (inclusive); The method according to any of the clauses or examples herein, particularly any one of Appendices 16-17, wherein the third period of time is within the range of 3 to 10 seconds (inclusive), or any combination of the above.

[0097] Appendix 19. (e) forming one of a cathode and an anode of an electrochemical energy device on a side of the composite solid electrolyte layer opposite the porous support layer; (f) forming at least a portion of the porous support layer as the other of the cathode and the anode.

[0098] Appendix 20. The method according to any of the sections or examples herein, particularly appendix 19, wherein the electrochemical energy device is a battery or a fuel cell.

[0099] Appendix 21. The method of any section or example herein, particularly any one of Appendices 19-20, wherein the forming of (f) comprises infiltrating at least a portion of the porous support layer with lithium to form an anode.

[0100] Appendix 22. The method according to any of the paragraphs or examples herein, particularly paragraph 21, wherein the penetration depth of lithium into the porous support layer is at least 0.5 μm.

[0101] Appendix 23. The method according to any of the sections or examples herein, in particular any one of Appendices 19 to 22, wherein (f) is performed after (d), after (e), or after both (d) and (e).

[0102] Appendix 24. The method of any of the sections or examples herein, particularly any one of Appendices 19-20, wherein the forming of (f) comprises infiltrating at least a portion of the porous support layer with one or more cathode active materials to form a cathode.

[0103] Appendix 25. The method according to any of the sections or examples herein, particularly appendix 24, wherein the one or more negative electrode active materials have a composition comprising lithium and another metallic element.

[0104] Appendix 26. The method according to any of the sections or examples herein, particularly any one of Appendix 24 to 25, wherein the impregnating with the one or more cathode active materials comprises disposing the one or more cathode active materials on the porous support layer together with the liquid electrolyte.

[0105] Appendix 27. The method according to any of the paragraphs or examples herein, particularly any one of appendices 24 to 26, wherein the penetration depth of the one or more cathode active materials into the porous support layer is at least 0.5 μm.

[0106] Appendix 28. The method according to any of the sections or examples herein, in particular any one of Appendices 24 to 27, wherein (f) is performed before (e), before (a), or before both (a) and (e).

[0107] Appendix 29. The method according to any of the sections or examples herein, particularly any one of Appendices 24 to 28, wherein the forming of (e) includes providing a metal film on the composite solid electrolyte layer to form an anode.

[0108] Appendix 30. The method of any of the sections or examples herein, particularly the method of Appendix 29, wherein the metal film is a lithium metal layer or a copper metal layer as a current collector.

[0109] Appendix 31. (e) The formation of providing another porous layer on the composite solid electrolyte layer; and impregnating the separate porous layer with lithium to form a positive electrode.

[0110] Appendix 32. The method according to any of the sections or examples herein, particularly appendix 31, wherein the further porous layer comprises carbon.

[0111] Appendix 33. The exposure treatment in (b) was approximately 10 3 ~about 10 5 heating to a first temperature at a first heating rate of 10 K / sec (inclusive); The process of (d) takes about 10 3 ~about 10 5 heating to a second temperature at a second heating rate of 10 K / sec (inclusive); The process of (b) is about 10 3 ~about 10 5 cooling from the first temperature at a first cooling rate of 10 K / sec (inclusive); The process of (d) takes about 10 3 ~about 10 5 or cooling from the second temperature at a second cooling rate of 10 K / sec (inclusive); or The method according to any section or example herein, particularly any one of appendices 1 to 32, including any combination of the above.

[0112] Appendix 34. A porous support layer; a non-porous composite solid electrolyte layer disposed on a porous support layer, the non-porous composite solid electrolyte layer comprising a porous scaffold and one or more fillers permeating the porous scaffold, the porous scaffold comprising an ion-conducting oxide, and the one or more fillers having a melting point in the range of 500 to 1100 K, inclusive; An electrochemical energy device, wherein at least a portion of the porous support layer is infiltrated with one or more materials to form an electrode of the electrochemical energy device.

