Hybrid variable speed sequential cold spray laser sintering / melting approach to advanced additive manufacturing

Abstract

The inventive concept relates to an additive manufacturing method and system including a Hybrid Variable Speed Sequential Cold Spray Laser Sintering / Melting (h-VSSCSLS / M) feature for lithium-ion battery electrode and any battery electrode, biodegradable and permanent biomedical device, automotive, construction, lightweight metal, and related component fabrication. The h-VSSCSLS / M deposits particles of a feedstock material by cold spraying, which is conducted at hybrid velocity that controls a velocity of the particles from a laminar field to supersonic velocity range such as to include deposition of any soft or hard polymeric particles, hard or soft ceramic, semiconductor, and metallic particles, and subsequently employs a laser energy source to sinter, fuse or melt the cold sprayed powder particles to form a sintered, fused or melted layer.

Description

HYBRID VARIABLE SPEED SEQUENTIAL COLD SPRAY LASER SINTERING / MELTING APPROACH TO ADVANCED ADDITIVE MANUFACTURINGCROSS REFERENCE TO RELATED APPLICATIONSThis patent application is filed under the Paris Cooperation Treaty (PCT) and claims priority to U.S. Provisional Patent Application No. 63 / 773,515, entitled “HYBRID VARIABLE SPEED SEQUENTIAL COLD SPRAY LASER SINTERING / MELTING APPROACH TO ADVANCED ADDITIVE MANUFACTURING”, filed in the U.S. Patent and Trademark Office on March 18, 2025, the contents of which are incorporated herein in its entirety.1. Field of the Invention

[0001] The inventive concept relates to an additive manufacturing method and system including a Hybrid Variable Speed Sequential Cold Spray Laser Sintering / Melting (h-VSSCSLS / M) feature that includes variable speed cold spray with controlled laser fluence and power, for lithium-ion battery electrode fabrication as well as fabrication of biodegradable and non-biodegradable biomedical implant devices, and light weight construction materials.2. Background

[0002] Li-ion batteries (LIBs), the solution to the 21st century greenhouse gas (GHG) free energy storage demands, need transformational advances to meet GHG-free abundant primary energy goals. Today, fabrication of electrodes for all liquid electrolyte-based LIBs (LELIB) relies on traditional slurry-based approaches sternly limited by inferior packing densities, porosity and pore size distribution, combined with removal of solvents offering poor control of composition and structure at the current collector-electrode and at all vital electrode-electrolyte interfaces. Conversely, all- solid- state Li-ion batteries (ASSLIBs) also suffer from lack of a single universal manufacturing approach, combined additionally the poor electrodes and solid-state electrolyte (SSE) interfaces control of composition and structure needing unfeasible high pressures, inferior electrode porosity and poor electrodes-current collector interfaces control. Thus, these deficiencies strongly limit the attainment of high energy densities and high specific capacities matching the theoretical limits and, rate-controlled cyclability of both LELIB s and ASSLIBs. Similarly, there is a critical need for generation of bioresorbable load-bearing implantsand scaffolds for critical sized segmental bone defect regeneration. There is an equally vital need for generation of patient specific bioresorbable metallic implants and scaffolds using additive manufacturing (AM) approaches. Currently, tissue engineering and regeneration of mineralized tissue severely lacks the availability of patient specific customized and tailored three-dimensional (3D) bioresorbable implant materials for regenerating critical sized segmental bone defects (CSBD). Presently available non-biodegradable implant materials approved by Food and Drug Administration (FDA) are dominated by Stainless Steel (SS), Cobalt-Chrome (Co-Cr), and Titanium- Aluminum- Vanadium (Ti6A14V) alloys that are significantly stronger and tougher than the human natural bone tissue while biodegradable systems that are FDA approved are driven primarily by poly-lactic acid (PLA), poly-glycolic acid (PGA) and co-polymer of PLA and PGA, namely, poly-lactic-co-glycolic acid (PLGA) that are limited by the inferior mechanical properties compared to natural bone. Additive manufacturing (AM) methods have been used extensively to fabricate constructs of these non-degradable metals and biodegradable polymer materials. There has been considerable research into bioresorbable Magnesium (Mg) and Mg-based alloys for various tissue engineering and mineralized tissue regeneration applications including of late, the emergence of Zinc (Zn) and Zn-based alloy systems. The Mg and Mg-based alloy systems are perfectly matched to the mechanical properties of the innate human bone tissue. However, their extreme reactivity to air and moisture is a major impediment to development of AM approaches for generation of patient- specific implants and scaffolds. The h-VSSCSLS / M approach described in this invention is ideally suited for creation of bioresorbable 3D implants and scaffolds for mineralized tissue engineering.

[0003] There is currently known in the art additive manufacturing (AM) approaches, commonly referred to as 3D printing, processes wherein a three-dimensional (3D) object is created by layered addition of material in predetermined locations over many layers. Each layer of material is fused with the underlying layer utilizing either thermal, electron beam, or laser energy to facilitate particle melting or sintering. Relying on either melting or sintering allows the use of many material types as feedstock particles, including numerous variants of conducting, insulating, or semiconducting plastics, ceramics, and metals.

[0004] The various types of additive manufacturing approaches include Selective Laser Melting (SLM), Selective Laser Sintering (SLS), Laser Engineered Net Shaping (LENS), high powered electron beams (E-Beam), Binder Jetting (BJ), and several other lesser-known variationsprimarily used for specific materials or custom builds. These aforementioned metal AM processes differ in the following aspects: (i) Feedstock (powdered metal versus metal wire filaments); (ii) The methods of material joining or fusing (melting, sintering, or a primary chemical binder followed by a secondary post AM process of binder burn-out and sintering phase); and (iii) Extent of the amount of post AM processing required for completion of a part. Despite many options, the SLM and the BJ processes are the most commonly used metal powder-bed based AM methods currently in use. The preference for these AM methods stems from process resolution and precision, ease of use, and applicability for a wide range of acceptable materials. Each of these two methods use different approaches to fuse the metal particles while creating the desired 3D object. In the case of SLM, the powder in the powder bed is melted with a high intensity laser traversing over selected areas of each layer within the powder- bed. With binder jetting, on the other hand, the particles within the powder bed are bound together during the printing process using a binder over selected areas of each layer dictated by the computer-controlled software. The process, however, requires post process sintering to eliminate the binder and induce densification to create a strong metallic bond between the metal particles.

[0005] The limitations of the above metal powder-based feedstock methods are categorized into two general areas: (i) The feedstock material requirements and (ii) The location- setupenvironment of the AM apparatus. In the feedstock material selection, it is crucial to select a material that is non-reactive and oxide free or has an oxide decomposition temperature much lower than that of the intrinsic melting temperature of the material. Furthermore, highly reactive metals such as aluminum (Al) and titanium (Ti) require tightly controlled inert environments within the printer to make the process amenable and safe. In the case of magnesium (Mg) and Mg-alloys (MA), however, the inert environment needs to be held at an elevated overpressure to compensate for the high vapor pressure of the material as well adding yet another level of complexity over and above the safety concerns posed by the handling of the reactive fine powder itself. Even with all the precautions observed, attempts to additively manufacture Mg and Mg-alloys results in a final structure that is insufficient for any industrial uses due to the mechanically weak structure caused by the high porosity and poor propensity for achieving sintering to full density. The porosity issue is not exclusive to Mg and Mg-alloys alone and thisissue is commonly found with many other materials, which have undergone any one of the several AM processes where high temperatures are observed.

[0006] The second area where the powder-based feedstock AM processes requires care to prevent poor quality prints is linked to the operational environment and setup of the overall AM apparatus. To prevent mid-process failures and maintaining high resolution while allowing homogeneous powder distribution for each additional layer, the AM printer needs to be correctly orientated. For the best viable outcome, it is essential that the printer is perfectly level, free from external vibrations and high- volume air flows while being operated within the correct external temperature and humidity range, placing the printer in an environment where gravity is the essential and primary dominant force limiting its applicability under microgravity and low earth orbit environments. Each of these factors have the propensity for negatively affecting the placement and retention of the micron-sized metal particles until they can be fused to the larger print. As a result, artifacts and voids are commonplace with the printing process combined with suboptimal printer conditions. Moreover, failed prints may lead to printer damage, which is a major limitation. Due to these elusive requirements, the AM apparatuses are not robust enough to be easily moved or kept on a mobile platform for onsite parts production during a repair at a remote location.

[0007] There is a desire in the art therefore, to develop new AM systems and methods that compensate for all of the above factors relating to material selection and provide a more robust printing platform. Moreover, there is a need for a versatile AM system that can offer generation of complex structures of full density of any material irrespective of its reactive nature and affinity to oxygen such as Mg and Mg-alloys without the problems associated with having a gravity dependent fixed powder bed aside from the other problems of vapor pressure and oxide layers akin to reactive metals.

[0008] Thus, there is a need in the art for the identification and development of an inventive concept as a transformative additive manufacturing (AM) Hybrid Variable Speed Sequential Cold Spray Laser Sintering / Melting (h-VSSCSLS / M), augmented by artificial intelligence (Al) and machine learning (ML) digital twin (DT) concepts, aided by density functional theory (DFT)-based computational and continuum modeling, to fabricate LELIB electrodes and the entire ASSLIBs. The h-VSSCSLS / M process addresses and mitigates issues associated with use of Additive Manufacturing (AM) in general as a method to control phase, composition, graingrowth, locations of the constituents making up a multi-layered structure, and mitigate the formation of detrimental structures such as dendrites for use as alternate anode electrodes to Lithium metal in objects such as energy storage devices.SUMMARY OF THE INVENTION

[0009] In one aspect, the invention provides a method of preparing a multi-layer or multi-layered structure. The method includes a) cold spraying a layer of feedstock material onto a substrate / build plate to create a cold sprayed coating, the cold spraying conducted at a hybrid velocity, wherein the hybrid velocity controls a particle velocity from a laminar field to supersonic velocity, and wherein the hybrid velocity includes deposition of soft or hard polymer particles, hard or soft ceramic, semiconductor, and metallic particles; b) subsequent to the cold spraying of each layer, employing a laser energy source to directly sinter, fuse or melt the cold sprayed coating, comprising directing the energy source to conduct the localized sintering, fusing or melting of the specific particles or regions of the cold sprayed coating that correspond to a preselected multi-lay er / multi- layered structure; and forming a sintered, fused or melted layer; and c) sequentially repeating the steps of a) and b) forming one or more additional material layers on the sintered, fused or melted layer, wherein the number of additional layers is determined based on a total number of layers needed to produce the preselected multi-layer or multi-layered 3D structure.

