WO2018183771A1 - Électrolytes hybrides à l'état solide, procédés de fabrication de ces derniers et utilisations de ces derniers - Google Patents

Électrolytes hybrides à l'état solide, procédés de fabrication de ces derniers et utilisations de ces derniers Download PDF

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WO2018183771A1
WO2018183771A1 PCT/US2018/025289 US2018025289W WO2018183771A1 WO 2018183771 A1 WO2018183771 A1 WO 2018183771A1 US 2018025289 W US2018025289 W US 2018025289W WO 2018183771 A1 WO2018183771 A1 WO 2018183771A1
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electrolyte
sse
garnet
solid
lithium
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PCT/US2018/025289
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English (en)
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Liangbing Hu
Eric D. Wachsman
Boyang Liu
Yunhui GONG
Kun Fu
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University Of Maryland, College Park
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Priority to EP18778216.4A priority Critical patent/EP3602657A4/fr
Priority to KR1020247011551A priority patent/KR20240051309A/ko
Priority to KR1020197031941A priority patent/KR20190139911A/ko
Priority to JP2019553946A priority patent/JP2020517049A/ja
Priority to US16/499,203 priority patent/US20200112050A1/en
Publication of WO2018183771A1 publication Critical patent/WO2018183771A1/fr
Priority to JP2023030805A priority patent/JP2023088911A/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0094—Composites in the form of layered products, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • Liquid organic electrolytes are the industry standard ion conductors for lithium-ion batteries (LIB). Liquid electrolytes feature high ionic conductivity and good wettability with electrodes. However, liquid system are flammable and inevitably lead to solvation and diffusion of active materials, and the transport of unwanted species from cathode to anode cause "chemical short circuit" that deteriorates electrodes and limits the deployment of new cathode chemistries, which are typical for high voltage cathode, sulfur, and air/02.
  • LiNio.5Mn1.4O4 (LNMO) spinel cathode In high-voltage LIB, the dissolution of transition metals in LiNio.5Mn1.4O4 (LNMO) spinel cathode and their diffusion to the anode surface cause Li + loss through continuous electrolyte decomposition that lead to rapid capacity decay.
  • LNMO LiNio.5Mn1.4O4
  • the diffusion of active materials are more dominating in Li-metal batteries.
  • Li-S batteries the diffusion of polysulfides corrodes Li metal anode and the repeatable shuttling of polysulfides between electrodes causes low coulombic efficiency and active material loss.
  • a short circuit shuttle caused by mobile redox mediators in Li-air/02 batteries should be avoided as well. Therefore, it is critical to prevent chemical short circuit in terms of minimizing or blocking those soluble component transport in batteries.
  • Solid-state electrolyte is the key to providing high energy density and addressing the flammability and safety issue as well as challenges of chemical and physical short circuits by blocking migration of unwanted active materials and penetration of metal dendrites.
  • solid electrolyte materials including conductive oxides, phosphates, hydrides, halides, sulfides, and polymer based composites.
  • Integration of solid lithium ion conductors into batteries has been demonstrated across a range of material sets, including: 0D nanoparticles, ID nanofibers, 2D thin films, 3D networks and bulk components.
  • the concept of a 3D lithium-ion conducting framework represents a creative solution to the shortcomings of current solid-state batteries' capabilities and cycling kinetics to provide continuous Li ion transport pathways and proper mechanical reinforcement.
  • Developing nanostructured fillers is an approach to increase the ionic conductivity of polymer composite electrolytes due to the increased surface area of the amorphous region and improved interface between fillers and polymers.
  • One dimensional nanowire fillers were demonstrated to enhance the ionic conductivity of the polymer composite electrolyte. This was because the nanowire fillers provide extended ionic transport pathways in the polymer matrix, instead of an isolated distribution of nanoparticle fillers in the polymer electrolyte.
  • the agglomeration of ceramic fillers may remain and it will become a challenge for its mixing with polymer to fabricate uniform solid polymer electrolyte in large-scale. To solve this challenge, in situ synthesis of ceramic filler particles with high monodispersity in polymer electrolyte was recently reported.
  • the present disclosure provides solid-state hybrid electrolytes.
  • the present disclosure also provides methods of making and uses of solid-state hybrid electrolytes.
  • the solid-state hybrid electrolytes have a layer of polymeric material disposed on at least a portion of an exterior surface or all of the exterior surfaces of a solid-state electrolyte (SSE).
  • a solid-state hybrid electrolyte is a polymeric material/solid-state hybrid electrolyte, a polymer/solid-state hybrid electrolyte, or a gel polymer/solid-state hybrid electrolyte.
  • the SSE is a monolithic or mesoporous SSE body or an SSE comprising a plurality of fibers or a plurality of strands.
  • the present disclosure provides methods of making inorganic fibers or strands.
  • the fibers or strands can form an inorganic SSE.
  • the methods are templating methods or electrospinning methods.
  • Strands can be formed using a templating method.
  • a template comprises continuous void spaces that can used to form strands of inorganic materials that can form an inorganic solid-state electrolyte (e.g., solid-state hybrid electrolyte).
  • the void spaces may be man-designed or naturally occurring in a biological material (e.g., wood, plant, and the like).
  • the present disclosure provides uses of solid-state hybrid electrolytes of the present disclosure.
  • the solid-state hybrid electrolytes can be used in various devices.
  • a device comprises one or more solid-state hybrid electrolyte of the present disclosure.
  • Non-limiting examples of devices include electrolytic cells, electrolysis cells, fuel cells, batteries, and other electrochemical devices such as, for example, sensors, and the like.
  • a device may be a battery.
  • a 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.
  • Non-limiting examples of ion- conducing batteries include lithium-ion conducting batteries, sodium-ion conducting batteries, magnesium-ion conducing batteries, and the like.
  • Figure 1 shows (a) a schematic of the solid-state gel polymer battery design with hybrid polymer/garnet-type SSE electrolyte, (b) Without interfacial gel polymer layer, the garnet SSE and electrode have poor interfacial contact. With the gel polymer layer, the contact between electrode and SSE can be improved.
  • Figure 2 shows impedance analysis of symmetric cells with hybrid electrolyte
  • Figure 3 shows impedance of the electrode
  • Figure 4 shows electrochemical performances of polymer
  • Figure 5 shows impedance of electrode
  • Figure 7 shows characterizations of bilayer garnet solid-state electrolyte.
  • Figure 9 shows electrochemical characterization of the hybrid liquid-solid electrolyte, (a-b) Schematic and SEM image of bare dense garnet layer surface, (c-d)
  • Dense garnet membrane and slurry-casted sulfur electrode with a mass loading of -1.2 mg/cm 2 were assembled into the hybrid cell, (d) Rate performance of the hybrid Li-S cell, (e) Schematic of hybrid solid-state bilayer Li-S battery. Sulfur and CNT were encapsulated in the pores. The mechanically stable bilayer garnet structure can accommodate the volume expansion of sulfur and maintain the electrode structure stable during cycling, (f) Cross-section of the bilayer sulfur cathode and elemental mappings show sulfur distribution inside of the porous layer, (g-h) Voltage profile and cycling performance of the hybrid bilayer Li-S cell with a loading of 7.5 mg/cm 2 at 0.2 mA/cm 2 .
  • Figure 11 shows Nyquist plots of the dense garnet SSE pellet at different temperatures (25, 30, 40, and 50 °C).
  • the dense garnet pellet has a thickness of -250 ⁇ .
  • Figure 12 shows Arrhenius plot of garnet SSE conductivity. The activation energy is 0.35 eV.
  • Figure 13 shows a conventional Li-S battery. The sulfur mass loading is -1.2 mg/cm 2 .
  • Figure 14 shows cycling performance of hybrid solid-state Li-S battery at a current of 0.1 mA/cm 2 .
  • the sulfur loading is 1.2 mg/cm 2 .
  • Figure 16 shows calculations of the specific energy density of the tested garnet bilayer Li-S battery.
  • Figure 17 shows a projected energy density of bilayer garnet solid-state Li-S batteries with optimized parameters.
  • Figure 18 shows a schematic of multi-scale aligned mesoporous garnet
  • the gamet-wood possesses multi-scale aligned mesostructure derived from natural wood, which enables the unobstructed Li ion transport along the garnet-polymer interface, through garnet, and through polymer electrolyte.
  • Figure 19 shows characterization of the wood template. Illustrations of the wood template fabrication through compressing and slicing; Top-view SEM image of (b) pristine wood and (c) compressed wood, with the apparent diameter reduction of the wood microchannels after compression; Cross-sectional SEM images comparing (d) pristine wood and (e) compressed wood, in which the channels are closed but the highly aligned structure is preserved; (f) SEM image of the aligned nanofiber with a diameter of around 10 nm.
  • Figure 20 shows calcination of the aligned garnet templated by wood.
  • Cross- sectional SEM image shows the alignment of channels at both (a) micro-scale and (b) nano- scale;
  • JCPDS#90-0457 which verifies the cubic garnet structure.
  • Figure 21 shows TEM characterization of garnet crystal structure, (a) HRTEM image of a nanoparticle broken off from the aligned garnet showing the (21 0) and (021) lattice planes; inset graph shows the FFT patterns of the HRTEM image; (b) TEM image of the edge of a garnet nanoparticle showing a clear multi-crystalline structure; (c) EELS spectrum of the garnet surface showing the ROI, spectrum image, and relative composition map of O, C, and La, respectively.
  • Figure 22 shows electrochemical characterizations of the garnet-wood with aligned mesoporous structure, (a) SEM and its corresponding EDX images showing the complete, uniform infiltration of polymer electrolyte throughout the aligned garnet.
  • Figure 23 shows a photo of an as sintered aligned mesoporous garnet.
  • the photograph shows a piece of as sintered aligned mesopores garnet.
  • the garnet membrane was white and flat with a similar area to the wood template.
  • Figure 24 shows a cross-sectional SEM image of garnet-wood.
  • the thickness of the garnet-wood can be controlled by the thickness of the wood template.
  • SEM image shows a thin garnet-wood sample with a thickness of -30 ⁇ , in which the low-tortuosity channels are highly aligned and penetrate throughout the whole garnet membrane.
  • Figure 25 shows a cross-sectional SEM image of the aligned garnet structure.
  • Figure 26 shows a cross-sectional SEM image of garnet-wood.
  • the SEM image shows the cross-section and top surface of the garnet wood.
  • the aligned structure is fully filled with PEO based polymer electrolyte.
  • Figure 27 shows weight change of the wood template during precursor infiltration.
  • the wood template was soaked in the precursor solution and the weight increases over time.
  • the weight change shows the high absorbency of the wood template.
  • Figure 28 shows (a) EIS measurements and (b) ionic conductivity of the
  • PEO/SCN/Li-TFSI polymer electrolyte at different temperatures The highlighted region indicates measurements performed around room temperature (RT).
  • RT room temperature
  • the inset shows that the PEO/LiTFSI/SCN polymer electrolyte film was sandwiched by two stainless steel electrodes.
  • a polyethylene (PE) separator ring was placed around the polymer electrolyte film to fix the thickness and avoid shorting at high temperatures.
  • Figure 29 shows galvanostatic cycling of Li/gamet wood/Li with a current density of 0.1 niA/cm 2 at room temperature for over 600 hours.
  • the fluctuation in the voltage is caused by changes to the ambient temperature of the cell.
  • the long-term cycling indicates the outstanding electrochemical and mechanical stability of the garnet wood composite electrolyte in Li metal cells.
  • Figure 30 shows a flexible lithium-ion conducting ceramic textile.
  • the lithium-ion conducting ceramic textile is flexible and retained the physical characteristics of the original template.
  • the unique textile structure enables long-range lithium-ion transport pathways via continuous fibers and yams, high surface area/volume ratio of solid ion conductors and multi-level porosity distribution.
  • Figure 31 show characterization of the gamet textile, (a) SEM image of the pretreated textile template; (b) SEM image of the template impregnated with the precursor solution; (c) SEM image of the gamet textile converted from the precursor solution impregnated template; (d) Reconstructed model of gamet textile flatness uniformity generated by 3D laser scanning; (e) Flexibility, workability and solvent tolerance of the garnet textile; (f) Powder XRD patterns of the crushed garnet textile sintered at different temperatures; (g) Elemental distribution mapping of a single garnet fiber sintered at 800 °C.
  • Figure 32 shows electrochemical characterization of garnet textile reinforced flexible composite polymer electrolyte, (a) Dried CPE showing flexibility and mechanical strength; (b) illustration of fibrous garnet dominated lithium-ion transfer mechanism; (c) Impedance spectra of the CPE at different temperatures; (d) Arrhenius plot of the lithium-ion conductivity of the CPE as a function of temperature; (e) Galvanostatic cycling
  • Figure 33 shows characterization of garnet textile 3D electrode architecture for solid state Li-S batteries loaded with 10.8 mg/cm 2 sulfur, (a) Photograph of a garnet textile sintered on the dense supporting electrolyte, (b) SEM image of the sulfur cathode infiltrated gamet textile electrode architecture; (c) EDX elemental mapping of the sulfur/carbon mixture loaded single garnet fiber; (d) Charge-discharge profiles of the solid-state Lithium-Sulfur battery.
  • Figure 34 shows characterization of the flexible gamet textile
  • Thermogravimetric analysis of the gamet precursor solution impregnated textile template (b) Cross-sectional SEM image of the pretreated textile template; (c) Cross-sectional SEM image of the precursor solution-impregnated textile template; (d) Cross-sectional SEM image of the garnet textile after pyrolysis of the template and sintering at high temperature.
  • Figure 35 shows a flexible garnet textile in large dimensions and different shapes.
  • Figure 36 shows a characterization of Li-ion conducting garnet and insulating
  • AI2O3 textile reinforced flexible CPE (a) Cross-sectional SEM image of the garnet textile reinforced flexible CPE; (b) The insulating AI2O3 textile fabricated using the identical template method; (c) Impedance plots of the controlled CPE at different temperatures.
  • Figure 37 shows electrochemical characterization of the garnet textile reinforced flexible CPE.
  • Figure 38 shows characterization of the sulfur infiltrated 3D electrode built with garnet textile architecture for solid-state Li-S batteries, (a) EDX elemental linear scan along the direction from the exposed yarn area to the dense electrolyte surface of the 3D sulfur cathode built with garnet textile; (b) High magnification cross-sectional SEM image and elemental mapping of the 3D sulfur cathode built with garnet textile.
  • Figure 40 shows discharge and charge profiles of the solid-state Li-S batteries built with garnet textile architecture with sulfur loading of 10.8 mg/cm 2 at 0.75 mA/cm 2 .
