Patent Publication Number: US-2022227624-A1

Title: Method for Wet Chemical Synthesis of Lithium Argyrodites

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This international patent application claims the benefit of and priority to U.S. Provisional Patent Application Ser. No. 62/835,173, with a filing date of 17 Apr. 2019, the contents of which are fully incorporated herein by reference. 
    
    
     STATEMENT OF GOVERNMENT RIGHTS 
     This invention was made with United States Government support under Grant No. 1355438 awarded by the National Science Foundation. The United States Government has certain rights in the invention. 
    
    
     FIELD OF INVENTION 
     The embodiments described herein include methods for rapidly and economically synthesizing solid electrolytes for use in battery systems, further embodiments relate to wet chemical synthesis of lithium argyrodites and the use of halide doping. 
     BACKGROUND 
     The rapidly growing electric vehicle industry has spurred a strong need for the development of safer and higher energy density portable energy storage. Currently, conventional liquid electrolyte batteries, such as lithium ion, are in use for such applications. However, conventional liquid electrolyte batteries have limited energy density and thus limited energy capacity. In addition, conventional liquid electrolyte batteries are highly flammable and unstable. As a result, conventional liquid electrolyte batteries present a significant safety hazard, especially to the electric vehicle industry. Furthermore, conventional liquid electrolyte batteries often decompose at high voltages, which limit the use of high voltage cathode materials, and they often pose a risk of leakage. 
     All-solid-state batteries (ASSBs), on the other hand, have shown promise as next-generation lithium battery systems that address many of the drawbacks of the conventional liquid electrolyte batteries. ASSBs are promising candidates for the battery storage industry and are expected to improve safety, increase energy density, and enhance stability and durability. ASSBs comprise solid electrodes and solid electrolytes, instead of the liquid or polymer electrolytes found in the typical lithium ion battery. The solid electrolyte is an important component of ASSBs for its role in transporting the lithium ions and separating the anode from the cathode. Common inorganic solid electrolytes include oxides (e.g., garnet, perovskite), phosphates (e.g., LiPON, LATP, LAGP) and sulfides (e.g., Li 2 S—P 2 S 5 , Li 3 PS 4 , Li 7 P 3 S 11 , Li 7 PS 6 ). Among these, sulfide solid electrolytes have garnered significant attention due to their superior lithium ion conductivities, wide electrochemical window, thermal stability, and favorable mechanical properties such as easy densification and elastic modulus. Other desirable properties for a solid electrolyte include an ionic conductivity above 10 −4  Siemens per centimeter (S cm −1 ) at room temperature, a large electrochemical stability window, and stability against electrodes, especially a metallic lithium anode. In addition, the production cost is an important factor in the large-scale development of solid electrolyte materials. 
     Lithium argyrodites are a new and promising class of solid electrolyte sulfide-based lithium ion superconductors. Lithium argyrodites originate from the silver germanium sulfide mineral with the formula Ag 8 GeS 6 , which is characterized by its high ionic conductivity (˜10 −3  S cm −1 ) and fast silver ion (Ag+) mobility. Pure lithium argyrodite (Li 7 PS 6 ) is reported to have a cubic phase at high-temperature (HT) or an orthorhombic phase at low-temperature (LT). In particular, the cubic HT-phase shows higher ionic conductivities (0.7-1.0 10 −3  S cm −1 ) and can be stabilized by the replacement of the sulfur by halogen anions, such as chlorine, bromine, and iodine. Such lithium argyrodites are expressed by the formula Li m PS n X o , where X is either chlorine, bromine, or iodine. Lithium argyrodites without a halide are expressed by the formula Li m PS n . 
     Recent studies of lithium argyrodite materials have yielded a basic understanding of the temperature-dependent diffusion paths of ions based on their structural properties. In addition, strong interest has grown in the use of lithium argyrodites as solid electrolytes for ASSBs because of its (1) high intrinsic lithium-ion conductivities (10 −2  to 10 −3  S cm - &#39;), (2) impressive stability within a large electrochemical window (up to 7V, which is suitable even for high voltage cathode materials), and (3) composition flexibility (due to flexibility in both anion and cation doping). 
     Despite these important findings, however, the large-scale manufacturing of lithium argyrodites has not been achieved due to the harsh conditions required by the conventional synthesis methods: melt-quenching or high-energy ball milling. With these conventional approaches, Li 7 PS 6  (as one example) has been synthesized through the solid-state reaction of Li 2 S with P 2 S 5  at 550° C. for several hours or even days. Moreover, the preparation conditions for melt-quenching are very difficult and harsh. For example, melt-quenching requires the careful and precise control of reactant concentrations, otherwise it results in impurities during the cooling process. Consequently, the industrial applicability and feasibility of the conventional melt-quenching synthesis method has shown limited to unlikely prospects. High-energy ball milling fabrication is also time consuming and it is difficult to obtain uniform products. For example, some conventional ball-milling methods require at least 5 hours and up to 4 days to complete (without accounting for the time required to complete full crystallization). For the entire crystallization process to be completed after the heating and cooling cycle, the conventional ball-milling method can take an additional 5 hours and up to 7 days. 
     Recently, wet chemical synthesis has attracted interest as an alternative to the conventional synthesis methods because of its flexibility for material preparation and manufacturing simplicity. However, the conventional wet chemical synthesis methods require expensive solvents such as tetrahydrofuran (THF), acetonitrile (ACN), and dimethoxyethane (DME). For the large-scale synthesis of lithium argyrodites, which is required for the development of ASSBs in next generation energy storage systems, lesser amounts of solvents, as well as inexpensive and less toxic would be preferred. Moreover, liquid synthesis for producing lithium argyrodites is always challenging due to the stability of precursors in a solvent; for example, P 2 S 5  reacts with the ethanol to form dialkyl dithiophosphoric acid. 
     In addition, non-toxic solvent based liquid synthesis would be a more efficient and environmentally friendly approach to prepare homogenous composite cathodes for ASSBs. Typically, cathode materials have poor conductivities and require mixing with carbon/solid electrolyte to enhance their electronic/ionic conductivities. For example, melt-quenching and high-energy ball milling typically results in the aggregation of each component, and such fouling limits the efficiency and life cycle duration of electrodes used in synthesis of lithium argyrodites. 
     Furthermore, the conventional solid-state synthesis methods have not explored the impact of halide doping content on the structure and conductive properties of produced lithium argyrodite. This limitation may be due to the difficulty in introducing additional halide(s) into a lithium argyrodite structure utilizing the traditional solid-state synthesis methods because of the slow atom diffusion and lattice reorganization. 
     Accordingly, there is a significant need for more optimal solid electrolyte synthetic methods capable of producing lithium argyrodites on the commercial scale, i.e. kgs or higher. There is also a significant need for a synthetic method that is simpler, more efficient, requires shorter preparation times, results in more homogenous products with higher conductivities, and utilizes more environmentally friendly and affordable solvents. Such improvements would allow for the success of ASSBs at scales large enough to serve the mobile electric market. Along with other features and advantages outlined herein, the methods described herein according to multiple embodiments and alternatives meet these and other needs. In doing so, the methods described herein further advance the use of Li-ion conducting argyrodites in ASSBs by producing improved halide doped materials. 
     SUMMARY OF EMBODIMENTS 
     Multiple embodiments and alternatives are disclosed herein for the liquid synthesis of lithium argyrodites using precursors and inexpensive and nontoxic ethanol (EtOH) solvent. Although EtOH is preferred, other solvents also can be used within the scope of present embodiments, which provide for, without limitation, a method for rapid synthesis of lithium argyrodites in about 2 hours and at low sintering temperatures (e.g. 150° C.). According to multiple embodiments and alternatives, structural and morphological investigations have determined that the synthesized lithium argyrodites have high phase purity, improved ionic conductivity at room temperature, high stability, and homogeneity. In some embodiments, halide doping occurs during the synthesis process to achieve higher ionic conductivity. 
     In some embodiments, the electrolyte Li 7 PS 6  is synthesized by dissolving the precursors Li 2 S and β-Li 3 PS 4  in a small quantity of anhydrous ethanol (e.g. 25 ml) in argon atmosphere. Next, in some embodiments the mixture is dried above room temperature (e.g. greater than 22° C.) under vacuum to evaporate the solvent yielding a white precipitate (not longer than 1 hour, preferably 40-50 minutes), and then treated above 150° C. for 1 hour to obtain the final product (Li 7 PS 6 ). In some embodiments, establishing a negative pressure of 10 −2 ˜10 −3  mbar or lower provides efficient evaporation. In some embodiments, instead of a vacuum, the mixture is dried above room temperature in an inert gas atmosphere until a dry powder is obtained. In the synthesis of Li 7 PS 6  noted above, the chemical reaction of β-Li 3 PS 4  and Li 2 S is: 
     
       
         
           
             
               
                 
                   
                     
