Silicon nanostructured active materials for lithium-ion batteries and related processes, compositions, components and devices

Abstract

To provide nanostructured materials for use in rechargeable energy source devices such as lithium batteries, particularly rechargeable secondary lithium batteries, or lithium-ion batteries (LIBs).SOLUTION: The present invention includes materials, components, and devices, including nanostructured materials for use as battery active materials, and lithium ion battery (LIB) electrodes comprising such nanostructured materials, as well as manufacturing methods related thereto. Exemplary nanostructured materials include silicon-based nanostructures such as silicon nanowires and coated silicon nanowires, nanostructures disposed on substrates comprising active materials or current collectors such as silicon nanowires disposed on graphite particles or copper electrode plates, and LIB anode composites comprising high-capacity active material nanostructures formed on a porous copper and / or graphite powder substrate.SELECTED DRAWING: Figure 44

Description

[Technical Field]

[0001] The present invention relates to nanostructured materials for use in rechargeable energy storage devices such as lithium batteries, particularly rechargeable secondary lithium batteries, or lithium-ion batteries (LIBs). The invention includes materials, components, and devices, such as nanostructured materials used as battery active materials, and lithium-ion battery (LIB) electrodes comprising such nanostructured materials, as well as related manufacturing methods. Exemplary nanostructured materials include silicon-based nanostructures, such as silicon nanowires and coated silicon nanowires; nanostructures disposed on substrates comprising active materials or current collectors, such as silicon nanowires disposed on graphite particles or copper electrode plates; and LIB anode composites comprising high-capacity active material nanostructures formed on porous copper and / or graphite powder substrates. The invention also relates to active material nanostructures and manufacturing methods related to nanostructure processing, such as electrochemical deposition (ECD) of silicon nanostructures on LIB anode active materials and current collectors. The invention also relates to LIB materials, such as binders, electrolytes, electrolyte additives, and solid electrolyte interfaces (SEIs) suitable for use in LIB anodes comprising silicon and graphite materials, as well as related components, devices, and manufacturing methods. [Background technology]

[0002]

[0002] Conventional LIBs suffer from poor capacity, energy density, and cycle life. Silicon (Si) has been extensively studied as an active material for LIBs due to its attractive properties, such as a high theoretical specific capacity of approximately 4200 mAh / g relative to lithium (Li) and a low discharge potential. Si has a slightly higher voltage plateau than graphite and therefore has attractive safety properties. Si is an abundant and inexpensive material, and lithiated Si is more stable than lithiated graphite in typical lithium-ion battery electrolytes.

[0003]

[0003] Despite the attractive properties of silicon, commercial attempts to use Si as an active material have not been successful. Several factors contribute to this failure, including the lack of suitable methods available for mass-producing high-quality Si-based anode materials, the lack of solutions to address the detrimental consequences of Si's high volume expansion and contraction rates during lithiation and delithiation, and the lack of solutions to address Si's low intrinsic conductivity. There is a need for high-quality, cost-effective Si-based anode materials for LIBs, materials, compositions, and LIB components for use in Si-based LIBs, methods for producing and using such materials, and related LIB devices and components, and related methods.

[0004]

[0004] Conventional lithium batteries, such as lithium-ion batteries (LIBs), typically include an anode, a cathode, a separator material separating the cathode and anode, and an electrolyte. The anodes of most commercially available LIBs typically include a copper foil current collector coated with a mixture of graphite powder and a binder material. The cathodes of most commercially available LIBs typically include an aluminum foil current collector coated with a lithium transition metal oxide-based cathode material. Conventional LIB anodes include intercalation-based active materials, such as graphite, which have limited discharge capacity and cannot meet the increasing demands for higher energy density, higher power density, and longer battery life. Extensive research and development efforts have been focused on lithium (Li) alloy active materials, such as silicon (Si), for LIBs, which have a theoretical discharge capacity of 4200 mAh / g. However, several issues have hindered the commercialization of silicon-based LIBs.

[0005]

[0005] Thin-film Si active materials have been the subject of recent investigation for use in LIBs, but thin-film Si lacks the large surface area of ​​nanostructures and is prone to shattering when subjected to large volumetric flow rates. Low-temperature methods for producing Si nanomaterials have involved ball milling Si to produce Si powder active materials, but such methods result in low-quality Si particles with large, non-uniform particle sizes and low crystallinity.

[0006]

[0006] Producing high-quality silicon nanostructures for LIB active materials typically involves chemical vapor deposition (CVD) or wet chemical techniques, including high-temperature catalytic growth of silicon nanostructures, such as silicon nanowires. For example, such methods are disclosed in U.S. Patent Nos. 7,842,432 and 7,776,760, U.S. Patent Application Nos. 12 / 824,485 and 12 / 783,243, and U.S. Provisional Patent Application No. 61 / 511,826, the disclosures of each of which are incorporated herein by reference in their entireties. A typical method for producing silicon-based nanostructures involves using gold (Au) as a catalytic material for catalytically growing silicon nanostructures at high temperatures. While gold is widely used as a catalytic material due to its high chemical stability, its high cost makes it an unideal material for mass production of silicon-based materials. As disclosed in U.S. Provisional Patent Application No. 61 / 511,826, copper catalytic materials have been proposed as an alternative to gold for catalytically growing silicon nanostructures for LIB active materials. The disclosure of this application is incorporated herein by reference in its entirety.

[0007]

[0007] There is a need for a cost-effective method for mass-producing high-quality silicon-based materials suitable for use in LIBs, particularly as active materials in LIB anodes. Furthermore, there is a need for a low-temperature process that does not require the use of catalytic materials to produce such silicon nanostructures. Furthermore, there is a need for improved control of the physical and chemical properties of such silicon nanostructures during production to ensure adequate device performance. Furthermore, there is a need for high-quality silicon active materials that have improved bond strength with the substrate to which the silicon is attached.

[0008]

[0008] There is also a need for materials, components, devices, and methods that accommodate the large volume expansion and contraction of silicon that occurs during lithiation and delithiation. Problems associated with large silicon volume changes include active material degradation, unexpected changes in active material structure, delamination of anode material from the current collector, loss of conductivity, SEI degradation, insufficient or excessive SEI formation, and undesirable side reactions due to excess silicon active sites. These side effects can cause unexpected changes in battery materials and systems, thereby causing large hysteresis in the operating characteristics of the battery system.

[0009]

[0009] The present invention provides solutions to these and other problems, including solutions that provide control over battery material and component properties during production and through multiple charge cycles and the various conditions to which the battery is exposed. What is needed are LIB binder materials, electrolyte materials, and SEI materials or layers that are suitable for use with Si active materials, particularly LIB anode materials that include Si and graphite active materials. Summary of the Invention

[0010] The present invention includes a novel, cost-effective method for producing high-quality silicon-based materials for use in LIB components and devices, particularly silicon-based LIB anodes. The present invention enables a highly controllable, low-temperature process for producing such silicon materials, particularly silicon nanostructures. Furthermore, the present invention includes catalyst-free production of such silicon materials, thereby eliminating the need for catalytic materials and high-temperature processes. These processes of the present invention consistently produce high-quality materials with physical and chemical properties that can be highly controlled to meet specific requirements. These high-quality materials provide consistency and predictability in the performance of battery systems, thereby controlling changes in these materials and battery devices over multiple charging cycles and across the various conditions to which they are exposed. The high-quality materials of the present invention prevent irreversible, undesirable side effects that can cause unexpected and detrimental changes in LIB devices and lead to significant hysteresis in the battery's operating characteristics.

[0011] The present invention includes methods for electrochemically depositing discrete nanostructures comprising at least one high-capacity LIB active material directly onto a substrate, as well as related compositions, devices, and components. In a preferred embodiment, Si is electrochemically deposited directly onto one or more active materials and / or current collector structures to form a Si-based LIB anode. In one exemplary embodiment, Si is electrochemically deposited onto a copper (Cu) current collector, such as a Cu plate, mesh, or sponge, which can be used as a LIB anode material. In another exemplary embodiment, Si is electrochemically deposited onto graphite particles to form a Si-graphite composite LIB anode material. This approach enables low-temperature, catalyst-free, and growth-template-free generation of active material nanostructures suitable for use in LIB anodes. This approach can produce highly crystalline Si nanostructures at low growth temperatures and allows for improved control of Si deposition and the physical and chemical properties of the Si nanostructures. Furthermore, this approach can improve adhesion between the Si nanostructure active material and the current collector and / or active material.

[0012]

[0012] The present invention further includes binders, electrolytes and electrolyte additives, and SEI materials and layers suitable for Si-based LIB anode active materials, such as Si and graphite composite anode materials, which have improved interactions with Si-based materials compared to conventional LIB materials that are not designed to interact with Si materials and cannot accommodate the volume expansion of high-capacity active materials during lithiation.

[0013] Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the invention. The advantages of the invention will be realized and attained by the structure and will be particularly pointed out in the description and claims, as well as the accompanying drawings.

[0014] It is to be understood that both the foregoing comparative description and the following detailed description are exemplary and explanatory and are intended to further explain the invention as claimed. It is also to be understood that the specific embodiments shown and described herein are examples of the invention and are not intended to limit the scope of the invention in any way. Indeed, for the sake of brevity, some of the conventional electronics, fabrication, devices, nanostructures, and other functional aspects of the system, components of the individual operating components of the system, and their associated methods will not be described in detail herein.

[0015] For the sake of brevity, this specification may not explicitly describe every possible combination of raw materials, crystal structures, crystallinity, morphology, shape, and size of active materials, substrates, substrate-active material composites, binders, electrolyte materials, and SEI layer and materials. However, the present invention includes any combination of the individual features described herein with respect to active material nanostructures, substrates, substrate-active material composites, binders, electrolyte materials, SEI layer and materials, and additional compositions, structures, and device components. Furthermore, while this specification may not explicitly describe every possible variation of the processes related to the present invention, the methods of the present invention include combinations of the individual process parameters described herein and modifications and variations thereof. As will be understood by those skilled in the art, the individual features of each embodiment of the present invention can be modified to achieve desired results. Such modifications are within the scope of the present invention. [Brief explanation of the drawings]

[0016]

[0016] The accompanying drawings, which are incorporated in and form part of this specification, illustrate the present invention and, together with the description, serve to further explain the principles of the present invention and enable those skilled in the art to make and use the present invention. [Figure 1A]

[0017] 1 shows an electrolytic cell for conventional electrochemical deposition (ECD) technology. [Figure 1B] 1 shows an electrolytic cell for conventional electrochemical deposition (ECD) technology. [Figure 2A]

[0018] 1 shows a nanostructure comprising at least one LIB active material deposited on a substrate using one or more ECD techniques of the present invention. [Figure 2B]

[0018] Nanostructures comprising at least one LIB active material deposited on a substrate using one or more ECD techniques of the present invention are shown. [Figure 2C]

[0018] Nanostructures comprising at least one LIB active material deposited on a substrate using one or more ECD techniques of the present invention are shown. [Figure 2D]

[0018] Nanostructures comprising at least one LIB active material deposited on a substrate using one or more ECD techniques of the present invention are shown. [Figure 2E]

[0018] Nanostructures comprising at least one LIB active material deposited on a substrate using one or more ECD techniques of the present invention are shown. [Figure 2F]

[0018] Nanostructures comprising at least one LIB active material deposited on a substrate using one or more ECD techniques of the present invention are shown. [Figure 2G]

[0018] Nanostructures comprising at least one LIB active material deposited on a substrate using one or more ECD techniques of the present invention are shown. [Figure 2H]

[0018] Nanostructures comprising at least one LIB active material deposited on a substrate using one or more ECD techniques of the present invention are shown. [Figure 2I]

[0018] Nanostructures comprising at least one LIB active material deposited on a substrate using one or more ECD techniques of the present invention are shown. [Figure 2J]

[0018] Nanostructures comprising at least one LIB active material deposited on a substrate using one or more ECD techniques of the present invention are shown. [Figure 2K]

[0018] Nanostructures comprising at least one LIB active material deposited on a substrate using one or more ECD techniques of the present invention are shown. [Figure 3A]

[0019] 1 shows nanostructures having different or varying material compositions throughout different spatial regions of an individual nanostructure. [Figure 3B]

[0019] Nanostructures are shown that have different or varying material compositions throughout different spatial regions of an individual nanostructure. [Figure 3C]

[0019] Nanostructures are shown that have different or varying material compositions throughout different spatial regions of an individual nanostructure. [Figure 3D]

[0019] Nanostructures are shown that have different or varying material compositions throughout different spatial regions of an individual nanostructure. [Figure 3E]

[0019] Nanostructures are shown that have different or varying material compositions throughout different spatial regions of an individual nanostructure. [Figure 3F]

[0019] Nanostructures are shown that have different or varying material compositions throughout different spatial regions of an individual nanostructure. [Figure 3G]

[0019] Nanostructures are shown that have different or varying material compositions throughout different spatial regions of an individual nanostructure. [Figure 3H]

[0019] Nanostructures are shown that have different or varying material compositions throughout different spatial regions of an individual nanostructure. [Figure 3I]

[0019] Nanostructures are shown that have different or varying material compositions throughout different spatial regions of an individual nanostructure. [Figure 4A]

[0020] 1 shows a scanning electron microscope (SEM) image of a graphite foil substrate. [Figure 4B]

[0020] A scanning electron microscope (SEM) image of a graphite foil substrate is shown. [Figure 4C]

[0020] A scanning electron microscope (SEM) image of a graphite foil substrate is shown. [Figure 4D]

[0020] A scanning electron microscope (SEM) image of a graphite foil substrate is shown. [Figure 5A]

[0021] Photographs of various composite LIB anode structures including a graphite foil current collector substrate and discrete Si nanostructures formed directly on the graphite foil by one or more ECD methods of the present invention are shown. [Figure 5B]

[0021] Photographs of various composite LIB anode structures including a graphite foil current collector substrate and discrete Si nanostructures formed directly on the graphite foil by one or more ECD methods of the present invention are shown. [Figure 5C]

[0021] Photographs of various composite LIB anode structures including a graphite foil current collector substrate and discrete Si nanostructures formed directly on the graphite foil by one or more ECD methods of the present invention are shown. [Figure 6A]

[0022] 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 6B]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 7A]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 7B]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 8A]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 8B]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 9A]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 9B]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 10A]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 10B]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 11A]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 11B]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 12A-B]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 12C]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 13A]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 13B]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 14A]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 14B]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 14C]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 15A]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 15B]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 16A]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 16B]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 17A]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 17B]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 18A]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 18B]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 19A]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 19B]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 19C]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 20A]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 20B]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 21A]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 21B]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 22A]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 22B]

[0022] Figure 1 shows SEM images of discrete Si active material nanostructures formed on a graphite foil substrate by various ECD methods of the present invention. [Figure 23]

[0023] 1 shows a graphite foil substrate having a graphite powder substrate formed thereon. [Figure 24A]

[0024] 24 shows an SEM image of the graphite powder layer of FIG. 23 before Si deposition using one or more ECD processes of the present invention. [Figure 24B]

[0024] Figure 24 shows an SEM image of the graphite powder layer of Figure 23 before Si deposition using one or more ECD processes of the present invention. [Figure 24C]

[0024] Figure 24 shows an SEM image of the graphite powder layer of Figure 23 before Si deposition using one or more ECD processes of the present invention. [Figure 25A]

[0025] 1 shows an SEM image of a layer of graphite powder having Si nanostructures formed thereon using one or more ECD processes of the present invention. [Figure 25B]

[0025] Figure 1 shows an SEM image of a layer of graphite powder having Si nanostructures formed thereon using one or more ECD processes of the present invention. [Figure 25C]

[0025] Figure 1 shows an SEM image of a layer of graphite powder having Si nanostructures formed thereon using one or more ECD processes of the present invention. [Figure 25D]

[0025] Figure 1 shows an SEM image of a layer of graphite powder having Si nanostructures formed thereon using one or more ECD processes of the present invention. [Figure 26A]

[0026] 1 shows a photograph of a perforated copper (Cu) substrate having graphite powder substrate material disposed therein. [Figure 26B]

[0026] A photograph of a perforated copper (Cu) substrate having graphite powder substrate material disposed therein is shown. [Figure 27A]

[0026] A photograph of a perforated copper (Cu) substrate having graphite powder substrate material disposed therein is shown. [Figure 27B]

[0026] A photograph of a perforated copper (Cu) substrate having graphite powder substrate material disposed therein is shown. [Figure 28]

[0027] 1 shows an optical image of a porous Cu mesh substrate material prior to deposition of SI nanostructures thereon. [Figure 29]

[0028] 1 shows an optical image of a porous Cu mesh substrate having Si nanostructures formed thereon by one or more ECD processes of the present invention. [Figure 30A]

[0029] 1 shows SEM images of Si nanostructures deposited on graphite powder disposed in a porous Cu mesh substrate scaffold by one or more ECD processes of the present invention. [Figure 30B]

[0029] Figure 1 shows SEM images of Si nanostructures deposited on graphite powder disposed in a porous Cu mesh substrate scaffold by one or more ECD processes of the present invention. [Figure 30C]

[0029] Figure 1 shows SEM images of Si nanostructures deposited on graphite powder disposed in a porous Cu mesh substrate scaffold by one or more ECD processes of the present invention. [Figure 30D]

