ALL SOLID-STATE SODIUM-SULFUR OR LITHIUM-SULFUR BATTERY PREPARED USING CAST-ANNEALING METHOD

Abstract

The present invention is directed to solid-state composite cathodes that comprise Na.sub.2S or Li.sub.2S, Na.sub.3PS.sub.4, or Li3PS4, and mesoporous carbon. The present invention is also directed to methods of making the solid-state composite cathodes and methods of using the solid-state composite cathodes in batteries and other electrochemical technologies.

Claims

1. A composition comprising: (a) an ordered mesoporous carbon, wherein the ordered mesoporous carbon comprises channels; (b) A.sub.3PS.sub.4, wherein A is Na.sup.+ or Li.sup.+; and (c) X.sub.2S, wherein X is Na.sup.+ or Li.sup.+.

2.-3. (canceled)

4. The composition of claim 1, wherein at least 90% of the channels in the ordered mesoporous carbon comprise X.sub.2S.

5. The composition of claim 1, wherein the channels in the ordered mesoporous carbon further comprise A.sub.3PS.sub.4.

6. (canceled)

7. The composition of claim 1, wherein the weight ratio of X.sub.2S to A.sub.3PS.sub.4in the composition is about 3:4.

8. (canceled)

9. The composition of claim 1, wherein the wherein the weight ratio of X.sub.2S to ordered mesoporous carbon in the composition is about 1:1.

10. (canceled)

11. The composition of claim 1, wherein the ordered mesoporous carbon is CMK-3.

12.-13. (canceled)

14. An electrochemical cell comprising the composition of claim 1.

15. A method of preparing a composite cathode comprising: (a) admixing X.sub.2S , P.sub.2S.sub.5, and an ordered mesoporous carbon, wherein X is Na.sup.+ or Li.sup.+; (b) raising the temperature of the admixture to between about 600 C. and about 1000 C.; (c) lowering the temperature of the admixture in (b); and (d) raising the temperature of the admixture in (c) to between about 100 C. and about 400 C.

16. The method of claim 15, further comprising: (e) lowering the temperature of the admixture in (d).

17. The method of claim 15, wherein the admixture in (a) is milled.

18.-19. (canceled)

20. The method of claim 15, wherein the weight ratio of X.sub.2S to P.sub.2S.sub.5is between about 4:1 to about 2:1.

21. (canceled)

22. The method of claim 15, wherein the weight ratio of X.sub.2S to ordered mesoporous carbon is between about 3:1 to about 1:1.

23.-26. (canceled)

27. The method of claim 15, wherein the ordered mesoporous carbon is CMK-3.

28. The method of claim 15, wherein the temperature in (b) is raised to between about 800 C. and about 900 C.

29.-34. (canceled)

35. The method of claim 15, wherein the temperature in (d) is raised to between about 200 C. and about 300 C.

36.-38. (canceled)

39. A composite cathode prepared by the method of claim 15.

40. A solid state battery comprising: (a) a cathode active material layer comprising the composition of claim 1; (b) an anode active material layer; and (c) a solid state electrolyte material.

41. The solid state battery of claim 40, wherein the anode active material layer comprises Na.sub.15Sn.sub.4-AB.

42. The solid state battery of claim 40, wherein the solid state electrolyte material comprises Na.sub.3PS.sub.4.

43. The solid state battery of claim 40, wherein the solid state battery provides a voltage of between about 0.5 V and about 4 V when measured at 60 C.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0062] The accompanying drawings, which are incorporated herein and form a part of the specification, illustrate one or more embodiments of the present invention and, together with the description, further serve to explain the principles of the invention and to enable a person skilled in the pertinent art to make and use the invention. The following drawings are given by way of illustration only, and thus are not intended to limit the scope of the present invention.

[0063] FIG. 1 is a schematic illustration of the synthesis of cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite.

[0064] FIG. 2 is a phase diagram for a Na.sub.2S and P.sub.2S.sub.5 melt.

[0065] FIG. 3 is a line graph depicting X-ray diffraction (XRD) patterns of the quenched Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite before and after annealing.

[0066] FIG. 4 is a line graph depicting XRD patterns for the ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite.

[0067] FIG. 5 is a line graph depicting Rietveld refinements of X-ray diffraction data of the as-synthesized cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite after heating at 270 C. for 2 hours. All of the peaks can be ascribed to Na.sub.2S and Na.sub.3PS.sub.4 phase.

[0068] FIG. 6 is a line graph depicting Raman spectra of the quenched and the cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite.

[0069] FIG. 7 is a line graph depicting Raman spectra of quenched Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite before and after annealing. Two characteristic peaks around 1330 and 1590 cm-could be ascribed to the D band and G band of graphitic carbon, respectively.

[0070] FIG. 8 is a scanning electron microscope (SEM) image of the CMK-3 mesoporous carbon.

[0071] FIG. 9 is an SEM micrograph of the in situ synthesized cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite.

[0072] FIG. 10 is a transmission electron microscope (TEM) image of the CMK-3 channel structure.

[0073] FIG. 11 is a TEM image of the as-synthesized cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite.

[0074] FIG. 12 is a line graph depicting N.sub.2 adsorption/desorption isotherm of the mesoporous carbon (CMK-3) and the as-synthesized cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite.

[0075] FIG. 13 is a line graph depicting the distribution curves of the corresponding Barrett-Joyner-Halenda pore size of CMK-3 and Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode.

[0076] FIG. 14 is a high angle annular dark-filed scanning transmission electron microscope (HAADF-STEM) image of the cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite.

[0077] FIG. 15 is a HAADF-STEM image of the elemental mapping of sodium (Na) in the cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite.

[0078] FIG. 16 is a HAADF-STEM image of the elemental mapping of phosphorus (P) in the cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite.

[0079] FIG. 17 is a HAADF-STEM image of the elemental mapping of sulfur (S) in the cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite.

[0080] FIG. 18 is a HAADF-STEM image of the elemental mapping of carbon (C) in the cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite.

[0081] FIG. 19 is a line graph depicting the elemental ratio results the cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite.

[0082] FIG. 20 is an SEM image of the cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite.

[0083] FIG. 21 is an SEM image of the corresponding elemental mapping of sulfur (S) in the ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite.

[0084] FIG. 22 is an SEM image of the corresponding elemental mapping of phosphorus (P) in the ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite.

[0085] FIG. 23 is an SEM image of the corresponding elemental mapping of sodium (Na) in the ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite.

[0086] FIG. 24 is an SEM image of the corresponding elemental mapping of carbon (C) in the ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite.

[0087] FIG. 25 is a line graph depicting the elemental ratio result of the ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite. It can be seen that significant phosphorus (P) segregation can be observed for the ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite.

[0088] FIG. 26 is a line graph depicting charge/discharge curves (the charge curves are labelled {circle around (1)} and {circle around (2)} on the right-hand side of the graph and the discharge curves are labelled {circle around (1)} and {circle around (2)} on the left-hand side of the graph) of the Na.sub.15Sn.sub.4-AB (AB=acetylene black) electrode vs. Na metal electrode using a carbonate electrolyte (1 M NaPF.sub.6 in EC/DMC).

[0089] FIG. 27 is a line graph depicting the electrochemical impedance spectra of the Na.sub.3PS.sub.4 electrolyte. The AC impedance spectra were obtained with a Pt/Na.sub.3PS.sub.4/Pt cell tested at room temperature (25 C.) and 60 C.

[0090] FIG. 28 is a line graph depicting the electrochemical performances of cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathodes in ASSB tested at 60 C. between 0.5 and 3 V. The upper axis (labelled {circle around (1)}, {circle around (2)}, and {circle around (3)}) shows the total capacity of the electrode, the lower one (labelled {circle around (1)}, {circle around (2)}, and {circle around (3)}) shows the specific capacity calculated based on the weight of Na.sub.2S in the electrode.

[0091] FIG. 29 is a line graph depicting the electrochemical performances of the ball-milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathodes in ASSB tested at 60 C. between 0.5 and 3 V. The upper axis shows the total capacity of the electrode, the lower on showing the specific capacity calculated based on the weight of Na.sub.2S in the electrode.

