Air-stable solid sulfide electrolyte

Abstract

A method comprising contacting a surface of a moisture-sensitive Li-ion conductor material with an amphiphilic surface protection agent to obtain a protected Li-ion conductor material, and assembling an electrochemical cell including the protected Li-ion conductor material. Another embodiment disclosed herein is a method comprising coating the surface of a sulfide-containing solid electrolyte material with an amphiphilic surface protection agent. Another embodiment disclosed herein is a material including a sulfide-containing solid electrolyte coated with an amphiphilic surface protection agent.

Description

[Technical Field]

[0001] This application claims the benefits of U.S. Provisional Application No. 63 / 104,718, filed October 23, 2020, which is incorporated in its entirety herein.

[0002] Approval of government support This invention was developed with government support under contract DE-AC0576RL01830, funded by the U.S. Department of Energy. The government has certain rights in this invention. [Background technology]

[0003] background Lithium-ion batteries (LIBs) have been widely used in our daily lives, particularly in portable electronic devices such as mobile phones and personal computers. In recent years, LIBs have also been adopted as power sources in electric vehicles (EVs), significantly expanding their size in the energy storage market. The EV market is expected to grow by a further 50% by 2030, creating an imminent demand for a new generation of LIBs with even higher energy / power density and superior safety features. However, safety concerns increase with increasing cell energy density, mainly due to the inherently high flammability, high volatility, and radical reactivity when in contact with oxidizing or reducing electrode materials in the processing of organic liquid electrolytes (OLEs). Compared to LIBs or lithium metal batteries (LMBs) using OLEs, the adoption of flammable inorganic solid electrolytes (SSEs) in all-solid-state batteries (ASSBs) can essentially eliminate these safety concerns.

[0004] High-performance solid-state electrolytes (SSEs), such as sulfide, oxide, and polymer-based electrolytes, are crucial for the success of all-solid-state batteries (ASSBs) with high energy and high power density. Among these SSEs, sulfides are considered more promising due to their soft nature and high ionic conductivity at room temperature, both of which ensure good SSE / electrode material contact and fast Li-ion conduction. However, the poor moisture stability of sulfide SSEs, accompanied by the generation of highly toxic H2S gas, hinders their evaluation and practical-scale applications. To address this critical issue, several strategies have been attempted so far.

[0005] One is to combine SSEs with H2S-absorbing inorganic additives (such as Fe2O3, ZnO, and Bi2O3) to chemically consume the generated H2S gas. Even when the amount of H2S released from the SSE can be reduced to some extent, the overall Li-ion conductivity significantly decreases due to the presence of the H2S release reaction and the non-conductive nature of these additives. Another strategy focuses on developing sulfide SSEs with inherently good moisture stability based on the hard / soft acid-base (HSAB) theory. Specifically, relatively soft acids such as Cu I Ge IV and As V prefer to bond with soft bases such as S 2- to form strong covalent bonds and rigid frameworks. Guided by the HSAB theory, quaternary sulfides such as Li 3.833 Sn 0.833 As 0.166 S4 and Li4Cu8Ge3S 12 have been developed, and they have shown improved moisture stability. However, these sulfide-containing SSEs (which also include Li 10 GeP2S 12 and Li 10 SnP2S 12 are also poor in chemical / electrochemical stability against Li metal anodes. At the anode, the SSE is reduced to form an electronically conductive Li metal alloy (LiGe x and LiSnx This ultimately short-circuits the cell. Furthermore, these "heavy metal"-containing SSEs typically involve the burden of high-temperature synthesis and high material density. In addition, existing solid sulfide electrolytes have poor air stability, which makes it difficult to produce the material in an ambient air environment. [Overview of the project] [Means for solving the problem]

[0006] summary One embodiment disclosed herein is The steps include: bringing the surface of a moisture-sensitive Li-ion conductor material into contact with an amphiphilic surface protective agent to obtain a protected Li-ion conductor material, and Steps to assemble an electrochemical cell containing a protected Li-ion conductor material. This method includes [something].

[0007] Another embodiment disclosed herein is: Step 1: Coating the surface of a sulfide-containing solid electrolyte material with an amphiphilic surface protectant. This method includes [something].

[0008] Another embodiment disclosed herein is a material comprising a sulfide-containing solid electrolyte coated with an amphiphilic surface protectant, wherein the amphiphilic surface protectant is -OH;-C(O)O-;-C=O-;-NH-;-Al n (OH) m (n≧1 and m≧1), -PO4-;-C(O)NH2;-NH2;-OSO3H;-SO3H;-SH;-Cl;-Br;-I; and -NR4 + (R is C x H 2x+1 Hydrophilic heads selected from (x≧1); and -CH3;-CH2-CH3;-R-C6H5(R is C x H 2x+1 (x≧1);-CH=CH2;-C3~C 50 Alkyl or substituted alkyl;-C3~C 50Alkenyl or substituted alkenyl; -C3~C 50 Alkynyl or substituted alkynyl; (CH2) n (n≧2);-CH2F;-CHF2;-CF3;(CF2) n (n≧2); and (Si(CH3)2-O-) n The material includes a hydrophobic tail selected from (n≧2).

[0009] Additional embodiments disclosed herein include: A sulfide-containing solid electrolyte coated with an amphiphilic surface protectant, wherein the amphiphilic surface protectant is -OH;-C(O)O-;-C=O-;-NH-;-Al n (OH) m (n≧1 and m≧1), -PO4-;-C(O)NH2;-NH2;-OSO3H;-SO3H;-SH;-Cl;-Br;-I; and -NR4 + (R is C x H 2x+1 Hydrophilic heads selected from (x≧1); and -CH3;-CH2-CH3;-R-C6H5(R is C x H 2x+1 (x≧1);-CH=CH2;-C3~C 50 Alkyl or substituted alkyl;-C3~C 50 Alkenyl or substituted alkenyl; -C3~C 50 Alkynyl or substituted alkynyl; (CH2) n (n≧2);-CH2F;-CHF2;-CF3;(CF2) n (n≧2); and (Si(CH3)2-O-) n A sulfide-containing solid electrolyte containing a hydrophobic tail selected from (n≧2). Cathode material, and Anode material It is a structure that includes [something].

[0010] The above will become even clearer from the following detailed explanation, which will proceed with reference to the attached drawings. [Brief explanation of the drawing]

[0011] [Figure 1] Figure 1 is a schematic diagram of the reversible coating and the release of 1-bromopentane on / from the SSE.

