JP2023088911A - Solid hybrid electrolyte, method for preparation thereof and use thereof - Google Patents

Abstract

To provide a solid hybrid electrolyte used for an ion-conductive battery, which achieves higher ion conductivity at room temperature.SOLUTION: There is provided a solid hybrid electrolyte which has a layer of a polymer material (which may be a polymer/copolymer layer or a gel polymer/copolymer layer) arranged at least partially or completely on the outer surface of the solid electrolyte. The hybrid electrolyte can form an interface with the electrode of an ion-conductive battery which exhibits desirable properties. The solid electrolyte can include a monolithic SSE body, a mesoporous SSE body or an inorganic SSE having fibers or strands (which may be aligned). For solid electrolytes having strands, the strands can be formed using sacrificial templates. Solid hybrid electrolytes can be used in ion-conductive batteries (which may be flexible ion-conductive batteries).SELECTED DRAWING: Figure 3

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application is made in accordance with U.S. Provisional Patent Application No. 62/478,396, filed March 29, 2017 and U.S. Provisional Patent Application No. 62/483,816, filed April 10, 2017. No. 1, 2003, the disclosure of each of which is hereby incorporated by reference.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH This invention is based on Contract Nos. DEEE0006860 and D
It was made with government support under EEE0006860. The Government has certain rights in this invention.

The present disclosure relates generally to solid state hybrid electrolytes. More particularly, this disclosure relates generally to solid state hybrid electrolytes used in ion-conducting batteries.

Over the last 20-30 years, lithium-ion battery technology has made significant progress. Pure lithium metal has the highest specific capacity (3860 mAh/g) and lowest electrochemical potential (-3.04 V vs standard hydrogen electrode) compared to any other lithium ion anode material. A significant problem associated with lithium metal anodes is the formation of metal dendrites in liquid electrolyte systems that can penetrate the polymer separator and lead to both safety concerns and reduced performance in long cycle applications. Solid electrolyte (SS
E) is recognized as a solution to prevent Li dendrite formation by acting as a strong impenetrable barrier.

SSEs generally have a wide electrochemical stability potential window and a high modulus that prevents penetration of Li dendrites, and are usually non-flammable, thus improving safety. A major challenge for SSE in Li metal batteries is the high interfacial resistance between the SSE and the cathode or anode. High interfacial resistance leads to high overvoltages and reduced coulombic efficiency when the cell is cycled.

Chemical/physical short circuit and electrode volume change are two other major problems in lithium batteries. In conventional batteries, polymer separators cannot effectively prevent chemical or physical short circuits. Dissolved active materials inevitably migrate through the pores of the polymer membrane, and highly elastic Li dendrites readily penetrate the membrane, resulting in reduced performance and safety concerns. Volume changes during lithiation and delithiation raise additional concerns such as desorption of active material at the interface and structural instability of the entire cell. For sulfur cathodes, the formation and migration across the liquid organic electrolyte of lithium polysulfides is another major limitation in achieving high energy density batteries. Although extensive research has been done to prevent short circuits and accommodate volume changes by developing cathode hosts, improving separators, or protecting Li metal, few methods can simultaneously address these challenges.

Liquid organic electrolytes are the industry standard ionic conductors for lithium-ion batteries (LIBs). Liquid electrolytes are characterized by high ionic conductivity and good electrode wetting. However, liquid systems are flammable, which inevitably leads to dissolution and diffusion of the active material, and migration of unwanted species from the cathode to the anode, both degrading the electrode and limiting the development of new cathodic properties. A "short circuit" occurs, which is typical of high voltage cathodes, sulfur, and air/ _O2 . In high voltage LIB, LiNi _0.5 Mn _1.4 O ₄ (LNMO)
Dissolution of the transition metals in the spinel cathode and diffusion to the respective anode surface results in Li ^{2 +} loss due to continuous electrolytic decomposition leading to rapid capacity degradation. Diffusion of the active material is more dominant in Li metal batteries as well as in LIBs. For example, in Li—S batteries, diffusion of polysulfides corrodes the Li metal anode, and the repeatable shuttling of polysulfides between electrodes leads to reduced coulombic efficiency and loss of active material. Similarly, short-circuit shuttle by mobile redox mediators in Li-air/O ₂ cells should be avoided. Therefore, it is important to prevent chemical short circuits in terms of minimizing or preventing migration of such soluble components through the battery.

There is a rapidly growing need for innovative approaches to developing new battery technologies that have higher energy densities while at the same time being less prone to catastrophic failure. It provides high energy density by blocking unwanted active material migration and metal dendrite penetration, and is key to addressing flammability and safety issues as well as chemical and physical shorting challenges. It is a solid electrolyte.

In the past decades, many prominent solid electrolyte materials have been developed for solid state batteries, such as conductive oxides, phosphates, hydrides, halides, sulfides, and polymer-based composites. Incorporation of solid state lithium-ion conductors into batteries has been demonstrated across a broad material ensemble including 0D nanoparticles, 1D nanofibers, 2D thin films, 3D networks and bulk components. Among these, the concept of a 3D lithium-ion conducting framework represents a creative solution to the deficiencies in current solid-state battery capabilities and cycling kinetics, and the continuous L
Provides ion migration paths and proper mechanical reinforcement.

Strategies to combat Li dendrite penetration and SEI formation include the development of solid electrolytes (SSEs) that mechanically inhibit lithium dendrites and essentially eliminate SEI formation. Among the various types of solid electrolytes (inorganic oxides/non-oxides and Li-salt-containing polymers), solid polymer electrolytes have been the most extensively studied. In PEO-based composites, the powder is incorporated into the host PEO polymer matrix and influences the recrystallization kinetics of the PEO polymer chains to promote local amorphous regions, thereby enhancing the ionic conductivity of the Li salt/polymer system. Improve. The addition of powder also improves electrochemical stability and increases mechanical strength. The development of nanostructured fillers is one way to increase the ionic conductivity of polymer composite electrolytes by increasing the surface area of the amorphous regions and improving the interface between the fillers and the polymer. One-dimensional nanowire fillers have been demonstrated to increase the ionic conductivity of polymer composite electrolytes. This is because nanowire fillers provide extended ionic migration paths in the polymer matrix, whereas the nanoparticle fillers in the polymer electrolyte are isolated and dispersed. However, agglomeration of the ceramic filler can remain, which poses a challenge in large-scale preparation of homogeneous solid polymer electrolytes by mixing with the polymer. To solve this problem, in situ synthesis of highly monodisperse ceramic filler particles in polymer electrolytes has recently been reported. P of nano-sized _SiO2 particles
By in-situ synthesis into EO/Li salt polymers, reported solid polymer electrolytes are
Although it exhibits an ionic conductivity of 4.4×10 ⁻⁵ S/cm at 30° C., further improvements are needed to achieve higher ionic conductivity at room temperature. Therefore, based on our understanding, continuous SSE with interconnecting long-range ion transport in composite hybrid electrolytes
There is a large unmet need for creating networks.

The present disclosure provides solid state hybrid electrolytes. The present disclosure also provides methods of making solid state hybrid electrolytes and uses thereof.

In one aspect, the present disclosure provides solid state hybrid electrolytes. A solid state hybrid electrolyte has a layer of polymeric material disposed on at least some or all of the outer surface of a solid state electrolyte (SSE). In various examples, the solid state hybrid electrolyte is a polymer material/solid state hybrid electrolyte, a polymer/solid state hybrid electrolyte, or a gel polymer/solid state hybrid electrolyte. In various examples, the SSE is a monolithic or mesoporous S
An SSE comprising an SE body or multiple fibers or multiple strands.

In one aspect, the present disclosure provides a method of making inorganic fibers or strands. A fiber or strand may form an inorganic SSE. In various examples, these methods are templating methods or electrospinning methods.

Strands can be formed by templating methods. The template comprises continuous voids that can be used to form strands of inorganic material that can form inorganic solid electrolytes (eg, solid hybrid electrolytes). Voids may be artificially designed or naturally occurring in biological materials (eg, wood, plants, etc.).

In one aspect, the present disclosure provides uses of the solid state hybrid electrolytes of the present disclosure. Solid state hybrid electrolytes can be used in a variety of devices. In various examples, the device comprises one or more solid state hybrid electrolytes of the present disclosure. Examples of devices include, but are not limited to, electrolyzers, electrolytic cells, fuel cells, batteries, and other electrochemical devices (eg, sensors, etc.).

The device may be a battery. The battery may be an ion-conducting battery. The battery may be configured for applications such as portable applications, transportation applications, stationary energy storage applications, and the like. Examples of ion-conducting batteries include lithium ion-conducting batteries, sodium ion-conducting batteries,
Examples include, but are not limited to, magnesium ion conductive batteries and the like.

For a further understanding of the operation and objectives of the present disclosure, reference should be made to the following detailed description in conjunction with the accompanying drawings.

Schematic of solid gel polymer battery design with (a) hybrid polymer/garnet type SSE electrolyte and (b) no interfacial gel polymer layer and poor interfacial contact between garnet SSE and electrode. (a gel polymer layer can improve the contact between the electrode and the SSE). Impedance analysis of symmetrical cells with hybrid electrolytes, (a) EIS of _LiFePO4 cathode|polymer|SSE|polymer|cathode symmetrical cells, (b) EIS of SS|polymer|SSE|polymer|SS symmetrical cells, (c) EIS for cathode|polymer|SSE|polymer|cathode symmetric cell, (d) EIS plot for Li|polymer|Li symmetric cell, (e) EIS plot for Li|polymer|SSE|polymer|Li symmetric cell, ( f) Comparison of SSE|electrode interfacial resistance with and without gel-polymer interface. FIG. 10 shows the impedance of electrode|SSE|electrode symmetrical cell components with and without a gel polymer interfacial layer. Electrochemical performance of polymer|SSE|polymer hybrid electrolytes in symmetrical finished cells: (a) Li stripping and plating in Li|polymer|SSE|polymer|Li symmetric cells at constant current over 15 h. Voltage profile, (b) EIS plot of cell before and after cycling, (c) charge-discharge voltage profile of cathode |SSE|Li cell with gel polymer interfacial layer, (d) discharge capacity and coulombic efficiency of cell over 130 cycles, ( e) EIS of the cell before cycling, after 20 cycles and after 130 cycles. Impedance of an electrode |SSE| electrode symmetric cell without a gel-polymer interface, showing (a) EIS for a cathodic |SSE| cathodic symmetric cell and (b) EIS for a Li|SSE|Li symmetric cell. be. FIG. 2 shows a comparison of a conventional battery with a solid state hybrid electrolyte focusing on a bilayer solid state electrolyte matrix. It is a property evaluation of a double-layer garnet solid electrolyte, and a schematic diagram of the 3D structure of the double-layer garnet structure, including (a) a photographic image of the double-layer garnet SSE, (b) an upward view SEM image of the porous layer (scale bar is 200 μm), (c) magnified view of the porous layer (scale bar is 50 μm), (d) SEM of the connection between the porous layer and the dense layer (scale bar is 10 μm). ), (e) Enlarged SEM images of granular dense microstructures (dense structures can block soluble active material and suppress penetration of Li dendrites. Scale bar is 10 μm), (f). FIG. 2 shows a cross-section of a bilayer garnet structure (two different layers of porous and dense garnet structures can be clearly observed (dense layer about 35 μm, porous layer 70 μm)). Chemical stability of garnet SSEs in polysulfide solutions, liquid electrolytes and molten sulfur: (a) (b) S 2p XPS spectra of dense garnet pellets before and after Ar sputtering on the surface (before XPS analysis; Dense garnet pellets were thoroughly immersed in polysulfide solution (Li ₂ S ₈ in DME/DOL) for 1 week), (c) Zr 3d XPS spectra of dense garnet pellets before and after Ar sputtering on the surface, ( d) (e) XRD pattern and Raman spectra of garnet powder after immersion in liquid electrolyte (LiTFSI in DME/DOL) and polysulfide solutions for 1 week (samples sealed in Kapton bags to avoid oxygen and moisture contamination) ), (f) TEM image of garnet nanopowder after soaking in polysulfide solution for 1 week, (g) XRD pattern of garnet powder after soaking in molten sulfur at 160°C for 1 week, (h) garnet, FIG. 3 is a diagram showing calculation of mutual reaction energies ΔE _D,mutual of Li ₂ S and Li ₂ S ₈ . Chemical stability of garnet SSEs in polysulfide solutions, liquid electrolytes, and molten sulfur: (a) (b) S 2p XPS spectra of dense garnet pellets before and after Ar sputtering on the surface (before XPS analysis; Dense garnet pellets were thoroughly immersed in polysulfide solution (Li ₂ S ₈ in DME/DOL) for 1 week), (c) Zr 3d XPS spectra of dense garnet pellets before and after Ar sputtering on the surface, ( d) (e) XRD pattern and Raman spectra of garnet powder after immersion in liquid electrolyte (LiTFSI in DME/DOL) and polysulfide solutions for 1 week (samples sealed in Kapton bags to avoid oxygen and moisture contamination) ), (f) TEM image of garnet nanopowder after soaking in polysulfide solution for 1 week, (g) XRD pattern of garnet powder after soaking in molten sulfur at 160°C for 1 week, (h) garnet, FIG. 3 is a diagram showing calculation of mutual reaction energies ΔE _D,mutual of Li ₂ S and Li ₂ S ₈ . Electrochemical characterization of liquid-solid hybrid electrolytes showing (a) (b) schematic and SEM image of exposed dense garnet layer surface, (c) (d) schematic of polymer-coated dense garnet layer surface. Figure and SEM, (e) EIS of symmetrical cell with polymer coating, (f) voltage profile of Li plating/stripping cycle at current density of 0.3 mA/ ^cm (red line shows molten Li at garnet density Form Li/Garnet/Li made directly attached to the layer Li/Garnet/Li shows high impedance and high voltage curve Black line is from symmetrical hybrid electrolyte cell Inset first (g) (h) Li plating/stripping cycles at current densities of 0.5 and 1.0 mA/ ^cm2. FIG. 10 is a diagram showing a voltage profile of . Electrochemical characterization of liquid-solid hybrid electrolytes showing (a) (b) schematic and SEM image of exposed dense garnet layer surface, (c) (d) schematic of polymer-coated dense garnet layer surface. Figure and SEM, (e) EIS of symmetrical cell with polymer coating, (f) voltage profile of Li plating/stripping cycle at current density of 0.3 mA/ ^cm (red line shows molten Li at garnet density Form Li/Garnet/Li made directly attached to the layer Li/Garnet/Li shows high impedance and high voltage curve Black line is from symmetrical hybrid electrolyte cell Inset first (g) (h) Li plating/stripping cycles at current densities of 0.5 and 1.0 mA/ ^cm2. FIG. 10 is a diagram showing a voltage profile of . Electrochemical characterization of solid-state hybrid Li-S batteries: (a) Schematic representation of conventional Li-S and solid-state hybrid Li-S batteries (in conventional Li-S, the polymer porous membrane is polysulfide In solid-state hybrid Li-S batteries, the ceramic dense membrane not only physically blocks the liquid electrolyte and polysulfides, but also prevents the growth of Li dendrites on the cathode side. (b) voltage profiles of conventional and hybrid Li-S cells (the extended plateau of the charging plateau indicates the shuttle effect of polysulfides in conventional Li-S; in hybrid Li-S cells the shuttle (no effect occurs), (c) voltage profile of a hybrid Li—S cell at high current density (a dense garnet film and a slurry-cast sulfur electrode with a mass loading of about 1.2 mg/ ^cm was assembled as a hybrid cell). , (d) Rate performance of hybrid Li-S cell, (e) Schematic of solid-state hybrid bilayer Li-S battery (sulfur and CNTs were encapsulated in the pores. The mechanically stable bilayer garnet structure is (f) Bilayer sulfur cathode cross-section (elemental mapping shows sulfur distribution inside the porous layer). , (g) (h) Voltage profile and cycling performance of a hybrid bilayer Li—S cell with a load of 7.5 mg/cm ² at 0.2 mA/cm ² . Electrochemical characterization of solid-state hybrid Li-S batteries: (a) Schematic representation of conventional Li-S and solid-state hybrid Li-S batteries (in conventional Li-S, the polymer porous membrane is polysulfide In solid-state hybrid Li-S batteries, the ceramic dense membrane not only physically blocks the liquid electrolyte and polysulfides, but also prevents the growth of Li dendrites on the cathode side. (b) voltage profiles of conventional and hybrid Li-S cells (the extended plateau of the charging plateau indicates the shuttle effect of polysulfides in conventional Li-S; in hybrid Li-S cells the shuttle (no effect occurs), (c) voltage profile of a hybrid Li—S cell at high current density (a dense garnet film and a slurry-cast sulfur electrode with a mass loading of about 1.2 mg/ ^cm was assembled as a hybrid cell). , (d) Rate performance of hybrid Li-S cell, (e) Schematic of solid-state hybrid bilayer Li-S battery (sulfur and CNTs were encapsulated in the pores. The mechanically stable bilayer garnet structure is (f) Bilayer sulfur cathode cross-section (elemental mapping shows sulfur distribution inside the porous layer). , (g) (h) Voltage profile and cycling performance of a hybrid bilayer Li—S cell with a load of 7.5 mg/cm ² at 0.2 mA/cm ² . FIG. 2 shows Nyquist plots of dense garnet SSE pellets at different temperatures (25, 30, 40 and 50° C.) (thickness of dense garnet pellets is about 250 μm). FIG. 3 shows an Arrhenius plot of the conductivity of garnet SSE (activation energy is 0.35 eV). A conventional Li—S battery (sulfur mass loading is about 1.2 mg/cm ² ), (a) of a conventional Li—S battery exhibiting a polysulfide shuttle effect with a long charge plateau; Fig. 2 shows voltage profile, (b) cycling performance of conventional Li-S cell (cell degrades fast after 10 cycles), (c) low coulombic efficiency of conventional Li-S cell. Fig. ² shows the cycling performance of a solid-state hybrid Li-S battery at a current of 0.1 mA/cm2 (sulfur loading is 1.2 mg/ ^cm2 , the hybrid cell has a high capacity of over 1000 mAh/g; fulfilled). SEM micrographs of CNT-coated garnet porous structures (CNTs were deposited on the garnet surface to provide an electronically conducting network of sulfur active material. Scale bars in (a) and (b) are 10 μm. and 500 nm). FIG. 4 shows the calculation of the specific energy density of the tested garnet bilayer Li—S battery. FIG. 3 shows estimated energy densities of parameter-optimized double-layer garnet solid-state Li—S batteries. Schematic of a multi-scale aligned mesoporous garnet Li _6.4 La ₃ Zr ₂ Al _0.2 O ₁₂ (LLZO) membrane with polymer electrolyte incorporated in a lithium symmetric cell (garnet wood is derived from natural wood It has a multi-scale ordered mesostructure, which eliminates blocking of Li ion migration through the garnet and polymer electrolyte along the garnet-polymer interface). Characterization of wood templates, preparation of wood templates by compression and slicing, (b) top view SEM image of original wood, (c) compressed wood (apparently smaller diameter of wood microchannels after compression). top-view SEM images of (d) pristine and (e) compressed wood (channels are closed but highly aligned structures are maintained), (f) 10 nm diameter SEM images of aligned nanofibers before and after. FIG. Firing of aligned garnet templated by wood, cross-sectional SEM images showing channel alignment at both (a) microscale and (b) nanoscale, (c) aligned mesoporous garnet and PEO base. (d) XRD pattern of aligned garnet consistent with JCPDS#90-0457 and confirming the cubic garnet structure. TEM characterization of garnet crystal structure: (a) HRTEM images of nanoparticles separated from ordered garnet exhibiting (210) and (021) lattice planes (inset shows FFT pattern of HRTEM images); (b) TEM image of the edge of a garnet nanoparticle showing a distinct polycrystalline structure, (c) ROI, spectral image, and EELS spectrum of the garnet surface showing relative composition maps for O, C, and La, respectively. It is a diagram. Electrochemical characterization of garnet wood with ordered mesoporous structure: (a) SEM and its corresponding EDX image showing complete homogenous infiltration of polymer electrolyte throughout the ordered garnet (scale bar is 100 μm). ), (b) Nyquist plot showing the decrease in impedance of garnet wood membranes with increasing temperature (inset schematic shows the structure of the test cell), (c) garnet wood and PE-based polymer electrolyte at different temperatures. (blue region indicates measurements performed within room temperature (RT)), (d) Schematic representation of a lithium symmetric cell with garnet wood showing low torsional and fast lithium migration paths. , (e) Galvanostatic cycling of Li/garnet wood/Li at a current density of 0.1 mA/cm ² at room temperature. Electrochemical characterization of garnet wood with ordered mesoporous structure: (a) SEM and its corresponding EDX image showing complete homogeneous infiltration of polymer electrolyte throughout the ordered garnet (scale bar is 100 μm). ), (b) Nyquist plot showing the decrease in impedance of garnet wood membranes with increasing temperature (inset schematic shows the structure of the test cell), (c) garnet wood and PE-based polymer electrolyte at different temperatures. (blue region indicates measurements performed within room temperature (RT)), (d) schematic of a lithium symmetric cell with garnet wood showing low torsional and fast lithium migration paths. , (e) Galvanostatic cycling of Li/garnet wood/Li at a current density of 0.1 mA/cm ² at room temperature. FIG. 10 is a photograph of a sintered ordered mesoporous garnet showing a portion of the sintered ordered mesoporous garnet (the garnet film was white and flat with similar area to the wood template). . Cross-sectional SEM image of garnet wood (the thickness of the garnet wood can be controlled by the thickness of the wood template. The SEM image shows that the low-twist channels are highly aligned and penetrate the entire garnet film, with a thickness of approx. 30 μm thin garnet wood sample). Figure 10 is a cross-sectional SEM image of an aligned garnet structure (SEM image shows part of a garnet wood sample with a thickness of 18 μm. The sample was sintered from a template thinned by slicing and grinding). Cross-sectional SEM image of garnet wood (SEM image shows cross-section and top surface of garnet wood. Alignment structure is completely filled with PEO-based polymer electrolyte). Fig. 2 shows the weight change of the wood template during precursor infiltration (the wood template was soaked in the precursor solution and the weight increased with time; the weight change indicates the high absorbency of the wood template). (a) EIS measurements and (b) ionic conductivity of PEO/SCN/Li-TFSI polymer electrolytes at different temperatures (highlighted areas are measurements performed around room temperature (RT). The inset shows a PEO/LiTFSI/SCN polymer electrolyte membrane sandwiched by two stainless steel electrodes, with a polyethylene (PE) separator ring placed around the polymer electrode membrane to increase the thickness at elevated temperature. (fixing the length and avoiding short circuits). Galvanostatic cycling of Li/garnet wood/Li at a current density of 0.1 mA/cm ² at room temperature for over 600 hours (variation in voltage is due to changes in the ambient temperature of the cell; long-term cycling is , demonstrating the outstanding electrochemical and mechanical stability of garnet wood composite electrolytes in Li metal cells). Fig. 2 shows a flexible lithium-ion conductive ceramic fiber (The lithium-ion conductive ceramic fiber was flexible and maintained the physical properties of the original template. The unique fiber structure allows continuous fiber and long-distance lithium-ion migration paths through yarns, high surface area/volume ratios of solid ionic conductors, and multi-level porosity distribution). Garnet fiber characterization: (a) SEM image of pretreated fiber template, (b) SEM image of precursor solution impregnated template, (c) garnet fiber converted from precursor solution impregnated template. SEM images of (d) reconstructed model of flat uniformity of garnet fibers generated by 3D laser scanning, (e) flexibility, workability and solvent resistance of garnet fibers, (f) sintering at different temperatures (g) elemental distribution mapping of a single garnet fiber sintered at 800° C.; Garnet fiber characterization: (a) SEM image of pretreated fiber template, (b) SEM image of precursor solution impregnated template, (c) garnet fiber converted from precursor solution impregnated template. SEM images of (d) reconstructed model of flat uniformity of garnet fibers generated by 3D laser scanning, (e) flexibility, workability and solvent resistance of garnet fibers, (f) sintering at different temperatures (g) elemental distribution mapping of a single garnet fiber sintered at 800° C.; Electrochemical characterization of flexible composite polymer electrolytes reinforced with garnet fibers showing (a) dry CPE exhibiting flexibility and mechanical strength, (b) fiber garnet dominated lithium ion. Transfer mechanism, (c) impedance spectra of CPE at different temperatures, (d) Arrhenius plot of lithium ion conductivity of CPE as a function of temperature, (e) Li/CPE/Li symmetry at various current densities and 60 °C. It is the figure which showed the constant current cycle measurement result of the cell. Electrochemical characterization of flexible composite polymer electrolytes reinforced with garnet fibers showing (a) dry CPE exhibiting flexibility and mechanical strength, (b) fiber garnet dominated lithium ion. Transfer mechanism, (c) impedance spectra of CPE at different temperatures, (d) Arrhenius plot of lithium ion conductivity of CPE as a function of temperature, (e) Li/CPE/Li symmetry at various current densities and 60 °C. It is the figure which showed the constant current cycle measurement result of the cell. Characterization of garnet fiber 3D electrode configuration for solid-state Li—S battery with 10.8 mg/cm ² sulfur loading: (a) photograph of garnet fiber sintered on dense supporting electrolyte, (b) sulfur cathode. SEM images of the infiltrated garnet fiber electrode configuration, (c) EDX elemental mapping of a single garnet fiber loaded with a sulfur/carbon mixture, (d) charge-discharge profile of a solid-state lithium-sulfur battery. Characterization of flexible garnet fibers comprising (a) thermogravimetric analysis of garnet precursor solution impregnated fiber template, (b) cross-sectional SEM image of pretreated fiber template, (c) precursor solution impregnated fiber template. Cross-sectional SEM images, (d) Cross-sectional SEM images of garnet fibers after pyrolysis and high temperature sintering of the template. Fig. 2 shows flexible garnet fibers of large size and different shapes; Characterization of Li-ion conducting garnet and insulating _Al2O3 fiber reinforced flexible CPE with (a) cross-sectional SEM images of garnet fiber _reinforced flexible CPE, (b) using the same templating method. ₍ c) Impedance plots of control _CPE at different temperatures. Electrochemical characterization of garnet fiber reinforced flexible CPE: (a) Impedance plot of Li/CPE/Li symmetrical cell before and after cycling at 60° C. for 500 h, (b) 0.05 mA/cm ^{2 .} (c) Galvanostatic cycling measurement results of the Li/CPE/Li symmetric cell at 1 mA/cm ² and 60° C.; Characterization of a sulfur-infiltrated 3D electrode constructed with a garnet fiber configuration in a solid-state Li—S battery, in the direction from (a) the exposed yarn area to the dense electrolyte surface of a 3D sulfur cathode constructed with garnet fibers. (b) High magnification cross-sectional SEM image and elemental mapping of a 3D sulfur cathode constructed with garnet fibers. Properties of Garnet Electrolyte Supports Made by Tape Casting and High Temperature Lamination and Chemical Compatibility of Garnet Electrolytes with Polysulfide Catholytes and Liquid Electrolytes: (a) Cross-sectional SEM of 500 μm thick dense garnet electrolyte supports. Images, (b) XRD pattern of ground garnet electrolyte, (c) Li-ion conductivity of dense garnet electrolyte in temperature range from 25°C to 100°C, (d) of fresh garnet electrolyte support ground in glovebox. Photograph, (e) Photograph of garnet electrolyte soaked in polysulfide catholyte and liquid electrolyte for 300 hours, (f) Photograph of garnet electrolyte then washed with DME/DOL solvent (no obvious discoloration observed). (g) XRD patterns of the garnet electrolyte before and after soaking experiments (no chemical changes were observed). Fig. ² shows the discharge and charge profiles of a solid state Li-S battery constructed with a garnet fiber configuration with a sulfur loading of 10.8 mg/ ^cm2 at 0.75 mA/cm2. FIG. 3 shows the discharge and charge profiles of a solid-state Li—S battery constructed with a garnet fiber configuration with a high sulfur loading of 18.6 mg/cm ² at 0.15 mA/cm ² . Relative weight and energy densities of solid state Li—S batteries with sulfur loadings of 18.6 mg/cm ² in different electrolyte support structural configurations, comprising: (a) garnet, cathode, anode, and solid state Li—S batteries; Relative weight distribution of current collectors and corresponding energy densities, (1) utilization of 500 μm thick electrolyte support and 63% electrolyte area, (2) utilization of 100 μm thick electrolyte support and 100% electrolyte area. , (3) a bilayer support structure consisting of a thin dense electrolyte (20 μm) and a porous substrate (70 μm) and utilization of 100% electrolyte area, (b) a representative SEM image of a low weight bilayer support structure. It is a diagram. FIG. 4 is a diagram showing the densities of the constituent materials of a solid-state Li—S battery; FIG. 4 illustrates structural parameters for different electrolyte support configurations; FIG. 4 shows the parameters of the cathode components; FIG. 4 illustrates the parameters of the anode component; Schematic of a solid-state hybrid composite electrolyte (ceramic garnet nanofibers act as reinforcement and lithium ion-conducting polymer as matrix. Interconnected garnet nanofiber networks provide continuous ion-conducting pathways in the electrolyte membrane. give). Fabrication of flexible solid fiber reinforced composite (FRPC) electrolytes comprising (a) schematic setup of electrospun garnet/PVP nanofibers, (b) schematic procedure for fabricating FRPC Li-ion conducting membranes. (c) SEM image of spun nanofiber network, (d) diameter distribution of spun nanofiber, (e) SEM image of garnet nanofiber network, (f) diameter distribution of garnet nanofiber, (g) flexibility. FIG. 2 shows a photographic image showing a flexible FRPC Li-ion conductive membrane. Morphological characterization of garnet nanofiber reinforcements and solid FRPC electrolytes showing (a) SEM images showing interconnected garnet nanofibers, (b) TEM images of polycrystalline garnet nanofibers (inset shows mean grain size). is a magnified image of a garnet nanofiber with a diameter of 20 nm), (c) high-resolution TEM image of an individual garnet nanofiber, (d) SEM image of the FRPC electrolyte membrane surface, (e) cross-sectional SEM image of the membrane, (f ) shows an enlarged SEM image of the cross-sectional morphology (empty spaces of the garnet 3D porous structure are filled with polymer). Thermal properties and flammability tests of solid FRPC electrolytes: (a) TGA curves of spun nanofibers, (b) TGA curves of Li salt/PEO polymer and FRPC electrolyte membranes, (c) mixed with garnet nanoparticles. (d) flammability test of FRPC electrolyte membrane; Phase structure of garnet fiber and electrical properties of solid FRPC electrolyte: (a) XRD pattern of garnet nanoparticles, (b) EIS profile of FRPC electrolyte membrane at different temperatures (25°C, 40°C and 90°C). , (c) Arrhenius plots of FRPC electrolyte membranes at elevated temperatures (recorded from 20° C. to 90° C. and every 10° C. increment), (d) LSV of FRPC electrolyte membranes showing an electrochemical stability window ranging from 0 to 6 V. FIG. 4 is a diagram showing curves; Electrochemical performance of FRPC electrolyte membranes measured in a Li|FRPC electrolyte|Li symmetric cell: (a) Schematic of the symmetric cell for the lithium plating/stripping experiment, (b) Current density at 15 °C is voltage profile of a lithium plating/stripping cycle of 0.2 mA/ ^cm2 , (c) voltage profile of a subsequent lithium plating/stripping cycle with a current density of 0.2 mA/ ^cm2 at 25°C, (d ) Impedance spectra of symmetrical cells measured at different cycle times (300 h, 500 h and 700 h), (e) extended EIS spectrum in high frequency region, (f) current density of 0.5 mA/cm at 25 °C. ² shows the voltage profiles of subsequent lithium plating/stripping cycles in FIG. FIG. 2 shows an enlarged TEM image of garnet nanofibers with an average particle size of 20 nm in diameter. C. The test temperature is increased to 25.degree. The voltage continued to drop to 0.2 V as the time elapsed up to 700 hours (the variation in voltage was due to temperature changes in the ambient environment). Figure 2 compares two voltage profiles of a symmetrical cell at two different stripping/plating process times; 1 is a schematic diagram showing an example of a battery of the present disclosure; FIG.