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     The Li 7 PS 6  product synthesized according to multiple embodiments and alternatives exhibits high phase purity, favorable ionic conductivity, and significant electrochemical stability with metallic lithium anode. In some embodiments, methods for wet chemical synthesis provided herein utilize the economic and nontoxic ethanol solvent to synthesize lithium argyrodite solid electrolyte in significantly shorter time than conventional approaches. 
     Present embodiments include those wherein steps include synthesis of electrolytes Li 6 PS 5 X (where X=Cl, Br, or I) by dissolving a stoichiometric mixture of Li 2 S, Li 3 PS 4  in acetonitrile (i.e., (ACN) 2  in this exemplary statement)) and LiX (X=Cl, Br, I) in a small quantity of anhydrous ethanol (25 ml) in argon atmosphere. In an exemplary embodiment, the Li 3 PS 4 .(ACN) 2  precursor is used (or pure Li 3 PS 4 , or Li 3 PS 4 .(THF)), then the solvent is evaporated above room temperature (e.g. more than 22° C.) under vacuum (not longer than 1 hour, preferably 40-50 minutes), and the precipitate then is treated with heat (above 150° C. for 1 hour) until the final product is synthesized (e.g. Li 6 PS 5 Cl, Li 6 PS 5 Br, and Li 6 PS 5 I). The chemical reaction is: 
     
       
         
           
             
               
                 
                   
                     
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     Structural and morphological investigations revealed the final product exhibits high phase purity, high ionic conductivity at room temperature, and good stability with metallic lithium without evidence of side reactions. 
     In some embodiments according to the present disclosure, Li 6 PS 5 Cl.xLiCl (0≤x≤2) materials were synthesized by stoichiometrically tuning an excess amount of LiCl as the precursor. According to multiple embodiments and alternatives, the synthesized product has a molar ratio of sulfur to chloride in the range of 1.5:1 to 5.1. In some embodiments, the synthesized product has a molar ratio of sulfur to chloride in the range of 2.5:1 to 5:1. An exemplary process includes first dissolving Li 2 S and LiCl in ethanol, followed by the addition of Li 3 PS 4 . Next, the mixture is stirred for 0.5 hours, dried above room temperature (e.g. 90° C. as a non-limiting example) under vacuum to evaporate the ethanol, and then annealed above 150° C. As desired, chlorine content in Li 6 PS 5 Cl.xLiCl (0≤x≤2) is tuned by controlling the amount of LiCl precursor. In some embodiments, the following ratios of LiCl:Li 3 PS 4  were controlled at 1:1, 1.5:1, 2:1, 2.5:1, and 3:1 to obtain the samples of Li 6 PS 5 Cl, Li 6 PS 5 Cl.0.5LiCl (i.e. Li 6.5 PS 5 Cl 1.5 ), Li 6 PS 5 Cl.LiCl (i.e. Li 7 PS 5 Cl 2 ), Li 6 PS 5 Cl.1.5LiCl (i.e. Li 7.5 PS 5 Cl 2.5 ) and Li 6 PS 5 Cl.2LiCl (i.e. Li 8 PS 5 Cl 3 ), respectively. To investigate the annealing effect, Li 6 PS 5 Cl.LiCl sample was heated at different temperatures (350° C., 550° C. as non-limiting examples) for 6 hours under an Argon environment, according to multiple embodiments and alternatives. Herein, the annealed samples are referred to as Li 6 PS 5 Cl.LiCl-350 and Li 6 PS 5 Cl.LiCl-550, respectfully. The chemical reaction is represented by: 
     
       
         
           
             
               
                 
                   
                     
                       
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     Advantageously, it has been discovered that when the Cl doping ratio is 2:1 (versus Li 3 PS 4 ), the synthesized lithium argyrodite solid electrolyte exhibits a higher ionic conductivity of 4.4×10 −4  S cm −1  at room temperature when compared to other Cl doping ratios studied. The inventors are unaware of any reported conductivity value higher than this for an argyrodite prepared via liquid synthesis. In addition, the synthesized lithium argyrodite exhibits stability against a metallic lithium anode and lower activation energy. 
     The liquid synthesis method according to multiple embodiments and alternatives opens new possibilities for the success of ASSBs by generating lithium argyrodites with higher purity and more homogenous material through a simpler and scalable manufacturing process. 
    
    
     
       BRIEF DESCRIPTION OF THE FIGURES 
       The drawings and embodiments described herein are illustrative of multiple alternative structures, aspects, and features of the multiple embodiments and alternatives disclosed herein, and they are not to be understood as limiting the scope of any of these embodiments and alternatives. It will be further understood that the drawing figures described and provided herein are not to scale, and that the embodiments are not limited to the precise arrangements and instrumentalities shown. 
         FIG. 1  is a flow chart showing the steps of a method for wet chemical synthesis of lithium argyrodites 
         FIG. 2  shows a comparison of x-ray diffraction patterns (XRD) of Li 7 PS 6  crystalline and β-Li 3 PS 4  phase [panel (a)], and Raman spectra of Li 7 PS 6  and β-Li 3 PS 4 [ panel (b)]. 
         FIG. 3  shows scanning electron microscope (SEM) images of SEM images of the final Li 7 PS 6  product [panel (a)] and Li 3 PS 4  precursor [panel (b)]. 
         FIG. 4  shows energy-dispersive X-ray spectroscopy (EDX) maps of Li 3 PS 4  precursor prepared from ACN solution, wherein [panel (a)] shows the distribution of P atoms and [panel (b)] shows the distribution of S atoms.  FIG. 4  also shows EDX maps of the final Li 7 PS 6  product prepared from ethanol solution, wherein [panel (c)] shows the distribution of P atoms and [panel (d)] shows the distribution of S atoms. 
         FIG. 5  shows Arrhenius plots of Li 7 PS 6  from ethanol and β-Li 3 PS 4  from ACN [panel (a)], and comparison of conductivity values and synthesis time of Li 7 PS 6  prepared by different methods [panel (b)]. 
         FIG. 6  shows cyclic voltammetry curves of Li 7 PS 6  and β-Li 3 PS 4  solid electrolytes with metallic Li anode with Li/SE/Pt cell (scanning rate at 50 mV s −1  between −0.5 and 5V vs. Li/Li +  at room temperature) [panel (a)], and cycling performance of Li/Li 7 PS 6 /Li symmetric cell (current density of 50 μA cm −2 ) [panel (b)]. 
         FIG. 7  is a flow chart illustrating the steps of a method for wet chemical synthesis of lithium argyrodites. 
         FIG. 8  shows XRD patterns of Li 7 PS 6  solid electrolyte using different precursors: Li 3 PS 4 .(ACN) 2  complex and Li 3 PS 4 . 
         FIG. 9  shows XRD patterns of Li 7 PS 6  obtained from ethanol evaporation and dried at 90 ° C. 
         FIG. 10  shows XRD patterns of Li 3 PS 4 .(ACN) 2  fresh precipitate and after 80° C. heat treatment, and β-Li 3 PS 4  phase above 150° C. annealing. 
         FIG. 11  shows XRD patterns of re-precipitated Li 3 PS 4  material from ethanol dried at 80° C. and heated above 150° C., as well as reference patterns for Li 3 PS 4  and Li 3 PS 4 .(ACN) 2 . 
         FIG. 12  shows Raman spectra of Li 3 PS 4 , Li 3 PS 4  re-precipitated from EtOH, and Li 7 PS 6  prepared from Li 3 PS 4  and Li 2 S in EtOH medium. 
         FIG. 13  shows SEM images of the re-precipitated Li 3 PS 4  sample from ethanol, wherein [panel (a)] has 5 μm scale and [panel (b)] has a 2 μm scale. 
         FIG. 14  shows Nyquist plots of synthesized Li 7 PS 6  and β-Li 3 PS 4  precursor, wherein the frequency range is from 1 MHz to 100 mHz. 
         FIG. 15  shows XRD patterns of Li 7 PS 6  pellet after cycled in a symmetric cell (Li/Li 7 PS 6 /Li). 
         FIG. 16  is a flow chart showing the steps of a method for wet chemical synthesis of lithium argyrodites. 
         FIG. 17  shows XRD patterns of Li 7 PS 6  and Li 6 PS 5 X lithium argyrodites, wherein [panel (b)] is a close-up view of [panel (a)]. The dashed lines vertical lines in the bottom of [panel (a)] refer to standard diffraction peaks for Li 6 PS 5 X. 
         FIG. 18  shows Raman spectra of Li 7 PS 6  and Li 6 PS 5 X lithium argyrodites (X=Cl, Br, or I) from ethanol solution and Li 2 S and P 2 S 5  for comparison. 
         FIG. 19  shows SEM images of Li 7 PS 6  [panel (a)] and Li 6 PS 5 X products prepared from ethanol solution, where X is Cl [panel (b)], Br [panel (c)], and I [panel (d)]. 
         FIG. 20  shows Arrehenius plots of Li 7 PS 6  and Li 6 PS 5 X lithium argyrodite samples from ethanol. 
         FIG. 21  panel shows cyclic voltammetry curves [panel (a)] of the liquid synthesized Li 6 PS 5 X materials with metallic Li anode in the voltage window of 0.5-5.0 (vs Li/Li+) and the cycling performance of symmetric cells under a current density of 0.02 mA cm −2  [panel (b)]. 
         FIG. 22  shows cycling of symmetric cells with Li/Li 6 PS 5 X/Li structure, wherein [panel (b)] is a close-up view of a portion of [panel (a)]. 
         FIG. 23  shows EDX maps of Li 6 PS 5 X products (where X is Cl, Br and I) prepared form ethanol solution showing the distribution of S, P, and X atoms. 
         FIG. 24  shows multiple unit cell three-dimensional simulation of the crystal structure of certain Li 6 PS 5 X products (where X is Cl [panel (a)], Br [panel (b)] and I [panel (c)]). 
         FIG. 25  shows XRD patterns of Li 7 PS 6  and Li 6 PS 5 X (X=Cl, Br, I) using Li 3 PS 4  from THF solvent. 
         FIG. 26  shows Arrehenius plots of Li 7 PS 6  and Li 6 PS 5 Cl using different Li 3 PS 4  precursors (from THF solvent or ACN). 
         FIG. 27  shows a SEM image of Li 6 PS 5 Cl. 
         FIG. 28  shows the XRD patterns [panel (a)] and the Raman spectra [panel (b)] for lithium argyrodites with different Cl contents. 
         FIG. 29  shows the XRD patterns [panel (a)] and analysis of the Li 6 PS 5 Cl.LiCl sample after annealing heat treatment under different temperatures [panel (b)]. 
         FIG. 30  shows SEM images of the lithium argyrodites with different Cl contents produced in accordance with inventive methods disclosed herein, wherein [panel (a)] is the SEM image for Li 6 PS 5 Cl.LiCl, [panel (b)] is the SEM image for Li 6 PS 5 Cl.2LiC1, and [panel (c)] is the EDX mapping of Li 6 PS 5 Cl.LiCl. 
         FIG. 31  shows Arrhenius plots of solvent-synthesized lithium argyrodites (Li 7 PS 6  and Li 6 PS 5 Cl.xLiCl with x=0, 0.5, 1, 1.5 and 2) [panel (a)] and also shows composition dependence of room temperature conductivities and activation energies for lithium argyrodites with excess Cl content [panel (b)]. 
         FIG. 32  shows cyclic voltammetry curves under scanning rate of 50 mV/s in the range of −0.5-5.0V (vs Li/Li + ) [panel (a)], and the cycling performance of symmetric cells (current density of 0.02 mA cm −2 ) [panel (b)] for the Li m PS n Cl o  samples with different Cl content (0&lt;o&lt;3). 
         FIG. 33  [panel (a)] shows Nyquist plots of lithium argyrodites with different Cl content Li 7 PS 6  and Li 6 PS 5 Cl.xLiCl (x=0, 0.5, 1, 1.5, 2) at room temperature and [panel (b)] compares the Nyquist plots of Li 6 PS 5 Cl and Li 6 PS 5 Cl.LiCl. 
         FIG. 34  shows the cyclic voltammetry curve of Li 5 PS 4 Cl 2  solid electrolyte in large voltage window up to 10 V (vs Li/Li + ). 
         FIG. 35  shows the symmetric cells cycling voltage profiles for Li 7 PS 6  solid electrolyte under different current densities (0.02, 0.03, and 0.05 mA cm −1 ). 
         FIG. 36  shows the symmetric cells cycling voltage profiles for Li 6 PS 5 Cl solid electrolyte under different current densities (0.02, 0.03, and 0.05 mA cm −1 ). 
         FIG. 37  shows the symmetric cells cycling voltage profiles for Li 5 PS 4 Cl 2  solid electrolyte under different current densities (0.02, 0.03, and 0.05 mA cm −1 ). 
         FIG. 38  shows the symmetric cells cycling voltage profiles for Li 6 PS 5 Cl.LiCl solid electrolyte under different current densities (0.02, 0.03, and 0.05 mA cm −1 ). 
         FIG. 39  shows the comparison of battery cycling performance of Li/LTO cells with Li 6 PS 5 Cl.LiCl and Li 6 PS 5 Cl as the solid electrolyte composition under 0.2 C. 
     
