All-solid-state lithium secondary battery and method of preparing the same

Abstract

Embodiments pertain to an interlayer suitable for use in solid-state batteries. Such interlayers generally include: (1) a plurality of carbon nanomaterials; and (2) a plurality of metallic nanoparticles uniformly dispersed on the carbon nanomaterials. The interlayers also include a percolating network operational for regulating ion flux through the interlayer. Additional embodiments pertain to solid- state batteries that include such interlayers, methods of forming such interlayers, and methods of forming solid-state batteries that include the interlayers.

Description

TITLEALL-SOLID-STATE LITHIUM SECONDARY BATTERY AND METHOD OF PREPARING THE SAMESTATEMENT REGARDING FEDERALLY SPONSORED RESEARCH

[0001] This invention was made with government support under DE-EE0008864 awarded by the U.S. Department of Energy. The government has certain rights in the invention.CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 533,518, filed on August 18, 2023. The entirety of the aforementioned application is incorporated herein by reference.BACKGROUND

[0003] All-solid-state lithium metal batteries are projected to offer one of the highest specific energy among rechargeable batteries, positioning them as a front-runner for electric vehicle batteries. To increase cell-level energy density, a lithium metal anode (3860 mAh g-1and -3.04 V vs. standard hydrogen potential) outperforms a conventional graphite anode. Metal-electrolyte contact, on the other hand, is a great challenge in all- solid- state batteries. Intrinsic surface roughness of both the lithium metal and the electrolyte results in poor interfacial contact, which acts as a precursor for lithium dendritic growth. The volumetric change of the lithium metal anode during stripping produces voids, which further deteriorates the metal-electrolyte contact.

[0004] An interlayer strategy has been introduced between solid electrolyte and lithium metal to buffer mechanical strain, promote better interfacial contact, alleviate chemical instability, improve stripping / plating homogeneity, and therefore suppress lithium dendrite formation and propagation. These interlayers are often composed of carbon-based materials that conduct both Li+ions and electrons and have certain lithium storage capacity (e.g., silver-carbon composites and vertically aligned carbon tube arrays). While some of these interlayers may require sophisticated fabrication techniques such as chemical vapor deposition, sputtering, etching, and atomic layer deposition, others are easier to be scalable. For example, prior studies have employed a screen-printed silver-carbon (Ag- C) composite as an interlayer between the anode current collector and the electrolyte, allowing over 1000 cycles at a high current density (6.8 mA cm2) at 60 °C while preventing dendrite growth and maintaining high Coulombic efficiency.

[0005] Current interlayers have numerous limitations, such as the need for elevated temperature to achieve high current density and the requirement of external pressure to assist Li stripping and plating. These challenges stem from the limited Li-ion conductivity and diffusivity within the interlayer. Numerous embodiments of the present disclosure aim to address the aforementioned limitations. For instance, with a faster Li transport capability in accordance with various embodiments of the present disclosure, solid-state batteries can operate at ambient temperatures as well as at low stack pressures of 0.5 MPa.SUMMARY

[0006] Embodiments of the present disclosure pertain to an interlayer suitable for use in solid-state batteries. In some embodiments, the interlayer includes: (1) a plurality of carbon nanomaterials; and (2) a plurality of metallic nanoparticles uniformly dispersed on the carbon nanomaterials. In some embodiments, the interlayer includes a percolating network operational for regulating ion flux through the interlayer. In some embodiments, the metallic nanoparticles form a coating on the carbon nanomaterials without aggregating.

[0007] Additional embodiments of the present disclosure pertain to solid-state batteries that include the interlayers of the present disclosure. In some embodiments, the solid-state batteries of the present disclosure may include: (1) a cathode; a (2) a solid electrolyte; (3) a current collector; and (4) an interlayer positioned between the solid electrolyte and the current collector. In some embodiments, the solid-state battery also includes an anode positioned between the current collector and the interlayer. In some embodiments, the solid-state batteries of the present disclosure include anode-free solid-state batteries that include: (1 ) a cathode; (2) a solid electrolyte in contact with the cathode; (3) a current collector; and (4) an interlayer positioned between the current collector and the solid electrolyte.

[0008] Additional embodiments of the present disclosure pertain to methods of forming the interlayers of the present disclosure. In some embodiments, the methods of the present disclosure include associating a plurality of metallic nanoparticles with a plurality of carbon nanomaterials to form a uniform metallic nanoparticle-carbon nanomaterial composite. In some embodiments, the methods of the present disclosure also include a step of incorporating a binder to form a film structure for scalable production.

[0009] Further embodiments of the present disclosure pertain to methods of forming solid-state batteries. In some embodiments, such methods include: (1) attaching an interlayer of the present disclosure to a solid electrolyte, where the solid electrolyte is attached to a cathode; and (2) attaching an anode to the interlayer. In some embodiments, the solid-state battery formation methods of the present disclosure include: (1) attaching an interlayer to a surface of an anode to form an anodeinterlayer assembly; and (2) attaching the anode-interlayer assembly to a solid electrolyte-cathode assembly to form an anode-interlayer-solid-electrolyte-cathode assembly.BRIEF DESCRIPTION OF THE DRAWINGS

[0010] FIGS. 1A-1C illustrate three different scenarios of Li growth in all-solid-state batteries. FIG. 1A shows Li growth between electrolyte and interlayer leads to short circuiting. FIG. IB shows Li growth within the interlayer and poor particle-particle adhesion results in interlayer mechanical cracking. FIG. 1C shows Li growth between interlayer and lithium metal anode (ideal). The scale bar is 5 pm. room FIGS, ID and IE provide various illustrations of solid-state batteries of the present disclosure.

[0012] FIGS. 2A-2J show morphology of silver-carbon complexes (Ag-C). FIGS. 2A-2B show zoom-out (FIG. 2A) and zoom-in (FIG. 2B) images of Ag-C with Ag (50-60 nm). The dark particle is silver and light particles are carbon. FIG. 2C shows a schematic of Li transport in Ag-C with large Ag particles prepared by mechanical mixing. FIGS. 2D-2E show zoom-out (FIG. 2D) and zoom-in (FIG. 2E) images of Ag-C with nano-dispersed Ag (5-10 nm) bonded to carbon. FIG. 2F shows a schematic of Li transport in Ag-C with small Ag particles prepared by chemical precipitation. FIG. 2G shows an in-situ scanning electron microscope (SEM) image of Ag particles placed on a piece of Li metal, accompanied by a schematic showing the dissolution process of Ag into Li. FIGS. 2H-2J show Li transport properties in the Ag-C. The ionic conductivity (FIG. 2H) and electronic conductivity (FIG. 21) of tape-cast Ag-C and C are measured at different temperatures. FIG. 2J shows the Li diffusivity in Ag-C measured by galvanostatic intermittent titration technique (GITT).

