Use of reductive electrophiles in solid-state batteries

Abstract

The present disclosure provides a solid-electrolyte material and / or an electrode comprising a coating that is formed by contacting the solid-electrolyte material and / or the electrode with a reductive-electrophile agent. The presence of coating on the solid-electrolyte material and / or the electrode (e.g., cathode, anode, or both) material reduces a detrimental effect of a solid-state electrolyte material and / or an electrode material. In this manner, a wide variety of solid-batteries, electronic devices, and electronic materials can be produced that includes such a coating.

Description

USE OF REDUCTIVE EEECTROPHIEES IN SOEID-STATE BATTERIESCROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of priority of United States provisional patent application No. 63 / 726,155 filed November 27, 2024, the contents of it being hereby incorporated by reference in its entirety for all purposes.FIELD OF THE DISCLOSURE

[0002] The present disclosure relates to using a reductive-electrophile agent to reduce a detrimental effect of a solid-state electrolyte material, an electrode material (e.g., cathode and / or anode), or a combination thereof.BACKGROUND OF THE DISCLOSURE

[0003] All-solid-state lithium metal batteries (ASSLMBs) promise high safety and energy density, but the practical realization is limited by inter a / za lowLi reversibility, limited cell loading, high-temperature and high-pressure operation requirement, solid-state electrolyte (SSE) reduction, oxidation decomposition of SSE, and / or lithium dendrite growth.

[0004] To overcome some of these problems, some elements (such as fluorine) has been doped into SSE to form lithiophobic agents and anti-oxidative agents such as lithium fluoride in solid electrolyte interphase (SEI) on the Li anode and cathode electrolyte interphase (CEI) on the cathode to stabilize anode and cathode. Unfortunately, these element doping have resulted in reduction in SSE ionic conductivity and cannot intrinsically change the SEI and CEI. In addition, conventional ASSLMBs have to work at elevated temperature and / or high stacking pressure to improve compatibility and maintain cell stability and mitigate Li dendrite.

[0005] Recent approaches have involved using artificial lithiophobic interlayers, e g., tungsten or silver-carbon composite, between SSE and Li electrode (i.e., interlayer@Li) in attempts to suppress Li dendrite formation. However, these materials suffer from high electronic conductivity, leading to SSE reduction and thus limiting their performance. Furthermore, use of these materials requires extra process and equipment in the battery manufacturing, thereby increasing the complexity and cost.

[0006] Accordingly, there is a continuing need for a composition or a method for overcoming current problems associated with conventional all-solid-state lithium metal batteries.SUMMARY OF THE DISCLOSURE

[0007] Some aspects of the disclosure provide a composition comprising solid-state electrolyte that is at least partially coated with a reductive-electrophile agent. Other aspects of the disclosure provide a cathode, an anode, SSE, or a combination of one or more thereof that is at least partially coated with a reductive-electrophile agent.

[0008] Still in other aspects of the disclosure provide a method for reducing a detrimental effect of solid-state electrolyte, cathode, anode, or a combination thereof in an all-solid-state battery. As used herein, the term “detrimental effect” and grammatical variations thereof refer to (i) preventing or reducing the rate of SSE reduction, (ii) suppressing or reducing the rate or possibility of Li dendrite formation, and / or (iii) improving the life-span of an electrode (e g , anode, cathode, or both).

[0009] Yet in other aspects of the disclosure provide a solid-state battery that does not require high temperature and / or high pressure for operation. Accordingly, some embodiments of the disclosure provide reducing the need for high temperature and / or pressure operation in a solid- state battery. In some embodiments, solid-state batteries of the disclosure can be operated at about 60 °C or less, typically at about 50 °C or less, often at about 40 °C or less and most often at about 30 °C or less at stacking pressure of about 2.5 MPa. Alternatively, solid-state batteries of the disclosure can be operated at about 10 MPa or less, typically at about 7.5 MPa or less, often at about 5.0 MPa or less, and most often at about 2.5 MPa or less of stacking pressure at 30 °C.