[0010] In certain embodiments, cold spraying is conducted in large passes over an entirety of the substrate / build plate, or in precisely located areas with a tight spray pattern to reduce an amount of feedstock material usage. In certain embodiments, cold spraying is conducted at variable speeds with controlled laser fluence and power at above or close to the melting temperatures or 1 / 2- 1 / 3 the melting temperatures of the material in (°K) to generate dense solid complex powder beds with particles of polymers, metals, semiconductors, and ceramics in contact or in precisely located areas within a tight spray pattern to reduce the amount of material used.

[0011] In certain embodiments, the feedstock material is in a dry form selected from the group consisting of particles, particulates, or granules of polymers, metals, semiconductors, and ceramics.

[0012] In certain embodiments, the cold spraying followed by immediately sintering, fusing or melting process results in a fragmented oxide dispersed within the sintered, fused or meltedmaterial and the preselected multi-layered structure. The dispersed fragmented oxide can serve as an oxide filler imparting an oxide dispersion-strength to the preselected multi-layer or multilayered structure.

[0013] In certain embodiments, adding a second material layer to the first material layer is effective to control or eliminate porosity in the first material layer.

[0014] In certain embodiments, incoming particles impinge and peen the first layer causing collapse of pores induced by sintering or fusion of the first layer.

[0015] In certain embodiments, following completion of the first material layer and a subsequent second material layer, power of the energy source is increased and used in trimming and shaping an outline of the preselected structure being prepared. Following the trimming and shaping, one or more additional material layers can be formed until the preselected multi-layer or multilayered structure is built in its entirety with the corresponding complexity, contiguity, shape, and size.

[0016] In certain embodiments, the feedstock material includes a material selected from the group consisting of metal, metal alloy, polymer, ceramic, semiconductor, and mixtures and combinations thereof. The metal or metal alloy can be selected from the group of any metal in the Periodic Table consisting of magnesium, calcium, strontium, zinc, copper, aluminum, stainless steel, tungsten, molybdenum, niobium, titanium, tantalum, Inconel, rhenium, osmium, ruthenium, iridium, platinum, palladium, tungsten-niobium alloy, tungsten-tantalum, tungstencobalt alloy, tungsten-rhenium alloy, tungsten- silver composite, tungsten-tungsten carbide composite, tungsten-molybdenum, and mixtures or alloys thereof including other reactive, refractory metals, rare-earth metals and rare-earth metal alloys and composites and mixtures or alloys thereof.

[0017] In certain embodiments, the method includes employing a CAD model corresponding to the preselected multi-layer or multi-layered structure for directing and controlling the laser energy source. Pores and / or pathways can be formed in the preselected multi-layer of multilayered structure.

[0018] In certain embodiments, the method further includes subjecting the sintered, fused or melted layer to subtractive machining, which includes smoothening the surface to eliminate the surface roughness or control the surface roughness to precise Ra values (i.e., the average peak-to-valley distance in defining surface roughness values) as-needed of the sintered, fused ormelted layer; and forming a first material layer of the preselected multi-layer or multi-layered structure.

[0019] In certain embodiments, the laser energy source is selected from the group consisting of laser, electron beam, electric arc, induction, magneto resistance, electrical resistance, plasma, or any suitable heat generating source, and combinations thereof.

[0020] In another aspect, the invention provides an additive manufacture device including a cold spray apparatus structured to deposit a coating of a feedstock material onto a substrate / build plate, the apparatus including a hybrid velocity that controls a particle velocity from a laminar field to supersonic velocity range, wherein the hybrid velocity includes deposition of soft or hard polymer particles, hard or soft ceramic, semiconductor, and metallic particles; a laser energy source structured to sinter, fuse or melt the coating of the feedstock material to form a sintered, fused or melted layer; and a CAD model to direct the laser energy source to sinter, fuse or melt the specific particles or regions of the feedstock material that correspond to a preselected multilayer or multi-layered structure, wherein one or more additional layers of the feedstock material are sequentially deposited on the formed sintered, fused or melted layer to produce one or more additional material layers, and wherein the number of additional material layers is determined based on those needed to produce the preselected multi-layer / multi-layered structure.

[0021] In certain embodiments, the feedstock material includes a material selected from the group consisting of metal, metal alloy, polymer, ceramic, semiconductor, and mixtures and combinations thereof.

[0022] In certain embodiments, the first material layer and one or more additional layers include engineered pores of desired pore size and shape, and / or pathways.

[0023] In certain embodiments, the multi-layer or multi-layered structure is a medical implant device. The medical implant device can be a scaffold. The medical implant device can be composed of a material selected from the group consisting of Mg, Mg alloy, and Mg composite as well as any other biodegradable alloys such as but not limited to zinc, and zinc alloys, molybdenum and molybdenum alloys, and non-biodegradable, inert and permanent materials such as stainless steel (SS), stainless steel alloys, titanium, and titanium alloys and titaniumaluminum- vanadium alloys, cobalt-chrome and cobalt-chrome alloys.

[0024] In certain embodiments, each of the one or more additional material layers is composed of the same feedstock material. In certain other embodiments, one or more of the additionalmaterial layers of the multi-layer or multi-layered structure is / are composed of a different feedstock material as compared to the other material layers.

[0025] In certain embodiments, the feedstock material for each material layer is randomly selected. In certain other embodiments, the feedstock material is selected such that alternating material layers are composed of the same feedstock material or a pattern of material layers is composed of the same feedstock material.

[0026] In certain embodiments, the device further includes a subtractive machining apparatus to smoothen the surface of the sintered, fused or melted layer.BRIEF DESCRIPTION OF THE DRAWINGS

[0027] FIGS. 1A and IB are schematics that illustrate the h-VSSCSLS / M system and method, in accordance with certain embodiments of the inventive concept.

[0028] FIG. 2 is a plot that shows Li-SIA symmetric cell cycling in 1.8M LiTSI + 0.4M LiNOs in DOL:DME, in accordance with certain embodiments of the inventive concept.

[0029] FIG. 3 is a plot that shows symmetric cell cycling of ceramic electrolyte for over 250 cycles, in accordance with certain embodiments of the inventive concept.

[0030] FIG. 4A is an image that illustrates a crystal structure of Li3PO4 and Li3PS4 with hopping pathways of Li-ions and interstitial channels, in accordance with certain embodiments of the inventive concept.

[0031] FIG. 4B is a plot that shows an energy profile for Li diffusion in doped and undoped Li3PO4 and Li3PS4, in accordance with certain embodiments of the inventive concept.

[0032] FIG. 5 is an image that illustrates different effects of varying gas pressure during the CS process of a structure build, in accordance with certain embodiments of the inventive concept.

[0033] FIG. 6 is an image that illustrates different effects of varying exposure during the laser melting step during a structure build, in accordance with certain embodiments of the inventive concept.

[0034] FIG. 7 is an image that illustrates different effects of varying boundaries during a 3D structure build, in accordance with certain embodiments of the inventive concept.

[0035] FIG. 8 is an EBSD SEM scanned image of a dendrite-free, micro-acicular-based structure, in accordance with certain embodiments of the inventive concept.

[0036] FIG. 9 is an image that illustrates a microstructure viewed with a SEM’s BSE detector, in accordance with certain embodiments of the inventive concept.

[0037] FIG. 10 is an image that illustrates a microstructure viewed with a SEM’s BSE detector, in accordance with certain embodiments of the inventive concept.DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[0038] The invention relates to systems and methods to create structures with engineered internal features, pores, and / or connected channels utilizing additive manufacturing and, more particularly, preparing structures including geometrically complex structures using a novel and transformative hybrid variable speed sequential cold spray laser sintering / melting (h-VSSCSLS / M) additive manufacturing process. The h-VSSCSLS / M system or process is a multistep additive manufacturing process comprised of components or procedures that mimic cold spray (CS), laser melting (LM), and laser sintering (LS) all in tandem or either in full or in part.

[0039] The h-VSSCSLS / M system or process provides the ability to control phase, composition, grain growth, locations of the constituents making up the multi-layered structure, and mitigate the formation of any detrimental structures such as dendrites for use as alternate anode electrodes to Lithium metal in objects such as energy storge devices. In certain embodiments, process parameters are developed with respect to controlling the grain morphology of a final structure, specifically for the prevention of unwanted dendritic structures for Lithium metal anodes in energy storage devices.

[0040] An additional feature of the h-VSSCSLS / M system or process is the ability to allow continual adjustability of all the process parameters throughout the process. These adjustments and variations to the building process allow for the creation of different material structures, grain morphologies, coating densities, and cooling rates in discrete and precisely located areas. These engineered variations within the structure result in the ability to control and create the intended geometries, with desired phase, composition, grain morphology and sizes, mechanical performances with desired mechanical properties, and materials characteristics.

[0041] Furthermore, the invention relates to an additive manufacturing printer or device in which CS is used as a method to deposit the next layer amount of material to advance the print while a laser immediately sinters, melts, or fuses and bonds the cold spray deposition to coalesce theparticles. Tn certain embodiments, the laser is specifically employed for sintering or densifying the particles.