[0012] [Figure 2A] Figures 2A-2C. Reversible chemical treatment of SSE with 1-bromopentane. Figure 2A is the high-resolution C 1s spectrum, Figure 2B is the atomic concentrations of Br and C, and Figure 2C is the electrochemical impedance spectrum of untreated LPSBI, LPSBI-bromo, and LPSBI-bromo-160 samples. [Figure 2B] Same as above. [Figure 2C] Same as above.

[0013] [Figure 3A] Figures 3A to 3D show the promising moisture stability of LPSBI-bromo. Figures 3A and 3B show H2S generation of 1-bromopentane-containing / uncontaining Li7P2S8Br0.5I0.5 powders exposed to air with relative humidity of 0.1% (in a dry room) (Figure 3A) and 20% (Figure 3B). Figures 3C and 3D show the electrochemical impedance spectra of untreated LPSBI (Figure 3C) and LPSBI-bromo (Figure 3D) before and after exposure to air with 20% relative humidity at room temperature. [Figure 3B] Same as above. [Figure 3C] Same as above. [Figure 3D] Same as above.

[0014] [Figure 4A] Figures 4A-4C. Spectroscopic characterization to identify surface changes in SSE after air exposure. a, b, c, high-resolution C 1s spectra (Figure 4A), atomic concentrations of Br, O, and C (Figure 4B), and Raman spectra of untreated LPSBI, LPSBI-20%, LPSBI-bromo, and LPSBI-bromo-20% samples (Figure 4C). [Figure 4B] Same as above. [Figure 4C] Same as above.

[0015] [Figure 5] Figure 5 is a graph showing the H2S generation of Li6PS5Cl powder containing / not containing 1-bromopentane when exposed to air with a relative humidity of 10%.

[0016] [Figure 6] Figure 6 is a graph showing H2S generation in Li3PS4 powders with and without 1-bromopentane when exposed to air with a relative humidity of 49%. [Modes for carrying out the invention]

[0017] Detailed explanation definition Anode: The electrode into which charge polarization flows in an electrical device. From an electrochemical perspective, negatively charged anions move toward the anode, and / or positively charged cations leave the anode to equilibrium the electrons that are leaving through the external circuit.

[0018] Cathode: The electrode from which the charge flows out of an electrical device where the charge is polarized. From an electrochemical perspective, positively charged cations always move towards the cathode, and / or negatively charged anions exit the cathode to equilibrium with electrons arriving from the external circuit.

[0019] Electrochemical cell: As used herein, a cell refers to an electrochemical device used to generate a voltage or current from a chemical reaction, or, in the reverse case, for a chemical reaction to be induced by an electric current. Examples include, among others, voltaic cells, electrolytic cells, and fuel cells. A battery contains one or more cells. The terms “cell” and “battery” are used interchangeably when referring to a battery containing only one cell.

[0020] Electrolyte: A substance containing free ions that act as a conductive medium.

[0021] Microparticles: As used herein, the term "microparticles" refers to particles having a size measured in microns, such as particles with a diameter of 1 to 100 μm.

[0022] Nanoparticles: As used herein, the term "nanoparticles" refers to particles having a size measured in nanometer units, such as particles having a diameter of 1 to 100 nm.

[0023] Separator: A battery separator is a porous sheet or film placed between the anode and the cathode. The separator prevents physical contact between the anode and cathode while simultaneously facilitating ion transport.

[0024] SSE surface protection The methods and materials disclosed herein improve processability and reduce costs associated with electrolyte generation and cell fabrication. A novel surface protection strategy for moisture-sensitive sulfide SSEs is disclosed herein. By using one or more amphiphilic compounds as surface protectants, ultrathin and effective layers can be constructed on the surface of the SSE via van der Waals force interactions. A single amphiphilic compound, a mixture of multiple amphiphilic compounds, or more amphiphilic compounds can be used. The SSE can be in the form of particles, films, or other shapes.

[0025] The amphiphilic compound comprises at least one hydrophilic head and at least one hydrophobic tail. The hydrophilic head is fixed to the surface of the SSE by van der Waals forces, forming an ultrathin layer that protects the interphase interface. The hydrophobic tail protects the sulfide SSE surface from water molecules that attack the SSE surface. Several advantages of such an amphiphilic interphase interface exist. Firstly, the molecule with the hydrophilic head is physically bonded to the surface of the sulfide, forming a very thin protective layer, and the influence of this protective layer on the bulk properties of the SSE is very limited. Secondly, the chemical composition and structure of this protective layer can be adjusted by designing or selecting appropriate functional groups depending on the desired structural / surface properties of the SSE. Thirdly, the protective layer can be released by heat treatment due to the weak interaction force between the protective layer and the SSE, restoring the ionic conductivity to its original value, which is desirable for practical applications and processing.

[0026] In certain embodiments, the surface protectant has a boiling point lower than the synthesis temperature of SSE.

[0027] Protected, air-stable sulfide-containing SSE facilitates the synthesis, storage, transport, and processing of solid electrolytes, as well as the fabrication of solid lithium batteries in ambient environments. The protected SSE is stable in O2, CO2, and N2 in air, and also stable in water (relative humidity <15%) with very limited H2S generation (<10 ppm within 2 hours). The exceptional air stability of the protected SSE significantly improves material processability for cell manufacturers, thereby greatly reducing processing costs. Furthermore, the developed air-stable solid electrolyte achieves excellent lithium-ion conductivity.

[0028] Exemplary parts that can function as hydrophilic heads are -OH;-C(O)O-;-C=O-;-NH-;-Al n (OH) m (n≧1 and m≧1);-PO4-;-C(O)NH2;-NH2;-OSO3H;-SO3H;-SH;-Cl;-Br;-I; and-NR4 + (R is Cx H 2x+1 Includes (where x ≥ 1).

[0029] An exemplary portion that can function as a hydrophobic tail is -CH3;-CH2-CH3;-R-C6H5(R is C x H 2x+1 (x≧1);-CH=CH2;-C3~C 50 Alkyl or substituted alkyl;-C3~C 50 Alkenyl or substituted alkenyl; -C3~C 50 Alkynyl or substituted alkynyl; (CH2) n (n≧2);-CH2F;-CHF2;-CF3;(CF2) n (n≧2); and (Si(CH3)2-O-) n Includes (n≧2).