[0013] FIGS. 3A-3E show the macroscopic distribution of Ag in Ag-C film. Shown are scanning electron micrographs of mechanically mixed (FIG. 3A) and chemically precipitated (FIG. 3B) Ag-C. The bright particles are Ag and dark background is C. FIG. 3C shows the Lacey mixing index of two Ag-C mixtures. Lacey index of 1.0 indicates homogeneous mixing and 0.0 indicates completesegregation. Chemically precipitated Ag-C exhibits significantly better homogeneity. FIG. 3D shows the particle area distribution of Ag in the mechanically-mixed Ag-C (FIG. 3A). FIG. 3E shows the particle area distribution of Ag in the chemically precipitated Ag-C (FIG. 3B).

[0014] FIGS. 4A-4I show the evolution of Ag-C interlayer during a cycling process. Shown are operando setup for cross-section imaging (FIG. 4A), voltage profile of full cells during resting (FIG. 4B), electrochemical impedance spectrum (EIS) of full cells after resting (FIG. 4C), voltage profiles of full cells during cycling, with mechanically mixed Ag-C (FIG. 4D) and chemically precipitated Ag-C (FIG. 4E). Also shown are schematics and operando cross-sectional SEM images of Ag-C interlayers in solid-state batteries with large Ag particles (50-60 nm) (FIG. 4F-4G) and small Ag particles (5-10 nm) (FIG. 4H-4I).

[0015] FIGSS. 5A-H summarize rate performance of full cells. FIG. 5A shows the voltage profile of a full cell with chemically precipitated Ag-C. FIG. 5B summarizes rate performance of all-solid- state batteries containing interlayers with different microstructures. FIG. 5C shows the differential voltage profile of all-solid-state batteries containing interlayers with different microstructures. FIG. 5D shows the longevity of a NMC | LiePSsCl | Ag-C (small Ag particle) | Li full cell cycled over 2500 cycles at 30 °C and 2.8 mA cm2(1 C rate). FIGS. 5E and 5F show the optical image and schematics of a pouch-type solid-state cell. FIGS. 5G and 5H show the voltage profile and cycling performance of a pouch-type solid-state cell with Ag-C (small Ag particle) operated at the pressure of 0.5 MPa.DETAILED DESCRIPTION

[0016] It is to be understood that both the foregoing general description and the following detailed description arc illustrative and explanatory, and arc not restrictive of the subject matter, as claimed. In this application, the use of the singular includes the plural, the word “a” or “an” means “at least one”, and the use of “or” means “and / or”, unless specifically stated otherwise. Furthermore, the use of the term “including”, as well as other forms, such as “includes” and “included”, is not limiting. Also, terms such as “element” or “component” encompass both elements or components comprising one unit and elements or components that include more than one unit unless specifically stated otherwise.

[0017] The section headings used herein are for organizational purposes and are not to be construed as limiting the subject matter described. All documents, or portions of documents, cited in thisapplication, including, but not limited to, patents, patent applications, articles, books, and treatises, are hereby expressly incorporated herein by reference in their entirety for any purpose. In the event that one or more of the incorporated literature and similar materials defines a term in a manner that contradicts the definition of that term in this application, this application controls.

[0018] All-solid-state lithium metal batteries (ASSLMBs) are projected to offer one of the highest specific energy among rechargeable batteries. To increase cell-level energy density, a lithium metal anode (3860 mAh g-1and -3.04 V vs. standard hydrogen potential) outperforms a conventional graphite anode.

[0019] Maintaining optimal Li-electrolyte contact without forming Li dendrite remains a great challenge in all- solid- state batteries. Intrinsic surface roughness of both the lithium metal and the electrolyte results in poor interfacial contact. The volumetric change of the lithium metal anode during stripping produces voids, which further deteriorates the metal-electrolyte contact.

[0020] An interlayer strategy has been reported by other groups between solid electrolyte and lithium metal to buffer mechanical strain, promote better interfacial contact, alleviate chemical instability, improve stripping / plating homogeneity, and therefore suppress lithium dendrite formation and propagation. For instance, it has been demonstrated that the use of mixed ionic-and-electronic conductor (MIEC) interlayer with silver-carbon (silver particle size 50-60 nm) enabled high energy (>900 Wh L ’). high current density (3.4 mA cm2) and long cycle life (>900 cycles) all- solid- state batteries at 60 °C.

[0021] For applications in the electric vehicle (EV) market, room-temperature operation (charge and discharge) is desirable. However, the aforementioned high-current-density charging occurs only at elevated temperatures (i.c., 60 °C).

[0022] To the best of Applicant’s knowledge, the minimum silver (Ag) particle size reported for this purpose is 38 nm. The particle size in existing work is comparable with that of carbon (50-60 nm), which does not provide a desirable Li-conducting percolation network. Furthermore, direct mixing of Ag nanoparticles and carbon powder may lead to strong agglomeration and further exacerbate the poor percolation.

[0023] Consequently, the Li-ion conductivity and diffusivity of directly mixed Ag-C powder does not meet the interlayer requirement for room-temperature operation of all-solid-state batteries. Numerous embodiments of the present disclosure aim to address the aforementioned limitations.

[0024] Solid-state battery interlayers

[0025] In some embodiments, the present disclosure pertains to an interlayer. In some embodiments, the interlayer is suitable for use in solid-state batteries. In some embodiments, the interlayer includes: (1) a plurality of carbon nanomaterials; and (2) a plurality of metallic nanoparticles uniformly dispersed on the carbon nanomaterials. In some embodiments, the interlayer includes a percolating network operational for regulating ion flux through the interlayer. In some embodiments, the metallic nanoparticles form a coating on the carbon nanomaterials without aggregating. As set forth in more detail herein, the interlayers of the present disclosure can have numerous embodiments.

[0026] Carbon nanomaterials

[0027] The interlayers of the present disclosure can include various carbon nanomaterials in various forms. In some embodiments, the carbon nanomaterials include nanometer- sized dimensions. In some embodiments, the nanometer-sized dimensions range from about 1 nm to about 1,000 nm. In some embodiments, the nanometer- sized dimensions range from about 1 nm to about 100 nm.