[0092] FIG. 30 is a line graph depicting the electrochemical performances of the cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite. The upper axis shows the total capacity of the electrode, the lower one showing the specific capacity calculated based on the weight of Na.sub.2S in the electrode.

[0093] FIG. 31 is a line graph depicting the electrochemical performances of the Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite at 60 C. between 0.5 and 3 V. The upper axis shows the total capacity of the electrode.

[0094] FIG. 32 is a line graph depicting the cycling properties of ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite and cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathodes at a current of 50 mA/g.

[0095] FIG. 33 is a graph depicting the impedance profile of the ASSB using ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite as cathode after different cycles.

[0096] FIG. 34 is a graph depicting the impedance profile of the ASSB cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 cathode after different cycles.

[0097] FIG. 35 is a line graph depicting the electrochemical performances of the ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode in ASSB tested at room temperature between 0.5 and 3 V. First three charge-discharge curves of ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite at 50 mA/g.

[0098] FIG. 36 is a line graph depicting the electrochemical performances of the cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathodes in ASSB tested at room temperature between 0.5 and 3 V. First three charge-discharge curves of cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathodes at 50 mA/g.

[0099] FIG. 37 is a line graph depicting charge-discharge profiles of the ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode in the ASSB at 60 C. between 0.5 and 3 V at different current densities from 20 mA/g to 150 mA/g. The cells were pre-cycled for 3 cycles at each current density, and the second charge-discharge profiles were provided.

[0100] FIG. 38 is a line graph depicting charge-discharge profiles of the cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode in the ASSB at 60 C. between 0.5 and 3 V at different current densities from 20 mA/g to 150 mA/g. The cells were pre-cycled for 3 cycles at each current density, and the second charge-discharge profiles were provided.

[0101] FIG. 39 is a scatter plot depicting rate performance of ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite and cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathodes in the ASSB at 60 C. between 0.5 and 3 V.

[0102] FIG. 40 is a line graph depicting cycling performance of ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite and cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathodes at a current of 50 mA/g.

[0103] FIG. 41 is a line graph depicting impedance profiles of the ASSBs using ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathodes and cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathodes. Electrochemical impedance spectroscopy (EIS) was measured at the fully discharged state of the batteries after 3 cycles.

[0104] FIG. 42 is a schematic depicting the front-view of a single rod of the cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite.

[0105] FIG. 43 is a line graph depicting XRD patterns for an annealed and quenched Li.sub.2SLi.sub.3PS.sub.4-CMK-3 composite.

DETAILED DESCRIPTION OF THE INVENTION

[0106] As used herein, the singular terms a and the are synonymous and used interchangeably with one or more and at least one, unless the language and/or context clearly indicates otherwise. As used herein, the term comprising means including, made up of, and composed of

[0107] All numbers in this description indicating amounts, ratios of materials, physical properties of materials, and/or use are to be understood as modified by the word about, except as otherwise explicitly indicated. The term about as used herein includes the recited number 10%. Thus, about ten means 9 to 11.

[0108] The present disclosure provides a method for preparing Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composites using a melting-casting process followed by a stress-release annealing-precipitation process which reduces the interface resistance and eliminates the residential stress in Na.sub.2S cathodes. The casting-annealing process guarantees close contact between the Na.sub.3PS.sub.4 solid electrolyte and the CMK-3 mesoporous carbon in a mixed ionic/electronic conductive matrix, while the in situ precipitated Na.sub.2S active species generated from the solid electrolyte during the annealing process guarantees the interfacial contact among these three sub-components without residential stress, which greatly reduces the interfacial resistance, and enhances the electrochemical performance. The in situ synthesized Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite delivers a stable and highly reversible capacity of 810 mAh/g at 50 mA/g for 50 cycles at 60 C.

Synthesis of the Composite Cathode

[0109] The present invention describes a method of preparing a composite cathode comprising: [0110] (a) admixing X.sub.25, P.sub.25.sub.5, and an ordered mesoporous carbon, wherein X is Na.sup.+ or Li.sup.+; [0111] (b) raising the temperature of the admixture to between about 600 C. and about 1000 C.; [0112] (c) lowering the temperature of the admixture in (b); and [0113] (d) raising the temperature of the admixture in (c) to between about 100 C. and about 400 C.

[0114] In some embodiments, the composite cathode is generated in situ.

[0115] In some embodiments, the admixture in (a) is milled. As used herein, milling refers to breaking solid materials into smaller pieces by grinding, crushing, or cutting. In some embodiments, the admixture in (a) is milled using a milling machine. In some embodiments, the admixture in (a) is ball milled. As used herein, ball milling refers to a hollow cylindrical shell filled with balls rotating about its axis, wherein the balls act as the grinding media. In some embodiments, the admixture is milled by hand. In some embodiments, the admixture is hand milled with a mortar and pestle.

[0116] In some embodiments, the weight ratio of X.sub.2S to P.sub.2S.sub.5 is between about 16:1 to about 1:1, about 16:1 to about 2:1, about 16:1 to about 3:1, about 16:1 to about 4:1, about 16:1 to about 8:1, about 16:1 to about 12:1, about 12:1 to about 1:1, about 12:1 to about 2:1, about 12:1 to about 3:1, about 12:1 to about 4:1, about 12:1 to about 8:1, about 8:1 to about 1:1, about 8:1 to about 2:1, about 8:1 to about 3:1, about 8:1 to about 4:1, about 4:1 to about 1:1, about 4:1 to about 2:1, about 4:1 to about 3:1, about 3:1 to about 1:1, about 3:1 to about 2:1, or about 2:1 to about 1:1. In some embodiments, the weight ratio of X.sub.2S to P.sub.2S.sub.5 is between about 4:1 to about 2:1.

[0117] In some embodiments, the weight ratio of Na.sub.2S to P.sub.2S.sub.5 is between about 16:1 to about 1:1, about 16:1 to about 2:1, about 16:1 to about 3:1, about 16:1 to about 4:1, about 16:1 to about 8:1, about 16:1 to about 12:1, about 12:1 to about 1:1, about 12:1 to about 2:1, about 12:1 to about 3:1, about 12:1 to about 4:1, about 12:1 to about 8:1, about 8:1 to about 1:1, about 8:1 to about 2:1, about 8:1 to about 3:1, about 8:1 to about 4:1, about 4:1 to about 1:1, about 4:1 to about 2:1, about 4:1 to about 3:1, about 3:1 to about 1:1, about 3:1 to about 2:1, or about 2:1 to about 1:1. In some embodiments, the weight ratio of Na.sub.2S to P.sub.2S.sub.5 is between about 4:1 to about 2:1.

[0118] In some embodiments, the weight ratio of X.sub.2S to ordered mesoporous carbon is between about 16:1 to about 1:1, about 16:1 to about 2:1, about 16:1 to about 3:1, about 16:1 to about 4:1, about 16:1 to about 8:1, about 16:1 to about 12:1, about 12:1 to about 1:1, about 12:1 to about 2:1, about 12:1 to about 3:1, about 12:1 to about 4:1, about 12:1 to about 8:1, about 8:1 to about 1:1, about 8:1 to about 2:1, about 8:1 to about 3:1, about 8:1 to about 4:1, about 4:1 to about 1:1, about 4:1 to about 2:1, about 4:1 to about 3:1, about 3:1 to about 1:1, about 3:1 to about 2:1, or about 2:1 to about 1:1. In some embodiments, the weight ratio of X.sub.2S to ordered mesoporous carbon is between about 3:1 to about 1:1.

[0119] In some embodiments, the weight ratio of Na.sub.2S to ordered mesoporous carbon is between about 6:1 to about 1:1, about 6:1 to about 2:1, about 6:1 to about 3:1, about 6:1 to about 4:1, about 6:1 to about 5:1, about 5:1 to about 1:1, about 5:1 to about 2:1, about 5:1 to about 3:1, about 5:1 to about 4:1, about 4:1 to about 1:1, about 4:1 to about 2:1, about 4:1 to about 3:1, about 3:1 to about 1:1, about 3:1 to about 2:1, or about 2:1 to about 1:1. In some embodiments, the weight ratio of Na.sub.2S to ordered mesoporous carbon is between about 3:1 to about 1:1.