    
    
     MULTIPLE EMBODIMENTS AND ALTERNATIVES 
     Methods for wet chemical synthesis of lithium argyrodites, according to multiple embodiments and alternatives, opens new possibilities for synthesizing highly pure and homogenous materials through a simple and scalable manufacturing process. Compared to conventional synthesis methods, methods presented herein according to multiple embodiments and alternatives are scalable, more efficient, easier to prepare, have a shorter synthesis time, and utilize an environmentally friendly and affordable solvent (e.g, ethanol). Moreover, the synthesized product according to multiple embodiments and alternatives exhibits high phase purity, excellent room temperature ionic conductivity, and high stability. Accordingly, inventive methods for wet chemical synthesis of lithium argyrodite as described herein may allow for the success of ASSBs at scales that are practical for serving the mobile electric vehicle market. 
     According to multiple embodiments and alternatives, a method for wet chemical synthesis of lithium argyrodites involves dissolving a stoichiometric mixture of precursors (Li 2 S, Li 3 PS 4 .(ACN) 2  and LiX [where X=Cl, Br, I] as non-limiting examples) in a small quantity of ethanol in an argon atmosphere. Next, drying the mixture above room temperature (i.e. greater than 22° C.) under vacuum, or in an inert gas atmosphere, to evaporate the ethanol (no longer than 1 hour, preferably 40-50 minutes), then annealing above 150° C. for one hour obtains a final lithium argyrodite product. Further embodiments comprise synthesizing the precursors by dissolving Li 2 S and P 2 S 5  in ACN, stirring the mixture for eight hours at room temperature, and then filtering the product. The obtained white powder is then dried at 80° C. under vacuum (Li 3 PS 4 .(ACN) 2 ) followed by a heat treatment above 150° C. (β-Li 3 PS 4 ). Further embodiments comprise the use of halide doping by modifying the ratios of LiCl vs. Li 3 PS 4 . According to multiple embodiments and alternatives, an argyrodite prepared with an excess amount of 2 moles of chloride achieves a desirable ionic conductivity at room temperature. It is expected that bromine or iodine doping will have a similar impact on increasing the ionic conductivity of the argyrodite. 
     According to multiple embodiments and alternatives, the synthesized argyrodites can be utilized as the electrolyte in an electrochemical energy storage device (such as an ASSB as a non-limiting example). In some embodiments, the electrochemical energy storage device comprises an anode, a cathode, and the synthesized argyrodite as the electrolyte. The anode releases electrons to the circuit and oxides during the electrochemical reaction, the cathode acquires electrons from the external circuit and is reduced during the electrochemical reaction, and the electrolyte is the medium that acts as the ionic conductor. ASSBs utilizing solid electrolyte compositions, prepared according to multiple embodiments and alternatives, achieve a desirable specific capacity likely due to the formation of a more stable solid electrolyte interphase layer and by blocking side reactions. 
     All examples provided herein are meant as illustrative of various aspects of multiple embodiments and alternatives of wet chemical synthesis of lithium argyrodites. These examples are non-limiting and merely characteristic of multiple alternative embodiments as described and claimed or to-be-claimed herein. 
     Example 1—Wet Chemical Synthesis of Li 7 PS 6    
     Synthesis of Li 3 PS 4  precursor—As illustrated in  FIG. 7 , the Li 2 S and P 2 S 5  with a stoichiometry of 3:1 is dissolved in acetonitrile (ACN), stirred for 8 h at room temperature and then filtrated. The obtained white powder is then dried at 80° C. under vacuum to remove excess solvent yielding Li 3 PS 4 .(ACN) 2 . Further heat treatment above 150° C. produces β-Li 3 PS 4 . 
     Synthesis of Li 7 PS 6 electrolyte—As illustrated in  FIG. 1 , a stoichiometric mixture (2:1 molar) of Li 2 S and β-Li 3 PS 4  is dissolved in a small quantity of anhydrous ethanol (25 ml) in argon atmosphere. Next, the mixture is dried above room temperature (i.e. greater than 22° C.) under vacuum or an inert gas atmosphere to evaporate the solvent yielding a white precipitate (not longer than 1 hour, preferably 40-50 minutes), and then treated above 150° C. for 1 hour to obtain a final product (Li 7 PS 6 ). As previously noted, the chemical reaction of β-Li 3 PS 4  and Li 2 S to produce cubic Li 7 PS 6  is: 
     
       
         
           
             
               
                 
                   
                     
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     Structural and Morphological Investigation—The phase composition and crystal structure of the Li 7 PS 6  electrolyte synthesized within the scope of embodiments were analyzed using X-ray diffraction (XRD) (Broker D8 Discover) with nickel-filtered Cu-Kα radiation (λ=1.5418 Å). The Scherrer equation was used to estimate the crystallite size of the obtained materials. The Scherrer equation, when utilized in XRD, is a formula that relates the size of crystallites in a solid to the broadening of a peak in a diffraction pattern. The Scherrer equation is a simple and well-known expression for obtaining a measure of the crystallite size from XRD peaks. The Scherrer equation is represented by the following formula: 
       τ=( K λ)/(βcos θ)   Equation (4)
 