[0029] Figure 1 shows SEM images of Si nanostructures deposited on graphite powder disposed in a porous Cu mesh substrate scaffold by one or more ECD processes of the present invention. [Figure 31A]

[0029] Figure 1 shows SEM images of Si nanostructures deposited on graphite powder disposed in a porous Cu mesh substrate scaffold by one or more ECD processes of the present invention. [Figure 31B]

[0029] Figure 1 shows SEM images of Si nanostructures deposited on graphite powder disposed in a porous Cu mesh substrate scaffold by one or more ECD processes of the present invention. [Figure 31C]

[0029] Figure 1 shows SEM images of Si nanostructures deposited on graphite powder disposed in a porous Cu mesh substrate scaffold by one or more ECD processes of the present invention. [Figure 31D]

[0029] Figure 1 shows SEM images of Si nanostructures deposited on graphite powder disposed in a porous Cu mesh substrate scaffold by one or more ECD processes of the present invention. [Figure 32A]

[0030] 1 shows SEM images of Si nanostructures formed directly on a porous Cu mesh substrate by one or more ECD processes of the present invention. [Figure 32B]

[0030] Figure 1 shows SEM images of Si nanostructures formed directly on a porous Cu mesh substrate by one or more ECD processes of the present invention. [Figure 32C]

[0030] Figure 1 shows SEM images of Si nanostructures formed directly on a porous Cu mesh substrate by one or more ECD processes of the present invention. [Figure 32D]

[0030] Figure 1 shows SEM images of Si nanostructures formed directly on a porous Cu mesh substrate by one or more ECD processes of the present invention. [Figure 33]

[0031] Electrochemically deposited Cu substrate material onto a graphite foil substrate structure is shown. [Figure 34]

[0031] The Cu-graphite substrate of Figure 33 after deposition of Si nanostructures using one or more ECD processes of the present invention. [Figure 35]

[0031] The Cu-graphite substrate of Figure 33 after deposition of Si nanostructures using one or more ECD processes of the present invention. [Figure 36A]

[0032] 35 shows an SEM image of Si nanostructures formed on the Cu-graphite substrate shown in FIG. 34. [Figure 36B]

[0032] Figure 34 shows an SEM image of Si nanostructures formed on a Cu-graphite substrate. [Figure 36C]

[0032] Figure 34 shows an SEM image of Si nanostructures formed on a Cu-graphite substrate. [Figure 37A]

[0033] 36 shows an SEM image of Si nanostructures formed on the Cu-graphite substrate shown in FIG. [Figure 37B]

[0033] Figure 35 shows an SEM image of Si nanostructures formed on a Cu-graphite substrate. [Figure 37C]

[0033] Figure 35 shows an SEM image of Si nanostructures formed on a Cu-graphite substrate. [Figure 38A]

[0034] 1 illustrates a LIB anode composite structure including a particle and / or layer substrate structure. [Figure 38B]

[0034] LIB anode composite structures including particle and / or layer substrate structures are shown. [Figure 38C]

[0034] LIB anode composite structures including particle and / or layer substrate structures are shown. [Figure 39A]

[0035] 1 illustrates an ECD substrate structure having one or more regions containing surface features. [Figure 39B]

[0035] An ECD substrate structure having one or more regions containing surface features is shown. [Figure 39C]

[0035] An ECD substrate structure having one or more regions containing surface features is shown. [Figure 39D]

[0035] An ECD substrate structure having one or more regions containing surface features is shown. [Figure 39E]

[0035] An ECD substrate structure having one or more regions containing surface features is shown. [Figure 39F]

[0035] An ECD substrate structure having one or more regions containing surface features is shown. [Figure 40A]

[0036] 1 shows a substrate structure including various surface features having discrete active material nanostructures formed thereon. [Figure 40B]

[0036] A substrate structure is shown that includes various surface features having discrete active material nanostructures formed thereon. [Figure 40C]

[0036] A substrate structure is shown that includes various surface features having discrete active material nanostructures formed thereon. [Figure 40D]

[0036] A substrate structure is shown that includes various surface features having discrete active material nanostructures formed thereon. [Figure 40E]

[0036] A substrate structure is shown that includes various surface features having discrete active material nanostructures formed thereon. [Figure 40F]

[0036] A substrate structure is shown that includes various surface features having discrete active material nanostructures formed thereon. [Figure 40G]

[0036] A substrate structure is shown that includes various surface features having discrete active material nanostructures formed thereon. [Figure 41A]

[0036] A substrate structure is shown that includes various surface features having discrete active material nanostructures formed thereon. [Figure 41B]

[0036] A substrate structure is shown that includes various surface features having discrete active material nanostructures formed thereon. [Figure 41C]

[0036] A substrate structure is shown that includes various surface features having discrete active material nanostructures formed thereon. [Figure 41D]

[0036] A substrate structure is shown that includes various surface features having discrete active material nanostructures formed thereon. [Figure 41E]

[0036] A substrate structure is shown that includes various surface features having discrete active material nanostructures formed thereon. [Figure 41F]

[0036] A substrate structure is shown that includes various surface features having discrete active material nanostructures formed thereon. [Figure 41G]

[0036] A substrate structure is shown that includes various surface features having discrete active material nanostructures formed thereon. [Figure 41H]

[0036] A substrate structure is shown that includes various surface features having discrete active material nanostructures formed thereon. [Figure 41I]

[0036] A substrate structure is shown that includes various surface features having discrete active material nanostructures formed thereon. [Figure 42A]

[0036] A substrate structure is shown that includes various surface features having discrete active material nanostructures formed thereon. [Figure 42B]

[0036] A substrate structure is shown that includes various surface features having discrete active material nanostructures formed thereon. [Figure 42C]

[0036] A substrate structure is shown that includes various surface features having discrete active material nanostructures formed thereon. [Figure 43A]

[0037] 1A-1C illustrate various multilayer substrates that include surface features and discrete active material nanostructures formed thereon. [Figure 43B]

[0037] Various multilayer substrates are shown that include surface features and discrete active material nanostructures formed thereon. [Figure 43C]

[0037] Various multilayer substrates are shown that include surface features and discrete active material nanostructures formed thereon. [Figure 43D]

[0037] Various multilayer substrates are shown that include surface features and discrete active material nanostructures formed thereon. [Figure 43E]

[0037] Various multilayer substrates are shown that include surface features and discrete active material nanostructures formed thereon. [Figure 43F]

[0037] Various multilayer substrates are shown that include surface features and discrete active material nanostructures formed thereon. [Figure 44]

[0038] 1 illustrates an electrolytic cell for one or more ECD processes of the present invention. [Figure 45A]

[0039] 1 shows current-voltage profiles for various Si precursors used in various ECD processes of the present invention. [Figure 45B]

[0039] Figure 1 shows the current-voltage profiles of various Si precursors used in various ECD processes of the present invention. [Figure 46]

[0040] 1 shows a current profile during Si deposition according to one or more ECD embodiments of the present invention. [Figure 47]

[0041] 1 illustrates an electrolysis cell including a magnetic stir plate for fluid movement within the electrolysis cell, in accordance with one or more embodiments of the present invention. [Figure 48]

[0042] 1 shows an electrolytic cell for ECD of discrete active material nanostructures on a particulate substrate. [Figure 49]

[0043] 1 shows a porous working electrode having ECD substrate particles contained therein.

[0017]

[0044] Although the nanostructures of the present invention are shown and described in certain figures or descriptions herein as individual nanostructures, the present invention also includes a plurality of such nanostructures having similar features to the individual nanostructures shown herein. As will be understood by those skilled in the art, the diagrams and elements presented in the figures may not be to scale with the actual elements of the present invention.

[0018]

[0045] The present invention is now described with reference to the accompanying drawings, where like reference numbers indicate identical or functionally similar elements.

[0019] definition

[0046] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art of the present invention. The following definitions supplement those in the art and are directed to this application and are not to be attributed to any related or unrelated case, for example, to any jointly owned patent or application. Although any methods and materials similar or equivalent to those described herein can actually be used to test the present invention, preferred materials and methods are described herein. Therefore, the terminology used herein is for the purpose of describing particular embodiments only and is not limiting.

[0020]

[0047] As used in the specification and claims, the singular forms "a," "an," and "said" include the plural forms unless the context clearly dictates otherwise. Thus, for example, reference to "a nanostructure" includes a plurality of such nanostructures, and so forth.

[0021]

[0048] As used herein, the term "about" indicates that the value of a given quantity may vary by ±10% of that value, or optionally by ±5% of that value, or in some embodiments, by ±1% of the stated value.

[0022]

[0049] A "nanostructure" is a structure having at least one region or characteristic dimension that is less than about 500 nm in size, e.g., less than about 200 nm, less than about 100 nm, less than about 50 nm, or even less than about 20 nm. Typically, the region or characteristic dimension is along the shortest axis of the structure. Examples of such structures include spherical nanostructures, nanowires, nanospikes, tapered nanowires, and nanowires. These include wires, nanorods, nanotubes, nanowhiskers, nanoribbons, nanodots, nanoparticles, nanofibers, branched nanostructures, nanotetrapods, nanotripods, nanobipods, nanocrystals, nanodots, quantum dots, nanoparticles, etc. Nanostructures can be, for example, substantially crystalline, substantially monocrystalline, polycrystalline, amorphous, or combinations thereof. In one embodiment, each of the three dimensions of the nanostructure has a dimension of less than about 500 nm, e.g., less than about 200 nm, less than about 100 nm, less than about 50 nm, or even less than about 20 nm.

[0023]

[0050] "Aspect ratio" refers to the length of the first axis of a nanostructure divided by the average of the lengths of the second and third axes of the nanostructure, where the second and third axes are two axes whose lengths are usually approximately equal to each other. For example, the aspect ratio of a perfect rod would be the length of its long axis divided by the diameter of its cross section perpendicular (or at right angles) to the long axis.

[0024]

[0051] As used herein, the "width" or "diameter" of a nanostructure refers to the width or diameter of a cross section perpendicular to the first axis of the nanostructure, the first axis having the greatest length difference relative to the second and third axes (the second and third axes are two axes whose lengths are often approximately equal to one another). The first axis is not necessarily the longest axis of the nanostructure; for example, in the case of a disk-shaped nanostructure, the cross section will be approximately a circular cross section perpendicular to the short longitudinal axis of the disk. If the cross section is not circular, the width or diameter is the average of the long and short axes of the cross section. For elongated or high aspect ratio nanostructures, such as nanowires, the diameter is measured in a cross section perpendicular to the longest axis of the nanowire. For spherical nanostructures, the diameter is measured from one side to the other through the center of the sphere.

[0025]

[0052] The nanostructures formed by the methods of the present invention preferably comprise highly crystalline nanostructures, e.g., highly monocrystalline nanostructures, e.g., highly monocrystalline Si nanowires or other nanostructures. In preferred embodiments, the nanostructures are substantially monocrystalline and substantially free of polycrystalline and amorphous material after formation. Preferably, the nanostructures are free of polycrystalline and amorphous material after formation. Highly crystalline nanostructures can be formed by the ECD processes of the present invention, and active material nanostructures having a high degree of crystallinity after formation are preferred for the LIB active material nanostructures of the present invention.

[0026]

[0053] The terms "crystalline" or "substantially crystalline," when used with respect to nanostructures, refer to the fact that nanostructures typically exhibit long-range order across one or more dimensions of the structure. Those skilled in the art will understand that the term "long-range order" depends on the absolute size of a particular nanostructure, as the order of a single crystal cannot extend beyond the boundaries of the crystal. In this case, "long-range order" refers to substantial order across at least most of the dimensions of the nanostructure. In some cases, nanostructures can carry an oxide or other coating, which includes a shell or coating of the same material as the nanostructure core but with a different crystalline structure than the nanostructure core, or the nanostructure can be composed of a core and at least one shell. In such cases, it is recognized that the oxide, shell, or other coating need not exhibit such long-range order (e.g., it can be amorphous, polycrystalline, or otherwise). In such cases, the phrases "crystalline," "substantially crystalline," "substantially monocrystalline," or "monocrystalline" refer to the central core of the nanostructure (excluding any coating layers or shells). Unless otherwise specified or distinguished, the general terms "crystalline" or "substantially crystalline," as used herein, are intended to encompass structures containing various imperfections, stacking faults, atomic substitutions, etc., so long as the structure exhibits substantial long-range order (e.g., order over at least about 80% of the length of at least one axis of the nanostructure or its core). It is also recognized that the interface between the core and exterior of a nanostructure, or between a core and an adjacent shell, or between a shell and a second adjacent shell, may contain amorphous regions or may even be amorphous. This does not prevent a nanostructure from being crystalline or substantially crystalline as defined herein.

[0027]

[0054] The term "monocrystalline" when used in reference to a nanostructure means that the nanostructure is substantially When used in reference to a nanostructure heterostructure comprising a core and one or more shells, "monocrystalline" indicates that the core is substantially crystalline and comprises substantially a single crystal.

[0028]

[0055] A "nanocrystal" is a nanostructure that is substantially monocrystalline. Thus, a nanocrystal has at least one region or characteristic dimension with a dimension of less than about 500 nm, e.g., less than about 200 nm, less than about 100 nm, less than about 50 nm, or even less than about 20 nm. The term "nanocrystal" is intended to encompass substantially monocrystalline nanostructures that contain various defects, stacking faults, atomic substitutions, etc., as well as substantially monocrystalline nanostructures that are free of such defects, defects, or substitutions. In the case of nanocrystal heterostructures comprising a core and one or more shells, the core of the nanocrystal is typically substantially monocrystalline, but the shells need not be. In one embodiment, each of the three dimensions of the nanocrystal has a dimension of less than about 500 nm, e.g., less than about 200 nm, less than about 100 nm, less than about 50 nm, or even less than about 20 nm. Examples of nanocrystals include, but are not limited to, substantially spherical nanocrystals, branched nanocrystals, and substantially single-crystalline nanowires, nanorods, nanospikes, tapered nanowires, nanotubes, nanowhiskers, nanoribbons, nanodots, nanoparticles, quantum dots, nanotetrapods, nanotripods, nanobipods, and branched nanotetrapods (e.g., inorganic dendrites).

[0029]

[0056] The term "heterostructure," when used with respect to nanostructures, refers to a nanostructure characterized by at least two different and / or distinguishable material types. Typically, one region of the nanostructure comprises a first material type and a second region of the nanostructure comprises a second material type. In certain embodiments, the nanostructure comprises a core of a first material and at least one shell of a second (or third, etc.) material, with the different material types distributed radially, e.g., along the long axis of a nanowire, the long axes of the arms of a branched nanowire, or the center of a nanocrystal. (The shell may, but need not, completely cover the adjacent materials to be considered a shell, or in the case of a nanostructure, a heterostructure. For example, a nanocrystal characterized by a core of one material surrounded by small islands of a second material is a heterostructure.) In other embodiments, the different material types are distributed at various locations within the nanostructure, e.g., along the major (long) axis of a nanowire or along the long axes of the arms of a branched nanowire. Different regions within a heterostructure can comprise entirely different materials, or the different regions can comprise a base material (eg, silicon) with different dopants or different concentrations of the same dopant.

[0030]

[0057] A "nanoparticle" is a nanostructure having each dimension (e.g., each of the three dimensions of the nanostructure) less than about 500 nm, e.g., less than about 200 nm, less than about 100 nm, less than about 50 nm, or even less than about 20 nm. Nanoparticles can be of any shape, including, for example, nanocrystals, substantially spherical particles (having an aspect ratio of about 0.8 to about 1.2), and irregularly shaped particles. Nanoparticles optionally have an aspect ratio of less than about 1.5. Nanoparticles can be amorphous, crystalline, monocrystalline, partially crystalline, polycrystalline, or other. Nanoparticles can be substantially homogeneous in material properties, or in certain embodiments, can be heterogeneous (e.g., heterostructured). Nanoparticles can be made from essentially any one or more convenient materials; for example, nanoparticles can include "pure" materials, substantially pure materials, doped materials, etc.