[0113] Appendix 35. The electrochemical energy device may be a battery or a fuel cell. The electrochemical energy device of any section or example herein, in particular the electrochemical energy device of appended claim 34.

[0114] Appendix 36. The electrochemical energy device according to any of the sections or examples herein, particularly any one of Appendices 34-35, wherein at least a portion of the porous support layer is permeated with lithium to form an anode of the electrochemical energy device.

[0115] Appendix 37. The electrochemical energy device of any of the paragraphs or examples herein, particularly paragraph 36, wherein the lithium permeates the porous support layer to a depth of at least 0.5 μm.

[0116] Appendix 38. The electrochemical energy device according to any section or example herein, particularly any one of Appendices 36-37, further comprising a cathode of the electrochemical energy device disposed on a side of the composite solid electrolyte layer opposite the porous support layer.

[0117] Appendix 39. The electrochemical energy device according to any of the sections or examples herein, particularly any one of Appendix 34-35, wherein at least a portion of the porous support layer is infiltrated with one or more cathode active materials to form a cathode of the electrochemical energy device.

[0118] Appendix 40. The electrochemical energy device of any section or example herein, particularly of Appendix 39, wherein the one or more positive electrode active materials have a composition comprising metal and lithium.

[0119] Appendix 41. The electrochemical energy device as described in any section or example herein, particularly as described in Appendix 39, wherein the cathode comprises one or more cathode active materials with a liquid electrolyte.

[0120] Appendix 42. The electrochemical energy device according to any of the sections or examples herein, particularly any one of Appendices 40-41, wherein the one or more cathode active materials penetrate into the porous support layer to a depth of at least 0.5 μm.

[0121] Appendix 43. The electrochemical energy device according to any section or example herein, particularly any one of Appendices 39-42, further comprising an electrochemical energy device anode disposed on a side of the composite solid electrolyte layer opposite the porous support layer.

[0122] Appendix 44. 44. The electrochemical energy device according to any of the sections or examples herein, in particular as described in Appendix 43, wherein the anode comprises a metal film.

[0123] Note 45. The electrochemical energy device according to any of the sections or examples herein, particularly appendix 44, wherein the metal film is a lithium metal layer or a copper metal layer as a current collector.

[0124] Appendix 46. 46. ​​The electrochemical energy device according to any of the sections or examples herein, particularly any one of Appendices 34 to 45, wherein the composite solid electrolyte layer conducts alkali metal ions, alkaline earth metal ions, anions, or any combination of the foregoing.

[0125] Appendix 47. 47. The electrochemical energy device according to any of the sections or examples herein, in particular any one of Appendices 34 to 46, wherein the composite solid electrolyte layer conducts lithium ions, sodium ions, potassium ions, magnesium ions, calcium ions, oxygen ions, or any combination of the foregoing.

[0126] Note 48. The electrochemical energy device according to any of the sections or examples of this specification, particularly any one of Appendices 34 to 47, wherein the porous support layer comprises carbon or metal.

[0127] Appendix 49. The electrochemical energy device according to any of the sections or examples herein, particularly any one of Appendices 34 to 48, wherein the porous support layer comprises a matrix of carbon nanofibers.

[0128] Note 50. The electrochemical energy device according to any of the sections or examples herein, particularly any one of Appendices 34 to 48, wherein the porous support layer comprises a metal mesh.

[0129] Note 51. The electrochemical energy device according to any of the sections or examples herein, particularly any one of Appendices 34 to 50, wherein the one or more fillers comprise a glassy ionically conductive material.

[0130] Appendix 52. The electrochemical energy device according to any of the sections or examples herein, particularly any one of Appendices 34 to 51, wherein the one or more filler materials comprise Li3BO3, LiCl, LiBr, LiI, LiF, Li3N, LiBH4, LiBF4, or any combination thereof.