  • Figure 41 discharge and charge profiles of the solid-state Li-S batteries built with garnet textile architecture with higher sulfur loading of 18.6 mg/cm 2 at 0.15 mA/cm 2 .
  • Figure 43 shows densities of the constituent materials in solid-state Li-S battery.
  • Figure 44 shows structural parameters of different electrolyte support configurations.
  • Figure 47 shows a schematic of the hybrid solid-state composite electrolyte, where ceramic garnet nanofibers function as the reinforcement and lithium ion conducting polymer as the matrix.
  • the inter-welded garnet nanofiber network provides continuous ion- conducting pathway in the electrolyte membrane.
  • Figure 48 shows fabrication of the flexible solid-state fiber-reinforced composite (FRPC) electrolyte, (a) Schematic setup of electrospinning gamet/PVP nanofibers. (b) Schematic procedure to fabricate the FRPC Li-ion conducting membrane, (c) SEM image of the as-spun nanofiber network, (d) Diameter distribution of the as-spun nanofibers. (e) SEM image of the garnet nanofiber network, (f) Diameter distribution of the garnet nanofibers. (g) Photo image to show the flexible and bendable FRPC Li-ion conducting membrane.
  • FRPC flexible solid-state fiber-reinforced composite
  • Figure 50 shows thermal properties and flammability tests of the solid-state
  • Figure 51 shows a phase structure of garnet fiber and electrical properties of solid-state FRPC electrolyte, (a) XRD pattem of the garnet nanofibers. (b) EIS profiles of the FRPC electrolyte membrane at different temperatures (25 °C, 40 °C, and 90 °C). (c)
  • Figure 52 shows electrochemical performance of FRPC electrolyte membrane measured in symmetric Li
  • Figure 53 shows the magnified TEM image of a garnet nanofiber with an average grain size of 20 nm in diameter.
  • Figure 54 shows when the testing temperature increased to 25 °C, the voltage dropped to 0.3 V due to the improved ionic conductivity at elevated temperature as shown in
  • Figure 55 shows two voltage profiles of the symmetric cell at two different stripping/plating process time were compared.
  • Figure 56 show schematic of an example of a battery of the present disclosure.
  • the present disclosure provides solid-state hybrid electrolytes.
  • the present disclosure also provides methods of making and uses of solid-state hybrid electrolytes.
  • the present disclosure provides solid-state hybrid electrolytes.
  • the solid-state hybrid electrolytes have a layer of polymeric material disposed on at least a portion of an exterior surface or all of the exterior surfaces of a solid-state electrolyte (SSE).
  • a solid-state hybrid electrolyte is a polymeric material/solid-state hybrid electrolyte, a polymer/solid-state hybrid electrolyte, or a gel polymer/solid-state hybrid electrolyte.
  • the SSE is a monolithic or mesoporous SSE body or an SSE comprising a plurality of fibers or a plurality of strands.
  • the present disclosure provides solid-state hybrid electrolytes with, for example, layers, including, but not limited to, polymer layers (e.g., polymer membranes), formed in different ways, to achieve solid-state hybrid electrolytes with, for example, desirable ionic conductivity, and stable and well-connected interfaces between such electrolyte and electrodes.
  • the solid-state hybrid electrolytes of the present disclosure can exhibit, for example, interfacial resistance of 248 Qxcm 2 or lower at an electrolyte/lithium ion cathode interface and/or 214 Qxcm 2 or lower at an electrolyte/lithium metal anode interface.
  • the present disclosure provides solid-state hybrid electrolytes with flexible inorganic SSEs.
  • the flexible inorganic SSEs can be low-cost, thin, flexible, ionically conductive membranes that are expected to enable next generation of ion conducing batteries (e.g., Li-metal batteries) that exhibit desirable safety.
  • ion- conductive 3D networks are be infiltrated with, for example, Li-ion conductive polymers to prepare the flexible ion-conductive SSE membranes.
  • a schematic example is shown in Figure 47.
  • oxide SSE materials including, but not limited to, LLZO garnet, LLTO perovskite and LATP glass were used to produce a 3D ion-conductive network.
  • the 3D structure can provide, for example, long-range ion transfer pathways and structural reinforcement to enhance the polymer matrix.
  • the membrane can exhibit desirable electrochemical stability to high voltage (e.g., greater than 6V), high ionic conductivity (e.g., greater than 10 "4 S cm -1 ) and high mechanical stability, for example, to effectively block lithium dendrites.
  • the inorganic SSE (e.g., of an F/S SSE) may have a three-dimensional network structure with one or more nodes formed by at least two fibers or strands.
  • the inorganic solid-state electrolyte (e.g., solid-state hybrid electrolyte) has a continuous ionic conduction path from one side of the inorganic solid-state electrolyte to an opposite side of the inorganic solid-state electrolyte.
  • the 3D ion-conductive network of the ionic SSE can function as reinforcement and ion-conducting (e.g., lithium ion conducting) polymer serves as a matrix.
  • the 3D network provides continuous ion-conducting pathway in the electrolyte membrane.
  • the inorganic solid-state material may be exposed on one or more surface of the solid-state hybrid electrolyte.
  • the inorganic SSE may be a continuous and, optionally, aligned, mesoporous structure.
  • the inorganic SSE can be formed from various inorganic materials.
  • the inorganic material may be a ceramic material.
  • the inorganic material is ion conducting (e.g., lithium-ion conducting, sodium-ion conducting, magnesium-ion conducting or the like) material.
  • An 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 conducing inorganic materials, sodium-ion conducting inorganic materials, magnesium-ion conducing inorganic materials, and the like. Any inorganic SSE electrolyte material known in the art can be used. Methods of making inorganic SSE electrolyte material are known in the art.
  • the inorganic material can have various structure (e.g., secondary structure).
  • an inorganic material is amorphous, crystalline (e.g., single crystalline and poly crystalline), or have various amorphous and/or crystalline domains.
  • the inorganic material may be a lithium-conducting inorganic (e.g., 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, L13N, Li- -alumina, Lithium Super-ionic Conductors
  • the lithium garnet SSE material is cation-doped L15 LasM ⁇ O ⁇ , where M 1 is Nb, Zr, Ta, or combinations thereof, cation-doped Li6La2BaTa20i2, cation-doped
  • the lithium garnet SSE material is Li5La3Nb20i2, Li5La3Ta20i2, LiiL ZnOu, Li6La2SrNb20i2, Li6La2BaNb20i2, Li6La2SrTa20i2, Li6La2BaTa20i2, Li7Y3Zr20i2, Li6.4Y3Zn.4Tao.6012, Li6.5La2.5Bao.5TaZrOi2, Li6BaY2M 1 20i2, Li7Y3Zr20i2, Li6.75BaLa2Nbi.75Zno.250i2, Li6.75BaLa2Tai.75Zno.250i2, or the like.
  • the inorganic material may be a sodium-ion conducting inorganic (e.g., ceramic) material.
  • the sodium-ion conducting inorganic material may be a sodium- containing material.
  • the sodium-ion conducting inorganic material is ⁇ "- ⁇ 2 ⁇ 3, Na4Zr 2 Si 2 POi2 (NASICON), cation-doped NASICON, or the like.
  • the inorganic material may be a magnesium-ion conducting inorganic (e.g., ceramic) material.
  • the magnesium-ion conducting inorganic material may be a magnesium- containing material.
  • the magnesium-ion conducting inorganic material is selected from doped magnesium oxide materials.
  • the magnesium-ion conducing material is Mgi+ x (Al,Ti)2(P04)6, where x is 4 to 5, NASICON-type magnesium- ion conducting materials, or the like.
  • the monolithic SSE or mesoporous SSE body can have various sizes (i.e., 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 (e.g., comprising only a dense layer of inorganic material) or a densely sintered body.
  • mesoporous SSEs include planar SSE structures comprising an external layer of porous (e.g., mesoporous) material (e.g., a multilayer SSE structure comprising a dense layer and at least one porous (e.g., mesoporous) layer).
  • Non- limiting examples of multilayer SSE structures include bilayer structures (comprising a porous layer disposed on a dense layer) and trilayer structures (comprising two porous layers disposed on opposite sides of a dense layer) are known in the art.
  • Examples of multilayer structures are described in U.S. Patent Application No. 14/222,306 (titled “Ion Conducting Batteries with Solid State Electrolyte Materials”), filed on March 21, 2014, and published on September 25, 2014, as U.S. Patent Application Publication No. 2014/0287305 and U.S. Patent Application No. 15/364,528 (titled “Ceramic Ion Conducting Structures and Methods of Fabricating Same, and Uses of Same"), filed on November 30, 2016, and published on June 1, 2017, as U.S. Patent Application Publication No. 2017/0155169, the disclosures of which are incorporated herein by reference.
  • the F/S SSE can comprise a fibers or strands having various sizes (i.e., dimensions) and/or shapes.
  • the fibers or stands are cylindrical or substantially cylindrical, polyhedral or substantially polyhedral shaped, irregularly shaped, or the like.
  • the fibers or strands can have a length corresponding to multiples of one or more dimension of the device in which they are used.
  • the fibers or strands have a length of 1 micron to 20 meters, including all integer micron values and ranges therebetween, and/or a greatest cross-sectional dimension (e.g., diameter) of 1 nm to 10 microns, including all integer nm values and ranges therebetween.
  • the F/S SSE comprises fibers or strands with a length to greatest cross-sectional dimension (e.g., diameter) of 10 or greater.
  • the F/S SSE can be flexible and provide a flexible solid- state hybrid electrolyte for use in a flexible device such as, for example, a battery.
  • the F/S SSE and polymeric material may form an electrolyte.
  • F/S SSEs can be made by methods described herein.
  • polymeric materials can be used. Mixtures of two or more polymeric materials (e.g., two or more polymers) can be used.
  • the polymeric materials can be conducting (e.g., ion-conducting and/or electronic conducting), non-conducting, or a combination thereof.
  • the polymeric material may be a dry polymer or a gel.
  • the polymeric material be conducting (e.g., ion-conducting and/or electronic conducting).
  • the polymeric material which may be a mixture of polymeric materials, provide mechanical strength to the SSE.
  • a thin layer e.g., having a thickness of 5 nm to 10 microns, including all integer nm values and range therebetween
  • a thin layer e.g., having a thickness of 5 nm to 10 microns, including all integer nm values and range therebetween
  • the polymeric material can be disposed on at least a portion of or all of the surfaces of the SSE (e.g., inorganic SSE).
  • the polymeric material is a layer (e.g., a conformal layer) disposed on at least a portion of (e.g., the portions of the SSE material on which an electrode (e.g., cathode and/or anode) would be disposed).
  • the polymeric material is disposed on the pore surface(s), the non-pore surface(s), or both. It may be desirable that the polymeric material be disposed on the portions of the porous SSE material on which an electrode (e.g., cathode and/or anode) would be disposed.
  • an electrode e.g., cathode and/or anode
  • the polymeric material is present at 1 volume percent or greater, 5 volume percent or greater, 10 volume percent or greater, 20 volume percent or greater, 30 volume percent or greater, 40 volume percent or greater, 50 volume percent or greater, or 60 volume percent or greater of the solid-state hybrid electrolyte.
  • the polymeric material can be a layer.
  • the layer can be formed by various methods known in the art. For example, a polymeric material layer is formed by dip coating, slurry casting, spray coating or spinning coating or the like.
  • the polymeric material is disposed in the void space formed by the individual fibers or strands of the SSE.
  • the void space may be a pore resulting from use of a template.
  • the polymeric material may be incorporated in the F/S SSE by methods known in the art. For example, the polymeric material is infiltrated or in situ synthesized into the void space (e.g., pores) of the F/S SSE.
  • the polymeric materials may comprise one or more polymer, one or more co-polymer, or a combination thereof.
  • Molecular weight of the polymer(s) and/or copolymer(s) is not particularly limited. For example, depending on the performance (e.g., ion conductivity) requirement of a devices (e.g., a solid- state, ion-conducting battery), polymer(s) and/or copolymer(s) can have a broad range of molecular weight. It may be desirable that the polymer(s) and/or copolymer(s) be conducting.
  • a polymeric material may comprise a mixture of conducting polymer(s) and/or copolymer(s) and non-conducting polymer(s) and/or copolymer(s).
  • Polymer(s) and/or copolymers can have various structure (e.g., secondary structure).
  • polymer(s) and/or copolymer(s) are amorphous, crystalline, or a combination thereof. It may be desirable that the polymer(s) and/or copolymers have low crystallinity.
  • Polymeric materials include, but are not limited to, polymers and copolymers.
  • the polymers and copolymers may be conducting or non-conducting.
  • Non-limiting examples of polymers and co-polymers include poly(ethylene) (PE), poly(ethylene oxide) (PEO), poly(propylene) (PP), poly (propylene oxide), polymethyl methacrylate (PMMA), polyacrylonitrile (PAN), poly[bis(methoxy ethoxyethoxide ⁇ phosphazene],
  • poly(dimethylsiloxane) PDMS
  • PDMS poly(dimethylsiloxane)
  • PDMS poly(dimethylsiloxane)
  • PDMS poly(dimethylsiloxane)
  • PDMS poly(dimethylsiloxane)
  • PVdF polyvinylidene difluoride
  • PVP polyvinylpyrrolidone
  • PSS polysulfonate
  • PVC polyvinylchloride
  • PVC poly(vinylidene chloride) polypropylene oxide, polyvinylacetate, polytetrafluoroethylene (e.g., Teflon ® ), poly(ethylene terephthalate) (PET), polyimide, polyhydroxyalkanoate (PHA), PEO containing co-polymers (e.g., polystyrene (PS) - PEO copolymers and poly(methyl methacrylate) (PMMA) - PEO copoly
  • the polymeric material may be a gel.
  • a gel comprises a polymeric material
  • the liquid may be a liquid electrolyte.
  • a liquid electrolyte may comprise a metal salt (e.g., one or more lithium salts, one or more sodium salts, one or more magnesium salts, and the like).
  • a non-limiting example of a liquid electrolyte is an aqueous liquid electrolyte.
  • Non-limiting examples of liquid electrolytes include L1PF6 (e.g., 1M) in ethylene carbonate (EC) / diethyl carbonate (DEC), LiTFSI (e.g., 1M) in dimethoxyethane (DME) / dioxolane (DOL), LiTFSI (e.g., 0.5 M) in N-Propyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide (PYR13TFSI) ionic liquid, and the like).
  • L1PF6 e.g., 1M
  • DEC dimethoxyethane
  • DOL dioxolane
  • LiTFSI e.g., 0.5 M
  • PYR13TFSI N-Propyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide
  • a polymeric material may comprise a filler.
  • the polymeric material comprises one or more ceramic filler (e.g., 2-25 wt% of a ceramic filler based on total weight of the polymeric material).