Although the claimed subject matter will be described in terms of particular embodiments, other embodiments, including embodiments that do not provide all the benefits and features described herein, are also
within the scope of this disclosure. Various structural, logical, process step, and electronic changes may be made without departing from the scope of the present disclosure.

All ranges provided herein include all values within the range to 10 decimal places, unless otherwise specified.

The present disclosure provides solid state hybrid electrolytes. The present disclosure also provides methods of making solid state hybrid electrolytes and uses thereof.

In one aspect, the present disclosure provides solid state hybrid electrolytes. A solid state hybrid electrolyte has a layer of polymeric material disposed on at least some or all of the outer surface of a solid state electrolyte (SSE). In various examples, the solid state hybrid electrolyte is a polymer material/solid state hybrid electrolyte, a polymer/solid state hybrid electrolyte, or a gel polymer/solid state hybrid electrolyte. In various examples, the SSE is a monolithic or mesoporous S
An SSE comprising an SE body or multiple fibers or multiple strands.

In various examples, the present disclosure provides solid hybrid electrolytes formed, e.g., in different ways, e.g., having desirable ionic conductivity, and polymeric layers that provide stable and well-connected interfaces between such electrolytes and electrodes. Solid state hybrid electrolytes with non-limiting layers such as (eg, polymer membranes) are provided. Solid hybrid electrolytes of the present disclosure may, for example, exhibit an interfacial resistance at the electrolyte/lithium ion cathode interface of 248 Ω×cm ² or less, and an interfacial resistance at the electrolyte/lithium metal anode interface of 214 Ω×cm ² or less. This layer can be a gel polymer (containing a liquid electrolyte inside the polymer), a dry polymer (no liquid inside the polymer, e.g. conductive Li ions with salt inside the polymer), or a variety of conductive thin films. It is possible to manufacture. A solid electrolyte with a polymer interface can be constructed with, for example, a carbon or Li metal anode and Li metal oxide, sulfur, or air to make a solid state Li battery. The present disclosure addresses the problem of interfacial resistance between solid electrolytes and electrodes, which facilitates further development of solid state ion conducting (eg, lithium ion conducting) batteries.

In various examples, the present disclosure provides solid state hybrid electrolytes with flexible inorganic SSEs. Flexible inorganic SSEs can be low-cost, thin, flexible, ion-conducting membranes that are expected to enable next-generation ion-conducting batteries (e.g., Li-metal batteries) that exhibit desirable safety. . For example, infiltration of ion-conducting 3D networks with Li-ion-conducting polymers and the like creates flexible, ion-conducting SSE membranes. A schematic example is shown in Fig. 47
shown. In various examples, oxide SSE materials have been used to create 3D ion-conducting networks, including but not limited to LLZO garnets, LLTO perovskites, and LATP glasses. 3D structures can enhance polymer matrices by, for example, providing long-distance ion migration paths and structural reinforcement. The membrane exhibits desirable electrochemical stability to high voltages (eg, greater than 6 V), high ionic conductivity (eg, greater than 10 ⁻⁴ Scm ⁻¹ ), and high mechanical properties to effectively block, for example, lithium dendrites. stability.

The solid state hybrid electrolyte comprises an inorganic SSE (e.g., an SSE body of inorganic (e.g., ceramic) monolithic or mesoporous structure or an SSE comprising a plurality of inorganic fibers or a plurality of inorganic strands (F/S SSE)) and an outer surface of the SSE. and a polymeric material disposed on at least a portion or all of the

Inorganic SSEs (eg, inorganic SSEs of F/S SSEs) may have a three-dimensional network structure with one or more nodes formed by at least two fibers or strands. An inorganic solid electrolyte (eg, a solid hybrid electrolyte) has a continuous ionic conduction path from one side of the inorganic solid electrolyte to the other side of the inorganic solid electrolyte. The 3D ion-conducting network of ionic SSEs acts as a reinforcement and increases the ionic conductivity (
For example, a lithium ion conductive) polymer can serve as the matrix. A 3D network provides a continuous ion-conducting pathway in the electrolyte membrane. In the case of solid hybrid electrolytes formed by strands or fibers, the inorganic solid material may be exposed on one or more surfaces of the solid hybrid electrolyte. For solid hybrid electrolytes formed by multiple strands, the inorganic SSE may be a continuous and optionally aligned mesoporous structure.

In various examples of solid state hybrid electrolytes, the polymeric material fills at least some or all of the voids in the inorganic fibers or templated inorganic strands. for solid hybrid electrolytes in which the polymer material partially fills the voids of the templated inorganic solid electrolyte, at least partially the voids open to the outer surface of the templated inorganic solid electrolyte are filled with the cathode material and/or the anode material; It may constitute an integrated cathode and/or electrode.

Inorganic SSEs can be formed from a variety of inorganic materials. The inorganic material may be a ceramic material. Inorganic materials are materials that are ionically conductive (eg, lithium ion-conducting, sodium ion-conducting, magnesium ion-conducting, etc.). The inorganic SSE may be an ion-conducting electrolyte. Examples of suitable inorganic materials are known in the art. Non-limiting examples of inorganic materials include lithium ion conductive inorganic materials, sodium ion conductive inorganic materials, magnesium ion conductive inorganic materials, and the like. Any inorganic SSE electrolyte material known in the art can be used. Methods of making inorganic SSE electrolyte materials are known in the art.

Inorganic materials can have a variety of structures (eg, secondary structures). In various examples, the inorganic material is amorphous, crystalline (eg, monocrystalline and polycrystalline), or
It has various amorphous and/or crystalline domains.

The inorganic material may be a lithium-conducting inorganic (eg, ceramic) material. The lithium-conducting inorganic material may be a lithium-containing material.

Non-limiting examples of lithium ion conducting SSE materials include lithium perovskite materials, Li ₃ N, Li-β-alumina, lithium superionic conductors (LISICON), Li
_{2.88PO3.86N0.14 ( LiPON} ), _{Li9AlSiO8 , Li10GeP
2} S ₁₂ , lithium garnet SSE materials, doped lithium garnet SSE materials, lithium garnet composite materials, and the like. In various _examples , the lithium ^garnet SSE material is cation _{- doped Li5La3M12O12} (where ^M1 _is Nb, Zr, Ta, or a _combination thereof), cation-doped _{Li6La2BaTa2O12 , cation} -doped _Li7La3Zr2O12 , and cation _- doped _{Li6BaY2M12O12} , where the cation dopant is _barium , ^yttrium , _zinc , or combinations thereof, and the _{like .} In various other examples, the lithium garnet SSE material is Li ₅ La ₃ Nb _{2
O12 , Li5La3Ta2O12 , Li7La3Zr2O12 , Li6La2SrNb _ _ _ _
2O12 , Li6La2BaNb2O12 , Li6La2SrTa2O12 , Li6La _ _ _ _
2BaTa2O12 , Li7Y3Zr2O12 , Li6.4Y3Zr1.4Ta0.6O _ _ _ _ _ _
12 , Li6.5La2.5Ba0.5TaZrO12 , Li6BaY2M12O12} ^, _{_ _ _ _
Li7Y3Zr2O12 , Li6.75BaLa2Nb1.75Zn0.25O12 , L _ _ _ _}
i _6.75 BaLa ₂ Ta _1.75 Zn _0.25 O ₁₂ and the like.

The inorganic material may be a sodium ion-conducting inorganic (eg, ceramic) material. The sodium ion-conducting inorganic material may be a sodium-containing material. For example, sodium ion conductive inorganic materials include β″-Al ₂ O ₃ , Na ₄ Zr ₂ Si ₂ PO ₁₂
(NASICON), cation-doped NASICON, and the like.

The inorganic material may be a magnesium ion-conducting inorganic (eg, ceramic) material. The magnesium ion-conducting inorganic material may be a magnesium-containing material. In various examples, the magnesium ion-conducting inorganic material is selected from doped magnesium oxide materials. In various examples, the magnesium ion-containing material is Mg _1+x (Al,T
i) ₂ (PO ₄ ) ₆ (where x is 4 or 5), NASICON type magnesium ion conductive material, and the like.

Monolithic SSE or mesoporous SSE bodies can have various sizes (ie, dimensions) and/or shapes. Suitable monolithic SSE or mesoporous SSE bodies are known in the art. A monolithic SSE body may be a dense body (eg, comprising only dense layers of inorganic material) or a dense sintered body.

Non-limiting examples of mesoporous SSEs include planar SSE structures comprising an outer layer of porous (eg, mesoporous) material (eg, a dense layer and at least one porous (eg, mesoporous) ) layers, including a multi-layer SSE structure). Non-limiting examples of multi-layer SSE structures include bilayer structures (including a porous layer disposed on the dense layer) and two porous layers (including two porous layers disposed on either side of the dense layer). ) trilayer structures, known in the art. An example of a multi-layer structure is U.S. patent application Ser.
, No. 306 (title of the invention "Ion Conducting Batteries wit
H Solid State Electrolyte Materials") and filed November 30, 2016, and U.S. Patent Application Publication No. 2017, filed June 1, 2017
U.S. patent application Ser. No. 15/364,528, published as Ser.
Methods of Fabricating Same, and Uses of
Same”), the disclosure of each of which is incorporated herein by reference.

The F/S SSE may include fibers or strands of various sizes (ie, dimensions) and/or shapes. In various examples, the fibers or strands are cylindrical or substantially cylindrical, polyhedral or substantially polyhedral, irregular shapes, and the like. The fibers or strands may have lengths that correspond to multiples of one or more dimensions of the equipment used. In various examples, the fibers or strands are from 1 micron to 20 meters long (including all integer micron values and ranges therebetween) and/or from 1 nm to 1
It has a maximum cross-sectional dimension (eg, diameter) of 0 microns (including all integer nm values and ranges therebetween). In one example, the F/S SSE includes fibers or strands of length up to 10 or more maximum cross-sectional dimensions (eg, diameters).

The F/S SSE fibers or strands are flexible and can provide flexible solid-state hybrid electrolytes for use in flexible devices such as batteries. The F/S SSE and polymeric material may form an electrolyte. F/S SSEs can be made by the methods described herein.

A variety of polymeric materials can be used. A mixture of two or more polymeric materials (eg, two or more polymers) can be used. The polymeric material can be conductive (eg, ionically and/or electronically conductive), non-conductive, or a combination thereof. The polymeric material may be a dry polymer or gel.

For monolithic SSEs or mesoporous bodies, the polymeric material is conductive (e.g.
ion-conducting and/or electronically-conducting). For inorganic SSEs comprising multiple fibers or strands, it may be desirable for the polymeric material, which may be a mixture of multiple polymeric materials, to provide mechanical strength to the SSE.

Solid state hybrid electrolytes with monolithic SSE or mesoporous SSE bodies have a thin layer of polymeric material (e.g., 5 nm to 10 microns thick, including all integer nm values and ranges therebetween). is desirable.

The polymeric material can be disposed on at least some or all of the surface of the SSE (eg, inorganic SSE). For dense SSE materials, the polymer material is a layer (eg, conformal layer) disposed in at least a portion (eg, the portion of the SSE material where the electrodes (eg, cathode and/or anode) are disposed). is. Porous SSE (monolithic SSE or mesoporous SSE body or SSE containing multiple fibers or strands
), the polymeric material is disposed on the pore surfaces, the non-pore surfaces, or both. It may be desirable to have a polymeric material disposed on the portion of the porous SSE material where the electrodes (eg, cathode and/or anode) are disposed.
In one example, the polymeric material is 1 volume percent or more, 5 volume percent or more, 10 volume percent or more, 20 volume percent or more, 30 volume percent or more, 40 volume percent or more, 50 volume percent or more, or 60 volume percent of the solid hybrid electrolyte. exist above.

For solid state hybrid electrolytes with monolithic SSEs or mesoporous bodies, the polymeric material can be a layer. This layer can be formed by various methods known in the art. For example, a layer of polymeric material is formed by dip coating, slurry casting, spray coating, spin coating, or the like.

In the case of solid state hybrid electrolytes with F/S SSE, the polymer material is disposed in the voids formed by the individual fibers or strands of the SSE. Voids may be pores as a result of the use of templates. Polymeric materials may be incorporated into the F/S SSE by methods known in the art. For example, a polymeric material is infiltrated or formed in situ into the voids (eg, pores) of the F/S SSE.

A variety of polymeric materials can be used. A polymeric material may include one or more polymers, one or more copolymers, or a combination thereof. The molecular weight of the polymer and/or copolymer is not particularly limited. equipment (for example,
Polymers and/or copolymers can have a wide range of molecular weights, depending on the performance (eg, ionic conductivity) requirements of the solid state ion-conducting battery. It may be desirable for the polymer and/or copolymer to be electrically conductive. The polymeric material may comprise mixtures of conducting and/or non-conducting polymers and/or copolymers.

Polymers and/or copolymers can have a variety of structures (eg, secondary structures). In various examples, the polymers and/or copolymers are amorphous, crystalline, or combinations thereof. It may be desirable for the polymer and/or copolymer to have low crystallinity.

Polymeric materials include, but are not limited to, polymers and copolymers. Polymers and copolymers may be conductive or non-conductive. Non-limiting examples of polymers and copolymers include poly(ethylene) (PE), poly(ethylene oxide) (PEO), poly(propylene) (PP), poly(propylene oxide)
, polymethylmethacrylate (PMMA), polyacrylonitrile (PAN), poly[bis(methoxyethoxyethoxide)-phosphazene], poly(dimethylsiloxane) (P
DMS), cellulose, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, polyvinylidene difluoride (PVdF), polyvinylpyrrolidone (PVP), polystyrene, sulfonate (PSS), polyvinyl chloride (PVC) group, poly (Vinylidene chloride) polypropylene oxide, polyvinyl acetate, polytetrafluoroethylene (for example,
Teflon®), poly(ethylene terephthalate) (PET)
, polyimides, polyhydroxyalkanoates (PHAs), PEO-containing copolymers (e.g., polystyrene (PS)-PEO copolymers and poly(methyl methacrylate) (PM
MA)-PEO copolymer), polyacrylonitrile (PAN), poly(acrylonitrile-methyl acrylate copolymer), PVdF-containing copolymers (for example, polyvinylidene fluoride-hexafluoropropylene copolymer (PVdF-HFP copolymer coal)), PMMA copolymers (eg, poly(methyl methacrylate-ethyl acrylate copolymer)). Non-limiting examples of these also include derivatives of polymers and copolymers. In various examples, the polymeric material is a combination of two or more of these polymers.

The polymeric material may be a gel. A gel includes a polymeric material (eg, one or more polymers and/or one or more copolymers) as well as a liquid.
Combinations of liquids can also be used. In various examples, the liquid is an organic liquid (eg, ethylene carbonate (EC), diethyl carbonate (DEC), dimethoxyethane (DME), dioxolane (DOL), etc.) or an ionic liquid (eg, N-propyl-N-methylpyrroli Dinium bis(trifluoromethanesulfonyl)imide (PYR _1
3 TFSI), etc.).

The liquid may be a liquid electrolyte. Liquid electrolytes are metal salts (e.g., one or more lithium salts, one or more sodium salts, one or more magnesium salts, etc.)
may contain A non-limiting example of a liquid electrolyte is an aqueous liquid electrolyte. Non-limiting examples of liquid electrolytes include ethylene carbonate (EC)/diethyl carbonate (D
_LiPF6 (eg 1 M) in dimethoxyethane (DME)/dioxolane (DOL) (eg 1 M), N-propyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide ( PYR ₁₃ TFSI), LiTFSI in ionic liquids (eg, 0.5 M), and the like.

The polymeric material may contain fillers. In one example, the polymeric material includes one or more ceramic fillers (eg, 2 to 2, based on the total weight of the polymeric material).
5 wt% ceramic filler). Non-limiting examples of ceramic fillers include:
conductive particles _, non-conductive particles (e.g. _Al2O3 , _SiO2 , _TiO2 nanoparticles, etc.),
Ceramic nanomaterials (eg, ceramic nanoparticles, ceramic nanofibers, etc.) can be mentioned. Ceramic nanomaterials may have the compositions of the inorganic materials disclosed herein.

In one aspect, the present disclosure provides a method of making inorganic fibers or strands. A fiber or strand may form an inorganic SSE. In various examples, these methods are templating methods or electrospinning methods.

Strands can be formed by templating methods. The template comprises continuous voids that can be used to form strands of inorganic material that can form inorganic solid electrolytes (eg, solid hybrid electrolytes). Voids may be artificially designed or naturally occurring in biological materials (eg, wood, plants, etc.).

Templating methods provide a simple yet effective way to generate the required structures.
After contacting (e.g., immersing) the fiber template with one or more inorganic SSE material precursors, the precursors are reacted in an optional heating step and heat treated (
For example, pyrolysis) to remove organic components. The resulting fibrous inorganic materials can exhibit desirable properties that allow integration into flexible or rigid battery configurations. For example, strands or fiber networks of inorganic materials have established lithium ion migration pathways within polymeric materials to enhance their mechanical strength. Alternatively, inorganic material (e.g., ceramic) fibers may be combined with the electrode material in an interlocking or concentric configuration to minimize electrolyte volume and maximize electrode utilization, thereby increasing the activity during charge/discharge. Increased electrolyte area, lithium ion interfacial migration, and electrode volume change resistance are possible.

The templating method provides a porous (eg, nanoporous and/or microporous) inorganic SSE comprising multiple strands. The strands may have the general shape of the template used to construct the individual strands (eg, cylindrical or substantially cylindrical, polyhedral or substantially polyhedral, irregular, etc.). For example, strands have lengths in the micrometer to meter range and/or maximum cross-sectional dimensions (eg, diameters) in the nanometer to micrometer range.

The pores (e.g., pore size, pore size distribution, pore morphology, etc.) of the inorganic SSE electrolyte are
It may vary depending on the method (eg, templating or electrospinning used). For templating methods, the pores may be formed by removal of the template material (eg, may have a size and/or shape corresponding to the template material). In the case of electrospinning, the pores may be formed by voids formed by the fibers. For example, for inorganic SSEs formed by templating methods, at least some or all of the pores have at least one dimension between 1 and 100 microns. For example, for inorganic SSEs formed by electrospinning, at least some or all of the pores are 1 nm
It has at least one dimension between ˜500 microns.

In various examples, the pores of the solid hybrid electrolyte, the strands of the solid hybrid electrolyte (e.g., some or all of the strands) (if present), and/or the pores of the solid hybrid electrolyte can be aligned. , may be substantially aligned. “Alignment” is defined such that the longitudinal axis of each strand is parallel, less than 30°, less than 20°, less than 15°, less than 10°, or less than 5° parallel to the longitudinal axis of the adjacent strand, It means that the strands and/or pores of the inorganic SSE are aligned. In one example, the strands and/or pores are not arranged end-to-end. Substantially aligned means that at least 50%, at least 60%, at least 70, 80%, at least 90%, at least 95%, at least 99% of the strands are aligned.

As an illustrative example, when a solid hybrid electrolyte formed by a biomaterial template (e.g., a wood template, a plant template, etc.) is used in a battery with planar discrete electrodes, the individual strands are one of the electrodes. Or aligned generally perpendicular (eg, perpendicular) to the plane defined by both, and the pores are also aligned generally perpendicular (eg, perpendicular) to the plane defined by one or both of the electrodes.

In various examples, strands of inorganic SSE (e.g., some or all of the strands)
is arranged as a fabric (eg, woven fabric, braided fabric, etc.). The strands of inorganic SSE may adopt the general structure of fiber templates used to make inorganic SSE. The dimensions of the inorganic SSE may be substantially smaller than the dimensions of the fiber template.

As an illustrative example, when a solid hybrid electrolyte formed by a carbon template (e.g., fiber template, etc.) is used in a battery with planar discrete electrodes, individual strands of inorganic SSE may Aligned generally parallel (eg, parallel) to the plane defined by both, the pores of the inorganic SSE are aligned perpendicular to the plane defined by one or both of the electrodes.

In various examples, templating methods for constructing inorganic solid electrolytes (e.g., solid state hybrid electrolytes) include:
contacting the template with one or more SSE material precursors;
optionally reacting the SSE material precursor to form a solid inorganic material (eg, comprising at least partially or wholly reacted and/or decomposed SSE material precursor);
heat treating the template with a solid inorganic material to remove the template (e.g. as carbon dioxide) and form an inorganic SSE (e.g. monolithic SSE or mesoporous or F/S SSE);
The fired template is contacted with a polymeric material to form a layer on the inorganic SSE material in the case of a monolithic SSE or mesoporous body (and optionally at least one of the pores exposed on the surface of the inorganic SSE material). part or all) or F/S S
in the case of SE, the polymeric material fills at least some or all of the pores of the F/S SSE (e.g., pores corresponding to the template);
including.