[0031]

[0058] A "nanowire" is a nanostructure with one major axis that is longer than the other two major axes. As a result, nanowires have an aspect ratio greater than 1, and the nanowires of the present invention typically have an aspect ratio greater than about 1.5, or greater than about 2. Short nanowires, sometimes called nanorods, typically have an aspect ratio between about 1.5 and about 10. Longer nanowires have aspect ratios greater than about 10, greater than about 20, greater than about 50, or greater than about 100, or even greater than about 10,000. The diameter of a nanowire is typically less than about 500 nm, preferably less than about 200 nm, and more preferably less than about 100 nm. Preferably, the nanowires are less than about 150 nm, and most preferably less than about 100 nm, less than about 50 nm, or less than about 25 nm, or even less than about 10 nm or about 5 nm. The nanowires of the present invention can be substantially homogeneous in material properties, or in certain embodiments, heterogeneous (e.g., nanowire heterostructures). Nanowires can be fabricated from essentially any convenient material or materials. Nanowires can include "pure" materials, substantially pure materials, doped materials, etc., and can include insulators, conductors, and semiconductors. Nanowires are typically substantially crystalline and / or substantially monocrystalline, but can be, for example, polycrystalline or amorphous. In some cases, nanowires can carry an oxide or other coating, or can be composed of a core and at least one shell. In such cases, it is recognized that the oxide, shell, or other coating need not exhibit such ordering (e.g., can be amorphous, polycrystalline, or otherwise). Nanowires can have variable diameters across the region of greatest variability and across a linear dimension of at least 5 nm (e.g., at least 10 nm, at least 20 nm, or at least 50 nm), or can have substantially uniform diameters, i.e., diameters that exhibit a variation of less than about 20% (e.g., less than about 10%, less than about 5%, or less than about 1%). Typically, the diameter is measured from the ends of the nanowire (e.g., across the central 20%, 40%, 50%, or 80% of the nanowire). Nanowires can be straight or, for example, curved or bent across the entire length or a portion of their longitudinal axis. In certain embodiments, nanowires or portions thereof may exhibit two- or three-dimensional quantum confinement. Nanowires according to the present invention can explicitly exclude carbon nanotubes and, in certain embodiments, can exclude "whiskers" or "nanowhiskers," particularly whiskers having diameters greater than 100 nm or greater than about 200 nm.

[0032]

[0059] "Substantially spherical nanoparticles" are nanoparticles having an aspect ratio between about 0.8 and about 1.2. Similarly, "substantially spherical nanocrystals" are nanocrystals having an aspect ratio between about 0.8 and about 1.2.

[0033]

[0060] As discussed herein, "active material" or "LIB active material" refers to one or more battery active materials, particularly LIB active materials that can be lithiated with Li ions and are suitable for use as active materials in LIB anode active materials. The active material can include any suitable LIB active material known in the art, including those mentioned herein.

[0034]

[0061] As referred to herein, one or more "inactive materials" refer to materials that are incapable of lithium insertion or have negligible lithium insertion capacity compared to the corresponding active materials in LIB components formed by the methods of the present invention. Whether a material is active or inactive depends on the properties of the LIB system in which it is included. Inactive materials may be useful for purposes other than providing lithium capacity, such as increasing electrical conductivity, improving adhesion between the active material and the substrate, or achieving specific properties of the active material during or after the electrochemical deposition process, as discussed in more detail below. Inactive materials may include inactive materials known in the art, as described herein.

[0035]

[0062] As used herein, a "current collector," "current collector material," "current collector structure," or "LIB current collector" refers to a conductive material or structure that collects electrons released during charging or discharging (i.e., lithiation or delithiation) in a LIB and transmits such electrons from an external device to or from an external circuit connected to the LIB. The current collector can include any current collector known in the art, including those described herein.

[0036]

[0063] As used herein, "binder" or "binder material" refers to a non-reactive, adhesive LIB component used to adhere one or more components to one another, such as to adhere graphite powder to one another, to coat the powder on a substrate, and to form a LIB device. Alternatively, a binder material can be added to a substrate containing graphite powder to form an ECD substrate.

[0037]

[0064] In preferred embodiments, the active material(s) formed by direct ECD comprise discrete nanostructures rather than a continuous active material structure, such as a continuous film comprising the active material. As the term "discrete" structure is used herein with respect to active material nanostructures, such term means that the structure comprises multiple, independent, discontinuous domains of material forming the nanostructure, although such structures need not be completely contiguous. That is, "discrete" structures may be in physical contact with one another unless otherwise specified. The nanostructures can comprise essentially any desired type of nanostructure, including, but not limited to, nanowires. The nanostructures can include nanowires, nanorods, nanospikes, tapered nanowires, nanotubes, nanowhiskers, nanoribbons, nanoparticles, nanofibers, nanocrystals, branched nanostructures, nanodots, quantum dots, spherical nanostructures, or other nanostructures, or any combination thereof. Preferably, the nanostructures comprise one-dimensional elongated or high-aspect-ratio nanostructures. For example, the nanostructures can include nanowires, nanorods, nanospikes, tapered nanowires, nanotubes, nanowhiskers, nanoribbons, branched nanostructures, or other one-dimensional elongated or high aspect ratio nanostructures, or any combination thereof. In a preferred embodiment, the nanostructures comprise Si, e.g., Si nanowires. More preferably, the nanostructures comprise monocrystalline Si nanostructures, e.g., monocrystalline Si nanowires.

[0038]

[0065] In certain embodiments, the surface of an ECD substrate can include discrete surface features to provide a modified substrate surface. As the term "discrete" substrate surface feature or substrate structure is used herein with respect to ECD substrates and ECD substrate surfaces, such term means that the structure includes a plurality of discrete regions or domains that exhibit a surface modification or surface feature, or a plurality of discrete regions or domains that exhibit a surface modification or surface feature to a greater extent than one or more adjacent locations on the substrate surface. However, such regions of modification on a surface or surface feature need not be completely contiguous, so long as the discrete surface features provide regions on the substrate surface with identifiable characteristics. That is, "discrete" surface features can physically contact one another unless otherwise specified.

[0039]

[0066] A "compound" or "chemical compound" is a chemical substance composed of two or more different chemical elements and having a unique, defined chemical structure, including, for example, molecular compounds held together by covalent bonds, salts held together by ionic bonds, intermetallic compounds held together by metallic bonds, and complexes held together by coordinate covalent bonds.

[0040]

[0067] An "alloy" is a metallic solid solution (complete or partial) composed of two or more elements. Complete solid-solution alloys have a single solid-phase microstructure, while partial solid-solution alloys have two or more phases that may or may not be homogeneously distributed.

[0041]

[0068] A "porous" substrate contains pores or gaps. In certain embodiments, the porous substrate can be an array or collection of particles, e.g., a randomly packed collection of particles or a dispersed collection of particles. The particles can be essentially any desired size and / or shape, e.g., spherical, elongated, elliptical / oval, plate-like (e.g., plate, flake, or sheet), etc. The individual particles can themselves be non-porous or porous (e.g., contain a capillary network throughout their structure). When used for nanostructure growth, the particles can be, but typically are not, cross-linked. In other embodiments, the porous substrate can be a mesh, woven fabric, or sponge.

[0042]

[0069] "Carbon-based substrate" refers to a substrate comprising at least about 50% carbon by mass. Suitably, the carbon-based substrate comprises at least about 60% carbon, 70% carbon, 80% carbon, 90% carbon, 95% carbon, or about 100% carbon by mass, e.g., 100% carbon. Preferably, the carbon-based substrate is highly pure carbon, e.g., greater than 98% or 99% carbon by mass. Most preferably, the carbon-based substrate is 100% carbon by mass. Exemplary carbon-based substrates that can be used in the practice of the present invention include, but are not limited to, graphite, graphene, natural graphite, artificial graphite, highly oriented pyrolitic graphite (HOPG), activated carbon, petroleum coke carbon, mesophase carbon, hard carbon, soft carbon, carbon black, desulfurized carbon black, porous carbon, fullerenes, fullerenic soot, carbon films or foils, carbon sheets, carbon paper, carbon powder, porous carbon powder, carbon fibers, carbon particles, carbon microbeads, mesocarbon microbeads (MCMB), carbon nanotubes, carbon nanoparticles, graphene fibers, particles, or powders, graphite fibers, particles, or powders, graphene foils, graphite foils, or other carbon-based structures, as well as combinations thereof. As used throughout, "carbon black" refers to a material produced by the incomplete combustion of petroleum products. Carbon black is a form of amorphous carbon with an extremely high surface area-to-volume ratio. "Graphene" refers to a single atomic layer of carbon formed as a sheet and can be prepared as graphene powder. See, for example, U.S. Patent Nos. 5,677,082, 6,303,266, and 6,479,030, the disclosures of each of which are incorporated herein by reference in their entirety. Carbon-based substrates specifically exclude metallic materials such as steels, including stainless steels. Carbon-based substrates can be in the form of sheets or discrete particles, as well as cross-linked structures.

[0043]

[0070] A "catalyst," "catalytic material," "catalyst particle," or "nanostructure catalyst" is a substance that promotes the formation or growth of nanostructures. Such terms are used herein in the same manner as commonly used in the art related to nanostructure growth. Therefore, the use of the term "catalyst" does not necessarily imply that the chemical composition of the catalyst particle as initially supplied to the nanostructure growth reaction is the same as that involved in the active growth process of the nanostructures and / or that is recovered upon growth cessation. For example, as described in U.S. patent application Ser. No. 12 / 824,485, the disclosure of which is incorporated herein by reference in its entirety, when gold nanoparticles are used as catalyst particles for growing silicon nanowires, elemental gold particles are disposed on a substrate, and elemental gold is present at the tips of the nanowires after synthesis, although gold exists as a eutectic phase with silicon during synthesis. A contrasting example is disclosed in U.S. provisional patent application Ser. No. 61 / 511,826, the disclosure of which is incorporated herein by reference in its entirety. For example, when copper nanoparticles are used for VLS or VSS nanowire growth, when elemental copper particles are disposed on a substrate, copper silicide may be present at the tips of the nanowires during and after synthesis. As another example, when copper oxide nanoparticles are used as catalytic particles for silicon nanowire growth, the copper oxide particles are disposed on a substrate, which may be reduced to elemental copper in the reducing atmosphere used for nanowire growth, and copper silicide may be present at the tip of the nanowire during and after nanowire synthesis. Both types of situations, i.e., situations in which the catalytic material maintains the same chemical composition and situations in which the chemical composition of the catalytic material changes, are expressly included in the use of the terms "catalyst," "catalytic material," "catalyst particle," or "nanostructure catalyst" herein. Catalytic particles are typically nanoparticles, particularly discrete nanoparticles. When terms such as "catalytic material," "catalyst particle," or "nanostructure catalyst" are used herein, they are distinct from "precursors" or "precursor materials" used during nanostructure growth. These are distinct in that precursors serve as sources of at least one type of atom incorporated into the entire nanostructure (or the entire core, shell, or other region of a nanostructure heterostructure), while catalysts merely provide diffusion sites for nanostructure precursors and typically do not contain nanostructure source materials.

[0044]

[0071] The direct electrochemical deposition method of the present invention allows for the simultaneous formation and deposition of LIB active materials onto a substrate. As used herein, "directly deposited" or "directly electrochemically deposited" refers to the simultaneous formation of one or more active materials in a LIB. It means that the active material is grown or formed directly on the surface of the desired substrate by the reduction of a precursor by an electrochemical deposition process. As used herein with respect to material deposition or nanostructure formation, these terms refer to the direct reduction of the active material onto the associated substrate such that the active material is formed in direct physical contact with the substrate.

[0045]

[0072] Unless expressly stated otherwise, the ranges recited herein are inclusive. Various additional terms are defined or otherwise characterized herein. DETAILED DESCRIPTION OF THE INVENTION

[0046] Electrochemical deposition of LIB active materials and structures

[0073] Electrochemical deposition is a well-known process in the field of plating. As shown in FIGS. 1A and 1B, conventional processes for electrochemical deposition typically involve using an electric field to transport metal ions 102 in a bath (or solution) 104 onto a cathode substrate 106. A power source 108 supplies direct current 111 from a cathode 106 to an anode 107, which transports electrons 110 from the cathode 106 toward the anode 107. In one conventional technique, as shown in FIG. 1A, a solution 104 is provided in a container 112. The solution 104 is an electrolyte solution 104 that contains one or more dissolved metal salts 103 and other ions, thereby allowing the flow of electricity through the solution 104. Dissolution or solvation of the metal salts produces metal ions 102 that can be reduced at the surface of the cathode 106 to coat the cathode surface with a solid layer 105 of metal on the cathode surface. Positively charged metal ions 102 in solution 104 migrate toward a cathode 106 due to the electric field generated by the directional flow of charge through the solution (i.e., direct current applied to the system). Ions of the metal to be plated are drawn from solution 104 by the coating process, and the bath 104 must be periodically replenished. In another conventional technique for electrochemical deposition, as shown in FIG. 1B, the process involves the use of a consumable anode 107, whereby the anode 107 contains the metal to be coated onto the cathode 106. This process is similar to that shown in FIG. 1A, except that the metal ions 102 are provided by a source material for the metal anode. Direct current applied to the system forces electrons 110 to escape from the anode 107, leaving the anode with a net positive charge. To establish equilibrium, positive metal ions 102 are forced from the anode surface into solution 104. The electric field through solution 104 causes the metal ions 102 to migrate toward the cathode 106, and the metal ions are deposited on the cathode surface, forming a solid metal layer 105. This process depletes the consumable anode 107 as shown in FIG. 1B.

[0047]

[0074] For the sake of brevity, some conventional electrochemical deposition (ECD) techniques, processes, materials, systems, and system components will not be described in detail herein. However, conventional ECD principles known in the art are included in the present invention, as understood by those skilled in the art. Conventional concepts of ECD can be found in literature such as Allen J. Bard and Larry R. Faulkner, "Electrochemical Methods: Fundamentals and Applications" (2nd ed., 2006), and Frank Endres, Douglas MacFarlane, and Andrew Abbott, "Electrodeposition in Ionic Liquids" (2008), each of which is incorporated herein by reference in its entirety.

[0048]

[0075] The present invention includes methods for depositing nanostructures comprising at least one LIB active material directly onto a substrate by electrochemical deposition, as well as related compositions, devices, and components, and methods and processes for forming such compositions, devices, and components.

[0049]

[0076] The direct electrochemical deposition method of the present invention allows for simultaneous formation and deposition of LIB active materials onto a substrate. As used herein, "direct deposition" or "direct electrochemical deposition" of one or more active materials means that the LIB active materials are grown or formed directly on the desired substrate surface by the reduction of precursors via an electrochemical deposition process. The active materials are reduced directly onto the substrate such that the active materials are formed in direct physical contact with the substrate.

[0050]

[0077] As used herein, "active material(s)" refers to one or more battery active materials, particularly LIB active materials that can be lithiated with Li ions and are suitable for use as active materials in LIB anodes. The active materials can include any suitable LIB active materials known in the art, such as silicon (Si), graphite, carbon (C), tin (Sn), germanium (Ge), titanium (Ti), lead (Pb), indium (In), aluminum (Al), bismuth (Bi), antimony (Sb), lithium (Li), cobalt (Co), zinc (Zn), or other active materials, including combinations, mixtures, intermetallic compounds, and alloys thereof. As used herein, "inactive material(s)" refers to materials that are incapable of lithium insertion or have negligible lithium insertion capacity compared to the corresponding active materials in LIB components formed by the methods of the present invention. The inactive material may be useful for purposes other than providing lithium capacity during or after the electrochemical deposition process, such as increasing electrical conductivity, improving adhesion between the active material and the substrate, or achieving specific properties of the active material, as discussed in more detail below. The inactive material may include, for example, copper (Cu), carbon (C), nickel (Ni), silver (Ag), aluminum (Al), gold (Au), or other inactive materials, as well as combinations, mixtures, and alloys thereof.

[0051]

[0078] In a preferred embodiment, LIB active materials are electrochemically deposited directly onto the substrate surface. The electrochemically deposited material can include a single active material, a mixture, composition, or alloy containing multiple different active materials, one or more inactive materials, a mixture, composition, or alloy containing multiple inactive materials, or a mixture, composition, or alloy containing one or more active materials and one or more inactive materials. Additionally or alternatively, the one or more active materials and / or one or more inactive materials can be formed or deposited on the substrate by any suitable known method, such as coating, chemical bonding, adsorption, adhesion of a binder material, lithography, sputtering, chemical vapor deposition (CVD), evaporation, electroless plating, or other methods, as will be understood by those skilled in the art.

[0052]

[0079] In a preferred embodiment, the active material(s) formed by direct ECD comprise silicon, preferably discrete silicon nanostructures, such as Si nanowires or Si nanospikes, which are preferably electrochemically deposited directly onto one or more LIB active materials and / or one or more conductive current collectors to form silicon-based composite structures for use in LIB anodes.

[0053]

[0080] In one preferred class of embodiments, one or more active materials, preferably one or more active materials comprising silicon, are electrochemically deposited onto one or more conductive current collector structures that can be used as current collectors in LIB anodes. The current collector preferably comprises one or more copper structures, such as copper sheets, thin films, plates, foils, meshes, foams, sponges, or powders or multiple particles / fibers / sheets / flakes / wires that can be packed, knitted, bonded, or otherwise associated with one another, or any combination thereof. In a preferred embodiment, silicon is electrochemically deposited directly onto the copper current collector, and a Cu-Si composite material can form the LIB anode material, in which copper is the conductive current collector and silicon is the active material for lithiation and delithiation during the charge and discharge cycles of the LIB.

[0054]

[0081] In another preferred class of embodiments, a first active material is electrochemically deposited directly onto at least a second active material to form a composite active material comprising the first and second active materials suitable for use as a LIB anode active material. In preferred embodiments, a first active material comprising silicon is electrochemically deposited directly onto at least a second active material, where the second active material comprises one or more graphite structures, forming a silicon-graphite composite LIB anode material. The one or more graphite structures may comprise one or more of a graphite sheet, film, plate, foil, powder, particle, or fiber, or a sheet, film, plate, mesh, foam, sponge, or powder or multiple particles / fibers / sheets / flakes that may be packed, knitted, adhered, or otherwise associated with each other, or any combination thereof.