[0042] The process of CS is used with a high-pressure gas into which a powder stream is introduced and allowed to accelerate with the expanding gas until the powder particles reach a critical velocity and are allowed to strike a substrate or build plate. Upon this collision, the particles experience rapid deceleration and transmit the kinetic energy gathered into a massive amount of plastic deformation, which allows the flowing material to interlock onto the substrate or the previously placed layer(s) of CS material.

[0043] In certain embodiments, the h-VSSCSLS / M process includes the following three steps / cycles that are combined and repeated to achieve the desired product, as illustrated in FIG.1A.

[0044] 1) Cold Spray (CS): Forming a layer is initiated with the CS process depositing a desired material on a substrate. During this initial step in the process, in certain embodiments, the material and substrate are of different or similar materials, along with being held at differing conditions (e.g., temperatures, alignments, surface finishes, and the like). The CS is used to place a powdered material in a singular pass or multiple passes depending on the desired thickness of the layer. Upon additional cycles where the prior layers replace the substrate as the base layer, operational parameters are adjusted as desired to incorporate differing base material conditions resulting from the prior cycles. In certain embodiments, these adjustments are implemented to counter the work-hardened layers or to aid in the creation of laminate structures where each layer is created from a different material.

[0045] Thus, the CS process includes the use of variable travel speeds and particle velocities covering laminar velocity regimes to supersonic velocity ranges to create the locations of differing densities and materials such as metals and ceramics that tend to be strong and brittle and polymers that tend to be mechanically soft required to ensure the formation of a dense layer having favorable grain growth. As an example, the Scan speeds and Velocities have an initial layer’s application value (Ss and Vs, respectively), as the process progresses, these values change over n-iterations where n is the number of changes required to create the given layer determined by size, boundary conditions, and optimized grain orientations.

[0046] 2) Laser Melting (LM) I Laser Sintering (LS): Upon completion of the desired thickness of CS material deposition, the LM portion of the cycle immediately follows that allows theenergy of the laser to raster, scan, or pulse at predetermined locations. This energy input either melts or sinters the CS placed powdered particles, resulting in different cooling rates from slow, in the range of 1-100 °C / s to as rapid as 106 oC / s allowing the creation of equilibrium and metastable common grains in different morphologies, e.g., equiaxed, columnar, acicular, platelet, spherical, faceted, and the like in fine nanoscale (-1-10 nm) and coarse (> 100 nm-10-100 microns), between the individual particles depending on the heat extraction mechanism, transforming them into a coalesced and homogenous structures. The laser is optionally reduced in power, allowing the heat input to be below that of the temperature required for sintering or melting depending on the melting temperature of the material being deposited by CS to provide a controlled cooling rate. This allows additional control of the resulting microstructure.Furthermore, the interaction of the laser melted pool at this phase allows the use of variable laser travel speeds and adjustable input power intensities at predefined locations, aiding in additional control to achieve optimal grain growth.

[0047] Depending on the material(s) being used (metal, ceramic, semiconductor, polymer) for the creation of the layer, LM or LS may be used. As is the case during the CS step, the laser’s transverse speed (Sv) and energy level (Ev) are varied to create the required microstructure while compensating for multiple materials and differing boundary conditions.

[0048] 3) Subtractive Machining I Manufacturing (SM): Upon completion of the laser induced particle coalescing, subtractive machining / manufacturing is optionally conducted to smooth, plane, or peen the surface. This step allows the surface to be prepared for additional layers as the process progresses. During this progression, the h-VSSCSLS / M creates each layer to differing materials and parameters in relation to the general layout of the design. Because of these variations in materials, the melt pool conditions used for the current material, and those of the layers directly below and following the current layer, the h-VSSCSLS / M process accordingly adapts the build parameters to compensate. This, for example, allows the structure to be normalized, ensuring a high-fidelity assembly for the creation of energy storage or high-performance structural aerospace applications.

[0049] Thus, in certain embodiments, the layer is finalized using SM such as a CNC-based mill to deck, smooth, or peen the surface and prepare it for the next layer. The optimal CNC Milling process also includes variations in the tool’s transverse speed (Sv) and the cutter’s speed (Cv) to achieve the intended layer interface.

[0050] 4) Final Part: In certain embodiments, subsequent layers of the aforementioned steps 1 -3 are required to meet the designed geometry, size, and layout of the final structure. Once the requirements are met, the process is completed to form the final structure.

[0051] Additionally, the h-VSSCSLS / M system or process affords the ability to deposit particles of the feedstock material by the cold spraying process being conducted at hybrid velocity, wherein hybrid velocity controls a velocity of the particles from a laminar field to supersonic velocity range (-0.01 m / s to 11,000 m / s), such as to include deposition of soft or hard polymeric particles, hard or soft ceramic, semiconductor, and metallic particles. The h-VSSCSLS / M system or process also affords subsequently employing a laser energy source to sinter, fuse or melt the cold sprayed powder particles deposited at the hybrid velocity regime, including directing the laser energy source to conduct localized sintering, fusing or melting of the powder particles to bond and form a dense solid complex construct such as a sintered, fused or melted layer to generate a fully dense 3D construct with no closed or open pores while also having the engineered (e.g.. controlled) pores of needed (e.g., selected) pore size dimensions and shape (-100-250 microns or larger) to generate dense and solid porous constructs or scaffolds as desired allowing ingression of biological animal or human cells.

[0052] The laser energy / laser promotes migration of material components and ensuing diffusion of the atoms or ions to induce particle-particle coalescence resulting in reduction in surface area with corresponding sintering and densification without inducing particle melting. The laser can, however, also induce energy to cause particle melting, fusion and corresponding densification. This step converts the physical adhesion methods installed to the system via CS into a metallurgical or metallic bond in the case of metals, a covalent or ionic bond in the case of a ceramic and a semiconductor, and a covalent, secondary, or hydrogen-bonded polymeric bond wherein the individual particles coalesce into a single structure. The coalescence occurs without melting in the case of the metal, semiconductor, and ceramic powder feedstock or fusion in the case of the polymer and metal powder feedstock, while eliminating porosity with the shared grains or polymer and metallic particles throughout the entire structure to generate a dense and solid 3D construct with no open or closed pores while also having the engineered (e.g., controlled) pores of needed (e.g., selected) pore size dimensions (-100-250 microns or larger for ingression of biological animal or human cells for biomedical devices such as implants and scaffolds) and shape to generate a dense and solid engineered porous construct as desired.

[0053] At the same time, the sintering and fusion process can lead to dispersing the fragmented oxide causing oxide dispersions within the sintered material part correspondingly contributing to strengthening the sintered material via dispersion strengthening mechanisms. The laser is precisely and meticulously moved while being controlled by geometric instructions, e.g., control file, to create a 3D part of the computer-designed rendering of said part.

[0054] As shown in FIG. IB, for the CS layer: in setup 1, powder particles (40 pm) shown in A impact the substrate or a previous layer at controlled supersonic speed; shock and severe plastic deformation fragments the oxide surface of the metal and semiconductor as shown in B ; and particles interlock as shown in C. Subsequently, laser sintering / melting (LS / LM) enhances interparticle bond, and enables micromachining (MM) of the cold sprayed layer and creates engineered porosity (-100-250 microns or larger for biomedical implants and scaffolds permitting biological animal and human cell ingression) and other features; if additional material layers are needed, the process is repeated to form a completed structure. Additionally, controlled laminar speed cold spray will deposit the ceramic or polymer particles on the substrate without inducing any plastic deformation. The particles will deposit and form a monolayer instead of being interlocked as in C. Subsequent laser sintering or melting step (LS / M) will lead to fusion of the particles forming a dense solid layer with micromachining (MM) of the laminar speed cold sprayed layer generating engineered porosity or full net shaped solid layered structures and other features; if additional material layers are needed, the process is repeated to form a completed structure.

[0055] The additive manufacturing h-VSSCSLS / M is augmented by artificial intelligence (Al) and machine learning (ML) digital twin (DT) concepts aided by density functional theory (DFT)-based computational, and continuum modeling, and is thus, effective to fabricate liquid electrolyte-based LIBs (LELIB) electrodes and an entire all-solid-state Li-ion batteries (ASSLIBs) in a single process. The h-VSSCSLS / M directly fabricates the LELIB electrodes with controlled engineered pores of desired pore size and shape, and thicknesses by a dry process that obviates use of solvents and binders. Active elements link to conductors aided by engineered pores of desired pore size and shape to provide improved electron and ion transport. The h-VSSCSLS / M is also a compelling versatile single AM approach to directly fabricate fire and explosion proof high performance ASSLIBs unlike LELIB s obviating the use of flammable organic liquid electrolytes.

[0056] The inventive concept also provides a method of preparing a multi-layer or multi-layered structure including a) cold spraying a layer of feedstock material onto a substrate / build plate to create a cold sprayed coating, wherein depositing particles of the feedstock material by cold spraying is conducted at hybrid velocity, wherein hybrid velocity controls (or varies) the velocity of the particle from a laminar field to supersonic velocity range, which allows for including deposition of soft or hard polymeric particles, hard or soft ceramic and semiconductor, and metallic particles, and is followed by b) employing subsequent laser energy that results in sintering, melting or fusing of the powder particles leading to a dense solid complex 3D construct with no open or closed pores; c) forming a sintered or melted layer; and d) sequentially repeating the steps of a), b) and c) forming one or more additional material layers on the first material layer, wherein the number of additional layers is determined based on a total number of layers needed to produce the preselected multi-layer or multilayered structure followed by e) laser machining of the final fused 3D structure as needed to result in smooth surface or surface with controlled surface roughness of any Ra value as needed depending on the application. It should be noted that this laser machining step is afforded by the h-VSSCSLS / M as needed. While the laser step in the h-VSSCSLS / M approach affords this capability following cold spraying of the preceding layer, surface machining of the final 3D construct generated following the h-VSSCSLS / M can also be realized by other surface machining techniques as well, such as electropolishing and microelectrochemical polishing, as well as molecular decomposition process (MDP).