In various examples, a templating method of forming an inorganic solid electrolyte (e.g., a solid hybrid electrolyte) includes:
contacting (e.g., infiltrating) a biomaterial template with one or more SSE material precursors (e.g., one or more inorganic SSE material sol-gel precursors); ) are at least partially or completely filled with the SSE material precursor;
and
Optionally, the SSE material precursor-filled template is reacted (e.g., by heating) to (e.g., at least partially or fully reacted and/or decomposed inorganic SS
forming a solid inorganic material (including an E material sol-gel precursor);
heat treating the heated template to remove substantially all or all of the template material to form an inorganic SSE material;
contacting the sintered template with a polymeric material, wherein the polymeric material is an inorganic SSE
at least partially filling the nanopores and/or micropores of
including.

In various examples, templating methods for constructing inorganic solid electrolytes (e.g., solid state hybrid electrolytes) include:
contacting the carbon template with one or more inorganic SSE material precursors (e.g., one or more metal salts);
optionally reacting (e.g., by heating) the carbon template-contacting carbon template to form a solid inorganic material (e.g., a plurality of nanoparticles of the inorganic material);
heat treating the template to remove substantially all or all of the template material to form an inorganic SSE material;
contacting (e.g., infiltrating) the inorganic SSE with a polymeric material, which at least partially fills the nanopores and/or micropores of the template;
including.

Various templates are available. The template is made of a polymer (e.g., biologically derived polymer (e.g., cellulose, protein fibers, etc.), artificial polymer (e.g., PET, polyamide such as nylon, regenerated cellulose such as rayon, polyester, etc.). It is formed. The template may have a hierarchical interconnect structure including interconnected nanoscale and/or microscale voids. For example, the template is a low-twist template (eg, a low-twist template formed by a wood template). As a template, biological materials (
wood, plants, etc.) or artificial templates, which can be formed by methods such as tape casting, screen printing, extrusion, 3D printing, weaving, braiding, non-woven knitting, and the like. In these methods, all or substantially all of the template is removed (ie, sacrificial template). For example, the template
It is removed by heat treatment.

A variety of carbon templates are available. Examples of carbon templates include, but are not limited to, fiber templates, paper templates, foam templates, and the like. A carbon template may be a fiber. In various examples, the fibers are textiles. The fabric may include various weaves, braids, etc., or may be non-woven. In the case of woven fabrics, the woven fabrics may be of any weave pattern.

A variety of biomaterial templates are available. The biomaterial template may be a wood template, a plant template, or the like.

A variety of wood and plant templates are available. A wood or plant template contains a plurality of nanochannels and/or microchannels. A plurality of nanochannels and/or microchannels are interconnected to form a three-dimensional network having at least one node. The wood template may be a compressed wood template. Wood templates are typically formed by removing at least some or all of the lignin from wood of a size and shape suitable for forming the F/S SSE. A template with a plurality of aligned channels (e.g., channels having a cross-sectional size (e.g., longest dimension such as diameter) from 1 nm to 10 microns, including all integer nm values and ranges therebetween, by removal of lignin) (eg, a template with aligned porous nanostructures) is formed. Compressing the template in the can can reduce the cross-section of the nanochannels and/or microchannels. Lignin can be removed by chemical treatment. Suitable treatments are known in the art. For example, lignin is removed by contacting a wood sample with an aqueous base solution. The wood template can be made from a variety of woods such as, for example, burdock, balsa wood, and the like.

Fibers of inorganic SSE can be formed by electrospinning. Suitable electrospinning methods are known in the art. Electrospinning can be performed by methods known in the art.

Inorganic SSE material precursors are formed by reaction (e.g., at least partial or total reaction and/or thermal degradation) to, for example, one or more solid inorganic materials (e.g., carbon-based residuals) of the precursor. (which may include residues such as solids). The inorganic material may be heat treated to provide an inorganic SSE material.

In various examples, an electrospinning method of forming an inorganic solid electrolyte (e.g., a solid hybrid electrolyte) includes:
electrospinning a precursor solution comprising an electrospun polymer and one or more inorganic SSE precursor materials to form the polymer and one or more inorganic SSE
providing nanofibers comprising a precursor material;
heat treating the nanofibers to remove all or substantially all of the polymer of the nanofibers to form an inorganic SSE material;
contacting the inorganic SSE with a polymeric material, wherein the polymeric material at least partially fills the voids of the inorganic SSE material;
including.

A variety of electrospun polymers are available. Suitable electrospinning polymers are known in the art. Non-limiting examples of electrospun polymers include polyvinylpyrrolidone (PVP), polyacrylonitrile (PAN)
, poly(ethylene oxide) (PEO), or polyvinyl chloride (PVC).

A variety of inorganic SSE precursor materials are available. Non-limiting examples of inorganic SSE precursor materials include sol-gel precursors, metal salts, and the like. The SSE material precursors may be one or more sol-gel precursors or one or more metal salts that upon reaction (eg, heating) provide an inorganic SSE of desired composition. Examples of suitable sol-gel precursors and sol-gel precursor combinations are known in the art. Examples of suitable metal salts and metal salt combinations are known in the art. In various examples, the heat treatment includes sintering and/or firing an inorganic SSE material precursor or a reacted (eg, at least partially or fully reacted) inorganic SSE material precursor.

The heat treatment removes (eg, pyrolyzes) the template material. The heat treatment removes at least a portion (eg, substantially) or all of the template to provide an inorganic SSE. In various examples, the heat treatment is performed at 700-1000° C. in an air atmosphere or an atmosphere containing oxygen.

In one aspect, the present disclosure provides uses of the solid state hybrid electrolytes of the present disclosure. Solid state hybrid electrolytes can be used in a variety of devices. In various examples, the device comprises one or more solid state hybrid electrolytes of the present disclosure. Examples of devices include, but are not limited to, electrolyzers, electrolytic cells, fuel cells, batteries, and other electrochemical devices (eg, sensors, etc.).

The device may be a battery. The battery may be an ion-conducting battery. The battery may be configured for applications such as portable applications, transportation applications, stationary energy storage applications, and the like. Examples of ion-conducting batteries include lithium ion-conducting batteries, sodium ion-conducting batteries,
Examples include, but are not limited to, magnesium ion conductive batteries and the like.

In various examples, the battery (e.g., an ion-conducting battery such as a solid-state ion-conducting battery) comprises:
A solid hybrid electrolyte of the present disclosure, an anode, and a cathode, with the solid hybrid electrolyte disposed between the anode and the cathode. In one example, the polymer material of the solid state hybrid electrolyte is combined with the inorganic SSE material of the solid state hybrid electrolyte and the anode and/or
or the cathode.

Inorganic SSE materials can be used in conventional ion-conducting batteries (eg, ion-conducting batteries include electrolytes as the base electrolyte). Conventional ion-conducting batteries are non-conducting (
For example, a non-ionically conductive separator. Thus, in one example, the battery
Inorganic SSE materials disclosed herein (e.g., F/S SSEs, which may be templated inorganic SSEs or electrospun inorganic SSEs) or solid state hybrid electrodes disclosed herein (e.g., F/SSEs) S SSE), and an electrolyte. The electrolyte can be any electrolyte used in conventional ion-conducting (eg, lithium ion-conducting) batteries known in the art. Non-limiting examples of conventional battery electrolytes include liquids such as organic liquids, gels, polymers, and the like. In various examples, the liquid electrolyte is not part of a solid hybrid electrolyte (eg, part of a polymeric material such as a gel polymer of a solid hybrid electrolyte). In this case, the inorganic SSE material or the solid state hybrid electrode is the conventional battery separator. In various examples, inorganic SSE materials or solid state hybrid electrodes replace conventional battery separators. Unlike the usual separators used in conventional batteries, either the inorganic SSE material or the solid state hybrid electrode separates the cathode and anode and is ionically conductive. In various examples, inorganic SSE materials or solid state hybrid electrodes are conventional battery ion-conducting separators. Various electrodes (eg, cathode and anode) can be used. Individual electrodes (eg, cathode and/or anode) can be independent (eg, separate) from the solid hybrid electrolyte (eg, planar electrodes) or can be integrated with the solid hybrid electrolyte. For integrated electrodes, a solid hybrid electrolyte (e.g., a monolithic SSE or mesoporous SSE body) has one or more porous regions exposed at the surface of the solid hybrid electrolyte, and discrete porosity of the solid hybrid electrolyte. An electrode is formed by the electrode material (eg, cathode material and/or anode material) disposed in the pores of the porous region.

Cathodes and anodes can be formed from a variety of materials (eg, cathodic or anodic materials, respectively). Examples of suitable cathode and anode materials are known in the art.

The cathode includes one or more cathode materials in electrical contact with a solid hybrid electrolyte. A variety of cathode materials can be used. Combinations of cathode materials may be used. For example, the cathode material is an ionically conductive material that stores ions by a mechanism such as intercalation or that reacts with ions to form a secondary phase (eg, air or sulfide electrodes). Examples of suitable cathode materials are known in the art.

In the case of an integrated cathode, the cathode material is disposed on at least a portion of the surface of the porous region (eg, the pore surface of one of the pores) of the solid hybrid electrolyte. The cathode material may at least partially fill one or more pores (e.g., a majority of the pores) of one of the porous region or regions of the ion-conducting solid electrolyte material. good. In one example, the cathode material infiltrates at least some of the pores of the porous region of the ionically conductive solid electrolyte material.

In one example, the cathode material is disposed on at least a portion of the pore surfaces on the cathode side of the porous region of the porous SSE material, and the cathode side of the porous region of the SSE material is a porous material on which the anode material is disposed. It faces the anode side of the porous region of pure SSE material.

In various examples, the cathode includes a conductive carbon material. Non-limiting examples of carbon materials include graphite, hard carbon, porous hollow carbon spheres and tubes, and the like. Cathode materials may further include organic or gel ion-conducting electrolytes. Suitable organic or gel ion-conducting electrolytes are known in the art.

It may be desirable to use an electrically conductive material as part of the ionically conductive cathode material. Also, in one example, the ion-conducting cathode material comprises a conductive carbon material (eg, graphene or carbon black) and optionally further comprises an organic or gel ion-conducting electrolyte. The electrically conductive material may be separate from the ionically conductive cathode material. For example, an electrically conductive material (e.g., graphene, carbon nanotubes, etc.) is disposed on at least a portion of the surface (e.g., pore surface) of the porous region of the ionically conductive SSE electrolyte material, and the ionically conductive cathode material is , is disposed on at least a portion of a conductive material (eg, graphene, carbon nanotubes, etc.).

In various other examples, the cathode includes a sulfur-containing material. In one example, the cathode material is an organic sulfide or polysulfide. Examples of organic sulfides include carbyne polysulfides and copolymerized sulfur. Non-limiting examples of sulfur-containing materials include sulfur, sulfur composites (eg, carbyne polysulfides, copolymerized sulfur, etc.), polysulfide materials, and the like.

In one example, the cathode is an air electrode. Examples of suitable materials for the air electrode include, for example, high surface area carbon particles (eg Super P, a conductive carbon black)
and catalyst particles (e.g. α- _MnO2 nanorods) bound to a mesh (e.g. a polymer binder such as a PVDF binder) used in ion-conducting batteries such as lithium-ion batteries with air cathodes. .

The cathode material may be a lithium ion conducting material. Non-limiting examples _of lithium ion _conductive cathode materials include lithium nickel manganese cobalt oxide (e.g., NMC, _{LiNixMnyCozO2} , where x+y+ _z =1, e.g., L
i(NiMnCo) _1/3 O ₂ etc.)), LiCoO ₂ , LiNi _1/3 Co _1/3 Mn _{1
/3O2 , LiNi0.5Co0.2Mn0.3O2 , lithium} manganese oxide ( _LMO
) (e.g. LiMn ₂ O ₄ and LiNi _0.5 Mn _1.5 O ₄ ), lithium iron phosphate (LFP) (e.g. LiFePO ₄ ), LiMnPO ₄ , LiCoPO ₄ and Li ₂ MMn ₃ O ₈ (where , M is selected from Fe, Co, etc.).

The cathode material may be a sodium ion-conducting material. Non-limiting examples of sodium ion conducting cathode materials include Na ₂ V ₂ O ₅ , P2-Na _2/3 Fe _1/2
Mn1 _{/ 2O2} , _Na3V2 ( _PO4 ) ₃ , NaMn1 _{/ 3Co1} / _{3Ni1 / 3PO4}
, and Na _2/3 Fe _1/2 Mn _1/2 O ₂ @graphene composites (eg, composites containing carbon black).

The cathode material may be a magnesium ion-conducting material. Non-limiting examples of magnesium ion-conducting cathode materials include doped manganese oxides (e.g., Mg _x
MnO ₂ · _y H ₂ O), Mg _1+x (Al, Ti) ₂ (PO ₄ ) ₆ (where x is 4 or 5), NASICON type magnesium ion conductive materials, and the like.

The anode includes one or more anode materials in electrical contact with the porous region of the solid hybrid electrolyte. For example, the anode material is a metallic form of ions that conduct in a solid electrolyte (eg, metallic lithium in lithium ion batteries) or a compound that inserts conducting ions (eg, lithium carbide, Li ₆ C in lithium ion batteries). Examples of suitable anode materials are known in the art.

In the case of an integrated anode, the anode material is disposed on at least a portion of the surface of the porous region of the solid hybrid electrolyte (eg, the pore surface of one of the pores). The anode material may at least partially fill one or more pores (eg, a majority of the pores) of the porous region of the solid hybrid electrolyte. In one example, the anode material infiltrates at least some of the pores of the porous region of the solid hybrid electrolyte.

In one example, the anode material is disposed on at least a portion of the pore surfaces of the anode-side porous region of the solid hybrid electrolyte, the anode side of the solid hybrid electrolyte being the cathode side of the solid hybrid electrolyte in which the cathode material is disposed. Oppose.

In various examples, the anode includes (or consists of) a conductive carbon material. Non-limiting examples of carbon materials include graphite, hard carbon, porous hollow carbon spheres and tubes, and the like. The anode material may further comprise an organic or gel ion-conducting electrolyte. Suitable organic or gel ion-conducting electrolytes are known in the art.

The anode material may be an electrically conductive material. Non-limiting examples of electrically conductive materials include electrically conductive carbon materials, tin and its alloys, tin/carbon, tin/cobalt alloys, silicon/carbon materials, and the like. Non-limiting examples of conductive carbon materials include graphite, hard carbon, porous hollow carbon spheres and tubes (eg, carbon nanotubes), and the like.

The anode may be metal. Non-limiting examples of metals include lithium metal, sodium metal, magnesium metal, and the like.

The anode material may be a lithium-containing material. Non-limiting examples of lithium-containing materials include lithium metal, lithium carbide, _Li6C , and lithium titanate (LTO).
(eg, Li ₄ Ti ₅ O ₁₂ , etc.).

The anode material may be a sodium-containing material. Non-limiting examples _of anode _materials include _sodium metal _{, Na2C8H4O4} and _{Na0.66Li0.22Ti0 .}
Ionically conductive sodium-containing anode materials such as ₇₈ O ₂ are included.

The anode material may be a magnesium containing material. In one example, the anode material is magnesium metal.

The battery may comprise a current collector. For example, the battery includes a cathode-side (first) current collector disposed on the cathode side of the solid hybrid electrolyte and an anode-side (second) current collector disposed on the anode side of the solid hybrid electrolyte. Prepare. Each current collector is independently made of a metal (eg, aluminum, copper, or titanium) or metal alloy (aluminum alloy, copper alloy, or titanium alloy).

The battery may include various additional structural elements (eg, bipolar plates, external packaging, electrical contacts/leads connecting wires, etc.). In one example, the battery further comprises bipolar plates. In various examples, the battery further comprises electrical contacts/leads connecting the bipolar plates and the outer package, as well as the wires. In one example, repeating battery cell units are separated by bipolar plates.

A solid hybrid electrolyte, a cathode, an anode, a cathode-side (first) current collector (if present), and an anode-side (second) current collector (if present) may form a cell. A battery may comprise multiple cells separated by one or more bipolar plates. The number of cells in a battery is determined by the battery's performance requirements (e.g. voltage output),
Limited only by fabrication constraints. For example, solid state ion-conducting batteries have
00 cells (including all integer cell numbers and ranges between them).

The method steps described in the various embodiments and examples disclosed herein are sufficient to carry out the method of the present disclosure. Thus, in one example, the method consists essentially of a combination of method steps disclosed herein. In another example, a method consists of such steps.

The following statements provide examples of the solid state hybrid electrolytes of this disclosure and their uses.
Statement 1. SSEs (e.g., inorganic (e.g., ceramic) SSEs) disclosed herein (or including inorganic SSE materials disclosed herein); and
a polymeric material disclosed herein disposed on at least a portion or all of the outer surface of a solid electrolyte (e.g., solid electrolyte material);
Hybrid electrolytes (eg, solid hybrid electrolytes), including
Statement 2. Hybrid electrolytes according to Statement 1 (as examples of mesoporous SSE body materials include bilayer and trilayer materials comprising one or more layers of porous SSE material disposed on a layer of dense SSE material).
Statement 3. The hybrid electrolyte of Statement 1 or 2, wherein the SSE material is a disc, sheet, or polyhedron (eg, has a polyhedral shape).
Statement 4. 4. The hybrid electrolyte of any one of Statements 1-3, wherein the polymeric material has a thickness at one or more points between 10 nm and 10 microns (eg, between 5 and 10 microns).
Statement 5. 5. The hybrid electrolyte of any one of Statements 1-4, wherein the SSE comprises a plurality of fibers or strands (eg, a plurality of nonwoven strands or a plurality of woven strands).
Statement 6. The hybrid electrolyte of statement 5, wherein the fiber is present as the woven substrate.
Statement 7. Statement 5, where the fibers are randomly placed or arranged
Or the hybrid electrolyte according to 6.
Statement 8. 8. The hybrid electrolyte of any one of statements 5-7, wherein the fibers or strands of polymeric material form an interconnected 3D network.
Statement 9. The SSE material is a lithium ion conducting (e.g. containing lithium ions) SSE material, a sodium ion conducting (e.g. containing sodium ion) SSE
9. The hybrid electrolyte of any one of Statements 1-8, comprising a material, or a magnesium ion-conducting (eg, magnesium ion-containing) SSE material.
Statement 10. Lithium ion conductive SSE materials include lithium perovskite materials, Li ₃ N, Li-β-alumina, lithium superionic conductors (LISICON), Li
_{2.88PO3.86N0.14 ( LiPON} ), _{Li9AlSiO8 , Li10GeP}
9. The hybrid electrolyte of Statement 9, wherein the hybrid electrolyte is selected from the group consisting of ₂ S ₁₂ , lithium garnet materials, doped lithium garnet materials, lithium garnet composite materials, and combinations thereof.
Statement 11. ^The lithium garnet material is cation _{- doped Li5La3M12
O12} (where ^M1 _is Nb, Zr _, Ta _, or _{a combination} thereof), cation-doped _{Li6La2BaTa2O12} , cation- _{doped Li7La3Zr2O12} , and _cation -doped _Li6BaY2M ^12. The hybrid electrolyte of Statement 10, _wherein ^M1 is Nb, Zr, Ta, or combinations thereof, and the cationic dopant is barium, yttrium, zinc _, or combinations thereof.
Statement 12. Lithium garnet materials are Li ₅ La ₃ Nb ₂ O ₁₂ , Li _{5
La3Ta2O12 , Li7La3Zr2O12 , Li6La2SrNb2O12 , Li _ _ _ _
6La2BaNb2O12 , Li6La2SrTa2O12 , Li6La2BaTa2O _ _ _ _ _ _
12 , Li7Y3Zr2O12 , Li6.4Y3Zr1.4Ta0.6O12 , Li6 . _ _ _
5La2.5Ba0.5TaZrO12 , Li6BaY2M12O12 , Li7Y3Zr _} ^_ _{_ _ _ _
2O12 , Li6.75BaLa2Nb1.75Zn0.25O12 , Li6.75Ba _ _ _
The} hybrid electrolyte of statement ₁₀ which is _{La2Ta1.75Zn0.25O12} , and combinations thereof _.
Statement 13. The sodium ion-conducting SSE material is β″-Al ₂ O ₃ , Na
9. The hybrid electrolyte of _{Statement 9, selected from the group consisting of 4Zr2Si2PO12 ( NASICON )} , cation-doped NASICON, and combinations thereof.
Statement 14. A magnesium ion-conducting SSE material is Mg _1+x (Al, T
i) The hybrid electrolyte of Statement 9 selected from the group consisting of ₂ (PO ₄ ) ₆ where x is 4 or 5, a NASICON-type magnesium ion-conducting material, and combinations thereof.
Statement 15. The inorganic SSE has pores exposed on the outer surface of the inorganic SSE, and the hybrid electrolyte further comprises at least one cathode material and/or at least one anode material disposed in at least a portion of the pores. , when the at least one cathode material and the at least one anode material are disposed in at least a portion of the pores, the at least one cathode material and the at least one anode material are discrete and electrically isolated from the inorganic SSE 15. The hybrid electrolyte of any one of statements 1-14, disposed in a region.
Statement 16. Polymer materials include poly(ethylene) (PE), poly(ethylene oxide) (PEO), poly(propylene) (PP), poly(propylene oxide), polymethyl methacrylate (PMMA), polyacrylonitrile (PAN), poly[bis (methoxyethoxyethoxide)-phosphazene], poly(dimethylsiloxane) (PDMS
), cellulose, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate,
Polyvinylidene difluoride (PVdF), polyvinylpyrrolidone (PVP), polystyrene, sulfonate (PSS), polyvinyl chloride (PVC) group, poly(vinylidene chloride) polypropylene oxide, polyvinyl acetate, polytetrafluoroethylene (for example , Teflon), poly(ethylene terephthalate) (PET), polyimides, polyhydroxyalkanoates (PHA), PEO-containing copolymers (e.g., polystyrene (PS
)-PEO copolymers and poly(methyl methacrylate) (PMMA)-PEO copolymers), polyacrylonitrile (PAN), poly(acrylonitrile-methyl acrylate copolymers), PVdF-containing copolymers (e.g. polyvinylidene fluoride - hexafluoropropylene copolymers (PVdF-HFP copolymers)), PMMA copolymers (e.g. poly(methyl methacrylate-ethyl acrylate copolymers)), derivatives thereof, and combinations thereof. 16. The hybrid electrolyte of any one of Statements 1-15, comprising (eg, being) a polymer that is a
Statement 17. 17. The hybrid electrolyte of any one of Statements 1-16, wherein the polymeric material is a gel (eg, a gel containing 60-80 wt% liquid, based on the total weight of the polymeric material).
Statement 18. If the liquid is a liquid electrolyte (e.g. ethylene carbonate (EC)
/ _LiPF6 (eg 1M) in diethyl carbonate (DEC), LiTFSI (eg 1M) in dimethoxyethane (DME)/dioxolane (DOL), N-propyl-N-methylpyrrolidinium bis(trifluoromethane sulfonyl)imide (PY
17. The hybrid electrolyte of any one of statements 1-17, wherein R ₁₃ TFSI) is a non-aqueous liquid electrolyte such as LiTFSI (eg, 0.5 M) in an ionic liquid).
Statement 19. The polymer material of the gel is polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVdF-HFP copolymer)
, polyvinylpyrrolidone (PVP), PEO, PMMA, PAN, polystyrene (PS)
, polyethylene (PE), and combinations thereof.
Statement 20. Statements 1-19, wherein the polymeric material comprises a metal salt (eg, a metal salt selected from the group consisting of lithium salts, sodium salts, magnesium salts, etc.)
The hybrid electrolyte according to any one of Claims 1 to 3.
Statement 21. The hybrid electrolyte of any one of Statements 1-20, wherein the polymeric material comprises a ceramic filler (eg, 2-25 wt%, based on the total weight of the polymeric material).
Statement 22. The ceramic filler contains conductive particles, non-conductive particles (e.g.
Al ₂ O ₃ , SiO ₂ , TiO ₂ nanoparticles, etc.), ceramic nanomaterials (e.g., ceramic nanoparticles, ceramic nanofibers), statement 2
2. The hybrid electrolyte according to 1.
Statement 23. A device comprising one or more hybrid electrolytes of the present disclosure (eg, the hybrid electrolytes of any one of Statements 1-22).
Statement 24. Hybrid electrolytes of the present disclosure (eg, statements 1-2
2. The hybrid electrolyte according to any one of 2);
an anode;
a cathode;
with
A hybrid electrolyte was disposed between the cathode and the anode (e.g., the polymer material of the hybrid electrolyte was disposed between the SSE material of the hybrid electrolyte and the anode and/or cathode (e.g., the hybrid electrolyte's fills substantially all voids between the SSE material and the anode and/or cathode)), a battery (eg, an ion-conducting battery such as a solid-state ion-conducting battery).
Statement 25. 25. The apparatus of Statement 24, wherein the battery further comprises a current collector disposed on at least a portion of the cathode and/or anode.
Statement 26. 26. The device of Statement 25, wherein the current collector is an electrically conductive metal or metal alloy.
Statement 27. The battery is a lithium ion conductive solid state battery and the hybrid electrolyte is a lithium ion conductive (eg lithium containing) SSE material (eg a lithium conductive (eg lithium 27. The device of any one of Statements 24-26 which contains) SSE material).
Statement 28. The battery is a sodium ion conducting solid state battery and the hybrid electrolyte is a sodium ion conducting (e.g. sodium containing) SSE material (e.g. a sodium ion conducting (e.g. sodium containing) SSE material as described in Statement 14).
SE material).
Statement 29. the battery is a magnesium ion-conducting solid state battery and the hybrid electrolyte is a magnesium ion-conducting (e.g., magnesium-containing) SSE material (e.g., a magnesium ion-conducting (e.g., magnesium-containing) SSE material as described in Statement 15) 27. The device of any one of Statements 24-26, which is
Statement 30. Statement 24 wherein the cathode and/or anode comprise a conductive carbon material (e.g., graphite, hard carbon, porous hollow carbon spheres and tubes, etc.), and the cathode material optionally further comprises an organic or gel ion conducting electrolyte. 30. A device according to any one of clauses -29.
Statement 31. to any one of Statements 24 to 29, wherein the cathode comprises a material selected from sulfur, sulfur composites (e.g., carbyne polysulfides, copolymerized sulfur, etc.), and polysulfide materials, or is air; equipment as described.
Statement 32. Statement 27, wherein the cathode (e.g., lithium-ion conductive, lithium-containing cathode) comprises a material selected from the group consisting of lithium-containing materials
Equipment described in .
Statement 33. The lithium-containing cathode material is lithium nickel manganese cobalt oxide (e.g., NMC, _{LiNixMnyCozO2} , where _x + _y + _z =1, e.g., Li(NiMnCo) _1/ 3O2 _{, etc.} ), _LiCoO2. , LiNi _{1/3
Co1 /3Mn1 /3O2} , _{LiNi0.5Co0.2Mn0.3O2 ,} lithium _manganese oxide ₍ LMO) ₍ e.g., _{LiMn2O4 and LiNi0.5Mn1.5O 4} )
, lithium iron phosphate (LFP) (e.g. _LiFePO4 ), _LiMnPO4 , LiC
33. The device of Statement ₃₂ , selected from the group consisting of _oPO4 , and _Li2MMn3O8 , where M _is selected from Fe, Co, and combinations thereof.
Statement 34. 29. The instrument of Statement 28, wherein the cathode (eg, sodium ion-conducting, sodium-containing cathode) comprises a material selected from the group consisting of sodium-containing cathode materials.
Statement 35. The sodium-containing cathode materials are Na ₂ V ₂ O ₅ , P2-Na _{2
/ 3Fe1/ 2Mn1/ 2O2} , _Na3V2 ( _PO4 ) ₃ , NaMn1 _{/3Co1 / 3N}
35. The device of Statement 34, selected from the group consisting of i1 _{/ 3PO4} , and Na2 _{/ 3Fe1} / _{2Mn1/ 2O2} @graphene composites.
Statement 36. The cathode (e.g., magnesium ion-conducting, magnesium-containing cathode) is a doped magnesium oxide (e.g., Mg _1+x (Al,Ti) ₂
(PO ₄ ) ₆ (where x is 4 or 5), NASICON-type magnesium ion-conducting materials, etc.).
Statement 37. Statement 24, wherein the anode comprises a material selected from the group consisting of silicon-containing materials (eg, silicon, silicon/carbon, etc.), tin and its alloys (eg, tin/cobalt alloys, etc.), tin/carbon, and phosphorus 37. The device according to any one of clauses -36.
Statement 38. The apparatus of any one of Statements 24-27 and 31-33, wherein the anode (e.g., lithium ion conducting anodes and lithium containing anodes) comprises a material selected from the group consisting of lithium ion conducting anode materials. .
Statement 39. The lithium ion conductive anode material is lithium carbide, _Li6C
, and lithium titanate (LTO) (eg, Li ₄ Ti ₁₅ O ₁₂ , etc.).
Statement 40. The device of Statement 38, wherein the anode is lithium metal.
Statement 41. according to any one of statements 24-26, 28, 34, and 35, wherein the anode (e.g., sodium-containing and sodium ion-conducting anode) comprises a material selected from the group consisting of sodium ion-conducting anode materials equipment.
Statement 42. _The sodium- _containing anode materials _{are Na2C8H4O4} and Na
Statement 41, selected from the group consisting of _0.66 Li _0.22 Ti _0.78 O ₄
Equipment described in .
Statement 43. The instrument of Statement 41, wherein the anode is sodium metal.
Statement 44. The device of any one of statements 24-26, 29, and 36, wherein the anode is a magnesium-containing anode material.
Statement 45. The instrument of Statement 44, wherein the anode is magnesium metal.
Statement 46. of statements 24-45, wherein the hybrid electrode, cathode, anode, and optional current collector form a cell, the battery comprising a plurality of cells, each adjacent pair of cells separated by a bipolar plate; A device according to any one of paragraphs.
Statement 47. A conventional ion-conducting battery with a liquid electrolyte (e.g., as the base electrolyte), where the battery includes an inorganic SSE disclosed herein or a solid hybrid electrolyte and a liquid electrolyte (e.g., a conventional liquid electrolyte used in batteries)
wherein the liquid electrolyte does not exist as a component of the solid hybrid electrolyte and the inorganic SSE
47. The device of any one of statements 23-46, wherein the material or solid hybrid electrolyte is the separator of a conventional battery.
Statement 48. The instrument of Statement 47, wherein the inorganic SSE is a F/S SSE disclosed herein (eg, templating inorganic SSE or electrospinning inorganic SSE).
Statement 49. A method of making a hybrid electrolyte (e.g., a solid hybrid electrolyte) (e.g., the hybrid electrolyte of any one of Statements 1-22), comprising:
contacting the template with one or more SSE material precursors;
reacting (e.g., by heating) the SSE material precursor to form a solid inorganic material (e.g., including at least partially or wholly reacted and/or decomposed SSE material precursor);
A heat treatment (e.g., sintering and/or firing) of the template with a solid inorganic material such that the template is removed (e.g., as carbon dioxide by combustion) and the inorganic SS
E (e.g. monolithic SSE or mesoporous or F/S SSE) is formed;
contacting (e.g., infiltrating) the fired template with a polymeric material;
including
In the case of monolithic SSE or mesoporous, forming a layer on the inorganic SSE material (
and optionally filling at least some or all of the pores exposed on the surface of the inorganic SSE material) or, in the case of F/S SSE, the polymeric material is the F/S SSE pores (e.g., filling at least some or all of the pores corresponding to the template);
Method.
Statement 50. 49. The method of Statement 49, wherein the SSE material precursor is a sol-gel precursor or a metal salt.
Statement 51. 51. The method of statement 49 or 50, wherein the template is a carbon template (eg, fiber template) or a biomaterial template (eg, wood or plant template).