[0030] Exemplary amphiphilic compounds that can function as surface protectants are: C x H 2x+1 Br(x≧1): For example, 2-bromopentane, 3-bromopentane, 1-bromo-3-methylbutane, 1-bromo-2-methylbutane, 1-bromo-2,2-dimethylpropane, 2-bromo-2-methylbutane, 1-bromobutane, 1-bromohexane and 1-bromooctane,

[0031] C x H 2x+1 Cl(x≧1): For example, 1-chloropentane, 2-chloropentane, 3-chloropentane, 1-chloro-3-methylbutane, 1-chloro-2-methylbutane, 1-chloro-2,2-dimethylpropane, 2-chloro-2-methylbutane, 1-chlorobutane, 1-chlorohexane and 1-chlorooctane,

[0032] C x H 2x+1I(x≧1): For example, 1-iodopentane, 2-iodopentane, 3-iodopentane, 1-iodo-3-methylbutane, 1-iodo-2-methylbutane, 1-iodo-2,2-dimethylpropane, 2-iodo-2-methylbutane, 1-iodobutane, 1-iodohexane and 1-iodooctane,

[0033] C x H 2x+1 SH(x≧1): For example, 1-butanethiol, 2-methyl-1-butanethiol, 3-methyl-1-butanethiol, 4-methoxy-2-methyl-2-butanethiol, 1-propanthol, 2-propanthol, 2-methyl-1-propanthol, 1-hexanethiol, 1-octanethol, 1-dodecanethiol,

[0034] Ether R 1 Ure 2 (In the formula, R 1 and R 2 Each of them is independent of C x H 2x+1 (x≧1): For example, diethyl ether, isoamyl ether, dibutyl ether, dipentyl ether, diisopropyl ether, dipropyl ether, dihexyl ether and dioctyl ether,

[0035] Ester R 1 COOR 2 (In the formula, R 1 and R 2 Each of them is independent of C x H 2x+1 (x≧1): For example, butyl valerate, butyl hexanoate, butyl octanoate, pentyl valerate, propyl butyrate, propyl hexanoate, hexyl hexanoate and hexyl octanoate Includes.

[0036] In certain embodiments, the surface protection layer forms a continuous layer of uniform thickness on the SSE surface. In certain embodiments, the layer has a thickness of ≥0.1 nm.

[0037] The surface protective layer can be removed by applying a temperature of 20 to 600°C, more specifically 20 to 150°C, to the coated SSE for 1 to 120 minutes, more specifically 10 to 60 minutes.

[0038] Surface protection can be applied to any SSE. Preferably, the SSE is air-stable, in particular, has high ionic conductivity (>1 mS / cm) at room temperature, high chemical stability to O2, N2, and CO2 in the air, and high chemical stability to water in the air with only limited H2S generation (<10 ppm within 2 hours at relative humidity <15%).

[0039] In certain embodiments, SSE is Li7P2S8X, where X is Cl, Br, I and / or F. Doping with halide ions allows for the modification of the crystal structure and bond strength, affecting Li metal and water. + Conductivity and chemical stability are enhanced.

[0040] In certain embodiments, SSE is Li3PS4(LPS) or Li 10 GeP2S 12 It is (LGPS).

[0041] In other embodiments, the protective coating is a moisture-sensitive Li-ion conductor (sulfide and oxide) and an active electrode material (e.g., LiNi 0.8 Co 0.1 Mn 0.1 It can be assigned to O2).

[0042] In certain embodiments, the sulfide-containing SSE is Li with a concentration of >5 mS / cm or >1 mS / cm at room temperature. + Conductivity, and <5Ωcm 2 It has a Li / SSE interface resistivity. In certain embodiments, the SSE is a solid ultrathin film (10-30 μm).

[0043] The surface protectant may be applied to the SSE surface by any method. For example, the surface protectant can be applied to the SSE surface by physical stirring and mixing, spraying, chemical vapor deposition, molecular layer deposition and / or atomic layer deposition. In certain embodiments, the surface protectant is a liquid mixed with SSE particles. The SSE particles may have an average particle size of, for example, 10 nm to 100 μm. The surface protectant / SSE particle mixture is heated under conditions sufficient to deposit the surface protectant onto the SSE particle surface. For example, the surface protectant layer can be deposited on the SSE particle surface by stirring and mixing the surface protectant and SSE for 1 to 120 minutes, more particularly 10 to 60 minutes, at a temperature of 0 to 200°C, more particularly 20 to 80°C.

[0044] SSE can be incorporated into an electrochemical cell that includes a cathode, anode, electrolyte, and a separator placed between the anode and cathode. The cell can be assembled into a lithium-ion battery system.

[0045] Examples of cathode materials include intercalated lithium, metal oxides (e.g., lithium-containing oxides such as lithium cobalt oxide, lithium iron phosphate, lithium magnesium oxide, lithium nickel manganese cobalt oxide, or lithium nickel cobalt aluminum oxide), or graphene.

[0046] In any of the embodiments described above or below, the cathode may further comprise one or more inert materials, such as a binder and / or additive (e.g., carbon). In some embodiments, the cathode may comprise 0 to 10% by weight of an inert material, such as 2 to 5% by weight. Suitable binders include, but are not limited to, polyvinyl alcohol, polyvinyl fluoride, ethylene oxide polymers, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, epoxy resin, nylon, and polyimide. Suitable conductive additives include, but are not limited to, carbon black, acetylene black, Ketjen black, carbon fibers (e.g., vapor-grown carbon fibers), metal powders or fibers (e.g., Cu, Ni, Al), and conductive polymers (e.g., polyphenylene derivatives).

[0047] In any of the embodiments described above or below, the anode may be any anode suitable for a lithium-ion battery. In some embodiments, the anode is lithium metal, lithium-metal alloy (e.g., lithium-metal alloy having a percentage of Li atoms ranging from 0.1 to 99.9% (e.g., Li-Mg, Li-Al, Li-In, Li-Zn, Li-Sn, Li-Au, Li-Ag, etc.)), graphite, intercalation material, or conversion compound. The intercalation material or conversion compound may be deposited on a substrate (e.g., a current collector) or provided as a self-supporting film typically containing one or more binders and / or conductive additives. Suitable binders include, but are not limited to, polyvinyl alcohol, polyvinyl chloride, polyvinyl fluoride, ethylene oxide polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, epoxy resin, nylon, and polyimide. Suitable conductive additives include, but are not limited to, carbon black, acetylene black, Ketjen black, carbon fibers (e.g., vapor-grown carbon fibers), metal powders or fibers (e.g., Cu, Ni, Al), and conductive polymers (e.g., polyphenylene derivatives). Exemplary anodes for lithium batteries include, but are not limited to, lithium metal, carbon-based anodes (e.g., graphite), silicon-based anodes (e.g., porous silicon, carbon-coated porous silicon, carbon / silicon carbide-coated porous silicon), Mo6S8, TiO2, V2O5, Li4Mn5O 12 Li4Ti5O 12 These include C / S composites and polyacrylonitrile (PAN)-sulfur composites. In some embodiments, the anode is lithium metal.