[0055]

[0082] In one class of embodiments, the first active material is electrochemically deposited directly onto one or more substrates comprising at least one conductive current collector and / or one or more second active materials. The first active material preferably comprises silicon. The first active material preferably comprises nanostructures, e.g., nanowires. The current collector and second active material can each comprise any suitable material and structure described herein, such as one or more of a sheet, thin film, plate, foil, mesh, foam, sponge, or powder or a plurality of particles / fibers / sheets / flakes / wires that can be packed, knitted, adhered, or otherwise associated with each other, or any combination thereof. The one or more substrates preferably comprise a current collector comprising one or more copper structures and / or a second active material comprising one or more graphite structures. In one embodiment, the first active material is electrochemically deposited directly onto at least one structure comprising at least the second active material, and the at least one structure comprising the second material is associated with at least one current collector. The first active material can also be deposited directly on at least one current collector by electrochemical deposition. The current collector and second active material can be combined or associated with each other using any suitable process known to those skilled in the art. For example, one or more conductive current collector materials and the second(er) active material can be mechanically bonded, mixed, laminated, layered, compressed, braided, chemically bonded, adsorbed, alloyed, or adhered using one or more adhesive binder materials, or the materials can be combined using ablation techniques, chemical deposition techniques such as ECD or CVD, vapor deposition, electroless plating, adsorption, spraying, coating, lithography, sputtering, dipping, bonding, or other techniques. The current collector and second active material can be combined or associated with each other before electrochemical deposition of the first active material, during the electrochemical deposition process, after electrochemical deposition of the first active material on the desired substrate, or any combination thereof.

[0056] LIB active material

[0083] As discussed above, the present invention includes methods for depositing nanostructures comprising at least one LIB active material directly onto a substrate by electrochemical deposition, as well as related compositions, devices, and components, and methods and processes for forming such compositions, devices, and components. As discussed above, the active material(s) formed by direct ECD preferably include, but are not limited to, silicon. While embodiments of the present invention are described in detail herein with respect to silicon active materials deposited by direct ECD, those skilled in the art will recognize that additional and alternative active materials are included in the compositions, methods, components, and devices of the present invention. For example, the active material(s) formed by direct ECD can include Si, Cu, Ni, Sn, Ge, Ti, Pb, In, Al, Bi, Sb, Li, Co, Zn, or other active materials, as well as compositions, mixtures, intermetallic compounds, alloys, or combinations thereof.

[0057]

[0084] In a preferred embodiment, the LIB active material is electrochemically deposited directly onto the substrate surface. The electrochemically deposited material can include a single active material, a mixture, composition, or alloy containing multiple different active materials, one or more inactive materials, a mixture, composition, or alloy containing multiple inactive materials, or a mixture, composition, or alloy containing one or more active materials and one or more inactive materials. Additional materials, such as one or more active materials and / or one or more inactive materials, can be formed on or associated with the substrate by any suitable method, such as mechanical or chemical bonding, mixing, laminating, layering, compressing, braiding, adsorbing, alloying, adhesive bonding, chemical deposition such as ECD or CVD, lithography, spraying, coating, sputtering, evaporating, dipping, bonding, or other methods, such as those available in the art.

[0058]

[0085] In certain embodiments, the electrochemically deposited material can include a plurality of different materials, such as a plurality of different active materials, a plurality of different inactive materials, or a combination of one or more active materials and one or more inactive materials. For example, the electrochemically deposited material can include Si and Cu, Si and Sn, Si and C, Si and graphite, Si and Li, Si and one or more titanates, Si and Pb, Si and In, Si and Al, Si and Bi, Si and Sb, Sn and Cu, Sn and C, Sn and graphite, Sn and Li, Sn and one or more titanates, Sn and Pb, Sn and In, Sn and Al, Sn and Bi, Sn and Sb, Cu and C, Cu and graphite, Cu and Li, Cu and one or more titanates, Cu and Pb, Cu and In, Cu and Al, Cu and Bi, Cu and Sb, C and Cu, non-graphitic C and graphite, C and Li, C and one or more titanates, C and Pb, C and In, C and Al, C and Bi, C and Sb; Si, Cu and Sn; Si, Cu and C; Si, Cu and graphite; Si, Cu and The metal oxide composition may include Li; Si, Cu and one or more titanates; Si, Cu and Pb; Si, Cu and In; Si, Cu and Al; Si, Cu and Bi; Si, Cu and Sb; Si, C and Sn; Si, C and Cu; Si, C and graphite; Si, C and Li; Si, C and one or more titanates; Si, C and Pb; Si, C and In; Si, C and Al; Si, C and Bi; Si, C and Sb; Cu, C and graphite; Cu, C and Li; Cu, C and one or more titanates; Cu, C and Pb; Cu, C and In; Cu, C and Al; Cu, C and Bi; Cu, C and Sb; Si and Ni, Si and steel, Ni and steel, Ni and C, C and steel, Sn and steel, Sn and Ni; Si, Sn and Ni; Si, Sn and steel; or compositions, mixtures, intermetallic compounds, alloys, or combinations thereof.

[0059]

[0086] In certain embodiments, the nanostructures can be formed by ECD of one or more alloy materials, by simultaneous deposition of multiple different materials using ECD (e.g., from the same EC electrolyte solution), or by separate ECD of multiple different materials (e.g., alternating deposition of multiple different materials), as well as any combination thereof. The relevant processes and process parameters are described in more detail below.

[0060]

[0087] Surprisingly, the present inventors have discovered that the low-temperature, template- and catalyst-free ECD process of the present invention can be used to achieve direct epitaxial growth of discrete active material nanostructures on one or more LIB components. Furthermore, the inventors have unexpectedly discovered that such ECD processes can be used to finely control and / or modify the physical and chemical properties of the nanostructures electrochemically deposited during the ECD growth process, such as the active material nanostructures' composition, crystal structure, morphology, size, and / or shape. The ECD process, materials, and additional parameters are explored in more detail below.

[0061]

[0088] In preferred embodiments, the active material(s) formed by direct ECD comprise discrete nanostructures rather than a continuous active material structure, such as a continuous thin film comprising the active material. The term "discrete" structure is used herein to mean that the structure comprises multiple, independent, discontinuous domains of material, although such structures need not be completely adjacent. That is, "discrete" structures may be in physical contact with one another unless otherwise specified. The nanostructures can comprise essentially any desired type of nanostructure, including, but not limited to, nanowires. The nanostructures can include nanowires, nanorods, nanospikes, tapered nanowires, nanotubes, nanowhiskers, nanoribbons, nanoparticles, nanofibers, nanocrystals, branched nanostructures, nanodots, quantum dots, spherical nanostructures, or other nanostructures, or any combination thereof. Preferably, the nanostructures comprise one-dimensional elongated or high-aspect-ratio nanostructures. For example, the nanostructures can include nanowires, nanorods, nanospikes, tapered nanowires, nanotubes, nanowhiskers, nanoribbons, branched nanostructures, or other one-dimensional elongated or high aspect ratio nanostructures, or any combination thereof. In a preferred embodiment, the nanostructures comprise Si, e.g., Si nanowires. More preferably, the nanostructures comprise monocrystalline Si nanostructures, e.g., monocrystalline Si nanowires.

[0062]

[0089] The nanowires or other nanostructures of the present invention are preferably formed as highly crystalline (e.g., highly monocrystalline) nanostructures during the direct electrochemical deposition process, such that no further processing is required to crystallize the nanostructures. For example, the nanowires or other nanostructures preferably comprise monocrystalline Si and have a high degree of crystallinity after formation. The methods of the present invention can produce nanostructures that exhibit a high degree of crystallinity after formation during the ECD process. This immediate crystallization of the nanostructures after deposition and formation eliminates the need for additional crystallization procedures, such as high-temperature annealing. Thus, the entire process of forming active material nanostructures can be accomplished using the low-temperature, e.g., room-temperature, ECD process of the present invention.

[0063]

[0090] The nanowires or other nanostructures of the present invention are preferably formed directly on the desired substrate by ECD without the use of a template. While such template-free deposition allows for the formation of highly crystalline active material structures, growth procedures based on porous templates disrupt the continuous crystalline formation, resulting in the formation of amorphous material. In template-based methods, the electrochemically deposited material is confined to the physical pores of the porous template, and the walls of the template pores prevent the deposition of material atoms beyond the pore boundaries, thereby preventing the crystalline formation of the material. Therefore, template-free ECD methods are preferred for forming the active material nanostructures of the present invention. The template-free deposition procedures of the present invention can form active material nanostructures exhibiting high crystallinity, e.g., high monocrystalline, high polycrystalline, or a mixture of high monocrystalline and polycrystalline. During the preferred ECD process of the present invention, as each successive atom of active material is deposited on the substrate, the nanostructures comprising the active material grow epitaxially, following the material's natural crystalline structure. In these preferred embodiments, the nanostructures exhibit a high degree of single crystallinity without boundaries or other crystalline defects. In preferred embodiments, the present invention includes highly crystalline Si nanostructures, e.g., highly crystalline Si nanowires, and methods for forming such highly crystalline Si nanostructures. The ECD methods of the present invention advantageously enable the growth of crystalline active material nanostructures, such as Si nanowires, without the use of a growth template. While crystalline nanostructures may become amorphous or lose crystallinity after LIB charging cycles, the initial crystallinity of these nanostructures allows them to maintain the one-dimensional structure of elongated nanostructures throughout LIB cycling. Furthermore, the highly crystalline active material nanostructures of the present invention exhibit high tolerance to rapid charge-discharge rates. That is, crystalline nanostructures can undergo rapid charging cycles while maintaining high capacity. That is, LIB cells having the highly crystalline nanostructures of the present invention (e.g., crystalline Si nanowires) have higher power densities than amorphous or polycrystalline active material nanostructures. Therefore, the crystalline nanostructures of the present invention are highly advantageous for use in LIBs for high-power applications.

[0064]

[0091] The nanostructures formed by the methods of the present invention preferably comprise highly crystalline nanostructures, e.g., highly monocrystalline nanostructures, e.g., highly monocrystalline Si nanowires or other nanostructures. In preferred embodiments, the nanostructures are substantially monocrystalline and substantially free of polycrystalline and amorphous material after formation. Preferably, the nanostructures are free of polycrystalline and amorphous material after formation. Highly crystalline nanostructures can be formed by the ECD process of the present invention, and active material nanostructures of the present invention preferably have a high degree of crystallinity after formation. For example, the active material nanostructures of the present invention may have 100% crystallinity after formation, at least 99% crystallinity after formation, at least 98% crystallinity after formation, at least 97% crystallinity after formation, at least 96% crystallinity after formation, at least 95% crystallinity after formation, at least 90% crystallinity after formation, at least 85% crystallinity after formation, at least 80% crystallinity after formation, or at least 75% crystallinity after formation, e.g., 100% single crystallinity after formation, at least 99% single crystallinity after formation, at least 98% single crystallinity after formation, at least 97% single crystallinity after formation, at least 96% single crystallinity after formation, at least 95% single crystallinity after formation. , may exhibit high degrees of crystallinity, including at least 90% monocrystalline after formation, at least 85% monocrystalline after formation, at least 80% monocrystalline after formation, or at least 75% monocrystalline after formation, or 100% polycrystalline after formation, at least 99% polycrystalline after formation, at least 98% polycrystalline after formation, at least 97% polycrystalline after formation, at least 96% polycrystalline after formation, at least 95% polycrystalline after formation, at least 90% polycrystalline after formation, at least 85% polycrystalline after formation, at least 80% polycrystalline after formation, or at least 75% polycrystalline after formation, or a mixture of monocrystalline and polycrystalline. Although crystalline nanostructures are preferred, the active material nanostructures of the present invention can comprise amorphous materials, mixtures of amorphous and polycrystalline materials, mixtures of amorphous and single crystalline materials, or mixtures of amorphous, polycrystalline, and single crystalline materials.

[0065]

[0092] Nanowires or other nanostructures can be formed from any suitable material, including, but not limited to, silicon. In embodiments in which the nanostructures comprise silicon, the nanostructures can comprise monocrystalline silicon, polycrystalline Si, amorphous Si, or a combination thereof. Thus, in one class of embodiments, the nanostructures comprise a monocrystalline core and a shell layer, and the shell layer comprises amorphous Si, polycrystalline Si, or a combination thereof. In one aspect, the nanostructures are Si nanowires.

[0066]

[0093] The present invention includes a low-temperature, e.g., room-temperature, ECD method for producing active material nanostructures without using high-temperature CVD processes. Conventional methods for producing nanowires or other nanostructures, such as high-temperature catalytic growth via CVD, require a metal catalyst material, such as metal catalyst particles, which is heated to a eutectic temperature to allow diffusion of precursors through the metal catalyst. Because the precursors diffuse through the metal catalyst material and are not consumed in the reaction, these conventional methods produce nanostructures that are attached or strongly bonded to the metal catalyst, requiring further processing to remove the metal catalyst. Unlike such conventional methods, the production method of the present invention does not require the use of a catalyst, such as metal catalyst particles. The catalyst-free production method of the present invention enables the production of active material nanostructures and LIB active material composite structures that are free of catalytic materials and their associated impurities, eliminating the need for further processing to remove the catalytic materials or impurities from the nanostructures. These catalyst-free active material structures enable LIBs and LIB components with reduced amounts of inactive materials, resulting in increased capacity, reduced weight, and reduced volume.

[0067]

[0094] In a preferred method, the ECD process of the present invention involves directly forming active material nanostructures, e.g., Si nanowires, on a LIB anode composite material, such as one or more LIB current collectors and / or LIB active materials, e.g., one or more copper current collectors and / or graphite active materials, without a template. Such a process eliminates the need for a separate growth substrate and non-conductive growth template, as well as the requirement to recover the active material by dissolving or otherwise removing the growth substrate and template. Because the active material nanostructures are formed directly on the LIB component or material, the composite of substrate and active material can be used as a LIB component without the need to remove the growth substrate or growth template. This simplifies the production process. Furthermore, impurities introduced by one or more of the separate growth substrates and templates are eliminated.

[0068]

[0095] In preferred embodiments, the active material nanostructures are free or substantially free of impurities, such as oxygen, including impurities introduced by catalytic materials, growth templates, external growth substrates, and procedures or materials used to remove such materials from the active material nanostructures or composite structures containing the active material nanostructures. For example, the active material nanostructures contain less than 10% impurities, less than 9% impurities, less than 8% impurities, less than 7% impurities, less than 6% impurities, less than 5% impurities, less than 4% impurities, less than 3% impurities, or less than 2% impurities, preferably less than 1% impurities, e.g., less than 0.5% impurities, less than 0.25% impurities, or less than 0.1% impurities. Most preferably, the active material nanostructure composition is completely free of impurities. Because neither high-temperature catalysts nor post-precipitation annealing are required to form crystalline active material nanostructures according to embodiments of the present invention, the present invention enables the epitaxial formation of highly crystalline active material nanostructures, where the entire formation process is carried out at low temperatures, e.g., room temperature.

[0069]

[0096] The nanowires or other nanostructures of the present invention, such as Si nanowires, can be essentially any desired size. For example, the nanowires or other nanostructures can have diameters of about 10 nm to about 500 nm, or about 20 nm to about 400 nm, or about 20 nm to about 300 nm, or about 20 nm to about 200 nm, or about 20 nm to about 100 nm, or about 30 nm to about 100 nm, or about 40 nm to about 100 nm. Preferably, the nanowires or other nanostructures have an average diameter of less than about 150 nm, e.g., between about 10 nm and about 100 nm, e.g., between about 30 nm and about 50 nm, or e.g., between about 40 nm and about 45 nm. The nanowires or other nanostructures preferably have an average length of less than about 100 μm, e.g., less than about 50 μm, less than about 10 μm, about 100 nm to about 100 μm, or about 1 μm to about 75 μm, about 1 μm to about 50 μm, or about 1 μm to about 20 μm. The aspect ratio of the nanowires is optionally up to about 2000:1 or about 1000:1. For example, the nanowires or other nanostructures can have a diameter of about 20 nm to about 200 nm and a length of about 0.1 μm to about 50 μm.

[0070]

[0097] As described above, the discrete nanostructures formed by the ECD methods of the present invention can include essentially any desired type of nanostructure, including, but not limited to, nanowires. The nanostructures can include nanowires, nanorods, nanospikes, tapered nanowires, nanotubes, nanowhiskers, nanoribbons, nanoparticles, nanofibers, nanocrystals, branched nanostructures, nanodots, quantum dots, spherical nanostructures, or other nanostructures, or any combination thereof. Preferably, the nanostructures include one-dimensional, elongated, or high-aspect-ratio nanostructures. For example, the nanostructures can include nanowires, nanorods, nanospikes, tapered nanowires, nanotubes, nanowhiskers, nanoribbons, branched nanostructures, or other one-dimensional, elongated, or high-aspect-ratio nanostructures, or any combination thereof. In a preferred embodiment, the nanostructures include Si, e.g., Si nanowires, Si nanospikes, or tapered Si nanowires. More preferably, the nanostructures include single-crystalline Si nanostructures, e.g., single-crystalline Si nanowires.