     where τ is the mean size of the ordered (crystalline) domains, K is a dimensionless shape factor, λ is the X-ray wavelength, β is the line broadening at half the maximum intensity (FWHM), after subtracting the instrumental line broadening, in radians, and θ is the Bragg angle. 
     The chemical and structural data was obtained from the Raman spectroscopy, which was measured using Renishaw in Via Raman/PL Microscope and a 632.8 nm emission line of a HeNe laser. Raman spectroscopy is a technique used to observe vibration, rotational, and other low-frequency modes in a system. Typically, a sample is illuminated with a laser beam, then electromagnetic radiation from the illuminated spot is collected with a lens and sent through a monochromator. Elastic scattered radiation at the wavelength corresponding to the laser line is filtered out by either a notch filter, edge pass filter, or a band pass filter, while the rest of the collected light is dispersed onto a detector. 
     General morphologies of all samples were also investigated using a TESCAN Vega3 scanning electron microscope (SEM). 
     Conductivity and Electrochemical Stability—Electrochemical impedance spectroscopy (EIS) was carried out to measure the ionic conductivities of samples, synthesized within the scope of embodiments, in the frequency range from 1 MHz to 100 mHz with an amplitude of 100 mV using Bio-Logic VSP300. For the measurements, dense pellets (½″ diameter) were prepared by cold pressing the powder with C/Al as blocking electrodes at each side and placed in Swagelok cells. A Swagelok cell is typically a cylindrical battery cell that is widely known to one of ordinary skill in the art. 
     As expected for pure ionic conductors, EIS spectra present a semi-arc at high frequencies and a straight line at lower frequencies. The intercept of a straight line at the axis is employed to determine the total ionic conductivity of the material. In addition, the temperature dependent spectra were recorded from room temperature (i.e. about 22° C.) to 90° C. to obtain the Arrhenius plot. An Arrehenius plot displays the logarithm of a reaction rate constant plotted against inverse temperature. 
     Swagelok cells were also used to complete cyclic voltammetry (CV) and cycling performance measurements. A CV test is an electrochemical technique which measures the current that develops in an electrochemical cell under conditions where voltage is in excess of the predicted amount. For the CV test, Li/SE/Pt cells were scanned at 50 mV s′ rate between 0.5 and 5V vs. Li/Li +  at room temperature using Bio-Logic VSP 300 potentiostat. For symmetric cell cycling, the Li/SE/Li symmetric cell were assembled and cycled on a battery system (Bio-Logic VSP) with current densities of 50 μA cm −2 . 
     Results and Discussion 
     Structural Analysis 
     In this Example, Li 7 PS 6  solid electrolyte was synthesized by reacting Li 3 PS 4  and Li 2 S in an anhydrous ethanol, and subsequent heat treatment at low temperature (as shown in  FIG. 1 ), according to multiple embodiments and alternatives. Li 3 PS 4  has a similar solubility as Li 2 S in ethanol and thus made the Li 7 PS 6  reaction possible. 
     As shown in  FIG. 7 , the pure phase of Li 7 PS 6  product was also obtained by using Li 3 PS 4 .(ACN) 2  complex as the precursor to react with Li 2 S in ethanol.  FIG. 8  illustrates the XRD patterns of Li 7 PS 6  solid electrolyte using different precursors: Li 3 PS 4 .ACN) 2  complex and Li 3 PS 4 .  FIG. 8  shows that the source of Li 3 PS 4  has no difference on the Li 7 PS 6  phase purity and expands to Li 3 PS 4  synthesized from other solid-state methods. 
     As shown in  FIG. 2  (panel a), the as-synthesized Li 7 PS 6  powder was characterized by XRD. Interestingly, the Li 7 PS 6  powder synthesized according to multiple embodiments and alternatives displays several sharp peaks at 2θ=25.5, 30, 31.2°, corresponding to (220), (311) and (222) planes in cubic HT-phase of Li 7 PS 6  (space group F-43m). These characteristic diffraction peaks shown in  FIG. 2  align with the pure phase of cubic Li 7 PS 6  that has been reported previously. The cubic structure of the synthesized product has a unit cell parameter equal to 9.88 Å and the crystal size is estimated at 34 nm. As shown in  FIG. 2  (panel a), Li 7 PS 6  shows totally different diffraction patterns than orthorhombic β-Li 3 PS 4  (space group Pnma, a=12.997 Å, b=8.081 Å, c=6.143 Å). Furthermore, due to stoichiometric amounts of reactants and a homogeneity of the liquid preparation method, the final material is free from Li 2 S impurity and other crystal phases. 
     The Raman spectra of cubic Li 7 PS 6  and β-Li 3 PS 4  are shown in  FIG. 2  (panel b). The precursor Li 3 PS 4  exhibits a peak at 421.1 cm −1  and this can be attributed to symmetric stretching vibration of (PS 4 ) 3−  (ortho-thiophosphate) group in orthorhombic β-Li 3 PS 4  structure. Furthermore, a few minor lines at 387.6, 530.2 and 568.5 cm −1  are observed, where the first mode corresponds to a trace of Li 4 P 2 S 6  and its (P 2 S 6 ) 4  (P—P bond) vibrational mode, and the latter two refer to the additional (PS 4 ) −3  vibrational modes. After the reaction, Li 7 PS 6  shows a PS 4   −3  vibrational mode at 421.6 cm −1  as expected. A small peak at 497.2 cm −1  and broad line around 575 cm −  are probably attributable to, similarly to Li 3 PS 4  structure, the additional (PS 4 ) −3  vibrational modes. Due to a strong ionic character of bonds between S −2  and Li +  ions in the crystal Raman, the lines from Li + —S −2  interaction are expected to be weak. 
     The XRD pattern of intermediate product after the evaporation of EtOH (as illustrated in  FIG. 9 ), shows that pure phase of Li 7 PS 6  exists before heat treatment at 200° C., suggesting that this reaction happens at room temperature without heating. This also indicates that Li 7 PS 6  is unlikely to form an adduct with ethanol, which makes it easy to remove the solvent. 
     To further understand the reaction mechanism, the dissolution and re-precipitation process of Li 3 PS 4  in ethanol was studied and compared with the case in acetonitrile.  FIG. 10  demonstrates that Li 3 PS 4  forms a complex of Li 3 PS 4 .(ACN) 2  in acetonitrile reverting to pure phase back after heat treatment. In contrast, the re-precipitated Li 3 PS 4  material from ethanol shows unknown crystal structure after drying at 80° C. and exhibits amorphization after heating at above 150° C. (see  FIG. 11 ). The reference bands in  FIG. 11  show the Li 3 PS 4  re-prec is different with Li 3 PS 4  and Li 3 PS 4 ACN. As shown in  FIG. 12 , the structural change of Li 3 PS 4  in ethanol is further supported by the Raman spectra, in which the characteristic peak of (PS 4 ) 3−  group vibration is not observed. Nevertheless, with the existence of Li 2 S in ethanol, the cubic phase of Li 7 PS 6  can be successfully produced from Li 3 PS 4  without any other crystal phase. 
     Morphological Analysis 
     According to multiple embodiments and alternatives, the morphology variation from Li 3 PS 4  precursor to Li 7 PS 6  product was also analyzed using SEM. As shown in  FIG. 3  (panel b), the Li 3 PS 4  sample prepared from ACN has an interesting flake-like morphology. In contrast, as shown in  FIG. 3  (panel a), the Li 7 PS 6  product shows a granular nano-sized morphology (agglomerated particles of about 100 nm size). The difference in morphology of these samples is related to the solvent involved in the synthesis. As shown in  FIG. 13 , Li 3 PS 4  dissolved in ethanol and the re-precipitated sample displays a grainy shape. 
     EDX analysis of the Li 3 PS 4  precursor and final Li 7 PS 6  product is shown in  FIG. 4 . The distribution of P and S atoms is practically the same for both materials, indicating homogeneity through liquid synthesis methods. The calculated ratio between P and S atoms in these samples are 1:3.2 and 1:4.6, respectively, which can indicate elemental disturbance at the surface of the materials. 
     Conductivity and Stability Measurements 
     EIS were employed to measure the conductive properties of both cubic Li 7 PS 6  and β-Li 3 PS 4 . As shown in  FIG. 5  (panel a), the synthesized Li 7 PS 6  has an ionic conductivity of about 0.11 mScm −1  to 0.5 mScm −1  at about room temperature, which is a much higher value compare to a previous report from the liquid synthesis of Li—P—S argyrodite. Furthermore, the synthesized Li 7 PS 6  has an ionic conductivity of about 1.5 mScm −1  at about 90° C. The Nyquist plots of Li 7 PS 6  and β-Li 3 PS 4  (as shown in  FIG. 14 ) show both solid electrolytes have decreased total resistance with increasing temperature. Compared with β-Li 3 PS 4 , Li 7 PS 6  exhibits faster Li-ion mobility at elevated temperatures. For instance, the ionic conductivity of Li 7 PS 6  is 1.5×10 −3  S cm −1  at 90° C. while 1.0×10 −3  S cm −1  for Li 3 PS 4  at the same temperature. The activation energy of Li 7 PS 6 is determined to be 38.73 kJ mol −1  (0.4 eV), whereas Li 3 PS 4  is equal to 32.39 kJ mol −1  (0.336 eV). 
       FIG. 5  (panel b) compares the conductivities and productivity for Li 7 PS 6  prepared through different methods: 3×10 −5  S cm −1  (conventional solid state reaction at 650° C. for 7 days, represented by “Ref 32” in  FIG. 5 ),  8 × 10   −5  S cm −1 (conventional crystal powder from solid state reaction, 40 hours, represented by “Ref 12, 13” in  FIG. 5 ), and methods according to the present disclosure: 1.1×10 −4  S cm −1  (liquid synthesis approach, 2 hours, represented by “This work” in 
       FIG. 5 ). In  FIG. 5  (panel b), the lighter bars represent the productivity and the darker bars represent the conductivities. Both synthetic approaches of solid-state reaction and mechanical milling require the reaction time longer than 40 hours and the yielded products show conductivity values of 10 −5 -10 −4  S cm −1 . In contrast, the Li 7 PS 6  synthesis according to multiple embodiments and alternatives can be completed in 2 hours. The findings from the present disclosure suggest that reacting and nucleating Li 7 PS 6  crystals straight from the solution is beneficial for the final ionic conductivity. In addition, the ionic conductivity value of Li 7 PS 6  from the present disclosure is also close to other Li 2 S—P 2 S 5  family materials previously prepared by solid-state methods (e.g., glasses and glass-ceramics). 
     As shown in  FIG. 6  (panel a), the electrochemical stability between the synthesized Li 7 PS 6  and metallic Li was investigated by cyclic voltammogram (CV) of a Li/Li 7 PS 6 /Pt cell, in which Li and Pt serve as the reference/courter electrode and working electrodes, respectively. The potential was scanned from −0.5 to 5.0V (vs. Li + /Li) at a scan rate of 50 mVs −1 . As illustrated in  FIG. 6  (panel a), for both solid electrolytes (cubic Li 7 PS 6  and β-Li 3 PS 4 ), a pair of reversible oxidation and reduction peaks is observed at around 0 V (vs. Li + /Li) without any other side reaction. Furthermore, the cathode current below 0 V is a Li deposition on working electrode (Li + +e − →Li), whereas the anode current above 0 V results from reversible lithium dissolution. The CV curves illustrated in  FIG. 6  (panel a) indicate that Li 7 PS 6 , synthesized in accordance with multiple embodiments and alternatives, exhibits as good stability with Li anode as Li 3 PS 4  over a broad electrochemical window (up to 5 V). 
     A symmetric cell of Li/Li 7 PS 6 /Li was configured to demonstrate the compatibility of Li 7 PS 6  solid electrolyte with metallic Li under a current density of 50 μAcm −2  at room temperature and the results are shown in  FIG. 6  (panel b). The values of overpotential for the symmetric cell are lower than 20 mV with a slight increase as cycling continues, suggesting the possible interfacial reactions between Li anode and Li 7 PS 6  solid electrolyte. Nevertheless, after cycling, shiny Li surface was still observed when peeling it off from Li 7 PS 6  solid electrolyte in the symmetric cell. The XRD patterns of the solid electrolyte pellet after cycling (shown in  FIG. 15 ) show characteristic peaks of Li 7 PS 6 , which indicates that the interfacial reaction is not severe. 
     In summary, crystalline lithium argyrodite solid electrolyte was rapidly and economically synthesized through the stoichiometric chemical reaction of Li 2 S and Li 3 PS 4  in ethanol medium. The synthesized Li 7 PS 6  has the room temperature ionic conductivity of at least 0.11 mS cm −1  at room temperature and 1.5 mS cm −1  at 90° C., a desirable value among pure materials prepared through liquid synthesis, and 40% higher than those crystalline Li 7 PS 6  powders from other synthesis methods (i.e. solid-state reaction and ball milling). Furthermore, the synthesized Li 7 PS 6  is highly compatible with the metallic Li anode. Accordingly, methods for wet chemical synthesis of lithium argyrodites, according to multiple embodiments and alternatives, leads to high purity phase of Li 7 PS 6  material with scalable and simple processing steps. Moreover, inventive methods for wet chemical synthesis of lithium argyrodites further position Li 7 PS 6  as a desirable electrolyte candidate in the large-scale all-solid-state battery technology. 
     Example 2—Wet Chemical Synthesis of Li 6 PS 5 X, where X=Cl, Br, or I 
     Synthesis of Li 3 PS 4  precursor—As illustrated in  FIG. 7 , the Li 2 S and P 2 S 5  with a stoichiometry of 3:1 is dissolved in acetonitrile (ACN), stirred for 8 h at room temperature and then filtrated. The obtained white powder is then dried at 80° C. under vacuum to remove excess solvent yielding Li 3 PS 4 .(ACN) 2 . Further heat treatment above 150° C. produces β-Li 3 PS 4 . 
     Synthesis of Li 7 PS 5 X electrolyte—As illustrated in  FIG. 16 , the Li 6 PS 5 X electrolyte (where X=Cl, Br, or I) was efficiently synthesized using a wet chemical method according to multiple embodiments and alternatives. A stoichiometric mixture of Li 2 S, Li 3 PS 4 .(ACN) 2  and LiX (X=Cl, Br, I) was dissolved in a small quantity of anhydrous ethanol (25 ml) in argon atmosphere. To bypass the P 2 S 5  insolubility problem, pure Li 3 PS 4  precursor was used. Next, the solvent was evaporated at 90° C. under vacuum until a white precipitate was present (not longer than 1 hour, preferably 40-50 minutes). The heat treatment continued above 150° C. (1 hour) and got a final product (Li 6 PS 5 Cl, Li 6 PS 5 Br, and Li 6 PS 5 I respectively) synthesized according to multiple embodiments and alternatives. As previously noted, the chemical reaction for the synthesis of Li 6 PS 5 X electrolyte is expressed by: 
     