[0057] The h-VSSCSLS / M can create single and multi-layers for single and stacked battery packs with one unit and manipulation of only gas pressure, temperature, flow rate, velocity, laser power and frequency parameters. Moreover, no clean room akin to semiconductor fabrication is needed.

[0058] The h-VSSCSLS / M process provides the ability to additively manufacture complex constructs of any polymer, ceramic or metal. The variation in velocity combined with sequential laser energy offers the ability to make bioresorbable, bioabsorbable. and biodegradable polymers, ceramics and metals, as well as non-resorbable polymeric, ceramic and metallic systems for variety of applications ranging from biodegradable and bioresorbable implants and scaffolds for tissue engineering, mineralized tissue regeneration, electrodes and architectures for LELIB and complete fabrication of ASSLIBs, as well as various components for light-weightmetal construction, automotive, aviation, navy, aerospace, and transportation including building and construction. The approach also affords manufacturing in microgravity and underwater environments. Additionally, the h-VSSCSLS / M approach provides the ability to join together various components that are formed.

[0059] The term “laser” or “laser energy” is used herein as an exemplary energy source for use in the invention, and it is contemplated and intended in accordance with the various embodiments of the invention that alternative energy or heat generating sources are essentially suitable for use, such as but not limited to, electron beam, electric arc, induction, magneto resistance, electrical resistance, plasma, and combinations thereof.

[0060] In certain embodiments, the invention provides systems and methods for producing biomedical bone implants, e.g., scaffolds, for regenerative medicine using magnesium (Mg) and / or Mg alloys, zinc (Zn) and / or Zn alloys, molybdenum (Mo) and / or Mo alloys including stents. The implants prepared according to the invention meet the desired mechanical in-vitro corrosion and cytotoxicity properties, provide a surface finish that is effective (e.g., optimized) for bone growth, promoting improved interface and integration with the bone tissue, and have designed / engineered pores of desired pore size and shape (-100-250 microns and larger) that allow a path for cells to ingress, and receive nutrients and start the bone regeneration and remodeling process from multiple sites within the implant. Similarly, in certain embodiments stents are made that have the mechanical strength and ductility to heal and regenerate the trachea as well as eliminate obstruction of any tissue in conditions, such as tracheostenosis, as well as provide support for tracheomalacia. Additionally, the stents can be used to eliminate obstruction and plaque in arteriosclerosis as well as atherosclerosis.

[0061] In certain embodiments, the systems and methods of the invention include deposition of a feedstock material on a surface or substrate (e.g., build plate) using a CS deposition apparatus and techniques to form a coating or layer. The feedstock material includes metal or metal alloy, ceramic, semiconductor, or polymer, or mixtures or combinations or composites thereof.Suitable forms of the feedstock material include a dry form, such as particles, particulates, or granules. In certain embodiments, the material is Mg particles or Mg alloy particles, Zn particles or Zn alloy particles, Mo particles or Mo alloy particles. CS is conducted at hybrid velocities, wherein hybrid velocity controls (or varies) the velocity of the particle from a laminar field to supersonic velocity range, which allows for including deposition of soft or hard polymericparticles, hard or soft ceramic, semiconductor, and metallic particles. The CS deposited coating or layer is then subjected to subsequent laser energy that results in sintering, melting or fusing of the powder particles leading to a dense solid complex 3D construct with no closed or open pores as well as generate dense complex 3D constructs with engineered pores of desired size and shape in the ~100-250-microns range or larger size range to allow for ingression of biological animal and human cells. The laser energy is directed and / or controlled by a control file, such as but not limited to Computer Aided Drafting (CAD) model / software, that corresponds to the desired or selected multilayer or multilayered structure that is to be formed. The sintered or melted CS coating or layer is then subjected to micromachining (MM) that creates engineered surface finish, surface roughness of any desired Ra value, porosity and other features. This process allows one layer of the multi-layer or multi-layered structure to be completed. Additional layers are then sequentially added to this first layer or base layer. The forgoing steps are then repeated for the sequential deposition of additional layers to form, e.g., build, the multi-layer or multilayered structure. Each of the additional layers includes a feedstock material, e.g.. metal or metal alloy, ceramic, semiconductor, or polymer, or mixtures or combinations thereof, that is the same or different than the feedstock material of the first layer. In certain embodiments, each of the layers of the multi-layer or multi-layered structure is composed of the same feedstock material. In other embodiments, one or more of the layers of the multi-layer or multi-layered structure is / are composed of a different feedstock material as compared to the other layers. In certain embodiments, the feedstock material for each layer is randomly selected, in other embodiments, the feedstock material is selected such that alternating layers are composed of the same feedstock material or a pattern of layers are composed of the same feedstock material.

[0062] The h-VSSCSLS / M system and method include a manufacturing process combining CS and LS or LM, and MM, to create parts with desired or controlled level (e.g., pre-selected) engineered characteristics or properties, e.g., minimum porosity of -100-250 microns or larger for biomedical devices such as implants and scaffolds permitting biological animal and human cell ingression, and micro-cracking, as compared to other AM systems and methods for refractory metals and their alloys. The process also produces application-specific 3D parts with excellent shape, size, pore geometry, and surface finish, composition, structure and texture control. The CS process creates a mechanical bond between particles. This interaction isfacilitated by extensive particle deformation creating a dense layer offering more pure material contact and thus, mass to transmit thermal energy.

[0063] As used herein relating to the h-VSSCSLS / M system and method, the term “layer-by-layer” or “layer” and like terms do not limit the process from working solely on a two-dimensional (X-Y) plane where an increase in a layer is a gain only in the Z direction. The term “layer-by-layer” also includes deposition and / or laser angles that may not be perpendicular to the X-Y plane and may include planes based in the Z-Y, Z-X, and any sub-planes within or any planes not orthogonal to X-Y, Z-Y, or Z-X planes.

[0064] The term “material(s)”, “feedstock material(s)” and like terms include metallic-, ceramic, semiconductor- or polymeric-based materials. A wide variety of materials are suitable for use in the h-VSSCSLS / M system and method, including metals, metal alloys, and metal composites selected from the group of any metal in the Periodic Table, such as but not limited to magnesium, calcium, strontium, zinc, copper, aluminum, stainless steel, Inconel, tungsten, titanium, molybdenum, tantalum, niobium, rhenium, osmium, ruthenium, iridium, palladium, platinum, tungsten-niobium alloy, tungsten-cobalt alloy, tungsten-tantalum, tungsten-rhenium alloy, tungsten-silver composite, tungsten-tungsten-carbide composite, tungsten-molybdenum, and other reactive, refractory metals, including rare-earth metals and rare-earth metal alloys, and mixtures or alloys or composites thereof, and ceramics, semiconductors, polymers and mixtures, blends, or composites thereof. In certain embodiments, the materials include tungsten, tungsten alloys, such as tungsten-titanium, tungsten-tantalum, tungsten-niobium, tungsten-cobalt, tungsten-tantalum, and tungsten-molybdenum alloys, and tungsten composites, such as tungstencopper, tungsten-silver, tungsten- tungsten carbide, and tungsten-rhenium composites. In certain other embodiments, the materials for use in the h-VSSCSLS / M system and method include polymers, semiconductors, and ceramics pertaining to both the sacrificial support structures and the primary and / or additional materials structures used to make the final structure or sacrificial features needed to ensure a proper final build. Suitable material(s) or feedstock material(s) for use in the invention includes a variety of forms. Non-limiting examples include a dry form, such as particles, particulates, or granules.

[0065] The term “control file” and like term is a generic term used to define any method to geometrically control any deposition or laser device(s) receiving commands from a structure rendered within a computer, digitalized to linear movements, and sent to the motion controldevices to precisely control the build of the model within the AM device. Non-limiting examples of such methods used include but are not limited to CAD software, G-code, STL files, CLI files, drafting program, slicer program, computer modeler, or digital modeler.

[0066] The h-VSSCSLS / M systems and processes additively create three-dimensional (3D) parts or structures from feedstock materials. Current parts made by known sintering- or melting-based AM methods are unsatisfactory, lacking control of engineered pore formation yielding undesired closed and open porosity and mechanical property attributes of strength, toughness, and ductility. Materials with intrinsic oxide layers sinter poorly entrapping impurities that create (nonengineered) porosity and inclusions within the structure. The mechanical strength is compromised due to the creation of internal micro-cracks and ensuing micro-channels preventing creation of any form of a hermetic seal. The non-engineered pores yield inferior mechanical properties requiring the creation of thick coatings for shielding and wear protection ensuring minimum thickness meeting protection needs. There are great benefits in creating a homogenous, thin, pore-engineered and defect-free coating hence, reducing weight without sacrificing protection.

[0067] Additionally, known AM methods fail to create complex parts of technologically viable refractory metals. Furthermore, AM-made parts fail to meet the mechanical strength of parts made by powder metallurgy (PM) mainly due to the large number of cracks and non-engineered pores. While PM-created parts are reliable and exhibit acceptable materials properties, the process considerably limits the complexity of the structure including the inability to add many internal features. The dense coating applied by CS most closely matches PM prior to sintering caused by the extreme plastic deformation enabling large particle-particle contact areas. In addition, the dense packing reduces shrinkage during sintering since there are fewer voids allowing the generation of complex 3D structures having low, or engineered, levels of porosity, reduced dimensional drift, and moreover, displaying improved mechanical properties.