[0028] The carbon nanomaterials of the present disclosure can be made of various materials. For instance, in some embodiments, the carbon nanomaterials include, without limitation, carbon powder, carbon nanoparticles, amorphous carbon, porous carbon, carbon black, Ketjen Black, carbon nanotube, vapor- grown carbon nanofiber, oxidized carbon, or combinations thereof.

[0029] In some embodiments, the carbon nanomaterials include oxidized carbon. In some embodiments, the oxidized carbon includes oxygen-based surface groups. In some embodiments, the oxygen-based surface groups include, without limitation, hydroxyl surface groups, oxide surface groups, or combinations thereof.

[0030] In some embodiments, the carbon nanomatcrials of the present disclosure arc in the form of a substrate. In some embodiments, the carbon nanomaterial substrate has a Lacey mixing index greater than 70% as determined from a cross-section image of the carbon nanomaterial substrate material imaged at 50,000x magnification and segmented into 20 by 20 subsets. In some embodiments, the interlayer contains from about 10 wt% to about 90 wt% of the carbon nanomaterial substrate. In some embodiments, the interlayer contains from about 10 wt% to about 50 wt% of the carbon nanomaterial substrate. In some embodiments, the interlayer contains from about 10 wt% to about 40 wt% of the carbon nanomaterial substrate. In some embodiments, the interlayer contains from about 10 wt% to about 25 wt% of the carbon nanomaterial substrate.

[0031] Metallic nanoparticles

[0032] The interlayers of the present disclosure can include various metallic nanoparticles with various sizes. For instance, in some embodiments, the metallic nanoparticlcs include diameters of less than about 50 nm. In some embodiments, the metallic nanoparticles include diameters of less than about 40 nm. In some embodiments, the metallic nanoparticles include diameters of less than about 38 nm. In some embodiments, the metallic nanoparticles include diameters of less than about 30 nm. In some embodiments, the metallic nanoparticles include diameters of less than about 20 nm. In some embodiments, the metallic nanoparticles include diameters of less than about 15 nm. In some embodiments, the metallic nanoparticles include diameters between about 5 nm to about 10 nm. In some embodiments, the metallic nanoparticles include diameters between about 1 nm to about 5 nm.

[0033] In some embodiments, over 80% of the metallic nanoparticles have diameters below 50 nm. In some embodiments, over 99% of the metallic nanoparticles have diameters below 120 nm. In some embodiments, the metallic nanoparticles include average diameters about 5 times to about 10 times smaller than the average diameters of the carbon nanomaterials. In some embodiments, the metallic nanoparticles include average diameters of about 10 nm or less.

[0034] In some embodiments, the metallic nanoparticles are bonded to the surface of the carbon nanomaterials. In some embodiments, the metallic nanoparticles are chemically bonded to the surface of the carbon nanomaterials. In some embodiments, the metallic nanoparticles are chemically adsorbed on the surface of the carbon nanomaterials. In some embodiments, the metallic nanoparticles do not detach from the surface of the carbon nanomaterials during interlayer processing.

[0035] In some embodiments, the metallic nanoparticles are uniformly dispersed on the carbon nanomatcrials without aggregating. In some embodiments, the metallic nanoparticlcs arc in nonaggregated form.

[0036] In some embodiments, the metallic nanoparticles of the present disclosure further include a group of non-agglomerated primary particles and a group of agglomerated secondary particles. In some embodiments, 80% of the secondary particles have diameters below 50 nm. In some embodiments, over 99% of the secondary particles have diameters below 120 nm.

[0037] The metallic nanoparticles of the present disclosure can include various metals. For instance, in some embodiments, the metallic nanoparticles of the present disclosure include, without limitation,silver (Ag), copper (Cu), gold (Au), titanium (Ti), platinum (Pt), zinc (Zn), magnesium (Mg), iron (Fe), or combinations thereof.

[0038] In some embodiments, the metallic nanoparticlcs include silver (Ag) nanoparticlcs. In some embodiments, the Ag nanoparticles include average diameters from about 5 times to about 10 times smaller than the average diameters of the carbon nanomaterials.

[0039] Interlayer structures and properties

[0040] The interlayers of the present disclosure can include various structures, components, and properties. For instance, in some embodiments, the interlayers of the present disclosure include a percolating network operational for regulating ion flux through the interlayer. In some embodiments, the percolating network is operable to selectively enhance flow of ions while restricting flow of electrons through the interlayer. In some embodiments, the percolating network is operable to enable rapid lithium transport through the interlayer and thereby prevent dendrite formation.

[0041] In some embodiments, the Lacey mixing index of the interlayer cross-section exceeds 70% when imaged at 50,000x magnification while segmenting the image into 20 by 20 subsets.

[0042] In some embodiments, the interlayer includes a mixed ionic-and-electronic conductor (MIEC) interlayer. In some embodiments, the interlayer further includes a binder. In some embodiments, the binder includes a polymer. In some embodiments, the polymer includes polyvinylidene fluoride. In some embodiments, the interlayer forms a eutectic alloy with lithium metal.

[0043] Solid-state batteries

[0044] Additional embodiments of the present disclosure pertain to solid-state batteries that include the interlayers of the present disclosure. In some embodiments, the solid-state battery includes, without limitation, an all- solid- state battery, an all- solid- state lithium metal battery, an anodc-frcc solid-state battery, or combinations thereof.

[0045] In some embodiments, the solid-state battery further includes an anode and a solid electrolyte. In some embodiments, the interlayer of the present disclosure is positioned between the anode and the solid electrolyte. In some embodiments, the interlayer is operational to optimize the interface between the anode and the solid electrolyte, thereby minimizing the formation of dendrites.

[0046] In some embodiments, the anode includes a layer of lithium metal. In some embodiments, the solid electrolyte includes an oxide-based electrolyte.

[0047] In some embodiments, the solid-state battery further includes a cathode. In some embodiments, the cathode includes a transition metal oxide cathode. In some embodiments, the cathode includes a cathode active material layer. In some embodiments, the cathode is a lithium-ion battery cathode.