[0010] Relative to the same batteries that do not contain a reductive-electrophile agent coating, batteries of the disclosure have enhanced cycling stability and / or increased operating voltage. In some embodiments, operating voltage of batteries of the disclosure is at least about 0.1 V or higher, typically at least about 0.2 V or higher, often at least about 0.3 V or higher, more often at least about 0.4 V or higher, and most often at least about 0.6 V or higher compared to the same battery that does not have a coating of reductive-electrophile agent. Still in other embodiments, the cycling stability of a lithium electrode using a coated SSE (e g., Li||Li symmetric half-cell) of the disclosure is at least about 100 h, typically at least about 200 h, often at least about 500 h, more often at least about 750 h, and most often at least about 1,000 h or more at 1.6 mA cm'2 / 1.6 mAh cm'2compared to the cycling stability of the same lithium electrode and SSE in the absence of the coating produced by a reductive-electrophile agent. Y et in other embodiments, the cycling stability of a full-cell solid-state battery of the disclosure having a coated SSE of the disclosure is at least about 1,000 h or more, typically at least about 2,500 h or more, often at leastabout 5,000 h or more, more often at least about 7,500 h or more, and most often at least about 10,000 h or more compared to the cycling stability of the same full -cell battery using the same SSE material but in the absence of the coating produced by a reductive-electrophile agentBRIEF DESCRIPTION OF THE DRAWINGSFig. 1. Schematic of the “electrochemical electrophile reduction” strategy (A) Tn the Li / LPSC / NCA solid-state cells, the lithiophilic SEI formed by LPSC cannot prevent the lithium dendrite and the LPSC is not compatible with 4V cathode. (B) Li / LPSC / NCA solid-state cells using EER-treated LPSC with the thin and dense LiF-LixPyOzFi SREI on LPSC particles. The Li dendrite is suppressed, and a high operating voltage is achieved. (C) Schematic on the electrochemical reduction of electrophile, where the reductive electrophiles gain the electron and Li+from LPSC or cathode powders upon contact with them, thus being electrochemical reduced on the surface of these materials. (D) The reduction potential of diphosphoryl fluoride (DPF), trifluoroacetic anhydride (TFAA), fluorinated solvents, carbonate solvents, and ether solvents, in comparison with the oxidation potential of LPSC and NCA. (E) Schematic illustration of the advancement of SREI-sulfide SSE over traditional SSE.Fig. 2. The electrophile design and reaction mechanism of electrophile reduction. (A) “Ionic reaction” to chemical coat discontinuous crystalline LiF, by tetrabutylammonium fluoride, TBAF. (B) “Electrochemical reduction” of electrophiles forms dense SREI, by organic acid anhydride (tri fluoroacetic anhydride, TFAA) and inorganic acid halide (diphosphoryl fluoride, DPF) (C-E) TEM images of particles with coating / SREI on (C) TBAF-LPSC, (D) TFAA-LPSC, AND (E) DPF-LPSC particles. (F) The thickness of the in-situ formed SREI compared with the widely reported ex-situ interlayer. (G) The net charge evolution of the LPSC during the reaction process of LPSC with TFAA, DPF, and TBAF. (H) The different properties of TFAA, DPF, and TBAF with Li+are reflected by the response of the 2M LiF SI DME solution after adding them. (I-K) Quantified atomic composition ratios of treated LPSC pellet at different sputtering times (Os, 10s, 45s, 100s, 300s, 900s from top to bottom).Fig. 3. Stability of SREI-LPSC on Li anode. (A-C) Voltage profiles of the Li / / Li cell under step- increased current densities for Ih / lh of Li plating / stripping time with (A) TBAF-LPSC, (B) TFAA-LPSC, (C) DPF-LPSC electrolytes. (D) The cycling profile forLi / DPF-LPSC / Li at current densities of 1.6 mA cm'2with Ih / lh plating / stripping time. (E) Critical capacity tested in Li / DPF- LPSC / Li symmetric cell with continuous Li plating at a constant current of 0.45 mA cm'2. (F) Thelithium coulombic efficiency with DPF-LPSC and pristine LPSC at a current of 0.3 mA cm'2and capacity of 0.3 mAh cm'2(first 900 cycles) and 0.6 mAh cm'2(after 900 cycles).Fig. 4. Electrochemical performance of DPF-LPSC in all-solid-state lithium metal cell. (A) Rate performance of NCA / DPF-LPSC / Li with 1C =1.3 mA cm'2at 2.7-4.2 cut-off voltage (B) Cycling performance NCA / DPF-LPSC / Li at a high rate of 2C, which is continued from the 31stcycle in the rate test of Fig. 4C. (C-D) Cycling performance of NCA / DPF-LPSC / Li at a high loading of 3.5 mAh cm'2(0.2C) and 7.1 mAh cm'2(0.1C). The insets are corresponding magnified CE.Fig. 5. The application of electrophile reduction strategy on electrodes and their electrochemical performance. (A-B) High-resolution TEM images of the DPF-NCA particles and the magnified DPF-SREI structure (C) Quantified atomic composition ratios of the DPF- SREI on DPF-NCA cathode at different sputtering times (0s, 120s, 300s, 600s, 900s from top to bottom). (D-E) Cycling performance of [DPF-NCA with pristine LPSC] / DPF-LPSC / Li at (D) cutoff voltage of 4.2V, 2.6 mAh cm'2, and (E) 4.5V, 1.8 mAh cm'2. The insets are corresponding magnified CE.Fig. 6.19F-NMR and31P-NMR of diphosphoryl fluoride. The19F NMR resonances are 1 : 1 doublets and31P-NMR resonances are triplets consistent with a single phosphorus coupled to two fluorine. Diphosphoryl fluoride was prepared by the reaction between difluorophosphoric acid and phosphoric anhydride. Difluorophosphoric acid (1.0 mol) and P40io (0.25 mol) were heated under gentle reflux for 1 hour and the mixture was then distilled. The fraction boiling below 75 °C was collected and purified by fractional distillation. The product had a boiling point of 72 °C.Fig. 7. Optimized geometries and reduction potential of (A) Li(TFAA) and (B) Li(DPF) complex from quantum chemistry calculations at B3LYP / 6-31+G(d) level. The red ball is O. The blue ball is F. The orange ball is P. The purple ball is Li The gray ball is C.Fig. 8. Calculated voltage profile of Lis 5PS45CI1 5. The pink region is the stability window of Li5.5PS4.5Cl1.5- The stepwise oxidation / reduction products were also shown.Fig. 9. HT-TEM images of coating on (A) TBAF-LPSC particles and SREI on (B) TFAA-LPSC, (C) DPF-LPSC. The inset is the corresponding Fast Fourier Transform pattern. Scale bar: 10 nm.Fig. 10. (A, B) High-angle annular dark-field imaging images and selected scanned area. (C) Three (labelled 1-3 from the surface to the inner layers) typical EELS spectra near the surfaces of the pristine LPSC particles. Scale bar: 200 nm.Fig. 11. (A-J) LiF distribution in amorphous interphases formed by “electrochemical electrophile reduction”: High-angle annular dark-field imaging images of (A) TFAA-LPSC and (F) DPF- LPSC. EELS spectral images showing the Li-O- based composition (green) and LiF (red) distribution and percentage of the scanned area for (B, D, E) TFAA-LPSC and (G, I, J) DPF-LPSC, as well as three (labelled 1-3 from surface to inner) typical EELS spectra near the surfaces of the LPSC particles of (C) TFAA-LPSC and (H) DPF-LPSC. Scale bar: 200 nm.Fig. 12. Typical standard EELS spectra of Li -based components.Fig. 13. STEM EDS elemental mapping of DPF-LPSC particles.Fig. 14. STEM EDS elemental mapping of DPF-LPSC particles.Fig. 15. The 3 steps to build LPSC / Liquid Reactant system, y represents the surface energy The purple polyhedral represents PS4 tetrahedron. The green polyhedral represents LiSj plane. Purple balls are P atoms, green balls are Li atoms and yellow balls are S atoms. Brown balls are C atoms. Blue balls are N atoms. Light blue balls are F atoms. Pink balls are H atoms. Red balls are O atoms. The model system has a supercell dimension of 10.26 A * 10.26 A * 42.14 A, consisting of 11 - 16 liquid molecules depending on the density of liquid and two layers of LPSC with the rotational symmetricity (100) surface.Fig. 16. Evolution of the average charge of Li, P, Cl atoms along the AIMD simulations for the reaction of (A) LPSC with TBAF, (B) LPSC with TFAA, (C) LPSC with DPF.Fig. 17. Using the coordination number to show the reaction process to form LiF in (A) LPSC (Li- S bond) and TBAF (N-C bond) and the formation of Li-F bond. (B) LPSC (Li-S bond) and TFAA (C-F bond) and the formation of Li-F bond. (C) LPSC (Li-S bond) and DPF (P-F bond) and the formation of Li-F bond.Fig. 18. Using the O coordination number to show the reaction process to form Li-0 in (A) LPSC and TFAA (O-C bond) and the formation of O-Li bond, and in (B) LPSC and DPF (O-P bond) and the formation of O-Li bond.Fig. 19. Snapshot of (A) LPSC and TBAF reaction, (B) LPSC and TFAA reaction, and (C) LPSC and DPF reaction after AIMD simulation. In the AIMD simulations, solvent molecules are presented by the sticks. Bulk LPSCs are presented by the balls without sticks. The formed SREI / coating is presented by the balls and sticks, which were marked by the red rectangular dash line. Purple balls are P atoms. Small green balls are Li atoms. Large green balls are Cl atoms.Yellow balls are S atoms. Brown balls are C atoms. Red balls are O atoms. Light blue balls are F atoms Blue sticks are N atoms. Pink sticks are H atoms.Fig. 20. Corresponding atomic number near the surface of LPSC after reacting with TBAF, TFAA, and DPF in the AIMD simulationsFig. 21. P 2p spectra of the surface of treated LPSC before / after sputtering for (A) TBAF -LPSC, (B) TFAA-LPSC, and (C) DPF-LPSC solid electrolyte pellets.Fig. 22. O Is spectra of the surface of treated LPSC before / after sputtering for (A) TBAF -LPSC, (B) TFAA-LPSC, and (C) DPF-LPSC solid electrolyte pellets.Fig. 23. S 2p spectra of the surface of treated LPSC before / after sputtering for (A) TBAF -LPSC, (B) TFAA-LPSC, and (C) DPF-LPSC solid electrolyte pellets.Fig. 24. F Is spectra of the surface of treated LPSC before / after sputtering for (A) TBAF -LPSC, (B) TFAA-LPSC, and (C) DPF-LPSC solid electrolyte pellets.Fig. 25. The composition of TBAF -coating and TFAA-, DPF-SREI on LPSC particle surface from (A) XPS experiment and (B) AIMD simulation.Fig. 26. The proposed reaction equation for (A) TBAF -coating and (B-C) TFAA-, DPF-SREI.Fig. 27. Resistance (ionic conductivity) of original LPSC, TFAA-LPSC, DPF-LPSC, and TBAF- LPSC solid electrolytes.Fig. 28. Ionic conductivity of LPSC after treating with different amounts (concentration) of TBAF, TFAA, and DPF in the same reaction time.Fig. 29. (A-C) SEM image of TBAF-, TFAA- and DPF-LPSC on the surface of treated LPSC particles. Scale bar: 2 pm.Fig. 30. (A-C) Cross-section SEM images along the depth of Ga+301 sputtered craters of (A) TBAF-LPSC, (B) TFAA-LPSC, (C) DPF-LPSC SSE particles.Fig. 31. XRD patterns of original LPSC, TBAF-LPSC, TFAA-LPSC, and DPF-LPSC solid electrolytes.Fig. 32. Direct current polarization data for electronic conductivity determination for (A) DPF- LPSC 5.19x lO'10S cm-1 and (B) LPSC 4.59* 10'9S cm'1. The electronic conductivity was calculated by using Ohm's law.Fig. 33. Quantified atomic composition ratios of the surface composition of SSE pellet of (A) TBAF-LPSC, (B) TFAA-LPSC, (C) DPF-LPSC processed by small (30MPa) and heavy (360MPa) pressing.Fig. 34. The XPS F Is (C-F), F Is (LiF), and S 2p peaks mapping of TBAF-LPSC pellet pressed under (A) 30MPa and (B) 360MPa.Fig. 35. The XPS F I s (C-F), F I s (LiF), and S 2p peaks mapping of TFAA-LPSC pellet pressed under (A) 30MPa and (B) 360MPa.Fig. 36. The XPS F Is (P-F), F Is (LiF), and S 2p peaks mapping of DPF-LPSC pellet pressed under (A) 30MPa and (B) 360MPa.Fig. 37. The contact angle test with molten lithium dropping on LPSC pellets of (A) TBAF-LPSC, (B) TFAA-LPSC, (C) DPF-LPSC.Fig. 38. The cycling profile for Li |Li symmetric cells with (A) TBAF-LPSC and (B) TFAA-LPSC at current densities of 1 mA cm'2with Ih / lh plating / stripping time.Fig. 39. EIS resistance evolution of Li|TFAA-LPSC|Li and Li|DPF-LPSC|Li. The first semi-circle belongs to the SEI and charge transfer.Fig. 40. The cycling profile forLi||DPF-LPSC||Li cells at increasing current densities and fixed at 3 mA cm'2with Ih / lh plating / stripping time.Fig. 41. SEM and backscattering SEM image for the cross-section of (A, B) DPF-LPSC||Li interfaces and (C, D) LPSC||Li and after 50 Li plating / stripping cycles. Scale bar: 50 pm.Fig. 42. (A) SEM images and the corresponding EDS spectra and (B-G) EDS mapping of Cl, F, O, P, S, and Mg elements for the cross-section of DPF-LPSC||Li interface after 50 Li plating / stripping cycles. The occurrence of F and O signals on the Li metal side, and that of the Mg in the SSE side is due to the contrast noise, as indicated by the EDS spectra.Fig. 43. The cross-section morphology of 6mAh cm'2lithium deposited in Li||DPF-LPSC||Cu half cell. Cu is used as a current collector for easy cutting to get the cross-section morphology. Fig. C is the backscattering SEM image.Fig. 44. Critical capacity tested in Li||LPSC||Li symmetric cell with continuous Li plating at a constant current of 0.45 mA cm'2.Fig. 45. Schematic to show the coulombic efficiency testing protocol. The Li||LPSC||Li cells were first charged / discharged for 5 cycles using capacity control, and then all the lithium in Li on one side of the cells was completely stripped and repeated this process for some cycles to ensure the Li was completely stripped as Li||LPSC||Mg@SS cell.Fig. 46. Charge / discharge profile of CE testing for Li||DPF-LPSC||Mg@SS at a current of 0.3 mA cm'2and capacity of (A) 0.3 mAh cm'2, and (B) 0.6 mAh cm'2.Fig. 47. (A) The lithium coulombic efficiency of DPF-LPSC at a cycle current of 0.3 mA cm'2and capacity of 0.3 mAh cm'2. ~50nm Mg layer was sputtered on the Ni foil as the current collector to help reduce the contact loss. (B) The corresponding initial CE in the first cycle with a capacity of 2 mAh cm'2.Fig. 48. Voltage profiles of cell NCA||DPF-LPSC||Li at different C -ratesFig. 49. The images depict the disassembly of the SSE after full cell cycling for (A) LPSC and (B) DPF-LPSCFig. 50. Voltage profiles ofNCA||DPF-LPSC||Li with a loading of 3.5 mAh cm'2at 2.7-4.2V cutoff voltage.Fig. 51. (A-C) SEM images of pristine NCA particles at different magnifications.Fig. 52. (A-D) SEM images of DPF-NCA particles at different magnifications.Fig. 53. (A) SEM image and (B-G) element mapping of DPF-NCA particles with Co, Al ,Ni, O, P, F elements.Fig. 54. (A-C) High-resolution TEM images of DPF-NCA particles at different magnificationsFig. 55. (A-G) High-resolution TEM images and mapping of DPF-NCA particles. (H) the color stack of element mappingFig. 56. (A,B) F Is, (C,D) O Is and (E,F) P 2p spectra of the surface on DPF-NCA before / after sputtering.Fig. 57. Leakage current of NCA||LPSC||Li and DPF-NCA||LPSC||Li cells when holding at 4.3V.Fig. 58. The EIS results before and after voltage hold of (A) NCA||LPSC||Li cells and (B) DPF- NCA||LPSC||Li.Fig. 59. Voltage profiles of [DPF-NCA with LPSC]||DPF-LPSC||Li.Fig. 60. The electronic conductivity of pure NCA pellet (left), “NCA with DPF-LPSC” pellet and “DPF-NCA with LPSC” pellet (right) were calculated by a potentiostatic polarization measurement. The powder was pressed into a pellet and stainless steel was used as an electronic conductor on both sides to do the test.Fig. 61. Cycling performance of [DPF-NMC811 with LPSC]||DPF-LPSC||Li cell at 4.4V.Fig. 62. Table SI. Summary of solid-state electrolytes and current technology.Fig. 63. Table S2. The comparison to the literature using SSE coating or core-shell strategy.Fig. 64. Table S3. Evaluation of the Li+inventory loss in the first cycle of DPF-LPSC and pristine LPSCFig. 65. Table S4. Assessment of the advances compared to state-of-the-art solid-state batteries.DETAILED DESCRIPTION OF THE DISCLOSURE

[0011] The present disclosure is described herein with sufficient details to provide an understanding of one or more particular embodiments of broader subject matters. The descriptions expound upon and exemplify features of those embodiments without limiting the scope of disclosure to the explicitly described embodiments and features. Considerations in view of these descriptions will give rise to additional and similar embodiments and features without departing from the scope of the presently disclosed subject matter.

[0012] The terms “comprise(s),” “include(s),” “having,” “has,” “can,” “contain(s),” and variants thereof, as used herein, are intended to be open-ended transitional phrases, terms, or words that do not preclude the possibility of additional steps or components or ingredients. The singular forms “a,” “an” and “the” include plural references unless the context clearly dictates otherwise. The present disclosure also contemplates other embodiments “comprising,” “consisting of’ and “consisting essentially of,” the embodiments or elements presented herein, whether explicitly set forth or not. Accordingly, the transitional phrases “consisting of’ and “consisting essentially of’ may be interpreted to be subsets of the open-ended transitional phrases, such as “comprising” and “including,” such that any use of an open-ended phrase to introduce a recitation of a series of elements, limitations, components, ingredients, materials, or steps should be interpreted to also disclose recitation of the series of elements, limitations, components, ingredients, materials, or steps using the closed terms “consisting of’ and “consisting essentially of.” For example, the recitation of a composition “comprising” components A, B and C should be interpreted as alsodisclosing a composition “consisting of’ components A, B, and C as well as a composition “consisting essentially of’ components A, B, and C

[0013] Throughout this disclosure, when an example is provided using terms “such as,” “for example,” “e.g.” and grammatical variations thereof, the list of examples provided thereafter is not intended to be limiting in scope but mere provided as representative examples. Accordingly, the scope of the disclosure includes other well-known materials, processes, methods, compositions, or other elements that may have not been explicitly disclosed but are known to one skilled in the art.