[0048] In any of the embodiments described above or below, the separator may be glass fiber, a porous polymer film with or without a ceramic coating (e.g., a polyethylene-based material or a polypropylene-based material), or a composite (e.g., a porous film consisting of inorganic particles and a binder). One exemplary polymeric separator is a Celgard® K1640 polyethylene (PE) membrane. Another exemplary polymeric separator is a Celgard® 2500 polypropylene membrane. Another exemplary polymeric separator is a Celgard® 3501 surfactant-coated polypropylene membrane.

[0049] The surface protective coating SSE can be assembled into an electrochemical cell using a cathode, anode, and, optionally, a separator.

[0050] SSE structures (e.g., thin films) can be fabricated from protective coating particles by any preferred method.

[0051] In one method, protective coating SSE particles are directly pelletized in a press die at 100-650 MPa to form SSE pellets.

[0052] Another method for producing SSE thin films involves mixing 1% to 99% by weight of a polymer binder with protective coating SSE particles to form a slurry, which is then cast to form an SSE thin film having a thickness in the range of 2 to 300 μm.

[0053] In a further method, 1% to 99% by weight of a polymer binder is dry-mixed with protective coating SSE particles, and then dry-processed into an SSE thin film having a thickness ranging from 2 to 300 μm. The entire process is protected under Ar gas.

[0054] The cells can be assembled from protective coating SSE by any preferred method.

[0055] In one method, protective coating SSE particles are pelletized using a press die at 100-650 MPa to form SSE pellets. A mixture of cathode powder, protective coating SSE particles, and carbon conductor is spread on top of the SSE pellets and pressed together with the SSE pellets at 100-650 MPa. Next, Li metal, Li alloy, or other anode material is pressed on the other side of the SSE pellets at 100-650 MPa to form cells.

[0056] In the method for producing SSE thin films, 1% to 99% by weight of a polymer binder is mixed with protective coating SSE particles to form a slurry, which is then cast to form an SSE thin film having a thickness in the range of 2 to 300 μm. Regarding the production of cathode films, 1% to 99% by weight of a binder is mixed with a cathode active material, protective coating SSE particles, and carbon additives, which is then cast to form a cathode film having a thickness in the range of 2 to 300 μm. The cathode film, SSE film, and Li metal, Li alloy, or other anode are sandwiched together and pressed under 100 to 650 MPa to form a cell.

[0057] Another method for producing SSE thin films involves dry mixing 1% to 99% by weight of a polymer binder with protective coating SSE particles, and then dry processing it into an SSE thin film having a thickness in the range of 2 to 300 μm. Regarding cathode film production, 1% to 99% by weight of a binder is dry mixed with a cathode active material, protective coating SSE particles, and carbon additives, and then processed into a cathode film having a thickness in the range of 2 to 300 μm. The cathode film, SSE film, and Li metal, Li alloy, or another anode material are sandwiched together and pressed under 100 to 650 MPa to form a cell. The entire process is protected under Ar gas.

[0058] In the final step of pressing the cathode, the SSE and Li / Li-alloy / other anodes are brought together, the entire cell is heated to remove the protective coating layer, and then the cell is vacuum-sealed in the packaging material. [Examples]

[0059] Reversible surface modification of SSE with 1-bromopentane

[0060] A typical process for amphiphilic molecule coating and release from / on SSE is illustrated in Figure 1. Sulfide SSE powder is immersed in the organic liquid 1-bromopentane and then vacuum-dried at 80°C for 12 hours to obtain 1-bromopentane-coated SSE (LPSBI-bromo). The 1-bromopentane molecules self-assemble on the SSE surface due to van der Waals force interactions between the Br of 1-bromopentane and the S originating from the SSE. Hydrophobic and long-chain alkyl tail, -(CH2) x -CH3 protects the SSE surface from water molecules that attack the SSE material. The 1-bromopentane coating layer can be released from the SSE surface by heat treatment at 160°C for 1 hour (LPSBI-bromo-160).

[0061] To investigate the changes in SSE surface properties before and after 1-bromopentane coating, X-ray photoelectron spectroscopy (XPS) analysis was performed on untreated LPSBI, LPSBI-bromo, and LPSBI-bromo-160 powders. Figures 2A and 2B show the high-resolution C 1s spectra of these three powders, and the changes in Br and C atomic concentrations during 1-bromopentane coating / release, respectively. In the case of untreated LPSBI, peaks with binding energies at 284.8, 286.7, and 289.1 eV were attributed to CH / CC, CO, and OC=O groups, respectively. These carbon signals may originate from absorbed organic species in the glove box or residual carbon in the XPS chamber. LPSBI-bromo showed suppression of the OC=O peak and an increase in the CH / CC peak after treatment with 1-bromopentane, indicating that the SSE surface is coated with 1-bromopentane, a CH / CC-rich species. This conclusion is supported by quantitative analysis of the atomic concentrations of C and Br. As shown in Figure 1B, when bound to 1-bromopentane in LPSBI-bromo (Brom), the atomic concentration of C increased sharply from 15.24% to 26.90%, while that of Br increased from 2.13% to 3.72%. The C / Br ratio measured in the detection region was approximately 7:1, which corresponds to 1-bromopentane (C5H 11 In Br, the ratio is close to 5:1, and C5H is present on the surface of LPSBI. 11 This confirms the presence of Br. The even higher C / Br ratio of 7:1 may be due to carbon species pre-existing on the surface of LPSBI. After heating LPSBI-bromo at 160°C for 1 hour, the C 1s spectrum of LPSBI-bromo-160 closely matched that of untreated LPSBI. The atomic concentrations of C and Br decreased back to values ​​comparable to those of untreated LPSBI (Figure 2B), indicating that 1-bromopentane can be released from the surface of LPSBI.