[0120] In some embodiments, the admixing is at a temperature between about 10 C. and about 40 C., about 10 C. and about 30 C., about 10 C. and about 20 C., about 20 C. and about 40 C., about 20 C. and about 30 C., or about 30 C. and about 40 C. In some embodiments, the admixing is at a temperature between about 20 C. and about 30 C.

Sodium Sulfur or Lithium Sulfur

[0121] In some embodiments, the method of preparing a composite cathode comprises admixing X.sub.2S, P.sub.2S.sub.5, and an ordered mesoporous carbon, wherein X is Na.sup.+ or Li.sup.+. In some embodiments, X.sub.25 is Na.sub.2S. In some embodiments, X.sub.25 is Li.sub.2S.

Mesoporous Carbon

[0122] Mesoporous carbon is a hydrophobic material with highly specific surface area and pore density and possesses excellent electrical conductivity. Mesoporous carbon is available as a powder or as a nano-powder with varying pore sizes in the nanoscale range. In some embodiments, the mesoporous carbon has a pore diameter between about 2 nm and about 50 nm.

[0123] In some embodiments, the mesoporous carbon is an ordered mesoporous carbon. Ordered mesoporous carbon is a flexible material providing interconnected channels for the diffusion of electroactive species in electrochemical systems. In some embodiments, the ordered mesoporous carbon is a CMK-n (carbon mesostructured by KAIST), wherein 0<n<10. A CMK-n can be synthesized using mesoporous silicas or aluminosilicate templates, constructed with 3-D pore connectivity. In some embodiments, the ordered mesoporous carbon is a commercially available ordered mesoporous carbon.

[0124] In some embodiments, the ordered mesoporous carbon is selected from the group consisting of CMK-1, CMK-2, CMK-3, CMK-5, and CMK-8. In some embodiments, the ordered mesoporous carbon is CMK-3.

Casting of the Composite Material

[0125] In some embodiments, after admixing X.sub.2S, P.sub.25.sub.5, and an ordered mesoporous carbon, the admixture is heated at a temperature between about 600 C. and about 1000 C.

[0126] In some embodiments, after admixing X.sub.2S, P.sub.25.sub.5, and an ordered mesoporous carbon, the temperature is raised to between about 700 C. and about 1000 C., about 700 C. and about 900 C., about 700 C. and about 850 C., about 700 C. and about 800 C., about 700 C. and about 750 C., about 750 C. and about 1000 C., about 750 C. and about 900 C., about 750 C. and about 850 C., about 750 C. and about 800 C., about 800 C. and about 1000 C., about 800 C. and about 900 C., about 800 C. and about 850 C., about 850 C. and about 1000 C., about 850 C. and about 900 C., or about 900 C. and about 1000 C. In some embodiments, after admixing X.sub.2S, P.sub.2S.sub.5, and an ordered mesoporous carbon, the temperature is raised to between about 800 C. and about 900 C.

[0127] In some embodiments, after admixing X.sub.2S, P.sub.2S.sub.5, and an ordered mesoporous carbon, the time to raise the temperature is between about 2 hours and about 10 hours, about 2 hours and about 8 hours, about 2 hours and about 6 hours, about 2 hours and about 4 hours, about 4 hours and about 10 hours, about 4 hours and about 8 hours, about 4 hours and about 6 hours, about 6 hours and about 10 hours, about 6 hours and about 8 hours, or about 8 hours and about 10 hours. In some embodiments, after admixing X.sub.2S, P.sub.2S.sub.5, and an ordered mesoporous carbon, the time to raise the temperature is between about 6 hours and about 8 hours.

[0128] In some embodiments, the raised temperature is maintained for between 10 minutes and about 10 hours, about 10 minutes and about 5 hours, about 10 minutes and about 2 hours, about 10 minutes and about 1 hour, about 10 minutes and about 30 minutes, about 30 minutes and about 10 hours, about 30 minutes and about 5 hours, about 30 minutes and about 2 hours, about 30 minutes and about 1 hour, about 1 hour and about 10 hours, about 1 hour and about 5 hours, about 1 hour and about 2 hours, about 2 hours and about 10 hours, about 2 hours and about 5 hours, or about 5 hours and about 10 hours. In some embodiments, the raised temperature is maintained for between 30 minutes and about 2 hours.

[0129] In some embodiments, after admixing X.sub.2S, P.sub.2S.sub.5, and an ordered mesoporous carbon, the temperature is raised to between about 800 C. and about 900 C. over a period of between about 6 hours and 8 hours.

[0130] In some embodiments, after raising the temperature of the admixture in (b), the temperature is lowered to a temperature between about 20 C. and about 20 C., about 20 C. and about 10 C., about 20 C. and about 0 C., about 20 C. and about 10 C., about 10 C. and about 20 C., about 10 C. and about 10 C., about 10 C. and about 0 C., about 0 C. and about 20 C., about 0 C. and about 10 C., or about 10 C. and about 20 C. In some embodiments, after raising the temperature of the admixture in (b), the temperature is lowered to a temperature between about 10 C. and about 10 C.

[0131] In some embodiments, the temperature of the mixture is lowered in (c) for between about 1 second and about 1 hour, about 1 second and about 30 minutes, about 1 second and about 10 minutes, about 1 second and about 1 minute, about 1 second and about 30 seconds, about 1 second and about 10 seconds, about 10 seconds and about 1 hour, about 10 seconds and about 30 minutes, about 10 seconds and about 10 minutes, about 30 seconds and about 1 hour, about 30 seconds and about 30 minutes, about 30 seconds and about 10 minutes, about 30 seconds and about 1 minute, about 1 minute and about 1 hour, about 1 minute and about 30 minutes, about 1 minute and about 10 minutes, about 10 minutes and about 1 hour, about 10 minutes and about 30 minutes, or about 30 minutes and about 1 hour. In some embodiments, the temperature of the mixture is lowered in (c) for between about 1 second and about 30 seconds.

[0132] In some embodiments, the lowered temperature is maintained for between 1 minute and about 10 hours, about 1 minute and about 5 hours, about 1 minute and about 2 hours, about 1 minute and about 1 hour, about 1 minute and about 30 minutes, about 30 minutes and about 10 hours, about 30 minutes and about 5 hours, about 30 minutes and about 2 hours, about 30 minutes and about 1 hour, about 1 hour and about 10 hours, about 1 hour and about 5 hours, about 1 hour and about 2 hours, about 2 hours and about 10 hours, about 2 hours and about 5 hours, or about 5 hours and about 10 hours. In some embodiments, the raised temperature is maintained for between 30 minutes and about 2 hours.

[0133] In some embodiments, the casting process generates a solid electrolyte. In some embodiments, the solid electrolyte is a lithium-containing solid electrolyte or a sodium-containing solid electrolyte.

[0134] In some embodiments, the solid-state electrolyte is X.sub.3PS.sub.4, wherein X is Na.sup.+ or Li.sup.+.In some embodiments, the solid electrolyte is Na.sub.3PS.sub.4. In some embodiments, the solid electrolyte is Li.sub.3PS.sub.4.

Annealing of the Composite Material

[0135] In some embodiments, after cooling the admixture in (c), the admixture is heated at a temperature between about 100 C. and about 600 C.

[0136] In some embodiments, the temperature of the admixture in (d) is raised to between about 100 C. and about 600 C., 100 C. and about 400 C., about 100 C. and about 300 C., about 100 C. and about 250 C., about 100 C. and about 200 C., about 100 C. and about 150 C., about 150 C. and about 600 C., about 150 C. and about 400 C., about 150 C. and about 300 C., about 150 C. and about 250 C., about 150 C. and about 200 C., about 200 C. and about 600 C., about 200 C. and about 400 C., about 200 C. and about 300 C., about 200 C. and about 250 C., about 250 C. and about 600 C., about 250 C. and about 400 C., about 250 C. and about 300 C., about 300 C. and about 600 C., about 300 C. and about 400 C., or about 400 C. and about 600 C. In some embodiments, the temperature of the admixture in (d) is raised to between about 200 C. and about 300 C.