[0014] When referring to a numerical value, the terms “about” and “approximately” are used interchangeably herein and refer to being within an acceptable error range for the particular value as determined by one of ordinary skill in the art. Such a value determination will depend at least in part on how the value is measured or determined, e.g., the limitations of the measurement system, i.e., the degree of precision required for a particular purpose. For example, the term “about” can mean within 1 or more than 1 standard deviation, per the practice in the art. Alternatively, the term “about” when referring to a numerical value can mean ± 20%, typically ± 10%, often ± 5% and more often ± 1 % of the numerical value. In general, however, where particular values are described in the application and claims, unless otherwise stated, the term “about” means within an acceptable error range for the particular value, typically within one standard deviation.

[0015] It should be noted that as used herein, the term “coated with a reductive- electrophile agent,” “coated with a reductive-electrophilic agent,” “encapsulating solid electrolyte material with reductive-electrophile agent" and grammatical variations thereof are used interchangeably herein and do not necessarily mean the material is coated with reductive- electrophile agent such that the reductive-electrophile agent remains on the surface of the material. Instead, it means the reductive-electrophile agent is contacted with the surface of a material such that any functional group(s) and / or reactive species that is present in the material or diffused to the surface of the material react with the reductive-electrophile agent to produce a coating of reaction product. Thus, the coating may, and most likely, be a different species than the original reactive-electrophile agent used. Thus, for example, DPF-coated LPSC (i.e., DPF-LPSC) means solid electrolyte LPSC is coated with DPF such that a layer of solid reductive-electrophile interphase (SREI) is formed from a reaction between DPF and reactive species that are present or are diffused to the surface (e.g., lithium ion and / or electron) of LPSC.

[0016] When referring to a variable, the terms “those defined above” and “those defined herein” as well as grammatical variations thereof are used interchangeably herein and incorporates by reference the broad definition of the variable as well as any narrower defmition(s).

[0017] As used herein, the term “and / or” includes any and all combinations of one or more of the associated listed items.

[0018] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which the presently disclosed subject matter pertains. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the presently disclosed subject matter, representative methods and materials are now described for illustrative purposes only and do not constitute any limitation of the present disclosure.

[0019] With the rapid popularization and development of lithium-ion batteries, associated safety issues caused by the use of flammable organic electrolytes have drawn increasing attention. To address this, solid-state electrolytes have become the focus of research for both scientific and industrial communities due to high safety and energy density. Despite these promising prospects, however, solid-state electrolytes face several challenges that hinder commercialization, including insufficient lithium-ion conduction, insufficient electrochemical stability, and surge transfer impedance, and / or lost contact at the interface between solid-state electrolytes and electrodes.

[0020] Some aspects of the present disclosure are based on the discovery by the present inventors that use of a reductive-electrophile agent (RE) significantly improves an all-solid-state battery (ASSB). As used herein, the term “improve” and its grammatical variations thereof when referring to ASSB refers to increase in life cycle, life span, Coulombic efficiency, critical capacity, critical current density, cycling stability, cell loading, lower temperature and / or stacking pressure requirement for stable operability, etc. Such increases can be due to, for example, preventing, suppressing, or reducing SSE reduction and / or of lithium dendrite formation (in a lithium ASSB (“ASSLB”)), and / or oxidative decomposition of SSE, etc.

[0021] Reductive-electrophile agents of the disclosure are compounds that can be used to coat or form a thin layer of coating on the surface(s) of cathode, anode, or solid-state electrolyte (SSE) to prevent, suppress, or reduce the rate of SSE reduction and / or, in lithium batteries, of lithium dendrite formation. In general, when used in a lithium battery, the reductive-electrophile agents (REs) are those forming a thin layer of coating on solid state electrolyte in which lithium- nucleophile materials may be present. In this manner, the presence of REs (i) provides reduction,prevention, or suppression of further reduction of solid electrolyte, lithium dendrite growth; (ii) increases Li reversibility; (iii) increases critical current density (CCD); and / or (iv) increases antioxidation stability. Exemplary reducing agents include, but are not limited to, Lewis acids (such as boron halides, e.g., BF3, BCL, and BBn); electron-deficient atom (such as CO2, SO3, phosphorous halides, e.g., PCI3, PBr and POCI3); acid anhydrides, and acid halides. Suitable acid anhydrides of the disclosure include, but are not limited to, organic acid anhydrides, phosphorous based anhydride (e.g., phosphoryl anhydride), sulfur-based anhydride (e g., sulfonic anhydride), and their derivatives. Organic acid anhydrides have a general formula R-C(=O)-O-C(=O)-R’, where R and R’ can be independently alkyl, haloalkyl, aryl, heteroaryl, aralkyl, heteroalkyl, or other hydro or halo carbon groups. Exemplary organic acid anhydrides include, but are not limited to, tri fluoroacetic anhydride, acetic anhydride, CF3C(=O)-O-C(=O)-CH3, F5PhC(=O)-O-C(=O)-PhF5 (where PhF? is pentafluorophenyl), etc. Similarly, phosphorous- based anhydride (e g., phosphoryl anhydride) and its derivatives are compounds having a general formula R2-P(=O)-O-P(=O)-R2’. In general, phosphoryl anhydride is any compound having a functional group -P(=O)-O-P(=O)-. In a similar manner, sulfur-based anhydride (e g., sulfonic anhydride) and its derivatives are compound having a general fonnula: R-S(=O)x-O-S(=O)y-R' (where each of x and y is independently 1 or 2). In general, sulfonic anhydrides are any compound having a functional group of the formula -S(=O)2-O-S(=O)2- As with anhydrides, acid halides can be organic acid halides, sulfur-based acid halide (i.e., sulfonyl halides), or phosphorous-based acid halides (i.e., phosphoryl halides). Organic acid halides are compounds having a general formula R-COX, where X is a halogen such as Cl, Br, or F. Similarly, sulfonyl halides are compounds of the formula R-SO2X, R-SOX3 and phosphoryl halides are compounds of the fonnula R-POX2.

[0022] Using REs and methods disclosed herein, solid-state batteries and all-solid-state batteries can be prepared. Batteries disclosed herein have a high cycle life. In some embodiments, the cycle life of batteries disclosed herein have at least about 1,000 h, typically at least about 5,000 h, often at least about 8,000 h, more often at least about 10,000 h, and most often at least about 15,000 h at a temperature of about 30 °C and at 2.5 MPa. Unless otherwise stated, all relevant physical properties discussed herein refers to a temperature of about 30 °C and at a pressure of about 2.5 MPa. Alternatively, batteries of the disclosure, compared to a similar battery in the absence of a reductive-electrophile agent, have at least about 100% or more, typically at least about 250% or more, often at least about 500% or more, more often at least about 750% or more, still more often at least about 1,000% or more, and most often at least about 1,500% or more cyclelife. Still in other embodiments, batteries of the disclosure maintain at least 99% Coulombic efficiency after about 100 cycles, typically after about 250 cycles, often after about 500 cycles, more often after about 750 cycles, and most often after about 1,000 cycles.

[0023] Other aspects of the disclosure provide RE coated SSEs having full cell Coulombic efficiency of at least 99% for at least about 100 cycles, typically at least about 500 cycles, often at least about 1,000 cycles, more often at least about 1,500 cycles, and most often at least 2,000 cycles. Alternatively, RE coated SSEs of the disclosure have at least about 50% or more, typically at least about 75% or more, often at least about 80% or more, more often at least about 85% or more, still more often at least about 90% or more, even more often at least about 95% or more, and most often at least about 98% or more decrease in SSE reduction compared to the same SSEs in the absence of RE coating.

[0024] Exemplary solid-state electrolytes that can be used in the disclosure include, but are not limited to, Sulfide solid electrolyte, oxide solid electrolytes, halide solid electrolytes, phosphate solid electrolytes, nitrides solid electrolytes and other new materials like Li3N, Li3N- Lil, as well as other materials known to one skilled in the art. It should be noted these materials and methods are not limited to Li-based SSE, they are also applicable to SSE materials in other batteries, such as Na batteries, K batteries, etc.

[0025] Exemplary materials suitable for use as a cathode of the disclosure include, but are not limited to, layered transition metal oxides, spinel oxides, polyanion compounds, conversiontype cathode, and organic cathodes material. Other suitable materials for a cathode can be found, for example, lithium halide cathode in Xu et al., “Lithium halide cathodes for Li metal batteries,” Joule, vol. 7, pp. 83-94, January 18, 2023. It should be noted these materials and methods are not limited to Li-based cathode, they are also applicable to cathode materials in other batteries, such as Na batteries, K batteries, etc.

[0026] Materials that can be used as an anode of the disclosure include, but are not limited to, lithium, metal-doped lithium (e.g., Mg doped Li), lithium metal alloy, silicon, electric conductive carbon (e g , graphite), and other materials known to one skilled in the art. Other suitable materials for an anode can be found, for example, in conversion type anode (e.g., Fe2O3, etc), organic anodes. Alloying type anode (e.g. Si, Sn, etc.) and other metal (Na, K) based materials. It should be noted these materials and methods are not limited to Li-based anode, they also applicable to anode materials in other batteries, such as Na batteries, K batteries, etc.

[0027] For the sake of clarity and brevity, the present disclosure will now be described in reference to all-solid-state Li metal batteries (ASSLMBs). However, it should be appreciated that the scope of the disclosure is not limited to ASSLMBs. Methods and SSEs of the disclosure can also be used in other metal batteries such as, but not limited to, sodium batteries, potassium batteries, etc. In fact, methods used herein is applicable to any liquid-state, solid-state or all-solid- state batteries having a solid electrode materials or electrolyte materials. In general, methods and composition of the disclosure are applicable to any batteries where modification of an interface between an electrode and the electrolyte leads to protection or improvement of the electrode and / or the electrolytes. In particular, methods of the disclosure is applicable to cathode, anode, in both batteries with solid state electrolytes and liquid electrolytes, and electrolytes. Discussion related to ASSLMBs below is provided solely for the purpose of illustrating the practice of the disclosure and do not constitute limitations on the scope thereof.