[0068] The h-VSSCSLS / M system and method according to the invention are effective to create complex 3D parts of metals, metal alloys, and metal composites, such as magnesium (Mg), tungsten (W), titanium (Ti), aluminum (Al), and other germane refractory metals, and systems mentioned earlier such as metals, metal alloys, and metal composites selected from the group of any metal in the Periodic Table, including but not limited to magnesium, calcium, strontium, zinc, copper, aluminum, stainless steel, Inconel, tungsten, titanium, molybdenum, tantalum,niobium, rhenium, osmium, ruthenium, iridium, palladium, platinum, tungsten-niobium alloy, tungsten-cobalt alloy, tungsten-tantalum, tungsten-rhenium alloy, tungsten-silver composite, tungsten-tungsten-carbide composite, tungsten-molybdenum, and other reactive and refractory metals, including rare-earth metals and rare-earth metal alloys, and mixtures or alloys or composites thereof, and ceramics, semiconductors, polymers and mixtures, blends, or composites thereof. In certain embodiments, the materials include tungsten, tungsten alloys, such as tungsten-titanium, tungsten-tantalum, tungsten-niobium, tungsten-cobalt, and tungstenmolybdenum alloys, and tungsten composites, such as tungsten-copper, tungsten-silver, tungsten-tungsten carbide, and tungsten-rhenium composites for use in a wide variety of applications. The h-VSSCSLS / M system and method are a hybrid AM- subtractive machining (SM) approach embedding current AM-SM technologies into a single process. Thus, the h-VSSCSLS / M system and method according to the invention utilize features found in several current AM processes resulting in the hybrid approach that offers a resilient, robust printing method extending its operation in terrestrial, underwater, as well as micro-gravity environments. The h-VSSCSLS / M system and method uses the sequential CS deposition approach for adding material to the system’s build plate followed by a LS or LM process to sinter, densify or coalesce the powder particles into a homogenous structure to enhance interparticle bonds, and followed by MM obviating a powder bed unlike hitherto AM powder bed based processes to create and control, e.g., reducing or eliminating, voids, and porosity with the aim of realizing a 3D structure of near-bulk material mechanical properties with no print quality relationships attached to the surrounding environment.

[0069] Since the h-VSSCSLS / M process combines AM and SM processing, the initially rough finish of a CS-laser fused surface can easily be corrected in operando during the formation of each layer in a seamless fashion (e.g., continuous with no interruption) which is not so readily possible with other AM methods including BJ, SLM, and SLS. It is also known that parts made by the directed energy deposition (DED) process can be machined in-situ while the other AM processes require ex-situ additional post processing (grinding / machining) to achieve a smooth surface finish. Conventional SM is conducted utilizing either a monolithic torus cubic boron nitride cutter (Ra >0.5 pm) or laser cutting / polishing (Ra >2.5 pm) methods. These roughness values are translatable to the h-VSSCSLS / M systems and methods since the process is designed to be created as a set of tool heads for use within a computer numerical controlled (CNC) mill orlathe. External surface finishing is necessary with AM-created parts, but having the ability to add a smooth finish in operando to internal passages as the structure is being created in h-VSSCSLS / M offers vast opportunities with the optimization of fluid flows relating to the preservation of laminar flow. Additional SM benefits to the h-VSSCSLS / M process include the creation of features rendered difficult to create via conventional AM processes such as threaded mounting holes and high-precision lateral circular passageways, as well as other features.

[0070] The h-VSSCSLS / M system and method provide improved particle fusion since the laser immediately interacts with a layer of particles generated by CS held tightly in a dense oxide-free CS deposited layer preserving the pristine metal-metal particle contact affording ease of melting, fusing and or sintering with the subsequent laser step. Due to the nearly homogeneous CS layers of a given system, once the melt pool is formed under steady state for uniform geometry and uniform CS process conditions, the surface tension cannot consume adjacent feedstock thus, maintaining a constant volume within the melt pool. The reduction in oxide volume within the dense CS -deposited layer also decreases the liberation of gaseous bubbles and hence, further eliminates creation of interlayer voids giving pore-free parts of fully dense 3D constructs or fully dense 3D constructs with desired or controlled engineered porosity of desired or selected pore size and shape (-100-250 microns or larger amenable for biomedical devices such as implants and scaffolds to allow biological animal and human cell ingression). The oxide particles are also either ejected from the surface of the CS layer depending on the interfacial energy of the oxide layer with the underlying metal or embedded and dispersed within the melt pool created by the LS / LM step in the h-VSSCSLS / M system or method thus resulting in an oxide dispersion strengthened structure leading to further enhancement in strength and other related and characteristic properties of the material. Furthermore, control of the cooling rate due to the laser melting can also result in metastable microstructures of fine grains or nanostructured grains, or even stabilization of non-equilibrium phases including amorphous layers or amorphous-amorphous phase separated, amorphous-crystalline or amorphous-nanocrystalline layers or unique mix of interpenetrating layers / phases (amorphous / crystalline / nanocrystalline) or composite architectures of two or more intertwined phases or grains thus, resulting in unique mechanical, electronic, optical, thermal, magnetic, refractory, anti or accelerated or controlled corrosion, wear resistant, and biological properties.

[0071] Micro-cracking is typically observed along the grain boundaries of SLM created material structures due to the liberated gas movement from the oxide layer to the grain boundaries during melt solidification. These voids, which act as stress concentrators paired with the strain associated with rapid melting and cooling of the localized thermal event, causes cracks to form and propagate. These cracks are not normally found in sintered parts due to the differing process dynamics and only have little correlation to the operational parameters of the laser. Whereas in the h-VSSCSLS / M system and method, the feedstock powder is plastically deformed upon impact within the h-VSSCSLS / M system, and the process method and thus, the oxide layer is prone to either fragmentation and / or being ejected from the surface of the build structure. This causes reduction of the oxide itself, thus mitigating the formation of micro-cracks and generation of (non-engineered) pores. With the reduction in cracks as a result of the h-VSSCSLS / M system and method, a higher densification percent can be attained while yielding a more homogenous structure that will likely display much higher mechanical strength values.

[0072] Simultaneous deposition of multiple materials is feasible within the h-VSSCSLS / M system and method. For fusing the different materials, laser sintering, melting, or a combination of both may be required at precise locations. In certain embodiments, the platform of a CNC mill allows for adjusting and applying different laser intensities directly to the material to which they correlate while not affecting the other surrounding materials. Issues may arise if dissimilar materials having no solubility in the liquid state and / or solid state or materials having widely varying melting temperatures are placed in close proximity. If this is desirable, in certain embodiments, the materials are built around each other with unique interlocking geometry sealing and then finally sealed with a conventional CS coating for prevention of a thermal expansion mismatch or vibration related loosening.

[0073] According to the invention, the process of CS is used because it is unique in that it uses a high-pressure gas to accelerate particles to a critical velocity, allowing particle collision under supersonic conditions with a given surface. The particles collide onto the substrate transferring the kinetic energy created by the heated, high-pressure gas stream traveling at a critical velocity. Once this collision occurs, the energy transmitted into the particle causes colossal plastic deformation of the particles while strongly adhering to the colliding surface. This adherence interaction between the particle and surface creates features such as adiabatic shear instabilities, cold welding, and interlocking due to the flow of the particles during deformation thus ensuring astrong bond (e.g., by firmly adhering the feedstock to the structure). Because of this strong bond, CS is a useful technique for applying strong coatings at low temperatures, relative to the melting point of the materials, onto base materials, thus allowing dissimilar metals to be cladded to one another while still being capable of performing structural repairs. Furthermore, the extreme particle deformation and speed at which the collisions occur causes fracture of the inherent thick oxide layer, particularly in reactive metals leading to violent removal and or likely ejection of the fractured oxide particles or films from the intermediate material building area. As this oxide layer removal occurs, the deforming particle simultaneously bonds with the other nearby particles, forming a tight bond between the particles, thus preventing the formation of an additional oxide layer. This oxide-free contact area allows the preservation of a clean metalmetal interaction area, favorable for thermal sintering.

[0074] The h-VSSCSLS / M system and method, on the other hand, offers the added attributes of generating complex 3D structures obviating fragmentation and plastic deformation which is not displayed by hard or soft ceramic, semiconductor and soft or hard polymer systems. The process thus, uniquely commences with a cold spray apparatus that deposits a layer of material onto a substrate / build plate. The CS according to the inventive concept includes depositing particles of the feedstock material at a hybrid velocity that controls the velocity of the particle from a laminar field to supersonic velocity range that includes monolayer deposition of soft or hard polymeric particles, hard or soft ceramic and semiconductor, and metallic particles. This step can be done either in large passes similar to generation of coatings over the entire substrate / build plate, or in precisely located areas with a tighter spray pattern to reduce the amount of material usage. Once the feedstock material is deposited by CS to create the first layer, the subsequent laser energy (resulting in sintering or melting and fusing of the powder particles) is immediately employed to move over the surface at a set power level and scanning speed, which leads to reduction and / or elimination of any residual stresses arising from the CS process and thus, resulting dense solid complex with no closed or open pores or dense solid complex construct with engineered porosity and pore size and shape as desired (-100-250 microns or larger for biomedical implants and scaffold applications permitting biological animal and human cell ingression), as per the directive of a control file, e.g., a Computer Aided Drafting (CAD) model / software corresponding to the desired structure. The laser sintering process also allows the fragmented oxide to be dispersed within the sintered material’s structure serving as an oxide filler creating an oxide-dispersion-strengthened 3D material structure. At the conclusion of this laser interaction with the first layer, the deposition of the second layer by CS is then initiated, as needed. In concurrence with the first layer, the CS feedstock powder is applied over the laser-sintered first layer thus forming the second layer. The process is then repeated sequentially, as needed causing fusion, melting and or sintering of the preceding CS layer eliminating or reducing any residual stresses. In certain embodiments, melting is optional. This interaction has the added benefit of eliminating any non-engineered porosity, which results from the incoming particles impinging and peening the first layer thus causing the collapse of any pores induced by laser sintering or laser melting of the first layer. Whereas MM creates engineered porosity and other features. Once the CS step creating the second layer coating is completed, the LS / LM laser is once again activated and directed by the control file, e.g., CAD file, as to which particles need to be sintered onto the second layer to coincide with creating the desired or selected structure. After the sintering or fusion or melting is completed, a break in the current cycle is performed where the power of the laser is increased and used to trace the outline of the object being manufactured and its interaction with the substrate / build plate. This step facilitates removal of the extra material placed during the CS interaction through vaporization or cutting of the nonsintered particles, such that the formed 3D structure is as precise as possible with the desired surface finish. At the conclusion of this trimming and shaping sequence, the third layer is initiated with a repeat of the same foregoing order of events to deposit the new material and fuse it with the growing structure, removing or reducing any residual stresses, repeating on each layer until the desired 3D object is built in its entirety preserving the complexity, contiguity, shape, and size of the part.