The following examples are presented as illustrative of the disclosure. They are not intended to be limiting in any way.

This example provides a description of the solid state hybrid electrolytes of the present disclosure. This example also provides an example of the preparation and characterization of such electrolytes.

Reduction of interfacial resistance ^of hybrid polymer/garnet-type electrolyte systems in lithium metal batteries Garnet-type solid electrolytes are characterized by their high ionic conductivity ( ¹⁰
cm) and a wide electrochemical stability window (0-6 V vs. Li ⁺ /Li) reveal promising results for Li metal batteries. One of the major problems with garnet-type solid electrolytes is the high interfacial resistance between the electrolyte and the electrode. _{This example} demonstrates _{a solid Li7La2.75Ca0.25Zr1.75Nb0.25O12 (} LLCZ
N) describes hybrid electrolytes containing garnet-type electrolytes. The gel-polymer electrolyte layer forms an advantageous interface of low interfacial resistance and long-term electrochemical stability between the garnet solid electrolyte (SSE) and the electrode. Hybrid gel polymers and LLCZN electrolytes are SS
A low interfacial charge transfer resistance of around 248 Ω×cm ² at the E/cathode interface and around 214 Ω×cm ² at the SSE/Li metal interface is achieved. Another advantage of this design is that the hybrid electrolyte can prevent the formation of lithium dendrites due to the dense LLCZN garnet layer. Our results show that hybrid symmetric cells can operate with stable stripping and plating profiles over long cycles. Also, this hybrid electrolyte can be used in Li metal batteries with low overvoltage and high reliability against dendrite short circuits. A hybrid electrolyte design with a gel-polymer interfacial layer is an interesting surface-engineered solution that is effective for garnet-solid interfacial resistance and demonstrates a high-performance, safe Li-metal battery.

Proposing a hybrid electrolyte with a gel-polymer electrolyte as the interfacial layer between the LLCZN garnet SSE reduces the interfacial resistance and demonstrates a Li metal finished cell that can operate at room temperature. FIG. 1a is a schematic of a solid polymer-Li metal battery design with a polymer/garnet-type SSE hybrid electrolyte. In this battery, interfacial resistance is reduced by using a gel polymer as an interfacial layer between the garnet-type SSE and the electrode. A gel-polymer electrolyte can help reduce the garnet-type SSE interfacial resistance to the cathode and Li metal by increasing the contact between the garnet-type SSE and the electrodes (Fig. 1b). The gel polymer electrolyte used in this study is porous PVdF-H
It is a combination of an FP polymer matrix and a limited amount of liquid electrolyte stored inside the polymer. Gel polymers made by known techniques exhibit good ionic conductivity (5 x 10
⁻⁴ S/cm) and is electrochemically stable in the voltage range of 0-4.5 V vs. Li ⁺ /Li, making it suitable for most commercially used cathode materials. Due to the hybrid design with a gel-polymer electrolyte at the interface between ^the garnet-type SSE and the active electrode, the interfacial resistance is 248 Ω×cm for the cathode interface and 214 Ω×cm for the Li metal anode interface.
As low as cm ² . Our results show that the hybrid symmetric cell can operate with stable stripping and plating profiles for up to 15 h and with low overvoltages, which is consistent with the combination of garnet-type SSE and metallic Li anode. shows a stable interface between Because the gel polymer interlayer contains a minimal amount of liquid electrolyte, the hybrid electrolyte does not leak like traditional liquid electrolyte-based batteries. A hybrid electrolyte design with a gel-polymer interfacial layer reduces the overall interfacial resistance to the electrodes, including both the cathode and the Li-metal anode in electrochemical cells, and is important in demonstrating high-performance, safe Li-metal batteries. It is considered as an effective surface engineering strategy.

Results and Discussion Characterization of Hybrid Electrolytes Characterization of garnet-type SSE and gel polymer electrolytes are described herein. A cross-sectional scanning electron microscopy (SEM) image of the garnet-type LLCZN pallet was obtained, showing a total thickness of approximately 450 μm, consistent between the samples in these trials. The surface of the garnet pallet is not smooth, resulting in poor contact with the electrode layer. A magnified cross-sectional SEM image of a garnet-type LLCZN pallet with fine grains as a result of high temperature sintering for 12 hours during the synthesis process was examined. The dense structure of garnet-type SSEs prevents lithium metal dendrites from penetrating the electrolyte during cycling. PVdF
- SEM images of the HFP polymer matrix were acquired. The porous structure of the matrix is sufficient to absorb and contain additional liquid electrolyte. For garnet-type LLCZN pallets,
X-ray diffraction (XRD) was performed. This is the cubic phase garnet-type Li ₅ La ₃ Nb ₂ O ₁₂
, indicating that the LLCZN palette has a cubic garnet phase with higher Li-ion conductivity compared to the tetragonal garnet phase. thickness is 100
Electrochemical impedance spectroscopy (EIS) was performed with two LLCZN pallets of 0 μm and 150 μm, tested in a symmetrical cell with gold deposited on both sides. The semicircles in the high frequency part of the impedance spectrum curve represent bulk and grain boundary resistances of LLCZN. LLCZN pallets with different thicknesses have the same bulk conductivity around 2×10 ⁻⁴ S/cm.
Conductivity was calculated using the formula σ=R ⁻¹ LS ⁻¹ (where R is the resistance, L is the thickness of the LLCZN pallet, and S is the area of the electrode). The bulk area resistivity (ASR) of the 450 μm thick LLCZN pallet is 225 Ω×cm ² , which is acceptable for the cell. This means that the internal resistance of garnet-type SSEs is relatively low, and the interface between the SSE and the electrodes mainly contributes to the resistance of the solid-state battery. Therefore, as long as the interfacial resistance can be reduced to the same level as the internal resistance, the solid electrolyte can have sufficiently low resistance for battery use. Li |
Cyclic voltammetry (CV) was performed with the polymer|Ti system. -0.3
Sharp peaks at V and 0.3 V correspond to lithium plating and stripping, with no peaks in the higher voltage range. 0.5V to 4.5V
The flatness of the CV curve over the voltage range of 0 indicates that the gel polymer electrolyte is electrochemically stable up to 4.5V. Also, since garnet-type LLZO is electrochemically stable from 0 to 6 V vs. Li ⁺ /Li, the hybrid electrolyte design is stable in the voltage range from 0 to 4.5 V vs. Li ⁺ /Li. This stable voltage range makes the hybrid electrolyte suitable for lithium metal designs with many cathode materials. The areal resistivity and ionic conductivity of the 40 μm thick gel polymer are 8 Ω×cm ² and 5×10 ⁻⁴ S/cm, respectively, from EIS plots of a simple symmetrical cell with stainless steel plates. This flexible, highly ionically conductive gel polymer can improve the contact between the SSE and the electrode, resulting in lower interfacial resistance.

Analysis of the interfacial impedance of the hybrid electrolyte Impedance analysis of the symmetrical cell with the garnet-polymer hybrid electrolyte is shown in Figure 2.
shown. FIG. 2a shows the impedance profile of a cathode|polymer|cathode symmetric cell. The bulk resistance of this cell is low because the gel polymer layer is thin and conductive. The mid-frequency half circle corresponds to a charge transfer resistance (R _ct ) of approximately 107 Ω×cm ² on each side. This value is calculated by equivalent circuit simulation. _Rct
represents the dynamic impediment of charge transfer between the cathode material and the gel polymer, and a small _Rct means good interfacial contact between the gel polymer and the cathode. The long tail in the low frequency part corresponds to the diffusion impedance in the cathode. Figure 2b shows the impedance profiles of stainless steel (SS)|polymer|SSE|polymer|SS symmetric cells, the bulk and grain boundary impedances of garnet-type SSE at high frequencies,
It combines three parts: the interface R _ct in the mid-frequency range and the diffusion impedance at low frequencies. From the impedance plot of the gel polymer, the R _ct between the gel polymer and the SS is nearly zero because the corresponding semicircle does not appear in the impedance plot. Therefore, the R _cts of SS|polymer|SSE|polymer|SS symmetric cells all come from the polymer|SSE interface. R _c of the polymer|SSE interface
_t is approximately 155Ω×cm ² for each side, calculated from the corresponding fitting results in FIG. 5b. This resistance is close to the _Rct of the cathode|polymer interface, implying that the polymer|SSE and cathode|polymer interfaces have similar contact performance.
FIG. 2c is an EIS plot of a cathode|polymer|SSE|polymer|cathode symmetric cell. The impedance curve is a combination of three parts. The high frequency part is the bulk and grain boundary impedance of the garnet-type SSE itself. In the mid-frequency portion, the interface _R
A combination of two semicircles corresponding to _ct . The low frequency part is linear and corresponds to the diffusion impedance of the cathode. The total interface R _ct of the cathode|polymer|SSE|polymer|cathode symmetric cell is 248Ω×cm ² for each side. This value was obtained by equivalent circuit fitting. The interface _Rct of a cathode|polymer|SSE|polymer|cathode symmetric cell is approximately equal to the sum of the polymer|cathode interface _Rct and the polymer|SSE interface _Rct , and the impedance of all three interfaces appears in the mid-frequency range.
This means that the cathode|polymer|SSE interface impedance is the sum of the polymer|cathode and polymer|SSE interface impedances. As a comparison of symmetric cells with and without a gel polymer interfacial layer, FIG. 5a is an EIS plot of a cathodic|SSE|cathode symmetrical cell without any interfacial modification. A symmetrical cell is
Constructed by direct brushing of the cathode slurry on the garnet-type SSE surface and subsequent drying. This indicates that the total R _ct of a cathode|SSE|cathode symmetric cell without a polymer interfacial layer is approximately 1×10 ⁶ Ω×cm ² . This large resistance is the SSE
Evidence of poor contact between the and the _LiFePO4 cathode material. This problem can be solved by a hybrid design gel polymer layer between the garnet-type SSE and the cathode.

FIG. 2d shows the impedance curve of a Li|polymer|Li symmetric cell. The intersection of the impedance curve with the Z'-axis is 6.4 Ω×cm ² , which is the bulk resistance of the gel polymer. The diameter of the semicircle is 180 Ω×cm ² , which is the R _ct of the two polymer|Li interfaces on either side of the symmetrical cell. Therefore, the interfacial resistance of one polymer|Li interface is 90 Ω×cm ² , which is close to the polymer|cathode interfacial resistance. This means that the contact between the gel polymer and the Li metal is as good as the contact between the gel polymer and the cathode,
It means that the surface of the Li metal electrode is also well wetted by the gel polymer. Figure 2e shows the EIS plot of the Li|polymer|SSE|polymer|Li symmetric cell, showing 4
Contains one part. The high frequency part is the garnet type SSE bulk resistance and grain boundary resistance.
The intermediate-frequency part has two regions corresponding to the interface R _ct between the garnet-type SSE and the Li metal, mainly derived from the impedances of the polymer|SSE and polymer|Li interfaces, since the impedance of the gel polymer layer itself is rather small. It's a half circle. From the corresponding equivalent circuit fitting results here, the total interface R _ct on one interface of the Li|polymer|SSE|polymer|Li symmetric cell is 214Ω×cm ² . Figure 5b shows that the total resistance of the Li|SSE|Li symmetric cell without interfacial modification is approximately 1400Ω to one side.
× cm ² . Lithium metal is melted and coats both sides of the garnet-type SSE. The reason for the lower resistance compared to the cathode|SSE|cathode symmetric cell of FIG. 5a is that the melting of lithium metal improves surface contact compared to solid cathode powder and binder. However, the interfacial resistance of 1400Ω×cm ² is still too large for battery use. This can be reduced by a gel polymer interfacial layer. In conclusion, gel interfacial layers can significantly reduce the interface _Rct between LLCZN solid electrolytes and electrodes, including many cathode materials and Li metal anodes. FIG. 2f compares the interfacial resistance of Li|SSE|Li and cathode|SSE|cathode symmetric cells with and without a gel-polymer interface. This clearly shows that the gel interface can reduce the interfacial resistance to an acceptable range. After applying the gel-polymer interface, the interfacial resistance between the cathode and the garnet-type SSE decreased from 6×10 ⁴ Ω×cm ² to 248 Ω×cm ² .
After applying the gel-polymer interface, the interfacial resistance between the Li metal anode and the garnet-type SSE decreased from 1400 Ω×cm ² to 214 Ω×cm ² .

FIG. 3 analyzes the impedance identified for each interface in a symmetric cell with and without a gel-polymer interface. The impedance analysis of the cathode|polymer|SSE|polymer|cathode symmetric cell is derived from FIGS. 2a-2c, and the impedance analysis of the cathode|SSE|cathode symmetric cell without gel-polymer interface is shown in FIG. 5a. A corresponding equivalent circuit is described herein. In each equivalent circuit, there is one parallel connection between the resistor and the capacitor/constant phase element (CPE) for one interface impedance.
exist. Capacitance/CPE is for the double layer capacitance on the interface and resistance is for the charge transfer resistance on the interface. The total interface R _ct of the cathode|polymer|SSE|polymer|cathode-symmetric cell was 496 Ω×cm ² and the interface R _ct of the cathode|SSE|cathode-symmetric cell without the gel-polymer interface (1.3×10 ⁵ Ω ×c
m ² ). This drop in resistance indicates that the gel-polymer interface is the cathode and SSE.
It means that the contact performance between and can be greatly improved. The analysis of the impedance of the Li|Polymer|SSE|Polymer|Li symmetric cell is derived from the analyzes of FIGS. Derived from FIG. 5b. This is the L
Figure 3 compares the impedance of i|SSE|Li symmetric cells. A corresponding equivalent circuit is described herein. Li|Polymer|SSE|Polymer|Li symmetric cell total interface _Rc
t is 428 Ω×cm ² , which is much smaller than the interface R _ct (2800 Ω×cm ² ) of the Li|SSE|Li symmetric cell without interface modification. This reduction in resistance means that the gel-polymer interface can greatly improve the contact performance between Li and SSE.

Electrochemical Performance of Hybrid Solid Polymer Electrolytes Electrochemical performance of lithium symmetric and finished cells with polymer/garnet-type SSE hybrid electrolytes is shown in FIG. Figure 4a shows the DC cycling voltage profile of a Li|SSE|Li symmetric cell with a gel polymer interfacial layer under galvanostatic cycling. The total DC ASR of the symmetrical cell is 1400Ω× ^cm2 , which corresponds to a voltage value of 180mV
is divided by the surface current density of 125 μA/cm ² . The inset of Figure 4a shows that the DC resistance remains constant for one cycle. This DC resistance comes from the bulk and grain boundary resistance of the SSE and the resistance of the SSE|polymer|Li interface, so the interfacial resistance remains constant over one cycle. The voltage drops from 180 mV to 160 mV in the first 5 hours as the lithium stripping and plating improves the interfacial contact between the lithium and the gel polymer electrolyte. After 5 hours the voltage remained constant and
The interfacial resistance is also kept constant and the interface is stable. Figure 4b shows EIS plots of the cells before and after cycling over 15 hours. During the cycle, the interfacial ASR is nearly constant, 10
It changes from 00Ω×cm ² to 1100Ω×cm ² . This means that the gel-polymer interface was stable and kept low resistance for a long time.

Figures 4c-4e show the cycling performance of the completed cell with the polymer/garnet SSE hybrid electrolyte. The cell is 65 μA/cm ² for 130 cycles
and a 1C rate (170 mA/g). FIG. 4c shows the first time,
10th, 50th, 100th, and 130th cycle charge/discharge profiles. The charge-discharge curves show a stable voltage plateau and the cycle overvoltage is consistent. This means that the interfacial resistance remains constant during 130 charge-discharge cycles. FIG. 4d shows the discharge capacity and coulombic efficiency for each cycle, with the coulombic efficiency being approximately 95% for each cycle after the second. The low coulombic efficiency of the first cycle is due to the formation of an SEI layer between the electrode and the gel during this first cycle. The discharge capacity is stable at 50-55 mAh/g over 130 cycles.
A stable discharge capacity indicates that the interfacial layer is stable over long cycles. The reason for the low specific capacity is that most of the liquid electrolyte is inside the gel and only a small amount is inside the cathode material, so not all of the cathode material is wet with the gel and all is active in the reaction. It is conceivable that it will not change. However, since the interfacial layer is chemically stable, the discharge capacity of the battery has good long-term stability. Figure 4e is an EIS plot of the cell before cycling, after 20 cycles, and after 130 cycles. R _ct , indicated as the diameter of the mid-frequency range semicircle, is approximately 500Ω×cm ²
, which means that the impedance of the gel polymer electrolyte is very stable and can maintain a small charge transfer resistance over 130 cycles.
In conclusion, the hybrid polymer/garnet electrolyte can be used for Li metal finished cells with small overvoltage and good stability.

This example demonstrates that instead of pure SSE, polymer/garnet hybrid electrolytes can be used in good solid polymer battery designs to reduce the interfacial resistance between the garnet-type SSE and the electrode. . Gel polymer electrolytes have high ionic conductivity and a wide electrochemical stable potential window. Therefore, LLZCN garnet SSE can be used as an interfacial layer between an electrode and an electrochemically stable ionically conductive interface. R _ct between the SSE with gel polymer interfacial layer and the electrode is 248 Ω×cm ² for the cathode and 214 Ω×cm ² for the Li metal anode as measured by impedance spectroscopy of the symmetrical and completed cells. is. This interfacial resistance is acceptable for production of commercial lithium metal cells. L with polymer/garnet-type SSE hybrid electrolyte
Demonstration of i-metal symmetric cells cycled over 15 hours with stable voltage profiles. This indicated that the gel-polymer interface between the Li metal anode and the garnet-type SSE was electrochemically stable. The realization of the battery has led to the Li metal anode, L
An _iFePO4 cathode and a polymer/garnet hybrid electrolyte were used for 130 cycles at room temperature. The interface _Rct of the finished cell was constant during cycling, which means that the gel polymer electrolyte can form a stable interface between the LLCZN garnet electrolyte and the lithium iron phosphate electrode. Overall, this study demonstrated a novel hybrid garnet-polymer electrolyte that is a combination of two layers of gel polymer coated on both sides of a pure solid electrolyte. Unfavorable performance without gel polymer layer and 6×10Ω×cm ²
The total interfacial resistance at room temperature is lower (about 500 Ω×cm ² ) after application of the gel-polymer interface compared to the total interfacial resistance of .

_{Synthesis of experimental LLCZN} pallet Garnet- _{type Li7La2.75Ca0.25Zr1.75Nb0.25O12} powder was synthesized by sol-gel method. Precursor _LiNO3 (99%, from Alfa Aesar), L
a( _NO3 ) _3.6H2O (99%, manufactured by Alfa Aesar), _Ca ( _NO3 ) _2.4
H2O (99.9%, Sigma Aldrich), _NbCl5 (99%, Alfa
Aesar), and zirconium (IV) propoxide (70 in 1-propanol).
wt%, from Sigma Aldrich) was dissolved in ethanol containing 10 wt% excess _LiNO in a stoichiometric amount, and after stirring the solution until it became clear, the volume ratio to the solution was 1:4.
Pure acetic acid was added at . Ethanol solvent was evaporated at 100° C. to obtain a gel precursor. After the gel was heated at 350° C. to obtain dry precursor powder, it was heated at 800° C. for 10 hours to obtain garnet powder. After ball milling the powder for 48 hours, it was pressed into a cylindrical pallet. The area of the pallet is 0.5 cm ² . The pallets were then sintered at 1150° C. for 12 hours. Grind the synthesized pallet with sandpaper to a thickness of 400 μm to 45 μm.
It was thinned to 0 μm and washed with isopropyl alcohol (IPA).

Synthesis of PVDF-HFP Based Gel Polymer Electrolytes PVDF-HFP based gel polymer electrolytes were made by the following method. First,
A homogeneous solution was obtained by dissolving 0.25 g of PVDF-HFP (from Sigma Aldrich) in a mixture of 4.5 g of acetone and 0.25 g of ethanol under mechanical stirring for 1 hour. The solution was then cast onto a flat aluminum foil and the solvent was allowed to evaporate in a constant humidity chamber at 80% humidity and 25°C. The samples were dried under vacuum at 60° C. for 5 hours. After that, a uniform self-supporting film was obtained. The thickness of the PVDF-HFP membrane is around 40 μm. Second, the prepared porous PVDF-HFP membrane was cut into small circular films with an area of 0.2 cm ² and 1:1 ethylene carbonate (EC):diethyl carbonate (
DEC) immersed in 1 M LiPF ₆ in liquid electrolyte for 1 minute to ensure complete immersion in the electrolyte. Excess liquid on the surface of the membrane was then wiped off with a wiper.

Material Characterization D8 Advanced using a CuKα radiation source operating at 40 kV and 40 mA
with LynxEye and SolX (Bruker AXS, WI, USA
) was performed on the LLCZN garnet palette by X-ray diffraction (XRD).
The microstructural morphology of the fabricated LLCZN garnet pallets and PVDF-HFP films was investigated by field emission scanning electron microscope (FE-SEM, JEOL 2100F).