[0029] Unless the context requires otherwise, any reference to the Li||Li cell cycle life reflects the stability of the lithium electrode, while the full cell cycle life measures the overall stability of all-solid-state lithium metal batteries. Furthermore, unless stated or context requires otherwise, use of lithium in Li||Li cell cycle life measurements are based on lithium that is doped with 1% Mg.Illustrative Embodiments

[0028] The use of lithium metal anodes in solid-state batteries has emerged as one of the most promising technologies for replacing conventional lithium-ion batteries All-solid-state Li metal batteries (ASSLMBs) offer high energy density and safety in transportation electrification. However, no solid-state electrolyte (SSE) has satisfied all the requirements for these applications. Materials like LiPON have wide electrochemical windows but suffer from low ionic conductivity Sulfide electrolytes have high ionic conductivity and suitable mechanical properties but are limited by narrow stability windows (1.08 to 2.24V), leading to formation of solid electrolyte interphase (SEI) on the Li anode and cathode electrolyte interphase (CEI) on the cathode. Unfortunately, the SEI cannot protect lithium anode from further reduction and Li dendrite growth, which reduces Li reversibility, and critical current density (CCD) (FIG. 1A). Furthermore, the CEI cannot protect the SSE from oxidation, which typically leads to low compatibility with 4 V cathode, such as LiNii-x-yCoxMnvO2 (FIG. 1 A). In addition, the limited SSE formulas constrain the modification of SEI / CEI composition. Some have used fluorine doping to introduce lithiophobic and anti- oxidative LiF in SEI / CEI to stabilize anode and cathode. Unfortunately, use of fluorine also resulted in a significant reduction in SSE ionic conductivity. In order to be operationally useful,such ASSLMBs have to work at elevated temperature and / or high stacking pressure to improve compatibility and mitigate Li dendrite.

[0029] Current state-of-the-art solution is to use interlayer between SSE and Li, for example, Ag-C which provides a balance between lithiophobicity and electronic conductivity, performing well when combined with the warm isostatic pressing. However, these interlayers are micro-level thick and non-native to the SSE, requiring high temperature (> 55 °C) and / or high stack pressure (> 50 MPa) to reduce interface resistance and enhance contact. Moreover, they require extra processing and advanced machinery, and involve costly materials (e.g., Ag). Thus, this system is not applicable or suitable for industrial applications. Furthermore, interlayer systems are located at between SSE and Li, so they do not significantly inhibit the Li deposition and growth of lithium dendrite within the bulk SSE, leaving the safety risk of short circuit. Therefore, achieving high-loading and long-life ASSLMBs at room temperature and / or at practical pressure has heretofore been illusive.

[0030] Some aspects of the disclosure provide lithiophobic and electron-blocking layer directly on SSE particles to prevent the SSE from reduction / oxidation decomposition and / or suppress the Li dendrite growth (FIG. IB) In some embodiments of the disclosure, a family of reductive electrophiles (REs) (e.g., acid anhydride and acid halide) are disclosed that can be used to encapsulate solid electrolyte particles, thereby allowing SSE to gain electrons and Li+from Li- nucleophile upon contact resulting in reduction of REs, thereby producing a thin protective layer (FIG. 1C). This thin protective layer called solid reductive electrophile interphase (SREI) establishes an interphase on lithium battery materials because most SSEs in lithium batteries are Li-nucleophile materials (e.g., Li-sulfide, Li-oxide, Li-halide). For effective electrochemical reduction of REs and to form lithiophobic and electron-blocking SREI on SSE particles (SREI@SSEs), REs should fulfdl one of the following criterias. REs should be strong electrophiles that allow pre-organization through interaction with nucleophilic sites and gain electrons from Li-nucleophile materials. REs possess a higher reduction potential than the oxidation potential of Li-nucleophile (FIG. ID), allowing electrochemical reduction to form SREI. Typically, the reduction potential of REs is at least about 0.01 V or higher, often at least about 0.2 V or higher, more often at least about 0.4 V or higher, and most often at least about 1 V or higher than oxidation potential of Li-nucleophile. As used herein, Li-nucleophile refers to a compound or a functional group in the solid electrolyte that forms a salt or a complex with a lithium ion. In some embodiments, REs are fluorinated reagents with less carbon content compared to SSE. Insome embodiments, REs form lithiophobic inorganic-rich SREI while improving the stability of the lithiophilic SSE.

[0031] It is believed that REs form intimate nucleophile-electrophile pairs on SSE’s surface upon contact. Without being bound by any theory, it is believed that the pre-organized REs facilitate electrochemical reduction to form dense and amorphous structure by gaining the cation (e.g., Li+) and e“ from SSEs due to proximity (FIG. 1C). The formation of SRE1 is controlled by electrons, with the interphase transitioning into electron insulating upon reaching a particular thickness, leading to uniform formation of dense and thin SREI. It appears this selflimiting electrochemical process resembles SEI formation in batteries, but it occurs through direct interaction between RE and SSE without requiring any external electric fields or special equipments. REs of the present disclosure surpasses traditional SEI and coating, offering greater flexibility and broader applicability in interphase design. In contrast, conventional chemical coatings of SSE yields thermodynamically stable products that are crystalline, non-uniform, and thick, which reduces protection efficacy and increasing resistance,|0032| One particular example of RE used in present disclosure include an all-inorganic diphosphoryl fluoride (DPF, Fig. 6) for ASSLMB. DPF is liquid at room temperature with a very high reduction potential of 3.15 V, substantially higher than that of typical battery solvents (< 1.5V, FIG. ID). When contacting with Li-sulfide SSE (Li5.5PS4.5Cl1.5, i.e., LPSC), DPF was electrochemically reduced on the LPSC surface to form lithiophobic and electron-blocking LiF- LixPyOzFi (i.e., SREI@SSEs). Coupled with Li-l%Mg anode of high Li diffusivity (referred to as Li anode for simplicity), the DPF-treated LPSC enabled a high Li reversibility at anode (CE 99.7%), a CCD > 3.4 mA cm'2 / 3.4 mAh cm'2. At a high loading of 3.5 mAh cm'2to 7.1 mAh cm'2, the Li / / LiNio.8Coo.i5Alo.o502 full cell exhibited stable cycling for over 600 cycles with a high full cell Coulombic Efficiency (CE) > 99.9% at 0.1C. Due to the low interface resistance, SREI@SSEs also enable full cell a high rate performance (2C=2.6 mA cm'2) for over 4500 cycles, retaining 90% capacity at 30 °C at low stack pressure. As used herein, the term “low stack pressure” means stack pressure of about 20 MPa or less, typically about 15 MPa or less, often about 10 MPa or less, more often about 5 MPa or less, and most often about 2.5 MPa or less. To demonstrate its broad applicability, DPF also established SREI on the metal-oxide cathode, high-nickel LiNi0.8Co0.15AI0.05O2 / LiNi0.8Mn0.1Co0.1O2, further enhancing the ASSLMB operating voltage (4.5 V) and cycle life. The SREI greatly improves sulfide SSE to satisfy the requirements for ASSLMBs (FIG. IE, based on FIG. 62 Table SI). This advancement can be extended to other SSEor electrodes, such as, but not limited to, Li-sulfide, Li -oxide, Li-halide, and Li-Si, as well as other metal-based (for example, but not limited to, Na or K) materials.

[0033] Understanding of Electrophile Reduction

[0034] To understand the reduction process of a reductive-electrophile agent to form SREI and the properties of the resulting SREI, the following experiments were carried out. As a control sample, traditional chemical coating method was carried out using tetrabutylammonium fluoride (TBAF) (FIG. 2A) as a fluoride source involving a reaction between Li+that diffuses from the solid electrolyte, LPSC, to form LiF coating. This result was then compared with the SREI formed by different reductive electrophiles; organic electrophile: trifluoroacetic anhydride (TFAA) and inorganic electrophile DPF. Acid anhydride, TFAA, (FIG. 2B, left) is a strong electrophile and has a higher reduction potential (2.84 V vs Li / Li+, Fig. 7A) than the potential of LPSC electrolyte (2.12 V, FIG. 8) and NCA / NMC cathode (~2.7 V). When TFAA was contacted with LPSC or NCA / NMC powders, TFAA formed intimate pairs with these materials (nucleophilic S in LPSC or nucleophilic O in NCA / NMC, respectively). Transfer of electrons or Li ions from LPSC or NCA / NMC resulted in the electrochemical reduction of TFAA to form organic-inorganic SREI on the surface of these materials, i.e., LPSC or NCA / NMC. The -OC(=O)CF3 group of TFAA may be replaced with other groups, such as F, to produce an organic acid halide with higher electrophilicity (FIG. 2B, mid) Trifluoromethyl acetyl fluoride is more reactive than TFAA, thus forming LiF more rapidly within the interphase during reduction. One can eliminate the organic components in SREI by replacing organic acid halide or organic acid anhydride with phosphoryl anhydride or phosphoryl halide, e g., diphosphoryl fluoride (DPF) (FIG. 2B, right). The reduction potential of DPF is 3.15 V vs Li / Li+(Fig. 7B), which is significantly higher than that of TFAA. Use of inorganic reductive-electrophile agent, such as DPF, allows formation of a LiF-rich interphase without any organic component.

[0035] RE-coated LPSCs were produced by contacting hand-milled LPSCs with a solution of RE and drying the resulting mixture. In this manner, TFAA-LPSC, DPF -LPSC, and TBAF- LPSC powder were obtained and tested Since the electrochemical reduction of reductive- electrophile agent is self-limited by forming electron-blocking interphases, the TFAA- and DPF- SRE1 (-20-30 nm) were much thinner than the TBAF-coating (> lOOnm) (Fig. 2C-E). The SREI represents exponential thickness reduction compared to documented artificial interlayers@Li constructed by various fabrication methods (Fig. 2F). It was observed that SREI had less crystallized material than the LiF coating formed by an ionic reaction (Fig. 9). This less crystallization of SREI was indicated by the featureless amorphous layers with diffuse ringpatterns in the FastFourier Transform (FFT) patterns contrast to the Bragg diffraction spots of LiF coating. The LiF in the amorphous SREI@SSEs was confirmed by Electron energy loss spectroscopy (EELS, Fig. 10-12), and DPF-SREI was more enriched with LiF than TFAA-SREI, as anticipated by (i) more reactive property and / or (ii) higher reduction potential of DPF compared to TFAA. The element mapping (Fig. 13-14) showed that the F and O signal were significantly stronger than the Cl and S signals, indicating that DPF-SREI has a thin thickness and consists of F- and O-based compositions. Such inorganic-rich interphase with an amorphous structure has been shown to facilitate Li transport, featuring a smaller thickness and higher interface energy than porous and crystalline coating, thereby exhibiting enhanced stability with lithium metal.Li compounds were commonly analyzed by using electron-energy loss near-edge fine structure (ELNES) features of the Li K-edge at ~55 eV energy loss1. Indeed, each Li compound also has its unique low-loss EELS spectrum, correlated to the electronic excitations between valence and conduction bands, including the volume plasmon and interband transitions2^4, and provides an additional characteristic fingerprint of Li compounds5,6. Hence, we performed the STEM-SI in the energy range between 0 and 75 eV for TFAA- and DPF-SREI and analyzed the composition by the multiple linear least squares (MLLS). Compared to the bare LPSC (Fig. 10), SREI is observed on the surface of TFAA-LPSC (Fig. 11 A) and DPF-LPSC (Fig. 1 IF). Fig. 1 IB and 11G are the STEM-SI database recorded from the yellow box area. We further retracted the corresponding EELS spectra as a function of electron probe positions from surface (position 1) to inner part (position 3) (Fig. 11C and 11H). We recorded the standard EELS spectra of LizO, LhS, LiCl, and LijPCU compounds in the energy loss range from 0.0 eV to 75 eV (Fig. 12), and analyzed the spectra of SREI to infer the possible distribution of products using the MLLS method. The wide peak marked green (Fig. 11C) is very close to the standard volume plasmon peak of LizO, LizPCfi, which probably suggests a mixture of LizO and other O-based components. Both TFAA-SREI and DPF-SREI (Fig. 1 1D,I) contain a uniform distribution of this O-included composition, which is attributed to the interconnected -Li-O-, -O-C- / O=C- from electrochemical reduction of TFAA, and -Li-O-P, -O-P- / O=P- from electrochemical reduction of DPF. The EELS spectral feature of the DPF-SREI surface (position 1) reveals a significant shoulder at ~15 eV, a predominant peak at ~ 25 eV (Fig. 11H), and Li K-edge at 62 eV followed by a wide peak until 70 eV, those spectral features are same with the standard LiF7,8. The distribution of LiF indicate that DPF-SREI (Fig. 11 J) was more enriched with LiF than TFAA-SREI (Fig. HE), agreeing with the electrophile design.