[0137] In some embodiments, the temperature of the admixture in (d) is raised for between about 2 minutes and about 24 hours, about 2 minutes and about 10 hours, about 2 minutes and about 5 hours, about 2 minutes and about 1 hour, about 2 minutes and about 30 minutes, about 30 minutes and about 24 hours, about 30 minutes and about 10 hours, about 30 minutes and about 5 hours, about 30 minutes and about 1 hour, about 1 hour and about 24 hours, about 1 hour and about 10 hours, about 1 hour and about 5 hours, about 5 hours and about 24 hours, about 5 hours and about 10 hours, or about 10 hours and about 24 hours. In some embodiments, the temperature of the admixture in (d) is raised for between about 1 hour and about 5 hours.

[0138] In some embodiments, the method further comprises: [0139] (e) lowering the temperature of the admixture in (d).

[0140] In some embodiments, the temperature of the admixture in (d) is lowered to a temperature between about 20 C. and about 50 C., about 20 C. and about 30 C., about 20 C. and about 20 C., about 20 C. and about 0 C., about 20 C. and about 10 C., about 10 C. and about 50 C., about 10 C. and about 30 C., about 10 C. and about 20 C., about 10 C. and about 0 C., about 0 C. and about 50 C., about 0 C. and about 30 C., about 0 C. and about 20 C., about 20 C. and about 50 C., about 20 C. and about 30 C., or about 30 C. and about 50 C. In some embodiments, the temperature of the admixture in (d) is lowered to a temperature between about 20 C. and about 30 C.

[0141] In some embodiments, the method produces a Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode. In some embodiments, the method produces a Li.sub.2SLi.sub.3PS.sub.4-CMK-3 composite cathode.

Composite Cathode

[0142] In some embodiments, the present invention describes a composition comprising: [0143] (a) an ordered mesoporous carbon; [0144] (b) A.sub.3PS.sub.4, wherein A is Na.sup.+ or Li.sup.+; and [0145] (c) X.sub.2S, wherein X is Na.sup.+ or Li.sup.+.

[0146] In some embodiments, the present invention describes a composition comprising: [0147] (a) an ordered mesoporous carbon, wherein the ordered mesoporous carbon comprises channels; [0148] (b) A.sub.3PS.sub.4, wherein A is Na.sup.+ or Li.sup.+; and [0149] (c) X.sub.2S, wherein X is Na.sup.+ or Li.sup.+;
wherein at least 30% of the channels in the ordered mesoporous carbon comprise X.sub.2S.

[0150] In some embodiments, at least 30%, at least 50%, at least 70%, or at least 90% of the channels in the ordered mesoporous carbon comprise X.sub.2S. In some embodiments, between about 30% and about 100%, about 30% and about 90%, about 30% and about 70%, about 30% and about 50%, about 50% and about 100%, about 50% and about 90%, about 50% and about 70%, about 70% and about 100%, about 70% and about 90%, or about 90% and about 100% of the channels in the ordered mesoporous carbon comprises X.sub.2S. In s ome embodiments, the percentage of channels that are filled with X.sub.2S can be determined using energy dispersive spectroscopy (EDS).

[0151] In some embodiments, the present invention describes a composition comprising: [0152] (a) an ordered mesoporous carbon, wherein the ordered mesoporous carbon comprises channels; [0153] (b) A.sub.3PS.sub.4, wherein A is Na.sup.+ or Li.sup.+; and [0154] (c) X.sub.2S, wherein X is Na.sup.+ or Li.sup.+;
wherein at least 30% of the channels in the ordered mesoporous carbon comprise A.sub.3PS.sub.4.

[0155] In some embodiments, at least 30%, at least 50%, at least 70%, or at least 90% of the channels in the ordered mesoporous carbon comprise A.sub.3PS.sub.4. In some embodiments, between about 30% and about 100%, about 30% and about 90%, about 30% and about 70%, about 30% and about 50%, about 50% and about 100%, about 50% and about 90%, about 50% and about 70%, about 70% and about 100%, about 70% and about 90%, or about 90% and about 100% of the channels in the ordered mesoporous carbon comprises A.sub.3PS.sub.4. In some embodiments, the percentage of channels that are filled with A.sub.3PS.sub.4. can be determined using energy dispersive spectroscopy (EDS).

[0156] In some embodiments, the present invention describes a composition comprising: [0157] (a) an ordered mesoporous carbon, wherein the ordered mesoporous carbon comprises channels; [0158] (b) A.sub.3PS.sub.4, wherein A is Na.sup.+ or Li.sup.+; and [0159] (c) X.sub.2S, wherein X is Na.sup.+ or Li.sup.+; wherein at least 30% of the channels in the ordered mesoporous carbon comprise X.sub.2S and A.sub.3PS.sub.4.

[0160] In some embodiments, at least 30%, at least 50%, at least 70%, or at least 90% of the channels in the ordered mesoporous carbon comprise X.sub.2S and A.sub.3PS.sub.4. In some embodiments, between about 30% and about 100%, about 30% and about 90%, about 30% and about 70%, about 30% and about 50%, about 50% and about 100%, about 50% and about 90%, about 50% and about 70%, about 70% and about 100%, about 70% and about 90%, or about 90% and about 100% of the channels in the ordered mesoporous carbon comprises X.sub.2S and A.sub.3PS.sub.4. In some embodiments, the percentage of channels that comprise X.sub.2S and A.sub.3PS.sub.4 can be determined using energy dispersive spectroscopy (EDS).

[0161] In some embodiments, the weight ratio of X.sub.2S to P.sub.2S.sub.5 in the composite is between about 1:4 to about 4:1, about 1:4 to about 3:1, about 1:4 to about 2:1, about 1:4 to about 1:1, about 1:2 to about 4:1, about 1:2 to about 3:1, about 1:2 to about 2:1, about 1:2 to about 1:1, about 1:1 to about 4:1, about 1:1 to about 3:1, or about 1:1 to about 2:1. In some embodiments, the weight ratio of X.sub.2S to P.sub.2S.sub.5 in the composite is between about 1:2 to about 2:1.

[0162] In some embodiments, the weight ratio of Na.sub.2S to P.sub.2S.sub.5 in the composite is between about 1:4 to about 4:1, about 1:4 to about 3:1, about 1:4 to about 2:1, about 1:4 to about 1:1, about 1:2 to about 4:1, about 1:2 to about 3:1, about 1:2 to about 2:1, about 1:2 to about 1:1, about 1:1 to about 4:1, about 1:1 to about 3:1, or about 1:1 to about 2:1. In some embodiments, the weight ratio of Na.sub.2S to P.sub.2S.sub.5 in the composite is between about 1:2 to about 2:1.

[0163] In some embodiments, the weight ratio of X.sub.2S to ordered mesoporous carbon is between about 16:1 to about 1:1, about 16:1 to about 2:1, about 16:1 to about 3:1, about 16:1 to about 4:1, about 16:1 to about 8:1, about 16:1 to about 12:1, about 12:1 to about 1:1, about 12:1 to about 2:1, about 12:1 to about 3:1, about 12:1 to about 4:1, about 12:1 to about 8:1, about 8:1 to about 1:1, about 8:1 to about 2:1, about 8:1 to about 3:1, about 8:1 to about 4:1, about 4:1 to about 1:1, about 4:1 to about 2:1, about 4:1 to about 3:1, about 3:1 to about 1:1, about 3:1 to about 2:1, or about 2:1 to about 1:1. In some embodiments, the weight ratio of X.sub.2S to ordered mesoporous carbon is between about 3:1 to about 1:1.