  • ceramic fillers include conductive particles, non-conductive particles (e.g., AI2O3, S1O2, TiC nanoparticles, and the like), ceramic nanomaterials (e.g., ceramic nanoparticles, ceramic nanofibers, and the like), and the like.
  • a ceramic nanomaterial may have the composition of an inorganic material disclosed herein.
  • the present disclosure provides methods of making inorganic fibers or strands.
  • the fibers or strands can form an inorganic SSE.
  • the methods are templating methods or electrospinning methods.
  • Strands can be formed using a templating method.
  • a template comprises continuous void spaces that can used to form strands of inorganic materials that can form an inorganic solid-state electrolyte (e.g., solid-state hybrid electrolyte).
  • the void spaces may be man-designed or naturally occurring in a biological material (e.g., wood, plant, and the like).
  • the inorganic material (e.g., ceramic) textile can be combined with electrode materials in interdigitated or concentric arrangements to minimize electrolyte volume and maximize electrode utilization, thereby increasing active electrolyte area, lithium-ion interfacial transport, and tolerance for electrode volume change during charging/discharging.
  • microporous inorganic SSEs comprising a plurality of strands.
  • the strands may have the general shape (e.g., cylindrical or substantially cylindrical, polyhedral or substantially polyhedral shaped, irregularly shaped, or the like) of the template used to form the individual strands.
  • the strands have a length ranging from micrometers to meters and/or a greatest cross-sectional dimension (e.g., diameter) ranging from nanometers to micrometers.
  • the pores of the inorganic SSE electrolyte e.g., the pore size, pore size distribution, pore morphology, etc.
  • the pores may be formed by removal of the template material (e.g. have a size and/or shape corresponding to the templated material).
  • the pores may be formed by void spaces formed by the fibers.
  • at least a portion of or all of the pores have at least one dimension of 1-100 microns.
  • at least a portion of or all of the pores have at least one dimension of 1 nm to 500 microns.
  • the pores of the solid-state hybrid electrolyte and/or, if present, the strands (e.g., a portion of the strands or all of the strands) of the solid-state hybrid electrolyte and/or the pores of the solid-state hybrid electrolyte are aligned or all substantially aligned.
  • aligned it is meant that the strands and/or pores of the inorganic SSE are arranged such than a longitudinal axis of each strand is parallel or within 30 degrees, within 20 degrees, within 15 degrees, within 10 degrees, or within 5 degrees of parallel) to longitudinal axes of adjacent strands.
  • the strands and/or pores are not arranged end to end.
  • substantially aligned it is meant 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.
  • a solid-state hybrid electrolyte formed using a biomaterial template e.g., a wood template, plant template, or the like
  • the individual strands are generally aligned perpendicular (e.g., perpendicular) to a plane defined by one or both of the electrodes and the pores are generally aligned perpendicular (e.g., perpendicular) to a plane defined by one or both of the electrodes.
  • the strands (e.g., a portion of the strands or all of the strands) of inorganic SSE are arranged as a fabric, e.g., arranged as a woven fabric, a braided fabric, and the like.
  • the strands of the inorganic SSE may take the general structure of the textile template used to fabricate the inorganic SSE.
  • the dimensions of the inorganic SSE may be substantially smaller than those of the textile template.
  • a templating method of forming an inorganic solid-state electrolyte comprises:
  • the template thermally treating the template with the solid inorganic material, wherein the template is removed (e.g., as carbon dioxide) and the inorganic SSE (e.g., monolithic SSE or mesoporous body or F/S SSE) is formed; and
  • the template e.g., as carbon dioxide
  • the inorganic SSE e.g., monolithic SSE or mesoporous body or F/S SSE
  • the polymeric material at least partially or completely fills the pores of the F/S SSE (e.g., pores which correspond to the template).
  • a templating method of forming an inorganic solid-state electrolyte comprises:
  • a biomaterial template e.g., one or more inorganic SSE material sol-gel precursor
  • one or more SSE material precursor e.g., one or more inorganic SSE material sol-gel precursor
  • a solid inorganic material e.g., comprising at least one or all partially or completely reacted and/or decomposed inorganic SSE material sol-gel precursors
  • the polymeric material at least partially fills the nanopores and/or micropores of the inorganic SSE.
  • a templating method of forming an inorganic solid-state electrolyte comprises:
  • contacting a carbon template with one or more inorganic SSE material precursors e.g., one or more metal salts
  • reacting e.g., heating
  • a solid inorganic material e.g., a plurality of nanoparticles of inorganic material
  • the inorganic SSE contacting (e.g., infiltrating) the inorganic SSE with a polymeric material, wherein the polymeric material at least partially fills the nanopores and/or micropores of the template.
  • the templates are formed from polymers (e.g., biologically derived polymers (e.g., cellulose, protein fibers, and the like), man-made polymers (e.g., PET, polyamides such, for example, Nylon, regenerated cellulose such as, for example, Rayon, polyesters, and the like), and the like.
  • the templates may have a hierarchical interconnected structure comprising interconnected nanoscale and/or microscale voids.
  • the template is a low tortuosity template (e.g., a low tortuosity template formed using a wood template).
  • the template can be a biological material (e.g., wood, plants, and the like) or a man-made template, which can formed using methods such as, for example, tape casting, screen printing, extrusion, 3-D printing, weaving, knitting, non- woven methods, and the like.
  • all or substantially all of the template is removed (i.e., it is a sacrificial template).
  • the template is removed by thermal treatment.
  • Various carbon templates can be used. Examples of carbon templates include, but are not limited to, textile templates, paper templates, foam templates, and the like).
  • a carbon template may be a textile.
  • a textile is a fabric.
  • a fabric may comprise various weaves, braids, and like, or be non-woven. In the case of woven fabrics, the woven fabric may be of any weave pattern.
  • a biomaterial template may be a wood template, plant template, or the like.
  • a wood or plant template comprises a plurality nanochannels and/or microchannels. The plurality of nanochannels and/or microchannels are interconnected to form a three-dimensional network with at least one node.
  • a wood template may be a compressed wood template.
  • a wood template is formed by removal of at least a portion or all of the lignin from a piece of wood having a size and shape appropriate for forming an F/S SSE.
  • an electrospinning method of forming an inorganic solid- state electrolyte comprises:
  • inorganic SSE precursor materials can be used.
  • Non-limiting examples of inorganic SSE precursor materials include sol-gel precursors, metal salts, and the like.
  • the SSE material precursor may one or more sol-gel precursors or one or more metal salts that on reaction, e.g., heating, provide an inorganic SSE of a desired composition.
  • a thermal treatment comprises sintering and/or a calcining the inorganic SSE material precursor(s) or reacted (e.g., at least partially reacted or completely reacted) inorganic SSE material precursor(s).
  • a thermal treatment removes (e.g., pyrolyzes) the template material.
  • the thermal treatment as least partially (e.g., substantially) removes or complete removes the template material to provide and inorganic SSE.
  • a thermal treatment is carried out at 700-1000 °C in an air atmosphere or an atmosphere comprising oxygen.
  • a device may be a battery.
  • a 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.
  • Non-limiting examples of ion- conducing batteries include lithium-ion conducting batteries, sodium-ion conducting batteries, magnesium-ion conducing batteries, and the like.
  • An inorganic SSE material can be used in a conventional ion-conducting battery, e.g., an ion-conducting battery comprises an electrolyte as the principle electrolyte.
  • a conventional ion-conducting battery comprises a non-conducting (e.g., non-ion conducting) separator.
  • a battery comprises an inorganic SSE material disclosed herein (e.g., an F/S SSE, which may be a templated inorganic SSE or an electrospun inorganic SSE) or a solid-state hybrid electrode disclosed herein (e.g., an F/S SSE), and electrolyte.
  • the electrolyte may be any electrolyte used in conventional ion- conducting (e.g., lithium-ion conducing) batteries known in the art.
  • electrolytes for conventional batteries include liquids such as, for example, organic liquids, gels, polymers, and the like.
  • the liquid electrolyte is not part of the solid-state hybrid electrolyte (e.g., part of the polymeric material such as, for example, a gel polymer of the solid-state hybrid electrolyte).
  • the inorganic SSE material or solid-state hybrid electrode is a separator in the conventional battery.
  • the inorganic SSE material or solid-state hybrid electrode replaces the separator in a conventional battery.
  • the inorganic SSE material or solid-state hybrid electrode both separates the cathode and anode and is ion- conducting.
  • the inorganic SSE material or solid-state hybrid electrode is an ion-conducting separator in a conventional battery.
  • Various electrodes e.g., cathodes and anodes
  • Individual electrodes e.g., cathode and/or anode
  • the solid-state hybrid electrolyte e.g., monolithic SSE or mesoporous SSE body
  • the solid-state hybrid electrolyte has one or more porous regions exposed to the surface of the solid-state hybrid electrolyte and an electrode is formed by an electrode material (e.g., cathode material and/or anode material) disposed in pores of a discrete porous region of the solid-state hybrid electrolyte.
  • Non-limiting examples of carbon materials include graphite, hard carbon, porous hollow carbon spheres and tubes, and the like.
  • the cathode material may further comprises an organic or gel ion-conducting electrolyte. Suitable organic or gel ion-conducting electrolytes are known in the art.
  • the ion-conducting cathode material also comprises an electrically conducting carbon material (e.g., graphene or carbon black), and the ion-conducting cathode material, optionally, further comprises an organic or gel ion- conducting electrolyte.
  • the electrically conductive material may separate from the ion- conducting cathode material.
  • electrically conductive material e.g., graphene, carbon nanotubes, and the like
  • a surface e.g., a pore surface
  • the electrically conductive material e.g., graphene, carbon nanotubes, and the like
  • the cathode comprises a sulfur-containing material.
  • the cathode material is an organic sulfide or polysulfide.
  • organic sulfides include carbyne polysulfide and copolymerized sulfur.
  • sulfur-containing materials include sulfur, sulfur composite materials (e.g., carbyne polysulfide, copolymerized sulfur, and the like), and polysulfide materials, and the like.
  • the cathode is an air electrode.
  • materials suitable for air electrodes include those used in ion-conducting batteries such as, for example, lithium ion batteries with air cathodes such as large surface area carbon particles (e.g., Super P which is a conductive carbon black) and catalyst particles (e.g., alpha-MnC nanorods) bound in a mesh (e.g., a polymer binder such as PVDF binder).
  • LiFeP04 LiMnP04, L1C0PO4, and Li2MMm08, wherein M is selected from Fe, Co, and the like.
  • the cathode material may be a sodium ion-conducting material.
  • sodium ion-conducting cathode materials include Na2V20s, P2- Na 2 /3Fei/ 2 Mni/ 2 0 2 , Na3V2(P04)3, NaMm/3Coi/3Nii/3P04 and composite materials (e.g., composites with carbon black) thereof such as Na2/3Fei/2Mm/202@graphene composite.
  • the cathode material may be a magnesium ion-conducting material.
  • magnesium ion-conducting cathode materials include doped manganese oxide (e.g., Mg x Mn0 2 » y H 2 0), Mgi+ x (Al,Ti) 2 (P04)6, where x is 4 to 5, NASICON-type magnesium-ion conducting materials, and the like).
  • An anode comprises one or more anode material in electrical contact with the porous region of the solid-state hybrid electrolyte.
  • the anode material is the metallic form of the ion conducted in the solid state electrolyte (e.g., metallic lithium for a lithium-ion battery) or a compound that intercalates the conducting ion (e.g., lithium carbide, LieC, for a lithium-ion battery). Examples of suitable anode materials are known in the art.
  • the anode material is disposed on at least a portion of a surface (e.g., a pore surface of one of the pores) of the porous region of the solid- state hybrid electrolyte.
  • the anode material may at least partially fill one or more pores (e.g., a majority of the pores) of the porous region of the solid-state hybrid electrolyte.
  • the anode material is infiltrated into at least a portion of the pores of the porous region of the solid-state hybrid electrolyte.
  • the anode material is disposed on at least a portion of the pore surface of an anode-side porous region of the solid-state hybrid electrolyte, where the anode side of the solid-state hybrid electrolyte is opposed to a cathode side of the solid-state hybrid electrolyte on which the cathode material is disposed.
  • the anode comprises (or consists of) a conducting carbon material.
  • carbon materials include graphite, hard carbon, porous hollow carbon spheres and tubes, and the like.
  • the anode material may further comprises an organic or gel ion-conducting electrolyte. Suitable organic or gel ion-conducting electrolytes are known in the art.
  • the anode material may be a conducting material.
  • conducting materials include conducting carbon materials, tin and its alloys, tin/carbon, tin/cobalt alloys, silicon/carbon materials, and the like.
  • conducing carbon materials include graphite, hard carbon, porous hollow carbon spheres and tubes (e.g. carbon nanotubes), and the like.
  • the anode may be a metal.
  • metals include lithium metal, sodium metal, magnesium metal, and the like.
  • the anode material may be a lithium-containing material.
  • lithium-containing materials include lithium metal, lithium carbide, LieC, and lithium titanates (LTOs) (e.g., Li4Ti50i2, and the like).
  • the anode material may be a sodium-containing material.
  • anode materials include sodium metal, and ion-conducting sodium-containing anode materials such as Na2CsH404 and Nao.66Lio.22Tio.78O2,
  • the anode material may be a magnesium-containing material.
  • the anode material is magnesium metal.
  • the batteries may comprise current collector(s).
  • a battery comprises a cathode-side (first) current collector disposed on the cathode-side of a solid-state hybrid electrolyte and an anode-side (second) current collector disposed on the anode-side of the solid-state hybrid electrolyte.
  • the current collector are each independently fabricated of a metal (e.g., aluminum, copper, or titanium) or metal alloy (aluminum alloy, copper alloy, or titanium alloy).
  • the batteries may comprise various additional structural components (such as, for example, bipolar plates, external packaging, electrical contacts/leads to connect wires, and the like).
  • a battery further comprises bipolar plates.
  • a battery further comprises bipolar plates and external packaging, and electrical contacts/leads to connect wires.
  • repeat battery cell units are separated by a bipolar plate.
  • the solid-state hybrid electrolyte, cathode, anode, the cathode-side (first) current collector (if present), and the anode-side (second) current collector (if present) may form a cell.
  • a battery may comprise a plurality of cells separated by one or more bipolar plates. The number of cells in the battery is determined by the performance requirements (e.g., voltage output) of the battery and is limited only by fabrication constraints.
  • the solid-state, ion- conducting battery comprises 1 to 500 cells, including all integer number of cells and ranges therebetween.
  • a method consists essentially of a combination of steps of the methods disclosed herein. In another example, a method consists of such steps.