[0048] In some embodiments, the solid-state batteries of the present disclosure may be illustrated as solid-state battery 10 in FIG. ID. In some embodiments, solid-state battery 10 includes: a cathode 12; a solid electrolyte 14; a current collector 18; and an interlayer 15 positioned between the solid electrolyte 14 and the current collector 18. In some embodiments, the interlayer 15 is in contact with the solid electrolyte 14. In some embodiments, interlayer 15 includes an interlayer of the present disclosure. For instance, in some embodiments, interlayer 15 includes: a plurality of carbon nanomaterials 16, and a plurality of metallic nanoparticles 17 uniformly dispersed on the carbon nanomaterials. In some embodiments, interlayer 15 includes a percolating network operational for regulating ion flux through the interlayer.

[0049] In some embodiments, solid-state battery 10 also includes an anode 20 positioned between current collector 18 and interlayer 15. In some embodiments, anode 20 includes a lithium metal. In some embodiments, metallic nanoparticles 17 of interlayer 15 are operable to inter-diffuse with the lithium metal to form an alloy. In some embodiments, metal elements in interlayer 15 inter-diffuse with the lithium metal at a comparable rate to form an alloy. In some embodiments, the diffusion coefficient of the lithium in the metal elements is of the same order of magnitude as the diffusion coefficient of the metal elements in the lithium. In some embodiments, the interdiffusion facilitates the formation of a lithium-conducting percolating network.

[0050] In some embodiments, the solid-state batteries of the present disclosure include anode-free solid-state batteries. Additional embodiments of the present disclosure pertain to anode-free solid- state batteries that include the interlayers of the present disclosure. Anode-free solid-state batteries of the present disclosure may be illustrated as anode-free solid-state battery 30 in FIG. IE. In some embodiments, anode-free solid-state lithium battery 30 includes: a cathode 32; a solid electrolyte 34 in contact with the cathode 32; a current collector 38; and an interlayer 35 positioned between the current collector 38 and the solid electrolyte 34.

[0051] In some embodiments, interlayer 35 includes an interlayer of the present disclosure. For instance, in some embodiments, interlayer 35 includes: a plurality of carbon nanomaterials 36. Insome embodiments, interlayer 35 also includes a plurality of metallic nanoparticles 37 uniformly dispersed on the carbon nanomaterials 36 to form a percolating network. In some embodiments, the percolating network is operable to regulate lithium ion flux through interlayer 35.

[0052] In some embodiments, metallic nanoparticles 37 include silver nanoparticles. In some embodiments, the silver nanoparticles include diameters between about 5 nm to about 10 nm.

[0053] In some embodiments, the carbon nanomaterials 35 are in the form of a substrate. In some embodiments, the metallic nanoparticles 37 (e.g., silver nanoparticles) are uniformly dispersed throughout the carbon nanomaterial substrate to form a percolating network. In some embodiments, the percolating network is operable to regulate lithium ion flux through interlayer 35 such that the battery is capable of high rate cycling greater than 2.5 mA cm at areal capacities greater than 2 mAh cm2under ambient temperatures of about 30 °C or less.

[0054] Methods of forming interlayers

[0055] Additional embodiments of the present disclosure pertain to methods of forming the interlayers of the present disclosure. In some embodiments, the method includes mixing carbon nanomaterials with metallic nanoparticle precursors to form a precipitated product, which includes metallic nanoparticles associated with the carbon nanomaterials. In some embodiments, the methods of the present disclosure also include a step of associating the precipitated product with a binder to form the interlayer. In some embodiments, the metallic nanoparticle precursor includes silver nitrate.

[0056] In some embodiments, the interlayer formation methods of the present disclosure include associating a plurality of metallic nanoparticles with a plurality of carbon nanomaterials to form a uniform metallic nanoparticle-carbon nanomaterial composite. In some embodiments, the formed interlayer includes a percolating network operational for regulating ion flux through the interlayer. In some embodiments, the methods of the present disclosure also include a step of incorporating a binder to form a film structure for scalable production.

[0057] In some embodiments, the methods of the present disclosure also include a step of incorporating the formed interlayer as a component of a solid-state battery. In some embodiments, the incorporation includes pressing the formed interlayer onto a surface of an anode. In some embodiments, the pressing occurs by a method that includes, without limitation, hydraulic pressing, isostatic pressing, or combinations thereof.

[0058] The methods of the present disclosure may utilize various types of carbon nanomaterials. Suitable carbon nanomaterials were described supra and are incorporated herein by reference. For instance, in some embodiments, the carbon nanomatcrials arc in the form of a substrate and include nanometer- sized dimensions. In some embodiments, the association results in the formation of a uniform metallic nanoparticle-carbon nanomaterial substrate composite.

[0059] In some embodiments, the methods of the present disclosure also include a step of treating the carbon nanomaterials with an acid to form oxidized carbon. In some embodiments, the treating occurs prior to associating the carbon nanomaterials with metallic nanoparticles. In some embodiments, the acid includes nitric acid. In some embodiments, the oxidized carbon includes oxygen-based surface groups. In some embodiments, the oxygen-based surface groups include, without limitation, hydroxyl surface groups, oxide surface groups, or combinations thereof.

[0060] The methods of the present disclosure may utilize various types of metallic nanoparticles. Suitable metallic nanoparticles were described supra and are incorporated herein by reference. For instance, in some embodiments, the metallic nanoparticles include average diameters from about 5 times to about 10 times smaller than the average diameters of the carbon nanomaterials. In some embodiments, the metallic nanoparticles include average diameters about 5 times to about 10 times smaller than the average diameters of the carbon nanomaterials. In some embodiments, the metallic nanoparticles include average diameters of about 10 nm or less.

[0061] In some embodiments, the metallic nanoparticles include silver nanoparticles. In some embodiments, the metallic nanoparticles include silver nanoparticles with diameters between about 5 nm to about 10 nm.

[0062] Various methods may be utilized to associate carbon nanomatcrials with metallic nanoparticles. For instance, in some embodiments, the associating occurs by a method that includes, without limitation, chemical precipitation, electrochemical deposition, ultrasonication, thermal decomposition, mechanical mixing, or combinations thereof. In some embodiments, the associating occurs by a method that includes chemical precipitation.

[0063] Methods of forming solid-state batteries

[0064] Further embodiments of the present disclosure pertain to methods of forming solid-state batteries. In some embodiments, such methods include: (1) attaching an interlayer of the present disclosure to a solid electrolyte, where the solid electrolyte is attached to a cathode; and (2) attachingan anode to the interlayer. In some embodiments, the solid-state battery formation methods of the present disclosure include: (1) attaching an interlayer to a surface of an anode to form an anodeinterlayer assembly; and (2) attaching the anodc-intcrlaycr assembly to a solid clcctrolytc-cathodc assembly to form an anode-interlayer-solid-electrolyte-cathode assembly.