[0164] In some embodiments, the weight ratio of Na.sub.2S to ordered mesoporous carbon is between about 6:1 to about 1:1, about 6:1 to about 2:1, about 6:1 to about 3:1, about 6:1 to about 4:1, about 6:1 to about 5:1, about 5:1 to about 1:1, about 5:1 to about 2:1, about 5:1 to about 3:1, about 5:1 to about 4:1, about 4:1 to about 1:1, about 4:1 to about 2:1, about 4:1 to about 3:1, about 3:1 to about 1:1, about 3:1 to about 2:1, or about 2:1 to about 1:1. In some embodiments, the weight ratio of Na.sub.2S to ordered mesoporous carbon is between about 3:1 to about 1:1.

Solid State Battery

[0165] In some embodiments, the composite cathode is used to produce a solid state battery. In some embodiments, the solid state battery comprises a cathode active material layer, an anode active material layer, and a solid state electrolyte material formed between the cathode composite layer and the anode active material layer.

[0166] Examples of the solid state battery of the present invention include a lithium solid state battery and a sodium solid state battery. The solid state battery of the present invention can be either a primary battery or a secondary battery. In some embodiments, the solid state battery is a secondary battery. A secondary battery can be repeatedly charged and discharged, and is useful as, for example, an in-vehicle battery. Examples of the shape of the solid state battery include, for example, a coin type, a laminated type, a cylindrical type, or a rectangular type. The method for producing the solid state battery is not limited and can be produced using methods known to one of ordinary skill in the art.

Cathode Active Material Layer

[0167] The cathode active material layer is a layer containing at least a cathode composite, and can further comprise a conductive material, a binder, or combinations thereof. In some embodiments, the cathode active material layer is a Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode. In some embodiments, the cathode active material is a Li.sub.2SLi.sub.3PS.sub.4-CMK-3 composite cathode.

Anode Active Material Layer

[0168] The anode active material layer is a layer containing at least an anode active material and can further comprise a conductive material, a binder, and combinations thereof. The type of the anode active material is not particularly limited, and examples of the anode active material include a carbon active material, an oxide active material, and a metal active material. Examples of the carbon active material include mesocarbon microbeads (MCMB), highly-oriented graphite (HOPG), hard carbon, and soft carbon. Examples of the oxide active material include Nb.sub.2O.sub.5, Li.sub.4Ti.sub.5O.sub.12, and SiO. Examples of the metal active material include In, Al, Si, and Sn. In some embodiments, the anode active material is Sn. In some embodiments, the anode active material is a NaSn alloy. In some embodiments, the anode active material is Na.sub.15Sn.sub.4-AB (AB is acetylene black).

Solid State Electrolyte

[0169] The solid state electrolyte is not particularly limited as long as the solid state electrolyte has ion conductivity. In some embodiments, the solid state electrolyte (SSE) is a lithium-containing SSE or a sodium-containing SSE.

[0170] In some embodiments, the SSE is a sodium-containing SSE. In some embodiments, the sodium-containing SSE is Na.sub.1+xZr.sub.2Si.sub.xP.sub.3xO.sub.12 (NASICON), wherein 0x3). In some embodiments, the sodium-containing SSE is sodium -alumina. In some embodiments, the SSE is Na.sub.3PS.sub.4.

[0171] In some embodiments, the SSE is a lithium-containing SSE. In some embodiments, the lithium-containing SSE has the formula Li.sub.2+2xZn.sub.1xGeO.sub.4 (LISICON), wherein 0x0.5. In some embodiments, the SSE is Li.sub.3PS.sub.4.

[0172] In some embodiments, the SSE is a lithium-containing SSE with a garnet structure.

[0173] Garnet structures have a general chemical formula of A.sub.3B.sub.2(XO.sub.4).sub.3, where A, B, and X are eight, six, and four oxygen-coordinated sites, respectively. High Li-containing garnet structures contain more than three lithium per formula (e.g., Li.sub.7La.sub.3Zr.sub.2O.sub.12 and Li.sub.5La.sub.3Ta.sub.2O.sub.12) and most commonly crystallize in face centered cubic structures (space group Ia3d) but tetragonal polymorphs are also known. Early work with garnet lithium ionic conductors focused on compositions of Li.sub.5La.sub.3M.sub.2O.sub.12 (M=Ta, Nb) and doped compositions of Li.sub.6ALa.sub.2M.sub.2O.sub.12 (A=Ca, Sr, Ba; M=Ta, Nb). The highest conductivity for these compositions was around 10.sup.5 S/cm at room temperature, which was not sufficiently high to use in a battery application. In 2007, the cubic garnet Li.sub.7La.sub.3Zr.sub.2O.sub.12 (LLZO) was successfully synthesized by Murugan, R., et al., Angew. Chem. 119:7925 (2007) and was shown to have a lithium ionic conductivity of about 10.sup.4 S/cm at room temperature. LLZO is a promising solid electrolyte as it is highly conductive, yet appears to be stable against reduction by lithium metal, even when in direct contact with molten or evaporated lithium. (See Awaka, J., et al., J. Solid State Chem. 182:2360 (2009)). Two polymorphs of LLZO have been reported with the cubic phase having an ionic conductivity two orders of magnitude higher than that of the tetragonal phase. LLZO suffers from several problems including the difficulty of processing the materials due to the requirement of a temperature as high as 1230 C. for densification and the surface chemical instability during air exposure.

[0174] In some embodiments, the lithium-containing SSE with a garnet structure comprises Li.sub.5La.sub.3Nb.sub.2O.sub.12, Li.sub.5La.sub.3Ta.sub.2O.sub.12, Li.sub.7La.sub.3Zr.sub.2O.sub.12, Li.sub.6La.sub.2SrNb.sub.2O.sub.12, Li.sub.6La.sub.2BaNb.sub.2O.sub.12, Li.sub.6La.sub.2SrTa.sub.2O.sub.12, Li.sub.6La.sub.2BaTa.sub.2O.sub.12, Li.sub.7Y.sub.3Zr.sub.2O.sub.12, Li.sub.6.4Y.sub.3Zr.sub.1.4Ta.sub.0.6O.sub.12, Li.sub.6.5La.sub.2.5Ba.sub.0.5TaZrO.sub.12, Li.sub.6.7BaLa.sub.2Nb.sub.1.75Zn.sub.0.25O.sub.12, Li.sub.6.75BaLa.sub.2Ta.sub.1.75Zn.sub.0.25O.sub.12, or Li.sub.6.75La.sub.2.75Ca.sub.0.25Zr.sub.1.75Nb.sub.0.25O.sub.12. In some embodiments, the solid state electrolyte is Li.sub.6.75La.sub.2.75Ca.sub.0.25Zr.sub.1.75Nb.sub.0.25O.sub.12.

Other Components

[0175] The solid state battery may further include a cathode current collector that collects current from the cathode composite material and an anode current collector that collects current from the anode active material layer. Examples of a material of the cathode current collector include SUS, aluminum, nickel, iron, titanium, and carbon. Examples of a material of the anode current collector include SUS, copper, nickel, and carbon. Further, for a battery case used in the present invention, one commonly used for solid state batteries may be used. An example of such a battery case includes a SUS battery case.

Properties of the Solid State Battery

[0176] Several important properties of rechargeable batteries include energy density, power density, capacity, particularly reversible capacity, rate capability, cycle life, thermal stability, cost, and safety. All of these properties are influenced by the choice of materials used to form the battery. The capacity of a battery is the amount of electronic charge that is transported at a constant current between the electrodes per unit weigh in the time A.sub.t for a complete discharge, and the energy density is the product of the average voltage during discharge and the capacity. Both decrease with increasing current and, therefore, power delivered. Moreover, the cycle life of a rechargeable battery is defined as the number of charge/discharge cycles before the capacity fades to 80% of its original capacity. Capacity fade is caused by a loss of the reversibility of the chemical reaction between the electrodes.

[0177] In some embodiments, battery performance can be quantified with four parameters: cell voltage, capacity, Coulombic efficiency, and cycling stability. While the first two determine the energy density, the latter two dictate the life and energy efficiency.

[0178] The energy density of a battery is the nominal battery energy per unit mass (Wh/kg). The energy density is the ability of a battery to store energy, i.e., a high energy density can store a lot of energy compared to a low energy density battery.