[0071]

[0098] As described in more detail below, the methods of the present invention allow for fine control and / or modification of the physical and chemical properties of the nanostructures electrochemically deposited during the ECD growth process, including the composition, crystal structure, morphology, size, and shape of the active material nanostructures.

[0072]

[0099] In certain embodiments, the electrochemically deposited nanostructures have a porous structure, which can be achieved by lithiation-delithiation cycling, including before lithiation / delithiation (i.e., before LIB formation), as described in detail below.

[0073]

[0100] According to embodiments of the present invention, the physical and / or chemical properties of the nanostructures, as well as the interaction between the substrate surface and the nanostructures comprising at least one active material, can be controlled.

[0074]

[0101] In preferred embodiments, the electrochemically deposited nanostructures have a sufficiently high bond strength with the underlying substrate to which they are attached, such that the bond between the substrate and the nanostructures remains intact during LIB charge and discharge cycles. In preferred embodiments, the nanostructures are directly bonded to the underlying substrate without any binder material disposed therebetween. In certain embodiments, a LIB anode comprises a current collector and an active material composite that does not contain a binder material. For example, active material nanostructures (e.g., Si nanowires) can be formed directly on a LIB current collector structure (e.g., graphite foil or Cu thin film or mesh) by direct electrochemical deposition, thereby resulting in a binder-free current collector-active material composite. The high bond strength between the substrate and the active material nanostructures obviates the need for a binder. However, certain embodiments of the present invention may include a binder material between one or more active material structures and / or inactive material structures.

[0075]

[0102] In certain embodiments, as shown in Figures 2A-2F, elongated nanostructures 220, e.g., nanowires or nanospikes, are formed directly on the surface 216 of a substrate 215 by ECD. Nanostructures comprising Si, e.g., Si nanowires or Si nanospikes, are preferably formed directly on a current collector or another active material structure, e.g., one or more of a planar Cu current collector, a graphite thin film, or graphite particles. The elongated nanostructures 220 can have a length L1, which represents the total length taken along the long axis of the nanostructure. For example, the elongated nanostructures can include nanowires as shown in Figures 2A-2C, tapered nanowires as shown in Figure 2C, or nanospikes as shown in Figures 2D and 2F.

[0076]

[0103] In preferred embodiments, the nanostructures exhibit both a large surface area for lithiation and a large surface area for bonding to the substrate. In certain embodiments, as shown in FIG. 2B, elongated nanostructure 220 is in direct physical contact with substrate surface 216 along length L2, where length L2 is a portion of overall length L1, such that L2 is less than L1. In certain embodiments, as shown in FIGS. 2A and 2C-2F, nanostructure 220 is in direct physical contact with substrate surface 216 along an end or base surface 216 of the nanostructure. As shown in FIGS. 2C, 2D, and 2E, the nanostructure can have a base width W1 measured at nanostructure base 221 of nanostructure 220 at the interface between nanostructure 220 and substrate 215, a central width W2 measured at a location 223 approximately equidistant from base end 221 and distal end 222 of the nanostructure along the length of the nanostructure's major axis, and a distal width W3 measured at distal end 222 of the nanostructure opposite base end 221. In embodiments in which the nanostructure has a circular cross-section (e.g., a tapered nanowire or nanospike), the widths described above can represent the diameter of the nanostructure at different individual locations along the nanostructure's long axis. The base width W1 can be greater than the central width W2, greater than the distal width W3, or greater than both the central and distal widths. As shown in Figures 2D and 2E, the base width W1 can be much greater than the central width W2 and the distal width W3.

[0077]

[0104] In certain embodiments, the discrete nanostructures comprising at least one active material can comprise a plurality or clusters of nanostructures, e.g., elongated nanostructures such as clusters of nanowires or nanospikes. Each cluster can comprise a plurality of elongated nanostructures joined at their base ends at the interface between the cluster and the substrate surface. As shown in the exemplary embodiment of Figure 2F, the discrete nanostructures comprise clusters 225 of nanospikes 220, each cluster 225 comprising a plurality of nanospikes 220 joined at their base ends 221 at the interface between the cluster 225 and the substrate surface 216.

[0078]

[0105] In certain embodiments, discrete nanostructures comprising at least one active material can have one or more circular surfaces, as shown in the exemplary embodiment of Figures 2G-2K. As shown in Figure 2G, the nanostructures can include spherical nanostructures 220, such as nanodots or spherical nanocrystals. The nanostructures can also include ellipsoidal nanostructures or any other nanostructures having one or more circular surfaces. As shown in Figure 2H, the nanostructures can include dome-shaped nanostructures 220 or hump-shaped nanostructures 220. As shown in Figures 2I-2K, the nanostructures 220 can include multiple circular surfaces. As shown in Figures 2I and 2J, the nanostructures 220 can have a rough surface structure. As shown in Figure 2K, the nanostructures 220 can be formed as discrete clusters 225, each cluster 225 including multiple nanostructures 220 with one or more circular surfaces.

[0079]

[0106] As discussed above, nanostructures comprising at least one active material can comprise a single material type or multiple different material types. Nanostructures can comprise one or more active materials, one or more inactive materials, or one or more conductive materials, including any of the material composites mentioned herein, as well as mixtures, alloys, or combinations thereof. Electrochemically deposited nanostructures can include heterostructured nanostructures formed by one or more ECD processes of the present invention. In certain embodiments, these structures can be formed by ECD of one or more alloy materials, co-deposition of multiple different materials using ECD, or separate ECD of multiple different materials, as well as any combination thereof. Relevant processes and process parameters are described in more detail below.

[0080]

[0107] The exemplary nanostructure embodiment of Figures 3A-3I illustrates nanostructures 320, each comprising different or varying material types throughout different portions (i.e., different spatial regions) of the nanostructure. As shown in Figure 3A, nanostructure 320 can include a first region 330 comprising a first material M1 and at least a second region 332 comprising a second material M2, where the first material M1 and the second material M2 are different. As discussed above, each of the different materials can comprise a single material composition, or a blend, alloy, or combination of multiple material compositions. Each of the different material types can comprise an active material, an inactive material, a conductive material, or any combination thereof. For example, M1 can comprise a first active material such as Si, and M2 can comprise a second active material such as Sn or graphite. M1 can comprise an active material such as Si, and M2 can comprise a conductive material such as Cu, or vice versa. As shown in FIG. 3B, the nanostructure 220 can include a plurality of first regions 330 including a first material M1 and at least a second region 332 including at least a second material M2, where the first material M1 and the second material M2 are different, and the second regions 332 are disposed between the plurality of first regions 330. As shown in FIGS. 3C-3E, each of the nanostructures 320 can include a plurality of first regions 330 including a first material M1 and a plurality of second regions 332 including a second material M2, where the first material M1 and the second material M2 are different. As shown in FIG. 3C, the first regions 330 and the second regions 332 can have an ordered pattern, e.g., an alternating pattern. Additionally or alternatively, as shown in FIGS. 3D-3E, the first regions 330 and the second regions 332 can have a random configuration. In certain embodiments, each nanostructure can include multiple different materials, with the amount or concentration of one or more of the different materials varying gradually across one or more regions of the nanostructure. For example, as shown in Figure 3F, nanostructure 320 can include a first material M1 and at least a second material M2, with the amount or concentration of both M1 and M2 varying gradually across one or more regions of the nanostructure.3F , in nanostructure 320, the amount or concentration of first material M1 gradually decreases toward the distal end 322 of the nanostructure and gradually increases toward the substrate surface 316, and the amount or concentration of second material M2 gradually increases toward the distal end 322 of the nanostructure and gradually decreases toward the substrate surface 316. In nanostructure 320, the amount or concentration of first material M1 gradually decreases toward both the substrate surface 316 and the distal end 322, and the amount or concentration of second material M2 gradually increases toward both the substrate surface 316 and the distal end 322.

[0081]

[0108] As shown in Figures 3G-3I, a nanostructure can include at least one core and at least one coating or shell layer, where at least one core material is different from at least one coating material. For example, as shown in Figure 3G, nanostructure 320 includes a core 335 including a first material M1 and at least one coating layer 336 including a second material M2, where M1 and M2 are different. As shown in Figure 3H, core 335 includes a first material M1, and the nanostructure includes multiple coating or shell layers 336a, 336b. The nanostructure includes a first shell 336a including a second material M2 and at least a second shell 336b including a third material M3, where at least two of the materials M1, M2, and M3 are different. As shown in Figure 3I, nanostructure 320 includes a core including a first region 335a including a first material M1 and a second region 335b including a second material M2, where M1 and M2 are different materials. Nanostructure 320 includes a shell 336 that includes a third material M3, which may be the same as M1 or M2, or different from both materials M1 and M2.

[0082]

[0109] In certain embodiments, nanowires or other nanostructures can include one or more coatings or shell layers formed on individual nanostructures. The coatings or shell layers can include a material having a different crystalline structure than the core, one or more SEI materials or layers, a binder material, an active material different from the core, a conductive material coating, or any other material or coating.

[0083]

[0110] In preferred embodiments, the nanostructures and one or more substrate materials are formed into a LIB anode composite. In certain embodiments, the composite anode structure can have one or more properties that vary across different spatial regions of the composite. For example, porosity, composition, or one or more other properties can vary across different spatial regions of the composite anode structure.

[0084]

[0111] In preferred embodiments, heterostructured nanostructures are formed on a desired substrate by ECD. In certain embodiments, at least one portion of the nanostructures is formed by ECD, and at least one portion of the nanostructures is formed using another method, such as coating, chemical bonding, adsorption, adhesion of a binder material, lithography, sputtering, chemical vapor deposition (CVD), evaporation, electroless plating, or other methods available in the art as will be understood by those skilled in the art. In one exemplary embodiment, the discrete nanostructures include a first material M1 and at least a second material M2, where the first material M1 is formed by ECD and the second material is formed by another method other than ECD. Preferably, M1 is an active material (e.g., Si), and M2 can comprise an active material (e.g., graphite or Sn) or an active material with a lower activity or lower lithiation capability than M1 (e.g., M1 comprises Si and M2 comprises graphite). M2 can include an inactive material such as a binder (e.g., carboxymethyl cellulose (CMC), polyvinylidene fluoride (PVDF), or polyacrylic acid (PAA), or poly(acrylamide-co-diallyldimethylammonium) (PAADAA)), or an inactive conductive material (e.g., Cu).

[0085] Substrate material and structure

[0112] As described above, the present invention includes methods for depositing nanostructures comprising at least one LIB active material directly onto a substrate by electrochemical deposition, as well as related compositions, devices, and components, and methods and processes for forming such compositions, devices, and components. Using the direct electrochemical deposition method of the present invention, LIB active materials can be simultaneously formed and deposited onto a substrate, whereby discrete nanostructures comprising one or more LIB active materials are grown directly on the desired substrate surface by precursor reduction during the ECD process. The active material is reduced directly onto the substrate, and thus the active material nanostructures are in direct physical contact with the substrate. The discrete nanostructures can include any of the nanostructure characteristics described herein. In a preferred embodiment, the discrete nanostructures comprise monocrystalline Si. Preferably, the discrete nanostructures comprise monocrystalline Si nanowires or nanospikes.

[0086]

[0113] The substrate can comprise any conductive material. For example, the substrate can comprise one or more metals, copper (Cu), carbon (C), graphite, nickel (Ni), steel, aluminum (Al), platinum (Pt), gold (Au), tin (Sn), titanium (Ti), zinc (Zn), lithium (Li), inorganic semiconductor materials, one or more conductive polymers, or one or more binder materials such as CMC, PVDF, PAA, or PAADAA, or other conductive materials, as well as any composition, mixture, intermetallic, alloy, or combination thereof. In certain embodiments, the substrate comprises multiple materials, such as Cu and graphite, non-graphitic C and graphite, Ni and graphite, steel and graphite, Al and graphite, Pt and graphite, Cu and C, Cu and Sn, C and Sn, multiple forms of graphite, multiple forms of C; Cu, non-graphitic C and graphite; graphite and one or more binder materials, or any composition, mixture, alloy, or combination thereof.

[0087]

[0114] The one or more substrate materials can include any combination of materials, crystalline structures, crystallinity, morphologies, shapes, and sizes. The substrate can include one or more of a conductive sheet, film, plate, foil, mesh, foam, sponge; or powder or a plurality of particles / fibers / sheets / flakes / wires that can be packed, knitted, glued, or otherwise associated with one another; and any combination thereof. In one general class of preferred embodiments, the substrate includes at least one porous substrate structure. In another general class of preferred embodiments, the substrate includes at least one planar substrate structure. The substrate preferably includes at least one metallic or conductive planar structure. For example, the substrate can include one or more films, sheets, foils, mesh, planar sponges, a plurality of particles, wires, or fibers formed into planar shapes or structures, or other planar structures, or any combination thereof.

[0088]

[0115] In one class of embodiments, a first active material is electrochemically deposited directly onto one or more substrates, the substrate including at least one conductive LIB current collector structure and / or at least one second active material. The first active material preferably includes silicon. The first active material preferably includes nanostructures, e.g., nanowires. The current collector and second active material can each include any suitable material and structure described herein, including one or more of a sheet, thin film, plate, foil, mesh, foam, sponge, or powder or a plurality of particles / fibers / sheets / flakes / wires that can be packed, knitted, adhered, or otherwise associated with each other, or any combination thereof. The one or more substrates preferably include a current collector including one or more copper structures and / or a second active material including one or more graphite structures. In one embodiment, the first active material is electrochemically deposited directly onto at least one structure including at least the second active material, and the at least one structure including the second material is associated with at least one current collector. The first active material can also be deposited directly on at least one current collector by electrochemical deposition. The current collector and second active material can be combined or associated with each other using any suitable process known to those skilled in the art. For example, one or more conductive current collectors and the second(er) active material can be mechanically bonded, mixed, laminated, layered, compressed, braided, chemically bonded, adsorbed, alloyed, or adhered using one or more adhesive binder substances, or the materials can be combined using ablation techniques, chemical deposition techniques such as ECD or CVD, adsorption, spraying, coating, lithography, sputtering, dipping, bonding, or other techniques. The current collector and second active material can be combined or associated with each other before electrochemical deposition of the first active material, during the electrochemical deposition process, after electrochemical deposition of the first active material on the desired substrate, or any combination thereof.

[0089]

[0116] In a preferred embodiment, the LIB active material is electrochemically deposited directly onto the substrate surface. The electrochemically deposited material can include a single active material, or a mixture, composition, or alloy containing multiple different active materials, or one or more inactive materials, or a mixture, composition, or alloy containing multiple inactive materials, or a mixture, composition, or alloy containing one or more active materials and one or more inactive materials. Additionally or alternatively, the one or more active materials and / or one or more inactive materials can be formed or deposited on the substrate by any suitable known method, such as coating, chemical bonding, adsorption, binder material adhesion, lithography, sputtering, chemical vapor deposition (CVD), or other method, as will be understood by those skilled in the art. Exemplary substrates include one or more of the following: graphite foil or plate, polished graphite foil or plate, graphite flakes or particles, graphite flakes or particles and one or more binder substances such as CNfC, PVDF, PAA, or PAADAA, graphite flakes or particles in combination with one or more binder substances coated on a graphite foil or plate, Cu-coated graphite foil, Cu-coated graphite foil coated with graphite flakes or particles, graphite flakes or particles in combination with one or more binder substances coated on a Cu-coated graphite foil or plate, Cu-coated graphite foil or plate subjected to gas treatment, porous Cu mesh or foam, Cu wire, Cu fiber, Ni-coated Cu Wire or fiber, patterned Cu wire, Ni-coated patterned Cu wire, carbon sheet, heat-treated carbon sheet, Cu foil or plate coated with graphite flakes or particles, graphite flakes or particles coated on Cu foil or plate in combination with one or more binder materials, graphite flakes or particles sandwiched between or wrapped in a porous Cu mesh sheet, graphite flakes or particles sandwiched between or wrapped in a porous Cu mesh sheet in combination with one or more binder materials, one or more binder materials such as CMC, PVDF, PAA, or PAADAA, and combinations thereof. In certain embodiments, the substrate can be gas-treated with one or more reducing gases to enhance the reduction of metallic ions onto the substrate surface. In certain embodiments, the substrate surface can be heat-treated. For example, the substrate can comprise heat-treated carbon, where the heat treatment produces graphite features on the surface of the carbon substrate structure.

[0090]

[0117] In one general class of embodiments, the substrate comprises carbon. The substrate can include one or more carbon structures. The carbon substrate structure can include any suitable form of carbon, such as graphite, graphene, natural graphite, artificial graphite, highly oriented pyrolitic graphite (HOPG), activated carbon, petroleum coke carbon, mesophase carbon, hard carbon, soft carbon, carbon black, porous carbon, fullerenes, heat-treated carbon, or other forms of carbon, as well as combinations thereof. The carbon substrate structure can include carbon thin films or foils, carbon sheets, carbon paper, carbon powders, porous carbon powders, carbon fibers, carbon particles, carbon microbeads, mesocarbon microbeads (MCMBs), carbon nanotubes, carbon nanoparticles, graphite fibers, graphite particles or powders, graphite foils, or other carbon structures, as well as combinations thereof.