[0065] In some embodiments, the anode includes lithium. In some embodiments, the anode includes a current collector. In some embodiments, the anode is in the form of an anode assembly. In some embodiments, the anode assembly includes a current collector. In some embodiments, the anode assembly includes a layer of anode metal. In some embodiments, the anode further includes a layer of anode metal. In some embodiments, the anode metal is lithium.

[0066] The methods of the present disclosure may attach various interlayers to solid electrolytes. Suitable interlayers were described supra and are incorporated herein by reference. For instance, in some embodiments, the interlayer includes a plurality of carbon nanomaterials, and a plurality of metallic nanoparticles uniformly dispersed on the carbon nanomaterials. In some embodiments, the interlayer includes a percolating network operational for regulating ion flux through the interlayer. In some embodiments, the interlayer includes a plurality of carbon nanomaterials that are in the form of a substrate, and a plurality of metallic nanoparticles uniformly dispersed on the carbon nanomaterials to form a coating on the carbon nanomaterials without aggregating.

[0067] In some embodiments, the metallic nanoparticles include diameters of less than about 50 nm. In some embodiments, the metallic nanoparticles include silver nanoparticles.

[0068] Additional embodiments

[0069] Reference will now be made to more specific embodiments of the present disclosure and experimental results that provide support for such embodiments. However, Applicant notes that the disclosure below is for illustrative purposes only and is not intended to limit the scope of the claimed subject matter in any way.

[0070] This Example aims to resolve the instability of Li metal anode in all- solid- state batteries (ASSBs). Mixed ionic-and-electronic conductor (MIEC)-type interlayer started to gain attention recently. A typical MIEC interlayer is composed of carbon (to provide structural support and electron conduction), metal (to assist Li transport), and binder (to enable scale-up processing). MIECs help to protect ASSBs from electrolyte penetration by mechanically insulating Li metal anode and solid electrolyte, as well as separating the redox reaction and Li deposition / dissolution process.

[0071] FIGS. 1A-1C show the structure of an all-solid-state lithium secondary battery with an interlayer, with an actual microscopic image of plated Li at different locations of the interlayer. Li growth between interlayer and lithium metal anode is desirable, as demonstrated in FIG. 1C. The presence of metal nanoparticles such as Ag may help decrease the nucleation barrier of lithium, as well as to increase lithium mobility by alloying, which enabled prolonged cycling at high current density and elevated temperature (60 °C).

[0072] Here, applicant demonstrates that an Ag-C interlayer with nano-dispersed Ag (5-10 nm) bonded to C enables stable cycling of ASSB at high current density and ambient temperature (30 °C). Applicant first unveils the correlation between Ag’s particle size and interlayer’s Li transport capability. The transmission electron microscope (TEM) image in FIGS. 2A-2E show a significant difference in the nanostructure of Ag-C prepared by two different methods. Mechanically mixing Ag nanoparticles (50-60 nm) leads to nanostructures demonstrated in FIGS. 2A-2B. The similar particle size of Ag and C decrease the overall Ag coverage and hinders the transport of Li on carbon particles, as shown in FIG. 2C. In contrast, nano-dispersed Ag (FIGS. 2D-2E) covers a large surface of carbon particles and tends to create a Li-conducting percolating network. More uniform Ag distribution result in faster Li transport kinetics. In-situ SEM images in FIG. 2G shows Ag and Li interdiffuse into each other. In a practical battery anode, Li is often excess and Ag nanoparticles dissolve into the Li phase. Decreasing the Ag particle shortens the diffusion path and facilitates the formation of percolating Li- Ag network within Ag-C.

[0073] FIG. 2H-2J show transport properties of Li in Ag-C. In mechanically-mixed Ag-C, the presence of large Ag slightly increases the ionic conductivity compared to the carbon interlayer (0.4 mS cm-1 vs. 0.3 mS cm-1) at 30 °C (FIG. 2H). Conversely, the chemically precipitated Ag-C interlayer with a percolating Li-Ag network exhibits twice the ionic conductivity of its mechanically - mixed counterpart, reaching 0.8 mS cm1at 30 °C, being comparable to most solid electrolytes. Contrary to the trend in ionic conductivity, chemically precipitated Ag-C exhibits the lowest electronic conductivity at around 0.2 S cm (FIG. 21), followed by mechanically-mixed Ag-C at 1.6 S cm1and carbon at 2.5 S cm L The discrepancy possibly originates from the contact resistance due to more insulating C-0 bonds at the carbon surface in the chemically deposited Ag-C. Higher ionic conductivity and lower ionic conductivity promote Li-ion transport across the interlayer (FIG. 1C) and mitigate Li deposition at undesirable locations (FIG. 1A-B).

[0074] FIG. 2J shows the diffusivity of Ag-C interlayer during a continuous lithiation process, measured by galvanostatic intermittent titration technique (GITT). Ag-C interlayer with nanodispersed Ag (prepared by chemical precipitation) has a high diffusivity (IxlO-10cm2s"1) at the pristine state at 30 °C, while the interlayer with larger Ag particles (50-60 nm) requires certain degree of lithiation to achieve the same level of diffusivity. Li diffusivity plays a critical role in cell stability during the charging process. With low Li diffusivity, the reduced Li cannot transport through the interlayer and achieve ideal plating shown in FIG. 1C. Instead, Li may grow between electrolyte and interlayer or within the interlayer (FIGS. 1A-1B), which are detrimental to cycling stability. In addition, the chemically precipitated Ag-C exhibits improved macroscopic homogeneity compared to its mechanically mixed counterpart.

[0075] FIGS. 3A-3B show the SEM image of casted Ag-C film. Ag particles tend to aggregate without any chemical treatment, as shown in the mechanically mixed Ag-C in FIG. 3A. In contrast, the residue surfactant and smaller particle size, chemically precipitated Ag-C shows uniform dispersion in the as- prepared film in FIG. 3B. This improved homogeneity is quantitatively verified by a higher Lacey mixing index (FIG. 3C). FIG. 3D highlights the wide distribution of Ag particle sizes in mechanically mixed Ag-C due to aggregation. Conversely, the Ag particles in chemically precipitated Ag-C are smaller and have a narrower size distribution (FIG. 3E). Uniform and fine Ag dispersion helps with the formation of Li-conduction network during cell operation.