[0179] The cycle life of a battery is the number of complete charge/discharge cycles that the battery is able to support before its capacity falls under 80% of its original capacity. The C-rate of a battery is a measure of the rate at which a battery is being discharged. A C-rate of 1 C is a one-hour discharge, a C-rate of 0.5 C is a two-hour discharge, and a C-rate of 0.2 C is a five-hour discharge.

[0180] In some embodiments, the number of cycles for the battery at a high C-rate of about 2.5 C is between about 10 and about 2000, about 10 and about 1500, about 10 and about 1000, about 10 and about 500, about 10 and about 100, about 100 and about 2000, about 100 and about 1500, about 100 and about 1000, about 100 and about 500, about 500 and about 2000, about 500 and about 1500, about 500 and about 1000, about 1000 and about 2000, about 1000 and about 1500, or between about 1500 and about 2000. In some embodiments, the number of cycles for the battery at a high C-rate of about 2.5 C is between about 10 and about 500.

[0181] The capacity retention of a battery is a measurement of the fraction of full capacity available from a battery under a specified set of conditions, after the battery has been stored for a given amount of time.

[0182] In some embodiments, the capacity decay rate (in mAh/g) for a battery at a high C-rate of about 2.5 C is between about 0.005% and about 0.1%, about 0.005% and about 0.05%, 0.005% and about 0.01%, about 0.01% and about 0.1%, about 0.01% and about 0.05%, or about 0.05% and about 0.01% per cycle. In some embodiments, the capacity decay rate (in mAh/g) for a battery at a high C-rate of about 2.5 C is between about 0.05% and about 0.01% per cycle.

[0183] In some embodiments, the capacity retention (in mAh/g) for a battery at a low C-rate of about 0.5 C is between about 30% and about 100%, about 30% and about 90%, about 30% and about 80%, about 30% and about 70%, about 30% and about 60%, about 60% and about 100%, about 60% and about 90%, about 60% and about 80%, about 60% and about 70%, about 70% and about 100%, about 70% and about 90%, about 70% and about 80%, about 80% and about 100%, about 80% and about 90%, or about 90% and about 100%. In some embodiments, the capacity retention (in mAh/g) for a battery at a low C-rate of about 0.5 C is between about 90% and about 100%.

[0184] In some embodiments, the number of cycles for the battery at a high C-rate of about 2.5 C is between about 10 and about 2000, about 10 and about 1500, about 10 and about 1000, about 10 and about 500, about 10 and about 100, about 100 and about 2000, about 100 and about 1500, about 100 and about 1000, about 100 and about 500, about 500 and about 2000, about 500 and about 1500, about 500 and about 1000, about 1000 and about 2000, about 1000 and about 1500, or between about 1500 and about 2000. In some embodiments, the number of cycles for the battery at a high C-rate of about 2.5 C is between about 500 and about 2000.

[0185] In some embodiments, the electrochemical cell operates at a temperature of less than about 100 C., about 90 C., about 80 C., about 70 C., about 60 C., about 50 C., about 40 C., about 30 C., about 20 C., or about 10 C. In some embodiments, the electrochemical cell operates at a temperature between about 40 C. and about 100 C., about 40 C. and about 90 C., about 40 C. and about 80 C., about 40 C. and about 70 C., about 40 C. and about 60 C., about 40 C. and about 50 C., about 40 C. and about 40 C., about 40 C. and about 30 C., about 30 C. and about 100 C., about 30 C. and about 90 C., about 30 C. and about 80 C., about 30 C. and about 70 C., about 30 C. and about 60 C., about 30 C. and about 50 C., about 30 C. and about 40 C., about 30 C. and about 30 C., about 20 C. and about 100 C., about 20 C. and about 90 C., about 20 C. and about 80 C., about 20 C. and about 70 C., about 20 C. and about 60 C., about 20 C. and about 50 C., about 20 C. and about 40 C., or about 20 C. and about 30 C.

[0186] In some embodiments, the electrochemical cell has a fuel cell output voltage greater than 1 V. In some embodiments, the electrochemical cell has a fuel cell output voltage greater than 1.5 V. In some embodiments, the electrochemical cell has a fuel cell output voltage between 1 V and 3 V, 1 V and 2.5 V, 1 V and 2 V, 1 V and 1.5 V, 1.5 V and 3 V, 1.5 V and 2.5 V, 1.5 V and 2 V, 2 V and 3 V, 2 V and 2.5 V, or 2.5 V and 3 V. In some embodiments, the electrochemical cell has a fuel cell output voltage between 1 V and 2 V.

EXAMPLES

[0187] The following examples are illustrative and non-limiting, of the products and methods described herein. Suitable modifications and adaptations of the variety of conditions, formulations, and other parameters normally encountered in the field and which are obvious to those skilled in the art in view of this disclosure are within the spirit and scope of the invention.

Example 1

Synthesis of Na.SUB.2.SNa.SUB.3.PS.SUB.4.-CMK-3 Composite

[0188] Na.sub.2S and P.sub.25.sub.5 (99%) powders were purchased from Sigma-Aldrich (St. Louis, Mo.). CMK-3 mesoporous carbon was purchased from ACS Material, LLC (Pasadena, Calif.). Na.sub.3PS.sub.4 solid electrolyte was synthesized by ball milling followed by an annealing process. The cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite was synthesized by a casting-annealing method.

[0189] A schematic illustration of the synthesis of cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode is shown in FIG. 1. The starting materials Na.sub.2S, P.sub.25.sub.5, and CMK-3 mesoporous carbon were hand milled with a mortar and pestle in the glovebox. The weight ratio of Na.sub.2S:P.sub.2S.sub.5:CMK-3 was set as 50.5:19.5:30 to make sure the weight ratio of Na.sub.2S, Na.sub.3PS.sub.4, and CMK-3 mesoporous carbon in the final Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite is 30:40:30. Based on the Na.sub.2S-P.sub.25.sub.5 phase diagram, different ratios of Na.sub.2S and Na.sub.3PS.sub.4 can be synthesized by adjusting the ratio of the starting materials of Na.sub.2S and P.sub.2S.sub.5. And, the nano-scaled electronic and ionic conductivity of Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composites can be balanced by adjusting the ratio of Na.sub.2S-P.sub.2S.sub.5 to CMK-3. In the phase diagram in FIG. 2, the adjusting areas have been denoted with a double-head-arrow dashed line and the concentration of Na.sub.2S and Na.sub.3PS.sub.4 in the final product is determined based on lever rules. The lever rule is a tool to determine the mole fraction or the mass fraction of each phase of a binary equilibrium phase diagram. The lever rule can be used to determine the fraction of liquid and solid phases for a given binary composition and temperature that is between the liquidus and solidus line. One of the merits of this technique is that the solid electrolyte and active species can be precipitated in situ from the starting materials Na.sub.2S and P.sub.2S.sub.5, forming a stable interface with a low interfacial resistance and interfacial stress/strain while the liquid Na.sub.2S and P.sub.2S.sub.5 wet with CMK-3, all which ensure perfect contact among the solid electrolyte, electron conducting agent, and active species. Therefore, the utilization of the Na.sub.2S species is optimized. And, using the pre-sodiated Na.sub.2S as the cathode active species can provide enough space for the volumetric change of the electrode during sodiation/desodiation reactions.

[0190] The mixture was then transferred into a graphite crucible, which was put into a clear quartz tube and sealed under vacuum. The tube was raised to 850 C. with a ramping rate of 2 C./minute which was maintained for 1 hour. After the temperature was raised to higher than the liquidus, the Na.sub.2S and P.sub.2S.sub.5 melted with each other and formed a homogeneous liquid. The tube was then immediately transferred into ice water and quenched to 0 C. over 10 seconds. Due to the fast temperature drop, the amorphous state of the liquid was kept at room temperature. After quenching, the tube was put into an oven and annealed at 270 C. for 2 hours.

[0191] After cooling down to 25 C., the cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite was taken out from the quartz tube in the glovebox. For the reference, a Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite with the same mass rate was prepared by ball milling the Na.sub.2S, Na.sub.3PS.sub.4, and CMK-3 mixture at a fixed rotation speed of 370 rpm for 1 hour.