[0131] Note 53. The ion-conducting oxide in the porous scaffold is Li A La B M' c M'' D Zr E O F , Li A La B M'' c M'' D Ta E O F , or Li A La B M' cD Nb E O F wherein: <A<8.5、1.5<B<4、0≦C≦2、0≦D≦2、0≦E<2、および10<F<13であり、 M' is a first element selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta; M’’ is a second one selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta, any item or example in this specification, in particular, the electrochemical energy device described in any one of Appendices 34 to 52.

[0132] Appendix 54. The ion-conductive oxide of the porous scaffold contains Li a La b Zr c Al d M’’’ e O f (where 5 < a < 7.7, 2 < b < 4, 0 < c ≤ 2.5, 0 ≤ d < 2, 0 ≤ e < 2, and 10 < f < 13), and contains a compound having M’’’ is Nb, Ta, V, W, Mo, or Sb, any item or example in this specification, in particular, the electrochemical energy device described in any one of Appendices 34 to 52.

[0133] Appendix 55. The ion-conductive oxide of the porous scaffold is perovskite-type Li 0.33 La 0.57 TiO3, NASICON-type Li 1.3 Al 0.3 Ti 1.7 (PO4)3, NASICON-type LiTi2(PO4)3, NASICON-type Li 1+x Al x Ge 2-x (PO4)3, garnet-type Li7La3Zr2O 12 (LLZO), tantalum-doped Li7La3Zr2TaO 12 (LLTZO), LISICON-type Li 14 Zn(GeO4)4, or any combination of the foregoing, where x represents a number, any item or example in this specification, in particular, the electrochemical energy device described in any one of Items 34 to 52.

[0134] Appendix 56. The ion-conductive oxide is tantalum-doped Li7La3Zr2TaO 12(LLTZO) and the one or more fillers are Li3BO3.

[0135] Note 57. The electrochemical energy device according to any of the sections or examples herein, in particular any one of Appendices 34 to 56, further comprising at least one additional solid electrolyte layer, the composite solid electrolyte layer being disposed between the at least one additional solid electrolyte layer and the porous support layer.

[0136] Note 58. The electrochemical energy device of any of the sections or examples herein, particularly of paragraph 57, wherein the at least one additional solid electrolyte layer has a different material composition than the composite solid electrolyte layer.

[0137] conclusion For example, any of the features shown or described herein with respect to Figures 1A-11F and Appendices 1-58 can be combined with any other features shown or described herein with respect to Figures 1A-11F and Appendices 1-58 to provide materials, systems, devices, structures, methods, and embodiments not otherwise shown or specifically described herein. All features described herein are independent of one another and can be used in combination with any other features described herein, except where structurally impossible. In view of the many possible embodiments to which the principles of the disclosed technology may be applied, it should be recognized that the illustrated embodiments are merely examples and should not be construed as limiting the scope of the disclosed technology. Rather, the scope is defined by the following claims. Accordingly, we claim all that comes within the scope and spirit of these claims.

Claims

1. (a) providing one or more precursors on a first surface of a porous support layer; (b) exposing one or more precursors to the porous support layer at a first temperature for a first time period to sinter the one or more precursors to form a porous scaffold, the first time period being less than or equal to about 60 seconds, wherein the porous scaffold comprises an ion-conducting oxide; (c) providing one or more fillers on the second surface of the porous scaffold having a melting point in the range of 500 to 1100 K, inclusive; (d) exposing the porous scaffolding with the one or more fillers to a second temperature for a second period of time to melt the one or more fillers and form a non-porous composite solid electrolyte layer with the one or more fillers infiltrating the porous scaffolding, wherein the second period of time is less than or equal to about 60 seconds.

2. The first temperature is about 1200 K or less, the second temperature is less than or equal to about 1200 K; the second temperature is about the same as or less than the first temperature; the first temperature is about 1100 K; the second temperature is about 1100 K; or 10. The method of claim 1, any combination of the above.

3. the porous support layer comprises a matrix of carbon nanofibers; or The method of claim 1 , wherein the porous support layer comprises a metal mesh.