[0076] The impact of Ag size and homogeneity on interlayer efficacy is examined via operando SEM during cell operation. FIGS. 4B-4C shows mechanically mixed Ag-C needs a longer resting time to reach equilibrium voltage after cell assembly. Even after equilibrium, it shows larger impedance than its chemically precipitated counterpart, indicating hindered Li transport in the cell. FIGS. 4D-4I show the morphological evolution of different Ag-C interlayer during lithiation and the cycling performance of full cell (LiNio.83Mno.nCoo.o602|Li6PS5Cl|Ag-C|Li) included of nano-dispersed Ag particles. Large Ag particles (50-60 nm) lead to preferential growth of Li onto Ag substrate and eventually resulted in non-uniform Li filament growth (FIGS. 4F and 4G). In contrast, cells with nano-dispersed Ag showed uniform Li growth (FIGS. 4H and 41).

[0077] Moreover, the unfavorable Li growth morphology and inferior Li diffusivity in large-p article Ag-C led to higher overpotential and lower cell capacity compared to counterparts with small Ag particles (FIG. 5A-5D). With nano-dispersed Ag in Ag-C, Applicant demonstrates ASSB that cyclesat a high current density (2.8 mA cm’2) at 30 °C for more than 2500 cycles. As a reference, other studies only demonstrated synthesis capability of moderate- sized Ag (38 nm) and high-rate cycling at 60 °C. Such studies failed to disclose the preparation of Ag-C composite with small Ag (5-10 nm) and the role of particle size in cell performance.

[0078] The nano-dispersed Ag-C further enables pouch-type all-solid-state battery cycling at an ultralow pressure at 0.5 MPa. FIGS. 5E-5H show the cell image, cell structure, voltage profile, and longterm performance of a pouch cell with nano-dispersed Ag-C. The cell shows stable cycling at 0.5 mA cm2at 0.5 MPa for 150 cycles. In contrast, previous studies have only achieved cycling performance at 2 MPa. Without being bound by theory, this improvement is likely due to the faster Li transport kinetics in the nano-dispersed Ag-C interlayer, which reduces the requirement of high stacking pressure to facilitate Li transport during the Li stripping process at the anode.

[0079] The preparation of Ag-C interlayer with nano-dispersed Ag (5-10 nm) that forms a uniformly percolating network is also a significant factor that contributes to improved performance shown in FIG. 5D. The small particle size and uniform distribution of Ag requires proper surfactant and nucleation / growth processes. The adhesion of Ag nanoparticles on carbon requires surface treatment of carbon. The preparation of nano-dispersed Ag-C for ASSBs is inspired by the preparation of similar products for catalytic and biomedical applications.

[0080] In a typical preparation process, carbon nanoparticles (50-60 nm) were first treated with concentrated nitric acid to introduce hydroxide surface groups. Then, the mixture was washed and centrifuged until the pH reaches 7. 10 mg silver nitrate and 100 mg polyvinylpyrrolidone were dissolved in two 5 mL ethylene glycol solutions, respectively. Two solutions are mixed with the treated carbon under agitation for 4 hours, followed by ultrasonication at 35 °C for two hours. The product was immediately vacuum filtrated and washed with deionized water. The obtained sludge was vacuum-dried at 80 °C overnight.

[0081] The interlayer coating was prepared by mixing the Ag-precipitated carbon with a polymeric binder (polyvinylidene fluoride, PVdF) and solvent (N-methylpyrrolidone, NMP). The slurry was tape-casted on Ni foil and vacuum-dried overnight. The as-prepared Ag-C interlayer can be directly used in the fabrication of ASSBs. After preparation of solid electrolyte layer (LiePSsCl), a composite cathode and an Ag-C interlayer were attached to its two sides and densified with hydraulic press orisostatic press. A piece of thin Li metal was attached to Ag-C interlayer after removal of metal substrate. The fabricated ASSB was tested in a constant-temperature oven.

[0082] In another example, as-prepared Ag-C interlayer can be directly used in the fabrication of ASSBs with oxide-based solid electrolytes (e.g. LLZO). In another example, as-prepared Ag-C interlayer can be directly used in the fabrication of ASSBs with polymer solid electrolytes (e.g. PEO).

[0083] An all- solid- state battery with a transition metal oxide cathode, a sulfide solid electrolyte pellet, a finely-dispersed Ag-based interlayer and a 50- .m thick lithium metal has been fabricated to test the room-tcmpcraturc cyclability. The cell shows stable cycling at 1C (2.8 mA cm-2) for over 2500 cycles at 30 °C. The cycling data is demonstrated in FIGS. 5A-5D. In contrast, the identical cell without interlayer short-circuited at a low current density (0.56 cm-2). The result demonstrates that an interlayer with nano-dispersed silver allows a lithium metal anode to cycle at high current density and areal capacity for thousands of cycles. The finely dispersed Ag-C also enables pouch cell cycling at a low stack pressure of 0.5 MPa, as shown in FIGS. 5E-5H.

[0084] Additional Examples

[0085] One or more embodiments of the disclosure will now be described in detail with reference to the following examples. However, these examples are only for illustrative purposes and are not intended to limit the scope of the one or more embodiments of the disclosure.

[0086] Example 1, Formation of a cathode layer

[0087] Composite cathodes were prepared using a dry process. The cathode active material (e.g., LiNio.83Mno.11Coo.06O2), solid electrolyte (LiePSsCl), and vapor-grown carbon fiber powders were hand-milled at a mass ratio of 70:27:3 with an agate mortar and pestle for 15 minutes until a homogenous mixture was achieved. Then, 0.5 wt% polytetrafluoroethylene (PTFE) powder was added and hand-milled for another 30 minutes. During the hand-milling process with PTFE, the materials adhered together, forming a homogeneous and malleable paste under shear force. The paste was then subjected to shear-rolling between two metal sheets until a desired loading (20 mg cm-2) was achieved.

[0088] Example 2, Formation of an interlayer

[0089] In Example 1, Ag-C was prepared by physically mixing Ag and C nanoparticles. Slurry for the interlayer was prepared by physically mixing nano-silver particles (~60 nm in diameter), C65 nanocarbon particles at 1:1.3 by weight, then mixing with solvent N-methyl-2-pyrrolidone (NMP) andpolyvinylidene fluoride (PVDF, 7 wt%) using a planetary mixer. After coating the slurry onto a 10- pm-thick Ni foil using a doctor blade, it was dried in air at 80 °C for 20 minutes, followed by further drying under vacuum at 100 °C for 12 hours. The thickness of the Ag-C nanocompositc layer was 5- 10 pm. The interlayer in Example 1 is a baseline following procedures described in prior art.