       
         
           
             
               
                 
                   
                     
                       L 
                       ⁢ 
                       
                         i 
                         3 
                       
                       ⁢ 
                       P 
                       ⁢ 
                       
                         S 
                         4 
                       
                     
                     + 
                     
                       L 
                       ⁢ 
                       
                         i 
                         2 
                       
                       ⁢ 
                       S 
                     
                     + 
                     LiX 
                   
                   ⁢ 
                   
                     → 
                     
                       etha 
                       ⁢ 
                       nol 
                     
                   
                   ⁢ 
                   
                     
                       Li 
                       6 
                     
                     ⁢ 
                     P 
                     ⁢ 
                     
                       S 
                       5 
                     
                     ⁢ 
                     X 
                   
                 
               
               
                 
                   Equation 
                   ⁢ 
                   
                       
                   
                   ⁢ 
                   
                     ( 
                     2 
                     ) 
                   
                 
               
             
           
         
       
     
     Structural and Morphological Investigation—The phase composition and crystal structure of the final product were examined using X-ray diffraction (Bruker D8 Discover) with nickel-filtered Cu-Kα radiation (λ=1.5418 Å). The crystallite size of the obtained materials was estimated using the Scherrer equation. In addition, the chemical and structural data was obtained from the Raman spectroscopy measured by Renishaw in Via Raman/PL Microscope with a 632.8 nm emission line of a HeNe laser. TESCAN Vega3 scanning electron microscope (SEM) was used to study the morphology of the samples synthesized according to multiple embodiments and alternatives. 
     Electrochemistry and conductivity—Electrochemical impedance spectroscopy (EIS) were performed to measure the ionic conductivities of produced samples in the frequency range from 1 MHz to 100 mHz with an amplitude of 50 mV using Bio-Logic VSP300. Measurements were done using dense pellets (½″ diameter) prepared by a cold pressing of powders between two electrodes of conductive carbon on aluminum current collector (blocking electrode) and placing them in homemade press cells. As expected for pure ionic conductor, EIS spectra present a semi-arc at high frequencies and a straight line at lower frequencies. The straight line intercept at the X axis is employed to determine the total ionic conductivity of the material. In addition, the temperature dependent spectra were recorded from room temperature to 90° C. to obtain the Arrhenius plot. Swagelok cells were also used to complete cyclic voltammetry (CV) and cycling performance measurements. For CV test, Li/SE/Pt cells were scanned at 50 mV s −1  rate between −0.5 and 5V vs. Li/Li +  at room temperature using. For symmetric cell cycling, the Li/SE/Li symmetric cell were assembled and cycled on a battery system (Bio-Logic VSP) with current densities of 50 μA cm −2 . 
     Results and Discussion 
     Crystal Structure Analysis of Anionic Substituted Li 6 PS 5 X 
     As illustrated in  FIG. 16 , for Li 6 PS 5 X (where X=Cl, Br or I) synthesis, stoichiometric mixtures of Li 3 PS 4 , Li 2 S and LiX (where X=Cl, Br or I) were dissolved in anhydrous ethanol, stirred, and followed by a heat treatment above 150° C., yielding white powders for halide doped lithium argyrodites. The final products synthesized according to multiple embodiments and alternatives were characterized by XRD (as shown in  FIG. 17 ), and were identified as Li 6 PS 5 Cl, Li 6 PS 5 Br, and Li 6 PS 5 I, corresponding to LiCl, LiBr and LiI reactants, respectively. Similar to the case of the pure Li 7 PS 6  powder from Example 1, all halide doped samples display several sharp peaks at 2θ≈25.5, 30, 31.2°, attributing to (220), (311), and (222) planes in cubic phase (space group F-43m), but with a slight peak shift due to the subtle change on unit cell parameters. The set of unit cell parameter, crystal size, ionic radius of the halides and sulfide anions for Li 7 PS 6  and Li 6 PS 5 X are presented in Table 1. 
     