[0036] The reaction mechanisms for SREI formation were supported by AIMD simulations (details of modeling in Fig. 15). During the reaction process of LPSCs with TFAA or DPF, the net charge of LPSC continuously increased (Fig. 2G), suggesting LPSCs were losing electrons while reductive-electrophile agents were gaining electrons for reduction. In contrast, no net charge changes of LPSCs were observed during the reaction with TB AF, confirming the “ionic reaction” nature of TBAF. This ionic reaction nature was also confirmed by measuring the average charges of Li, P, S, and Cl atoms in LPSC, where the average charges of these four atoms in LPSC remain unchanged during the reaction with TBAF. In contrast, nucleophile sulfur atoms acted as electron donors during the reaction with reductive electrophile agents (Fig. 16). As a result, reductive-electrophile agents exhibit distinct reaction pathway compared to that of TBAF. In fact, LPSC / TBAF reaction involved only an increase in Li-F bond formation (Fig. 17A), originating from the ionic bonding between Li+and F“. In sharp contrast, LPSC / TFAA and LPSC / DPF reactions involved change in coordination numbers of chemical bonds, indicating the breaking of Li-S, C-F / P-F, and C-O / P-O bonds (reduction of TFAA and DPF) and the formation of Li-F and Li-0 bonds (Fig. 17B-C and 18). This distinction between the “ionic reaction” and “electrochemical reduction” was also experimentally observed, where TFAA and DPF were stable in the presence of Li+(2 M LiFSI / DME solution) (Fig. 2H) in the absence of electrons, while TBAF rapidly reacted with Li+forming a suspension containing crystalline LiF

[0037] The different reaction mechanisms explain the structural differences between SREI and traditional coating. Without being bound by any theory, it is believed that in the electrochemical reduction of reductive-electrophile agents, the reductive-electrophile agent first interacts with nucleophilic site S, forming intimate nucleophile-electrophile pairs on the surface, and then being reduced to form SREI by gaining electrons and lithium ions. This kinetics- controlled reaction process forms amorphous phases. AIMD simulations (Fig. 19) showed that the Li and O atoms form coordinated bridges among carbon or phosphorus atoms, creating “crosslinked” bonds like -Li-O-, -C-O- / -C=O-, C-C, -Li-F-C- in TFAA-SREI (LixCyOzFi), and - Li-O-, -P-O- / -P=O-, -Li-F-P- bonds in DPF-SREI (LixPyOzFi). This promotes the amorphization of the interphase, similar to amorphous LIPON materials. In contrast, in the ionic reaction of TBAF with LPSC, lithium ions diffuse from LPSC to the solution, where it combines with fluoride ions to form LiF. This reaction is under thermodynamic control yielding more thermodynamic stable products, i.e., crystalline LiF, to form crystalline coatings. AIMD also indicated that the reaction product is sparsely distributed with discontinuous Li-F and F-Li-F. The atom numbers near the SSE surface were lower in TBAF-Coating than TFAA- and DPF-SREI (Fig. 20), suggesting the amorphous structure contributed to dense interphases.

[0038] The proposed composition of the SREI on the LPSC particles' surface was then examined via X-ray photoelectron spectroscopy (XPS) with an Ar+sputtering depth profiling on the pressed SSE pellets (Fig. 2I-K and Fig. 21-24). With increasing sputtering time, they exhibit a sharp decrease in C, O, and F elements but a sharp increase in S, and Cl elements, indicating coating / SREI layer coverage of SSE. In general, to increase suppression of Li dendrite formation, a lower organic content is desirable due to the lithiophilicity of organic components. The TBAF- Coating has the highest organic ratio (Fig. 21) due to the large ratio of organic components of TBAF. The C element of TFAA also contributes to the organic species in SREI (Fig, 2J). In contrast, due to the inorganic nature of DPF, much less organic product is observed in DPF-LPSC (Fig. 2K). The carbon on the surface of DPF-LPSC may come from the unavoidable carbon impurities during the XPS test DPF-SREI also showed the highest O and F-based components among the inorganic species. This high amount of O and F elements in DPF-SREI from XPS analysis is in agreement with the AIMD simulation (Fig. 25), indicating the superior ability of DPF to form F and O-rich SREI.

[0039] The P, O, S, and F spectra (Fig. 21-24) were analyzed to understand the specific compositions in the interphase. The TFAA-SREI mainly showed LiF, Li2O, C-O, C=O, Li-O-C, C-F, and the DPF-SREI showed it was mainly composed of LiF, Li2O, P-O-P, O=P-O-, Li+-O-P, P-F. These groups, as supported by modeling results, form LixCyOzFi / LixPyOzFi (where x, y, z, and i are number of each atom) large molecular, resulting in more amorphous and homogeneous interphases. Since F-based components stabilize the Li anode, F spectra were compared. TBAF- coating primarily showed LiF. TFAA-SREI showed both LiF and CFXthrough reduction of some of the -CF3 moieties. It should noted that CFXcan lead to SSE reduction and Li dendrite growth when it contacts with lithium ions to form electronically conducting carbon. In contrast, DPF- SREI showed mostly LiF and P-F, which, as observed in LiPFe- or LiPCLFi-based liquid electrolytes, promote the formation of robust and lithiophobic SEI with lithium, with minimal undesirable LLP detected.

[0040] TBAF chemically coats crystalline LiF via ionic reactions without charge transfer. In contrast, strong reductive electrophiles, such as TFAA and DPF, form intimate nucleophileelectrophile pairs with LPSC, gaining electrons from LPSC and undergoing electrochemical reduction (reaction equation in Fig. 26) to form a thin and dense SREI. Among these, the LiF- LixPyOzFi SREI, which lacks organic components, provides largely improved stability on both Li anode, SSE bulk, and high voltage cathode.

[0041] Properlies of Electrophile-Treated SSE

[0042] SREIs formed from REs and methods of the disclosure exhibited lower ionic resistance than chemical coatings resulting in only a slight reduction in the ionic conductivity of reductive-electrophile agent treated LPSC, e.g., from 6.42 x 10'3S cm'1for bare LPSC to 3.98 x 10'3S cm'1for TFAA-LPSC, and to 3.65 x 10'3S cm'1for DPF-LPSC (Fig. 27), while the conductivity of TBAF-LPSC drops significantly to 1.70 x 10'3S cm'1due to its crystalline and thick coating. The self-limit property of electrochemical reduction makes the ionic conductivity of reductive-electrophile agent treated LPSC much less sensitive to the amount of reacting agent, compared to chemical-coated LPSC (Fig. 28).

[0043] An effective coating could passivate LPSC particles and prevent continuous reactions, but the porous and crystalline TBAF-coating allowed continuous reaction and etching on the LPSC particles (similar to HF etching on glass), leading to surface fissures and distinct inner and outer morphology in the cross-section of TBAF-LPSC particles (Fig. 29A, 30A). In contrast, LPSC particles coated with TFAA (i.e., TFAA-LPSC and DPF-LPSC particles, respectively) exhibit intact morphology both on the surface (Fig. 29B, 29C) and in cross-sections (Fig. 30B, 30C). This was also confirmed by X-ray powder diffraction (XRD) of TFAA-LPSC and DPF-LPSC, where the main phase of LPSC remained unchanged after the reaction with reductive-electrophile agents, with no observable impurity peaks or Li-deficient phases (Fig. 31). In contrast, an impurity peak LiF was observed on the XRD of TBAF-LPSC. With no bulk changes, the electron-blocking DPF-SREI on the SSE surface reduced the electric conductivity of DPF-LPSC SSE (5.19 x 10'10S cm'1), which is nine times lower than of bare LPSC SSE (4.59 x 10'9S cm'1), i.e., in the absence of a reductive-electrophile agent, (Fig. 32), effectively inhibiting SSE reduction and Li nucleation inside the SSE bulk.

[0044] After cold-pressing the treated SSE powder into a pellet, surface analysis of the pellet under low (30 MPa) and high (360 MPa) pressure using XPS imaging confirmed that the SREI remained intact during cell assembly. Both high and low-pressure processed pellets exhibit similar element ratios (Fig. 33), and XPS imaging revealed the surface remained fully covered by SREI without obvious exposure of LPSC after compression (Fig. 34-36). These demonstrate that the SREI is robust and remains stable during cell assembly (Fig. 63 Table S2).We confirm the intact coating / SREI by the following three evidences:Comparing the pressure and particle size with the reported literature with core / shell strategy: The particle size of our SSE after modification primarily ranges from lum~3 um, with lots of smaller particles around 500 nm. Upon comparison with previous work on the coating of SSEparticles or the core-shell structure of SSE (as shown in Fig. 62 Table SI), our particle size and pressure values are slightly lower. Therefore, we anticipate that our SREI layer should be relatively intact based on those reports in previous studies.XPS element ratio on SSE pellet ofSREI coated LPSC pressing under 30MPa and 360 MPa: A very low pressing pressure of 30MPa was first employed to press the pellets, ensuring the preservation of the coating layer as the control group. Then we used a much higher pressure of 360 MPa to press another batch of SSE pellets for comparative analysis with the low-pressure batch, as depicted in Fig. 33. Notably, there is no discernible difference between the surfaces pressed with low and high pressure, confinning the relative integrity of the coating and SREI after pressing the particles into pellet, and no obvious fresh LPSC surface (no increase in P, S, Cl) is exposed after pressing.XPS imaging on SSE pellet of SREI coated LPSC pressing under 30MPa and 360 MPa:XPS imaging is an advanced technology that allows mapping the specific peak rather than just elements. Unlike EDS mapping, XPS mapping is a mapping technology that can get accurate information near the very surface. Here, we use it to map the F Is (C-F, P-F, LiF) with S 2p peaks on the surface of these pellets processed under 30MPa and 360MPa. Each mapping has a size of 480um x 480 um, including at least hundreds of particles. Areas without signal occur due to artifacts from probe effects, as evidenced by consistent patterns in the same positions across all samples. A comparison of SSE pellet processed under 30MPa and 360MPa revealed no increase in S signal intensity alongside a decrease in F signal intensity (Fig. 34-36). This suggests that 360MPa is an acceptable pressure to maintain the stability of the coating layer during particle pressing in this study. If there were a freshly exposed LPSC surface, we would expect to observe an area with a strong S signal but little or no F signal. However, such areas were not observed in any of the three samples. Additionally, the F signal (max value) consistently remained much stronger than the S signal. These characteristics are particularly pronounced in the DPF-LPSC pellet (Fig. 36), indicating the relatively robust properties of DPF-SREI compared to TFAA-SREI and TBAF-Coating.