[0091]

[0118] In another general class of embodiments, the ECD substrate comprises copper. The substrate can include one or more copper structures. For example, the substrate can include one or more copper thin films, foils, plates, or sheets, or copper mesh, foam, or sponge, or copper wire, braided copper wire, copper particles, copper flakes, or one or more layers of copper coated with another substrate material such as graphite foil, carbon paper, or graphite particles, or other copper structures, as well as combinations thereof.

[0092]

[0119] In a preferred embodiment, the substrate comprises one or more conductive current collector structures and / or one or more LIB active material structures, whereby the one or more substrate materials and the discrete nanostructures comprising at least one active material form a composite structure for use in a LIB anode. For example, nanostructures can be formed directly on the current collector structures to form an anode current collector comprising discrete active material nanostructures. The anode current collector structure can comprise an active material (e.g., graphite) and / or an inactive material (e.g., Cu).

[0093]

[0120] In one general class of embodiments, nanostructures comprising a first active material (e.g., Si) can be formed directly on one or more structures comprising a second active material (e.g., graphite), resulting in a composite active material structure comprising the first and second active materials. The composite structure comprising the first and second active materials can be associated with a current collector structure, e.g., a Cu current collector. For example, the composite structure comprising the first and second active materials can be associated with the current collector substrate after the composite structure is formed. In other embodiments, the substrate structure comprising the second active material can be associated with the current collector substrate before the discrete nanostructures are formed thereon. In other embodiments, the substrate structure comprising the second active material can be associated with the current collector substrate at the same time that the discrete nanostructures are formed thereon. For example, the second active material and the discrete nanostructures comprising the first active material can be co-deposited onto the current collector substrate structure.

[0094]

[0121] The one or more substrates can include a LIB anode active material, a LIB anode current collector, or both an active material and a current collector. After ECD of the LIB active material nanostructures onto the LIB anode active material and / or current collector substrate structure, the resulting composite is preferably included in the LIB as an anode component. In preferred embodiments, the active material is electrochemically deposited onto one or more substrates including a LIB current collector and / or additional anode active material. The current collector can include copper, a copper plate, a copper mesh, a copper sponge, carbon, or carbon paper. The active material can include graphite, e.g., graphite particles or graphite powder. In one class of preferred embodiments, the substrate includes a LIB current collector including carbon, copper, or a combination thereof. The substrate can include a copper material, such as a copper plate, mesh, or sponge. Additionally or alternatively, the substrate can include a carbon-based material, such as carbon paper or graphite, e.g., graphite powder or a plurality of graphite particles. The substrate can also include combinations of materials, such as copper and carbon, copper and graphite, or graphite and non-graphitic carbon. For example, copper is electrochemically deposited onto graphite particles to form a silicon-graphite composite LIB anode material. In another class of preferred embodiments, the substrate comprises a LIB active material such as graphite, preferably a plurality of graphite particles, more preferably graphite fine powder or flakes.

[0095]

[0122] In one preferred class of embodiments, one or more active materials, preferably one or more active materials including silicon, are electrochemically deposited onto one or more conductive current collectors, which can be used as current collectors in LIB anodes. The current collectors preferably include one or more copper structures, such as copper sheets, thin films, plates, foils, meshes, foams, sponges, or powders or multiple particles / fibers / sheets / flakes / wires that can be packed, knitted, glued, or otherwise associated with one another, or any combination thereof. In a preferred embodiment, silicon can be electrochemically deposited directly onto the copper current collector, and a Cu-Si composite material can form the LIB anode material, in which copper is the conductive current collector and silicon is the active material for lithiation and delithiation during the charge and discharge cycles of the LIB.

[0096]

[0123] In another preferred class of embodiments, a first active material is electrochemically deposited directly onto at least a second active material to form a composite active material comprising the first and second active materials, where the composite active material structure is suitable for use as a LIB anode active material. In a preferred embodiment, a first active material comprising silicon is electrochemically deposited directly onto at least a second active material, where the second active material comprises one or more graphite structures, forming a silicon-graphite composite LIB anode material. The one or more graphite structures may comprise one or more of graphite sheets, thin films, plates, foils, powders, particles, or fibers, or sheets, films, plates, meshes, foams, sponges, or powders or multiple particles / fibers / sheets / flakes that may be packed, knitted, adhered, or otherwise associated with each other, or any combination thereof.

[0097]

[0124] In one general class of embodiments, silicon nanostructures, e.g., Si nanowires, are formed by electrochemical deposition directly onto a plurality of graphite particles, preferably graphite particulates. The graphite particles with the deposited silicon nanostructures on them are combined to form a porous, three-dimensional silicon-graphite composite anode active material. In another general class of embodiments, the silicon nanostructures, e.g., Si nanowires, are formed by electrochemical deposition directly onto a plurality of distinct current collectors. For example, the current collectors can include a plurality of carbon and / or copper sheets, preferably porous sheets containing copper, such as mesh or sponge sheets. Multiple current collectors can be combined to form a LIB component, preferably a current collector and active material composite anode component. Multiple current collectors can be combined in any suitable manner to form the component, and the configuration of the current collector can be tailored to fit the structural requirements of any particular battery system, as will be understood by those skilled in the art. In one exemplary class of embodiments, the LIB component includes a stack of multiple sheets containing a conductive material and an active material composite. One or more of the sheets in the stack may be porous, such as a conductive mesh or sponge sheet having active material deposited thereon. One or more of the sheets in the stack may be non-porous or less porous than the other sheets. For example, the sheets may have a porosity that increases with increasing distance from the bottom anode current collector sheet.

[0098]

[0125] In preferred embodiments, the substrate comprises at least one graphite structure, such as one or more graphite foil, thin film, or sheet structures; graphite powder, flakes, or particles; packed graphite powder / flakes / particles; organized graphite powder / flakes / particles; graphite powder / flakes / particles bonded together with one or more binder materials (e.g., CMC, PVDF, PAA, or PAADAA); other graphite structures; or any combination thereof. The one or more graphite structures may comprise natural graphite, synthetic graphite, HCMB, HOPG, graphite powder, porous graphite, porous graphite thin film or graphite felt, heat-treated carbon with a graphitic surface, or other forms of graphite. Preferably, the one or more graphite structures comprise a natural graphite surface. In certain embodiments, the graphite layer may be formed on one or more other materials, such as non-graphitic carbon. In preferred embodiments, the substrate comprises graphite foil or synthetic graphite (e.g., synthetic graphite powder) coated on a graphite foil.

[0099]

[0126] In embodiments of the present invention that include a graphite thin film or foil substrate structure, the graphite thin film or foil substrate can be used as a LIB anode active material, a LIB anode current collector, or both the active material and current collector. The graphite thin film or foil substrate can be laminated, adhered, or otherwise combined with another current collector structure, such as a Cu foil or thin film structure. In embodiments of the present invention, the graphite thin film or foil substrate, or a portion or one or more layers thereof, can be removed from a composite structure formed by one or more ECD processes of the present invention. This can minimize the thickness of the graphite layer while leaving the electrochemically deposited active material intact. The graphite foil substrate, or one or more portions thereof, can be removed by methods available in the art, such as peeling, grinding, etching, scraping, dissolving, or applying shear forces to the graphite foil. In a preferred embodiment, the graphite thin film or foil substrate has a thickness of about 1 μm to about 100 μm, preferably about 1 μm to about 50 μm, 1 μm to 50 μm, about 1 μm to about 25 μm, or 1 μm to 25 μm.

[0100]

[0127] In one preferred class of embodiments, the ECD substrate comprises a graphite powder comprising a plurality of graphite particles or flakes, the graphite particles preferably having an average size of about 1 μm to about 100 μm, 1 μm to 100 μm, about 1 μm to about 50 μm, 1 μm to 50 μm, about 1 μm to about 50 μm, 1 μm to 50 μm, or preferably about 5 μm to about 30 μm, or 5 μm to 30 μm.

[0101]

[0128] The graphite powder or binder-graphite powder composite can be coated on, formed on, or otherwise associated with another substrate structure (e.g., graphite foil, Cu thin film, Cu mesh, Cu sponge). The graphite powder or binder-graphite powder composite can be associated with a porous substrate. For example, the graphite powder can be packed into pockets formed in or on the substrate structure. In another embodiment, the graphite is disposed between two or more structures, where at least one of the structures is porous or permeable to allow the active material to pass through and deposit on the graphite powder during the ECD process.

[0102]

[0129] The graphite powder or binder-graphite powder composite can be formed into a layer and optionally coated onto another substrate / scaffold structure. The graphite-binder layer has a thickness of about 1 μm to about 200 μm, 1 μm to 200 μm, about 1 μm to about 100 μm, 1 μm to 100 μm, about 1 μm to about 50 μm, or 1 μm to 50 μm. The graphite powder layer or binder-powder layer is preferably a porous layer. The graphite-binder layer preferably has a porosity of about 10% to 70%. The graphite powder or binder-powder layer can have a porosity or concentration that varies across different spatial regions of the layer. For example, the graphite powder layer can have a relatively low efficiency in the interior region of the layer and a relatively high efficiency near one or more outer surfaces. When coated onto an electrode, current collector, or another structure, the graphite powder layer may have a relatively low porosity near the interface and an increasing porosity with increasing distance from the interface between the graphite powder layer and the structure. Alternatively, the porosity may be high at the interface and decrease with increasing distance from the interface. Other characteristics of the graphite layer, such as graphite particle size, graphite particle concentration, or binder concentration, may also vary across a spatial region of the graphite powder layer. For example, the binder concentration may be high near the interface between the graphite powder layer and another structure, and the graphite powder layer may have a binder concentration that decreases with increasing distance from the interface.

[0103]

[0130] In one exemplary embodiment, the substrate comprises graphite, such as the bare graphite foil shown in Figures 4A-4D, which show scanning electron microscope (SEM) images of the graphite foil surface at 300x, 1000x, 1500x, and 3000x magnification, respectively. The graphite foil substrate can be used as the substrate for both the active material nanostructures and / or the LIB current collector structure. In other embodiments, the graphite foil is both the current collector and the substrate / scaffold for depositing one or more ECD substrate materials (e.g., graphite powder or Cu).

[0104]

[0131] In one general class of embodiments, LIB active material nanostructures (eg, Si nanowires or other nanostructures) are formed directly on a graphite foil substrate by one or more direct ECD methods of the present invention.

[0105]

[0132] 5A-5C show photographs of various composite LIB anode structures, each including a graphite foil current collector substrate 215 and discrete Si nanostructures formed directly on the graphite foil by various ECD methods of the present invention. As seen in FIGS. 5A-5C, when a bottom portion 538 of graphite foil 515 was subjected to an ECD process according to embodiments of the present invention, at least one layer 540 including discrete Si nanostructures formed directly on the graphite foil substrate 515 was formed. While FIGS. 5A-5C show layer 540 including discrete active material nanostructures formed only on bottom portion 538 of graphite foil substrate 515, layer 540 can be formed over the entire surface or any selected portion of the substrate surface. This general concept applies to each of the embodiments of the present invention described herein, for example, to the embodiments shown in FIGS. 5A-5C, 23, 26A-26B, 27A-27B, 38, 39, and 40. As seen in the SEM images of Figures 6-22, discrete Si active material nanostructures are formed on the graphite foil substrate. As described in more detail below, ECD process parameters affect the properties of the electrochemically deposited material. ECD processes corresponding to the exemplary embodiments of Figures 6-22 are described in more detail below. In preferred embodiments, the composite LIB anode structure includes elongated Si nanostructures formed directly on the substrate by ECD. For example, as shown in the exemplary embodiments illustrated in Figures 6A, 6B, 8A-12C, and 14A-14C, various direct ECD methods of the present invention can deposit Si nanowires 520 on the substrate. Additional active material nanostructures, such as the various active material nanostructures described herein, are also encompassed by the methods and compositions of the present invention. Preferably, the discrete active material nanostructures comprise crystalline Si, e.g., crystalline Si nanowires. However, active material nanostructures comprising additional forms of Si are also encompassed by the present invention. For example, the active material nanostructures can include nanostructures that include amorphous Si structures, polycrystalline Si structures, both amorphous and polycrystalline Si structures, or a combination of crystalline Si and amorphous and / or polycrystalline Si.

[0106]

[0133] In another general class of embodiments, LIB active material nanostructures (e.g., Si nanowires or other nanostructures) are formed directly on a first substrate comprising graphite powder or a plurality of graphite particles by one or more direct ECD methods of the present invention. The graphite powder or ECD substrate comprising a plurality of graphite particles can be coated on or otherwise associated with a second substrate or scaffold structure, such as a graphite foil structure, a Cu thin film or network structure, or a combination thereof. The ECD substrate preferably comprises graphite powder, such as a plurality of graphite particles, graphite flakes, round graphite particles, or spherical graphite particles. Discrete nanostructures comprising at least one active material can be electrochemically deposited on the graphite particles to form a composite LIB anode active material structure.

[0107]

[0134] In certain embodiments, the graphite particles do not bond to one another during the ECD process. In other embodiments, the graphite powder substrate comprises multiple groups of interconnected graphite particles, where one or more groups of graphite particles form discrete groups of graphite particles. That is, the groups are physically separated from one another during the ECD process. In certain embodiments, the graphite particles are provided on another substrate structure, such as a conductive plate, thin film, or sheet. For example, a first substrate material comprising individual graphite particles or discrete groups of graphite particles can be provided on a second substrate (e.g., a graphite foil, a Cu thin film, or a porous Cu substrate / scaffold), whereby the discrete graphite particles or discrete groups of graphite particles form discrete protrusions or surface features on the surface of the second substrate structure. The discrete protrusions or surface features are spatially separated from one another, such that the plurality of discrete surface features (each comprising at least one graphite particle) collectively provide roughness to the second substrate surface.

[0108]

[0135] In certain embodiments of the present invention, the graphite particles of the graphite powder substrate can be physically associated with one another (e.g., bonded or adhered to one another). The graphite particles can be physically associated with one another before, after, or during the ECD process. In a preferred embodiment, the graphite particles are bonded to one another using one or more adhesive binder materials to form a graphite powder and binder composite structure. The binder preferably comprises carboxymethyl cellulose (CMC), polyvinylidene fluoride (PVDF), poly(acrylamide-co-diallyldimethylammonium) (PAADAA), or polyacrylic acid (PAA). The graphite powder / particles can be combined with one or more binder materials and coated onto a scaffold or substrate structure, such as a planar conductive material structure, a graphite foil structure, a Cu thin film structure, a Cu mesh or sponge structure, or a combination thereof. The binder and graphite powder can be deposited on the scaffold / substrate using any suitable coating or deposition method available in the art, such as a battery slurry coating method, including those described in U.S. Patent Application No. 12 / 783,243, which is incorporated herein by reference in its entirety. The planar scaffold / substrate preferably comprises a porous layer comprising a graphite powder ECD substrate, a binder-graphite powder composite, a composite material comprising graphite powder having active material nanostructures formed thereon, or a composite material comprising graphite powder and a binder having discrete nanostructures formed thereon. In one class of embodiments, the graphite powder can be deposited on the scaffold / substrate prior to the ECD process, such that the planar scaffold / substrate and graphite powder form a composite substrate structure onto which the nanostructures are deposited directly by ECD. The discrete active material nanostructures can be deposited by ECD directly on the graphite particles or on both the graphite particles and the planar scaffold / substrate. In other embodiments, discrete active material nanostructures can be precipitated onto graphite powder / particles to form an active material composite, and the nanostructure-containing graphite powder / particles can then be bonded to one another and coated onto a planar scaffold / substrate, for example, using one or more adhesive binder materials. As will be appreciated by those skilled in the art, the composite material can be coated onto the scaffold / substrate using conventional methods for coating a battery slurry composite onto a substrate.

[0109]

[0136] As seen in FIG. 23, porous layer 2340 is formed on lower portion 2338 of graphite foil substrate 2315. However, according to the present invention, layer 2340 can be formed on the entire surface of graphite foil 2315a or on selected portions. FIGS. 24A-24C include SEM images of porous layer 2340 at magnifications of 500×, 2000×, and 5000×, respectively. FIGS. 24A-24C illustrate porous layer 2340 before the direct ECD process, i.e., before the formation of discrete active material nanostructures on graphite particles 2415b. FIGS. 25A-25D include SEM images of porous layer 2340 including graphite particles 2515b after direct ECD of Si active material nanostructures 2520 onto graphite particles 2515b. As can be seen in the images of Figures 25A-25D, discrete Si nanowires 2520 are formed directly on the graphite particles 2515b by direct ECD according to the method of the present invention. The discrete active material nanostructures preferably comprise crystalline Si, e.g., crystalline Si nanowires. However, active material nanostructures comprising additional forms of Si are also encompassed by the present invention. For example, the active material nanostructures can include nanostructures comprising amorphous Si structures, polycrystalline Si structures, both amorphous and polycrystalline Si structures, or combinations of crystalline Si with amorphous and / or polycrystalline Si.