       
         
           
               
             
               
                 TABLE 1 
               
             
            
               
                   
               
               
                 Structural and Spectral Properties of 
               
               
                 Li 7 PS 6  and Li 6 PS 5 X lithium argyrodite samples. 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                   
                 Crystal 
                 Unit cell 
                 Ionic 
                 Raman 
                   
                   
                   
               
               
                   
                 Size 
                 parameter 
                 radius 
                 shift 
                 FWHM 
                 E a   
               
               
                 Sample 
                 (nm) 
                 (A) 
                 (pm) 
                 (cm −1 ) 
                 (cm −1 ) 
                 (kJ/mol) 
                 E a  (eV) 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 Li 7 PS 6   
                 34 
                 9.88 
                 (S −2 ) 170 
                 421.5 
                 10.7 
                 41.46 
                 0.430 
               
               
                 Li 6 PS 5 Cl 
                 45 
                 9.84 
                 (Cl − ) 167 
                 425.1 
                 10.7 
                 38.57 
                 0.400 
               
               
                   
                   
                   
                   
                 392.6 
                 16 
               
               
                 Li 6 PS s Br 
                 39 
                 9.89 
                 (Br − ) 182 
                 423.3 
                 9 
                 40.24 
                 0.417 
               
               
                   
                   
                   
                   
                 388.8 
                 12 
               
               
                 Li 6 PS 5 l 
                 32 
                 9.95 
                 (I − ) 206      
                 422.7 
                 11.6 
                 40.47 
                 0.419 
               
               
                   
                   
                   
                   
                 390.1 
                 17 
               
               
                   
               
            
           
         
       
     
     Based on the results shown in Table 1, the lattice parameter a decreases from 9.88 A for Li 7 PS 6  to 9.84 Å for Li 6 PS 5 Cl and then increases to 9.89 Å for Li 6 PS 5 Br and 9.95 Å for Li 6 PS 5 I, respectively. This trend is consistent with the ion&#39;s radius variations, due to Cl −  (167 pm)&lt;S 2−  (170 pm)&lt;Br −  (182 pm)&lt;I −  (206 pm). Larger anions (Br −  and I − ) lead to the expansion of the lattice parameter in the cubic structure. This observation fits well with the trend from the previous experimental reports on the Li 6 PS 5 X series. Due to stoichiometric amounts of used ingredients in liquid-based synthesis method, the final products are mostly free from impurities. Only in the case of Li 6 PS 5 Br, were trace amounts of LiBr observed. It is important to mention that the preparation time of these solid electrolyte materials according to the disclosure herein is only about 2 hours. On the other hand, the preparation time for ball-milling takes at least 5 hours (and up to 4 days), not even counting the much longer heating/cooling process required for full crystallization to occur (e.g. 5 hours and up to 7 days). 
     To confirm the crystal structure, the Raman spectra of of Li 6 PS 5 X samples (Li 6 PS 5 Cl, Li 6 PS 5 Br, and Li 6 PS 5 I), were collected and compared with that of pure Li 7 PS 6 , as shown in  FIG. 18 . Similar with Li 7 PS 6  material, all three halide doped samples (Li 6 PS 5 X) exhibit strong lines in the range between 422 and 425 cm −1  attributed to PS 4   −3  ion vibration and the minor lines at about 390 cm −1 . The exact line positions and their full width at half maximum (FWHM) values are shown in Table 1 (above). The results indicate that PS 4   −3  ion vibration is influenced by the surrounding halide ions which likely change the force constants and cause the evident peak shift. The Raman shift of PS 4   −3  ion vibration decreases while the unit cell of argyrodite increases. The minor line mode can correspond to a trace of Li 4 P 2 S 6  and its P 2 S 6   −4  vibrational mode. For comparison, the Li 7 PS 6  has a similar PS 4   −3  vibrational mode at 421.6 cm −1  as expected. 
     The morphology of the products synthesized according to present embodiments were also analyzed by SEM images. As previously stated, the solvent may play a role in the final morphology of the material. As shown in  FIG. 19 , the morphology of the Li 6 PS 5 X material series was compared to the Li 7 PS 6  product prepared from ethanol.  FIG. 19  illustrates that the reaction of Li 3 PS 4 , Li 2 S, and LiX in ethanol solvent results in grainy nanosized morphology (agglomerated particles of about 500 nm size) as expected. 
     In addition, the EDX maps of the Li 6 PS 5 X (see  FIG. 23 ) show uniform distribution of P, S, and X (Cl, Br, and I) atoms, suggesting a homogeneity in the final product after the liquid synthesis method, according to multiple embodiments and alternatives. 
     Electrochemical Performance of Li 7 PS 6  Electrolyte from Liquid Phase 
     The conductivity measurements in a blocking cell show that Li 6 PS 5 Cl and Li 6 PS 5 Br materials prepared according to the synthesis method disclosed herein have higher ionic conductivities than pure Li 7 PS 6  samples. In particular, their values at room temperatures are 1.4×10 −4  S cm −1  and 1.2×10 −4  S cm −1  compared to 1.1×10 −4  S cm −1  of Li 7 PS 6  material. This enhancement on ionic conductivity is closely related with the replacement of Cl and Br to S ions, which results in more defects in Li 6 PS 5 Cl and Li 6 PS 5 Br. As expected, the Li 6 PS 5 I shows the lower ionic conductivity of 2.9×10 −5  S cm −1  compared with its Cl— and Br— analogues. This effect was recently explained and experimentally proven by correlating the lattice softness with the ionic transport. The latest results suggest that the softer bonds lower the activation energy and simultaneously decrease the moving ion prefactor. The addition of Cl, Br, or I ions to the crystal structure leads to an obvious change in the unit cell volume (as illustrated in the XRD patterns shown in  FIG. 17 ), as well as the lattice site disorder. The decreasing disorder increases the activation barrier of the ionic transport. The electrochemical performance results further confirm these theoretical findings. 
     In addition to room temperature conductivity, the total activation energy of the prepared samples was calculated from the temperature dependent EIS spectra.  FIG. 20  shows Arrhenius plots which reflect the temperature dependence of ionic conductivities for Li 6 PS 5 X (X=Cl, Br, I) samples and pristine Li 7 PS 6 . All materials show linear relations of ionic conductivity vs temperature, and the slopes are proportional to the activation energy (E a ) for Li-ion conduction according to the following equation: 
     
       
         
           
             
               
                 
                   σ 
                   = 
                   
                     
                       σ 
                       0 
                     
                     ⁢ 
                     
                       e 
                       
                         
                           E 
                           a 
                         
                         
                           k 
                           ⁢ 
                           T 
                         
                       
                     
                   
                 
               
               
                 
                   Equation 
                   ⁢ 
                   
                       
                   
                   ⁢ 
                   
                     ( 
                     5 
                     ) 
                   
                 
               
             
           
         
       