  • a hybrid electrolyte e.g., a solid-state hybrid electrolyte comprising: a SSE (e.g., an inorganic (e.g., ceramic) SSE) disclosed herein (or comprising an inorganic SSE material disclosed herein); and
  • a SSE e.g., an inorganic (e.g., ceramic) SSE
  • solid-state electrolyte material e.g., solid-state electrolyte material
  • a hybrid electrolyte according to Statement 1 where the SSE material is a monolithic (e.g., a porous monolithic, a dense monolithic) SSE body or a mesoporous SSE body disclosed herein.
  • the SSE material is a monolithic (e.g., a porous monolithic, a dense monolithic) SSE body or a mesoporous SSE body disclosed herein.
  • mesoporous SSE body materials include bilayer and trilayer materials comprising one or more porous SSE material layers disposed on a dense SSE material layer).
  • Statement 3 A hybrid electrolyte according to Statement 1 or Statement 2, where the SSE material is a disc, a sheet, or a polyhedron (e.g., has a polyhedral shape).
  • Statement 7 A hybrid electrolyte according to Statement 5 or Statement 6, where the fibers are randomly arranged or aligned.
  • Statement 8 A hybrid electrolyte according to any one of Statements 5-7, where the fibers or strands of the polymeric material form an interconnected 3-D network.
  • the SSE material comprises a lithium-ion conducting (e.g., lithium-ion containing) SSE material, a sodium-ion conducting (e.g., sodium-ion containing) SSE material, or a magnesium-ion conducting (e.g., magnesium-ion containing) SSE material.
  • a lithium-ion conducting e.g., lithium-ion containing
  • a sodium-ion conducting e.g., sodium-ion containing
  • magnesium-ion conducting e.g., magnesium-ion containing
  • Statement 10 A hybrid electrolyte according to Statement 9, where the lithium-ion conducting SSE material is selected from the group consisting of lithium perovskite materials, L13N, Li- -alumina, Lithium Super-ionic Conductors (LISICON), Li2.88PO3.86N0.14 (LiPON), Li9AlSi08, LiioGeP2S i2, lithium garnet materials, doped lithium garnet materials, lithium garnet composite materials, and combinations thereof.
  • the lithium-ion conducting SSE material is selected from the group consisting of lithium perovskite materials, L13N, Li- -alumina, Lithium Super-ionic Conductors (LISICON), Li2.88PO3.86N0.14 (LiPON), Li9AlSi08, LiioGeP2S i2, lithium garnet materials, doped lithium garnet materials, lithium garnet composite materials, and combinations thereof.
  • the sodium-ion conducting SSE material is selected from the group consisting of ⁇ "- ⁇ 2 ⁇ 3, Na4Zr2Si2POi2 (NASICON), cation-doped NASICON, and combinations thereof.
  • the polymeric material comprises (e.g., the polymeric material is) a polymer selected from the group consisting of poly(ethylene) (PE), poly(ethylene oxide) (PEO), poly(propylene) (PP), poly(propylene oxide), polymethyl methacrylate (PMMA), polyacrylonitrile (PAN), poly[bis(methoxy ethoxyethoxide ⁇ ⁇ phosphazene], poly(dimethylsiloxane) (PDMS), cellulose, cellulose acetate, cellulose acetate butylate, cellulose acetate propionate, polyvinylidene difluoride (PVdF), polyvinylpyrrolidone (PVP), polystyrene, sulfonate (PSS), polyvinylchloride (PVC) group, poly(vinylidene chloride) polypropylene oxide,
  • PE poly(ethylene oxide)
  • PEO poly(propylene)
  • PMMA polymethyl methacrylate
  • PAN polyacryl
  • polyvinylacetate polytetrafluoroethylene (e.g., Teflon®), poly (ethylene terephthalate) (PET), polyimide, polyhydroxyalkanoate (PHA), PEO containing co-polymers (e.g., polystyrene (PS) - PEO copolymers and poly(methyl methacrylate) (PMMA) - PEO copolymers), polyacrylonitrile (PAN), poly(acrylonitrile-co-methylacrylate), PVdF containing co-polymers (e.g., polyvinylidene fluoride-co-hexafluoropropylene (PVdF-co-HFP)), PMMA co-polymers (e.g., poly(methylmethacrylate-co-ethylacrylate)), derivatives thereof, and combinations thereof.
  • PEO containing co-polymers e.g., polystyrene (PS) - PEO copolymers and poly(methyl
  • liquid electrolyte e.g., non-aqueous liquid electrolytes such as, for example, LiPFe (e.g., 1M) in ethylene carbonate (EC)/diethyl carbonate (DEC), LiTFSI (e.g., 1M) in dimethoxy ethane (DME)/dioxolane (DOL), LiTFSI (e.g., 0.5 M) in N-Propyl-N- methylpyrrolidinium bis(trifluoromethanesulfonyl) imide (PYR13TFSI) ionic liquid, and the like).
  • a liquid electrolyte e.g., non-aqueous liquid electrolytes such as, for example, LiPFe (e.g., 1M) in ethylene carbonate (EC)/diethyl carbonate (DEC), LiTFSI (e.g., 1M) in dimethoxy ethane (DME)/dioxolane
  • a metal salt e.g., a metal salt selected from the group consisting of lithium salts, sodium salts, magnesium salts, and the like.
  • the ceramic filler is selected from the group consisting of conductive particles, non-conductive particles (e.g., AI2O3, S1O2, T1O2 nanoparticles, and the like), ceramic nanomaterials (e.g., ceramic nanoparticles, ceramic nanofibers), and the like.
  • a device comprising one or more hybrid electrolyte of the present disclosure (e.g., a hybrid electrolyte of any one of Statements 1-22).
  • Statement 24 A device according to Statement 23, where the device is a battery (e.g., an ion- conducting battery such as, for example, a solid-state, ion-conducting battery) comprising: a hybrid electrolyte of the present disclosure (e.g., a hybrid electrolyte of any one of Statements 1-22); an anode; and
  • a battery e.g., an ion- conducting battery such as, for example, a solid-state, ion-conducting battery
  • a hybrid electrolyte of the present disclosure e.g., a hybrid electrolyte of any one of Statements 1-22
  • an anode e.g., a hybrid electrolyte of any one of Statements 1-22
  • the hybrid electrolyte is disposed between the cathode and anode (e.g., the polymeric material of the hybrid electrolyte is disposed between, for example, fills substantially all of the void space between, the SSE material of the hybrid electrolyte and the anode and/or cathode).
  • Statement 25 A device according to Statement 24, where the battery further comprises a current collector disposed on at least a portion of the cathode and/or the anode.
  • Statement 27 A device according to any one of Statements 24-26, where the battery is a lithium-ion conducting solid-state battery and the hybrid electrolyte is a lithium ion- conducting (e.g., lithium containing) SSE material (e.g., a lithium-conducting (e.g., lithium containing) SSE material of any one of Statements 11-13).
  • a lithium ion- conducting (e.g., lithium containing) SSE material e.g., a lithium-conducting (e.g., lithium containing) SSE material of any one of Statements 11-13).
  • Statement 28 A device according to any one of Statements 24-26, where 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 of Statement 14).
  • a sodium ion- conducting (e.g., sodium containing) SSE material e.g., a sodium-ion conducting (e.g., sodium containing) SSE material of Statement 14).
  • Statement 29 A device according to any one of Statements 24-26, where 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 of Statement 15).
  • a magnesium ion- conducting (e.g., magnesium containing) SSE material e.g., a magnesium-ion conducting (e.g., magnesium containing) SSE material of Statement 15).
  • Statement 30 A device according to any one of Statements 24-29, where the cathode and/or anode comprises a conducting carbon material (e.g., graphite, hard carbon, porous hollow carbon spheres and tubes, and the like), and the cathode material, optionally, further comprises an organic or gel ion-conducting electrolyte.
  • a conducting carbon material e.g., graphite, hard carbon, porous hollow carbon spheres and tubes, and the like
  • the cathode material optionally, further comprises an organic or gel ion-conducting electrolyte.
  • the cathode e.g., lithium ion- conducting, lithium-containing cathode
  • the cathode comprises a material selected from the group consisting of lithium-containing materials.
  • the cathode e.g., a magnesium ion-conducting, magnesium-containing cathode
  • the cathode comprises a material selected from the group consisting of doped magnesium oxides (e.g., Mgi+ x (Al,Ti)2(P04)6, where x is 4 to 5, NASICON-type magnesium-ion conducting materials, and the like).
  • Statement 37 A device according to any one of Statements 24-36, where the anode comprises a material selected from the group consisting of silicon-containing materials (e.g., silicon, silicon/carbon, and the like), tin and its alloys (e.g., tin/cobalt alloys and the like), tin/carbon, and phosphorus.
  • silicon-containing materials e.g., silicon, silicon/carbon, and the like
  • tin and its alloys e.g., tin/cobalt alloys and the like
  • tin/carbon e.g., tin/carbon, and phosphorus.
  • Statement 38 A device according to any one of Statements 24-27 and 31-33, where the anode (e.g., a lithium ion-conducting anode and lithium containing anode) comprises a material selected from the group consisting of lithium-ion conducting anode materials.
  • LTOs lithium titanates
  • Statement 41 A device according to any one of Statements 24-26, 28, and 34-35, where the anode (e.g., a sodium-containing and sodium ion-conducting anode) comprises a material selected from sodium-ion conducting anode materials.
  • the anode e.g., a sodium-containing and sodium ion-conducting anode
  • the anode comprises a material selected from sodium-ion conducting anode materials.
  • Statement 43 A device according to Statement 41, where the anode is sodium metal.
  • Statement 44 A device according to any one of Statements 24-26, 29, and 36, where the anode is a magnesium-containing anode material.
  • Statement 47 A device according to any one of Statements 23-46, wherein the device is a conventional ion-conducting battery comprising a liquid electrolyte (e.g., as the principle electrolyte) and the battery comprises an inorganic SSE disclosed herein or a solid-state hybrid electrolyte disclosed herein and a liquid electrolyte (e.g., a liquid electrolyte used in a conventional battery), where the liquid electrolyte is not present as component of the solid- state hybrid electrolyte, and where the inorganic SSE material or the solid-state hybrid electrolyte is a separator in the conventional battery.
  • a liquid electrolyte e.g., as the principle electrolyte
  • the battery comprises an inorganic SSE disclosed herein or a solid-state hybrid electrolyte disclosed herein and a liquid electrolyte (e.g., a liquid electrolyte used in a conventional battery), where the liquid electrolyte is not present as component of the solid
  • Statement 48 The device according to Statement 47, wherein the inorganic SSE is an F/S SSE disclosed herein (e.g., templated inorganic SSE or an electrospun inorganic SSE) Statement 49.
  • a method of making a hybrid electrolyte e.g., a solid-state hybrid electrolyte (e.g., a hybrid electrolyte of any one of Statements 1-22) comprising:
  • contacting a template with one or more SSE material precursors reacting (e.g., by heating) the SSE material precursor(s) to form a solid inorganic material (e.g., comprising at least partially or completely reacted and/or decomposed SSE material precursors); and
  • thermally treating e.g., sintering and/or calcining
  • the template is removed (e.g., as carbon dioxide, for example, by combustion) and the inorganic SSE (e.g., monolithic SSE or mesoporous body or F/S SSE) is formed; and
  • the inorganic SSE e.g., monolithic SSE or mesoporous body or F/S SSE
  • Statement 50 The method according to Statement 49, where the SSE material precursors are sol-gel precursors or metal salts.
  • Statement 51. The method according to Statement 49 or Statement 50, where the template is a carbon template (e.g., a textile template) or a biomaterial template (e.g., a wood or plant template).
  • Garnet-type solid state electrolyte has demonstrated promising results for Li metal batteries, due to its high ionic conductivity (10 "4 S/cm ⁇ 10 "3 S/cm) and wide electrochemically stable window (0-6 V vs. Li + /Li).
  • One of the main challenges for garnet-type solid state electrolyte is the high interfacial resistance between the electrolyte and electrodes.
  • This examples described a hybrid electrolyte with a solid state Li7La2.75Cao.25Zn.75Nbo.25012 (LLCZN) garnet-type electrolyte between two gel polymer electrolyte layers to decrease the interfacial resistance of a lithium metal symmetric cell and protect against dendrite penetration.
  • the gel polymer electrolyte layers form favorable interfaces between the garnet solid state electrolyte (SSE) and the electrodes with low interfacial resistance and long term electrochemical stability.
  • the hybrid gel polymer and LLCZN electrolyte achieves low interfacial charge transfer resistance around 248 Qxcm 2 at the SSE/Cathode interface and 214 Qxcm 2 at the SSE/Li metal interface.
  • hybrid electrolyte can prevent lithium dendrite formation, because of the dense LLCZN garnet layer.
  • Our results show that the hybrid symmetric cells can run with stable stripping and plating profiles for long periods of cycling.
  • this hybrid electrolyte can be used for Li metal batteries with small over potentials and increased reliability against dendrite short circuiting.
  • the hybrid electrolyte design with gel polymer interface layers is an exciting surface engineering solution to combat the garnet solid state interface resistance and demonstrate safe Li metal batteries with high performance capabilities.
  • FIG. 1 A hybrid electrolyte with gel polymer electrolyte as interfacial layers in between LLCZN garnet SSE is proposed to reduce the interfacial resistance and demonstrate Li metal full cells that can operate at room temperature.
  • Figure la shows a schematic of the solid-polymer Li metal battery design using the polymer/garnet-type SSE hybrid electrolyte.
  • gel polymer is used as interfacial layers, in between of garnet-type SSE and electrodes, to reduce interfacial resistance.
  • Gel polymer electrolyte can help to increase the contact between garnet-type SSE and electrodes, so as to decrease the garnet-type SSE interfacial resistance against cathode and Li metal ( Figure lb).
  • Gel polymer electrolyte used in this study is a combination of a porous PVDF-HFP polymer matrix and a controlled amount of liquid electrolyte stored inside the polymer.
  • the gel polymer prepared by a known technique, has good ionic conductivity (5x l0 "4 S/cm) and is electrochemically stable in the voltage range of 0 to 4.5 V vs. Li + /Li, which is suitable for most commercially employed cathode materials.
  • the interfacial resistance is measured to be as low as 248 ⁇ ⁇ ⁇ 2 for cathode interface, and 214 Qxcm 2 for Li metal anode interface.
  • Our results show that the hybrid symmetric cells can run with stable stripping and plating profiles for up to 15 hours and with a low over potential, which is indicative of a stable interface between the garnet-type SSE and metallic Li anode. Since minimal amounts of liquid electrolyte are stored in the gel polymer interlay er, the hybrid electrolyte will not suffer from leakage as do conventional liquid electrolyte-based batteries.