[0045] Compatibility ofSREI-SSE with Li anode

[0046] The lithiophobicity of TBAF-Coating, TFAA-, and DPF-SREI (i.e., a solid- reactive electrophile interphase formed from DPF and the solid electrolyte) was evaluated by testing their contact angle with molten lithium (Fig. 37), which exhibited 1320(TBAF-LPSC), 148 ° (TFAA-LPSC), and 153 ° (DPF-LPSC). This highlights the pronounced lithiophobicity ofdense SREI over traditional porous coating and the higher lithiophobicity of inorganic components over organic components The high electron-blocking ability and high lithiophobicity of DPF- SREI substantially reduced SSE reduction and suppressed the lithium dendrite formation, as indicated by the high critical current density (CCD) and cycling stability in Li / / Li cells. To avoid the Li diffusivity being a limiting factor on the anode, 1% of Mg in Li (Lio.99Mgo.o1) was used to enhance the Li diffusivity and suppress the void formation, which exhibited a CCD > 0.9 mA cm'2with bare LPSC (Fig. 3A), agreeing with the reported value. Following the tendency on lithiophobicity, the TBAF-Coating on LPSC particles enhances the CCD of TBAF-LPSC to 1.4 mA cm'2with much larger overpotential (Fig. 3A), while the strong lithiophobic SREI increased the CCD to a very high value > 2.3 mA cm'2 / 2.3 mAh cm'2for TFAA-LPSC (Fig. 3B) and > 3.4 mA cm'2 / 3.4 mAh cm'2for all-inorganic DPF-LPSC (Fig. 3C). The cycling stability was also evaluated at a constant current for Ih charge / discharge. The cells using TBAF-LPSC cycled for less than 100 hours at 1 mA cm'2(Fig. 38A), while the cells using TFAA-LPSC maintained stable cycling for over 800 hours at 1 mA cm'2 / I mAh cm'2(Fig. 38B). Unless otherwise stated explicitly, all cycling stability referred to herein means measuring cycling stability at a constant current of 1 mA cm'2 / 1 mAh cm2) The all-inorganic LiF-rich DPF-SREI can further allow the DPF-LPSC to deliver stable cycling at 1.6 mA cm'2for over 1200h (Fig. 3D). DPF-LPSC’s higher stability over TFAA-LPSC was also confirmed by the less interface resistance increase in Electrochemical Impedance Spectroscopy (EIS) (Fig. 39). DPF-LPSC can stably charge / discharge even after increasing the current to 3 mA cm'2(Fig. 40). The Li / SSE interface study with SEM and EDS reveal that Li / DPF-LPSC exhibited uniform and flat morphology (Fig. 41A-B) with a F and O enriched Li / DPF-LPSC interface (Fig. 42), distinct from Li / bare-LPSC interface that are not in intimate contact after cycling with lithium dendrite observed inside the SSE bulk (Fig. 41C-D).

[0047] It is believed that the high interfacial energy of lithiophobic DPF-LPSC with Li promotes the Li planar plating along the Li / DPF-LPSC interface but suppresses the vertical Li dendrite growth into DPF-LPSC. During the Li deposition test, a very dense and uniform crosssection and flat surface of the deposited Li was observed (Fig. 43). As a result of this high electrochemical stability during Li deposition, the Li / DPF-LPSC / Li deliver a very high critical capacity of more than 36 mAh cm'2at 0.45 mA cm'2without short (Fig. 3E), while the Li / bare- LPSC / Li cells can only discharge to 12.3 mAh cm'2before shorting (Fig. 44).

[0048] By suppressing SSE reduction and Li dendrite growth, DPF-LPSC enhances Li reversibility significantly at anode. To reduce contact issues with the stainless steel (SS), the Li / DPF-LPSC / Li cells underwent 5 cycles with capacity control, followed by complete Listripping to form Li / DPF-LPSC / Mg@SS cells (testing protocol in Fig. 45). After these activation cycles, the Li CE was measured, and the Li CE reached 99.5% within 40 cycles (Fig. 3F (red)), with an average CE -99.7% from 200 cycles to 1000 cycles (charge / discharge profile in Fig. 46). In contrast, with the same activated Li / LPSC / Mg@SS cell, pristine LPSC achieved -97% CE but shorted quickly (Fig. 3F, blue). Without the pre-cycling activation, DPF-LPSC still reaches 99.5% CE after 200 cycles (Fig. 47) in Li / LPSC / Mg@Ni cells. Due to the reduction of lithiophobic SREI in the first cycle, the initial CE (ICE) (62.3%) of DPF-LPSC is only slightly higher than that of bare LPSC (60.3%) (Fig. 64 Table S3), but the ICE could reach a high value of 84% at an increased initial capacity of 2.0 mAh cm'2(Fig. 47). These results highlight the LiF-LixPyOzFi SREI’ s ability to reduce SSE decomposition and suppress Li dendrite, making SREI-LPSC promising for high- loading, long-life ASSLMB applications.

[0049] Performance ofSREI-SSE in ASSLMBs

[0050] Sulfide-based SSEs are oxidized at a low potential, making them electrochemically incompatible with a typical 4 V cathode, and the low compatibility with lithium anode limits their performance at high rates and high loading. Due to the small interface resistance and high stability of DPF-SREI, it was observed that a high-rate performance was delivered in the NCA / DPF- LPSC / Li with a 4 2 V cut-off voltage at 30 °C and 2.5 MPa. At a rate of 0.1 C, the full cell achieved a high reversible capacity of 160.3 mAh g (NCA)'1. At higher rates (0.3, 0.5, 1.0, and 2.0 C), the cell maintained capacities of 139, 129, 109, and 76 mAh g'1, respectively (Fig. 4A and Fig. 48), with full recovery when returning to 1 C. Notably, at a high rate of 2 C (2.6 mA cm'2), the cell exhibited stable cycling for over 4500 cycles with a very high capacity retention of 90% (Fig. 4B).

[0051] A high loading requires high stability at both cathode and Li anode, the NCA / / Li with pristine LPSC faded very quickly at a high loading of 3.5 mAh cm'2, with short circuits occurring quickly (Fig. 4C) and visible dark spots inside SSE (Fig. 49A). However, theNCA / DPF- LPSC / Li cell exhibited stable cycling at 0.2 C for over 370 cycles with 75% capacity retention (Fig. 4C), and showing no signal of lithium dendrite (Fig. 49B). The voltage profile is shown in Fig. 50, with an average full cell CE achieving > 99.9% after 5 cycles due to high stability at both high-voltage cathode and Li anode. Even at a very high loading of 7.1 mAh cm'2, the full cell maintains stability for over 600 cycles (-10,000 h), with CE quickly reaching 99.9% (Fig. 4D). This excellent endurance in cycle life, coupled with its high-rate charge / discharge capabilities at room temperature and low pressure, represents a breakthrough (Fig. 64 Table S4) for practical applications of ASSLMB.

[0052] The Universality of Electrophile Reduction Strategy

[0053] The electrochemical reduction of reductive-electrophile agents provides a general solution for materials protection, such as cathode or anode materials as well as solid-state electrolytes (SSE). The strong electrophilicity and high reduction potential of reductive- electrophile agents, such as TFAA and DPF, successfully established SREI on the cathode such as NCA powder (e g., DPF-NCA) by the same method, which substantially enhanced cycling stability and the operating voltage of ASSLMB.

[0054] Characterization via SEM revealed DPF-NCA showed the same morphology and structure as pristine NCA (Fig. 51-52) but featured a uniform distribution of F / P / O elements on particle surface (Fig. 53). The TEM images (Fig. 5A and Fig. 54) and element mapping (Fig. 55) of DPF-NCA particles indicated that these SREI are very thin (5-10 nm) and uniform Magnified images of DPF-SREI on DPF-NCA (Fig. 5B) indicated a highly amorphous feature, XPS confirmed strong F, O, and P signals on the surface of DPF-NCA (Fig. 5C, Fig. 56), with minimal Ni and Co signals which increased after sputtering. Similar to SREI on SSE, it is also composed primarily of LiF-LixPyOzFi. These agreed well with the observation of SREI on SSE particles, indicating the high consistency and applicability of methods of the disclosure.

[0055] The DPF-SREI on the cathode can effectively inhibit deterioration (e.g., formation of cracks) and O2 loss of the cathode, because LiF and I.iiPCh are excellent interphase components for high-voltage cathodes. To evaluate DPF-SREI on cathodes, bare LPSC was used rather than DPF-LPSC in the composite cathode (e g., DPF-NCA with LPSC). The high-voltage stability of the DPF-NCA cathode was evaluated by monitoring the leakage current when holding the [DPF- NCA with LPSC] / LPSC / Li cell at 4.3 V, where the cell with DPF-NCA exhibited a much lower current than that using pristine NCA (Fig. 57). This aligns well with the less interphase resistance increase in the cells with DPF-NCA than that with pure NCA (Fig. 58). The cycling stability of [DPF-NCA with LPSC] / DPF-LPSC / Li full cells was also evaluated, and the charge-discharge curve was obtained (Fig. 59), where a slightly higher cell polarization was observed because the DPF-SREI acts as an electron blocking layer to reduce the electron conduction between cathode (lower electronic conductivity of composite cathode ~ 1.07xl0'4S cm'1, Fig. 60). Due to the activation of LiF-LixPyOzFi on DPF-NCA, the discharge capacity was reduced in the first cycle, but it recovered in the second cycle. The full cells with an area capacity of 2.6 mAh cm'2exhibited excellent durability, as indicated by stable cycles exceeding 2,000 cycles at 0.2 C with an excellent capacity retention of 70% at 1 ,200th cycle (Fig. 5D). This is because the DPF-SREI on the cathode not only prevents the side reaction of LPSC but also protects the cathode itself. Even at a low rateof 0.2 C, the average CE can reach >99.96%, indicating the fading on the cathode is effectively halted by the DPF-SREI (Fig 5D). Despite the incompatibility of pristine sulfide-based SSEs with typical 4 V cathode, the DPF-NCA extends the operating voltage of ASSLMB to 4.5 V with a high average CE >99.94%, with 79% capacity retention after 400 cycles (Fig. 5E). With high consistency, DPF-LiNio sMno iCoo 1O2 (DPF-NMC811) also facilitated stable cycling of [DPF- NMC811 with LPSC] / DPF-LPSC / Li at 4.4 V with average CE >99.93% and 82.5% capacity retention after 350 cycles (Fig. 61). The broad applicability of methods of the disclosure allow their applicability in various metal-nucleophile materials (e.g., SSE or electrodes based on Li- sulfide, Li-oxide, Li-Si, and other metal -based (e g., Na-, K-) materials).