[0062] Thickness of the 1-bromopentane interphase interface on the surface of SSE

[0063] The thickness of the 1-bromopentane interfacial layer was calculated based on the molecular size and density of 1-bromopentane, the mass change of LPSBI before and after treatment with 1-bromopentane, and the Brunauer-Emmett-Teller (BET) surface area. The molecular length of 1-bromopentane is approximately 0.75 nm. The density of 1-bromopentane is 1.2 g / cm -3 . The BET surface area of LPSBI is approximately 10 m 2 / g -1 . After treatment with 1-bromopentane, 1 g of LSPBI increased in mass by approximately 9.7 mg, which is equivalent to a near monolayer of 1-bromopentane molecules on the surface of the LSPBI particles. A more detailed picture of the interaction between 1-bromopentane and LPSBI can be obtained from XPS. The inventors observed that after absorption, the intensities of the signal Li 1s, P 2p, and S 2p of the LPSBI substrate decreased, from which the inventors deduced the following: [Number] According to this, the thickness d of the adsorption layer can be estimated. (In the formula, I x,corr is the core level intensity of element x in LPSBI, I x,meas is the intensity of the signal of element x attenuated by the absorbed layer, λ x is the inelastic mean free path (IMFP) of the photoelectrons of x in the absorption coating layer, and θ is the radiation angle relative to the normal sample). Using Equation 1, the inventors calculated that for 1-bromopentane on LPSBI, d = 0.59 nm (±0.05 nm). The binding energies and peak shapes of the signals of Li 1s, P 2p, and S 2p remain unchanged after monolayer adsorption. The XPS results are in good agreement with the inventors' thermal gravimetric analysis, confirming that 1-bromopentane on LPSBI is adsorbed as a monolayer.

[0064] Figure 2D shows the electrochemical impedance spectra (EIS) of untreated LPSBI, LPSBI-bromo, and LPSBI-bromo-160 samples at room temperature. All powder samples were pressed into pellets with a diameter of 1 mm and a thickness of 0.7 mm for EIS measurements. For untreated LPSBI, a straight line with a crossover value of 17 ohms on the x-axis was detected in its spectrum, representing the impedance contribution from the blocking electrode. Compared to untreated LPSBI, the area behind the semicircle was observed in the higher frequency range of the LPSBI-bromo EIS, which corresponds to the transport of Li ions across particles and grain boundaries. The presence of the semicircle in the LPSBI-bromo EIS, rather than in the untreated LPSBI, was due to the presence of a 1-bromopentane coating on the surface of the LPSBI, which has low Li ion conductivity. After heating, the semicircle disappeared in the impedance spectrum of LPSBI-bromo-160, indicating that the interphase interface was removed from the LPSBI surface. The EIS reproduction further demonstrates the reversible coating observed in XPS characterization. The calculated ionic conductivity for untreated LPSBI, LPSBI-bromo, and LPSBI-bromo-160 was 5.3, 2.8, and 4.8 mScm, respectively. -1 Combining XPS, EIS analysis, and ionic conductivity measurements, it was confirmed that 1-bromopentane was successfully coated onto the surface of LPSBI and could be reversibly released without affecting the Li ion transport properties.

[0065] Water stability of SSE treated with 1-bromopentane

[0066] To investigate the effect of 1-bromopentane coating on the moisture stability of LPSBI, the inventors monitored H2S generation from LPSBI and LPSBI-bromo during 120 minutes of exposure to a dry chamber (RH=0.1%) and ambient (RH=20%) environment (see Supplementary Information for H2S measurement procedure). As shown in Figure 3A, the concentration of H2S gas released from untreated LPSBI after 120 minutes of exposure to the dry chamber continued to rise, reaching a peak of 8.9 ppm. In striking contrast, the H2S gas concentration for LPSBI-bromo was low at 1.6 ppm during the 120 minutes of exposure, which was 82% lower than the amount derived from untreated LPSBI. The 1-bromopentane coating dramatically improved the moisture stability of LPSBI by virtually halting the reaction between LPSBI and H2O. Even under much higher ambient conditions of RH=20%, the 1-bromopentane coating still demonstrated reasonable effectiveness in protecting LPSBI. In Figure 3B, the concentration of H2S gas emitted from untreated LPSBI surged to 48.6 ppm by the end of the test. In contrast, the concentration of H2S gas emitted from LPSBI-bromo remained much lower, peaking at only 33.5 ppm after 80 minutes of exposure, and this value remained constant until the end of the test. These results clearly demonstrate that the 1-bromopentane coating on the surface of LPSBI suppressed H2S generation.

[0067] Figure 3C shows the comparison of the EIS of LPSBI before and after exposure to air with 20% R.H. The EIS of LPSBI after exposure (LPSBI-20%) was analyzed by fitting it to an equivalent electrical circuit consisting of a resistance (R) in parallel with a constant phase element (CPE), representing the impedance of Li-ion transport through the bulk / particles and grain boundaries, and the Warburg impedance (W0) represents the impedance contribution from the electrode. During exposure, a large semi-circle was detected in the EIS of LPSBI-20%, corresponding to a large total (bulk / particles and grain boundaries) impedance, which is probably due to a severe reaction between LPSBI and H2O. The calculated ionic conductivity of LPSBI-20% is 5.5×10 -5 mScm -1 at room temperature, which is five orders of magnitude lower than that of the untreated LPSBI before exposure (5.3 mScm -1 ). In sharp contrast, a much smaller semi-circle was identified in the EIS of LPSBI-bromo-20% (LPSBI-bromo after exposure to air with 20% R.H.). The calculated ionic conductivity is 1.5×10 -2 mScm -1 at room temperature, which is three orders of magnitude higher than that of LPSBI-20%.

[0068] To examine the surface details of these samples before and after exposure, XPS measurements were performed on LPSBI, LPSBI-20%, LPSBI-bromo, and LPSBI-bromo-20% powders. Figure 4A shows the high-resolution C 1s spectra of these powders. Compared to untreated LPSBI, a novel peak centered at approximately 290.2 eV, corresponding to CO3, was detected in LPSBI-20%, indicating that carbonate species may be reaction products between LPSBI and H2O / CO2 in the air. This is also supported by the changes in the atomic densities of C and O, as shown in Figure 4B. The atomic concentration of C increased from 15.2% to 15.7%, while the atomic concentration of O surged from 4.9% to 8.9%. The higher O / C ratio compared to CO3 suggested that other O-rich species were also generated after air exposure. In stark contrast, the intensity of the CO3 peak in LPSBI-bromo-20% was remarkably low. As shown in Figure 4B, only the O concentration increased from 6.4% to 8.0% after exposure, further indicating that a less significant reaction occurred between LPSBI and H2O / CO2.

[0069] To investigate the effect of 1-bromopentane coating on the moisture stability of Li6PS5Cl(LPSC), the inventors monitored H2S generation from LPSC and LPSC-bromo-25C while they were exposed to an ambient environment with RH=10% for 50 minutes. As shown in Figure 5, the concentration of H2S gas released from untreated LPSC continued to rise, reaching a peak of 100 ppm (test limit) after 25 minutes of exposure. In striking contrast, the concentration of H2S gas from LPSC-bromo-25C was low at 40 ppm during the 25 minutes of exposure, which was 60% less than the amount derived from untreated LPSC. The 1-bromopentane coating dramatically improved the moisture stability of LPSC by slowing the reaction between LPSC and H2O.