  • the hybrid electrolyte design with gel polymer interface layers can be considered as an important surface engineering strategy to decrease the overall interfacial resistance against electrodes, including both cathode and Li metal anode within the electrochemical cells, and demonstrate safe Li metal batteries with high performance.
  • X-Ray diffraction was performed on a garnet-type LLCZN pallet. It matched well with the standard XRD plot of cubic phase garnet-type Li5La3Nb20i2, which indicates that the LLCZN pallet has a cubic garnet-phase, which has higher Li ion conductivity compared with tetragonal garnet-phase.
  • Electrochemical impedance spectroscopy was performed with two LLCZN pallets, with thicknesses of 1000 ⁇ and 150 ⁇ , tested in a symmetric cell with gold deposited on both sides. The semicircle in the high frequency portion of the impedance spectroscopy curve represents the bulk resistance and the grain boundary resistance of LLCZN.
  • the LLCZN pallets with different thicknesses have the same bulk conductivity of around 2* 10 "4 S/cm.
  • the bulk areal specific resistance (ASR) of a 450 ⁇ thick LLCZN pallet is 225 ⁇ ⁇ ⁇ 2 , which is acceptable for a battery. This means that the inner resistance of the garnet-type SSE is relatively small, and the main contribution to the resistance of the solid state battery comes from the interfaces between the SSE and the electrodes.
  • FIG. 1 shows the impedance profile of a cathode
  • the bulk resistance of this cell is small, because of the thin and conductive gel polymer layer.
  • the semi-circle in the middle frequency part corresponds to the charge transfer resistance (Ret), which is about 107 ⁇ ⁇ ⁇ 2 for each side. This value is calculated with equivalent circuit simulations.
  • Ret charge transfer resistance
  • the impedance curve is combined of three parts.
  • the high frequency part is the bulk and grain boundary impedance of the garnet-type SSE itself.
  • the middle frequency part is a combination of two semi-circles corresponding to interfacial Ret between garnet-type SSE and cathode, including Ret of the polymer
  • the low frequency part is a straight line, corresponding to diffusion impedance of the cathode.
  • cathode symmetric cell is 248 ⁇ ⁇ ⁇ 2 for each side. This value was got from equivalent circuit fitting.
  • cathode symmetric cell is approximately the sum of polymer
  • SSE interface is sum up of polymer
  • Figure 5a is the EIS plot of cathode
  • the symmetric cell was made by directly brushing the cathode slurry on the gamet-type SSE surface and then drying up. It shows that the total Ret of cathode
  • SSE I cathode symmetric cell without polymer interfacial layer is about 1 x lO 6 ⁇ ⁇ ⁇ 2 .
  • the huge resistance is evidence of poor contact between SSE and LiFePC cathode materials. This problem can be solved with gel polymer layer in the hybrid design between garnet-type SSE and the cathode.
  • Figure 2d shows the impedance curve of a Li
  • Figure 2e shows the EIS plot of Li
  • the high frequency part is the bulk resistance and the grain boundary resistance of the garnet-type SSE.
  • the middle frequency part are two semi-circles corresponding to interfacial Ret between garnet-type SSE and Li metal, which mainly come from the impedance of the polymer
  • Li symmetric cell is 214 ⁇ ⁇ ⁇ 2 .
  • Figure 5b shows that the total resistance of a Li
  • the metallic lithium is melted and coated on both sides of garnet- type SSE.
  • cathode symmetric cell in Figure 5a, is that the melting of lithium metal improved the surface contact, compared to the solid state cathode powders and binder.
  • the 1400 ⁇ ⁇ ⁇ 2 interfacial resistance is still too large for battery use, and this can be reduced by the gel polymer interfacial layers.
  • gel interfacial layer can significantly reduce the interfacial Ret between the LLCZN solid state electrolyte and the electrodes, including numerous cathode materials and Li metal anodes.
  • Figure 2f compares the interfacial resistance of Li
  • the interfacial resistance between cathode and garnet type SSE was decreased from 6* 10 4 ⁇ ⁇ ⁇ 2 to 248 ⁇ ⁇ ⁇ 2 , after applying the gel polymer interface.
  • the interfacial resistance between the Li metal anode and garnet type SSE was decreased from 1400 Qxcm 2 to 214 ⁇ ⁇ ⁇ 2 , after applying gel polymer interface.
  • Figure 3 analyses the impedance identified for each interface in symmetric cells with and without gel polymer interfaces.
  • cathode symmetric cell comes from Figures 2a-c, and the analysis of the impedance in a cathode
  • Corresponding equivalent circuits are described herein. In each equivalent circuit, there is one parallel connection between a resistor and capacitor/constant phase element (CPE) for impedance on one interface.
  • the capacitor/CPE is for double layer capacitance on the interface, and the resistor is for charge transfer resistance on the interface.
  • cathode symmetric cell is 496 Qxcm 2 , much less than the interfacial Ret of the cathode
  • This reduced resistance means that the gel polymer interface can significantly improve the contact performance between the cathode and SSE.
  • Li symmetric cell comes from analysis of Figures 2b, d-e, and the analysis of the impedance in a Li
  • FIG. 4a shows the DC cycling voltage profiles of a Li
  • the total DC ASR of the symmetric cell is 1400 ⁇ ⁇ ⁇ 2 , which is measured from the voltage value 180 mV divided by the areal current density 125 ⁇ /cm 2 .
  • the inset of Figure 4a shows that the DC resistance is kept constant in one cycle.
  • This DC resistance comes from the bulk and grain boundary resistance of SSE, and the resistance of the SSE
  • the voltage is smaller in the first 5 hours from 180 mV to 160 mV, because lithium stripping and plating can improve the interfacial contact between lithium and gel polymer electrolyte. After 5 hours the voltage is kept constant, the interfacial resistance is kept constant, and the interface is stable.
  • Figure 4b shows the EIS plots of the cell before and after cycling for 15 hours. While cycling, the interfacial ASR is almost constant and changes from 1000 ⁇ ⁇ ⁇ 2 to 1100 Qxcm 2 . This means that the gel polymer interface was stable and kept a small resistance for a long time.
  • Figure 4c-e shows the cycling performances of a full cell with
  • FIG. 4c is the charge and discharge profiles of the 1st, 10th, 50th, 100th, and 130th cycles. The charge and discharge curves show stable voltage plateaus, and the over potentials of the cycles are consistent. This means that the interfacial resistance is constant during 130 charge and discharge cycles.
  • Figure 4d shows the discharge capacity and coulombic efficiency of each cycle and the coulombic efficiency is about 95% for each cycle beyond the first. The Columbic efficiency of the first cycle is low, owing to that an SEI layer was formed between electrodes and gel during the first cycle.
  • the Ret shown as the diameter of the semicircle in the middle frequency range, is almost constant at about 500 Qxcm 2 , which means that the impedance of the gel polymer electrolyte is very stable, and can maintain a small charge transfer resistance for 130 cycles.
  • the hybrid polymer/garnet electrolyte can be used for Li metal full cells with small over potentials and good stability.
  • polymer/garnet hybrid electrolyte can be used in a successful solid-polymer battery design, instead of pure SSE, to reduce the interfacial resistance between the garnet-type SSE and the electrodes.
  • Gel polymer electrolyte has high ionic conductivity and a wide electrochemically stable voltage window. Therefore, it can be used as an interfacial layer between the LLZCN garnet SSE and electrodes, to provide an electrochemically stable and ionically conductive interface.
  • the Ret between SSE and electrodes, with a gel polymer interfacial layer is 248 Qxcm 2 for the cathode, and 214 Qxcm 2 for Li metal anode, as measured by impedance spectroscopy of symmetric and full cells.
  • This interfacial resistance is acceptable for commercial lithium metal cell production.
  • a Li metal symmetric cell with polymer/garnet-type SSE hybrid electrolyte was demonstrated and cycled for over 15 hours with a stable voltage profile. It proves that the gel polymer interface between Li metal anode and garnet-type SSE is electrochemically stable.
  • a battery was realized and cycled 130 times at room temperature using a Li metal anode, LiFeP04 cathode and the polymer/garnet hybrid electrolyte.
  • PVDF-HFP based gel polymer electrolyte was made by the following way. First dissolve 0.25 g of PVDF-HFP (Sigma-Aldrich) into a mixture of 4.5 g acetone and 0.25 g ethanol under mechanical stirring for 1 h, to get homogeneous solution. The solution was then cast onto a flat aluminum foil and the solvent was evaporated in a constant humidity chamber with 80% humidity and 25 °C temperature. The samples are dried under vacuum at 60 °C for 5 h. After that a homogeneous freestanding membrane was obtained. The thickness of the PVDF-HFP membrane is around 40 ⁇ .
  • the as-prepared porous PVDF-HFP membrane was cut into small round films with an area of 0.2 cm 2 , and immersed into 1 M L1PF6 in 1 : 1 ethylene carbonate (EC): diethyl carbonate (DEC) liquid electrolyte for 1 minute to be fully soaked by electrolyte, and the excess liquid on the surface of the membrane was moved away by wipers.
  • 1 ethylene carbonate (EC): diethyl carbonate (DEC) liquid electrolyte for 1 minute to be fully soaked by electrolyte, and the excess liquid on the surface of the membrane was moved away by wipers.
  • the electrodes, gel membranes, and garnet pallets were pressed together in sequence by clips, with one stainless steel pallet on each side of the cell.
  • the electrochemical performance of the cells were tested by a Bio-Logic tester. EIS tests of the symmetrical cells have a voltage amplitude of 10 mV and a frequency range of 0.1 Hz to 1 MHz. Constant current cycling of Li I SSE I Li with gel interface layers used the same assembly method as with the EIS test, and were conducted with a current density of 0.125 niA/cm 2 with a period of 10 minute. The EIS of the cell before cycling and after cycling for 15 hours was measured and compared.
  • Li I SSE LiFePCU full cell with gel polymer interfaces was made by pressing the garnet, gel and electrode layers together in a CR2016 coin cell, and sealed by epoxy. This cell was cycled with a constant current of 50 ⁇ /cm 2 in the voltage range of 2 V to 4.5 V, and the EIS of the cell before and after cycling was measured.
  • This example provides a description of solid-state hybrid electrolytes of the present disclosure. This example also provides examples of making and characterization of such electrolytes.
  • Short Circuits in Li-Metal Batteries Chemical and physical short circuits are two important challenges in Li-metal batteries associated with transport of soluble materials and penetration of Li dendrite, leading to limited battery cycle-life and thermal runaway.
  • a hybrid solid-state electrolyte system consisting of a structural garnet-type solid- state electrolyte (SSE) and liquid electrolyte are described in this example.
  • the hybrid electrolyte utilizes regular liquid electrolyte to maintain high ion transport kinetics in electrodes and employs SSE to not only separate electrodes as well as liquid electrolyte apart but also block the unwanted species diffusion and Li dendrites.
  • the example describes investigation of garnet SSE chemical and electrochemical stability in sulfur, polysulfides and liquid electrolyte, and development of a bilayer garnet SSE framework for hybrid Li-S battery with a continuous Li + /electron pathway in porous layer for high sulfur loading cathode and a dense layer to block polysulfides diffusion and dendrite penetration.
  • This work showed that the integrated sulfur loading can reach >7 mg/cm 2 and an energy density of >280 Wh/kg based on full cell level.
  • the initial coulombic efficiency is as high as 99.8%, and no chemical or physical short circuit was observed in the hybrid system.
  • this structural hybrid electrolyte design with high surface reaction sites for cathode and blocking layer for Li anode can be expected to use other cathode materials, such as high voltage cathode (LNMO) and air/02 cathode, paving the way to transition from conventional battery towards all-solid-state batteries.
  • LNMO high voltage cathode
  • air/02 cathode paving the way to transition from conventional battery towards all-solid-state batteries.
  • garnet SSE is much chemically stable in dry air and can be handled in dry -room environment.
  • Schematic of the bilayer garnet SSE structure is shown in Figure 7.
  • the porous structure was sitting on top of dense layer and the porous structure can enhance the mechanical strength of the ultrathin dense layer.
  • the further encapsulation of cathode materials through these pores makes an integrated cathode and electrolyte structure.
  • Figure 7b is the top view of the scanning electron microscopy (SEM) image of porous layer. Micro-sized pores are evenly distributed, allowing electrode slurry to easily get into the interior structure.
  • the cross-section of the bilayer garnet SSE in shown in Figure 7c-e.
  • Garnet powders were sintered into a 3D network, with a porosity of -70%.
  • Figure 7d shows the connection part of porous layer and dense layer, suggesting that the porous and dense layer were well sintered and no delamination was observed.
  • the dense garnet layer in Figure 7e demonstrates that large garnet crystal grains make up the dense microstructure and this dense layer can block dissoluble active material and liquid electrolyte go through the solid electrolyte.
  • Figure 7f is the cross-section of bilayer garnet with a total thickness of 105 ⁇ including 35 ⁇ dense part and 70 ⁇ porous part.
  • Li5La3Nb20i2 (PDF 80-0457).
  • the broad and partially overlapped bands confirms the cubic phase of LLCZNO garnet, which agrees with garnet spectrum reported elsewhere.
  • the ionic conductivity was measured by electrochemical impedance spectroscopy (EIS) using a blocking cell setup. A dense garnet pellet was used to make the symmetric Au/garnet SSE/Au blocking cell. The EIS of garnet SSE was measured in a temperature range of 25 °C to 50 °C ( Figure 1 l). The intercept in the real axis at high frequency is assigned to the bulk resistance of garnet SSE, and the depressed semicircle is associated with the grain boundary of garnet SSE.
  • the total resistance including the bulk and grain boundary contributions were calculated by using the low frequency intercept, which is corresponding to the capacitive behavior of the Au electrodes.
  • the logarithmic ionic conductivity of garnet SSE against the inverse of temperature is plotted in Figure 12.
  • the activation energy of 0.35 eV were calculated from the conductivities as a function of temperature using the Arrhenius equation.
  • the Zr 3d spectra of garnet with and without ion sputtering in Figure 9c shows that before sputtering there is no Zr 3d detected on garnet surface, but after sputtering the Zr 3d, which is an indicator of LLCZNO garnet, was detected, indicating the formation of a solid interphase on garnet surface and the solid interphase has a finite thickness on garnet.
  • Our results can be confirmed by a recent study reported that a solid electrolytes tend to dissolve into liquid electrolyte and within the contact region a so-called solid-liquid electrolyte interphase (SLEI) was observed and contained decomposition products from both solid electrolyte and organic electrolyte.
  • SLEI solid-liquid electrolyte interphase
  • the X-ray diffraction patterns (XRD) in Figure 9d show that garnet powders remained cubic phase structure and no phase change was observed after soaking in lithium polysulfides and liquid electrolyte.