     
     where σ is the photo-ionization cross-section, σ 0  is the pre-exponential photo-ionization cross-section, E a  is the activation energy, k is Boltzmann&#39;s constant, and T is the temperature. The activation energies of Li 6 PS 5 Cl, Li 6 PS 5 Br, and Li 6 PS 5 I are estimated to be 38.57 kJ mol −1  (0.399 eV), 40.24 kJ mol −1  (0.417 eV), and 40.47 kJ mol −1  (0.419 eV) while Li 7 PS 6  is equal to 41.46 kJ mol −1  (0.430 eV), as specified in Table 1. The comparison indicates that introducing halide ions (X=Cl, Br, I) reduces the barrier for Li ion mobile along the framework and thus decreases the values of activation energy. The total activation energies of halide doped materials show lower values than pure Li 7 PS 6 . The Li 6 PS 5 Cl sample has the lowest activation energy and also shows the best conductivity among all doped samples. This suggests that Li 6 PS 5 Cl has the lowest barrier for lithium ions to move along the material. The main reason for the best conductivity of Li 6 PS 5 Cl is due to the distribution of disorder of Cl ions over the 4a and 4c sites together, which provides both high Li +  intercage jump rates and doublet jump rates in the Li 6 PS 5 Cl structure. 
     For a solvent-based synthesis method, Li 3 PS 4  is the most important precursor to produce high purity Li 6 PS 5 X argyrodites. Previously, Li 3 PS 4  was reported to yield either flaky or chunky morphology from different solvent-based processes. Accordingly, Li 3 PS 4  precursors from two synthesis solvents (ACN and THF) were used to prepare Li 6 PS 5 X (X=Br, Cl) argyrodites following the inventive methods disclosed herein. The synthesized Li 6 PS 5 X (X=Br, Cl) solid electrolytes were characterized by XRD for phase identification ( FIG. 25 ), which confirm the products of Li 6 PS 5 Cl and Li 6 PS 5 Br (containing a small amount LiBr).  FIG. 26  shows the Arrhenius plots of Li 6 PS 5 Cl and Li 6 PS 5 Br, which display similar ionic conductivities (at least 0.1 mS cm −1 ) between Li 6 PS 5 Cl (or Li 6 PS 5 Br) samples prepared using Li 3 PS 4  from either ACN or THF. As shown in  FIG. 26 , Li 6 PS 5 C1 and Li 6 PS 5 Br displayed an ionic conductivity of about 0.11 mScm −1  to 0.5 mScm −1  at room temperature, and an ionic conductivity of about 1.5 mScm −1  at about 90° C. SEM image shows granular morphology ( FIG. 27 ). These observations indicate that the source of Li 3 PS 4  doesn&#39;t have a significant influence on the structure, conductivity or morphology of solvent-synthesized Li 6 PS 5 X materials. 
     CV Testing in a Symmetric Lithium Cell 
     CV was employed to evaluate the electrochemical stability of solvent-synthesized Li 6 PS 5 X (X=Br, Cl, I) materials against Li metal in a voltage window of 0.5-5.0 vs Li/Li +  ( FIG. 21 ). The assembled cells have structure of Li/Li 6 PS 5 X/SS, with Li as the reference/courter electrode and stainless steel (SS) as the working electrode. For all Li 6 PS 5 X (X=Br, Cl, I) materials, only one pair of oxidation and reduction peaks are observed near 0 V vs Li/Li + , attributing to the lithium dissolution (Li→Li + +e − ) and lithium deposition (Li +  e − →Li), respectively. There is no other peak observed up to 5 V, suggesting good electrochemical stability of Li 6 PS 5 X (X=Br, Cl, I) solid electrolyte against Li metal in a cell structure of Li/SE/SS. Among them, Li 6 PS 5 Cl shows a highly desirable oxidative/reductive current. 
     Symmetric cells of Li/Li 6 PS 5 X/Li were assembled to evaluate the long-term compatibility of liquid synthesized Li 6 PS 5 X with Li metal at room temperature. All the cells were cycled at room temperature with a current density of 20 uA cm −2 .  FIG. 21  (panel b) and  FIG. 22  show smooth cycling profiles for for these symmetric cells with Li 6 PS 5 X (X=Br, Cl, I) as solid electrolytes and the resulting voltages are stable over 3000 mins (50 cycles). However, the voltage for Li 6 PS 5 X-based symmetric cells follows a trend of (Li 6 PS 5 I)&gt;(Li 6 PS 5 Br)&gt;(Li 6 PS 5 Cl), which is in reverse with the ionic conductivity of solid electrolyte. Li 6 PS 5 Cl has a desirable ionic conductivity and lowest resistance, thus the lowest voltage under the same current density. 
     In conclusion, Li 6 PS 5 X argyrodite materials were successfully synthesized utilizing the synthesis method according to multiple embodiments and alternatives. The conductivity values at room temperature of the synthesized materials reached as high as 1.4×10 −4  S cm −1 . Accordingly, inventive methods for wet chemical synthesis of lithium argyrodites, according to multiple embodiments and alternatives, also produce materials with high ionic conductivity, the possibility of further halide substituting tuning, and easier fabrication prospects. A significant advantage of the wet chemical synthesis method within the scope of embodiments is scalability, production of high quality thin film electrolytes, and selenium impregnation of electrodes. In addition, the shorter and more convenient material processing steps, without the ionic conductivity decrease, is an important advantage of the current method for wet chemical synthesis of lithium argyrodites. 
     Example 3—Excess Chloride Doping Effect on Lithium Argyrodite Solid Electrolyte 
     Materials Synthesis—Since Li 6 PS 5 Cl exhibited a desirable ionic conductivity amongst three halogen ions, it was selected to study the effect of excess Cl content on the crystal structure, ionic conductivity, and electrochemical stability of LiCl rich argyrodites Li 6 PS 5 Cl.xLiCl (0≤x≤2). Accordingly, said Li 6 PS 5 Cl.xLiCl (0≤x≤2) materials were synthesized by dissolving Li 2 S, LiCl and β-Li 3 PS 4  in ethanol in an argon atmosphere, according to multiple embodiments and alternatives. In particular, Li 2 S and LiCl were first dissolved in ethanol, followed by the addition of Li 3 PS 4 . The mixture was stirred for 0.5 hours and then dried above room temperature (i.e. 90°) under vacuum to evaporate the ethanol and then annealed above 150° C. to collect white powder. The Cl content in Li 6 PS 5 Cl.xLiCl (0≤x≤2) was tuned by controlling the amount of LiCl precursor. According to multiple embodiments and alternatives, the following ratios of LiCl:Li 3 PS 4  were controlled at 1:1, 1.5:1, 2:1, 2.5:1, and 3:1 to obtain the samples of Li 6 PS 5 Cl, Li 6 PS 5 Cl.0.5LiCl (or Li 6.5 PS 5 Cl 1.5 ), Li 6 PS 5 Cl.LiCl (or Li 7 PS 5 Cl 2 ), Li 6 PS 5 Cl.1.5LiCl (or Li 7.5 PS 5 Cl 1.5 ), and Li 6 PS 5 Cl.2LiCl (or Li 8 PS 5 Cl 3 ), respectively. The chemical reaction is represented by: 
     
       
         
           
             
               
                 
                   
                     
                       
                         ( 
                         
                           x 
                           + 
                           1 
                         
                         ) 
                       
                       ⁢ 
                       LiCl 
                     
                     + 
                     
                       L 
                       ⁢ 
                       
                         i 
                         3 
                       
                       ⁢ 
                       P 
                       ⁢ 
                       
                         S 
                         4 
                       
                     
                     + 
                     
                       L 
                       ⁢ 
                       
                         i 
                         2 
                       
                       ⁢ 
                       S 
                     
                   
                   ⁢ 
                   
                     → 
                     
                       etha 
                       ⁢ 
                       nol 
                     
                   
                   ⁢ 
                   
                     
                       Li 
                       6 
                     
                     ⁢ 
                     P 
                     ⁢ 
                     
                       S 
                       5 
                     
                     ⁢ 
                     
                       Cl 
                       · 
                       xLiCl 
                     
                   
                 
               
               
                 
                   Equation 
                   ⁢ 
                   
                       
                   
                   ⁢ 
                   
                     ( 
                     3 
                     ) 
                   
                 
               
             
           
         
       