[0090] In Example 2, Ag was chemically plated on nanocarbon particles using a simple Tollen process. Briefly, C65 carbon was first pre-treated with concentrated nitric acid and washed with deionized (DI) water until the pH reached 7. Silver nitrate was dissolved in DI water and mixed with ammonium hydroxide at 1:2 molar ratio. Acid-treated C65 and silver-ammonia solution was mixed (Ag:C = 1:1.3 by weight) in 2% polyvinylpyrrolidone (PVP) aqueous solution, followed by the addition of excess ethylene glycol (EG) (Ag:EG = 1:350 by molar). The mixture was stirred at 160 °C in an oil bath for 4 hours, then washed in DI water, followed by vacuum-drying at 120 °C to obtain Ag-C powder. As-prepared Ag-C powder was slurry-coated onto Ni foil following the process described in Example 1.

[0091] Example 3. Fabrication of pellet-type solid-state batteries

[0092] In Examples 1 and 2, electrochemical tests were carried out in pellet cell format in polyether- ether-ketone (PEEK) die with a diameter of 12.7 mm. Typically, 130 mg sulfide solid electrolyte powder (LiePSsCl) was compressed in the die under 150 MPa to form a pellet. A dry-process composite cathode (17.8 mg active material, 2.8 mAh cm2) and a tape-cast interlayer on Ni substrate were placed on both sides of the solid electrolyte and further densified at 375 MPa. Ni substrate becomes easily detachable from the rest of the cell. After densification, a piece of ~50 pm Li foil was added between the Ni substrate and interlayer and further pressed at 50 MPa for 10 seconds to improve intcrfacial contact. The cell is subject to a stack pressure of 7 MPa. The cells were heated at 60 °C for 2 hours to facilitate lithiation of Ag-C interlayer.

[0093] All evaluations were conducted at a temperature of 30 °C within a climate-controlled oven. Cycling performance of Examples 1 and 2 are shown in FIG. 5D. Both cells are first charged at a constant current of 0.1 C (0.28 mA cm2) until 4.25 V and discharged until 2.6 V at the same rate (0.1 C, 0.28 mA cm2) for two cycles. Then, the current density gradually increased every two cycles. For Example 1, the current density was increased following 0.1 C, 0.2 C, 0.33 C, and 0.5 C. For Example 2, the current density was increased following 0.1 C, 0.2 C, 0.33 C, 0.5 C, and 1 C. Example 1 with existing technique shows a short cycle life of 45 cycles even at a compromised current density of 0.5C (1.4 mA cm2). In contrast, Example 2 with nano-dispersed Ag in Ag-C enables more than 2600 cycles at a high current density of 1 C (2.8 mA cm2).

[0094] Example 4, Formation of a cathode layer

[0095] Composite cathodes were prepared using a dry process. The cathode active material (e.g., LiNio.83Mno.11Coo.06O2), solid electrolyte (LiePSsCl), and vapor-grown carbon fiber powders were hand-milled at mass ratio 70:27:3 with an agate mortar and pestle for 15 minutes until a homogenous mixture was achieved. Then, 1 wt% PTFE powder was added and hand-milled for another 30 minutes. During the hand-milling process with PTFE, the materials adhered together, forming a homogeneous and malleable paste under shear force. The paste was then subjected to shear-rolling between two metal sheets until a desired loading (11 mg cm2) and area (3.24 cm2) was achieved.

[0096] Example 5. Formation of an interlayer

[0097] Ag was chemically plated on nanocarbon particles using a simple Tollen process. C65 nanocarbon was first pre-treated with concentrated nitric acid and washed with deionized (DI) water until pH reached 7. Silver nitrate was dissolved in DI water and mixed with ammonium hydroxide at a 1:2 molar ratio. Acid-treated C65 and silver- ammonia solution was mixed (Ag:C = 1:1.3 by weight) in 2% polyvinylpyrrolidone (PVP) aqueous solution, followed by the addition of excess ethylene glycol (EG) (Ag:EG = 1:350 by molar). The mixture was stirred at 160 °C in an oil bath for 4 hours, then washed in DI water, followed by vacuum-drying at 120 °C to obtain Ag-C powder. The deposited Ag-C powder was mixed with solvent N-methyl-2-pyrrolidone (NMP) and PVDF (7 wt%) using a planetary mixer. After coating the slurry onto a 10-pm-thick Ni foil using a doctor blade, it was dried in air at 80 °C for 20 minutes, followed by further drying under vacuum at 100 °C for 12 hours. The thickness of the Ag-C nanocompositc layer was 5-10 pm.

[0098] Example 6. Fabrication of a solid electrolyte thin membrane

[0099] The interlayer was integrated in a pouch cell. The thin solid electrolyte membrane was prepared by slurry casting. 93 wt% Li PSsCl powder and 7 wt% hydrogenated nitrile butadiene rubber (H-NBR) binder were dissolved in isobutyl isobuterate solvent at a solid content of 54%. The mixture was agitated in a planetary mixer and cast on a polyester (Mylar) film at an initial thickness of 100 pm. The solid electrolyte thin membrane was dried in vacuum oven overnight at 80 °C.

[0100] Example 7. Fabrication of pouch-type solid-state batteries

[0101] In Example 6, the as-prepared film was densified with warm isostatic press (WIP) at 490 MPa together with the composite cathode layer. The densified electrolyte layer was 60 pm in thickness. The cathode loading was 11 mg cm2. Then, the coated Ag-C was attached to the counter side of the electrolyte layer using a similar WIP process. After removing Ni foil, a 50 pm Li foil was further attached to the Ag-C. The cell stack is sealed in an aluminum-laminated pouch, as shown in FIGS. 5E and 5F. The cell active material was 3.24 cm2in area.

[0102] Electrochemical tests were carried out at an ultra-low stack pressure of 0.5 MPa in a custom-designed fixture. The cell was cycled at 0.1 C (0.15 mA cm2). 0.2 C (0.3 mA cm2| for 2 cycles each between 2.6 and 4.25 V, then cycled at 0.33 C (0.5 mA cm2) for more than 150 cycles (FIG. 5G and H).