Electrochemical Testing of Battery Fabrication Interfacial impedance was measured for both the Li|SSE interface and the _LiFePO4 cathode|SSE interface. From the Li belt (manufactured by Sigma Aldrich), the area is 0
. Lithium metal electrodes were press die cut into circular disks of 2 cm ² and 0.5 mm thickness. To make the cathode, LiFePO ₄ , carbon black, and polyvinylidene difluoride (PVDF) were combined in a mass ratio of 3:2:1 with N-methyl-2-pyrrolidone (N
MP) and mixed to form a slurry. After coating the slurry on aluminum foil, heat at 100°C
oven for 12 hours. After drying, the cathode was cut into circular discs with an area of 0.2 ^cm2 and immersed in 1 M _LiPF6 in a 1:1 ethylene carbonate (EC):diethyl carbonate (DEC) liquid electrolyte prior to testing to remove excess. removed the liquid electrolyte. Cells were assembled and electrochemically tested in an argon-filled glovebox. Li|gel polymer|T
Cyclic voltammetry (CV) of the i-cell was tested. A symmetrical cell for EIS testing was also fabricated. A schematic of each test cell is shown in the corresponding EIS plot. With one stainless steel pallet on each side of the cell, the clips held the electrodes, gel membrane,
and the garnet palette were pressed together sequentially. The electrochemical performance of the cells was tested by a Bio-Logic tester. For EIS testing of symmetrical cells, the voltage swing is 10 m
V, the frequency range was 0.1 Hz to 1 MHz. Li|SSE|Li with a gel interfacial layer
constant current cycles were performed using the same assembly method as the EIS test, with a current density of 0.125 m
A/cm ² for 10 minutes. EIS of cells before and after cycling over 15 hours
were measured and compared. Li|SSE| _LiFePO4 finished cells with gel-polymer interfaces were fabricated in CR2016 coin cells by pressing the garnet, gel, and electrolyte layers together and sealed with epoxy. This cell is 50 μA/
The cells were cycled at a constant current of cm ² and the EIS of the cells before and after cycling was measured.

A system of lithium metal batteries was investigated. The bulk resistance of a 40 μm thick gel polymer layer is 7 Ω×
^cm2 . FIG. 5 shows the impedance of the electrode |SSE|
|SSE|Li shows the EIS of a symmetric cell.

This example provides a description of the solid state hybrid electrolytes of the present disclosure. This example also provides an example of the construction and characterization of such electrolytes.

Solid ion-conducting framework to prevent chemical and physical shorting in Li metal batteries Chemical and physical shorting are associated with fusible material migration and Li dendrite penetration, limiting battery cycle life and thermal runaway There are two important issues in Li metal batteries that lead to To address these issues, in this example, a structural garnet-type solid electrolyte (
SSE) and a solid hybrid electrolyte system consisting of a liquid electrolyte is described. The hybrid electrolyte utilizes a conventional liquid electrolyte to maintain high ion migration kinetics in the electrode and employs SSE to not only separate the electrode and liquid electrolyte, but also to prevent diffusion of unwanted species and Li dendrites. prevent. This example demonstrates the investigation of the chemistry and electrochemical stability of garnet SSEs in sulfur, polysulfides, and liquid electrolytes, and the continuous Li ⁺ /electron pathways and polysulfides in the porous layers of high-sulfur-loaded cathodes. We describe the development of a bilayer garnet SSE framework for hybrid Li—S batteries with dense layers that inhibit material diffusion and dendrite penetration. This study indicates that the integrated sulfur loading is 7, based on finished cell levels.
mg/cm ² , indicating that the energy density can exceed 280 Wh/kg. The initial coulombic efficiency was as high as 99.8% and no chemical or physical short circuit was observed in the hybrid system. This bilayer hybrid configuration is expected to improve Li—S batteries,
This design is expected to be extended to other cathode materials such as high voltage cathodes (LNMO) and air/ _O2 cathodes to pave the way for the transition from conventional to all-solid-state batteries.

Investigating the chemical properties of garnet SSEs and their electrochemical stability in sulfur, polysulfide, and liquid electrolytes, as well as continuous Li ⁺ in porous layers of high-sulfur-loaded cathodes
A bilayer garnet SSE framework for hybrid Li-S batteries with electronic pathways and dense layers that block polysulfide diffusion and dendrite formation was developed. Compared to conventional battery configurations, solid-state hybrid batteries are capable of increasing cathode mass loading, entrapping liquid electrolyte, and releasing cathode volume changes, as well as preventing chemical and physical short circuits. A schematic diagram of a bilayer hybrid Li—S battery is shown in FIG. In the bilayer SSE, the thicker porous garnet layer can reduce the thickness of the supported dense layer to a few micrometers, contributing to a small electrolyte impedance. Since the bilayer SSE directly encapsulates the active material in the pores, these pores are tuned to accommodate changes in the volume of the active material,
It can keep the battery structure stable during cycling. Integrated sulfur cathode loading of 7 mg/cm
² , the proposed hybrid Li—S battery exhibits high initial coulombic efficiency (>99.8%) and high coulombic efficiency (>99%) for each subsequent cycle, indicating that neither chemical shorting nor physical No short circuit was observed. This bilayer SSE represents a promising approach to revolutionizing Li—S batteries. This structural hybrid electrolyte design with high surface reactive sites for the cathode and a blocking layer for the Li anode is also useful for high voltage cathodes (LNMO
) and other cathode materials such as air/O ₂ cathodes can be expected to pave the way for the transition from conventional batteries to all-solid-state batteries.

Characterization of Garnet Solid Electrolyte LLCZN powder slurry containing poly(methyl methacrylate) (P
The porous structure was fabricated by a tape casting method using MMA) spheres as the tape. A bilayer garnet SSE was made by laminating a porous tape to a dense tape and then removing the organic polymer by co-sintering. Details of fabrication can be referred to herein. FIG. 7a shows a photographic image of a bilayer garnet SSE. It has adequate mechanical strength for manual handling and integral stacking in series to obtain high voltage cells. Unlike sulfide-type superionic conductors, which are sensitive to air and moisture, garnet SSEs are much more chemically stable in dry air and can be handled in dry room environments. A schematic diagram of the bilayer garnet SSE structure is shown in FIG. Since the porous structure is placed on the high-density layer, it can improve the mechanical strength of the ultra-thin high-density layer. Further encapsulation of the cathode material by these pores results in a monolithic cathode and electrolyte structure. FIG. 7b is a top view of a scanning electron microscope (SEM) image of the porous layer. The micro-sized pores are uniformly distributed, and the electrode slurry can easily reach the internal structure. Cross-sections of the double-layer garnet SSE are shown in FIGS. 7c-7.
shown in e. Garnet powder was sintered into a 3D network with a porosity of about 70%. FIG. 7d shows the connection of the porous and dense layers, indicating that the porous and dense layers are sufficiently sintered and no delamination is observed. The dense garnet layer in Fig. 7e is
The large garnet grains constitute a dense microstructure, indicating that this dense layer can block the soluble active material and liquid electrolyte from passing through the solid electrolyte. FIG. 7f is a cross-section of a bilayer garnet with a total thickness of 105 μm containing a dense section of 35 μm and a porous section of 70 μm.

X-ray diffraction (XRD) confirmed the phases of the sintered garnet SSE. _{Li7La2 .}
The synthesized garnet SSE based on ₇₅ Ca _0.25 Zr _1.75 Nb _0.25 O ₁₂ (LLCZNO) exhibited a cubic structure. Cubic garnet Li ₅ with all peaks standard
Good match with La ₃ Nb ₂ O ₁₂ (PDF80-0457). In the Raman spectrum, broad and partially overlapping bands confirm the cubic phase of the LLCZNO garnet, which is consistent with garnet spectra reported elsewhere. Ionic conductivity was measured by electrochemical impedance spectroscopy (EIS) using a blocking cell set-up. Dense garnet pellets were used in the construction of the symmetrical Au/garnet SSE/Au blocking cell. The EIS of garnet SSE was measured in the temperature range of 25° C. to 50° C. (FIG. 11). The intercepts of the real axis at high frequencies are assigned to the bulk resistance of the garnet SSE, and the recessed semicircles are associated with the grain boundaries of the garnet SSE. A low frequency intercept corresponding to the capacitive behavior of the Au electrode was used to calculate the total resistance including bulk and grain boundary contributions. Ionic conductivity was calculated using σ=L/(Z×A), where Z is the impedance of the real axis in the Nyquist plot, L is the garnet ceramic disk length, and A is the surface area. The log ionic conductivity of garnet SSE versus inverse temperature is plotted in FIG. The activation energy of 0.35 eV was calculated from the conductivity as a function of temperature by using the Arrhenius equation.

および

を検出した（図９ａ）。３０分間のＡｒイオンスパッタリングで表面を清浄して、急峻な
ピークおよび高い強度によりＳ^－２信号を検出した（図９ｂ）。

およびＳ^－２のピークは、多硫化リチウムＬｉ_２Ｓ_８の分解であるＬｉ_２Ｓ_２およびＬｉ
_２Ｓに由来すると考えられる。図９ｃのイオンスパッタリングを伴う場合および伴わない
場合のガーネットのＺｒ ３ｄスペクトルは、スパッタリング前にはガーネット表面にＺ
ｒ ３ｄが検出されないものの、スパッタリング後にはＬＬＣＺＮＯガーネットの指標で
あるＺｒ ３ｄが検出され、ガーネット表面上に固体相間が形成されていることと、固体
相間がガーネット上で有限の厚さを有することとを示している。本発明者らの結果は、固
体電解質が液体電解質中に溶ける傾向にあり、接触領域においては、いわゆる固体－液体
電解質相間（ＳＬＥＩ）が観察され、固体電解質および有機電解質の両者からの分解生成
物が含まれることを報告した近年の研究により確認可能である。図９ｄのＸ線回折パター
ン（ＸＲＤ）は、ガーネット粉末が立方相構造を維持し、多硫化リチウムおよび液体電解
質に浸した後には相変化が観察されないことを示している。ＸＰＳの結果は、液体電解質
およびガーネット固体電解質がある程度まで多硫化物溶液中で分解したことを示すものの
、Ｌｉ／ＳＳＥ／Ｌｉ対称セルおよびＬｉ－Ｓ完成セルの安定した立方相および電気化学
的性能から、液体電解質および硫黄還元種の環境においてガーネット固体電解質がうまく
機能し得ることが十分に示されている。同じ条件下で処理されたガーネットのラマンスペ
クトルから、ガーネット立方構造が安定を維持していることが確認される（図８ｅ）。高
分解能透過電子顕微鏡法（ＴＥＭ）は、厚さが約４ｎｍのアモルファス層がガーネットナ
ノ粉末表面に形成されたことを示しており、ガーネットがわずかに分解したものと考えら
れる（図８ｆ）。また、ガーネットナノ粉末を硫黄と混合して１６０℃で２４時間にわた
って加熱することにより、ガーネットおよび硫黄の化学的安定性を調べた。サンプルを二
硫化炭素（ＣＳ_２）で洗浄して硫黄を除去した後、ＸＲＤにおいてガーネットの構造を特
性評価した。図８ｆのＸＲＤパターンからも、標準的なガーネットＬＬＺＯのＸＲＤパタ
ーンと同じ立方構造が確認される。硫黄還元種を伴うガーネット固体電解質の安定性を理
解するため、コンピュータ解析の実行によって、ガーネットおよび多硫化物の化学的安定
性をシミュレーションした。コンピュータ解析の結果は、Ｌｉ_２Ｓの形成により界面で自
己抑制効果が生じ、ガーネットと多硫化物との間の反応がそれ以上進まなくなることを示
している。 Chemical Stability of Liquid-Solid Hybrid Electrolyte Systems Garnet SSEs were immersed in lithium polysulfide solutions (Li ₂ S ₈ dissolved in DME/DOL) and liquid electrolytes (LiTFSI in DME/DOL) to determine the respective surface compositions and Experiments were conducted to understand the compatibility of garnet SSEs with liquid Li—S chemistries by examining the phase structure. Li ₂ C by cleaning the surface of the garnet pellet with sandpaper
After removing _O3 , they were immersed in liquid electrolyte or lithium polysulfide solution for one week. After soaking in the solution, the garnet SSE was washed with DME/DOL solvent, dried and separately characterized. Sample transfers were performed in a protected environment to avoid oxygen and moisture contamination. After immersing the garnet pellets in Li ₂ S ₈ /DME/DOL for 1 week, X-ray photoelectron spectroscopy analysis (XPS) revealed

and

was detected (Fig. 9a). After cleaning the surface with Ar ion sputtering for 30 minutes, the S ^-2 signal was detected with a sharp peak and high intensity (Fig. 9b).

and S ⁻² peaks are the decomposition of lithium polysulfide Li ₂ S ₈ Li ₂ S ₂ and Li
_2S . The Zr 3d spectra of garnet with and without ion sputtering in Fig. 9c show that Z on the garnet surface before sputtering.
Although r 3d is not detected, Zr 3d, which is an indicator of LLCZNO garnets, is detected after sputtering, indicating that solid interphases are formed on the garnet surface and that the solid interphases have a finite thickness on the garnet. is shown. Our results show that the solid electrolyte tends to dissolve in the liquid electrolyte, and in the contact area a so-called solid-liquid electrolyte interphase (SLEI) is observed, with decomposition products from both solid and organic electrolytes. This can be confirmed by a recent study that reported that The X-ray diffraction pattern (XRD) in Fig. 9d shows that the garnet powder maintains a cubic phase structure and no phase change is observed after soaking in lithium polysulfide and liquid electrolyte. Although the XPS results indicate that the liquid electrolyte and the garnet solid electrolyte decomposed to some extent in the polysulfide solution, the stable cubic phase and electrochemical performance of the Li/SSE/Li symmetric cell and the Li—S finished cell well demonstrated that garnet solid electrolytes can perform well in the environment of liquid electrolytes and sulfur-reducing species. The Raman spectrum of garnet treated under the same conditions confirms that the garnet cubic structure remains stable (Fig. 8e). High-resolution transmission electron microscopy (TEM) showed that an amorphous layer with a thickness of ~4 nm was formed on the surface of the garnet nanopowder, possibly due to slight decomposition of the garnet (Fig. 8f). The chemical stability of garnet and sulfur was also investigated by mixing garnet nanopowder with sulfur and heating at 160° C. for 24 hours. The garnet structure was characterized in XRD after the sample was washed with carbon disulfide ( _CS2 ) to remove sulfur. The XRD pattern in FIG. 8f also confirms the same cubic structure as that of standard garnet LLZO. To understand the stability of garnet solid electrolytes with sulfur reducing species, computer analysis was performed to simulate the chemical stability of garnet and polysulfides. Computer analysis indicates that the formation of Li ₂ S causes a self-limiting effect at the interface, preventing further reaction between garnet and polysulfide.

Electrochemical Characterization of Hybrid Liquid-Solid Electrolytes The structure and chemistry of the interface between the SSE and the electrode is a major challenge for solid electrolytes.
Recent studies have shown that poor contact at the interface is the main factor leading to the large interfacial resistance of garnet SSEs to Li. Introducing a liquid phase using a liquid electrolyte interlayer between the solid electrolyte and the electrode should be an effective way to reduce the respective interfacial resistance. As part of this work, the focus is on interfacial modification of garnet SSEs to Li metal. FIG. 9a is a schematic representation of a garnet SSE dense surface. Individual pores are distributed on the garnet surface and these cavities limit the garnet's surface area with Li metal (Fig. 9b). Also, the rough and rigid garnet surface makes poor conformal contact with the Li metal, resulting in high interfacial resistance. In FIG. 9c, a polymer gel-like layer is designed to conformally coat the garnet SSE surface. Not only can this layer absorb the liquid electrolyte, but the elastic intermediate layer can ensure intimate contact between the garnet SSE and the lithium metal. Figure 9d shows a cross-section of a polymer-coated garnet SSE. A polyethylene oxide (PEO) polymer was deposited on the garnet SSE surface by spin coating. The PEO has a thickness of 2 μm and conformally coats the garnet SSE (Fig. 8e). This elastic polymer layer can compensate for the undulations of the garnet and Li metal and ensure a uniform Li ion flux through the interface. The Nyquist plot of the electrochemical impedance spectroscopy (EIS) measurement shows that the total impedance is approximately 90
0 Ω·cm ² (Fig. 9e).

The interfacial stability was characterized by mimicking the operating conditions of a real lithium metal battery by galvanostatic plating and stripping of Li ions in a symmetrical cell by applying a galvanostatic current. Fig. 8f shows the Li/ ^Hybrid SSE/
Figure 3 shows the voltage profile as a function of time for a Li cell; A positive voltage indicates Li stripping and a negative voltage is Li plating. The cell was operated for 0.5 hours per cycle. The cell initially showed a voltage of ±0.3V, but the voltage gradually decreased to ±0.2V after the 10 hour cycle. As a comparison, a Li/garnet/Li symmetrical cell was also constructed and tested. For the hybrid cell, the stripping/plating voltage remained relatively stable while cycling over 160 hours. The inset shows the initial cycle for the two types of cells and the 140th hour cycle for the hybrid cell. High impedance and large polarization were observed. A non-smooth voltage plateau suggests a large interfacial resistance between Li and garnet. Hybrid cells showed a smooth voltage curve. The symmetrical total resistance is determined according to Ohm's Law, where the resistance is calculated by dividing the voltage by the current, resulting in an initial resistance of about 1000 Ω ^cm , and thereafter a cell resistance of about 6
It was maintained at 60 Ω·cm ² , which is consistent with the EIS of FIG. These direct currents (DC
) resistance is slightly higher than the alternating current (AC) resistance measured by EIS. The drop in resistance is
It shows that the resistance between garnet and Li metal was improved by the gel electrolyte interlayer in repeated Li stripping and plating. The periodic variation of the voltage profile indicates the temperature dependence of the solid hybrid electrolyte. Li/Hybrid SSE/Li under currents of 0.5 and 1.0 mA/cm ² in FIGS. 8g and 8h
The voltage profile of the cell demonstrates the high ampacity of the hybrid electrolyte.

Electrochemical Characterization of Hybrid Li—S Batteries Electrochemical characterization of solid state hybrid electrolytes of Li—S batteries is shown in FIG. Figure 10
In a, schematics of Li—S batteries with conventional and solid-state hybrid electrolytes are compared. Soluble polysulfides can diffuse through the porous polymer separator and migrate to the Li metal anode, but cannot penetrate the dense ceramic ion conductor, resulting in polysulfide shuttle effects, side reactions on Li, and Li Avoid metal corrosion. As shown in Figure 10b, the shuttling behavior of polysulfides occurs during the charging process. The prolongation of the charge voltage plateau is a typical polysulfide shuttle effect, causing a long charging time before reaching the upper cut-off voltage. The rapid capacity decay and low coulombic efficiency (Fig. 13) in conventional Li-S make the use of solid-state hybrid configurations imperative. In the hybrid cell, the charge curve does not show an extended plateau, the capacity value is close to the discharge capacity and the coulombic efficiency is close to 100%, resulting in stable cycling performance (Fig. 14), and the solid hybrid electrolyte system demonstrated the absence of polysulfide shuttling.

FIG. 10c shows charge-discharge curves of the hybrid cell at different current densities. A hybrid cell was fabricated using a dense garnet SSE and a slurry cast sulfur cathode. The sulfur mass loading is about 1.2 mg/cm ² . Ordinary liquid electrolyte (DME/D
LiTFSI in OL) is used as the liquid electrolyte. No LiNO ₃ was added to the liquid electrolyte. At a current density of 200 mA/g, the sulfur cathode yielded a specific capacity of about 1000 mAh/g with a coulombic efficiency of about 100%. Current density 800mA/g (1m
A/cm ² ), with a specific capacity of 550 mAh/g, the cell still
A high coulombic efficiency close to 100% was maintained. The rate performance is shown in Figure 10d. The hybrid cells showed good cycling stability at high current densities and good capacity retention at low currents.

FIG. 10e is a schematic diagram of a solid-state hybrid bilayer Li—S battery. Sulfur is encapsulated in a thick porous layer, and the volume change of sulfur and its soluble polysulfides can be accommodated by the solid garnet matrix. Sulfur was loaded by directly melting sulfur powder into the porous matrix at 160°C. Carbon nanotubes (CNTs) were infiltrated into the porous garnet microstructure to form an electronically conductive network inside before sulfur melting (Fig. 15).
). Figure 1 shows the cross-section and elemental mapping of the bilayer Li-S cathode (La is red, S is green).
0f. Elemental mapping images clearly show the sulfur content in the pores of the garnet. The voids between the sulfur and the garnet allow the liquid electrolyte to easily enter the internal channels and wash the sulfur. FIG. 10g shows charge-discharge voltage profiles of a hybrid bilayer Li—S cell with an S mass loading of about 7.5 mg/cm ² at a current density of 0.2 mA/cm ² . The first cycle discharge capacity is about 645 mAh/g and the coulombic efficiency is 99.8.
%, which is an exceptionally high value. A long, flat voltage plateau indicates an irreconcilable polarization between the charge-discharge curves. This should be attributed to the porous garnet SSE, which has a higher surface area and more reaction sites with sulfur, allowing for lower voltage polarization and better capacity. Cycle performance is shown in Figure 10h. No sharp capacity growth occurred in the first few cycles, indicating that polysulfides are not lost in hybrid cells with such high mass loading of sulfur. Coulombic efficiency remains above 99%, confirming that no shuttle effect occurs in the hybrid design. A hybrid bilayer Li—S cell with a mass loading of 7.5 mg/cm ² has an energy density of 280 Wh/kg based on cathode, Li anode, and electrolyte. Although cycle performance is slightly degraded, this is due to the fact that the charge products _Li2S and _Li2S2 are not reactivated in subsequent cycles and the high mass loading of sulfur _leads to further reactions inside the bulk sulfur loading. This is thought to be due to the fact that it prevented An electronically conductive network and increased sulfur distribution are highly desirable. In this example, in addition to investigating hybrid electrolytes and hybrid cells using solid sulfur as a model material, the use of a catholyte with liquid polysulfides is also applicable to the two-layer porous high-density design of garnet SSEs. It is anticipated that this will be a method.

Thus, we have disclosed the chemistry and electrochemical stability of garnet SSEs in sulfur, polysulfides, and liquid electrolytes, along with continuous Li ⁺ /electron pathways and A bilayer garnet SSE framework for hybrid Li—S batteries with dense layers that inhibit polysulfide diffusion and dendrite penetration was developed. Compared to conventional battery configurations, solid-state hybrid batteries are capable of increasing cathode mass loading, capturing liquid electrolyte, and releasing cathode volume changes, as well as preventing chemical and physical short circuits. Since the bilayer SSE directly encapsulates the active material in the pores, these pores can be adjusted to accommodate volume changes of the active material to keep the battery structure stable during cycling. Our studies show that the integrated sulfur cathode loading is 7 m
g/cm ² , the proposed hybrid Li—S battery exhibits high initial coulombic efficiency (>99.8%) and high coulombic efficiency (>99%) for each subsequent cycle, and no chemical short circuit in the hybrid system. No physical shorts were observed. This structural hybrid electrolyte is considered an improvement of the Li—S battery. This design also uses a high voltage cathode (LNMO
) and air/ _O2 cathodes for high-performance batteries, paving the way for the transition from conventional to all-solid-state batteries.

LLCZN powder was synthesized by a modified sol-gel method. The starting material is LiNO ₃ (99%
, Alfa Aesar), La( _NO3 ) ₃ (99.9%, Alfa Aesar), Ca( _NO3 ) ₂ (99.9%, Sigma Aldrich), ZrO ( _NO3
) ₂ (99.9%, from Alfa Aesar), and NbCl ₅ (99.99%, Al
fa Aesar). Dissolve stoichiometric amounts of these chemicals in deionized water and
0% excess LiNO ₃ was added to compensate for lithium volatilization during hot pellet making. Citric acid and ethylene glycol (1:1 molar ratio) were added to the solution. the solution at 120°C for 1
After evaporating for 2 hours to form a precursor gel, it was calcined at 400° C. and 800° C. for 5 hours to synthesize garnet powder. The garnet powder was then uniaxially pressed into pellets, covered with the same powder and sintered at 1050° C. for 12 hours.

Material Characterization D8 Advanced using a CuKα radiation source operating at 40 kV and 40 mA
with LynxEye and SolX (Bruker AXS, WI, USA
) was performed by powder X-ray diffraction (XRD). field emission scanning electron microscope (
The morphology of the samples was examined by FE-SEM, JEOL 2100F).

Electrochemical Characterization A Li|solid electrolyte|Li symmetric cell was fabricated and assembled in an argon-filled glovebox. To measure the ionic conductivity of the garnet solid electrolyte, a high-density ceramic disc was coated on both sides with Au paste to act as a blocking electrode. Gold electrodes were sintered at 700° C. to form good contact with the ceramic pellet. The cell was then assembled as a 2032 coin cell with a highly conductive carbon sponge. The carbon sponge acted as a buffer and prevented damage to the garnet ceramic disc. Using the battery test clip,
It held and provided good contact with the coin cell. The edges of the cell were sealed with epoxy resin.
EIS was performed in the frequency range from 1 MHz to 100 mHz with a perturbation amplitude of 50 mV. σ=L
Conductivity was calculated using /(ZxA), where Z is the impedance of the real axis in the Nyquist plot, L is the garnet ceramic disc length, and A is the surface area. Activation energy was determined from conductivity as a function of temperature by using the Arrhenius equation.

First-principles calculations Using the same approach as defined in previous work, the interface is Li ₂ S/Li ₂ S ₈
and garnet SSE. A phase diagram was constructed to identify possible thermodynamically favorable reactions. The energy of the material used in our study is Mate
obtained from the rials Project (MP) database and also from the pymatgen
A compositional phase diagram was constructed using the package. We calculated the interaction energies of the quasi-binary system using the same procedure defined in our previous work.

Fabrication and evaluation of solid-state hybrid batteries All cells were assembled in an argon-filled glovebox. A solid state hybrid cell was assembled as a 2032 coin cell. The sulfur electrode consists of 70% elemental sulfur powder (Si
gma), 20% carbon black, and 10% polyvinylpyrrolidone in water (P
VP, manufactured by Sigma, M _w =360,000) binder. The electrodes were dried in vacuum at 60° C. for 24 hours. 1 M bis(trifluoromethane)sulfonimide lithium salt (LiTFSI, S) in a mixture of dimethoxyethane (DME) and 1,3-dioxolane (DOL) (1:1 by volume) as the electrolyte for solid-state hybrid Li-S batteries.
igma) was used. No LiNO ₃ was added. The electrolyte/sulphur mass ratio is about 10 ml/g on the cathode side. Cells were tested in 2032 coin cells. 1 to 3
. Galvanostatic charge-discharge tests were measured using a cut-off voltage window of 5V. To prepare the bilayer cathode, elemental sulfur powder was uniformly dispersed on the porous garnet and heated at 160° C. to melt the sulfur. A 10 wt% carbon nanotube (CNT) ink in dimethylformamide (DMF) was prepared, dropped into the porous layer of bilayer garnet SSE and dried in vacuum at 100 °C for 12 h before sulfur melting. .