[0070] To investigate the effect of 1-bromopentane coating on the moisture stability of Li3PS4 (LPS), the inventors monitored H2S generation from LPS and LPS-bromo-25C during 120 minutes of exposure to an environment with RH=49%. As shown in Figure 6, the concentration of H2S gas released from untreated LPS continued to rise, reaching a peak of 36 ppm after 120 minutes of exposure. In striking contrast, the H2S gas concentration for LPS-bromo-25C remained low at 20 ppm during the 120 minutes of exposure. The 1-bromopentane coating dramatically improved the moisture stability of LPS by slowing the reaction between LPS and H2O.

[0071] method Preparation of solid electrolytes. Glass-ceramic Li7P2S8Br 0.5 I 0.5 The materials were prepared using a ball milling technique, but with low-temperature heat treatment. Stoichiometric amounts of Li2S (Sigma-Aldrich, anhydrous, 99%), P2S5 (Sigma-Aldrich, 99%), LiBr (Sigma-Aldrich, 99.99%), and LiI (Sigma-Aldrich, 99.99%) were manually ground and then transferred to a zirconium oxide grinding jar. This mixture was ball-milled using a planetary ball mill (RETSCH PM 100 planetary ball mill) at a speed of 600 rpm for 40 hours. The resulting powder was heated at 160°C for 1 hour. The entire process was carried out under argon atmosphere protection. Glass ceramic Li3PS4 was prepared using the same ball milling method, but heated at 243°C for 2 hours.

[0072] Surface modification. 1-Bromopentane (Sigma-Aldrich, 98%) was dried on molecular sieves before use. 450 mg each of Li3PS4, Li7P2S8Br 0.5 I 0.5 and Li 10 GeP2S 12This was mixed with 3 g of 1-bromopentane for 8 hours. The mixture was dried overnight under vacuum at 80°C to obtain the final product. To release 1-bromopentane from the surface, the solid electrolyte including the surface treatment was heated at 160°C for 1 hour. This entire process was protected under an Ar atmosphere.

[0073] Moisture stability characterization. To monitor the amount of H2S gas released from untreated and surface-treated powder samples, 150 mg of each powder was placed in a 7112 cm³ solution. 3 The samples were sealed in desiccators of a certain volume, and the concentration of H2S and the relative humidity at the detectors were detected using calibrated gas detectors (FORENSICS DETECTORS) and humidity detectors (ThermoPro), respectively. One day before the test, the desiccators were placed in an ambient environment with a relative humidity of 20% and in a drying room with a relative humidity of 0.5%.

[0074] XRD and Raman spectra. Powder XRD measurements were performed using a Rigaku Miniflex II spectrometer with Cu Kα radiation irradiation, utilizing an XRD holder (Rigaku Corp.) with a beryllium window for air-sensitive samples. SEM and TEM characterization. The morphology of the SSE powder was observed using a scanning electron microscope (JSM-IT-200, JOEL).

[0075] Electrochemical measurements. The Li-ion conductivity of SSE was measured by electrochemical impedance spectroscopy using a Biologic SP 200 at an amplitude of 5 mV over a frequency range of 7 MHz to 0.1 Hz. SSE pellets were prepared by pressing powder under a pressure of 400 MPa, with carbon-coated aluminum foil attached to both sides of the pellets to act as blocking electrodes.