[0075] The h-VSSCSLS / M system and method according to the inventive concept provides for LELIB electrode fabrication and assembly of ASSLIBs overcoming known limitations and yielding novel outcomes of:1. An -30% increase in specific capacity of the electrodes and ~2-fold increase in energy density of LELIB s and ASSLIBs.2. Transformative change in electrode manufacturing with precise thickness, porosity, grain size, morphology, dendrite-free architecture for metal anodes, composition, and phase control.3. An -30% reduction in LELIBs weight offering full compliant and conformal interface control with 100% coulombic efficiency gain in ASSLIBs.4. Transformation of LELIB and ASSLIB manufacturing offering a 10-fold increase in scalability, reproducibility, and accuracy of fabricated LELIBs and ASSLIBs with a remarkable 10-fold or 90% reduction in cost.5. Additionally, h-VSSCSLS / M AM systems and methods provide versatility in creating metals by plastic deformation induced interlocking, monolayer deposition of ceramics and semiconductors, polymers and composites with a single control of velocity (from supersonic to laminar), temperature, gas pressure, laser power, and frequency thereby assembling varied battery chemistries from currently used lithiated metal oxides, phosphates, oxynitrides, oxyphosphates, oxysulfates, oxyphospho-sulfo-nitrides, oxysulfides, oxyphosphides, sulfide-based cathodes, polymers, inorganic oxide, halide, phosphide, sulfide, phosphosulfide, phosphotelluride, phosphoselenide-based solid state electrolytes (SSEs), and lithium, sodium, potassium, aluminum, calcium, magnesium, reactive and rare-earth metals and alloys, and novel dendrite-free metal alloy anodes.

[0076] Traditional ASSLIB fabrication is complex and tedious, creating very thin incoherent structures. The h-VSSCSLS / M device and methods create coherent single and multi-layers for single and stacked battery packs with one unit and manipulation of only gas pressure, temperature, flow rate, velocity, laser power and frequency parameters. Moreover, no clean room akin to semiconductor fabrication is needed.

[0077] The inventive concept is also suitable for evolving rechargeable Na+, K+, Ca2+, Mg2+, other unary and multi-ion battery systems giving - 2-fold higher energy and power densities beyond hitherto battery and electrode manufacturing methods. The h-VSSCSLS / M and state of the art (SOA), LELIBs and ASSLIBs metrics are listed in Table 1.TABLE 1 - COMPARISON OF h-VSSCSLS / M WITH CURRENT TECHNOLOGIES Metric State-of-the-Art LELIB and ASSLIBs h-VSSCSLS / M Targets Processing 24-72 hours 4-6 hoursTimeEnergy Density 200-250 Wh kg-1300-500 Wh kg-1; 1000 cycles;<0.01% capacity loss cycle’1Interfacial Control Poor Conformal and Excellent Porosity Random and poor Precise and engineered Fabrication Complex / disparate for each component Continuous one process ProcessEfficiency Very inefficient (about 30%) based Highly efficient (about 80%) of Process on energy usageWaste 50% Recyclable wasteEnergy Usage 100% 50% conservedOverall Cost Cost intensive - about $150 / kWh About $15 / kWh; about $2K for About $20K for battery pack battery pack

[0078] According to the inventive concept, the layer-by-layer AM process includes where a structure is made by CS feedstock delivery and partly laser- sintered or welded allowing the powder feedstock to gain some strength until a post-processing sintering is competed upon the entire net-shape / near-net-shape part / structure either still connected to or removed from the substrate / build plate. In certain embodiments, a layer-by-layer AM process is where the deformation of the CS particle is done at a velocity and angle to aid in the removal and ejection of the oxide layer from the process making laser sintering / fusing / melting / welding much more effective on all reactive materials such as Mg, Al, Ti, etc. and alloys of these, etc. Furthermore, a cycle operates with only the high-pressure gas flow to facilitate each layer to be clean or certain locations for the print. In certain embodiments, the layer-by-layer AM process is where the addition of feedstock material via CS is performed at different powder velocities to coincide with different laser sintering / fusing / melting / welding techniques and power levels to aid in creating internal pores / channels / support structures along with different surface finishes of the part and differing mechanical properties of the material. In certain embodiments, the layer-by-layer AM process is capable of switching feedstock materials during the CS material addition steps. This changing of the powders is possible at any point or plane of the structure along with having the ability to mix several powders on the same plane during the CS material deposition phase. Differing materials may be used to form composites, different alloy structures, control corrosion rates of the resulting structures, control harmonics, control dampening for use indynamic systems, adsorb or reflect differing wavelengths of electromagnetic radiation, control the mechanical properties, or even place materials which will act differently during the laser’s interaction (example: installation of size-controlled internal gas pores).

[0079] The h-VSSCSLS / M system and method provide the ability to fragment the inherent oxide layer present on the surface of reactive metals such as Mg, Al, Ti, reactive, and rare-earth metals, and alloys of these elements. The h-VSSCSLS / M approach allows the fragmented oxide to be dispersed within the sintered particles creating a nano to sub-micron size oxide dispersion-strengthened 3D metal structure. The h-VSSCSLS / M system and the ensuing method additionally, allow the coalescence of voids and porosity generated in the CS process eliminating any closed or open voids or porosity trapped within the intrinsic sintered 3D structure or 3D structure with engineered porosity of desired pore size and shape (~100-250-microns or larger as desired for biomedical implants and scaffolds to allow for biological animal and human cell ingression). The h-VSSCSLS / M system and method for metal feedstock powder result in a final 3D metal structure that is fully bonded by a metallurgical bond representative of the metal with minimal or no residual stresses The h-VSSCSLS / M system and ensuing method for ceramic and semiconductor feedstock powder result in a final 3D ceramic and semiconductor structure that is fully bonded by a covalent bond representative of the covalent ceramic and semiconductor. The h-VSSCSLS / M system and ensuing method for ceramic and semiconductor feedstock powder result in a final 3D ceramic and semiconductor structure that is fully bonded by an ionic and covalent bond representative of the ionically or covalently bonded ceramic and semiconductor. The h-VSSCSLS / M system and ensuing method for polymer feedstock powder result in a final 3D polymer structure that is fully bonded by a polymeric bond representative of the covalently bonded polymer. The h-VSSCSLS / M system and ensuing method result in a final 3D structure that is mechanically strong and exhibiting physicochemical properties matching the intrinsic bulk structures. The h-VSSCSLS / M system and method for a metal, ceramic, semiconductor, or polymer feedstock powder are used to overlay on sacrificial support structures made of ceramic, semiconductor, polymer, and non-reactive material that is then removed to generate engineered porous 3D structures. The CS conformed structures of metal, ceramic, semiconductor, or polymer are made from metal, ceramic, semiconductor, or polymer powder feedstock or pre-formed construct inclusive of metal injection molding (MIM) processes. The h-VSSCSLS / M system and method are used to overlay on sacrificial support structures made ofceramic, semiconductor, polymer, and non-reactive materials made by MIM. The h-VSSCSLS / M system and method are used to overlay on sacrificial support structures made of ceramic, semiconductor, polymer, and non-reactive materials made by MIM followed by removal of the underlying support structures to create engineered porous structures with defined porosity.

[0080] In certain embodiments, CS is used to generate thick magnesium (Mg) and Mg alloy, zinc (Zn) and Zn alloy, molybdenum (Mo) and Mo alloy deposits followed by separating these thick structures of Mg and Mg-alloys, Zn and Zn alloys, Mo and Mo alloys from the underlying substrate and then subjecting the cold sprayed structure to sintering conditions to generate mechanically strong 3D structures. In certain embodiments, sintering / melting / fusing is also conducted on the cold sprayed structures to generate sintered, melted, and / or fused structures. According to the invention, the h-VSSCSLS / M system and method are performed on titanium (Ti) structures. Following CS of titanium exposing the cold sprayed titanium to selective laser treatment shows that the sintering of the cold sprayed titanium layer clearly demonstrates the benefit of treatment to cold sprayed metal resulting in a structure with significant elimination of voids indicating the formation of dense 3D structures with no closed or open pores. The following benefits are realized by the h-VSSCSLS / M system and ensuing method as opposed to performing a sintering step after the entire structure has been created by cold spray.

[0081] Fixed Build-up Layer: Inherent bond strength of the CS deposition fixes the powder to the build plate prior to laser fusion. Generation of CS powders at variable speeds also enables powder bed compaction without inducing particle deformation affording particle contact enabling also melting and fusion of the particles during the subsequent laser melting step enabling operation in underwater environments as well as particularly under microgravity and low earth orbit conditions. The process will work extremely well for certain non-reactive metals including ceramics, semiconductors, and especially for polymeric systems. Thus, h-VSSCSLS / M system and method create vital medical, transportation, construction, electronic, optical, thermal, magnetic, structural, military, aerospace, marine and other parts of any configuration on earth, underwater environments, or microgravity at any location on nonstationary and inconsistent platforms with any environment of gas or fluid with powder-bed based AM process resolutions. The process also obviates the need for stationary powder bed / build platform with limited translational (x, y, z) and rotational (0) movement including thedesire for complex methods to replace the gravitational force needed to steady the powder-bed as in conventional AM processes.

[0082] Six-degrees of Freedom: The flexibility of h-VSSCSLS / M system and method allow it to be placed on a robotic arm providing additional functionality in many environments.