4. 2. The method of claim 1, wherein the melting in (d) is such that the one or more filler materials penetrate the porous scaffold to a depth of 0.5 μm or more from the second surface of the porous scaffold.

5. The one or more fillers are Li ３ BO ３ , LiCl, LiBr, LiI, LiF, Li ３ N, LiBH ４ , LiBF ４ or any combination thereof.

6. (i) The ion-conducting oxide of the porous scaffold is Li Ａ La Ｂ M' ｃ M'' Ｄ Zr Ｅ O Ｆ , Li Ａ La Ｂ M'' ｃ M'' Ｄ Ta Ｅ O Ｆ , or Li Ａ La Ｂ M' Ｃ M'' Ｄ Nb Ｅ O Ｆ and a compound having the formula: wherein 4<A<8.5, 1.5<B<4, 0≦C≦2, 0≦D≦2, 0≦E<2, and 10<F<13; M' is a first element selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta; M″ is a second element selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta; or (ii) the ion-conducting oxide of the porous scaffold comprises a compound having the formula Li A La B Zr C Al D M''' E O F, where 5<A<7.7, 2<B<4, 0<C<2.5, 0<D<2, 0<E<2, and 10<F<13; M''' is Nb, Ta, V, W, Mo, or Sb; or (iii) the ion-conducting oxide of the porous scaffold is selected from the group consisting of perovskite-type Li0.33La0.57TiO3, NASICON-type Li1.3Al0.3Ti1.7(PO4)3, NASICON-type LiTi2(PO4)3, NASICON-type Li1+xAlxGe2-x(PO4)3, garnet-type Li7La3Zr2O12 (LLZO), tantalum-doped Li7La3Zr2TaO12 (LLTZO), LISICON-type Li14Zn(GeO4)4 or any combination thereof, wherein x is a number.

7. The ion-conducting oxide is tantalum-doped Li ７ La ３ Zr ２ TaO １２ (LLTZO), wherein the one or more fillers are Li ３ BO ３ The method of claim 1, wherein

8. After (d), further forming one or more additional solid electrolyte layers on the composite solid electrolyte layer by sintering the one or more additional precursors at a third temperature for a third time period, the third time period being less than or equal to about 60 seconds; The method of claim 1 , wherein the one or more additional solid electrolyte layers have a material composition that is different from a material composition of the composite solid electrolyte layer.

9. (e) forming one of a positive electrode and a negative electrode of a battery on the surface of the composite solid electrolyte layer opposite the porous support layer; 10. The method of claim 1, further comprising: (f) forming at least a portion of the porous support layer as the other of the cathode and the anode.

10. The method of claim 9, wherein forming (f) comprises infiltrating lithium into at least a portion of the porous support layer to form an anode.

11. The method of claim 9, wherein forming (f) comprises infiltrating at least a portion of the porous support layer with one or more cathode active materials to form a cathode.

12. the forming step of (e) includes providing a metal film on the composite solid electrolyte layer to form the anode; or The formation of (e) providing another porous layer on the composite solid electrolyte layer; and infiltrating another porous layer with lithium to form the anode.

13. The method of claim 12 , wherein the another porous layer comprises carbon.

14. The exposure treatment of (b) is performed for about 10 ３ ~about 10 ５ heating at a first heating rate of 100 K / sec to a first temperature; The treatment (d) is carried out for about 10 ３ ~about 10 ５ heating at a second heating rate of 100 K / sec (inclusive) to a second temperature; The treatment (b) is carried out for about 10 ３ ~about 10 ５ cooling from the first temperature at a first cooling rate of 100 K / sec, inclusive; The treatment (d) is carried out for about 10 ３ ~about 10 ５ cooling from the second temperature at a second cooling rate of 100 K / sec (inclusive); or The method of claim 1 , including any combination of the above.

15. a porous support layer; a non-porous composite solid electrolyte layer formed by the method of any one of claims 1 to 14; A battery assembly wherein at least a portion of said porous support layer is infiltrated with one or more materials to form an electrode of the battery.

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