[0076] In view of the many possible embodiments to which the principles of the present invention can be applied, it should be recognized that the exemplary embodiments are merely preferred examples of the present invention and should not be considered to limit the scope of the invention. The present invention provides, for example, the following items: (Item 1) It is a method, The steps include: bringing the surface of a moisture-sensitive Li-ion conductor material into contact with an amphiphilic surface protective agent to obtain a protected Li-ion conductor material, and Steps to assemble an electrochemical cell containing the protected Li-ion conductor material. A method that includes this. (Item 2) The method according to item 1, wherein the Li ion conductor material is a sulfide-containing solid electrolyte material. (Item 3) The aforementioned amphiphilic surface protective agent is -OH;-C(O)O-;-C=O-;-NH-;-Al n (OH) m (n≧1 and m≧1), -PO 4 -;-C(O)NH 2 ;-NH 2 ;-OSO 3 H;-SO 3 H;-SH;-Cl;-Br;-I; and -NR 4 + (R is C x H 2x+1 Hydrophilic heads selected from (x≧1); and -CH 3 ;-CH 2 -CH 3 ;-RC 6 H 5 (R is C x H 2x+1 (x≧1); -CH=CH 2 ;-C 3 ~C 50 Alkyl or substituted alkyl;-C 3 ~C 50 Alkenyl or substituted alkenyl;-C 3 ~C 50 Alkynyl or substituted alkynyl; (CH 2 ) n (n≧2);-CH 2 F;-CHF 2 ;-CF 3 ;(CF 2 ) n (n≧2); and (Si(CH) 3 ) 2 -O-) n The method according to item 1 or 2, comprising a hydrophobic tail selected from (n≧2). (Item 4) The amphiphilic surface protectant comprises a hydrophilic head selected from -SH, -Cl, -Br, or -I; and -C 3 ~C 50 Alkyl or substituted-C 3 ~C50 The method according to item 1 or 2, having an alkyl hydrophobic tail. (Item 5) The aforementioned amphiphilic surface protective agent is C x H 2x+1 Br(x≧1);C x H 2x+1 Cl(x≧1);C x H 2x+1 I(x≧1);C x H 2x+1 SH(x≧1);R 1 Ure 2 (R 1 and R 2 Each of them is independent of C x H 2x+1 (x≧1);R 1 COOR 2 (R 1 and R 2 Each of them is independent of C x H 2x+1 The method described in item 1 or 2, wherein (x ≥ 1) or a mixture thereof. (Item 6) The method according to item 2, wherein the amphiphilic surface protectant is 1-bromopentane. (Item 7) The sulfide-containing solid electrolyte material is Li 7 P 2 S 8 The method described in any one of items 2 through 6, wherein X is Cl, Br, I, and / or F. (Item 8) The sulfide-containing solid electrolyte material is Li 3 PS 4 or Li 10 GeP 2 S 12 The method described in any one of items 2 through 6. (Item 9) The method according to any one of items 2 to 8, wherein the step of assembling the electrochemical cell includes the steps of forming the sulfide-containing solid electrolyte, forming a cathode, and forming an anode, wherein the sulfide-containing solid electrolyte is interposed between the anode and the cathode. (Item 10) It is a method, Step 1: Coating the surface of a sulfide-containing solid electrolyte material with an amphiphilic surface protectant. A method that includes this. (Item 11) The method according to item 10, further comprising the steps of processing the coated sulfide-containing solid electrolyte material and then removing the coating from the coated sulfide-containing solid electrolyte material. (Item 12) The amphiphilic surface protectant comprises a hydrophilic head selected from -SH, -Cl, -Br, or -I; and -C 3 ~C 50 Alkyl or substituted-C 3 ~C 50 The method according to item 10 or 11, having an alkyl hydrophobic tail. (Item 13) The aforementioned amphiphilic surface protective agent is C x H 2x+1 Br(x≧1);C x H 2x+1 Cl(x≧1);C x H 2x+1 I(x≧1);C x H 2x+1 SH(x≧1);R 1 Ure 2 (R 1 and R 2 Each of them is independent of C x H 2x+1 (x≧1);R 1 COOR 2 (R 1 and R 2 Each of them is independent of C x H 2x+1 The method described in item 10 or 11, wherein (x ≥ 1) or a mixture thereof. (Item 14) The method according to item 10 or 11, wherein the amphiphilic surface protectant is 1-bromopentane. (Item 15) The sulfide-containing solid electrolyte material is Li 7 P 2 S 8 The method described in any one of items 10 to 14, wherein X is Cl, Br, I, and / or F. (Item 16) Sulfide-containing solid electrolyte material, Li 3 PS 4 or Li 10 GeP 2 S 12 The method described in any one of items 10 to 14. (Item 17) A material comprising a sulfide-containing solid electrolyte coated with an amphiphilic surface protectant, wherein the amphiphilic surface protectant is -OH;-C(O)O-;-C=O-;-NH-;-Al n (OH) m (n≧1 and m≧1), -PO 4 -;-C(O)NH 2 ;-NH 2 ;-OSO 3 H;-SO 3 H;-SH;-Cl;-Br;-I; and -NR 4 + (R is C x H 2x+1 Hydrophilic heads selected from (x≧1); and -CH 3 ;-CH 2 -CH 3 ;-RC 6 H 5 (R is C x H 2x+1 (x≧1); -CH=CH 2 ;-C 3 ~C 50 Alkyl or substituted alkyl;-C 3 ~C 50 Alkenyl or substituted alkenyl;-C 3 ~C 50 Alkynyl or substituted alkynyl; (CH 2 ) n (n≧2);-CH 2 F;-CHF 2 ;-CF 3 ;(CF 2 ) n (n≧2); and (Si(CH) 3 ) 2 -O-) n A material containing a hydrophobic tail selected from (n≧2). (Item 18) The sulfide-containing solid electrolyte material is Li 7 P 2 S 8 X (where X is Cl, Br, I and / or F); Li 3 PS 4 ; or Li 10 GeP 2 S 12 The amphiphilic surface protective agent is C xH 2x+1 Br(x≧1);C x H 2x+1 Cl(x≧1);C x H 2x+1 I(x≧1);C x H 2x+1 SH(x≧1);R 1 Ure 2 (R 1 and R 2 Each of them is independent of C x H 2x+1 (x≧1);R 1 COOR 2 (R 1 and R 2 Each of them is independent of C x H 2x+1 The materials listed in item 17, which are (x≧1) or mixtures thereof. (Item 19) The material described in item 18 or 19, wherein the material is in the form of a film. (Item 20) The material described in item 18 or 19, wherein the material is in particulate form. (Item 21) The material described in item 18 or 19, wherein the material is a pellet. (Item 22) It is a structure, A sulfide-containing solid electrolyte coated with an amphiphilic surface protectant, wherein the amphiphilic surface protectant is -OH;-C(O)O-;-C=O-;-NH-;-Al n (OH) m (n≧1 and m≧1), -PO 4 -;-C(O)NH 2 ;-NH 2 ;-OSO 3 H;-SO 3 H;-SH;-Cl;-Br;-I; and -NR 4 + (R is C x H 2x+1 Hydrophilic heads selected from (x≧1); and -CH 3 ;-CH 2 -CH 3 ;-RC 6 H 5 (R is C x H 2x+1 (x≧1); -CH=CH 2 ;-C 3 ~C 50 Alkyl or substituted alkyl;-C 3 ~C 50 Alkenyl or substituted alkenyl;-C 3 ~C 50 Alkynyl or substituted alkynyl; (CH 2 ) n (n≧2);-CH 2 F;-CHF 2 ;-CF 3 ;(CF 2 ) n (n≧2); and (Si(CH) 3 ) 2 -O-) n A sulfide-containing solid electrolyte having a hydrophobic tail selected from (n≧2), Cathode material, and Anode material A structure that includes the following features. (Item 23) The structure described in item 22, wherein the structure is a pellet. (Item 24) The structure according to item 22 or 23, wherein the electrolyte is interposed between the cathode material and the anode material. (Item 25) The structure according to item 22, wherein the film containing the electrolyte is interposed between the film containing the cathode material and the film containing the anode material.

Claims

1. It is a method, The steps include: bringing the surface of a moisture-sensitive Li ion conductor material into contact with an amphiphilic surface protective agent to obtain a protected Li ion conductor material, and Steps to assemble an electrochemical cell containing the protected Li-ion conductor material. Includes, The Li ion conductor material is a sulfide-containing solid electrolyte material. The amphiphilic surface protectant is a hydrophilic head selected from -NH-; -Al n(OH) m (n≧1 and m≧1), -PO4-; -C(O)NH2; -NH2; -OSO3H; -SO3H; -SH; -Cl; -Br; -I; and -NR4+ (where R is CxH2x+1 (x≧1)); and -CH3; -CH2-CH3; -R-C6H5 (where R is CxH2x+1 (x≧1)); -CH=CH2; -C3-C50 alkyl or substituted alkyl; -C3-C50 alkenyl or substituted alkenyl; -C3-C50 alkynyl or substituted alkynyl; (CH2)n A method comprising a hydrophobic tail selected from (n≧2); -CH₂F; -CHF₂; -CF₃; (CF₂)n (n≧2); and (Si(CH₃)₂-O-)n (n≧2).

2. The amphiphilic surface protectant comprises a hydrophilic head selected from -SH, -Cl, -Br, or -I; and -C ３ ~C ５０ Alkyl or substituted C ３ ~C ５０ The method according to claim 1, having an alkyl hydrophobic tail.

3. where the amphiphilic surface protecting agent is C ｘ H ２ｘ＋１ Br (x ≧ 1); C ｘ H ２ｘ＋１ Cl (x ≧ 1); C ｘ H ２ｘ＋１ I (x ≧ 1); C ｘ H ２ｘ＋１ SH (x ≧ 1); R １ OR ２ (R １ and R ２ are each independently C ｘ H ２ｘ＋１ (x ≧ 1)); or a mixture thereof, the method according to claim 1.