[0083] Multi-functional: The step of CS is a main feature within the h-VSSCSLS / M system and method which is a trusted standalone coating process for cladding dissimilar metals, sealing pressure vessels, and repairing structural members.

[0084] Economic: The feedstock powder is kept within a hopper and is thus, protected from any unintentional laser interactions. By contrast, in current AM powder bed processes, the unneeded powder is still placed around the laser interaction area and oftentimes captures the partly melted droplets (splatters) or fine mist of spatters which are randomly ejected from the melt pool giving rise to contamination if mixed with the feedstock powders. These ejected particles, when mixed in with the feedstock could also prevent the feedstock material from being reused increasing the amount of feedstock material needed for a series of uses.

[0085] The work described in the following Examples provides evidence of the type of grain morphology and microstructures in the constructs being made via the h-VSSCSLS / M process and having the ability to be directly affected by varying the operational parameters. This process was designed as a means to create AM based energy storage devices by mitigating many of the known issues with the current production methods using melt-solidified and extruded materials for anode materials that are prone to dendrite formation during electrochemical cycling which is deleterious to the safety and long-term cycling of the rechargeable Li-ion batteries. The formation of dendrites is a major deterrent, and the current work shows a single pathway to eliminate and control the generation of dendritic microstructure for use as anodes in Li-ion and Li metal batteries. The results shown here clearly depict three distinct grain morphologies created in the same structure by simply changing the build creation process to affect the heat input and cooling rates at predetermined zones. With the highest heat inputs, dendrites were formed, with the lowest heat inputs, a more refined micro structure was created eliminating dendrites. The h-VSSCSLS / M process is thus amenable to any metallic alloy systems using normal cold spray regimes of supersonic velocities (> 340 m / s), as well as other soft materials systems such as polymers and hard materials such as ceramics by controlling the CS velocity to laminar flow regions of few mm / s (0.03 mm / s - 500 mm / s). The introduction of a controlledenvironment will also allow additional process parameters to be varied and, also the ability to test highly reactive materials such as lithium and magnesium.EXAMPLESProposed Work:1. Fabricate LELIB LiNiCL (-200 mAh g1) and carbon (C) electrodes, 350 Wh kg-1, 1000 cycles, <0.01% capacity fade cycle-1.2. Full fabrication of 500 Wh kg-1(Table 1), 1000 cycles, <0.01% fade ASSLIBs of doped Li2S or S, dendrite free solid solution structurally isomorphous alloy anodes with Li (Li-SIA) and w / o Li (SIA) current collector with >90 at. % Li, facile cycling, <~4% volume change (FIG. 2), and SSE (LisYCL and LisInCL or LiePSsCl or LiePSsBr) by high energy mechanical milling (HEMM) with room temperature Li-ion conductivity (LIC) of -1 mS cm-1over >4V, (FIG. 3) ensuring apt Li transport and thickness proven by interface modeling and theory.Technical Approach

[0086] For LELIBs: derived LiNiChand commercial C coated with conducting Polypyrrole, PPy (Melting Point Temperature (TMP) -300 °C will be deposited and fused by h-VSSCSLS / M enabled AM electrode designs locked into roughened Al (r-Al) and Cu (r-Cu) current collector grooves, respectively. For ASSLIBs: Li2S doped with DFT identified dopants by scalable HEMM lowering Li removal overpotential and S both coated with PPy and polyethylene oxide, PEG (TMP -70 °C) will mitigate electron and LIC issues. Conformal electrode layers (~ 100-150 mm) will be made by h-VSSCSLS / M fusing the PPy and PEG layers onto r-Al. For SSE, HEMM derived LnlnCL and LLYCL or LirPSsCI or LiePSsBr with melting / sintering points (>400-550 °C) will be deposited on graphite foil (GF) by h-VSSCSLS / M with control of gas (He, Ar, N2) pressure and temperature, nozzle design, powder feed rate, distance from substrate and traverse rate along with laser energy, frequency, and power. Few mm thick PPy and PEG coated doped Li2S, and S deposited on SSE will then be fused onto pre-deposited cathodes on r-Al. GF will be peeled and few mm thick PPy will be deposited by h-VSSCSLS / M and the assembly fused into roughened Li-SIA (r-Li-SIA) melt casted foils for S and HEMM derived and cold rolled r-SIA -80 mm anode foils for doped Li2S.Future h-VSSCSLS / M - Related Work

[0087] LELIB electrodes and ASSLIBs will be created by h-VSSCSLS / M, AM aided by reaction diffusion, mesoscale modeling and detailed characterization along with interface materials design and discovery by DFT, and molecular dynamics (MD) simulation coupled with system integration aided by ML, DFT, MD and interface modeling. MD with varying parameter settings will pre-train ML models for adapting to real states and matched to known physical relations. ML will also reflect processes rooted in simulation to model intermediate variables for further optimization. Utilization of optical, profilometry, and temperature sensors will collect real time data in massive sizes with process sensor data, enabling Al, ML and DT to hasten progress of h-VSSCSLS / M including use of convolutional neural networks to create functionally graded 3D LIB components. New Al methods will be created for: (i) control of variable speeds for metals, polymers, semiconductors, and ceramics, (ii) data-driven modeling of substratematerials interface interactions, and (iii) laser melting / sintering process simulation at each step. New ML models will be built leveraging both observation and simulated data using physical knowledge to regularize data driven models and build DTs. Additionally, over-potential, impedance change, electrochemically induced thermal and mechanical stresses, composition gradients across interfaces under equilibrium and dynamic cycling data will be obtained combined with mesoscale modeling implemented as a coupled mechanics and diffusion type system in a continuum setting. Mechanical integrity will be followed by a damage mechanicsbased formulation coupled with diffusion solved by our custom nonlinear finite element code capable of solving coupled mechanical, diffusion, and electrochemical phenomena. Molecular mechanics of electrodes, anode-SSE and cathode-SSE interfaces will be studied by ab-initio MD available in VASP / Quantum Espresso / Abinit or using classical MD with LAMMPS (Large-scale Atomic / Molecular Massively Parallel Simulator) for nanoscale simulation giving insights into all the electrochemical system responses with traits of varying potential, current and time. Key Li-transport data in electrodes, SSE as in PIGS. 4A and 4B for SSE and SSE-electrode interfaces got by ab initio or classical MD simulations will also be used to train neural network models for Al and ML efforts. Dopants identified for Li2S and alloying elements for Li diffusion enhancements in Li-SIA / SIA enabling 15 mAh cm'2capacity along with dynamic stability of interfaces with electrochemical potential and currents with time from experiments will give dataon structural, mechanical and electrochemical state of the interfaces including integrity of h-VSSCSLS / M derived DFT modified LiF (Sintering temperature, Tsinter- 400 °C) at anode-SSE and cathode-SSE interfaces made to boost Li transport over interfaces. This will also be aided by theoretical studies above. Of note, MD simulations on model SSE and electrode-SSE interfaces carried out over long-time scales will provide insights into Li+transport mechanisms, within the LIB to modify interfaces and improve performance. Thus, robust h-VSSCSLS / M, AM approach will revolutionize the LELIB and ASSLIB industry. A major task is equipment fabrication and scalable manufacturing.Performed Work:

[0088] The h-VSSCSLS / M process in accordance with the inventive concept was used to create a multilayered structure. An initial CS layer of grade 23 titanium (Ti 64 ELI) was held constant with respect to the travel speed (2 mm / sec), and the gas pressure was allowed to vary. The variation in gas pressure resulted in control over the particle’s velocity at 600 psi for the central part of the build structure, and 400 psi for the outer edges. This variation in pressure allowed a higher deposition rate for the desired structure as well as minimizing the waste on the overspray portions of the build. Two passes were required before the first interaction with the laser. The image in FIG. 5 illustrates the different effects of varying the parameters during the CS process of the Ti 64 ELI build. Area A shows the results of a 600 psi deposition, Area B shows the location where the pressure fell below the critical value of 200 psi and the resulting lack of deposition, and Area C shows the limited deposition outcome from using the 400 psi. Additional CS passes not contacting the substrate (i.e., passes which occurred later in the process), utilized 3-4 layers depending on the phase of the experiment.

[0089] Post CS material application, the laser’s path was varied from a linear perimeter pass having a rastered fill with two passes. For the microstructure study, the samples were divided into three regions having region zone 1-low exposure, zone 2-medium exposure, and zone 3-high exposure to provide different thermal cycles and overall build temperatures. In all cases, the particles melted having an estimated temperature > melting temperature (MT) of 1670°C. FIG. 6 shows the h-VSSCSLS / M process during the laser melting step. For zones 2 and 3, the melting instances correlated to the number of exposures allowing several cycles of melt-solidification-melt (e.g., 2 thermal cycles for zone 2 and 3 thermal cycles for zone 3). The defined laser’s path,raster methods, and boundaries of the multiple zones did not change throughout the 20 cycles required to make the intended structure. As illustrated in FIG. 6, area A shows the laser working on zone 2, medium laser exposure, zone 3 shows the area having the most laser interaction, and zone 1 is shown receiving the least laser interaction. Samples for cross section microscopy were removed from these areas.

[0090] During the structure-build, CNC machining was only used to deck the surfaces and provide a planer interface for additional layers. The CNC tool’s transverse speed (2500 mm / min) and cutter speed (1200 rpm) did not change during this trial. These values were defined by published machinist guides for milling the forged Ti 64 ELI material. Additional layers were created in a similar manner with the exception that the variations of CS parameters starting on the second set of passes, where the gas was kept constant at 600 psi and nozzle alignment of 30-45°, were used to mitigate the overspray.