[0056] As can be seen, the present disclosure provides a breakthrough in the interphase designation through the introduction of a number of reductive electrophile agents that can gain electrons and metal cations from metal-nucleophile materials to form SREI. By designing and / or using appropriate reductive-electrophile agents, a highly lithiophobic and electron-blocking allinorganic LiF-LixPyOzF SREI can be produced on the surface of sulfide-SSEs to significantly improve its electrochemical stability at both cathode and anode. Notably, SREI-protected ASSLMBs have shown outstanding durability, delivering 4500 cycles at a moderate loading of 1.3 mAh cm'2and 600 cycles even at a high loading of 7.1 mAh cm'2. To prove its applicability to other solid-state batteries, this SREI was also applied to metal oxide cathodes, which extend the operating voltage. Accordingly, REs and methods of the disclosure are applicable to protecting a wide range of materials, thereby providing applications in batteries as well as other electrochemical materials and devices.

[0057] Additional objects, advantages, and novel features of this disclosure will become apparent to those skilled in the art upon examination of the following examples thereof, which are not intended to be limiting. In the Examples, procedures that are constructively reduced to practice are described in the present tense, and procedures that have been carried out in the laboratory are set forth in the past tense.EXAMPLES

[0058] Materials and Methods

[0059] Materials and Preparation of Electrolytes : Reagents tetrabutylammonium fluoride(TBAF) solution (1.0M in THF) and trifluoroacetic anhydride (TFAA) (>99%) were purchased from Sigma-Aldrich. Diphosphoryl fluoride (DPF) was prepared by the reaction between difluorophosphoric acid and phosphoric anhydride. Difluorophosphoric acid (1.0 mol) and P4O10(0.25 mol) were under gentle reflux for 1 hour and the mixture was then distilled. The fraction boiling below 75 °C was collected and purified by fractional distillation. The product has a boiling point of ~72 °C.19F-, and31P- spectra were recorded at 25 °C on a Bruker 400 MHz high resolution spectrometers with DMSO-de as deuterated solvents. Dilute including Hexane (>99%, boiling point 69 °C), 1 ,2-Dimethoxy ethane (DME, 99.9%, inhibitor-free, boiling point 85 °C) were bought from Sigma-Aldrich and dried by molecular sieves overnight.

[0060] The Lis.5PS4 sCli.s (LPSC) electrolyte was prepared by milling a mixture of U2S, P2S5, and LiCl in a stoichiometric ratio followed by annealing at 550 °C for 4h.

[0061] SREI coated SSE and cathode (TBAF-LPSC, TFAA-LPSC, DPF-LPSC, DPF-NCA,DPF-NMC811) : All the fabrication processes and battery assembling, were in an Ar-filled glovebox with H2O content <0.1 ppm to avoid moisture in the air. The coating reagent was diluted with hexane to obtain a solution (22-27 mg / mL). Because the THF solution of tetrabutylammonium fluoride is immiscible in hexane, 100 mL of 1.0 M tetrabutylammonium fluoride in THF solution was diluted with 900 mL of DME. A solution of TFAA was prepared by mixing tri fluoroacetic anhydride with 1 mL hexane. A solution of DPF was prepared by mixing diphosphoryl fluoride with 0.94 mL of hexane and 0.06 mL of DME as a co-solvent.

[0062] LPSC particles were hand-milled with a coating solution (e g., TBAF solution, TFAA solution, or DPF solution). The weight ratio of coating agent (e g., TBAF, TFAA, or DPF) to LPSC particles was around 1.4 wt%. During the hand-milling processing, the coating agent reacted and the solvent evaporated quickly The resulting coated particles were dried to yield white / gray color solids, and there was no color change compared with the pristine LPSC particles. The particle size primarily ranges from 500 nm to 3 pm. The coated powder was further dried in vacuum before using. The DPF-NCA powder was obtained with the same process as the DPF- LPSC

[0063] Mg-doped Li (Lio.99Mgo.o1) was used to mitigate the contact loss. Briefly, Mg- doped Li was prepared by melting Li and Mg at 400 °C and removing the impurities. The atomic ratio of Mg in Li was around 1%.

[0064] Cell assembling

[0065] Li / / Li symmetric cell was assembled as follows. Firstly, 130-150 mg of LPSC / treated LPSC powder was pressed at 360 MPs to form a pellet. Li foil was attached to bothsides of the LPSC pellets and the resulting stack was pressed at 2.5 MPa to produce a two-electrode Li||Li symmetric cell.

[0066] A composite cathode powder was prepared by mixing an active material (NCA or DPF-NCA, DPF-NMC811), and SSE (LPSC or DPF-LPSC) in a weight ratio of 75 : 25. Two- electrode full cell was assembled as follows. Firstly, 130 mg of LPSC electrolyte was pressed at 120 MPa to form an electrolyte pellet. The composite cathode powder was spread on one side of the electrolyte pellet and pressed at 360 MPa, after which Li( 1 % Mg) foil was attached to the other side of the electrolyte pellet and pressed at 2.5 MPa.

[0067] For pre-cycling test: the Li@SS / LPSC / Li@SS cells (where Li@SS refers to lithium interfaced with stainless steel) were first charged / discharged for 5 cycles using capacity control, and then all the lithium on one side of the cells was removed and the charge / discharge cycles were repeated to ensure Li was completely removed to form Li / LPSC / SS cell. After these activation cycles, the Li CE was measured.

[0068] Three current collectors were used: Stainless steel (stainless-steel cell mold itself acts as current collector): full cell test, CCD test, and Li / DPF-LPSC / SS test. Copper: Copper was chosen for its ease of cutting among all anode current collectors to ensure intact cross-sections during sample preparation. Mg@Ni: Since some of the copper will react with sulfide-based SSE, Ni was used as the current collector for the Li / DPF-LPSC / Ni CE test, a ~50 nm of Mg was deposited to make good contact between SSE and the current collector.

[0069] Characterizations

[0070] X-ray powder diffraction (XRD) was performed on D8 Advance with LynxEye and SolX (Bruker, 31 USA) using Cu Ka radiation. The morphologies and element distribution were obtained on a field-emission scanning electron microscope (SEM, SU-70, Hitachi) equipped with an energy dispersive spectroscopy (EDS). The distribution of different elements on the surface of SREI-protected LPSC was analyzed on Ga+focused ion beam (FIB) / scanning electron microscope (Tescan GAIA3) equipped with time-of-flight secondary ion mass spectroscope (ToF-SIMS). For X-ray photoelectron spectroscopy (XPS) measurements, all the particles were pressed into pellets before XPS tests. The data of LPSC SSE were collected with Kratos Axis 165. The data of the NCA cathode were acquired with a K-alpha Thermo system using Al Ka radiation (hv = 1486.6 eV). The tests were conducted under ultra-high vacuum (<1xl O'12atm) with a measured spot size of 500 pm in diameter. A flood gun was used during the analysis to compensate for the charging of the samples. The samples were transferred from the argon glove box into the XPS chamber witha vacuum transfer vessel to avoid exposure to air. Sputter depth profiling was carried out using an Ar+ion gun with ion energy at 200 eV with a roster size of 2 mm. The angle between the surface normal and the ion gun beam was 0°. The binding energy was corrected based on the Cis spectrum, assigning C-C to 284.8 eV. Relative atomic concentrations were calculated by integrating respective peaks with a Shirley background, using The CasaXPS software, accounting for respective atomic sensitivity factors.

[0071] TEM specimens were prepared by directly dropping the LPSC or cathode powder onto a Cu grid. Microstructures and electronic excitations were examined in a JEOL-2100F (scanning) transmission electron microscope [(S)TEM] equipped with a Gatan Image Filter (GIF, a Tri diem 863 model), operating at 200 kV. The energy resolution was 0.8 eV throughout the (S)TEM-EELS spectrum-imaging (SI) (STEM-EELS-SI) experiments. The contribution of individual reference spectra to an experimental spectrum could then be calculated through the multiple linear least square (MLLS) fitting using the DigitalMicrograph software package (Gatan Microscopy Suite, Gatan- AMETEK).|0072| Computational details

[0073] DFT calculations were carried out using the Vienna ab initio simulation package (VASP) 6.3 code. Total energies and electron densities were computed with the Perdew-Burke-Emzerhof (PBE) exchange-correlation functional A plane-wave basis set was used with a kinetic energy cut-offs of 520 was used for bulk and surface calculations. Core electrons were treated with the projector-augmented wave (PAW) method.

[0074] LPSC surface slabs were constructed by cleaving the optimized bulk structures along low-index facets with different exposed surface atoms. To reconcile the loss of the symmetricity of LPSC during cleavage, we generated additional slabs by moving atoms from the outer-face sites to their rotation and axis-symmetric equivalent positions on the opposite side of the slab. Periodic slab images were separated in the z-direction (perpendicular to the surface) by 15 °A of vacuum. The surface energy was calculated as:where E slab) is the total energy of low index surface slab with different exposed surface atoms. E(bulk) is the energy of bulk LiePSsCl phase, n is the number of bulk LPSC unit in surface slab. A is the surface area of slab

[0075] The molecular structures of liquid-phase solvents were first constructed and relaxed from a classical molecular dynamics using OPLS-AA force field in Large-scale Atomic / Molecular Massively Parallel Simulator (http: / / lammps.sandia.gov.) package. Then, the structure was optimized with the Perdew-Burke-Ernzerhof (GGA-PBE) functional until the force tolerance was lower than 104eV / A and the energy difference was lower than 104eV.

[0076] The LPSC / liquid slab model was built up by placing the liquid on the energetically stable LPSC surface. Ab Initio Molecular Dynamics (AIMD) simulations were performed applying an NVT ensemble with a time step of 1 fs. The velocities were rescaled every 20 MD steps to readjust the target temperature to equilibrium. A Nose-Hoover thermostat with a Nosemass parameter of 1 was used to control the temperature. Atomic charge analysis was carried out by means of the Bader approach implemented in the Bader code The VASPKTT code was used for postprocessing the VASP calculated results.

[0077] The frontier molecular orbital energies of solvent molecules and LPSC crystal were obtained from Quantum chemistry calculations using Gaussianl6 quantum chemical program. For solvent molecules calculation, the density functional is B3LYP. PCM solvation model with the parameter of heptane was used for TFAA and DPF molecules while the parameter of acetone was used for other molecules. For LPSC crystal, periodic boundary condition with PBE functional was adopted. The basis sets are 6-31+g(d,p).