Figures 11-15 represent the characterization of the bilayer garnet structure described in this example.

This example provides a description of the solid state hybrid electrolytes of the present disclosure. This example also provides an example of the construction and characterization of such electrolytes.

High Energy Density Lithium Metal-Sulfur Battery Based on Three-Dimensional Bilayer Garnet Solid Electrolyte A novel design of an energy-dense solid-state hybrid battery is described. This solid electrolyte framework may open new research directions for next-generation high-energy-density Li-metal batteries.

To simultaneously address the challenges of chemical/physical short circuit and electrode volume change, we presented a three-dimensional (3D) bilayer garnet solid electrolyte framework towards advanced Li-metal batteries. Reducing the thickness of the dense layer down to a few microns while retaining good mechanical stability enables the safe use of Li metal anodes. The thick porous layer acts as a mechanical support for the thin dense layer which functions both as a host for the highly loaded cathode material and as a pathway for continuous ion migration. The results show that while the integrated sulfur cathode loading exceeds 7 mg/cm ² , the proposed hybrid Li—S battery exhibits high initial coulombic efficiency (>99.8%) and high average coulombic efficiency (99.8%) in subsequent cycles. %). This electrolyte framework is expected to improve Li-metal batteries by transitioning to all-solid-state batteries, and is also extendable to other cathode materials.

In hybrid batteries, chemical and physical short circuits can be prevented by a dense solid electrolyte that physically blocks the dissolved cathode material and reduces the penetration of Li dendrites. Volume changes in the active material can be accommodated by designing compatible host structures for the porous solid electrolyte. To achieve this goal, we present a 3D solid electrolyte framework with a dense and porous bilayer structure. The 3D bilayer solid electrolyte framework includes: (a) a thin dense bottom layer is a rigid barrier with high modulus, which can effectively separate the electrode and the liquid electrolyte and prevent the penetration of Li dendrites; (b) the thick top porous layer mechanically supports the thin dense layer; (c) the interface between the dense layer and the porous layer has good mechanical integrity and ion continuity. (d) the solid framework may provide electronic and ionic conductive pathways to the encapsulated cathode material; (e) the solid framework may localize the cathode material It has several unique advantages, such as being able to confine it to accommodate volume changes such as those caused by solid sulfur and polysulfide catholytes. Our results show that while the integrated sulfur cathode loading exceeds 7 mg/cm ² , the proposed hybrid Li—S battery exhibits high initial coulombic efficiency (>99.8%) and It exhibits high average coulombic efficiency (>99%). This electrolyte framework is expected to improve Li-metal batteries by transitioning to all-solid-state batteries, such as high voltage (LNMO) and air/ _O2 cathodes, and is also extendable to other cathode materials.

Preparation of Garnet Bilayer Framework A bilayer framework was prepared by laminating the dense porous tape as a bilayer tape and then removing the organic binder and polymer by co-sintering. Garnet powder slurry containing poly(methyl methacrylate) (PMMA) as a sacrificial pore former with 70% porosity
) A porous garnet structure was fabricated by scalable tape casting with spheres. Further details of the fabrication process are given in the experimental section. Unlike sulfide-type superionic conductors, which are sensitive to air and moisture, garnets are chemically stable to processing in dry air and have sufficient mechanical strength for handling. . This allows the tape casting method to be easily scaled for fabrication of low cost garnet solid electrolyte frameworks. During sintering, the organic filler was decomposed and integrally sintered with the garnet powder to form a porous layer. The thickness of the porous layer and the dense layer are controlled by the tape thickness.

Characterization of Garnet Bilayer Framework The interfaces of well-sintered porous dense layers without observable delamination show good contact at the interfaces. This interface can allow good ion transfer from the porous to the dense solid electrolyte. A dense garnet layer with large garnet grains can prevent chemical and physical short circuits between active electrodes. The bilayer garnet cross-section has a total thickness of 105 μm, including a dense layer of 35 μm and a porous support of 70 μm.

By X-ray _{diffraction (} XRD), _the sintered _{Li7La2.75Ca0.25Zr1.75Nb}
Confirming the standard cubic phase of _0.25 O ₁₂ (LLCZNO) garnet, cubic L
It matches well with i ₅ La ₃ Nb ₂ O ₁₂ (PDF80-0457). The broad and partially overlapping bands of the Raman spectrum also confirm the cubic phase of the LLCZNO garnet. The ionic conductivity of dense garnet pellets was measured by electrochemical impedance spectroscopy (EIS) in an Au/garnet/Au symmetrically blocked cell. 25℃～
EIS was performed in a temperature range of 50°C. A low frequency intercept corresponding to the capacitive behavior of the Au electrode was used to calculate the total resistance including bulk and grain boundary contributions. Ionic conductivity was calculated using σ=L/(Z×A), where Z is the impedance of the real axis in the Nyquist plot, L is the garnet ceramic disk length, and A is the surface area. This is 2.2 at 22°C.
It corresponds to ×10 ⁻⁴ S/cm. The logarithmic ionic conductivity of the garnet electrolyte was plotted against the reciprocal temperature. The activation energy of 0.35 eV was calculated from the conductivity as a function of temperature by using the Arrhenius equation.

Garnet Solid Electrolyte/Li Metal Electrochemical Characterization The structure and chemistry of the garnet-electrode interface is a major source of challenges in the application of solid electrolytes. Recent studies have shown that poor contact at the interface is a major factor leading to high interfacial impedance of solid electrolytes and electrodes. For example, a thin (about 5n
m) Atomic layer deposition (ALD) interfacial layers can significantly reduce the interface resistance of Li metal/garnet. Compared to reported vacuum-based processes, gel electrolytes as artificial intermediate layers between solid electrolytes and electrodes can be more scalable for battery fabrication. In this case, a gel electrolyte with good wettability can not only provide a uniformly distributed Li ion flux at the interface, but also prevent potential depletion of the solid electrolyte after contact with Li metal. Individual pores are distributed on the garnet surface and the cavities reduce the surface area of contact with the Li metal, resulting in non-uniform Li ion migration and high interfacial resistance. A polymer gel layer was implemented to conformally cover the garnet surface. The liquid-filled intermediate layer ensures intimate contact between garnet and lithium metal. 2 μm thick polyethylene oxide (PEO)
The polymer conformally coats the garnet. This polymer layer compensates for interfacial undulations and allows uniform Li-ion flux through the interface.

Symmetric hybrid cell (Li/polymer/garnet/polymer/
The interfacial stability was evaluated by galvanostatic plating and stripping of Li metal in Li). Voltage profiles as a function of time for Li/hybrid electrolyte/Li cells under a current density of 0.3 mA/cm ² were determined. A positive voltage indicates Li stripping,
Negative voltage is Li plating. The cell was operated for 0.5 hours per cycle.
The cell initially showed a voltage of ±0.3V, but after the 10 hour cycle the voltage decreased to ±0.2V.
gradually decreased to V. The stripping/plating voltage remained relatively stable as the hybrid cells were cycled for over 160 hours. As a comparison, a Li/garnet/Li symmetrical cell without polymer interfaces was also fabricated and tested. The inset shows the initial cycle for the two types of cells and the 140th hour cycle for the hybrid cell. For the Li/garnet/Li cell, high impedance and large polarization are observed, with a non-smooth voltage plateau suggesting a large interfacial resistance between Li and garnet. In contrast, hybrid cells exhibit a smooth voltage curve. The periodic variation of the voltage profile indicates the temperature dependence of the solid hybrid electrolyte performance. Voltage profiles of Li/hybrid electrolyte/Li cells under loads of 0.5 and 1.0 mA/cm ² demonstrate the high applied current capability of the hybrid electrolyte.

Proof-of-Concept Li—S Battery with Bilayer Garnet Framework The electrochemical performance of a Li—S battery with a bilayer solid garnet hybrid electrolyte was determined. CNTs were infiltrated into the porous garnet microstructure to form an improved electronically conducting network. Photographs and SEM images of the CNT-infiltrated bilayer garnet framework show that the inside of the porous structure is CNT-coated. Volumetric expansion of sulfur and its soluble polysulfides can be accommodated by a solid garnet framework. Sulfur was loaded directly by melting the sulfur powder into the porous matrix at 160°C. Cross-sectional and elemental mapping of the Li—S cathode was performed. Elemental mapping images clearly show the sulfur distribution in the pores of the bilayer garnet. Additional pores between the sulfur and the garnet allow the liquid electrolyte to enter the internal channels and coat the sulfur.

A hybrid bilayer cell with a sulfur mass loading as high as about 7.5 mg/cm ² was fabricated. Charge-discharge voltage profiles of hybrid Li—S cells were constructed at a current density of 0.2 mA/cm ² . The first cycle discharge capacity is around 645 mAh/g and the coulombic efficiency is 99.8%, which is an exceptionally high value. A long, flat voltage plateau indicates an irreconcilable polarization between the charge-discharge curves. This can be attributed to the thin dense and porous garnet layers that have high surface area and increased number of reaction sites with sulfur, allowing for reduced voltage polarization and better capacity. Cycle performance was plotted. No sharp capacity growth occurred in the first few cycles, indicating that polysulfides are not lost in hybrid cells with such high mass loading of sulfur. In subsequent cycles, coulombic efficiency remains above 99%, confirming that no shuttle effect occurs in the hybrid design.
Moreover, the hybrid bilayer Li—S cell with a mass loading of 7.5 mg/cm ² far exceeds any solid-state battery available today, with a total cell Energy density (calculated in FIG. 16) is 248.2 Wh/k
is g. There is a slight decrease in cycling performance, which is believed to be due to the charging products Li ₂ S and Li ₂ S ₂ not being reactivated in subsequent cycles. High mass loading of sulfur prevents further reactions inside the bulk sulfur cathode.

This study demonstrates for the first time the feasibility of using a bilayer solid electrolyte framework in a hybrid battery. Developing this further, the focus will be on increasing the amount and loading of active sulfur by incorporating carbon-sulfur composites into hybrid cells. For example, if the bilayer framework is further optimized by thinning the dense layer and increasing the active material in the thick porous layer, an energy density of over 900 Wh/kg is estimated (FIG. 17).

This example describes a 3D bilayer solid electrolyte framework that addresses both chemical and physical shorting problems in Li metal batteries. To minimize the impedance of the solid electrolyte, we reduced the thickness of the dense garnet film to a few microns while maintaining adequate mechanical strength for battery assembly. A bilayer solid electrolyte framework was designed using a thick porous layer to mechanically support a thin dense layer while hosting the electrode materials and liquid electrolyte.
The thick porous layer has continuous Li ⁺ /electron paths that host the sulfur cathode. again,
A thin dense layer prevents the diffusion of polysulfides and the formation of Li dendrites. A bilayer garnet solid electrolyte framework was applied to Li—S batteries to demonstrate its feasibility, as well as high energy density and excellent performance. Demonstrated hybrid Li-S
The cell has a high sulfur loading of over 7 mg/cm ² , a high initial coulombic efficiency for subsequent cycles (
99.8%) and high average coulombic efficiency (>99%). This electrolyte framework is expected to improve Li metal batteries, and battery designs supported by this framework are commercially viable and _essentially It is extensible to other cathode materials for safe Li metal batteries.

Methods Preparation of Garnet Solid Electrolytes LLCZN powders were synthesized by a modified sol-gel method. The starting material is LiNO ₃ (99%
, Alfa Aesar), La( _NO3 ) ₃ (99.9%, Alfa Aesar), Ca( _NO3 ) ₂ (99.9%, Sigma Aldrich), ZrO ( _NO3
) ₂ (99.9%, from Alfa Aesar), and NbCl ₅ (99.99%, Al
fa Aesar). Dissolve stoichiometric amounts of these chemicals in deionized water and
0% excess LiNO ₃ was added to compensate for lithium volatilization during hot pellet making. Citric acid and ethylene glycol (1:1 molar ratio) were added to the solution. the solution at 120°C for 1
After evaporating for 2 hours to form a precursor gel, it was calcined at 400° C. and 800° C. for 5 hours to synthesize garnet powder. The garnet powder was then uniaxially pressed into pellets and then covered with the same powder and sintered at 1050° C. for 12 hours for conductivity and stability experiments.

A two-layer framework was prepared by tape casting to prepare the dense and porous layers respectively and then laminated as a two-layer tape. The thickness of each individual layer was well controlled. A slurry was made using LLZCN that had been fully calcined in the desired phase. LLZCN powder with fish oil as dispersant was added to toluene, isopropanol (IPA). Polyvinyl butyral (PVB) and butyl benzyl phthalate (BBP) after 24 hours of milling
was added as a binder and plasticizer, followed by ball milling for an additional 24 hours. The slurry was degassed by stirring in a vacuum chamber for 2 hours to remove air bubbles. Immediately after the degassing process, the slurry was poured into a suspended chamber with slots through which it was drawn as a thin film onto a Mylar sheet. After that, the resulting tape is 12
It was dried at 0° C. for 1 hour. To make the porous tape, poly(methyl methacrylate) (PMMA) spheres were mixed into the well-mixed slurry 1 hour prior to degassing. The pore size of the porous layer can be controlled by the size and content of the polymer-based pore former. By laminating the tapes and hot pressing at 80° C. for 2 hours,
The porous layer and the dense layer fused at their respective interfaces, allowing them to form good connections at their respective interfaces. The sample was pre-sintered at 700°C for 4 hours to remove organic components and then sintered at 1100°C for final sintering. Good control of the sintering process ensured that the samples remained flat during sintering, which is important for Li/S infiltration and Li—S electrochemical performance tests.

Material Characterization D8 Advanced using a CuKα radiation source operating at 40 kV and 40 mA
with LynxEye and SolX (Bruker AXS, WI, USA
) was performed by powder X-ray diffraction (XRD). field emission scanning electron microscope (
The morphology of the samples was examined by FE-SEM, JEOL 2100F).

Electrochemical Characterization A Li|solid electrolyte|Li symmetric cell was fabricated and assembled in an argon-filled glove box. To measure the ionic conductivity of the garnet solid electrolyte, a high-density ceramic disc was coated on both sides with Au paste to act as a blocking electrode. Gold electrodes were sintered at 700° C. to form good contact with the ceramic pellet. The cell was then assembled as a 2032 coin cell with a highly conductive carbon sponge. The carbon sponge acted as a buffer and prevented damage to the garnet ceramic disc. Using the battery test clip,
It held and provided good contact with the coin cell. The edges of the cell were sealed with epoxy resin.
EIS was performed in the frequency range from 1 MHz to 100 mHz with a perturbation amplitude of 50 mV. σ=L
Conductivity was calculated using /(ZxA), where Z is the impedance of the real axis in the Nyquist plot, L is the garnet ceramic disc length, and A is the surface area. Activation energy was determined from conductivity as a function of temperature by using the Arrhenius equation.

Preparation and Characterization of Garnet Solid-Based Li—S Batteries All cells were assembled in an argon-filled glovebox. A solid state hybrid cell was assembled as a 2032 coin cell. Dimethoxyethane (DME) and 1,3-dioxolane (DOL) (volume ratio 1:
1) 1M bis(trifluoromethane)sulfonimide lithium salt (LiT
FSI, manufactured by Sigma) was used. Galvanostatic charge-discharge tests were measured using a cut-off voltage window of 1-3.5V. Dimethylformamide (DM
F) 10wt% carbon nanotube (CNT) ink was prepared, adding a few drops of CNT ink to the porous layer of the double-layer garnet framework and dried in vacuum at 100°C for 12 hours, then the porous Elemental sulfur powder was evenly distributed on the garnet and heated at 160° C. to melt the sulfur. The bilayer garnet framework was about 17 mg, which corresponds to about 20 mg/cm ² . The actual sulfur infiltrated into the bilayer garnet framework was about 2.5 mg, which corresponds to a mass loading of about 7.5 mg/cm ² . Completed cells were assembled in an Ar-filled glovebox. Liquid electrolyte was added to wash the sulfur cathode. The same amount of liquid electrolyte was used. The Li anode was made by thinning Li grains (from Sigma) in a hydraulic press. The cells were packaged as 2032 coin cells and sealed with epoxy to prevent air leaks at the edges.
Calculation of specific energy density (calculation of specific energy density of tested garnet bilayer Li—S battery) is shown in FIG.

With further optimization of Li metal and S cathode thickness and mass loading, 900 W
Cell energy densities in excess of h/kg are achievable.

FIG. 17 shows the estimated energy density of the parameter-optimized bilayer garnet solid-state Li—S battery.

This example provides a description of the solid state hybrid electrolytes of the present disclosure. This example also provides an example of the construction and characterization of such electrolytes.

Naturally Inspired Aligned Garnet Nanostructures Solid State Li Batteries (SSLiB) with Solid Electrolyte (SSE) Potentially Block Li Dendrite Penetration to High Energy Density with Improved Safety from the Application of Metallic Lithium Anodes is feasible. The ion migration behavior and ionic conductivity in Li-ion batteries are
It is greatly affected by torsion of electrode and electrolyte materials. Low tortuosity structures with straight ionic paths are highly desirable, but rather difficult to achieve in solid ionic conductors. We have developed a highly conductive garnet framework with multi-scale ordered mesostructures by a scalable top-down approach. Ion-conducting polyethylene oxide (PEO) was incorporated into mesoporous wood-templating aligned garnet nanostructures to yield a mixed hybrid ionic conductor termed garnet wood. Synergistic integration of aligned garnet with flexible and mechanically robust polymers leads to high ionic conductivity (1
. 8×10 ⁻⁴ S/cm) and good mechanical flexibility were both obtained. This work provides a new direction for the development of naturally-inspired low-torsion fast ionic conductors.

Inspired by the ordered structure of natural wood, a highly ionically conductive garnet network with a well-ordered mesostructure is disclosed by templated synthesis. By employing wood as a sacrificial template, we obtained multi-scale ordered porosity, low tortuosity and high specific surface area of garnet mesostructure. Garnet-type LLZO was chosen as a model system for making low-torsion ordered solid electrolytes because of its high ionic conductivity, good chemical stability with the Li anode, and wide electrochemical window. A composite electrolyte was developed by incorporating a PEO polymer electrolyte into aligned garnet templated by wood (referred to as garnet wood). The polymer electrolyte provides additional migration paths and supplements the mechanical strength of the composite structure. Li ions pass through garnet, polymer, and garnet-
It can effectively migrate along the polymer interface. As a result, garnet wood membranes provide an outstanding ionic conductivity of 1.8×10 ⁻⁴ S/cm at room temperature. Based on this concept, the design principles and fabrication process of aligned garnet wood electrolytes can be extended to a variety of solid electrolytes.

Because of its high growth rate, low cost, and high porosity, the American body tree was selected as a template for developing an ordered garnet solid electrolyte framework. A wood template was obtained by partially removing the lignin from the natural Polygonum tree by chemical treatment and then slicing it by compressing it perpendicular to the longitudinal direction (natural growth direction) of the wood (Fig. 19).
a). The wood was densified by mechanical pressing. The dense structure of the framework is maintained by the additional hydrogen bonds formed between adjacent cellulose fibers during densification. Morphological changes due to mechanical compression were investigated by scanning electron microscopy (SEM) measurements of multiple samples. Before compression, the microchannels in wood have a proximal cylindrical shape with an average diameter of 10-50 μm (FIGS. 19b and 19d). After compression, most of the previously observed microchannels were crushed into fissure-like gaps and some of the adjacent channels were connected (Figs. 19c and 19e). Although these open channels were severely deformed by compression, their respective highly ordered multiscale pore structures were unchanged (Fig. 19f),
It showed excellent absorbency when immersed in the precursor solution. For example, after soaking for 48 hours and vacuum drying at 70° C. for 4 hours, the mass of the wood template is 2.7 m
27.8% increase from g to 3.45 mg (Figure 25). The high absorptivity of the precursor solution, the flexibility of the template pore, and the scalability of the procedure indicate a cost-effective and productive method to fabricate SSEs with ordered mesostructures.

The LLZO films were obtained by calcining the garnet precursor-infiltrated wood in oxygen at 800° C. for 4 hours. The channel-aligned wood template has two unique features. First, the free channels in the wood template provide a reservoir that feeds the precursor solution to the template combustion reaction. Second, the 2-10 nm diameter aligned nanofibers in the wood template act as sacrificial pore formers for additional aligned porosity in the garnet film. Morphological changes after firing were characterized by SEM. The wood-templated ordered pore structure was also inherited in the resulting garnet framework at both the microscale (Fig. 20a) and the nanoscale (Fig. 20b). A highly ordered garnet film inherited directly from wood becomes flexible upon infiltration with a PEO-based polymer electrolyte (Fig. 20c). The crystalline phases of the garnet films were identified by X-ray diffraction (XRD). The XRD pattern of the ordered mesoporous garnet synthesized using the wood template (Fig. 20d) shows a cubic phase garnet, despite slight peak shifts at high angles due to aluminum (Al) doping and varying Li concentration. _{Li5La3Nb2O12 ( JCPDS #}
80-0457). As a representative structure of fast lithium-ion conducting garnets, Li ₅
La ₃ M ₂ O ₅ (M=Nb, Ta) is widely used. JCPDS#80-0457
A good XRD pattern match of the aligned mesoporous garnet with confirms that the wood-templating garnet is a conductive cubic phase.

High-resolution transmission electron microscopy (HRTEM) of the resulting ordered garnet reveals a well-defined and well-crystallized lattice structure of the garnet (Fig. 22a). The Miller index was calculated by the corresponding Fast Fourier Transform (FFT) pattern (inset of Fig. 22a)
. The lattice constant derived by HRTEM and FFT is 12.982 Å, consistent with previously reported values. In the HRTEM image of the larger garnet grains detached from the structure, grains with different orientations can be clearly distinguished (Fig. 21b). T.
The EM results show that the ordered mesoporous garnets are highly crystalline and have a well-connected polycrystalline structure. The composition of the garnet films was analyzed by electron energy loss spectroscopy (EELS). FIG. 21 shows the EELS spectrum with a fringed region of interest (ROI). EELS mapping shows the relative composition and distribution of oxygen, carbon and lanthanum. The overlapping region of the oxygen k-edge signal and the lanthanum n-edge signal is LL
Identify the ZO location. Carbon k-edge signals were rare throughout the sample, but small overlapping regions of oxygen and carbon k-edge signals were identified. This is due to the L
It shows that _{the i2CO3} impurity is minimal.

Garnet wood was made by infiltrating the ordered garnet with the PEO polymer electrolyte. Figure 2
2a characterizes polymer infiltration by energy dispersive X-ray spectroscopy (EDX). Uniformly distributed carbon signals from top and bottom to the aligned garnet channels indicate complete and uniform infiltration of the polymer electrolyte, which is essential for establishing sufficient Li-ion migration pathways. As suggested herein, three Li-ion migration pathways are possible. The first route is
An aligned PEO polymer electrolyte whose bulk ionic conductivity (no filler) is typically
It is as low as 10 ⁻⁷ S/cm at room temperature. The second route is the ordered garnet-polymer interface.
At the interface, the ordered mesoporous garnet behaves like a ceramic filler that can induce changes in the partial dynamics of the polymer to affect lithium ion migration. Intensive studies on the effect of fillers on the ionic conductivity of polymer electrolytes suggest that ceramic fillers with Lewis acid properties can facilitate lithium ion migration by anion binding and providing favorable conduction pathways. . A third route is a high volume percentage (approximately 6
8%) through aligned garnet nanostructures. Recent studies have shown that among the three migration pathways in garnet-polymer composite electrolyte systems, conduction through the garnet phase is the most favorable, using nuclear magnetic resonance (NMR) to track the migration of isotopically labeled Li ions. It is pointed out that it is clear by It should be noted that the typical bulk ionic conductivity of dense LLZO realized in our laboratory with the same composition is up to 2.2×10 ⁻⁴ at room temperature.
S/cm. However, this bulk ionic conductivity is difficult to achieve in conventional mesoporous structures due to high torsional migration paths due to random pores and poor solid-solid interfacial contact in numerous pore interstices. In contrast, the low tortuosity of the ordered mesoporous garnet structure does not block Li-ion migration along the normal direction of the flexible garnet wood and can effectively promote ionic conductivity.

The ionic conductivity of garnet wood was characterized by electrochemical impedance spectroscopy (EIS). A garnet wood membrane (0.1 cm ² area, 0.4 μm thickness) was assembled into a symmetrical cell with stainless steel as the blocking electrode and scanned from 1 MHz to 100 mHz. Figure 22b shows the Nyquist plots of electrolyte membranes tested from room temperature (25°C) to the melting temperature of PEO (65°C). The thickness and area of the electrolyte membrane were used to calculate the experimental ionic conductivity and the results are shown in Figure 22c. The garnet wood film is 1 at room temperature.
. An ionic conductivity of 8×10 ⁻⁴ S/cm was achieved. The theoretical ionic conductivity of a composite is the total contribution of each phase weighted by volume fraction. Given the conductivity of the PEO polymer electrolyte of 1.03×10 ⁻⁶ S/cm and the conductivity of garnet of 2.2×10 ⁻⁴ S/cm, the theoretical conductivity of garnet wood is 1.5×10 ⁻⁴ S/c
is m. In this low tortuosity structure with continuous conduction paths in each phase, the theoretical conductivity should be preserved if there is no conductivity enhancement at the two-phase interface. Therefore, the inventors believe that the increased interface contribution to the total ionic conductivity can lead to differences between theoretical and experimental conductivities.

と表現可能である。 As the operating temperature increases, the intersection of the semicircle with the real impedance axis decreases, indicating that increasing temperature improves ionic conductivity (Fig. 22b). At 95° C., the ionic conductivity increases to 1.1×10 ⁻³ S/cm, which exceeds room temperature performance6
. A threefold improvement. The temperature dependence of the ionic conductivity of garnet wood is expressed by the Arrhenius equation as

can be expressed as

where σ is the total ionic conductivity of garnet wood, A is the frequency factor, T is the absolute temperature, _EA
is the activation energy of garnet wood and k is the Boltzmann constant. The calculated activation energy of garnet wood is 0.38 eV, but it can be lowered further by adjusting the proportion of polymer electrolyte. This effect is attributed to various enhancement effects, such as increased volume fraction of the amorphous conducting phase and improved long-range polymer chain mobility.