[0091] Upon completion of the structure-build, visual observations of the final part revealed minimal distortions or surface variations between the three areas caused by the varied heat inputs. There were edge effects caused by the varying boundary conditions, which led to a section of the final structure to be removed by perimeter milling via the CNC process. FIG. 7 is an image of the completed structure that shows the edge boundaries of zone 1. Area A depicts the substrate structure interface, area B shows the central part of the structure where the SEM microscopy was performed on samples removed from the different zones, and area C shows the boundary between the structure and the environment. Additional work will be conducted to understand the correlation between the structure’s response to heat dissipation when located in the center of the structure as compared to those particles located at the edge and in direct contact with the substrate. Subsequently, additional process variations (laser intensity and travel speed adjustments) will be optimized to prevent the formation of this condition.Results and Discussion

[0092] The three different zones within the build (zone 1 -minimal laser interaction and lowest heat, zone 2 - moderate laser interaction due to an increase laser power and more thermal cycles, and zone 3 - higher laser interaction caused by increased laser power, slowest transverse speeds and the greatest number of thermal cycles).Zone 1

[0093] Zone 1 offered the lowest heat input and fastest cooling rates allowing the elimination of dendritic formations. Additionally, this microstructure offered minimal locations of prior Ingrains and had mostly small and randomized a - acicular grains. Interestingly, of the samples tested, the grain morphology in zone 1 did not allow the SEM’s secondary electron (SE) or back scattered electron (BSE) detectors to clearly resolve the microstructure and thus required the use of electron backscatter diffraction (EBSD) to study them. FIG. 8 shows the EBSD SEM scanned image of the micro structure discovered in zone 1. The minimal heat input and associated rapid cooling created by the ability to vary the h-VSSCSLS / M process inputs, allowed the creation of this dendrite-free, micro- acicular based a-structure.Zone 2

[0094] Zone 2 offered a higher heat input as compared to zone 1, but still lower than zone 3. This was performed by additional energy into the laser and multiple passes within this area. This microstructure offered locations of prior ^-grains at every location and had a lamellar colonies within those prior [3-locations. Unlike the sample from zone 1, zone 2’s micro structure was able to be viewed with the SEM’s BSE detector (FIG. 9). As shown in FIG. 9, zone 2 provided an area having a medium heat input grain growth example for comparison to zone 1 (lowest thermal input) and zone 3 (highest thermal input). Unlike zone 1, this structure provided many occurrences of the converted prior |3-grains with internal lamellar a-grains. This sample also had detectable P-grains discovered on EBSD mapping.Zone 3

[0095] Zone 3 offered the highest heat input of the three created samples and provided the lowest cooling rates due to the variations in the CS deposition resulting in minimal particle to particle contact in the coating. The laser’s energy was at its highest and allowed to make multiple passes at a slower speed than what was used for zones 1 and 2. This microstructure offered locations of prior B-grains, had a lamellar colonies within those prior B-locations, and the formation of dendritic grains that were much larger than any examples observed within zones 1 and 2. This sample was able to use the SEM’s BSE detector; see FIG. 10 that illustrates a cross-sectional image of zone 3, the area having the highest heat input. The image in FIG. 10 depictsone of the many dendritic microstructure formations that were discovered in zone 3. Since this was one of the microstructures known to reduce the performance of energy storage devices such as rechargeable metal-ion batteries wherein the dendrites cause short circuiting of the battery leading to hazards of explosion and fire, the example serves to illustrate the potential of this technology. It offers the ability to control the micro structure within the same structure build and provides the necessary evidence of the h-VSSCSLS / M process to be able to control this by varying the parameters during the process. In general, the occurrence of many observable regions of dendrite formations is co-relatable to other materials created from conventional processing methods which result in poor energy storage characteristics and cycling rates in devices such as rechargeable Li-ion and Li metal batteries.

[0096] Whereas particular embodiments of the invention have been described herein for purposes of illustration, it will be evident to those skilled in the art that numerous variations of the details may be made without departing from the invention as set forth in the appended claims.

Claims

We claim:

1. A method of preparing a multi-layer / multi-layered structure, comprising:a) cold spraying a layer of a feedstock material onto a substrate / build plate to create a cold sprayed coating, the cold spraying conducted at a hybrid velocity,wherein the hybrid velocity controls a particle velocity from a laminar field to supersonic velocity range, andwherein the hybrid velocity includes the deposition of soft or hard polymer particles, hard or soft ceramic, semiconductor, and metallic particles;b) subsequent to the cold spraying step, employing a laser energy source to sinter, fuse or melt the cold sprayed coating, comprising:directing the energy source to conduct localized sintering, fusing or melting of specific particles or regions of the cold sprayed coating that correspond to a preselected multi-layer / multi-layered structure; andforming a sintered, fused or melted layer; andc) sequentially repeating the steps of a) and b) forming one or more additional material layers on the sintered, fused or melted layer,wherein the number of additional layers is determined based on a total number of layers needed to produce the preselected multi-layer / multi-layered structure.

2. The method of claim 1, wherein cold spraying is conducted in large passes over an entirety of the substrate / build plate, or in precisely located areas with a tight spray pattern to reduce an amount of feedstock material usage.

3. The method of claim 1, wherein the feedstock material is in a dry form selected from the group consisting of particles, particulates, or granules.

4. The method of claim 1, wherein following completion of the first material layer and a subsequent second material layer, power of the laser energy source is increased and used intrimming, machining, and shaping an outline of the preselected multi-layer / multi-layered structure being prepared.

5. The method of claim 4, wherein following the trimming, machining, and shaping, one or more additional material layers are formed until the preselected multi-layer / multi-layered structure is built in its entirety with the corresponding complexity, contiguity, shape, and size.

6. The method of claim 1, wherein the feedstock material comprises a material selected from the group consisting of metal, metal alloy, polymer, ceramic, semiconductor, and mixtures and combinations thereof.

7. The method of claim 6, wherein the metal or metal alloy is selected from the group consisting of magnesium, calcium, strontium, zinc, copper, aluminum, stainless steel, tungsten, molybdenum, niobium, titanium, tantalum, Inconel, rhenium, osmium, ruthenium, iridium, platinum, palladium, tungsten-niobium alloy, tungsten-tantalum, tungsten-molybdenum, tungsten-cobalt alloy, tungsten-rhenium alloy, tungsten- silver composite, tungsten-tungsten carbide composite, reactive, and rare-earth metal and rare-earth metal alloys, and mixtures or alloys thereof.

8. The method of claim 1, further comprising employing a CAD model corresponding to the preselected multi-layer / multi-layered structure for directing and controlling the laser energy source in step b).

9. The method of claim 1, wherein step b) forms engineered pores and / or pathways in the preselected multi-layer / multi-layered structure.

10. The method of claim 1, further comprising following step b) subjecting the sintered, fused, or melted layer to subtractive machining, comprising:smoothening the surface of the sintered, fused, or melted layer; and forming a first material layer of the preselected multi-layer / multi-layered structure.

11. The method of claim 1 , wherein the laser energy source is selected from a thermal energy generating source consisting of laser, electron beam, plasma, electric arc, induction, magneto resistance, electrical resistance, and combinations thereof.

12. An additive manufacture device, comprising:a cold spray apparatus structured to deposit a coating of a feedstock material onto a substrate / build plate, the apparatus comprising a hybrid velocity that controls a particle velocity from a laminar field to supersonic velocity range, wherein the hybrid velocity includes deposition of soft or hard polymer particles, hard or soft ceramic, semiconductor, and metallic particles;a laser energy source structured to sinter, fuse or melt the coating of the feedstock material;a formed sintered, fused or melted layer; anda CAD model to direct the laser energy source to sinter, fuse or melt specific particles or regions of the coating of the feedstock material that correspond to a preselected multi-layer / multi-layered structure,wherein one or more additional layers of the feedstock material are sequentially deposited on the formed sintered, fused or melted layer to produce one or more additional material layers, and wherein the number of additional material layers is determined based on those needed to produce the preselected multi-layer / multi-layered structure.

13. The device of claim 12, wherein the feedstock material comprises a material selected from the group consisting of metal, metal alloy, polymer, ceramic, semiconductor, and mixtures and combinations thereof.

14. The device of claim 12, wherein the multi-layer or multi-layered structure is a medical implant device.

15. The device of claim 14, wherein the medical implant device is a scaffold.

16. The device of claim 14, wherein the medical implant device is composed of a material selected from the group consisting of Mg, Mg alloy, and Mg composite, Zn, Zn alloy and Zn composite, and Mo, Mo alloy and Mo composite.

17. The device of claim 12, wherein each of the one or more additional material layers is composed of the same feedstock material.

18. The device of claim 12, wherein the one or more of the additional material layers of the multi-layer structure is / are composed of a different feedstock material as compared to the other material layers.

19. The device of claim 12, wherein the feedstock material is selected such that alternating material layers are composed of the same feedstock material or a pattern of material layers is composed of the same feedstock material.

20. The method of claim 1, wherein the multi-layer / multi-layered structure comprises one or more LELIB electrodes and / or ASSLIBs prepared by h-VSSCSLS / M including AM aided by reaction diffusion, mesoscale modeling and detailed characterization along with interface materials design and discovery by density functional theory (DFT), and molecular dynamics (MD) simulation coupled with system integration aided by machine learning (ML), digital twin (DT), DFT, MD and interface modeling.

21. The method of claim 20, wherein MD with varying parameter settings pre-trains ML and DT models for adapting to real states and matched to known physical relations, and ML and DT reflects processes rooted in simulation to model intermediate variables for further optimization of the process.

22. The device of claim 12, wherein the multi-layer / multi-layered structure comprises one or more LELIB electrodes and / or ASSLIBs prepared by h-VSSCSLS / M including AM aided by reaction diffusion, mesoscale modeling and detailed characterization along with interface materials design and discovery by density functional theory (DFT), and molecular dynamics(MD) simulation coupled with system integration aided by ML, DT, DFT, MD and interface modeling.

23. The device of claim 22, wherein MD with varying parameter settings pre- trains ML and DT models for adapting to real states and matched to known physical relations, and ML and DT models reflect processes rooted in simulation to model intermediate variables for further optimization of the process.

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