[0078] The foregoing discussion of the disclosure has been presented for purposes of illustration and description The foregoing is not intended to limit the disclosure to the form or forms disclosed herein. Although the description of the disclosure has included description of one or more embodiments and certain variations and modifications, other variations and modifications are within the scope of the disclosure, e.g., as may be within the skill and knowledge of those in the art, after understanding the present disclosure. It is intended to obtain rights which include alternative embodiments to the extent permitted, including alternate, interchangeable and / or equivalent structures, functions, ranges or steps to those claimed, whether or not such alternate, interchangeable and / or equivalent structures, functions, ranges or steps are disclosed herein, and without intending to publicly dedicate any patentable subject matter. All references cited herein are incorporated by reference in their entirety.References:1. Wang, F. et al. Chemical distribution and bonding of lithium in intercalated graphite: Identification with optimized electron energy loss spectroscopy. ACS Nemo 5, 1190—1197 (2011).2. Jeanguillaume, C. & Colliex, C. Spectrum-image: the next step in EELS digital acquisition and processing. Ultramicroscopy 28, 252-257 (1989).3. Egerton, R F. Electron Energy-Loss Spectroscopy in the Electron Microscope. (Springer Science & Business Media, 2011).4. Liou, S.-C., Oleshko, V. P., Kuo, W. C.-H., Yang, T.-J. & Shu, G.-J. Investigation of the excitations of plasmons and surface exciton polaritons in monoclinic gadolinium sesquioxide by electron energy-loss spectroscopy and plasmon spectroscopic imaging. RSC Adv 12, 10345- 10354 (2022).5. Boniface, M. et al. Nanoscale chemical evolution of silicon negative electrodes characterized by low-loss STEM-EELS. Nano Lett 16, 7381-7388 (2016).6. Castro, F. C. & Dravid, V. P. Characterization of Lithium Ion Battery Materials with Valence Electron Energy-Loss Spectroscopy. Microscopy and Microanalysis 24, 214-220 (2018).7. Boniface, M. et al. Low-loss STEM-EELS analysis of beam-sensitive lithium-ion negative electrodes, in European Microscopy Congress 2016: Proceedings 802-803 (Wiley Online Library, 2016).8. Wang, F. et al. Conversion reaction mechanisms in lithium ion batteries: study of the binary metal fluoride electrodes. J A m Chem Soc 133, 18828-18836 (201 1).9. Song, R. el al. Metastable decomposition realizing dendrite-free solid-state Li metal batteries. Adv Energy: Mater 13, 2203631 (2023).10. Zhang, X. et al. Spontaneous gas-solid reaction on sulfide electrolytes for high-performance all-solid-state batteries. Energy Environ Sci 16, 1091-1099 (2023).11. Hood, Z. D. et al. Multifunctional Coatings on Sulfide-Based Solid Electrolyte Powders with Enhanced Processability, Stability, and Performance for Solid-State Batteries. Advanced Materials 35, 2300673 (2023).12. Ye, L. & Li, X. A dynamic stability design strategy for lithium metal solid state batteries. Nature 593, 218-222 (2021).13. Lee, Y.-G. et al. High-energy long-cycling all-solid-state lithium metal batteries enabled by silver-carbon composite anodes. Nat Energ ’ 5, 299-308 (2020).14. Tan, D. H. S. et al. Carbon-free high-loading silicon anodes enabled by sulfide solid electrolytes. Science (1979) 373, 1494-1499 (2021).15. Zhou, L. et al. High areal capacity, long cycle life 4 V ceramic all-solid-state Li-ion batteries enabled by chloride solid electrolytes. Nat Energy 7, 83-93 (2022).16. Yin, Y.-C. et al. A LaC13-based lithium superionic conductor compatible with lithium metal. Nature 616, 77-83 (2023).17. Cheng, D. et al. A free-standing lithium phosphorus oxynitride thin film electrolyte promotes uniformly dense lithium metal deposition with no external pressure. Nat Nanotechnol 18, 1448- 1455 (2023).

Claims

What is Claimed is:

1. An all-solid-state battery comprising: a solid-state electrolyte; a cathode having an interior surface that is proximal to said solid-state electrolyte; and an anode having an interior surface that is proximal to said solid-state electrolyte, wherein at least one of said cathode, said anode, and said solid-state electrolyte is coated with a reductive-electrophile agent such that an interface between interior surface of said cathode, said anode, or both and said solid-state electrolyte comprises said coated reductive-electrophile agent.

2. The all-solid-state battery of claim 1, wherein said solid-state electrolyte comprises solid-state electrolyte material particles are coated with said reductive-electrophile agent.

3. The all-solid-state battery of claim 1, wherein said interior surface of said anode is coated with said reductive-electrophile agent.

4. The all-solid-state battery of claim 1 , wherein said interior surface of said cathode is coated with said reductive-electrophile agent.

5. The all-solid-state battery of claim 1, wherein said reductive-electrophile agent comprises a Lewis acid, an anhydride, an acid halide, a compound having an electron-deficient atom, or a mixture thereof.

6. The all-solid-state battery of claim 1 having a loading of at least about 0.5 mAh / cm2 , typically at least about 1.5 mAh / cm2 , often at least about 3.5 mAh / cm2 , more often at least about 5 mAh / cm2 , and most often at least about 7 mAh / cm2 at 30 °C and 2.5 MPa.

7. The all-solid-state battery of claim 1 having a life cycle of at least about 350 cycles, typically at least about 650 cycles, often at least about 1,000 cycles, more often at least about 2,000 cycles, and most often at least about 4,500 cycles.

8. A composition comprising solid-state electrolyte comprising solid electrolyte material with a coating formed by a reductive-electrophile agent.

9. The composition of claim 8, wherein an average particle size (Dso) of said solid electrolyte material is about 500 pm or less, typically about 250 pm or less, often about 200 pm or less, more often about 100 pm or less, still more often about 50 pm or less, yet more often about 25 pm or less, still more often about 10 pm or less, and most often about 1 pm or less.

10. The composition of claim 8, wherein said reductive-electrophile agent comprises acid anhydride, acid halide, or a combination thereof.

11. A solid-state metal battery comprising: a cathode layer; an anode layer; and a solid-state electrolyte layer located between said cathode and said anode, wherein said solid-state electrolyte comprises solid electrolyte salt particles with a coating formed by reductive-electrophile agent.

12. The solid-state metal battery of claim 11, wherein said reductive-electrophile agent treated solid electrolyte material occupies substantially all of an interface between said anode and said solid-state electrolyte.

13. The solid-state metal battery of claim 11, wherein said reductive-electrophile agent treated solid electrolyte salt particles occupies substantially all of interfaces between said cathode and said solid-state electrolyte.

14. The solid-state metal battery of claim 11, wherein is said solid-state metal battery is an all-solid-state lithium metal battery.

15. The solid-state metal battery of claim 11, wherein said solid-state metal battery is an all-solid-state lithium metal battery with high nickel metal oxide cathode.

16. The solid-state metal battery of claim 11, wherein said anode comprises lithium, silicon, graphite, or a combination thereof17. The solid-state metal battery of claim 16, wherein said cathode is a metal-oxide cathode.

18. The solid-state metal battery of claim 11 having a cycling Coulombic efficiency of at least about 99% after 500 cycles at 30 °C and 2.5 MPa.

19. The solid-state metal battery of claim 1 1 having a cycle life of at least about 500, hours (typically at least about 1,000 hours, often at least about 4,000 hours, more often at least about 10,000 hours, and most often at least about 15,000 hours at 30 °C and 2.5 MPa.

20. The solid-state metal battery of claim 11 having a loading of at least about 0.5 mAh / cm2, typically at least about 1.5 mAh / cm2, often at least about 3.5 mAh / cm2, more often at least about 5 mAh / cm2cycles, and most often at least about 7 mAh / cm2at 30 °C and 2.5 MPa.

21. A method for preventing or reducing solid-state electrolyte reduction in a solid- state battery comprising a solid-state electrolyte that comprises a solid electrolyte material, said method comprising coating said solid electrolyte material with a reductive-electrophile agent.

22. The method of claim 21, wherein coating of said solid electrolyte material with a reductive-electrophile agent reduces the rate of solid-state electrolyte reduction by at least 50% (typically by at least 75%, often by at least 80%, more often by at least 90%, and most often by at least 95%) compared to the same solid electrolyte material in the absence of said coating formed by reductive-electrophile agent.

23. A method for preventing or reducing lithium dendrite formation in an all-solid- state lithium battery comprising a solid-state electrolyte that comprises solid electrolyte material, said method comprising encapsulating said solid electrolyte material with a coating formed by reductive-electrophile agent.

24. The method of claim 23, wherein said solid electrolyte material with a coating formed by reductive-electrophile agent reduces the rate lithium dendrite formation by at least 50% (typically by at least 60%, often by at least 70%, more often by at least 80%, and most often by at least 95%) at 7 mAh cm'2loading compared to the same solid electrolyte material in the absence of said coating formed by reductive-electrophile agent.

25. A method for increasing an efficiency and / or useful life of an electrode in a solid- state metal battery comprising a solid-state electrolyte that comprises solid electrolyte material, said method comprising producing a coating on said solid electrolyte material by contacting said solid electrolyte material with a reductive-electrophile agent, thereby increasing the efficiency and / or the life of said electrode compared to a similar battery in the absence of said coating formed by said reductive-electrophile agent.

26. The method of claim 25, wherein said all-solid state metal battery is an all-solid- state lithium battery.

27. The method of claim 25, wherein said coating increases the useful life (i.e., having capacity retention of at least 70-80%) of said electrode by at least about 100% (typically by at least about 200%, often by at least about 500%, more often by at least about 1,000%, and most often by at least about 2,000%, alternatively by at least about 100 hours or more, typically by at least 200 hours or more, often at least about 500 hours or more, and most often by at least 1,000 hours or more) compared to the same solid electrolyte material in the absence of said coating.

28. A method for reducing a detrimental effect of solid-state electrolyte in an all-solid- state battery (ASSB), wherein said solid-state electrolyte comprises solid electrolyte salt particles, said method comprising encapsulating said solid electrolyte salt particles with a reductive- electrophile agent, thereby reducing the detrimental effect of said solid-state electrolyte in said ASSB compared to a similar battery in the absence of said reductive-electrophile agent.

29. The method of claim 28, wherein said ASSB is a lithium battery.

30. The method of claim 29, wherein said detrimental effect comprises said solid-state electrolyte (SSE) low-voltage reduction, high-voltage decomposition of said SSE, lithium dendrite growth, or a combination thereof.

31. An all-solid-state lithium battery (ASSLB) comprising: a lithium anode; a cathode; and a solid-state electrolyte, wherein said solid-state electrolyte comprises solid electrolyte salt particles with a coating formed by reductive-electrophile agent.

32. The ASSLB of claim 31, wherein said cathode comprises lithium nickel cobalt aluminum oxides (i.e., Li-NCA, LNCA, or NCA), or lithium metal oxide (e.g., LixNiyMnzCoiOj as well as doped with other metals).

33. The ASSLB of claim 31 having a life cycle of at least about 500 hours (typically at least about 1,000 hours, often at least about 4,000 hours, more often at least about 10,000 hours, and most often at least about 15,000 hours at 30 °C and 2.5 MPa.

34. The ASSLB of claim 31 having a loading of at least about 0.5 mAh / cm2, typically at least about 1.5 mAh / cm2, often at least about 3.5 mAh / cm2, more often at least about 5 mAh / cm2cycles, and most often at least about 7 mAh / cm2at 30 °C and 2.5 MPa.

35. The ASSLB of claim 31, wherein said cathode is a metal-oxide cathode36. The ASSLB of claim 35, wherein an average particle size (Dso) of said solid electrolyte salt particles is about 500 pm or less, typically about 250 pm or less, often about 200 pm or less, more often about 100 pm or less, still more often about 50 pm or less, yet more often about 25 pm or less, still more often about 10 pm or less, and most often about 1 pm or less.

37. The ASSLB of claim 31, wherein said reductive-electrophile agent comprises acid anhydride, acid halide, Lewis acid, or a combination thereof.

38. The ASSLB of claim 37, wherein said reductive-electrophile agent comprises diphosphoryl fluoride, trifluoroacetic anhydride, or a combination thereof39. A method for reducing a detrimental effect of a battery material (battery material comprising a solid-state electrolyte material, a cathode material, an anode material, or a combination thereof) in an all-solid-state lithium battery (ASSLB), said method comprising forming a coating of an electron blocking and / or lithiophobic outer layer on said battery material using a reductive-electrophile agent.

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