[0103] Without further elaboration, it is believed that one skilled in the art can, using the description herein, utilize the present disclosure to its fullest extent. The embodiments described herein are to be construed as illustrative and not as constraining the remainder of the disclosure in any way whatsoever. While the embodiments have been shown and described, many variations and modifications thereof can be made by one skilled in the art without departing from the spirit and teachings of the invention. Accordingly, the scope of protection is not limited by the description set out above, but is only limited by the claims, including all equivalents of the subject matter of the claims. The disclosures of all patents, patent applications and publications cited herein are hereby incorporated herein by reference, to the extent that they provide procedural or other details consistent with and supplementary to those set forth herein.

Claims

CLAIMS1. An interlayer structure comprising a percolating network operable for regulating an ion flux therethrough, wherein the interlayer comprises: a plurality of carbon nanomaterials, wherein the carbon nanomaterials are in the form of a substrate; and a plurality of metallic nanoparticles uniformly dispersed on the carbon nanomaterials, wherein the metallic nanoparticles form a coating on the carbon nanomaterials without aggregating.

2. The interlayer of claim 1, wherein the carbon nanomaterials comprise nanometer- sized dimensions ranging from about 1 nm to about 100 nm, and wherein the carbon nanomaterials are selected from the group consisting of carbon powder, carbon nanoparticles, amorphous carbon, porous carbon, carbon black, Ketjen Black, carbon nanotube, vapor-grown carbon nanofiber, oxidized carbon, or combinations thereof.

3. The interlayer of claim 1, wherein the metallic nanoparticles comprise silver (Ag) nanoparticles, wherein the Ag nanoparticles comprise average diameters from about 5 times to about 10 times smaller than the average diameters of the carbon nanomaterials.

4. The interlayer of claim 1, wherein the metallic nanoparticles further comprise a group of nonagglomerated primary particles and a group of agglomerated secondary particles.

5. The interlayer of claim 5, wherein 80% of the secondary particles have diameters below 50 nm, and wherein over 99% of the secondary particles have diameters below 120 nm.

6. The interlayer of claim 1, wherein the carbon nanomaterial substrate has a Lacey mixing index greater than 70% as determined from a cross-section image of said the carbon nanomaterial substrate material imaged at 50,000x magnification and segmented into 20 by 20 subsets.

7. The interlayer of claim 1, wherein the percolating network is capable of selectively conducting flow of ions while restricting flow of electrons.

8. The interlayer of claim 1, wherein the interlayer contains from about 10 wt% to about 90 wt% of the carbon nanomaterial substrate.

9. A solid-state battery comprising: a cathode; a solid electrolyte; a current collector; and an interlayer positioned between the solid electrolyte and the current collector, wherein the interlayer is in contact with the solid electrolyte, and wherein the interlayer comprises: a plurality of carbon nanomaterials, and a plurality of metallic nanoparticles uniformly dispersed on the carbon nanomaterials, wherein the interlayer comprises a percolating network operational for regulating ion flux through the interlayer.

10. The solid-state battery of claim 9, further comprising an anode positioned between the current collector and the interlayer.

11. The solid-state battery of claim 9, wherein the cathode is a lithium-ion cathode.

12. The solid-state battery of claim 10, wherein the anode comprises lithium metal, wherein metal elements in the interlayer inter-diffuses with the lithium metal at a comparable rate to form an alloy, wherein the diffusion coefficient of the lithium in the metal elements is of the same order of magnitude as the diffusion coefficient of the metal elements in the lithium, and wherein the interdiffusion facilitates the formation of a lithium-conducting percolating network.

13. An anode-free solid-state lithium battery comprising: a cathode; an electrolyte in contact with the cathode; a current collector; and an interlayer positioned between the current collector and the solid electrolyte, wherein the interlayer comprises: a plurality of carbon nanomaterials, wherein the carbon nanomaterials are in the form of a substrate, and a plurality of silver (Ag) nanoparticles comprising diameters between about 5 nm to about 10 nm, wherein the Ag nanoparticles are uniformly dispersed throughout the carbon nanomaterial substrate to form a percolating network, wherein the percolating network is operable to regulate lithium ion flux through the interlayer such that the battery is capable of high rate cycling greater than 2.5 mA cm2at areal capacities greater than 2 mAh cm2under ambient temperatures of about 30 °C or less.

14. A method of forming an interlayer comprising a percolating network capable of regulating ion flux therethrough, the method comprising: associating a plurality of metallic nanoparticles with a plurality of carbon nanomaterials, wherein the carbon nanomaterials are in the form of a substrate and comprise nanometer- sized dimensions, wherein the metallic nanoparticles comprise average diameters from about 5 times to about 10 times smaller than the average diameters of the carbon nanomatcrials, and wherein the associating results in the formation of a uniform metallic nanoparticle- carbon nanomaterial substrate composite,.

15. The method of claim 14, wherein the associating step occurs by a method selected from the group consisting of chemical precipitation, electrochemical deposition, ultrasonication, thermal decomposition, or a combination thereof.

16. The method of claim 14, wherein the metallic nanoparticles comprise silver (Ag) nanoparticles comprising diameters between about 5 nm to about 10 nm.

17. A method of forming a solid-state battery, comprising: attaching an interlayer to a solid electrolyte, wherein the solid electrolyte is attached to a cathode, and wherein the interlayer comprises: a plurality of carbon nanomaterials, wherein the carbon nanomaterials are in the form of a substrate, a plurality of metallic nanoparticles uniformly dispersed on the carbon nanomaterials, wherein the metallic nanoparticles form a coating on the carbon nanomaterials without aggregating, and a percolating network operable for regulating an ion flux therethrough; and attaching an anode assembly to the interlayer, wherein the anode assembly comprises a current collector, and optionally a layer of anode metal.

18. A method of forming a solid-state battery, comprising: attaching an interlayer to a surface of an anode to form an anode-interlayer assembly, wherein the interlayer comprises: a plurality of carbon nanomaterials, wherein the carbon nanomaterials are in the form of a substrate, a plurality of metallic nanoparticles uniformly dispersed on the carbon nanomaterials, wherein the metallic nanoparticlcs form a coating on the carbon nanomatcrials without aggregating, and a percolating network operable for regulating an ion flux therethrough; and attaching the anode-interlayer assembly to a solid electrolyte-cathode assembly to form an anode-interlayer- solid-electrolyte-cathode as sembly .

19. The method of claim 18, wherein the anode comprises lithium, and wherein the metallic nanoparticles comprise silver (Ag) nanoparticles.

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