As a proof of concept, a Li metal/garnet wood/Li metal symmetric cell was fabricated and Li stripping/plating tests were performed at room temperature (Fig. 22d). FIG. 22e shows each direction 3
A characteristic 180 hour cycle at a current density of 0.1 mA/cm ² for 0 minutes is shown. The voltage response of the symmetrical cell was stable at 50 mV with minor fluctuations. The symmetrical cell cycled successfully for over 600 hours with small polarization (Fig. 27). This long-term cycling performance indicates that garnet wood membranes enhanced by ordered mesoporous garnets can enable fast and stable ion transfer. Polymer electrolytes also greatly improve the mechanical flexibility of aligned garnets, making them viable for Li metal batteries.

Thus, garnet wood composite electrolytes with multi-scale ordered mesoporous structures have been described. Scalable compressed wood templates provide unique low tortuosity and high surface area mesostructures that are important for improved electrochemical performance and mechanical stability. The ion-conducting polymer supplements the mechanical strength of the ordered mesoporous garnet membrane and acts as a matrix to provide additional ion migration paths through the amorphous conducting phase and the garnet-polymer interface. Benefiting from these structural advantages combined with the inherent high ionic conductivity and low tortuosity of ordered mesoporous garnets, garnet wood composite electrolytes have a
. A high Li ion conductivity of 8×10 ⁻⁴ S/cm and 1.1×10 ⁻³ S/cm at 95° C. is realized. This is close to the bulk conductivity of garnet itself and further indicates an increased contribution due to the garnet/polymer interface. Garnet wood shows good potential as a low-torsion structure for highly conductive SSEs and provides model studies for the design and optimization of solid CPEs.

EXPERIMENTAL SECTION Material Preparation Stoichiometric LiNO ₃ (>99.0% from Aldrich), L
a(NO ₃ ) ₃ (99.9% or more, manufactured by Aldrich), Al( _{NO 3} ) 3.9H ₂ O (
98.0% or more, manufactured by Aldrich), ZrO(NO ₃ ) ₂ ·xH ₂ O (99.9%, A
ldrich), and acetic acid (>99.7%, Aldrich) in ethanol (>99.8%, Aldrich) at room temperature to make a garnet precursor solution. The total cation concentration of the precursor solution was 2 mol/L. 15% excess lithium nitrate was added to compensate for lithium loss at high firing temperatures.

The wood template was soaked in the above solution for 48 hours to impregnate with the garnet precursor. Excess solution was removed from the wood template and the sample was dried at 70°C for 4 hours. A subsequent heat treatment was performed in oxygen at 800° C. for 4 hours to burn out the wood template and sinter the dispersed precursor. Careful control of the sintering process preserved the microstructure of the wood template. Garnet film grinding and isopropanol (IPA)
) to obtain garnet nanoparticles and nanofibers for TEM investigation.

Bis(trifluoromethane)sulfonimide lithium salt (LiTFSI, >99.85%, Aldrich, EO:Li ^{+ )} in an argon-filled glovebox at room temperature.
= 8:1) containing PEO (Mv = 600,000, Aldrich) was dissolved in acetonitrile (anhydrous, 99.8%, Aldrich) by magnetic stirring to make a PEO-based polymer electrolyte. 15 wt% succinitrile (SCN, 99%, Aldri
ch) was added to the solution and the mixture was magnetically stirred until the SCN was completely dissolved. Prior to electrochemical testing, the drop-cast polymer electrolyte in ordered mesoporous garnet (garnet wood) was dried completely in vacuum at room temperature for 1 hour.

Material Characterization XRD was performed on a Bruker D8 Advance by Cu K radiation.
SEM images and their corresponding EDX images were acquired using a Hitachi SU-70 field emission SEM equipped with an energy dispersive X-ray spectrometer. TEM images were acquired using a JEM2100 field emission gun TEM equipped with an electron energy loss spectrometer for EELS studies. FFT images were calculated from high-resolution TEM images using the Gatan microscopy suite. EIS measurements were performed using a Solartron-1260 Impedance Gain Phase Analyzer on a symmetrical cell consisting of garnet wood between stainless steel plates as blocking electrodes. Before each EIS test, leave the cell in an environmental chamber at a given temperature for 30 minutes to reach thermal equilibrium, then scan from 1 MHz to 100 mHz,
Impedance curves at different temperatures were obtained. Li stripping/plating tests were performed using a Bio-Logic VMP3 multichannel potentiostat on symmetric cells consisting of garnet wood between Li metal foils as electrodes. 0.1 mA/c in each direction for 30 minutes at room temperature in an argon-filled glovebox
The cell was cycled at a current density of ^m2 .

23 to 29 show the production of the solid electrolyte of this example and its characteristic evaluation.

This example provides a description of the solid state hybrid electrolytes of the present disclosure. This example also provides an example of the construction and characterization of such electrolytes.

Lithium-ion Conductive Ceramic Fibers: A New Configuration for Flexible Solid-State Lithium-Metal Batteries Solid-state lithium-metal battery designs include fast lithium-ion conductors, good electrochemical stability, and scalable processing for device integration. A method is required. This example demonstrates a unique design of flexible lithium ion conductive ceramic fibers with the above characteristics for use in solid state batteries. The ceramic fibers are based on _{the garnet} -type conductor _Li7La3Zr2O12 , with a variety of lithium- _ion conductive cubic structures, low density, multi-scale porosity, large surface area/volume ratio, and good flexibility. showed desirable chemical and structural properties. The solid garnet fibers reinforced the solid polymer electrolyte and enabled high lithium-ion conductivity and long term Li cycling without failure and stable for more than 500 hours. This fiber also provided an electrolyte framework for designing 3D electrodes to achieve ultra-high cathode loadings (10.8 g/cm ² sulfur) for high-performance Li-metal batteries.

To achieve a finely distributed ion-conducting phase, the ideal configuration for the ion conduction and electrochemical reactions that occur in the battery is a fiber structure with a large area/volume ratio. Templating methods provide a simple yet effective way to generate the required structures. After soaking the fiber template in the ceramic precursor solution, the organic components are removed by pyrolysis. The resulting fibrous ceramics feature desirable properties that allow integration into flexible or rigid battery configurations. For example, the use of a ceramic fiber network builds lithium ion transport pathways within the polymer electrolyte and enhances the mechanical strength of the polymer. Alternatively, ceramic fibers can be combined with the electrode material in an interdigitated or concentric configuration to minimize electrolyte volume and maximize electrode utilization, thereby increasing the active electrolyte area during charge/discharge, the lithium ion interface. Movement and increased resistance to electrode volume change are possible.

This example demonstrated the fabrication of template-derived garnet-based lithium-ion conductive ceramic fibers that produced fibers with excellent properties for incorporation into solid-state batteries. The use of garnet fibers simultaneously reinforces the polymer electrolyte and 3D electrode structure for >500 hours of stable Li cycling to 10.8 for high performance Li metal batteries.
We have provided a solid lithium-ion conductive framework that achieves ultra-high sulfur loading of g/cm ² . The simplicity of the templating method is useful for the fabrication of ceramics with controlled composition and structure, opening up the possibility of constructing low-cost, durable solid-state batteries.

Materials and Methods Synthesis of Garnet Fibers Various heterovalent cations have been proposed to effectively stabilize cubic phase garnets and obtain high lithium ion conductivity at room temperature. 30ml containing 15vol% acetic acid
of ethanol to a stoichiometric amount of 2.31 g LiNO ₃ (99%, Alfa Ae
sar), 0.48 g Al( _NO3 ) _3.9H2O ( ₉₈ %, Alfa Aesar
), 6.94 g La( _NO3 ) _3.6H2O ( _99.9 %, from Alfa Aesar), and 5.0 g zirconium propoxide solution (70 wt%, Sigma Ald
Rich), Li _6.28 Al _0.24 La ₃ Zr ₂ O _11.98
Al-doped LLZO having a chemical composition of Excess LiNO ₃ (15 wt %) was added to compensate for lithium loss in the subsequent firing procedure. Cellulose fiber templates were made by annealing in air at 270°C for 10 hours, followed by ethanol (Sigma A
ldrich) and dried at 100° C. for 12 hours. After pretreatment, the templates were soaked in 2.5 mol/L LLZO precursor solution for 24 hours. The multi-scale porosity present in the porous template allowed uniform impregnation of the LLZO precursor. The thermal behavior of the LLZO precursor-infiltrated fiber template was analyzed by thermogravimetric analysis (TGA, STAR System). Calcination of the precursor-impregnated template was performed in oxygen at different temperatures to obtain garnet fibers. The 3D morphology of the garnet fibers was scanned using a 655 nm wavelength LK-H082 semiconductor laser model (from Keyence). 40
Using a CuKα radiation source operating at kV and 40 mA, the D8 Advanced Wi
The crystalline phase of LLZO was analyzed by powder X-ray diffraction on th LynxEye and SolX (XRD, manufactured by Bruker AXS). Energy dispersive spectrometer (EDS, Oxf
ord Instruments) equipped with an analytical scanning electron microscope (SEM, Hita
Chi SU-70) investigated the microstructure and elemental distribution.

Preparation of Garnet Fiber Reinforced Composite Polymer Electrolytes LiTFSI (Sigma
Aldrich) and PEO (about 600,000, Sigma Aldrich)
was dissolved to prepare a polymer matrix. Garnet fibers mounted on a Teflon block were repeatedly infiltrated with the lithium salt/polymer mixture. The composite polymer electrolytes were first dried in an argon-filled glovebox and then in a vacuum oven to remove residual solvent and then characterized for morphological and electrochemical performance. As a comparison, insulating Al ₂ O ₃ fibers made by the same templating method were made and incorporated into a polymer matrix as a control composite electrolyte. A Solartron-1260 impedance analyzer was used to measure the electrochemical impedance of the composite polymer electrolyte in a stainless steel/composite polymer electrolyte/stainless steel sandwich configuration. A Teflon spacer was provided to fix the thickness. Impedance tests were performed from 25° C. to 100° C. with an AC amplitude of 20 mV in the frequency range of 1 Hz to 1 MHz. A Li/composite polymer electrolyte/Li sealed symmetrical cell was used to evaluate the long-term lithium cycle stability and compatibility of the composite polymer electrolyte. In an environmental chamber (manufactured by Tenney), Arbin
A BT-2000 monitored the charge-discharge cycles of the symmetrical cells.

Fabrication of Garnet Fiber Electrode Configurations for Solid-State Li—S Batteries Following the same process as our previous work, Li ₇ La _2.75 Ca _0.25 Zr
A garnet powder with a composition of _1.75 Nb _0.25 O ₁₂ was synthesized. Dense electrolyte supports were fabricated by scalable tape casting and high temperature lamination methods. The laminated green tape was sintered at 1050° C. in a tube furnace under an oxygen atmosphere. Garnet fibers were sintered onto a garnet electrolyte support in oxygen to form the framework for cathodic infiltration. The cell was assembled in an argon-filled glove box with both O ₂ and H ₂ O levels below 0.1 ppm. Proper interfacial contact was achieved by melting lithium metal onto a dense garnet electrolyte support coated with an ultra-thin amorphous Si layer.

In N-methylpyrrolidone (manufactured by Sigma Aldrich), a mass ratio of 8:1:1
sulfur powder (manufactured by Sigma Aldrich), carbon nanotubes (Carbon
Solutions), and PVP (about 40,000, Sigma Aldrich
A sulfur slurry was made by mixing the product) to achieve a concentration of approximately 10 mg/mL. After 5 hours of sonication to obtain a homogeneous suspension of low concentration, droplets of sulfur slurry were repeatedly applied to the garnet fibers to wet out the open pores and dry them. The final sulfur loading was calculated by subtracting the weight of the unfinished cell before cathode slurry infiltration from the total weight of the finished battery and then multiplying by the weight ratio of sulfur in the cathode mixture. 1M in trace DME/DOL
LiTFSI was introduced to the cathode to promote sulfur/garnet contact before carbon felt was placed on the cathode side as a spacer and current collector. The battery was sealed as a coin cell with epoxy and connected to an Arbin BT-2000 for charge/discharge measurements.

Results and Discussion Lithium-ion conductive ceramic fibers were made by impregnating the template with the precursor solution followed by pyrolytic conversion. As shown in Figure 30, the flexible ceramic fibers retained the structural properties of the original fiber template, which differed significantly from the rigid network of discrete particles in conventional sintered porous ceramic compacts. The fibrous structure consisted of a network of continuous interlaced fibers and crossed yarns by weaving that influenced the spatial distribution of the lithium-ion conductive material and open pores. Lithium ion migration can occur throughout the fiber pattern and along the interior and surface of the polycrystalline fibers. Small polydisperse interconnecting pores existed between individual fibers, while large discrete pores of relatively uniform size and shape were found between adjacent yarns.

Characterization of Flexible Garnet Fibers Fibrous ceramic fibers are commercial products in various technical fields. Ceramic fiber and fiber production can be classified into direct spinning and indirect templating processes. The general steps of the templating process are shown in Figures 31a-31.
is illustrated by the representative image in c. (2) impregnating the template with a precursor solution; and (3) pyrolyzing the template at high temperature and sintering the remaining structure to transform the precursor into nano-sized ceramic oxides. (thermogravimetric analysis in FIG. 34a). The garnet fibers essentially retained the characteristic physical properties of the original template, which consisted of continuous individual microfibers approximately 10 μm in diameter arranged mostly parallel and twisted to each other. For cross-sectional SEM images, see Figures 34b-34d. The fibers were bundled together as intersecting threads of approximately 200 μm diameter, forming a periodic weave pattern. The heat treatment formed inter-fiber pores and large inter-yarn pores ranging in diameter from 10 to 20 μm.

For quality control and inspection purposes, a large area of garnet fiber geometry was mapped by application of non-destructive 3D laser scanning. The reconstructed digital structure of FIG.
A book-by-book plain weave fiber pattern is shown. The height profile of this topology indicates the distance between the highest point of crossing yarn branches in the pattern and the lowest point that touches the ground. While the branch areas were typically around 200 μm high, some of the edge areas showed slightly higher values. Edge curl-up can be eliminated by strict process control to ensure proper sintering. Figure 31e shows the salient physical features of garnet fibers. Unlike the rigid appearance of regular sintered ceramics, the garnet fibers were similar to the template with respect to constant flexural strength, geometric accommodation, and resistance to organic solvent attack. The simplicity, rapidity, and cost-reduction properties of the templating method also enable a smooth transition from small-scale fabrication to large-scale manufacturing. FIG. 35 illustrates how garnet fibers can be tailored to specific shapes in large dimensions.

In addition to making versatile ceramic structures, the templating method offers chemical flexibility in synthesizing complex oxides. Garnet-type conductors with a nominal composition of Li ₇ La ₃ Zr ₂ O ₁₂ exist in two phases, cubic and tetragonal. The cubic structure favors high ionic conductivity, but is stable only at high temperatures. As shown in Fig. 31f, by simple compositional design by doping multivalent cations and optimizing the lithium concentration in the precursor solution, 800 °C
Stabilization of the cubic phase can be achieved at a low sintering temperature. Care should be taken that the firing process avoids oversintering, which causes excessive volatilization of lithium and separation of the lanthanum zirconate (LZO) phase. In Fig. 31g, the uniform distribution of the constituent chemical elements of the garnet fiber was confirmed by EDS. Elemental aluminum, due to its simplicity and low cost, served as a doping cation to stabilize the cubic phase and promote sintering.

Garnet Fiber Reinforced Flexible Composite Polymer Electrolytes As shown in Figure 32, the structural and chemical advantages of garnet fibers make them ideal for reinforcing the mechanical and electrochemical properties of composite polymer electrolytes (CPEs). becomes. Free-standing CPEs were made by vacuum infiltrating garnet fibers with a solution containing PEO and lithium salts. The dried CPE in Fig. 32a is soft and flexible in appearance, which successfully draws fluid into multi-level pores through efficient wetting and capillary action, and strong physical interaction between the garnet fibers and the polymer matrix. This indicates that a physical connection is now possible. Cross-sectional microstructural analysis further confirmed that the CPE appeared fully densified without the conspicuous pores of Figure 36a. The cured CPE, while appearing as a uniform solid, was composed of physically and chemically unique ceramic and polymer phases separated by different interfaces. Thus, both components influence lithium ion migration kinetics within the CPE, which is illustrated by the schematic diagram in Figure 32b. Most continuous ceramic fibers are
Bundled as threads penetrating the PEO matrix. Threads are generally oriented perpendicular to the vertical direction of lithium ion migration within the CPE (thick arrows). Lithium ions migrate (1) through the PEO to the "bottom" of the garnet fiber and from the PEO into the highly conductive fiber, and (2) along the length of the fiber until they reach the "top" of the yarn. after moving with PE
Move across the CPE in a multi-step process of returning to O. This process
Involvement of the resistant garnet/polymer interface or diffusion through the polymer bulk (dotted arrow)
, the diffusion of lithium ions becomes independent of the solvated lithium content of the polymer matrix.

FIG. 32c shows typical impedance plots of CPE measured at different temperatures.
The lithium ion migration process was divided into ionic conduction within the CPE (high frequency arc) and ion blocking at the CPE/stainless steel interface (low frequency sloping tail). The resistance of the CPE was determined by reading the real impedance value at the high frequency intercept of the arc. FIG. 32d is an analysis of the temperature dependence of lithium ion conductivity using an Arrhenius plot. In general, lithium ion conductivity exhibited nonlinear behavior with increasing temperature. temperature is 60
Above °C, the activation energy decreased slightly, which corresponds to the phase transition temperature of PEO. It is known that when the PEO-LiX system undergoes a thermal phase transition, the conductivity changes sharply with the activation energy. In contrast, the energy barrier to lithium-ion conduction in crystalline garnet is expected to remain constant over the tested temperature range. Therefore, from the smooth transition of activation energies observed in CPEs, the formation of long-range garnet fibrous networks and continuous channels along the fiber surface leads to the dominance of the fibrous garnet phase in lithium-ion conduction within the CPEs. is suggested. Li
To further illustrate the effect of ion-conducting garnet fibers on the electrochemical performance of CPE, a control sample was constructed using insulating Al ₂ O ₃ fibers made by the same templating method (Fig. 36b). The EIS of this control sample was measured as a function of temperature (Fig. 36c). The resulting high impedance and corresponding low room temperature of 2.48×10 ⁻⁶ S/
The conductivity of cm is for Al ₂ O ₃ since this is essentially the room temperature polymer conductivity.
phases and the ceramic/polymer interface contribute little to the Li-ion conduction within the CPE, confirming the dominant contribution by the Li-ion conducting garnet fiber phase.

The measured lithium ion conductivity of Garnet CPE is 2.7×10 ⁻⁵ S/
cm and 1.8×10 ⁻⁴ S/cm at 60° C. These are ^an order ^of magnitude higher than the conductivity of the PEO-LiX polymer electrolyte system with 85 vol. This has a reported ionic conductivity of 4× at 25°C.
10 ⁻⁴ S/cm, while due to the Al-doped garnet containing only 15 vol % CPE in volume fraction. The corresponding theoretical volume fraction normalized CPE conductivity at 25° C. is 6
×10 ⁻⁵ S/cm, which is consistent with the measured CPE conductivity. Therefore, by increasing the garnet phase volume fraction by optimizing the densification process of garnet ceramic fibers, a significant improvement in conductivity can also be easily realized.

Long-term lithium cycling stability and compatibility of CPE was evaluated by galvanostatic stripping (0.5 h) and plating (0.5 h) measurements. In Fig. 36e, we achieved stable DC cycling as a function of current density over the entire test period at 60°C. When the current density is set to 0.05 mA/cm ² and 0.1 mA/cm ² ,
Symmetric cells achieved overvoltages as low as 15 mV and 27 mV, respectively. As the current density increased to 0.2 mA/cm ² , the overpotential increased sharply and reached a maximum value of 47 mV. Over the rest of the test period, the overvoltage gradually decreased and stabilized at 41 mV. The overall resistance and impedance measurements obtained by voltage versus current density (Fig. 37a) decreased with increasing current density and operation time, which was attributed to the activation diffusion process in the CPE and the improvement of the lithium/CPE interface. be done. We also achieved stable galvanostatic cycling of CPE at low operating temperature (Fig. 37b) and high current density (Fig. 37c).
For practical applications, further reduction of overvoltage and extension of operating life requires increased garnet phase loading in multi-level pores and adoption of sulfur-crosslinked polymers.

3D Electrode Configurations in Garnet Fiber Structures Garnet fibers can also be used to construct 3D electrode configurations by sintering the fibers on a dense electrolyte support (FIG. 33a) and infiltrating the fiber structure with electrode material. A Li—S battery is presented here as a proof-of-concept due to the high energy density and low materials cost of a sulfur cathode. The well-distributed pores of the fibrous structure made the fibers readily available for high sulfur loadings. FIG. 33b shows an SEM image of garnet fibers loaded with 10.8 mg/cm ² of sulfur. The garnet fibers were bound together and the open pores were filled with a sulfur/carbon mixture. In Figure 38a, an EDX linear scan across the region of the yarn/electrolyte interface reveals sulfur/carbon on the garnet yarns and the exposed surface of the electrolyte. In FIG. 38b, cross-sectional analysis shows that the sulfur/carbon mixture penetrates through the porous fibers and coats the individual fibers to reach the dense electrolyte surface. In Fig. 33c, under high magnification, EDX mapping confirms uniform elemental distribution of sulfur/carbon supported on garnet fibers and intimate contact between successive lithium-ion-conducting, electronic-conducting, and sulfur phases. .

A solid-state Li—S battery was assembled to demonstrate the electrochemical advantages of the garnet fiber 3D electrode configuration. A trace amount of liquid electrolyte was added to activate the sulfur and improve the contact between the garnet and the sulfur without creating an undesirable lithium ion barrier. This hybrid configuration was still predominantly solid despite the addition of trace amounts of liquid electrolyte. In FIG. 39, the dense garnet electrolyte support acted as a lithium ion conductor, an electronic insulator, and a lithium polysulfide shuttle shield.

The charge-discharge profile for a solid Li—S battery loaded with 10.8 mg/cm ² sulfur and cycled at 0.15 mA/cm ² is shown in FIG. 33d. Sulfur cathode is about 2.1V
and two discharge plateaus at about 1.8 V, whereas the charge profile showed about 2.38 V
There was a plateau corresponding to V and about 2.43V. The relatively large polarization overvoltage (approximately 0.6 V) during charging and discharging is thought to be due to the relatively thick garnet electrolyte and the contribution of polarization by impurities on the surface of the garnet electrolyte, but these contribute to the thinning of the electrolyte and the moisture-proof L
It can be improved by adding an iF phase or another liquid electrolyte. The discharge capacity reached a high value of 1,250 mAh/g at the 5th cycle due to the improved utilization of sulfur by the continuous wetting process with the addition of trace amount of liquid electrolyte. A solid-state Li—S battery was also successfully cycled at a current density of 0.75 mA/cm ² with a 3D Li-ion conducting electrode structure (FIG. 40). To maximize the volume utilization of the fiber electrode configuration, almost double the sulfur content (approximately 18.6 mg/cm ² ) was tried. These high sulfur loadings led to premature cycle degradation as well as reduced utilization (FIG. 41). However, 800mAh/
The stable and reversible high capacity of g confirmed the energy storage capacity of the electrode framework constructed with garnet fibers.

The theoretical energy density of a Li—S battery that separates lithium and sulfur using a high-density solid electrolyte was estimated to be as high as 500 Wh/kg at the cell level. As a comparison,
Figure 42a shows the energy density of a solid-state Li-S battery utilizing ceramic fibers for sulfur support and a variable density electrolyte structure at the interface with lithium. With a 500 μm thick electrolyte support and 63% utilization of the electrolyte area, the achievable energy density is 71 Wh/
kg. A high energy density of 281 Wh/kg is also possible by reducing the thickness of the electrolyte support to 100 μm and carrying more sulfur by matching the electrolyte/electrode area. Further thinning of the electrolyte support requires the development of complex electrolyte structures to maintain mechanical strength. Figure 42b shows a thin dense electrolyte (20 µm
) and a porous substrate (70 μm). It is also possible to inject lithium metal into the pores to create a sufficient lithium/garnet migration interface and further enhance mechanical strength. By integrating garnet fibers and bilayer supports, even higher energy densities of 352 Wh/kg can be achieved, which far exceeds the capacity of state-of-the-art lithium-ion batteries.

The inventors have successfully demonstrated flexible lithium-ion conducting garnet fibers made by a simple templating method. The unique structural advantages of flexible fiber garnet fibers allow the creation of solid electrolyte frameworks with continuous lithium-ion conducting pathways and high surface-to-volume ratios. By incorporating this fiber into a solid polymer electrolyte,
Improved lithium ion conductivity and stable Li cycling for more than 500 hours are possible.
Also, through the use of tuned garnet fibers, 3D porous electrodes were fabricated to accommodate high sulfur loadings (10.8 mg/cm ² ) and the resulting batteries yielded capacities as high as 1000 mAh/g. . Current laboratory scale fabrication procedures are transferable to affordable and reliable industrial scale production. Initial efforts to date have focused on solid-state lithium-metal batteries, but the novel structural design strategies utilized in this example apply to other solid-state devices for energy storage and conversion beyond lithium-ion technology. expected to be possible.

Figures 32-42 represent the flexible solid electrolytes of this example and the characterization of these electrolytes. These figures include thermogravimetric analysis, additional SEM images, photographs of garnet fibers in large dimensions, characterization of composite polymer electrolytes, SEM images of sulfur-infiltrated garnet fiber electrodes, characterization of garnet and sulfur stability, Performance of high sulfur supported solid-state batteries as well as energy density calculations are presented.

This example provides a description of the solid state hybrid electrolytes of the present disclosure. This example also provides an example of the construction and characterization of such electrolytes.

Flexible Solid Ion-Conducting Membrane with 3D Garnet Nanofiber Network for Lithium Batteries ), the state-of-the-art lithium-ion battery (LI
B) Beyond technology, it is highly desirable to replace conventional ion intercalation anode materials with metallic lithium anodes. In the present example, garnet _{- type Li6.4La3Zr2Al0.2} , which provides continuous Li ⁺ _transport channels in PEO-based composites
A three-dimensional (3D) Li-ion conducting ceramic network based on O ₁₂ (LLZO) lithium-ion conductors is described. This composite structure further provides structural reinforcement that enhances the mechanical properties of the polymer matrix. Flexible solid electrolyte composite membranes are 2.5×
It showed an ionic conductivity of 10 ⁻⁴ S/cm. This membrane demonstrates a Li|electrolyte|Li symmetric cell in repeated lithium stripping/plating at room temperature at current densities of 0.2 mA/ ^cm for around 500 hours and 0.5 mA/ ^cm for over 300 hours. dendrites can be effectively blocked. These results provide an all-solid-state ionically conductive membrane applicable to other electrochemical energy storage systems such as flexible lithium-ion and lithium-sulphur batteries.