Example 2

Characterization of the Na.SUB.2.SNa.SUB.3.PS.SUB.4.-CMK-3 Composite

[0192] X-ray powder diffraction (XRD) was performed on a SMART 1000 diffractometer (Bruker, Billerica, Mass.) with Cu K radiation. Scanning electron microscopy (Hitachi SU-70, Tokyo, Japan) and transmission electron microscopy (JEM-2100 (LaB.sub.6 electron gun, 200 kV), JEOL, Tokyo, Japan) were utilized to characterize the morphology and microstructure of the samples. N.sub.2 adsorption by means of a Micromeritics ASAP 2020 Porosimeter Test Station (Micromeritics Instruments Corp., Norcross, Ga.) was used to obtain the specific surface areas, pore volumes, and related pore size distributions of the samples. Before characterization, all of the samples were evacuated and degassed at 180 C. for 12 hours. The specific surface areas of the samples were obtained using the Brunauer-Emmett-Teller method. The Barrett-Joyner-Halenda equation was utilized to obtain the porosity distribution of the samples. Raman spectra were tested on a LabRAM Aramis (Horiba Jobin Yvon, Kyoto, Japan) with a 532 nm diode-pumped solid-state laser.

[0193] XRD patterns of the quenched Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composites before and after heating at 270 C. for 2 hours are shown in FIG. 3. Several small peaks were observed in the quenched sample, which can be indexed to the (111), (220), (311), and (400) of Na.sub.2S. The formation of the tiny crystalline Na.sub.2S may be due to the ready crystallization during the quenching process. After heating at 270 C. for 2 hours, the peak intensity of Na.sub.2S dramatically increased along with the appearance of new peaks from crystallization of the Na.sub.3PS.sub.4 phase. The unusual background between 10 and 30 arises from amorphous scattering caused by the KAPTON film used to seal the sample during XRD characterization. XRD patterns of the ball milled Na.sub.2SNa.sub.3PS.sub.4 (FIG. 4) and Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite (FIG. 5) show only Na.sub.3PS.sub.4 and Na.sub.2S phases. No impurities were detected in either sample.

[0194] Raman spectra of the quenched and the annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composites are shown in FIG. 6. The Raman spectra reveals that the thiophosphate ions have been formed in the melting process and preserved after quenching as evidenced by the characteristic peak of PS.sub.4.sup.3ions at 420 cm.sup.1. In the casting and subsequent annealing process, Na.sub.3PS.sub.4 was formed, as shown in equation (1):

3Na.sub.2S+P.sub.2S.sub.5.fwdarw.2Na.sub.3PS.sub.4(1)

[0195] After annealing, a shoulder at 380 cm.sup.1 appeared in the Raman spectra, which can be ascribed to precipitated Na.sub.2S species. As shown in FIG. 7, two characteristic peaks detected at around 1590 and 1330 cm.sup.1 were from the G band and D band of graphitic carbon in CMK-3, respectively.

[0196] FIG. 8 and FIG. 9 show SEM images of CMK-3 and the cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite after heating at 270 C. for 2 hours. CMK-3 shows a rod-like macrostructure with uniform size of 2-3 m (FIG. 8). After impregnation of Na.sub.2SNa.sub.3PS.sub.4, CMK-3 retains its original morphology without any fracture. All of the pores in CMK-3 mesoporous particles were infiltrated by the melting Na.sub.2SNa.sub.3PS.sub.4 composite due to capillarity. Apart from the Na.sub.2SNa.sub.3PS.sub.4 inside the channels of the CMK-3, some Na.sub.2SNa.sub.3PS.sub.4 composites were also coated on the surface of the mesoporous carbons, forming an ionic conducting network (FIG. 9). These infiltrated CMK-3 particles agglomerated into large particles during the solidification process of melting solid electrolyte between the CMK-3 particles. The cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 in the graphite crucible forms a free-standing rod. The 1D highly ordered channel structure of the CMK-3 with uniform channel diameter of 4 nm is confirmed by the transition electron microscopy (TEM) image shown in FIG. 10. As shown in FIG. 11, almost all of the CMK-3 channels are filled after impregnation with Na.sub.2SNa.sub.3PS.sub.4. The Na.sub.2SNa.sub.3PS.sub.4 infiltration dramatically reduced the Brunauer-Emmett-Teller specific surface area from 1002 m.sup.2/g for CMK-3 to 80 m.sup.2/g for Na.sub.2SNa.sub.3PS.sub.4-CMK-3, (FIG. 12), and decreased the pore volume from 0.91 cm.sup.3/g of CMK-3 to 0.07 cm.sup.3/g of Na.sub.2SNa.sub.3PS.sub.4-CMK-3, (FIG. 13). As shown in FIG. 12, the nitrogen adsorption-desorption isotherms of CMK-3 shows a typical IV isotherm, presenting a feature of the mesoporous structures with a clear H1 hysteresis loop and narrow mesopore distribution peaks at 4 nm, in line with the TEM images of CMK-3 (FIG. 10). After infiltration of the Na.sub.2SNa.sub.3PS.sub.4 materials into the CMK-3 channels, the hysteresis loop disappeared, and the mesoporous volume decreased dramatically, indicating that Na.sub.2SNa.sub.3PS.sub.4 was occupying the mesoporous channels. To further confirm the penetration/infiltration of Na.sub.2SNa.sub.3PS.sub.4 into the porous CMK-3, high angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) with EDX mapping was carried out (FIG. 14 and FIGS. 15-18). The intensity of the HAADF-STEM images is proportional to z1.7 (z is the atomic number). In FIG. 14, the bright areas correspond to the Na.sub.2SNa.sub.3PS.sub.4. Even in the less bright areas, all of the Na, P, S, and C are totally overlapped, indicating the homogeneous distribution of the Na.sub.2S active species, Na.sub.3PS.sub.4 solid electrolyte, and CMK-3 mesoporous carbon. Large scale energy dispersive spectroscopy (EDS) analysis confirms the presence of the Na, P, S, and C in all of the composite particles, and all of these elements are ideally overlapped in the composite; therefore, close contacts among the three components are obtained in the cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite. And, as shown in FIG. 19, elemental analysis further confirmed the presence of the Na, P, S, and C in all of the composite particles.

[0197] Significant elemental segregation was detected in the ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite (FIGS. 20-25), synthesized by ball milling the mixture of Na.sub.2S, Na.sub.3PS.sub.4 and CMK-3 for 1 hour. All the characterizations of cast-annealed Na.sub.2S-NPS-C nanocomposite demonstrate that the casting-annealing process is a promising technology for synthesis of composite cathodes for ASSBs.

Example 3

Electrochemical Measurements of the Na.SUB.2.SNa.SUB.3.PS.SUB.4.-CMK-3 Composite

[0198] An all-inorganic solid-state sodium-sulfur battery was fabricated using the Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite as a working electrode and Na.sub.3PS.sub.4 as the solid electrolyte. Na metal is highly reactive to the sulfide solid electrolyte and readily forms Na.sub.2S and Na.sub.3P. The in situ formed Na.sub.2S and Na.sub.3P interphases can dramatically increase the interfacial resistance between a Na anode and Na.sub.3PS.sub.4. Besides, Na dendrites would also grow in the solid-state electrolyte if Na metal was utilized as the anode. Therefore a Na.sub.15Sn.sub.4-AB composite (AB is acetylene black) was adopted as the reference electrode and anode (FIG. 26). The ionic conductivities of Na.sub.3PS.sub.4 solid electrolyte were measured in an ion-blocking Pt/Na.sub.3PS.sub.4/Pt cell using electrochemical impedance spectroscopy (EIS) at 25 C. and 60 C. The ion-blocking Pt/Na.sub.3PS.sub.4/Pt cell was prepared by cold pressing 150 mg of Na.sub.3PS.sub.4, followed by Pt sputtering. The ion conductivity of Na.sub.3PS.sub.4 calculated from the EIS profiles (FIG. 27) is 1.4310.sup.4 S/cm at 25 C. At a high temperature of 60 C., the ion conductivity increased to 3.4510.sup.4 S/cm. The Na.sub.15Sn.sub.4-AB composite was prepared as described in Hayashi, A., et al., J. Power Sources 258:420-423 (2014). To assemble the cell, the cast-annealed or ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 powder (5 mg) composite cathodes were put on one side of the Na.sub.3PS.sub.4 solid electrolyte (120 mg) in a PTFE tank. The diameter of the PTFE tank is 10 mm, and Na.sub.15Sn.sub.4-AB anode powders (100 mg) were placed on the other side of the solid electrolyte membrane and then pressed together. The applied pressure between two stainless steel rods is 360 MPa. Galvanostatic discharge-charge cycles were conducted using a battery cycler (LAND CT-2001A, China) with a voltage range of 0.5-3.0 V at 60 C. No extra pressure was applied during the battery test. The specific capacities and current densities were calculated based on the mass of active material (Na.sub.2S). The ratio of Na.sub.2S to Na.sub.3PS.sub.4 was calculated based on the lever rule in the phase diagram. EIS were obtained using an electrochemistry workstation (Solatron 1287/1260) over a range from 110.sup.5 Hz to 0.1 Hz, with an AC amplitude of 0.02 V.