     
     Materials Characterization—To perform ionic conductivity measurements, 100 mg of the synthesized materials were pressed between carbon-coated aluminum (serving as blocking electrodes) into pellets under high pressure (i.e. 300 MPa) to a disk roughly 10 mm in diameter and 50 mm thick. The pellets were tested via a pressed cell using electrochemical impedance spectroscopy (EIS) and Arrhenius activation energy measurements in the frequency range of 5MHz-1Hz with an amplitude of 100 mV using Bio-Logic VSP300. 
     Results and Discussion 
     Cl-Doping Content Affects the Phase Purity 
     A method for wet chemical synthesis of lithium argyrodites was employed to synthesize Li 7 PS 6  with different amount of Cl doping, with a general formula of Li 6 PS 5 Cl.xLiCl (0≤x≤2). As previously noted, the Cl content was controlled by tuning the stoichiometric ratio of LiCl precursor vs Li 3 PS 4  (from 1:1 to 3:1) to obtain a series of samples (Li 6 PS 5 Cl, Li 6 PS 5 Cl.0.5LiCl, Li 6 PS 5 Cl.LiCl, Li 6 PS 5 Cl.1.5LiCl, and Li 6 PS 5 Cl.2LiCl). 
       FIG. 28  (panel a) shows both the XRD patterns of Li 6 PS 5 Cl.xLiCl materials containing different amounts of Cl content as well as pure Li 7 PS 6  without any Cl doping. Without Cl doping, cubic phase of pure Li 7 PS 6  (space group F-43m) was obtained with the characteristic diffraction peaks at 2θ=25.5, 30, 31.2° corresponding to (220), (311) and (222) planes, respectively. When small amounts of LiCl are introduced, Li 6 PS 5 Cl has almost identical diffraction patterns to those of Li 7 PS 6 , suggesting the formation of a solid solution where Cl −  replaces S 2− . As Cl content is increased, a secondary phase of LiCl (2θ=34.9°, 49.9°) is observed in addition to the dominant phase of Li 6 PS 5 Cl, and peak intensity continually increases with increasing LiCl. This observation indicates that the excess Cl cannot properly enter the Li 6 PS 5 Cl structure at highly doped samples after 200° C. heating treatment; instead, heterogeneous composite electrolytes of Li 6 PS 5 Cl.xLiCl are formed from the solvent-based synthesis method. 
     To study whether Cl can enter the Li 6 PS 5 Cl structure at a higher temperature, the obtained Li 6 PS 5 Cl.LiCl sample was further annealed in an Argon filled environment under 350° C. and 550° C. for 6 hours, respectively. Although LiCl diffraction peaks are still observed in annealed samples (as shown in  FIG. 29 ), the weight ratio of LiCl to Li 6 PS 5 Cl decreases as the annealing temperature increases, indicating that excess Cl can partially enter Li 6 PS 5 Cl structure after high temperature annealing causing an increase of ionic conductivity (−1.9 10 −3  mS cm −1  for a sample annealed at 550° C.). 
       FIG. 28  (panel b) shows the Raman spectra of Li 7 PS 6  and Cl-doped samples. The samples synthesized according to multiple embodiments and alternatives all exhibited a strong peak around 421-425 cm −1 , corresponding to the symmetric stretching mode of the P—S bond in the (PS 4 ) −3  vibrational mode. This peak is also the primary vibrational mode for argyrodite-type materials. The Cl-doping leads to a slight right shift of the dominate peak (to 425 cm −1 ) and a broad bump around 575 cm −1  which is attributed to the asymmetric PS 4   3−  vibrational mode. However, the excess amount of LiCl does not result in an obvious change on Raman spectra. 
       FIG. 30  shows the SEM images of Li 7 PS 6 , Li 6 PS 5 Cl, Li 5 PS 4 Cl 2  samples, produced in accordance with inventive methods disclosed herein. The SEM images (panels (a) and (b)) of the Li 6 PS 5 Cl.LiCl and Li 6 PS 5 Cl.2LiCl materials exhibit similar granular morphologies and homogeneous S, P, and Cl EDX mapping (panel c)). 
     Conductivities Depend on Cl-Doping 
     The Li-ion conductivities of Li 7 PS 6  and Li 6 PS 5 Cl.xLiCl (x=0, 0.5, 1, 1.5, and 2) were evaluated by the electrochemical impedance spectra (EIS) measurements. For EIS tests, all powder samples were cold-pressed under 360 MPa with Al/C foils as the blocking electrodes.  FIG. 31  (panel a) shows the Arrhenius plots of Li 7 PS 6  and Li 6 PS 5 Cl.xLiCl (x=0, 0.5, 1, 1.5, and 2) with the temperature range up to 90° C. The conductivities of all samples increase linearly with increasing temperatures, and the slopes reflect the activation energy barriers for Li-ion diffusion across the crystalline framework. The compositional dependence between conductivities and activation energies for Li 6 PS 5 Cl.xLiCl (0≤x≤2) materials is shown in  FIG. 31  (panel b). As Cl content increases, the room temperature ionic conductivity increases from 0.34 mS cm −1  for Li 6 PS 5 Cl to the desirable value of 0.53 mS cm −1  for Li 6 PS 5 Cl.LiCl and then decreases beyond it. Among them, Li 6 PS 5 Cl.LiCl exhibits the highest ionic conductivity (0.53 mS cm −1  at room temperature) and the lowest activation energy (0.29 eV). 
       FIG. 33  panel (a) shows the Nyquist plots of lithium argyrodites with different Cl content Li 7 PS 6  and Li 6 PS 5 Cl.xLiCl (x=0, 0.5, 1, 1.5, 2) at room temperature and panel (b) compares the Nyquist plots of Li 6 PS 5 Cl and Li 6 PS 5 Cl.LiCl. All the spectra consist of a semicircle at high frequency (the total resistance) and a spike at lower frequency (Li-diffusion from blocking electrode). In the case of Li 6 PS 5 Cl.LiCl, excess Cl exists in the form of LiCl instead of entering into the argyrodite&#39;s structure, thus the increased ionic conductivity can be explained by the space-charge effect in composites. Similar with other composites, the slight excess amount of LiCl may cause less resistance for the charged particles, which leads to enhanced Li-ion conductivity for the parent electrolyte (Li 6 PS 5 Cl). However, when the LiCl content is high, it will impede the forward motion of Li-ions since LiCl displays a worse room temperature conductivity (10 −7  S cm −1 ) than Li 6 PS 5 Cl. Notably, Li 6 PS 5 Cl.LiCl also exhibits the lowest activation energy of 0.29 eV, in comparison with 0.39 eV for Li 6 PS 5 Cl. 
     Li 5 PS 4 Cl 2  Shows Better Electrochemical Performance 
     Cyclic voltammetry (CV) was employed to evaluate the electrochemical stabilities of Cl-doped Li m PS n Cl o  samples with Li metal anode. The cell structure of Li/Li x+5 PS 6−X Cl o /SS was constructed in a Swaglock cell, with metallic Li serving as the reference electrode and stainless-steel (SS) acting as the working electrode. The CV scanning was collected in the potential range of −0.5 to 5V vs. Li/Li +  at a scan rate of 50 mV s−1. 
     As shown in  FIG. 32  (panel a), there is only a pair of oxidation (Li dissolution, Li→Li + +e − ) and reduction (Li deposition, Li + +e − →Li) peaks near 0 V vs Li/Li +  without other side reactions, indicating good electrochemical stability with a Li anode. Li 6 PS 5 Cl.LiCl shows the highest values of anodic/cathodic current. In addition, symmetric cells of Li/Li 6 PS 5 Cl.xLiCl/Li were assembled to study long-term compatibility against Li metal.  FIG. 32  (panel b) displays smooth voltage profiles for three solid electrolytes (Li 7 PS 6 , Li 6 PS 5 Cl and Li 6 PS 5 Cl.LiCl) under a constant current density of 0.02 mA cm −1 , suggesting good cyclability of these solid electrolytes in symmetric cells. Among the three solid electrolytes, Li 6 PS 5 Cl.LiCl exhibits the lowest polarization. Li 5 PS 4 Cl 2  also exhibits desirable values of anodic/cathodic current in CV curves, suggesting the lowest resistance in the Li/Li 5 PS 4 Cl 2 /SS cell.  FIG. 34  shows the CV scan of Li 5 PSCl 2  carried out in a wider electrochemical window up to 10 V vs. Li/Li+. The CV curves are relatively flat in the range of 0.5-10 V except minor peaks around 7.5 V. 
     As illustrated in  FIGS. 35-38 , the Li/Li 5 PS 4 Cl 2 /Li symmetric cell was demonstrated to cycle well under different current densities (0.02, 0.03 and 0.05 mA cm−1). By replacing nonbonded S −2  with Cl in Li 6 PS 5 Cl, Li 5 PS 4 Cl 2  is believed to increase the interface stability. When higher densities are applied (as shown in  FIG. 38 ), Li 6 PS 5 Cl.LiCl was also demonstrated to show better electrochemical stability with Li anode in comparison with Li 6 PS 5 Cl, Li 7 PS 6 , and Li 5 PS 4 Cl 2  in symmetric cells ( FIGS. 35-37 ). 
     In summary, a solvent-based synthesis method according to multiple embodiments and alternatives was employed to investigate the effects of halide anion doping on the structure and properties of liquid synthesized lithium argyrodites. Pure phase Li 6 PS 5 X (X=Cl, Br, I) was obtained through a stoichiochemical reaction of LiX, Li 2 S and Li 3 PS 4  in ethanol solvent. In line with solid-state synthesized Li 6 PS 5 X materials, Li 6 PS 5 Cl argyrodite showed a desirable room temperature ionic conductivity of 0.34 mS cm −1 , followed by Li 6 PS 5 Br and then Li 6 PS 5 I. When excess Cl was introduced, Li 6 PS 5 Cl.xLiCl composites were obtained instead of a solid solution, suggesting excess Cl cannot enter the argyrodite structure. As Cl content increased, Li 6 PS 5 Cl.LiCl composite electrolyte exhibited a desirable ionic conductivity of 0.53 mS cm −1  at room temperature (5×10 −3  S cm - &#39; at 90° C.), which then decreased as Cl content was further increased. The CV and symmetric cell cycling results indicate that solvent-synthesized halide doped lithium argyrodites (Li 6 PS 5 Cl, Li 6 PS 5 Br and Li 6 PS 5 I, Li 6 PS 5 Cl.LiCl) had good electrochemical stability with Li metal. 
     Example 4—Electrochemical Energy Storage Device Fabrication 
     Synthesis—The battery performance of the solid electrolytes, synthesized according to multiple embodiments and alternatives, was tested with Li 4 Ti 5 O 12  (LTO)/Li cells, wherein LTO serves as the cathode and lithium as the anode in the cell (as non-limiting examples). To prepare the electrode, LTO nanopowder, polyvinylidene fluoride (PVDF) and Super P carbon black (80:10:10 in weight ratio) were mixed in N-methylpyrrolidone (NMP) to form a homogeneous slurry which was subsequently coated on aluminum foil. The prepared electrodes, with an active material loading of around 2.4 mg cm −2 , were dried at 80° C. for 24 h under vacuum prior to use. Thin Li foil (˜120 μm, as a non-limiting example) was used as the anode. The solid electrolyte compositions (Li 6 PS 5 Cl or Li 6 PS 5 Cl.LiCl as non-limiting examples) were cold-pressed to dense pellets with a thickness of around 500 μm and ½ inch diameter. Prior to electrochemical tests, trace amount of propylene carbonate/LiTFSI (Lithium bis(trifluoromethanesulfonyl)imide) electrolyte was added at both sides of the solid electrolyte pellet. Charge and discharge tests were performed over 1.0-3.0 V with 2032-coin cell after the cells were rested for 8 h. 
     Cycling Results—All solid-state Li/Li 4 Ti 5 O 12  (LTO) batteries were assembled with Li 6 PS 5 Cl or Li 6 PS 5 Cl.LiCl as the respective solid electrolyte compositions, according to multiple embodiments and alternatives.  FIG. 39  displays the cycling performance of Li/LTO cells at a C-rate of 0.2 C within a voltage range of 1.0-3.0 V. In batteries, the discharge current is often expressed as a C-rate in order to normalize against battery capacity. A C-rate is a measure of the rate at which a battery is discharged relative to its maximum capacity. In comparison, the cell with LiCl rich solid electrolyte composition shows a higher specific capacity (135 mAh g −1 ) than Li 6 PS 5 Cl-based cell (110 mAh g −1 ) after 50 cycles of charge/discharge, suggesting the positive role of excess Cl on the enhancement of electrochemical properties. The presence of lithium halide at the interface likely stabilizes the solid electrolyte composition/electrode interface and blocks side reactions. Accordingly, the improved cycling performance of the ASSB with Li 6 PS 5 Cl.LiCl as the solid electrolyte composition (as shown in  FIG. 39 ) likely relates to the formation of a more stable solid electrolyte interphase layer due to the excess amount of Cl. 
     It will be understood that the embodiments described herein are not limited in their application to the details of the teachings and descriptions set forth, or as illustrated in the accompanying figures. Rather, it will be understood that the present embodiments and alternatives, as described and claimed herein, are capable of being practiced or carried out in various ways. Also, it is to be understood that words and phrases used herein are for the purpose of description and should not be regarded as limiting. The use herein of “including,” “comprising,” “e.g.,” “containing,” or “having” and variations of those words is meant to encompass the items listed thereafter, and equivalents of those, as well as additional items. 
     Accordingly, the foregoing descriptions of several embodiments and alternatives are meant to illustrate, rather than to serve as limits on the scope of what has been disclosed herein. The descriptions herein are not intended to be exhaustive, nor are they meant to limit the understanding of the embodiments to the precise forms disclosed. It will be understood by those having ordinary skill in the art that modifications and variations of these embodiments are reasonably possible in light of the above teachings and descriptions.