This example describes flexible solid state lithium ion conducting membranes based on three-dimensional (3D) ion conducting networks and polymer electrolytes for lithium batteries. The 3D ion-conducting network is a percolation garnet-type Li _6.4 La ₃ Zr ₂ Al _0.2 O ₁₂ (L
LZO) based on solid electrolyte nanofibers. The film exhibits excellent electrochemical stability to high voltage and high mechanical stability as it effectively blocks lithium dendrites. This work represents a major breakthrough in enabling high performance lithium batteries.

In the present example, garnet-type _Li6.4La3 , which provides continuous Li ⁺ transport channels in PEO-based composite electrolytes, as _an all-solid-state ionically conductive membrane for lithium batteries.
We have successfully developed a three-dimensional (3D) ceramic network based on Zr ₂ Al _0.2 O ₁₂ (LLZO) nanofibers. (a) high ionic conductivity approaching 10 ⁻³ S/cm at room temperature due to optimized element substitution, (b) good chemical stability to lithium metal, and (c
) Garnet-type lithium-ion conductive ceramics were selected as the inorganic component due to several desirable physical and chemical properties such as good chemical stability to air and moisture.
Figure 47 shows a schematic structure of a 3D LLZO/polymer composite membrane. The LLZO porous structure consists of randomly distributed and interconnected nanofibers that form a continuous lithium-ion conducting network. The Li salt/PEO polymer is then filled into the porous 3D ceramic network to form a 3D garnet/polymer composite membrane. Unlike conventional methods of making polymer electrolytes, the 3D garnet/polymer composite membrane does not require mechanical mixing of the filler with the polymer, instead we use a preformed 3D ceramic structure with Li The desired polymer-composite-electrolyte hybrid structures can be obtained by direct immersion in salt/polymer solutions, which simplifies the fabrication process and avoids filler agglomeration.

Results and Discussion Figure 48 schematically illustrates the procedure for synthesizing a flexible solid garnet LLZO nanofiber reinforced polymer composite electrolyte. As shown in Fig. 48a, the associated garnet LLZO
After making garnet LLZO nanofibers by electrospinning of polyvinylpyrrolidone (PVP) polymer mixed with salt, in air at 800° C. for 2 hours,
The produced nanofibers were sintered. Nanofibers were collected over a thin non-woven fabric on the drum collector of the electrospinning setup.

Schematic fabrication of FRPC Li-ion conducting membranes using 3D porous garnet nanofiber networks is shown in Fig. 2b. A PEO polymer mixture is made with a Li salt such as bis(trifluoromethane)sulfonimide lithium salt (LiTFSI). and Li salt/
The PEO polymer is reinforced with 3D nanofibers to form a composite electrolyte, which can be referred to as a fiber reinforced polymer composite (FRPC) electrolyte membrane. Compared to filler-containing polymer electrolytes, FRPC electrolyte membranes have superior mechanical properties due to the continuous nanofiber structure that maintains the framework of the 3D garnet nanofiber network and improves the integrity of the polymer electrolyte. It is thought that

The morphologies of spun PVP/garnet salt nanofibers and calcined garnet nanofibers were characterized by scanning electron microscopy (SEM), as shown in Figures 48c and 48e. Before firing, the PVP/garnet salt nanofibers have a smooth surface,
The diameter is 256 nm on average. The corresponding diameter distribution is shown in Figure 48d. After calcination in air at 800° C., the PVP polymer was removed to obtain garnet LLZO nanofibers. The average diameter of nanofibers decreased to 138 nm. Fig. 48 shows the diameter distribution of each
f. After annealing, the garnet nanofibers are “cross-bonded” to each other and cross-linked 3D
A garnet nanofiber network was constructed. The large spatial volume between the nanofibers facilitates Li salt/polymer infiltration to construct composite membranes. Fig. 48
shown in g. By adopting a flexible electrolyte membrane, a flexible solid lithium battery can be constructed. It should be noted that the design of flexible 3D ion-conducting networks mainly relies on ceramic garnet nanofibers, for which thin and mechanical A stable structure is desirable. In order to achieve thinner polymer composite electrolytes while maintaining good mechanical stability, several important parameters need to be considered and the electrospinning process (e.g. collection time, drum rotation speed, syringe movement rate, etc.), precursor solution preparation (e.g., garnet salt concentration, polymer concentration, polymer molecular weight, solvent selection, etc.), and thermal annealing optimization (e.g., heating rate, temperature, time, cooling rate, etc.). .

FIG. 49 shows the morphological characterization of garnet nanofibers and the resulting FRPC electrolyte. The garnet nanofibers were joined together at their respective intersections to form a crosslinked network, as shown in Figure 49a. These interconnected garnet nanofibers provide continuous ionic conduction pathways by extending long-distance lithium transport channels, which should be superior to isolated particle fillers dispersed in regular polymer matrices. Figures 49b and 49c show transmission electron microscopy of garnet nanofibers (
TEM) image. Garnet nanofibers have a polycrystalline structure consisting of interconnected small crystallites that make up long continuous nanofibers (Fig. 49b). Figure 53 shows
FIG. 2 shows a magnified TEM image of garnet nanofibers with an average particle size of 20 nm in diameter. Figure 4
9c shows a highly crystalline structure of garnet grains.

The morphology of the FRPC electrolyte was examined by SEM (Figures 49d-f). The FRPC electrolyte exhibited a smooth surface derived from the PEO-LiTFSI polymer (Fig. 49d).
Inside the FRPC electrolyte, a 3D porous garnet nanofiber network supports the main structure of the composite, and the PEO-LiTFSI polymer is observed to infiltrate the porous garnet membrane and fill the spaces between the garnet nanofibers. rice field. A cross-sectional image of the FRPC electrolyte showed a thickness of 40-50 μm (FIG. 49e). Garnet nanofiber and PEO
- Heat treatment of the FRPC electrolyte at 60 °C, slightly above the polymer melting temperature (T _m ), to improve the interphase contact between the LiTFSI polymer and transform the molten PEO-LiTFSI polymer into a 3D porous garnet nanofiber network. Allow sufficient infiltration. After heat treatment, enough garnet nanofibers were embedded in the PEO-LiTFSI polymer, as shown in Fig. 49f. Garnet nanofibers were grown up to 500 nm in average diameter by the PEO-LiTFSI polymer coating. The interconnected pores were filled with polymer to maintain good lithium ion transport. FRPC electrolyte membranes are proposed to have three ion-conducting pathways: an interconnected ceramic garnet nanofiber network, a continuous garnet fiber/polymer interface, and a Li-salt-containing polymer matrix. Due to the higher ionic conductivity of garnet-type electrolytes than Li-salt-containing polymer electrolytes, we believe that the former two ionic conduction pathways are the dominant factors that improve the ionic conductivity of electrolyte membranes.

Garnet nanofiber formation during the sintering process was investigated by thermogravimetric analysis (TGA). TGA was performed under air flow with a rapid heating rate of 10°C/min. Figure 50a shows the PV
Fig. 2 shows TGA profiles of spun nanofibers containing P-polymer and garnet precursor. This result indicates that stable garnet nanofibers were formed with a stable weight above 750°C. Figure 50b compares the TGA profiles of PEO/LiTFSI and FRPC electrolytes. Both electrolytes were thermally stable up to around 200°C. In the rapid heating process, the polymer begins to decompose above 200°C and
It showed a large mass reduction due to almost complete decomposition at around °C. A ramp of 400° C. was the decomposition of LiTFSI. For the FRPC electrolyte, the weight was stable at 500° C., the others were garnet nanofiber membranes due to the excellent stability of the garnet material in air. In the case of the polymer electrolyte, the weight was stable at 650° C., leaving the decomposed LiTFSI salt.

Thermal stability is an important consideration when using solid electrolytes, especially polymer electrolytes.
Conventional liquid electrolytes, such as carbonate electrolytes, are prone to thermal runaway when the battery is in extreme conditions of short circuit, overcharge, and high temperature. Polymer electrolytes are a safer option than liquid electrolytes due to their relatively high thermal stability. Because conventional polymer electrolytes are built on their own polymer structure and the fillers cannot provide sufficient mechanical support for the electrolyte, they inevitably melt and shrink at high temperatures, especially above the polymer pyrolysis temperature, resulting in Direct contact between the cathode and anode can result, which is a major safety concern. FRPC electrolytes can address this issue because the garnet nanofiber membrane in the polymer electrolyte provides a ceramic barrier that physically prevents contact between the cathode and anode even after loss of polymer.

Figures 50c and 50d compare combustion tests of a conventional polymer electrolyte and the novel FRPC electrolyte developed in this study. PEO-LiTFSI in the same way
While making the polymer, a conventional polymer electrolyte was made by using garnet nanopowder (vs. 3D garnet network) as a filler. The mass ratio of polymer and filler was controlled at 4:1. In Figure 50c, the polymer electrolyte ignited the moment it approached the igniter and quickly burned out to ash. This high flammability indicates poor thermal stability of the polymer electrolyte. In comparison, the FRPC electrolyte exhibited outstanding thermal stability even when the polymer component was lost, and the garnet nanofiber membrane still retained its structure (Fig. 50d). The low flammability that FRPC electrolytes can offer enhances the safety of all lithium metal and lithium ion batteries.

The powder X-ray diffraction (XRD) pattern of LLZO garnet nanofibers calcined at 800° C. for 2 hours is shown in FIG. 51a. Almost all diffraction peaks are cubic phase garnet Li
Matches very well _{with 5La3Nb2O12 (} JCPBS card _80-0457 ) _. Li
₅ La ₃ M ₂ O ₅ (M=Nb, Ta) is the first example of a garnet-like structure treated with high-speed lithium ion conduction, and is a representative structure widely used as a model for investigating the garnet structure of LLZO materials. is. Therefore, here the standard Li ₅ La ₃ Nb ₂ O ₁₂ X
RD profiles were used to identify synthesized garnet nanofiber structures. Traces of La ₂ Zr ₂ O ₇ were identified, but other impurities were below detection limits. According to the TG results, decomposition of the precursor to oxide is complete at about 750°C. Further heating to 800° C. caused the oxides to react to form a cubic phase LLZO garnet structure. However, a small amount of L
The a ₂ Zr ₂ O ₇ phase can also be formed by lithium loss at high temperatures.

The overall lithium ion conductivity of the FRPC electrolyte was characterized by electrochemical impedance spectroscopy (EIS). FIG. 51b shows a typical Nyquist plot of an FRPC electrolyte sandwiched between stainless steel blocking electrodes in the frequency range of 1 Hz to 1 MHz. Each impedance profile has a real axis intercept at high frequencies, a semicircle at intermediate frequencies,
and a sloping straight line at low frequencies. The extended semicircle on the real axis and the intercept of the semicircle in the high and intermediate frequency regions represent the bulk relaxation of the FRPC electrolyte. The low frequency tail is due to lithium ion migration and non-uniformities in the surface of the blocking electrode. Figure 51c shows the FRPC
Figure 3 shows Arrhenius plots of electrolytes; Lithium ion conductivity was calculated based on the thickness of the FRPC electrolyte and the diameter of the stainless steel electrode. The lithium ion conductivity of cubic phase LLZO garnet pellets is as high as 10 ⁻³ S/cm, while lithium salt-filled PEO is typically on the order of 10 ⁻⁶ to 10 ⁻⁹ S/cm at room temperature. Our FRPC electrolyte, which combines a conductive cubic LLZO garnet and lithium PEO, is 2.0 at room temperature.
It can exhibit a fairly high ionic conductivity of 5×10 ⁻⁴ S/cm.

Another major factor determining polymer electrolyte application in high voltage lithium batteries is the large electrochemical window. Figure 51d shows the results of a linear sweep voltammetry (LSV) profile of the FRPC electrolyte using lithium metal as the reference counter electrode and stainless steel as the working electrode. The FRPC electrolyte exhibits a stable potential window up to 6.0 V vs. Li/Li ^{2 +} , indicating that this conductive membrane can meet most requirements of high voltage lithium batteries.

A Li|FRPC electrolyte|Li symmetric cell was used to evaluate the mechanical stability of FRPC electrolyte membranes against Li dendrites. In the constant current charging/discharging process, lithium ions mimic the charging/discharging behavior of lithium metal batteries by plating/stripping the lithium metal electrodes. Figure 52a presents a schematic diagram of a symmetrical cell setup. The FRPC electrolyte membrane was sandwiched between two lithium metal foils and sealed to form a coin cell. Figure 52b shows 0.
Figure ² shows the voltage profile as a function of time for a cell with a FRPC electrolyte membrane cycled at a constant current density of 2 mA/cm2 and a temperature of 15°C for over 230 hours. Symmetrical cells were charged and discharged cyclically for 0.5 hours. A positive voltage is Li stripping and a negative voltage value represents the Li plating process. In the first 70 hours, the cell voltage rose slightly from 0.3V to 0.4V and then stabilized at 0.4V.

As the test temperature increased to 25° C., the voltage decreased to 0.3 V due to the enhancement of ionic conductivity at high temperature, as shown in FIG. 52c. In subsequent long cycles, the voltage continued to drop to 0.2 V as the cycle time progressed to 700 hours (Fig. 54).
. Voltage fluctuations were caused by temperature changes in the surrounding environment. Two voltage profiles of a symmetrical cell at two different stripping/plating process times were compared, as shown in FIG. The voltage hysteresis decreased significantly with increasing cycle time. This voltage drop is significantly different from liquid electrolyte systems, where voltage typically increases over time, and is primarily due to non-uniform Li deposition and severe electrolyte decomposition leading to an increase in impedance. Similar voltage drops have been observed in recent research on polymer electrolytes, but the reason why the voltage continues to drop with cycle time has not been explained. Based on our understanding, the drop in voltage is attributed to the improvement of the interface between the electrolyte membrane and lithium metal during repeated electrodeposition of Li, measured at 300, 500, and 700 hours. This is confirmed by the EIS spectrum of the symmetrical cell that was processed (Fig. 52d).
. The depressed semicircle at low frequencies indicates a decrease in interfacial impedance between the electrolyte membrane and lithium metal during cycling. Even at high frequency (Fig. 52e), the semicircle becomes smaller with cycle time, indicating a decrease in the bulk impedance of the electrolyte membrane. As the current density increased to 0.5 mA/cm ² , the voltage increased to 0.3 V, and the cell also decreased in voltage slightly with time up to 1000 hours (Fig. 52f), but this It shows good cycle stability with cycle life.

Thus, a 3D garnet/polymer composite all-solid-state ion-conducting membrane was synthesized for lithium batteries. A 3D garnet nanofiber network was fabricated by electrospinning and high temperature annealing. The garnet nanofibers constructed an 'interconnected' 3D structure that provides long-distance lithium-ion migration pathways and enhances the polymer matrix by providing structural reinforcement. This flexible solid electrolyte composite membrane is 2.5×
It showed an ionic conductivity of 10 ⁻⁴ S/cm. This membrane has a current density of 0.2 mA/ ^cm2 for around 500 hours and a current density of 0.5 mA/cm2 for 300 hours and over 300 hours.
The dendrites of |electrolyte|Li symmetric cells can be effectively blocked in repeated lithium stripping/plating at room temperature at A/cm ² . A decrease in voltage is observed with cycle time for the symmetric cell, which is attributed to the improvement of the interface during repeated electrodeposition of lithium. This example describes the development of 3D Li-ion conducting ceramic materials in solid electrolytes with potential applications in other electrochemical energy storage systems such as flexible lithium-ion and lithium-sulphur batteries.

While the present disclosure has been described with respect to one or more specific embodiments and/or examples, it is understood that other embodiments and/or examples of the disclosure are possible without departing from the scope of the present disclosure. be.

Claims (53)

an inorganic solid electrolyte (SSE);
a polymer material disposed on at least part or all of the outer surface of the solid electrolyte material;
A solid hybrid electrolyte comprising: Claim 1, wherein the SSE material is a monolithic SSE body or a mesoporous SSE body.
A hybrid electrolyte as described in . 2. The hybrid electrolyte of claim 1, wherein said SSE material is a disc, sheet, or polyhedron. 2. The hybrid electrolyte of claim 1, wherein said polymeric material has a thickness of between 10 nm and 10 microns at one or more points. 2. The hybrid electrolyte of Claim 1, wherein the SSE comprises a plurality of fibers or strands. 6. The hybrid electrolyte of claim 5, wherein said fiber is present as a woven substrate. 6. The hybrid electrolyte of claim 5, wherein said fibers are randomly arranged or arranged. 6. The hybrid electrolyte of claim 5, wherein said fibers or strands of said inorganic SSE material form an interconnected 3D network. wherein the SSE material is a lithium ion conducting SSE material, a sodium ion conducting SSE
material, or a magnesium ion-conducting SSE material. The lithium ion conductive SSE material is a lithium perovskite material, _Li3N ,L
i-β-alumina, lithium superionic conductor (LISICON), Li _2.88 PO _3.
9. Selected from _the group _{consisting of86N0.14} (LiPON), _Li9AlSiO8 , _Li10GeP2S12 , _lithium garnet materials, doped lithium garnet materials, lithium garnet composites, and combinations thereof _. A hybrid electrolyte as described in . _The lithium garnet material is cation-doped Li ₅ La ₃ M ¹² O ₁₂ (where
M ¹ is Nb, Zr, Ta, or a combination thereof), cation-doped Li ₆ La ₂ B
_aTa2O12 , cation _- doped _{Li7La3Zr2O12 ,} and _cation -doped _Li
11. ^The _{claim 10} , wherein ^M1 is Nb, Zr, Ta, or combinations thereof, and _the cationic dopant is barium, yttrium, zinc, or combinations thereof. hybrid electrolyte. The lithium garnet material is Li ₅ La ₃ Nb ₂ O ₁₂ , Li ₅ La ₃ Ta ₂ O _{1
2 , Li7La3Zr2O12 , Li6La2SrNb2O12 , Li6La2BaNb _ _ _ _
2O12 , Li6La2SrTa2O12 , Li6La2BaTa2O12 , Li7Y3 _ _ _ _ _
Zr2O12 , Li6.4Y3Zr1.4Ta0.6O12 , Li6.5La2.5Ba _ _ _ _
0.5 TaZrO12} ^, _{Li6BaY2M12O12 , Li7Y3Zr2O12 , Li6 _ _ _ _
. 75BaLa2Nb1.75Zn0.25O12 , Li6.75BaLa2Ta1.7 _ _ _ _ _
11.} The hybrid electrolyte of claim 10, which is _5Zn0.25O12 , and _combinations thereof. The sodium ion conducting SSE material is β″-Al ₂ O ₃ , Na ₄ Zr ₂ Si ₂ P
10. The hybrid electrolyte of claim 9 selected from the group consisting of _O12 (NASICON), cation-doped NASICON, and combinations thereof. The magnesium ion-conducting SSE material is Mg _1+x (Al,Ti) ₂ (PO ₄ )
₆ , where x is 4 or 5, a NASICON-type magnesium ion-conducting material, and combinations thereof. at least one cathode material wherein the inorganic SSE has pores exposed to the outer surface of the inorganic SSE, and the hybrid electrolyte is disposed in at least a portion of the pores; and/or
or further comprising at least one anode material,
When at least one cathodic material and at least one anodic material are disposed in at least a portion of the pores, the at least one cathodic material and the at least one anodic material are discrete and electrically isolated from the inorganic SSE. 11. The hybrid electrolyte of claim 1, disposed in a region with a ridge. The polymer material is poly(ethylene) (PE), poly(ethylene oxide) (PEO)
), poly(propylene) (PP), poly(propylene oxide), polymethylmethacrylate (PMMA), polyacrylonitrile (PAN), poly[bis(methoxyethoxyethoxide)-phosphazene], poly(dimethylsiloxane) (PDMS) ,cellulose,
Cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, polyvinylidene difluoride (PVdF), polyvinylpyrrolidone (PVP), polystyrene, sulfonate (
PSS), polyvinyl chloride (PVC) group, poly(vinylidene chloride) polypropylene oxide, polyvinyl acetate, polytetrafluoroethylene, poly(ethylene terephthalate) (
PET), polyimides, polyhydroxyalkanoates (PHA), PEO-containing copolymers (e.g., polystyrene (PS)-PEO copolymers and poly(methyl methacrylate) (PMMA)-PEO copolymers), polyacrylonitrile (PAN ), poly(acrylonitrile-methyl acrylate copolymer), PVdF-containing copolymer, PMMA copolymer,
derivatives thereof, and polymers selected from the group consisting of combinations thereof (
The hybrid electrolyte of claim 1, which is, for example, such a polymer. 2. The hybrid electrolyte of claim 1, wherein said polymeric material is a gel. The gel contains ethylene carbonate (EC), diethyl carbonate (DEC), dimethoxyethane (DME), dioxolane (DOL), N-propyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR ₁₃ TFSI). , and combinations thereof and/or LiPF ₆ , LiT
a salt selected from the group consisting of FSI, LiTFSI, and combinations thereof;
18. The hybrid electrolyte of claim 17. The polymer material of the gel is polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVdF-HFP copolymer), polyvinylpyrrolidone (PVP), PEO, PMMA, PAN, polystyrene (PS). 18. The hybrid electrolyte of claim 17, comprising (eg, being) a polymer selected from the group consisting of, polyethylene (PE), and combinations thereof. 2. The hybrid electrolyte of Claim 1, wherein the polymeric material comprises a metal salt. 2. The hybrid electrolyte of Claim 1, wherein the polymeric material comprises a ceramic filler. 22. The hybrid electrolyte of claim 21, wherein said ceramic filler is selected from the group consisting of conductive particles, non-conductive particles, ceramic nanomaterials. A device comprising the hybrid electrolyte of claim 1. the hybrid electrolyte;
an anode;
a cathode;
with
24. The device of claim 23, wherein said hybrid electrolyte is a battery disposed between said cathode and said anode. 25. The device of claim 24, wherein said battery further comprises a current collector disposed on at least a portion of said cathode and/or said anode. 26. The device of Claim 25, wherein the current collector is a conductive metal or metal alloy. 25. The device of claim 24, wherein said battery is a lithium ion conducting solid state battery and said hybrid electrolyte is a lithium ion conducting SSE material. 25. The device of claim 24, wherein said battery is a sodium ion conducting solid state battery and said hybrid electrolyte is a sodium ion conducting SSE material. wherein the battery is a magnesium ion conductive solid state battery, and the hybrid electrolyte comprises
25. The device of claim 24, which is a magnesium ion-conducting SSE material. 25. The device of claim 24, wherein said cathode and/or said anode comprise a conductive carbon material, said cathode material optionally further comprising an organic or gel ion-conducting electrolyte. 25. The apparatus of claim 24, wherein the cathode comprises a material selected from sulfur, sulfur composites and polysulfide materials, or is air. 28. The device of claim 27, wherein said cathode comprises a material selected from the group consisting of lithium-containing cathode materials. The lithium-containing cathode material is Lithium Nickel Manganese Cobalt Oxide, LiC
_{oO2 ,} LiNi1 _{/3Co1 / 3Mn1} / _3O2 , _{LiNi0.5Co0.2Mn0 .
3} O ₂ , lithium manganese oxide (LMO), lithium iron phosphate (LFP), LiMnP
33. The device of claim ₃₂ , selected from the group consisting of _O4 , _LiCoPO4 , and _Li2MMn3O8 , where M _is selected from Fe, Co, and combinations thereof. 29. The cathode comprises a material selected from sodium-containing cathode materials.
Equipment described in . The sodium-containing cathode material is Na ₂ V ₂ O ₅ , P2—Na _2/3 Fe _1/2 M
n1 _{/2O2 , Na3V2} ( _PO4 ) ₃ , NaMn1 _{/ 3Co1/ 3Ni1 / 3PO4} ,
and Na2 _{/ 3Fe1/ 2Mn1/ 2O2} @graphene composites. 36. The device of claim 35, wherein said cathode comprises a material selected from the group consisting of doped magnesium oxide. 25. The device of claim 24, wherein the anode comprises a material selected from the group consisting of silicon-containing materials, tin and its alloys, tin/carbon, and phosphorous. 25. The device of claim 24, wherein said anode comprises a material selected from the group consisting of lithium ion conductive anode materials. 39. The device of claim 38, wherein the lithium ion conductive anode material is a lithium-containing material selected from the group consisting of lithium carbide, _Li6C , and lithium titanate (LTO). 39. The device of claim 38, wherein said anode is lithium metal. 25. The device of claim 24, wherein the anode comprises a material selected from sodium ion conducting anode materials. _The sodium- _containing anode material comprises _{Na2C8H4O4 and Na0.66Li0 .
42.} The device of claim 41 selected from _{the group consisting of22Ti0.78O2 .} 42. The device of claim 41, wherein the anode is sodium metal. 25. The device of Claim 24, wherein the anode is a magnesium-containing anode material. 45. The device of claim 44, wherein the anode is magnesium metal. said hybrid electrode, cathode, anode, and optionally said current collector comprising:
25. The apparatus of claim 24, forming cells, said battery comprising a plurality of said cells, each adjacent pair of said cells separated by a bipolar plate. 1. A conventional ion-conducting battery with a liquid electrolyte, said battery comprising an inorganic SSE or a solid hybrid electrolyte and a liquid electrolyte, said liquid electrolyte not being present as part of said solid hybrid electrolyte,
24. The device of claim 23, wherein said inorganic SSE material or said solid state hybrid electrolyte is the separator of said conventional battery. 48. The device of claim 47, wherein said inorganic SSE is a F/S SSE. A method of making a solid state hybrid electrolyte, comprising:
contacting the template with one or more SSE material precursors;
optionally reacting the SSE material precursor;
heat treating the template with the solid inorganic material to remove the template and form the inorganic SSE;
contacting the fired template with a polymeric material;
including
A method wherein a solid state hybrid electrolyte is formed. 48. The method of claim 47, wherein the SSE material is a sol-gel precursor or metal salt. 5. The template is a carbon template or a biomaterial template.
7 or 48. 52. The method of claim 51, wherein the carbon template is a fiber template. 52. The method of claim 51, wherein the biomaterial template is a wood template or a plant template.

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