  • XPS results indicate that liquid electrolyte and garnet solid electrolyte, to a certain extent, were decomposed in polysulfides solution, the stable cubic phase and the electrochemical performance in Li/SSE/L symmetric cells and Li- S full cells fully demonstrate that garnet solid electrolytes could perform well in the liquid electrolyte and the reduced species of sulfur environment.
  • Raman spectra of garnet treated under the same conditions confirm that garnet cubic structure remained stable ( Figure 8e).
  • TEM transmission electron microscopy
  • This elastic polymer layer can compensate the roughness of 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 was -900 ohm-cm 2 ( Figure 9e).
  • Electrochemical evaluation of hybrid Li-S batteries Electrochemical characterization of the hybrid solid-state electrolyte in Li-S battery are shown in Figure 10.
  • Figure 10a schematic of Li-S battery with conventional and hybrid solid-state electrolyte are compared.
  • the soluble polysulfides can diffuse through porous polymer separator and migrate to the Li metal anode, but cannot penetrate through the dense ceramic ion conductor, thus avoiding polysulfides shuttling effect, side reactions on Li, and Li metal corrosion.
  • Poly sulfide shuttling behavior occurs in charge process as shown in Figure 10b.
  • the extended charge voltage plateau is a typical polysulfides shuttle effect, causing long-time charging before getting to the upper cut-off voltage.
  • Figure 10c shows the discharge and charge curves of a hybrid cell at different current density.
  • the hybrid cell was made by using a dense garnet SSE and a slurry-casted sulfur cathode.
  • the sulfur mass loading is -1.2 mg/cm 2 .
  • Regular liquid electrolyte LiTFSI in DME/DOL
  • no LiNC was added in the liquid electrolyte.
  • current density of 200 mA/g the sulfur cathode delivered a specific capacity of -1000 mAh/g with a -100% coulombic efficiency.
  • Figure lOe shows the schematic of hybrid solid-state bilayer Li-S battery.
  • Figure lOg shows discharge and charge voltage profiles of the hybrid bilayer Li-S cell with a S mass loading of -7.5 mg/cm2 at a current density of 0.2 mA/cm 2 .
  • the first cycle's discharge capacity is -645 mAh/g with a coulombic efficiency of 99.8%, which is an exceptionally high value.
  • the long and flat voltage plateaus indicate the uncompromised polarization between discharge and charge curves. This should be contributed to the porous garnet SSE that has high surface area to increase reaction sites with sulfur, leading to low voltage polarization and good capacity.
  • the cycling performance is shown in Figure lOh. No sudden capacity jump occurred in the beginning of few cycles, demonstrating that no polysulfides were lost in this hybrid cell with such a high sulfur mass loading.
  • solid sulfur as a model material was used to study the hybrid electrolyte and hybrid cells, and also it can be envisioned that use of catholyte having liquid polysulfides can be another way to apply to the bilayer porous-dense design of garnet SSE.
  • garnet SSE chemical and electrochemical stability in sulfur, polysulfides and liquid electrolyte and developed a bilayer garnet SSE framework for hybrid Li-S battery with a continuous Li + /electron pathway in porous layer for high sulfur loading cathode and a dense layer to block polysulfides diffusion and dendrite formation.
  • the hybrid solid-state battery cannot only prevent chemical and physical short circuits, but also allow high cathode mass loading, trap liquid electrolyte, and release cathode volume change.
  • the bilayer SSE encapsulates active materials directly into the pores and these pores can be tailored to accommodate volume change of active materials thus keeping battery structure stable during cycling.
  • the solution was evaporated at 120 °C for 12h to produce the precursor gel and then calcined to 400 °C and 800 °C for 5 hours to synthesize the garnet powder.
  • the garnet powders were then uniaxially pressed into pellets and sintered at 1050 °C for 12 hours covered by the same type of powder.
  • the activation energies were obtained from the conductivities as a function of temperature using the Arrhenius equation.
  • Hybrid solid-state battery preparation and evaluation All the cells were assembled in an argon-filled glove-box.
  • the hybrid solid-state cells were assembled in 2032 coin cells.
  • 1M bis(trifluoromethane)sulfonimide lithium salt (LiTFSI, Sigma) in a mixture of dimethoxy ethane (DME) and 1,3-dioxolane (DOL) (1 : 1 by volume) was used as the electrolyte for the hybrid solid-state Li-S batteries.
  • This example provides a description of solid-state hybrid electrolytes of the present disclosure. This example also provides examples of making and characterization of such electrolytes.
  • the 3D bilayer solid-state electrolyte framework has several unique advantages: (a) the thin dense bottom layer is a rigid barrier with high elastic modulus that can efficiently separate electrodes and liquid electrolytes and prevent Li dendrite penetration; (b) the thick top porous layer mechanically supports the thin dense layer; (c) the interface between the dense and porous layers is well sintered with good mechanical integrity and continuous ion transport; (d) the solid-state framework can provide electronically and ionically conductive pathways for the encapsulated cathode materials; (e) the solid-state framework can locally confine cathode materials and accommodate their volume change, such as with solid sulfur and polysulfide catholyte.
  • the bilayer framework was prepared by laminating dense and porous tapes into a bilayer tape, then co-sintering to remove the organic binders and polymers.
  • the porous garnet structure was fabricated by scalable tape casting using garnet powder slurry containing poly(methyl methacrylate) (PMMA) spheres as sacrificial pore formers for a porosity of 70% . Further details of the fabrication process are given in the Experimental Section. Unlike sulfide-type superionic conductors that are sensitive to air and moisture, garnet is chemically stable for processing in dry air and has sufficient mechanical strength for handling.
  • the tape casting method can be readily scaled to fabricate low cost garnet solid-state electrolyte frameworks.
  • organic fillers were decomposed and garnet powders were sintered together to form the porous layer.
  • the thickness of porous layer and dense layer is controlled by the tape thickness.
  • LLCZNO LLCZNO garnet was confirmed by X-ray diffraction (XRD) and matches well with cubic Li5La3Nb20i2 (PDF 80-0457). Additionally, the broad and partially overlapped bands in the Raman spectra confirm the cubic phase of LLCZNO garnet.
  • the logarithmic ionic conductivity of the garnet electrolyte against the inverse of temperature was plotted.
  • An activation energy of 0.35 eV was calculated from the conductivities as a function of temperature using the Arrhenius equation.
  • the structure and chemistry of the garnet and electrode interfaces are the main source of challenges for the application of solid-state electrolyte.
  • Recent work suggests that poor contact at the interface is a key factor that leads to the high interfacial impedance of solid electrolytes and electrodes.
  • ALD atomic layer deposition
  • the interfacial resistance of Li-metal/garnet can be significantly decreased.
  • a gel electrolyte as an artificial interlayer between the solid electrolyte and electrodes can be more scalable toward battery
  • the gel electrolyte with good wetting can not only provide an evenly distributed Li ion flux at the interface, but also prevent potential reduction of the solid electrolyte after contact with Li metallsolated pores are distributed on the garnet surface and cavities reduce the surface area contact with Li metal, leading to inhomogeneous Li ion transport and high interfacial resistance.
  • a polymeric gel layer was implemented to conformally coat the garnet surface. The liquid filled interlayer ensures close contact between the garnet and lithium metal. Polyethylene oxide (PEO) polymer with a thickness of 2 ⁇ conformally coats the garnet. This polymer layer compensates for interfacial roughness and enables a homogeneous Li ion flux through the interface.
  • PEO polyethylene oxide
  • Li/polymer/garnet/polymer/Li Li/hybrid electrolyte/Li cell under a current density of 0.3 niA/cm 2 .
  • the positive voltage indicates Li stripping and the negative voltage is Li plating.
  • the cell was run 0.5 h for each cycle.
  • the cell exhibited a voltage of ⁇ 0.3 V in the beginning, and the voltage gradually decreased to ⁇ 0.2 V after 10 hours cycling.
  • the hybrid cell was cycled for over 160 hours and the stripping/plating voltage remained relatively stable.
  • a symmetric Li/garnet/Li cell without the polymer interface was also prepared and tested.
  • the inset shows the initial cycling of the two types of cells and the 140 th hour of the hybrid cell.
  • Electrochemical performance of Li-S batteries using the bilayer solid-state garnet hybrid electrolyte was determined.
  • CNT were infiltrated into the microstructure of the porous garnet to form an enhanced electronically conductive network.
  • a photograph of the CNT infiltrated bilayer garnet framework and an SEM image showed CNT coated inside the porous structure.
  • the volume expansion of sulfur and its soluble polysulfides can be accommodated by the solid garnet framework.
  • Sulfur was loaded directly by melting sulfur powder into the porous matrix at 160 °C.
  • Cross-sections of the Li-S cathode and elemental mapping was performed.
  • An elemental mapping image clearly indicated the sulfur distribution in the pores of the bilayer garnet. Additional pore space between sulfur and garnet allows liquid electrolyte to penetrate into interior channels and coat the sulfur.
  • a hybrid bilayer cell with higher sulfur mass loading of approximately 7.5 mg/cm 2 was prepared. Discharge and charge voltage profiles were made with the hybrid Li-S cell at a current density of 0.2 niA/cm 2 . The first cycle's discharge capacity is around 645 mAh/g with a coulombic efficiency of 99.8%, an exceptionally high value. The long and flat voltage plateaus indicate the uncompromised polarization between the discharge and charge curves. This can be attributed to the thin dense layer and porous garnet layer with high surface area to increase the number of reaction sites for sulfur, therefore leading to low voltage polarization and good capacity. The cycling performance is was plotted.
  • the hybrid bilayer Li-S cell with a mass loading of 7.5 mg/cm 2 has a total cell energy density (as calculated in Figure 16) of 248.2 Wh/kg considering the total mass for cathode, Li anode and electrolyte far beyond any solid battery available today.
  • the cycling performance exhibited slight decay, which is possibly due to the charged products L12S and L12S2 not being reactivated in the following cycles.
  • the high sulfur mass loading impedes further reaction inside the bulk sulfur cathode.
  • This example describes a 3D bilayer solid-state electrolyte framework that addresses the issue of both chemical and physical short circuits in Li-metal batteries.
  • the dense garnet membrane thickness was reduced to a few microns while maintaining adequate mechanical strength for battery assembly.
  • the bilayer solid-state electrolyte framework was designed with a thick porous layer to mechanically support the thin dense layer, while hosting electrode material and liquid electrolyte.
  • the thick porous layer has continuous Li + /electron pathways to host the sulfur cathode.
  • the thin dense layer additionally blocks polysulfide diffusion and impedes Li dendrite formation.
  • the bilayer garnet solid electrolyte framework was applied to Li-S batteries to demonstrate its feasibility as well as high energy density and excellent performance.
  • the demonstrated hybrid Li-S battery exhibits high sulfur loading >7 mg/cm 2 , high initial coulombic efficiency (>99.8%), and high average coulombic efficiency (>99%) for the subsequent cycles.
  • This electrolyte framework is expected to improve Li-metal batteries and this framework supported battery design can be extended to other cathode materials, such as high voltage (LNMO) and air/02 cathodes, for commercially viable and intrinsically safe Li-metal batteries.
  • the solution was evaporated at 120 °C for 12h to produce the precursor gel and then calcined to 400 °C and 800 °C for 5 hours to synthesize the garnet powder.
  • the garnet powders were uniaxially pressed into pellets and sintered at 1050 °C for 12 hours covered by the same type of powder for conductivity and stability experiments.
  • the slurry was poured into a hanging chamber with a slot through which the slurry would be pulled out as thin film on a mylar sheet.
  • the resulting tape was then dried at 120 °C for one hour.
  • PMMA poly (methyl methacrylate)
  • the pore size of the porous layer can be controlled by the size of polymer based pore formers and its content.
  • the tapes were laminated and hot-pressed at 80 °C for 2h to enable porous and dense layer to melt at their interface, forming a good connection at their interface.
  • Samples were pre-sintered at 700 °C for 4h to remove the organic component and then sintered at 1100 °C for final stage sintering.
  • the sintering process was well controlled to ensure sample remained flat during sintering, which is critical for Li/S infiltration and Li-S electrochemical performance tests.
  • EIS was performed over a frequency range of 1 MHz to 100 mHz with a 50 mV perturbation amplitude.
  • the activation energies were obtained from the conductivities as a function of temperature using the Arrhenius equation.
  • Garnet solid-state based Li-S battery preparation and characterization All the cells were assembled in an argon-filled glove-box.
  • the hybrid solid-state cells were assembled in 2032 coin cells.
  • 1M bis(trifluoromethane)sulfonimide lithium salt (LiTFSI, Sigma) in a mixture of dimethoxy ethane (DME) and 1 ,3-dioxolane (DOL) (1 : 1 by volume) was used as the electrolyte for the hybrid solid-state Li-S batteries.
  • Galvanostatic discharging and charging was measured using a cut-off voltage window of 1 -3.5 V.
  • a 10 wt.% carbon nanotube (CNT) ink in dimethylformamide (DMF) was prepared and several drops of CNT ink were added into the porous layer of bilayer garnet framework and dried at 100 °C for 12 hours in vacuum, then elemental sulfur power was evenly spread on top of porous garnet, and heat at 160 °C to melt sulfur.
  • the bilayer garnet framework was -17 mg, corresponding to -20 mg/cm 2 .
  • the actual sulfur infiltrated to the bilayer garnet framework was -2.5 mg, corresponding to a mass loading of -7.5 mg/cm 2 .
  • the full cell was assembled in Ar-filled glovebox. Liquid electrolyte was added to rinse the sulfur cathode.
  • Figure 17 shows proj ected energy density of bilayer garnet solid-state Li-S batteries with optimized parameters.
  • EXAMPLE 4 [0210] This example provides a description of solid-state hybrid electrolytes of the present disclosure. This example also provides examples of making and characterization of such electrolytes.
  • Solid-state Li-batteries with solid state electrolytes (SSEs) can potentially block Li dendrite penetration, enabling the application of metallic lithium anodes to achieve high energy density with improved safety.
  • the ion transport behavior and ionic conductivity in Li-ion batteries is significantly influenced by the tortuosity of the electrode and electrolyte materials.
  • Low- tortuosity structures with straight ion pathways are highly desirable yet very hard to achieve in solid state ion conductors.
  • Ion conductive polyethylene oxide was incorporated into the mesoporous, wood-templated aligned garnet nanostructure, resulting in an intermixed hybrid ion conductor called gamet-wood.
  • the synergistic integration of the aligned garnet with soft, mechanically robust polymer results in both a high ionic conductivity (1.8* 10 "4 S/cm at room temperature) and good mechanical flexibility. This work provides a new direction for developing low-tortuosity, fast ion conductors inspired by nature.