[0199] The electrochemical performances of the Na.sub.2SNa.sub.3PS.sub.4-CMK-3 cathodes were evaluated in ASSBs at 60 C. using 0.75Na.sub.2S.0.25P.sub.2S.sub.5 (Na.sub.3PS.sub.4) glass-ceramic as the solid electrolyte and NaSn alloy mixed with carbon black as an anode. For reference, the Na.sub.2Na.sub.3PS.sub.4-CMK-3 composite synthesized by ball milling the mixture of Na.sub.2S, Na.sub.3PS.sub.4, and CMK-3 for 1 hour was also tested. The utilization of NaSn alloy as the anode material during the battery test can lower the interfacial resistance/instability at the anode/solid-electrolyte interface, and suppress the detrimental Na dendrites formed during cycling. Therefore Na-Sn alloy anodes will not limit the performance of ASSBs, and the performance differences of ASSBs using different cathodes are attributed to cathode performance.

[0200] The critical challenge for an ASSB is the large volume change (up to 74%) of Na.sub.2S during the S sodiation and desodiation, which dramatically damages the interface contact between Na.sub.2S and Na.sub.3PS.sub.4, and quickly deteriorates the electrochemical performance of the batteries. High performance of all solid-state LiS batteries are normally achieved only under pressure to minimize the impact of volume change of sulfur. To evaluate the robustness of casting-annealing technology, the performance of ASSB without the application of pressure were analyzed. FIG. 28 presents the charge/discharge profiles of the ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode. The ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode delivered a discharge capacity of 600 mAh/g in the first cycle, accompanied by a large over-potential and fast capacity decrease in the subsequent charge/discharge cycles. In contrast, the charge/discharge profiles of the cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode (FIG. 29) provided a significantly higher reversible capacity (>800 mAh/g) with a significantly reduced over-potential to about of the ball milled material (FIG. 28). One small plateau at about 0.6 V in the sodiation profile of the ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 and cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathodes is due to the reduction of P in the Na.sub.3PS.sub.4 solid electrolyte of Na.sub.2SNa.sub.3PS.sub.4-CMK-3 cathode. In Yue, J., ACS Nano 11:4885-4891 (2017) it was shown that certain reversible capacities can be achieved once the Na.sub.3PS.sub.4 solid electrolyte homogeneously mixed with the carbon black. In the cast-annealed composite, the electrolyte also provided about 25% of the total reversible capacities (FIGS. 30-31).

[0201] FIG. 32 compared the cycling properties of the cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 and the ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathodes at the same current density of 50 mA/g. The ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode exhibited a reversible capacity of 600 mAh/g for the initial cycle, but the capacity quickly dropped to 350 mAh/g after 10 cycles, and further decayed to only 110 mAh/g after less than 50 cycles. In sharp contrast, a much higher discharge capacity of >800 mAh/g was achieved for the cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode in the first cycle. After 50 cycles, it still possessed a high reversible capacity of 650 mAh/g, which is about 6 times higher than that of the ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode. The high reversible capacity of >650 mAh/g at the average discharge potential of 1.3 V provided an energy density of >800 Wh/kg. This value was even higher than that of the present high temperature (>300 C.) NaS batteries (760 Wh/kg). The cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathodes also show a high Coulombic efficiency (100%) without any shuttle reactions. Besides, the electrochemical performance of the ASSB using cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composited cathodes was also much better than that of the NaS batteries based on polymer or ether electrolytes, which only show low capacities of <400 mAh/g with limited cycling performance (<10 cycles). The significant capacity decay for the ball milled sample could be due to the dramatic increase of the interfacial resistance as confirmed by the continuous increase of the over-potential (FIG. 31).

[0202] The resistances of the ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode and the cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode at different charge/discharge cycles were measured using electrochemical impedance spectroscopy (EIS). FIG. 33 shows the EIS for the ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode and FIG. 34 shows the EIS for the cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode at the fully discharged state at 1st, 2nd, 5th, 10th, 30th, and 50th cycles. The semicircles in the EIS Nyquist plots represent the interfacial resistances, whereas the low-frequency slope line is ascribed to the sodium ion diffusion inside t he cathodes. The cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode exhibited a much lower interfacial resistance than that of the ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode. The dramatically decreased interfacial resistance between the active species of the electrolyte benefits from the intimate contacts among Na.sub.2S, Na.sub.3PS.sub.4 solid electrolyte, and the CMK-3 electron conducting agent. Although the interface resistances of both cathodes increased due to large volume change of Na.sub.2S and lack of pressure to recover the volumetric change during repeated sodiation/desodiation reactions, the amount of resistance increase of the cast-annealed ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode (FIG. 33) was much smaller than that of the ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode (FIG. 34), demonstrating the high robustness of the cast-annealed materials. Moreover, a high Coulombic efficiency of 100% was obtained after the second cycles for the cast-annealed ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode, implying the excellent reversibility of the sodiation/desodiation process and the total suppression of the polysulfide shuttle reactions. The polysulfide shuttle has proven to be a key challenge for room-temperature liquid electrolyte NaS batteries.

[0203] The ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode (FIG. 35) also exhibited a significantly improved kinetics with a much lower voltage hysteresis than that of the cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode at room temperature (FIG. 36). The rate capabilities of the ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode and the cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode were also tested at 60 C. by enlarging the current density from 20 to 150 mA/g. The sodiation/desodiation profiles of ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode and cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode at different current densities are shown in FIG. 37 and FIG. 38, respectively, and FIG. 39 and FIG. 40 show their rate capacities. For the ball milled Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode, only a reversible capacity of 150 mAh/g was achieved at a current of 100 mA/g. As the current density is raised to 150 mA/g, the reversible capacity dramatically decays to less than 10 mAh/g. However, for the cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode, high capacities of 1050, 750, 500, and 200 mAh/g were achieved at a charge-discharge current of 20, 50, 100, and 150 mA/g, respectively. Moreover, once the current density finally decreased back to 20 mA/g, the capacity returned to 900 mAh/g, indicating the good tolerance for the volume change for the cast-annealed Na.sub.2SNa.sub.3PS.sub.4-CMK-3 composite cathode during the rapid sodiation/desodiation reactions.

[0204] While various embodiments of the present invention have been described above, it should be understood that they have been presented by way of example only, and not limitation. It will be apparent to persons skilled in the relevant art that various changes in form and detail can be made therein without departing from the spirit and scope of the invention. Thus, the breadth and scope of the present invention should not be limited by any of the above-described exemplary embodiments, but should be defined only in accordance with the following claims and their equivalents.

[0205] All publications, patents, and patent applications mentioned in this specification are indicative of the level of skill of those skilled in the art to which this invention pertains, and are herein incorporated by reference to the same extent as if each individual publication, patent or patent application was specifically and individually indicated to be incorporated by reference.