[0110]

[0137] In one exemplary embodiment, a porous layer comprising graphite powder / particles and an adhesive binder material is formed on a graphite foil substrate / scaffold structure by one or more direct ECD methods of the present invention, and discrete Si nanostructures are formed on the graphite particles. The ECD process of this exemplary embodiment is described in further detail below. Graphite powder substrate material 2315b is coated onto graphite foil substrate structure 2315a to produce a composite graphite foil-graphite powder substrate for ECD of one or more active material nanostructures thereon. Graphite powder can be coated directly onto the graphite foil. In certain embodiments, graphite powder can be coated onto a graphite foil or another substrate structure without the use of a binder material. In a preferred embodiment, the graphite foil is combined with at least one binder material (preferably CMC) and coated onto the graphite foil using conventional LIB slurry coating techniques. Figure 23 shows a photograph of a composite anode structure 2350 comprising a graphite foil current collector 2315a and a porous layer 2340 formed thereon, before Si deposition. After the ECD process in which Si nanostructures are formed on the graphite powder, porous layer 2340 includes graphite powder, CMC binder material, and discrete Si nanostructures formed on the graphite powder. As seen in FIG. 23, porous layer 2340 is formed on graphite foil 2315a at bottom portion 2338, which was subjected to the ECD process. FIGS. 24A-24C include SEM images of porous layer 2340 at magnifications of 500×, 2000×, and 5000×, respectively. FIGS. 24A-24C show porous layer 2340 before the direct ECD process, i.e., before discrete active material nanostructures are formed on graphite particles 2415b. FIGS. 25A-25D include SEM images of porous layer 2340 including graphite particles 2515b after direct ECD of Si active material nanostructures 2520 onto graphite particles 2515b. As can be seen in the images in Figures 25A-25D, direct ECD according to the method of the present invention forms discrete Si nanowires 2520 directly on the graphite particles 2515b. The ECD process of the present invention is described in further detail below. Once the LIB anode is formed, the graphite foil 2515a and graphite powder 2515b coating can be used as the current collector material for the LIB, and the Si nanostructures can be used as the active material for the LIB. The graphite foil can also contribute to the active material for the LIB.

[0111]

[0138] In another class of embodiments, the ECD substrate comprises graphite powder physically associated with a Cu substrate and a scaffold structure, and discrete Si nanostructures are formed on the graphite particles by one or more direct ECD methods of the present invention. The Cu substrate structure preferably comprises a porous Cu structure, such as a porous Cu thin film or a Cu network or sponge structure. The Cu substrate structure, e.g., a planar Cu structure, is preferably both the working electrode of the electrochemical cell used in the ECD process and the LIB current collecting structure. The graphite particles can be deposited on one or more surfaces of the Cu structure, deposited within the pores of the porous Cu structure, located within pockets formed by the Cu substrate, located between two or more sides of a folded Cu substrate structure, located or sandwiched between multiple Cu substrate structures, or any combination thereof. The porous Cu substrate (e.g., a porous Cu network or sponge) preferably has a porosity of about 10-80%, about 10-50%, or about 10-30%, preferably about 30% or 30%. As discussed above, the graphite particles can be deposited with or without a binder material, and the graphite powder can be configured to provide protrusions or surface features on one or more surfaces of the Cu substrate.

[0112]

[0139] In one exemplary embodiment, as shown in Figures 26A-27B, the ECD substrate includes graphite powder 2615b, 2715b. By one or more direct ECD methods of the present invention, the graphite powder physically associates with the porous Cu substrate / scaffold 2615a, 2715a to form a graphite powder coating on at least one surface of the Cu structure, and discrete Si nanostructures are formed on the graphite particles. In this example, the graphite powder was deposited without the use of a binder material; however, a binder material can be included to adhere the graphite particles to each other or to the Cu substrate. An example of a porous Cu substrate / scaffold is illustrated in the optical microscope image of Figure 28, which shows the porous Cu material prior to the addition of graphite or other materials. Figures 26A-27B include photographs of the resulting LIB anode composite structure 2650, 2750, which includes a porous Cu current collector, graphite powder active material, and Si active material nanostructures on the graphite powder particles. Figures 30A-30D and 31A-31D show SEM images of Si active material nanostructures 3020, 3120 deposited directly onto graphite particles disposed within a porous Cu substrate scaffold. During the direct ECD process of this exemplary embodiment, a graphite powder substrate was placed between two surfaces of a porous Cu mesh electrode structure. Figures 30A-30D show Si-coated graphite particles disposed at the center of the composite, while Figures 31A-31D show Si-coated graphite particles disposed toward the outer surface of the composite (i.e., closer to the porous Cu substrate scaffold). As shown in Figures 31A-31D, relatively heavy Si deposition onto the graphite particles was achieved in the outer region of the composite. As seen in Figure 29 and Figures 32A-32D, Si-containing LIB active material nanostructures 3220 were electrochemically deposited directly onto the porous graphite structure by one or more ECD methods of the present invention. The ECD process of this exemplary embodiment is described in further detail below.

[0113]

[0140] In yet another embodiment, as shown in FIG. 33, a Cu substrate material 3315b is coated onto a graphite foil substrate structure 3315a for ECD of one or more active material nanostructures thereon, creating a composite graphite foil-Cu substrate. Cu can be directly coated onto the graphite foil using conventional metal coating techniques, such as ECD or evaporation. FIG. 33 shows the Cu-coated graphite foil substrate before Si deposition, and FIGS. 34 and 35 show two different substrate samples similar to the substrate shown in FIG. 33, with Si nanostructures formed thereon using one or more ECD processes of the present invention. Once a LIB anode is formed, the graphite foil 3315a and Cu coating 3315b can be used as the current collector material in the LIB, and the Si nanostructures can be used as the active material in the LIB. The graphite foil can also contribute to the active material in the LIB. Figures 36A-36C show SEM images of the Si-coated Cu with the structure shown in Figure 34, and Figures 37A-37C show SEM images of the Si-coated Cu with the structure shown in Figure 35. The ECD process of this exemplary embodiment is described in further detail below.

[0114] Multi-material or multi-structure substrates

[0141] In one general class of preferred embodiments of the present invention, the LIB anode comprises a multi-component or multi-material substrate having high-capacity active material nanostructures, e.g., Si nanostructures, formed on one or more of the multi-substrate components and / or materials.

[0115]

[0142] In one class of embodiments, LIB active material is electrochemically deposited on a first substrate, the first substrate being physically associated with a second substrate, the first substrate and the second substrate comprising one or more different materials, shapes, sizes, morphologies, or other characteristics. Nanostructures can be electrochemically deposited on the first substrate before, after, or simultaneously with the first and second substrates being physically associated with each other. A LIB anode component can be formed, the anode component comprising the second substrate, the first substrate, and the active material nanostructures formed on the first substrate.

[0116]

[0143] In another class of embodiments, LIB active materials are electrochemically deposited on a substrate, the substrate including a first substrate component and a second substrate component, the first and second components including one or more different materials, shapes, sizes, morphologies, or other properties. Active material nanostructures can be electrochemically deposited on the first material only, the second material only, or both the first and second materials. LIB anode components can be formed, the anode component including the composite substrate and the active material nanostructures formed thereon.

[0117]

[0144] In another class of embodiments, active material nanostructures are electrochemically deposited onto multiple substrates or multiple substrate layers to form a three-dimensional LIB anode composite structure. The multiple substrates or multiple substrate layers and the active material nanostructures electrochemically deposited thereon are combined to form a three-dimensional LIB anode structure comprising a mixture of substrates and active material nanostructures throughout a majority of the thickness t of the LIB anode. The substrates can be electrochemically deposited onto the substrates before, after, or simultaneously with combining the multiple substrates. By way of example only, the multiple substrates can include multiple particulate substrates, multiple fibrous substrates, multiple flake substrates, multiple planar substrate layers, at least one planar substrate layer and multiple particles, graphite particles, one or more graphite foil layers, one or more Cu thin film layers, one or more porous Cu structures, one or more carbon sheets or foils, or combinations thereof. As shown in the exemplary embodiment of FIG. 38A , the substrate includes multiple particles 3815b having active material nanostructures 3820 formed thereon. The particles preferably include graphite particles. The anode structure can have decreasing porosity from the top 3850a to the bottom 3850b of the anode structure, which allows for uniform flow of the LIB electrolyte through the thickness t of the LIB anode structure. For example, graphite particles 3815b SizeThe active material nanostructures 3820 may decrease from the top 3850a to the bottom 3850b of the anode structure, and / or the particles 3815b may be more densely packed toward the bottom 3850b of the anode structure. As shown in the exemplary embodiment of FIG. 38B , the LIB composite anode structure includes multiple substrate layers 3815a having electrochemically deposited active material nanostructures 3820 on one or more surfaces of each layer. The bottom substrate layers may be solid conductive thin films or porous structures. Preferably, each of the top substrate layers 3815a includes a porous substrate layer. In one embodiment, the porosity of the layers 3815a decreases from the top 3850a of the anode structure to the bottom 3850b of the anode structure. That is, each top layer is more porous than the underlying substrate layer. 38C, the LIB composite anode structure includes at least one layer of a plurality of graphite particle substrates 3815b disposed between substrate layers 3815, with the particles 3815b and layers 3815a each including active material nanostructures formed thereon. One or more of the layers 3815a can include a porous structure. The porosity of the composite can decrease from the top 3850a to the bottom 3850b of the anode structure.

[0118]

[0145] In preferred embodiments, the ECD substrate has a total thickness of about 500 μm or less, 500 μm or less, about 300 μm or less, 300 μm or less, about 100 μm or less, preferably 100 μm or less, or less than 100 μm. Most preferably, the substrate has a thickness of about 5-300 μm, most preferably about 5-100 μm. In one preferred embodiment, the substrate and active material nanostructures formed thereon comprise a composite LIB anode structure. The composite LIB anode structure is preferably thin enough to be easily and conveniently formed into a LIB device, for example, a cylindrical LIB cell structure. Most preferably, the composite LIB anode structure comprising the substrate and active material nanostructures formed directly thereon has a total thickness of 100 μm or less, preferably less than 100 μm.

[0119] Substrate surface modifications and surface features

[0146] The substrate surface can include one or more surface modifications to control the deposition of one or more materials during the ECD process and to control the resulting properties of the electrochemically deposited nanostructures that include at least one LIB active material. ECD substrate surface modifications can be achieved by modifying one or more physical or chemical properties of the substrate surface, such as the physical structure or chemical composition of the substrate surface. The physical or chemical properties of the substrate surface can be modified by one or more mechanical, chemical, electrical, or temperature-based surface modification techniques, as well as additional surface modification techniques available in the art. Modification of the substrate surface can be achieved by etching (e.g., chemical, mechanical, laser, or microetching), scratching, polishing, roughening, laser ablation, heat treatment, annealing, chemical treatment (e.g., acid treatment, gas treatment, foam gas treatment, alloying, or doping), deposition of one or more materials onto the substrate surface (e.g., by coating, chemical bonding, adsorption, adhesion of a binder material, lithography, sputtering, ECD or CVD, evaporation, or electroless plating), or other modification techniques available in the art, as well as combinations thereof. In preferred embodiments, the substrate surface is modified to create discrete spatial regions on the substrate surface that have one or more distinguishable properties compared to other regions of the substrate. The discrete regions result in a difference in the surface charge of the regions compared to other regions of the substrate, such as an opposite charge, an increased charge, or a decreased charge.

[0120]

[0147] In one general class of embodiments, one or more discrete surface features, e.g., protrusions, can be formed on the substrate surface, thereby enabling a rough substrate surface with increased activation energy at the discrete protrusions or other discrete surface features. In one aspect of the invention, the protrusions on the substrate surface increase electron flow through the substrate at the locations of the protrusions compared to nearby locations on the substrate surface. In preferred embodiments, the counter electrode comprises a uniform or substantially uniform structure, such that the protrusions or other surface features are closer to the counter electrode compared to nearby locations on the substrate that do not include the surface protrusions. Thus, the substrate surface features or protrusions can provide localized, discrete active sites for direct electron covalent deposition of discrete active material nanostructures on the substrate. Additional language is provided to describe the mechanisms at work herein. As will be understood by those skilled in the art, the size, shape, morphology, pattern, and other properties of the discrete substrate surface area and surface features can be tailored to control the size, shape, morphology, and other properties of the nanostructures formed on the substrate surface. In preferred embodiments, the discrete surface regions have a height and / or width of 1 μm or less, more preferably 500 nm or less, 400 nm or less, or 300 nm or less, even more preferably 250 nm or less, 200 nm or less, or 150 nm or less, and most preferably 100 nm or less, 75 nm or less, 50 nm or less, 25 nm or less, 20 nm or less, 15 nm or less, or 10 nm or less.The discrete surface regions having modified surface properties are preferably spaced apart by a distance of at least 10 nm and less than 1 μm from one another, for example the surface regions may be spaced apart by 10-750 nm, 10-500 nm, 10-250 nm, 10-100 nm, 10-75 nm, 10-50 nm, 10-20 nm, 20-750 nm, 20-500 nm, 20-250 nm, 20-100 nm, 20-75 nm, 20-50 nm, 50-750 nm, 50-750 nm, 50-850 nm, 50-950 nm, 50-100 nm, 50-200 nm, 50-300 nm, 50-400 nm, 50-500 nm, 50-60 ...100 nm, 50-200 nm, 50-300 nm, 50-400 nm, 50-500 nm, 50-500 nm, 50-600 nm, 50-750 nm, 50-100 nm, 50-200 nm, 50-200 nm, 50-300 nm, 50-400 nm, 50-500 nm, 50-500 nm, 50-100 nm, 50 The distance between the center points of the surface regions may be 0 to 500 nm, 50 to 250 nm, 50 to 200 nm, 50 to 150 nm, 50 to 100 nm, 75 to 250 nm, 75 to 200 nm, 75 to 150 nm, 75 to 100 nm, 100 to 500 nm, 100 to 250 nm, 100 to 200 nm, 150 to 250 nm, 150 to 200 nm, more preferably about 100 nm, about 75 nm, about 50 nm, about 25 nm, or about 20 nm. Most preferably, the distance between the center points of the discrete surface regions is about twice the width of the discrete surface regions.

[0121]

[0148] As shown in the exemplary embodiments of Figures 39A-39F, which show top views of exemplary substrate surfaces, and Figures 40A-40E, which show cross-sectional views of various exemplary substrate surfaces, an ECD substrate surface can include one or more first regions 3955 that include at least one surface modification, such as a protrusion or other surface feature or modification, and one or more second regions 3956, where the one or more second regions 3956 are free of surface features or have lesser surface features than the one or more first regions 3955. Substrate surfaces having more than two classes of surface modification regions are also encompassed by the present invention. As shown in Figures 39A, 39B, 39E, and 40A-40C, the first regions 3955 and second regions 3956 are formed by one or more notches or grooves. The notches or grooves can have any shape or pattern, such as rectangular, as shown in Figures 39A, 39B, and 40A, or prismatic, angled, or V-shaped, as shown in Figures 39E, 40B, and 40C. As shown in Figure 39F, protrusions 3960 are high points on the substrate surface formed by V-shaped grooves including peaks 3958 and valleys 3959. The surface features or protrusions can have any suitable shape, such as domes, lumps, circular features, spikes, lines, prismatic, conical, V-shaped features, or square or rectangular features, as well as combinations thereof. As shown in the exemplary embodiments of Figures 39D and 39E, the first and second surface regions can be formed by scratching, etching, or roughening the substrate surface. As shown in the exemplary embodiments of Figures 39C, 39E, 40D, and 40F, the first and second regions can have a random pattern on the substrate surface. As shown in the exemplary embodiments of Figures 39A, 39C, 39D, 39F, 40A-40C, 40F, and 40G, the first and second regions can have an orderly or repeating pattern on the substrate surface. In certain embodiments, the first and second regions can be defined by differences in chemical composition or other surface material properties, as shown, for example, in Figures 40E and 40G. For example, discrete surface features 4060 can be formed by doping, thermal treatment, chemical treatment, or other modification of the substrate material at discrete locations on the substrate surface.As will be appreciated by those skilled in the art, the size, shape, morphology, pattern, and other properties of the discrete substrate surface protrusions can be adjusted to control the size, shape, morphology, and other properties of the nanostructures formed on the substrate surface.

[0122]

[0149] In one exemplary embodiment, one or more active materials, one or more inactive materials, and / or one or more conductive materials can be formed or deposited on the substrate by any suitable method available in the art, such as coating, chemical bonding, adsorption, adhesion, adhesion of a binder material, lithography, sputtering, ECD, CVD, evaporation, electroless plating, or other material deposition techniques available in the art or mentioned herein, or a combination thereof.

[0123]

[0150] Nanostructures comprising at least one active material are deposited by ECD directly onto at least one surface of the ECD substrate surface 4116. In certain embodiments, as shown in the exemplary embodiment of FIG. 41A, the ECD substrate surface can include a smooth surface, whereby nanostructures 4120 (e.g., nanowires, tapered nanowires, dome-shaped or hump-shaped nanostructures, nanospikes, or clusters of nanospikes) are formed on the smooth substrate surface 4116. In preferred embodiments, the ECD substrate surface is rough rather than smooth. In preferred embodiments, one or more ECD substrate structures include at least one surface having one or more surface features or protrusions. As shown in the exemplary embodiment of FIG. 41B, the substrate includes one or more surface features or protrusions 4160, and the nanostructures 4120 are formed directly on the surface features 4160. Preferably, at least some of the nanostructures are formed on the protrusions or surface features. Multiple nanostructures can be formed on each surface feature or protrusion. The surface protrusions 4160 can comprise the same material or structure as the substrate. Additionally or alternatively, the substrate can comprise a first material, and the surface protrusions 4160 can comprise a second material different from the first material. In another exemplary embodiment shown in Figure 41C, the substrate comprises a first surface feature or protrusion 4160a comprising the substrate material and a second surface feature or protrusion 4160b comprising a second material different from the substrate material. At least a portion of the second surface feature or protrusion 4160 is formed directly on the first protrusion 4160a, thereby forming a surface protrusion 4160 having a larger size or height compared to the first or second feature alone. The nanostructures 4120 are formed directly on at least a portion of the stacked first and second surface protrusions 4160b.