  • a composite electrolyte was developed by incorporating PEO polymer electrolyte into the aligned garnet templated by wood, which is called garnet- wood (Figure 18).
  • the polymer electrolyte provides additional transport pathways and also reinforces the mechanical strength of the composite structure. Li-ion can effectively transport through garnet, polymer, and along garnet-polymer interfaces. As a result, the gamet-wood membrane delivers an outstanding ionic conductivity of 1.8* 10 "4 S/cm at room temperature. Based on this concept, the design principle and fabrication process for aligned garnet-wood electrolyte can be extended to other types of solid-state electrolytes.
  • Basswood was chosen as a template to develop the aligned garnet solid-state electrolyte framework due to its high growth rate, low cost, and high porosity.
  • the wood template was obtained after partially removing lignin from a piece of natural basswood by chemical treatment, followed by compressing and slicing perpendicular to the longitudinal direction (natural growth direction) of the wood ( Figure 19a). Mechanical pressing was used to density the wood. Additional hydrogen bonds formed between adjacent cellulose fibers during densification, which maintains the dense structure of the framework.
  • the wood with infiltrated garnet precursor was calcined at 800 °C for 4 hours in oxygen to obtain the LLZO membrane.
  • the wood template with aligned channels has two unique functions. First, the free channels in the wood template provide reservoirs to supply precursor solutions to the template combustion reaction. Second, the aligned nanofibers with a diameter of 2-10 nm in the wood template serve as sacrificial pore formers for additional aligned porosity in the garnet membrane. Morphological changes after calcination were characterized by SEM. The aligned porous structure from the wood template was inherited in the resulting garnet framework at both the microscale (Figure 20a) and nanoscale ( Figure 20b).
  • the well-aligned garnet membrane inherited directly from wood is flexible after infiltration with the PEO based polymer electrolyte ( Figure 20c).
  • X-ray diffraction (XRD) was employed to identify the crystal phase of the garnet membrane.
  • the XRD pattern of the aligned mesoporous garnet synthesized using wood template ( Figure 20d) matched well with the cubic-phase garnet Li5La3Nb20i2 (JCPDS#80-0457), despite minor peak shifts at higher angles due to aluminum (Al) doping and variations in Li concentration.
  • the well XRD pattern match of the aligned mesoporous garnet with JCPDS#80-0457 verifies that the wood templated garnet is the conductive cubic phase.
  • High-resolution transmission electron microscopy (HRTEM) of the resulting aligned garnet reveals the clear, well crystallized lattice structure of the garnet ( Figure 22a).
  • the miller indices were calculated from the corresponding fast Fourier transform (FFT) pattern (Inset of Figure 22a) and the lattice constant derived from the HRTEM and FFT is 12.982 A, which agrees with previously reported values. Crystal grains with various orientations can be clearly distinguished in the HRTEM image of a larger garnet particle broken off from the structure ( Figure 21b).
  • the TEM results indicate that the aligned mesoporous garnet has a highly crystallized, well-connected multi crystalline structure.
  • Electron energy loss spectroscopy was employed to analyze the composition of the garnet membrane.
  • Figure 21 c shows the EELS spectrum with the region of interest (ROI) outlined.
  • EELS mapping indicates the relative composition and distribution of oxygen, carbon, and lanthanum.
  • the overlapping region of oxygen k-edge signal and lanthanum n- edge signal identifies the location of LLZO.
  • the carbon k-edge signal is rare throughout the sample, a small overlapping region of oxygen k-edge signal and carbon k- edge signal was identified, which indicates that the L12CO3 impurities caused by calcining in oxygen is minimum.
  • the garnet-wood was fabricated by infiltrating PEO polymer electrolyte into the aligned garnet.
  • Figure 22a characterizes the polymer infiltration with energy dispersive X-ray spectroscopy (EDX).
  • EDX energy dispersive X-ray spectroscopy
  • the evenly distributed carbon signal from the top, down to the aligned garnet channels indicates complete and uniform infiltration of the polymer electrolyte, which is crucial for establishing sufficient Li ion transport pathways.
  • the first pathway is the aligned PEO polymer electrolyte, whose bulk ionic conductivity (without fillers) is usually as low as 10 "7 S/cm at room temperature.
  • the second pathway is the aligned garnet-polymer interface.
  • the aligned mesoporous garnet behaves like ceramic fillers that can induce changes to the polymer segmental dynamics, and therefore influences lithium ion transport.
  • Intensive studies on the influence of fillers on the ionic conductivity of polymer electrolyte suggests that ceramic fillers with Lewis acid
  • the third pathway is transport through the high volume percentage ( ⁇ 68%) aligned garnet nanostructure.
  • NMR nuclear magnetic resonance
  • EIS electrochemical impedance spectroscopy
  • a garnet-wood membrane (0.1 cm 2 area, 0.4 ⁇ thick) was assembled into symmetric cells with stainless steel as the blocking electrodes and scanned from 1 MHz to 100 mHz.
  • Figure 22b shows the Nyquist plot of the electrolyte membrane tested from room temperature (25 °C) up to the melting temperature of PEO (65 °C).
  • the experimental ionic conductivity is calculated using the electrolyte membrane thickness and area, and the results are shown in Figure 22c.
  • the garnet-wood membrane achieved an ionic conductivity of 1.8* 10 "4 S/cm at room temperature.
  • the theoretical ionic conductivity of the composite is the total contribution of each phase weighted by the volume fractions.
  • the calculated activation energy of garnet-wood is 0.38 eV, which can be lowered further by adjusting the proportion of polymer electrolyte. This effect is due to various enhancement effects including the increase in the volume fraction of amorphous conducting phase as well as improvement in the long range polymer chain mobility.
  • garnet-wood composite electrolyte with a multiscale aligned mesoporous structure is described.
  • the scalable compressed wood template results in the unique low tortuosity and high surface area mesostructure that is critical to the improved electrochemical performance and mechanical stability.
  • Ionically conductive polymer serves as a matrix to reinforce the mechanical strength of the aligned mesoporous garnet membrane and also provide additional ion transport pathways through the amorphous conductive phase and the garnet-polymer interfaces.
  • the garnet-wood composite electrolyte achieves a high Li ion conductivity of 1.8* 10 "4 S/cm at room temperature and 1.1 ⁇ 10 "3 S/cm at 95 °C. This is close to the bulk conductivity of garnet itself and moreover exhibits an enhanced contribution from the garnet/polymer interface.
  • the garnet-wood demonstrates great potential as a low-tortuosity structure for highly conductive SSE and it also provides a model study for the design and optimization of solid state CPEs.
  • the garnet precursor solution was prepared by dissolving stoichiometric LiNCb (>99.0%, Aldrich), La(NCb)3 (>99.9%, Aldrich), A1(N0 3 ) 3 9H 2 0 £98.0%, Aldrich), ZrO(N0 3 ) 2 xH 2 0 (99.9%, Aldrich), and acetic acid (>99.7%, Aldrich) in ethanol (>99.8%, Aldrich) at room temperature under magnetic stirring.
  • 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 calcination temperature.
  • the PEO-based polymer electrolyte was prepared by dissolving PEO
  • the cells were rested in an environmental chamber for 30 minutes at the predetermined temperature before each EIS test to reach thermal equilibrium and then scanned from 1 MHz to 100 mHz to acquire the impedance curves at various temperatures.
  • the Li stripping/plating tests were performed with a BioLogic VMP3 multi-channel potentiostat on symmetric cells consisting of the garnet- wood between Li metal foils as electrodes.
  • the cells were cycled at a current density of 0.1 niA/cm 2 for 30 minutes in each direction at room temperature in an argon filled glovebox.
  • This example provides a description of solid-state hybrid electrolytes of the present disclosure. This example also provides examples of making and characterization of such electrolytes.
  • Lithium-Ion Conductive Ceramic Textile A New Architecture for Flexible
  • Solid-State Lithium Metal Batteries Designing solid-state lithium metal batteries requires fast lithium-ion conductors, good electrochemical stability, and scalable processing approaches to device integration.
  • This example demonstrates a unique design for a flexible lithium-ion conducting ceramic textile with the above features for use in solid-state batteries.
  • the ceramic textile was based on the garnet-type conductor Li7La3Zr20i2 and exhibited a range of desirable chemical and structural properties, including: lithium-ion conducting cubic structure, low density, multi-scale porosity, high surface area/volume ratio and good flexibility.
  • the solid garnet textile enabled reinforcement of a solid polymer electrolyte to achieve high lithium-ion conductivity and stable long-term Li cycling over 500 h without failure.
  • the textile also provided an electrolyte framework when designing a 3D electrode design to realize ultrahigh cathode loading (10.8 g/cm 2 sulfur) for high performance Li-metal batteries.
  • the ceramic textile can be combined with electrode materials in interdigitated or concentric arrangements to minimize electrolyte volume and maximize electrode utilization, thereby increasing active electrolyte area, lithium-ion interfacial transport, and tolerance for electrode volume change during charging/discharging.
  • This example demonstrated the fabrication of garnet based lithium-ion conductive ceramic textiles derived from templates, producing textiles with superior characteristics for integration into solid state batteries.
  • the garnet textiles were used to provide a solid lithium-ion conducting framework that simultaneously reinforces polymer electrolyte for stable Li cycling over 500 h, and 3D electrode structure to achieve ultrahigh sulfur loading of 10.8 g/cm 2 for high performance Li-metal batteries.
  • the simplicity of the template method makes it useful for fabricating ceramics with tailored compositions and structures, opening the possibility of building solid state batteries that are low cost and durable.
  • the multi-scale porosity existing in the porous templates enabled homogenous impregnation by the LLZO precursor.
  • Thermal behavior of the LLZO precursor-infiltrated textile template was analyzed with Thermogravimetric analysis (TGA, STAR System). Calcination of the precursor impregnated templates was conducted in oxygen at different temperatures to obtain garnet textiles.
  • the 3D morphology of garnet textile was scanned using a LK-H082 semiconductor laser model with a wavelength of 655 nm
  • Garnet powder with a composition of Li 7 La2.75Cao. 2 5Zn. 7 5Nbo. 2 50i 2 was synthesized following the same processes in our early work. Scalable tape casting and hot laminating methods were used to fabricate the dense electrolyte support. The laminated green tape was sintered at 1050 °C in a tube furnace under oxygen atmosphere. Garnet textiles were sintered onto the garnet electrolyte support in oxygen to form a framework for cathode infiltration. The cell was assembled in an argon-filled glovebox with C and H2O level both under 0.1 ppm. Lithium metal was melted onto the dense garnet electrolyte support coated with an ultrathin layer of amorphous Si to achieve proper interfacial contact.
  • the sulfur slurry was prepared by mixing Sulfur powder (Sigma Aldrich), carbon nanotubes (Carbon Solutions) and PVP ( ⁇ 40,000, Sigma Aldrich) in a mass ratio of 8: 1 : 1 in N-methylpyrrolidone (Sigma Aldrich) to achieve a concentration of -10 mg/mL. After sonication for 5 h to obtain a dilute and uniform suspension, drops of the sulfur slurry were repeatedly applied to the garnet textile to infiltrate the open porosity and dried. The final sulfur loading was calculated by subtracting the weight of the half-cell before cathode slurry infiltration from the total weight of the full battery and then multiplying the weight ratio of sulfur in the cathode mixture.
  • a small amount of 1M LiTFSI in DME/DOL was introduced into the cathode to facilitate sulfur/garnet contact before carbon felt was placed on the cathode side as a spacer and current collector.
  • the battery was sealed in a coin-type cell with epoxy and connected to an Arbin BT-2000 for charge and discharge measurement.
  • Lithium-ion conductive ceramic textiles were created by impregnating the templates with precursor solutions followed by pyrolysis conversion. As illustrated in Figure 30, the flexible ceramic textile retained the structural characteristics of the original textile template, which differed significantly from the rigid network of discrete particles in conventionally sintered porous ceramic powder compacts.
  • the textile structure consisted of a network of continuous interlocked fibers and interlaced yarns through weaving that impact the spatial distribution of lithium-ion conducting material and open pores.
  • Movement of lithium-ions can occur inside and along the surface of poly crystalline fibers over the entire textile pattern. Small, poly disperse and interconnected pores existed between individual fibers, while discrete large pores in relatively uniform size and shape were found between adj acent yarns.
  • FIG. 32 The structural and chemical advantages of the gamet textile make it ideal for reinforcing the mechanical and electrochemical properties of a composite polymer electrolyte (CPE), as shown in Figure 32.
  • CPE composite polymer electrolyte
  • the free-standing CPE was prepared by vacuum infiltrating a solution containing PEO and lithium salts into the garnet textile.
  • the dried CPE in Figure 32a appeared soft and flexible, indicating that efficient wetting and capillary action successfully drew the fluid into the multi-level open pores, which allowed strong physical bonding between the garnet fibers and the polymer matrix.
  • Cross-sectional microstructure analysis further confirmed the CPE appeared fully densified without any noticeable porosity in Figure 36a.
  • This process minimizes the involvement of resistive garnet/polymer interfaces or diffusion through the polymer bulk (dotted arrow), making lithium-ion diffusion less dependent on the solvated lithium content of the polymer matrix.
  • Figure 32c presents typical impedance plots for the CPE measured at different temperatures.
  • Lithium-ion transfer processes were divided into ion conduction within the CPE (high frequency arc) and ion blocking at the CPE/stainless steel interface (low frequency inclined tail).
  • the resistance of the CPE was obtained by reading the real impedance values at the high frequency intercept of the arc.
  • Figure 32d analyzes the temperature dependence of lithium-ion conductivity using an Arrhenius plot. In general, lithium-ion conductivity exhibited non-linear behavior as temperature increased. A slight reduction in activation energy occurred when temperatures exceeded 60 °C, corresponding to the phase transition temperature of PEO. It is known that when a PEO-LiX system undergoes a thermal phase transition, the conductivity shows a sharp change in activation energy.
  • Garnet Textile structured 3D Electrode Architecture Garnet textiles can also be used to make 3D electrode architectures, wherein the textile is sintered on a dense electrolyte support (Figure 33a) and electrode material is infiltrated into the textile structure. Li-S batteries are demonstrated here as a proof of concept due to the high energy density and low material cost of sulfur cathodes. The well-distributed porosity of the fibrous structure allowed the textile to easily accommodate high sulfur loading.
  • Figure 33b shows the SEM image of the garnet textile loaded with 10.8 mg/cm 2 of sulfur. Garnet fibers were linked together and the open porosity was filled with the sulfur/carbon mixture.
  • EDX linear scan across the region of the yarn/electrolyte boundary reveals sulfur/carbon on the exposed surface of the garnet yam and the electrolyte in Figure 38a.