4. The method according to claim 1, wherein the amphiphilic surface protective agent is 1-bromopentane.

5. The sulfide-containing solid electrolyte material is Li ７ P ２ S ８ The method according to any one of claims 1 to 4, wherein X is Cl, Br, I and / or F.

6. The sulfide-containing solid electrolyte material is Li ３ PS ４ or Li １０ GeP ２ S １２ The method according to any one of claims 1 to 4.

7. The method according to any one of claims 1 to 6, wherein the step of assembling the electrochemical cell includes the steps of forming a sulfide-containing solid electrolyte, forming a cathode, and forming an anode, wherein the sulfide-containing solid electrolyte is interposed between the anode and the cathode.

8. It is a method, Step 1: Coating the surface of a sulfide-containing solid electrolyte material with an amphiphilic surface protectant. Includes, The amphiphilic surface protectant is a hydrophilic head selected from -NH-; -Al n(OH) m (n≧1 and m≧1), -PO4-; -C(O)NH2; -NH2; -OSO3H; -SO3H; -SH; -Cl; -Br; -I; and -NR4+ (where R is CxH2x+1 (x≧1)); and -CH3; -CH2-CH3; -R-C6H5 (where R is CxH2x+1 (x≧1)); -CH=CH2; -C3-C50 alkyl or substituted alkyl; -C3-C50 alkenyl or substituted alkenyl; -C3-C50 alkynyl or substituted alkynyl; (CH2)n A method comprising a hydrophobic tail selected from (n≧2); -CH₂F; -CHF₂; -CF₃; (CF₂)n (n≧2); and (Si(CH₃)₂-O-)n (n≧2).

9. The method according to claim 8, further comprising the steps of processing the coated sulfide-containing solid electrolyte material and then removing the coating from the coated sulfide-containing solid electrolyte material.

10. The amphiphilic surface protectant comprises a hydrophilic head selected from -SH, -Cl, -Br, or -I; and -C ３ ~C ５０ Alkyl or substituted C ３ ~C ５０ The method according to claim 8 or 9, having an alkyl hydrophobic tail.

11. The aforementioned amphiphilic surface protective agent is C ｘ H ２ｘ＋１ Br(x≧1); C ｘ H ２ｘ＋１ Cl(x≧1); C ｘ H ２ｘ＋１ I (x ≥ 1); C ｘ H ２ｘ＋１ SH (x ≥ 1); R １ OR ２ (R １ and R ２ Each of them is independent of C ｘ H ２ｘ＋１ The method according to claim 8 or 9, wherein (x ≥ 1); or a mixture thereof.

12. The method according to claim 8 or 9, wherein the amphiphilic surface protective agent is 1-bromopentane.

13. The sulfide-containing solid electrolyte material is Li ７ P ２ S ８ The method according to any one of claims 8 to 12, wherein X is Cl, Br, I and / or F.

14. Sulfide-containing solid electrolyte material, Li ３ PS ４ or Li １０ GeP ２ S １２ The method according to any one of claims 8 to 12.

15. A material comprising a sulfide-containing solid electrolyte coated with an amphiphilic surface protectant, wherein the amphiphilic surface protectant is -NH-;-Al ｎ (OH) ｍ (n≧1 and m≧1), -PO ４ -;-C(O)NH ２ ;-NH ２ ;-OSO ３ H; -SO ３ H; -SH; -Cl; -Br; -I; and -NR ４ ＋ (R is C ｘ H ２ｘ＋１ Hydrophilic heads selected from (where x ≥ 1); and -CH ３ ;-CH ２ -CH ３ ;-R-C ６ H ５ (R is C ｘ H ２ｘ＋１ (x≧1); -CH=CH ２ ;-C ３ ~C ５０ Alkyl or substituted alkyl; -C ３ ~C ５０ Alkenyl or substituted alkenyl; -C ３ ~C ５０ Alkynyl or substituted alkynyl; (CH ２ ) ｎ (n≧2); -CH ２ F; -CHF ２ ;-CF ３ ; (CF ２ ) ｎ (n≧2); and (Si(CH) ３ ) ２ -O-) ｎ A material containing a hydrophobic tail selected from (n≧2).

16. The sulfide-containing solid electrolyte is Li ７ P ２ S ８ X (X is Cl, Br, I, and / or F); Li ３ PS ４ ; or Li １０ GeP ２ S １２ and the amphiphilic surface protecting agent is C ｘ H ２ｘ＋１ Br (x ≥ 1); C ｘ H ２ｘ＋１ Cl (x ≥ 1); C ｘ H ２ｘ＋１ I (x ≥ 1); C ｘ H ２ｘ＋１ SH (x ≥ 1); R １ OR ２ (R １ and R ２ are each independently C ｘ H ２ｘ＋１ (x ≥ 1)); or a mixture thereof, the material according to claim 15.

17. The material according to claim 15 or 16, wherein the material is in the form of a film.

18. The material according to claim 15 or 16, wherein the material is in the form of particles.

19. The material according to claim 15 or 16, wherein the material is a pellet.

20. It is a structure, A sulfide-containing solid electrolyte coated with an amphiphilic surface protectant, wherein the amphiphilic surface protectant is -NH-;-Al ｎ (OH) ｍ (n≧1 and m≧1), -PO ４ -;-C(O)NH ２ ;-NH ２ ;-OSO ３ H; -SO ３ H; -SH; -Cl; -Br; -I; and -NR ４ ＋ (R is C ｘ H ２ｘ＋１ Hydrophilic heads selected from (where x ≥ 1); and -CH ３ ;-CH ２ -CH ３ ;-R-C ６ H ５ (R is C ｘ H ２ｘ＋１ (x≧1); -CH=CH ２ ;-C ３ ~C ５０ Alkyl or substituted alkyl; -C ３ ~C ５０ Alkenyl or substituted alkenyl; -C ３ ~C ５０ Alkynyl or substituted alkynyl; (CH ２ ) ｎ (n≧2); -CH ２ F; -CHF ２ ;-CF ３ ; (CF ２ ) ｎ (n≧2); and (Si(CH) ３ ) ２ -O-) ｎ A sulfide-containing solid electrolyte comprising a hydrophobic tail selected from (n≧2), Cathode material, and Anode material A structure that includes the following features.

21. The structure according to claim 20, wherein the structure is a pellet.

22. The structure according to claim 20 or 21, wherein the electrolyte is interposed between the cathode material and the anode material.

23. The structure according to claim 20, wherein the film containing the electrolyte is interposed between the film containing the cathode material and the film containing the anode material.

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