  • Cross-sectional analysis exhibits that the sulfur/carbon mixture has penetrated the porous textile to coat individual fibers and reached the dense electrolyte surface in Figure 38b.
  • EDX mapping confirms homogeneous elemental distribution of sulfur/carbon loaded onto the garnet fibers and intimate contact between the continuous lithium-ion conducting phase, electron conducting phase and sulfur phase in Figure 33c.
  • Solid-state Li-S batteries were assembled to demonstrate the electrochemical advantages of the garnet textile 3D electrode architecture. A small amount of liquid electrolyte was added to activate the sulfur and improve contact between the garnet and the sulfur without creating an undesirable lithium-ion barrier. This hybrid configuration was still predominantly solid-state despite the small amount of liquid electrolyte.
  • the dense garnet electrolyte support functioned as lithium-ion conductor, electron insulator, and lithium- poly sulfide shuttle shield in Figure 39.
  • the 3D Li-ion conductive electrode structure also allowed successful cycling of the solid-state Li-S battery at a current density of 0.75 mA/cm 2 (Figure 40).
  • the stabilized reversible high capacity of 800 mAh/g confirmed the energy storage capacity of an electrode framework built with a garnet textile.
  • FIG 42b shows a representative SEM image of the necessary bi-layer structure consisting of a thin dense electrolyte (20 ⁇ ) and a porous substrate (70 ⁇ ). Lithium metal could be infused into the pores to create abundant lithium/garnet transfer interfaces and further promote mechanical strength. Integrating the garnet textile and the bi-layer support will make it possible to achieve an even higher energy density of 352 Wh/kg, which significantly exceeds the capability of the state-of-the-art lithium-ion batteries. [0247] We successfully demonstrated a flexible lithium-ion conducting garnet textile fabricated by a simple template method.
  • the unique architectural advantages of the flexible fibrous garnet textile allow the creation of a solid-state electrolyte framework with continuous lithium-ion conducting paths and high surface-volume ratio. Incorporation of the textile into solid polymer electrolyte enables improved lithium-ion conduction and stable Li cycling over 500 h.
  • the tailored garnet textile was used to fabricate 3D porous electrode to accommodate high sulfur loading (10.8 mg/cm 2 ) and the resulting battery delivered a high capacity of 1000 mAh/g.
  • Current laboratory scale fabrication procedures can be translated to affordable, reliable and industrially-relevant scale production. While initial efforts have so far been directed to solid state lithium metal battery, the novel structural design strategies utilized in this example is expected to be able to be applied to other solid- state devices for energy storage and conversion beyond lithium-ion technology.
  • This example provides a description of solid-state hybrid electrolytes of the present disclosure. This example also provides examples of making and characterization of such electrolytes.
  • the flexible solid-state electrolyte composite membrane exhibited an ionic conductivity of 2.5 ⁇ 10 "4 S/cm at room temperature.
  • the membrane can effectively block dendrites in a symmetric Li I electrolyte
  • This example describes a flexible, solid-state lithium ion-conducting membrane based on a three-dimensional (3D) ion-conducting network and polymer electrolyte for lithium batteries.
  • the 3D ion-conducting network is based on percolative garnet-type Li 6.4 La 3 Zr 2 Alo.2Oi2 (LLZO) solid-state electrolyte nanofibers, which enhance the ionic conductivity of the solid-state electrolyte membrane at room temperature and the mechanical strength of conventional polymer electrolyte.
  • the membrane has shown superior electrochemical stability to high voltage, and high mechanical stability to effectively block lithium dendrites. This work represents a significant breakthrough to enable high
  • a three dimensional (3D) ceramic network based on garnet- type Li6.4La3Zr2Alo.2012 (LLZO) nanofibers to provide continuous Li + transfer channels in PEO-based composite electrolytes as all solid ion-conducting membranes for lithium batteries was successfully developed.
  • a garnet-type lithium-ion conducting ceramic was selected as the inorganic component due to several desired physical and chemical properties, including: (a) high ionic conductivity approaching 10 "3 S/cm at room temperature with optimized element substitution; (b) good chemical stability against lithium metal; and (c) good chemical stability against air and moisture.
  • Figure 47 shows the schematic structure of 3D
  • the LLZO porous structure consists of randomly distributed and interconnected nanofibers, creating a continuous lithium-ion conducting network.
  • the Li salt/PEO polymer is then filled into the porous 3D ceramic networks, forming the 3D garnet/polymer composite membrane.
  • the 3D gamet/polymer composite membrane doesn't need to mechanically mix fillers with polymers, instead we can directly soak a pre-formed 3D ceramic structure into Li salt/polymer solutions to get the desired polymer composite electrolyte hybrid structure, thus simplifying fabrication process and avoiding the agglomeration of fillers.
  • FIG. 2b The schematic fabrication of FRPC Li-ion conducting membrane using the 3D porous garnet nanofiber network is shown in Figure 2b.
  • a PEO polymer mixture with Li salt such as bis(trifluoromethane)sulfonimide lithium salt (LiTFSI)
  • LiTFSI bis(trifluoromethane)sulfonimide lithium salt
  • the Li salt/PEO polymer is reinforced by the 3D nanofibers to form a composite electrolyte, which can be called fiber-reinforced polymer composite (FRPC) electrolyte membrane.
  • FRPC electrolyte membrane maintains the framework of 3D garnet nanofiber networks and is believed to have a better mechanical property due to the continuous nanofiber structure that enhances the integrity of polymer electrolyte.
  • garnet nanofibers were "inter-welded” with each other, forming cross-linked 3D garnet nanofiber networks.
  • the large volume of inter-space between nanofibers can facilitate Li salt/polymer infiltration to form the composite membrane.
  • the flexibility of the membrane is demonstrated in Figure 48g.
  • the bendable electrolyte membrane can then be employed to construct flexible solid- state lithium batteries. Note that the design of flexible 3D ion-conducting networks mainly depends on ceramic garnet nanofibers, for which a thin and mechanically stable structure are desired for good ionic conductivity and feasible battery fabrication.
  • FIG. 49 shows the morphological characterization of the garnet nanofibers and resulting FRPC electrolyte. As shown in Figure 49a, garnet nanofibers were bonded together at their intersection points, forming a cross-linked network.
  • FIG. 49b and 49c show the transmission electron microscopy (TEM) images of the garnet nanofibers.
  • the gamet nanofiber has a
  • Figure 49b poly crystalline structure, consisting of interconnected small crystallites to form the long, continuous nanofiber
  • Figure 53 shows the magnified TEM image of a garnet nanofiber with an average grain size of 20 nm in diameter.
  • Figure 49c indicates the highly crystalized structure of the garnet grain.
  • the FRPC electrolyte was thermally treated at 60 °C, which is slightly above the polymer melting temperature (Tm), to enable the melted PEO-LiTFSI polymer to fully infiltrate the 3D porous gamet nanofiber network.
  • Tm polymer melting temperature
  • FIG. 49f after thermal treatment PEO-LiTFSI polymer was fully embedded with garnet nanofibers. Gamet nanofibers increased to an average diameter of 500 nm due to the PEO-LiTFSI polymer coating. The interconnected pores were filled with polymer to maintain good lithium ion transfer.
  • TGA Thermogravimetric analysis
  • Thermal stability is an important consideration for using solid-state electrolytes, especially polymer electrolyte.
  • Traditional liquid electrolytes such as carbonate electrolytes, tend to cause thermal runaway when batteries are under extreme conditions of short circuits, overcharge, and high temperature. Due to its relatively high thermal stability, polymer electrolytes becomes a safer choice compared to liquid electrolytes. Since traditional polymer electrolytes are built on their own polymer structure and fillers cannot offer sufficient mechanical support for the electrolyte, the polymer electrolyte is inevitable to melt and shrink at high temperature, especially above the polymer thermal decomposition temperature, which may cause direct contact between cathode and anode and is a significant safety concern.
  • the FRPC electrolyte is able to address this concern because the garnet nanofiber membrane within the polymer electrolyte provides a ceramic barrier to physically block cathode and anode contact even after loss of the polymer.
  • Figure 50c and 50d compares the combustion tests of a traditional polymer electrolyte and the novel FRPC electrolyte developed in this work.
  • the traditional polymer electrolyte was prepared using the same recipe to prepare the PEO-LTFSI polymer, but using garnet nanopowders (vs. the 3D garnet network) as fillers.
  • the mass ratio of polymer and filler was controlled at 4: 1.
  • the polymer electrolyte caught fire instantly when it came close to the ignited lighter and was quickly burned off into ashes. This high fiammability indicates poor thermal stability of the polymer electrolyte.
  • the small amount of LaiZ Oi phase could also be formed by lithium loss at elevated temperature.
  • FIG. 51b shows the typical Nyquist plots of FRPC electrolyte sandwiched between stainless steel blocking electrodes in the frequency range of lHz to lMHz.
  • Each impedance profile shows a real axis intercept at high frequency, a semicircle at intermediate frequency and an inclined straight tail at low frequency.
  • the intercept of the extended semicircle on the real axis and semicircle in high and intermediate frequency range represent the bulk relaxation of FRPC electrolyte.
  • the low frequency tail is due to the migration of lithium ions and the surface inhomogeneity of the blocking electrodes.
  • Figure 51c shows the Arrhenius plot of the FRPC electrolyte.
  • Lithium ion conductivity was calculated based on the thickness FRPC electrolyte and diameter of stainless electrodes. Lithium ion conductivity of cubic phase LLZO garnet pellet would reach as high as 10 "3 S/cm, while lithium salt stuffed PEO is generally in the order of 10 "6 -10 "9 S/cm at room temperature.
  • Our FRPC electrolyte combining conductive cubic LLZO garnet and lithium-PEO could exhibit reasonably high ionic conductivity of 2.5x 10 "4 S/cm at room temperature.
  • FIG. 51d shows the result of the linear sweep voltammetry (LSV) profile of the FRPC electrolyte using lithium metal as counter and reference electrode, and stainless steel as working electrode.
  • the FRPC electrolyte exhibits a stable voltage window up to 6.0 V versus Li/Li + , indicating that this ion-conducting membrane can satisfy the requirement of most of high-voltage lithium batteries.
  • FIG 52a represents the schematic of the symmetric cell setup.
  • the FRPC electrolyte membrane was sandwiched between two lithium metal foils and sealed in coin cell.
  • Figure 52b shows the time-dependent voltage profile of the cell with FRPC electrolyte membrane cycled over 230 hours at a constant current density of 0.2 mA/cm 2 and a temperature of 15 °C.
  • the symmetric cell was periodically charged and discharged for 0.5 hour.
  • the positive voltage is the Li stripping, and the negative voltage value refers to the Li plating process. In the first 70 hours, the cell's voltage slightly increased from 0.3 V to 0.4 V and then stabilized at 0.4 V.
  • the decrease in voltage might be due to the improved interface between the electrolyte membrane and lithium metal during the repeated Li electrodeposition, which is confirmed by the EIS spectra of the symmetric cell measured at 300 hours, 500 hours, and 700 hours (Figure 52d).
  • the depressed semicircles at lower frequency indicate decreased interfacial impedance between electrolyte membrane and lithium metal during cycling.
  • the semicircle also decreased with the increased cycle time, indicating the decreased bulk impedance of the electrolyte membrane.
  • the current density increased to 0.5 mA/cm 2
  • the voltage increased to 0.3 V and the cell also exhibited slight decrease in voltage with increasing time to 1000 hours (Figure 52f), showing good cycling stability with long cycle life.

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Abstract

La présente invention concerne des électrolytes hybrides à l'état solide. Les électrolytes hybrides comportent une couche de matériau polymère, qui peut être une couche polymère/copolymère ou une couche polymère/copolymère de gel, disposée sur au moins une partie d'une surface extérieure ou sur la totalité des surfaces extérieures d'un électrolyte à l'état solide. Un électrolyte hybride peut former une interface avec une électrode d'une batterie conductrice d'ions qui présente des propriétés souhaitables. L'électrolyte à l'état solide peut comprendre un corps SSE monolithique, un corps SSE mésoporeux ou un SSE inorganique ayant des fibres qui peuvent être alignées, ou des brins qui peuvent être alignés. Dans le cas d'électrolytes à l'état solide qui comportent des brins, les brins peuvent être formés à l'aide d'un modèle sacrificiel. Les électrolytes hybrides à l'état solide peuvent être utilisés dans des batteries conductrices d'ions, qui peuvent être des batteries conductrices d'ions flexibles.
PCT/US2018/025289 2017-03-29 2018-03-29 Électrolytes hybrides à l'état solide, procédés de fabrication de ces derniers et utilisations de ces derniers WO2018183771A1 (fr)

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EP18778216.4A EP3602657A4 (fr) 2017-03-29 2018-03-29 Électrolytes hybrides à l'état solide, procédés de fabrication de ces derniers et utilisations de ces derniers
KR1020247011551A KR20240051309A (ko) 2017-03-29 2018-03-29 고체 상태 하이브리드 전해질, 이의 제조 방법 및 이의 용도
KR1020197031941A KR20190139911A (ko) 2017-03-29 2018-03-29 고체 상태 하이브리드 전해질, 이의 제조 방법 및 이의 용도
JP2019553946A JP2020517049A (ja) 2017-03-29 2018-03-29 固体ハイブリッド電解質、その作製方法、およびその使用
US16/499,203 US20200112050A1 (en) 2017-03-29 2018-03-29 Solid-state hybrid electrolytes, methods of making same, and uses thereof
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WO2021069904A3 (fr) * 2019-10-08 2021-05-20 Sumitomo Chemical Co., Ltd Batterie métallique
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WO2021189083A1 (fr) * 2020-03-18 2021-09-23 Piersica Inc. Anode à base de métal lithium à haute densité d'énergie pour batteries lithium-ion à l'état solide
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CN114122386B (zh) * 2020-08-31 2024-03-19 中南大学 一种锂硫电池的磷化锡@碳复合负极活性前驱材料、负极活性材料、负极及其制备
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CN113675462A (zh) * 2021-08-21 2021-11-19 西南石油大学 一种快钠离子导体nasicon型固态电解质材料及其制备方法和应用
WO2023055237A1 (fr) * 2021-10-01 2023-04-06 Lionvolt B.V. Électrolyte solide hybride et batterie comprenant un électrolyte solide hybride
WO2023055234A1 (fr) * 2021-10-01 2023-04-06 Lionvolt B.V. Électrolyte solide hybride et batterie
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WO2023147384A1 (fr) * 2022-01-25 2023-08-03 Global Graphene Group, Inc. Électrolytes à semi-conducteurs hybrides élastomères/inorganiques, batteries au lithium les contenant et procédés de production
US12006387B1 (en) 2022-11-14 2024-06-11 Piersica, Inc. Polymer composition and methods for making same

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