[0124]

[0151] As shown in the exemplary embodiments of Figures 41E-41F, the surface features can include at least a second material different from the first substrate material. These embodiments are preferred when the underlying substrate surface is relatively smooth. Surface features or protrusions including the second material can provide increased roughness to the substrate surface, increased conductivity at the surface feature location, or other properties recognized by those skilled in the art. As shown in Figure 41D, the surface features include particles 4162 formed on the underlying substrate surface 4116, thereby forming one or more nanostructures 4120 on the surface feature particles 4162. In one embodiment, the surface features include graphite particles formed on the substrate surface 4116. The particles can include other materials, such as conductive materials, copper particles, or carbon particles. As shown in Figure 41E, the surface features include one or more dome- or hump-shaped features 4060, thereby forming one or more nanostructures 4120 on the surface hump or dome 4160. Additional surface feature shapes are encompassed by the present invention, such as spikes, circular features, linear features, spheres, or other feature shapes. In one embodiment, the surface features include copper formed on the substrate surface 4116. In one exemplary embodiment, Cu is electrochemically deposited on the underlying substrate surface to form feature 4160. Additional material deposition or formation techniques, such as those described herein, can be used. Feature 4160 can include other materials, such as one or more conductive materials, one or more metals, alloys, conductive polymers, one or more binder materials, or other materials. In yet another exemplary embodiment, as shown in FIG. 41F , the surface features or protrusions include one or more particles 4162 including a first material deposited on the substrate surface 4116 and one or more protrusions 4160 including a second material formed on the particles 4162. One or more nanostructures 4120 are formed on the second material. In one exemplary embodiment, graphite particles are deposited on the substrate surface 4116, and protrusions including a conductive material, e.g., Cu, are formed on the graphite particles. In another embodiment (not shown), particles can be formed on protrusions formed on the substrate surface.As shown in the exemplary embodiment of Figures 41G-41I, a plurality of nanostructures 4120 can be formed on each surface feature 4160. As shown in Figure 41I, a plurality of protrusions 4160 can be formed on each particle 4162 deposited on the substrate surface 4116, and a plurality of nanostructures 4120 can be formed on the plurality of protrusions 4160. In another embodiment (not shown), a plurality of particles can be formed on each protrusion formed on the substrate surface.

[0125]

[0152] In another general class of embodiments, as shown in Figures 42A-42C, the substrate surface features can include grooves or depressions 4264 having one or more nanostructures 4220 thereon. Discrete regions of the substrate surface are defined by the depressions 4264, which can include a variety of shapes, as shown in Figures 42A-42C. Nanostructures 4220 comprising at least one active material are formed directly in or on the grooves / depressions 4264.

[0126]

[0153] In another general class of embodiments, the substrate includes multiple layers, with one or more of the substrate layers including discrete surface features, e.g., protrusions, as shown in Figures 43A-43G. As shown in the figures, each LIB composite anode structure includes a first substrate layer 4366, at least a second substrate layer 4368, surface protrusions on the first layer 4366 and / or second layer 4368, and at least one active material nanostructure 4320 formed on the protrusions 4160. Two or more substrate layers may include different materials or other distinguishing characteristics. In certain embodiments, as shown in Figures 43A, 43C, and 43D, the protrusions or other surface features are formed by the surface layer itself. That is, the substrate layer and the protrusions are integral features of the same material structure or layer. In other embodiments, as shown in Figures 43B, 43E, and 43F, protrusions or other surface features are formed on one or more layers by depositing or physically associating one or more structures with the substrate layer to form protrusions, which are distinct from the substrate layer. The structures preferably comprise a material that is different from the substrate material of the substrate on which the structures are formed. As shown in Figures 43A-43G, the substrate can include a first layer 4366 comprising a first material, and at least a second layer 4368 comprising a second material formed on an upper surface of and on the first layer 4366. The first and second materials can be the same or different materials. Preferably, the first and second materials comprise different materials, different morphologies, or at least one distinguishable characteristic.

[0127]

[0154] As shown in FIG. 43A , the top surface 4366a of the first layer 4366 is substantially smooth or flat, the second layer 4368 includes protrusions 4360 on the top surface 4368a of the second layer 4368, where the protrusions 4360 are an integral part of the second layer 4368, and the active material nanostructures 4320 are formed directly on the protrusions 4360 by ECD such that the nanostructures 4320 are in direct physical contact with the protrusions 4360 and extend outward from the second layer 4368 and the protrusions 4360. As shown in FIG. 43B, upper surface 4366a of first layer 4366 and upper surface 4368a of second layer 4368 are substantially smooth or flat, second layer 4368 includes protrusions 4360 formed on upper surface 4366a of second layer 4368, and active material nanostructures 4320 are formed directly on protrusions 4360 by ECD such that nanostructures 4320 are in direct physical contact with protrusions 4360 and extend outward from protrusions 4360 and second layer 4368. As shown in FIG. 43C , the top surface 4366a of the first layer 4366 includes protrusions 4360 that are an integral part of the first layer 4366, the top surface 4368a of the second layer 4368 is substantially smooth or flat, and the active material nanostructures 4320 are formed by ECD directly on the top surface 4368a of the second layer 4368 directly above the protrusions 4360, such that the nanostructures 4320 are physically separated from the protrusions 4360 by the second substrate 4368, and the nanostructures 4320 extend outward from the top surface 4368a of the second substrate layer 4368. In the embodiment shown in Figure 43D, the LIB anode structure is substantially the same as the embodiment shown in Figure 43C, except that second substrate 4368 conforms to the shape of first substrate 4366, including protrusions 4360a, such that second substrate 4368 consequently includes protrusions 4360b that are an integral part of second substrate 4368, and nanostructures are formed on first protrusions 4360a and second protrusions 4360b. In the embodiment shown in Figure 43E, the LIB anode structure is substantially the same as the embodiment shown in Figure 43C, except that protrusions 4360 are separate structures from first substrate 4366, rather than formed from the first substrate structure itself. In the embodiment shown in Figure 43F, the LIB anode structure is substantially the same as the embodiment shown in Figure 43F, except that protrusions 4360 are separate structures from first substrate 215, rather than formed from the first substrate structure itself.

[0128]

[0155] In preferred embodiments, one or more surface features comprise at least one conductive material and / or at least one active material. For example, the surface features can comprise a current collector material such as Cu and / or an active material such as graphite. As will be appreciated by those skilled in the art, the size, shape, morphology, material, pattern, and other properties of the surface features can be tailored to control the size, shape, morphology, and other properties of the nanostructures formed thereon. The surface features or protrusions can have any suitable shape, such as domes, bumps, circular features, spikes, lines, prisms, cones, angled features, V-shaped features, or square or rectangular features, as well as combinations thereof. In preferred embodiments, the discrete surface protrusions have a height and / or width of 1 μm or less, more preferably 500 nm or less, 400 nm or less, or 300 nm or less, more preferably 250 nm or less, 200 nm or less, or 150 nm or less, and most preferably 100 nm or less, 75 nm or less, 50 nm or less, 25 nm or less, 20 nm or less, 15 nm or less, or 10 nm or less. The discrete surface protrusions having modified surface properties are preferably spaced apart by a distance of at least 10 nm and less than 1 μm from one another, for example surface regions 10-750 nm apart, 10-500 nm apart, 10-250 nm apart, 10-100 nm apart, 10-75 nm apart, 10-50 nm apart, 10-20 nm apart, 20-750 nm apart, 20-500 nm apart, 20-250 nm apart, 20-100 nm apart, 20-75 nm apart, 20-50 nm apart, 50-750 nm apart, The distance between the peaks or high points of each protrusion may be 50 to 500 nm, 50 to 250 nm, 50 to 200 nm, 50 to 150 nm, 50 to 100 nm, 75 to 250 nm, 75 to 200 nm, 75 to 150 nm, 75 to 100 nm, 100 to 500 nm, 100 to 250 nm, 100 to 200 nm, 150 to 250 nm, 150 to 200 nm, more preferably about 100 nm, about 75 nm, about 50 nm, about 25 nm, or about 20 nm. Most preferably, the distance between the peaks or high points of each protrusion is about twice the width of the discrete surface protrusions.

[0129]

[0156] Alternatively, or in addition to the substrate surface modifications described above, one or more properties of the ECD substrate surface can be controlled or modified using one or more ECD process parameters or techniques of the present invention. For example, ECD process parameters such as current, temperature, fluid movement, precursor concentration, or solution-substrate surface interaction could be adjusted to have different values ​​in different regions of the substrate surface. These process conditions are described in more detail below.

[0130]

[0157] In a preferred embodiment, nanostructures comprising at least one LIB active material and one or more substrate materials are formed into a LIB anode structure comprising a substrate-nanostructure composite. Using techniques available to those skilled in the art, including those mentioned herein or incorporated by reference, the substrate and active material nanostructures formed thereon can be formed into a LIB anode, which can be formed into a LIB fuel cell or half-cell for use as a rechargeable or disposable energy source.

[0131]

[0158] In preferred embodiments, the anode composite structure comprises a porous composite including one or more substrate materials and a plurality of nanostructures formed thereon using one or more of the ECD methods described herein. The substrate-active material nanostructure composite is preferably a porous structure having a porosity of about 10-70%, 10-50%, 20-40%, or about 30%. The anode current collector and active material composite preferably has a planar structure. The current collector and active material composite preferably has a thickness of about 100 μm or less, preferably 100 μm or less, and most preferably less than 100 μm. In certain embodiments, the composite anode structure can have one or more properties that vary across various spatial regions of the composite. For example, the porosity, composition, or one or more other properties can vary across various spatial regions of the composite anode structure.

[0132] Binder, electrolyte, electrolyte additive, and solid electrolyte interface

[0159] Due to inherent differences between standard LIB active materials, high capacity materials, and nanostructures such as Si nanostructures, conventional LIB materials are not ideal for use with LIBs incorporating non-traditional high capacity active materials such as Si. The present invention includes novel LIB materials, such as binder materials, electrolyte materials, electrolyte additive materials, and solid electrolyte interface (SEI) materials formed on one or more battery components, as well as related components, devices, and manufacturing methods.

[0133] binder

[0160] One aspect of the present invention relates to LIB materials including binders, as well as related components, devices, and methods of manufacture. In particular, the present invention includes LIB electrolytes and LIB electrolyte additives suitable for use with LIBs including Si active materials or Si and graphite active materials, as well as related components, devices, and methods. In a preferred embodiment, the present invention includes a LIB anode including one or more binder materials selected from the group consisting of carboxymethyl cellulose (CMC), polyvinylidene fluoride (PVDF), poly(acrylamide-co-diallyldimethylammonium) (PAADAA), polyacrylic acid (PAA), and styrene butadiene rubber (SBR).

[0134]

[0161] In preferred embodiments, the LIB anode comprises Si nanostructures (e.g., Si nanowires) and at least one binder material comprising CMC, PVDF, PAADAA, PAA, SBR, or a combination thereof. In another preferred class of embodiments, the LIB anode comprises one or more graphite structures (e.g., graphite foils or graphite particles), a plurality of Si nanostructures (e.g., Si nanowires formed on graphite particles) formed on the one or more graphite structures, and at least one binder material comprising CMC, PVDF, PAADAA, PAA, SBR, or a combination thereof.

[0135]

[0162] In a preferred embodiment, the binder is combined with a plurality of graphite particles to form a slurry, which is then coated onto a substrate structure (e.g., a graphite foil, a thin carbon film, or a porous carbon mesh) using, for example, conventional battery slurry coating methods. After the slurry solvent evaporates, a plurality of discrete Si nanostructures are formed on the graphite particles using one or more ECD methods of the present invention.

[0136]

[0163] In certain embodiments, a layer of one or more binder materials (e.g., CMC, PVDF, PAADAA, PAA, SBR, or combinations thereof) is applied directly onto the current collector substrate, and the binder-graphite particle composite or binder-graphite particle-Si nanostructure composite is coated onto the current collector structure. For example, the composite can be coated onto a Cu thin film or graphite foil current collector substrate.

[0137]

[0164] In another class of embodiments, Si nanostructures are first formed on a substrate comprising a plurality of graphite particles, and then the Si-graphite particle composite is combined with one or more binder materials, including CMC, PVDF, PAADAA, PAA, SBR, or combinations thereof, to form a LIB anode. For example, conventional battery slurry coating techniques can be used to form the graphite-Si-binder composite into a LIB anode. In certain embodiments, the graphite-Si-binder composite is coated onto a LIB current collector substrate (e.g., a thin Cu film or graphite foil structure) to form a LIB anode component.

[0138]

[0165] The LIB anodes and LIBs of the present invention preferably include one or more binder materials, including one or more of CMC, PVDF, PAA, SBR, and PAADAA. In a preferred embodiment, the binder includes CMC, PAADAA, SBR, and / or PAA. For example, a LIB anode structure can include a plurality of graphite particles having Si nanostructures formed thereon, where the graphite particles are bonded to each other using CMC, PAADAA, SBR, and / or PAA binder materials. Alternatively, a graphite-Si-CMC binder composite can be formed on a current collector substrate (e.g., a planar Cu substrate) using one or more binder materials, such as PAA. In one embodiment, a graphite-Si composite material is formed on a current collector, where one or more of the CMC, PVDF, PAA, and PAADAA binder materials are disposed between the current collector structure and the graphite-Si active material composite, thereby improving the bond strength between the current collector and the graphite-Si composite material.

[0139]

[0166] In a preferred embodiment, PAA is disposed between the LIB current collector structure and the graphite powder-Si composite material, and the graphite powder particles are bound together using the same binder material or one or more different binder materials. For example, CMC and / or PAADAA can be used to bind the graphite particles together in the Si-graphite powder composite structure, and PAA can be used as an interfacial binder material between the graphite powder-Si composite and the current collector.

[0140]

[0167] In certain embodiments, the binder composition, binder concentration, or concentrations of various binder materials can be varied across various spatial regions of a LIB anode or LIB anode active material composite. For example, a first binder material (e.g., PAA) can have a higher concentration than a second binder material (e.g., CMC) at the interface between the LIB anode current collector structure (e.g., Cu thin film) and the active material composite structure (e.g., graphite powder-Si nanostructure composite), and the concentration of the first binder material can decrease with distance from the interface. For example, the first binder material can have a decreasing gradient concentration away from the interface.

[0141]

[0168] The ratio of binder material to dielectric and active materials in a LIB anode varies depending on the composition of the individual components. The LIB anode active material composite can include a binder material, where the active material composite is composed of less than 10% binder material, less than 5% binder material, less than 4% binder material, or about 3-4% binder material. In preferred embodiments, the LIB anode contains less than 10% binder material. Most preferably, the binder concentration is less than about 5%, less than 5%, less than about 4%, less than 4%, less than about 3%, or less than 3%. The LIB anode can include any suitable binder material, including CMC and PAA, CMC and PAA, or CMC, PAA, and PAA, including CMC, PVDF, PSS, SBR, or PAADAA, or combinations thereof.

[0142]

[0169] In certain embodiments, LIB anodes can be formed without any binder material. For example, if the active material nanostructures are formed directly on a LIB anode current collector structure, such as a Cu thin film or graphite foil, no binder material is required. These embodiments are advantageous because they reduce the overall weight of the anode structure and the number of various materials and impurities in the LIB anode.

[0143] Electrolytes, electrolyte additives, and SEI

[0170] One aspect of the present invention relates to LIB materials, such as electrolytes and electrolyte additives, as well as related components, devices, and methods of manufacture. In particular, the present invention includes LIB electrolytes and LIB electrolyte additives suitable for use in LIBs containing Si active material or Si and graphite active material, as well as related components, devices, and methods. In a preferred embodiment, the electrolyte is a liquid polymer electrolyte. In one embodiment, the present invention relates to a LIB containing at least one liquid polymer solvent selected from the group consisting of diethyl carbonate (DEC), ethylene carbonate (EC), or ethyl methyl carbonate (EMC), and a fluorinated ethylene carbonate (FEC), diallyl pyrocarbonate (DAPC), diethyl pyrocarbonate (DEPC), diallyl carbonate (DAC), diallyl succinate (DAS), tris(pentafluorophenyl)borane (TPFPB), tris(2,2,2-trifluoroethyl)phosphate (TTFP), N,N'-dicyclohexylcarbodiimide (DCC), methoxytrimethyl The present invention also includes a LIB anode comprising one or more electrolyte materials including at least one polymer additive selected from the group consisting of silane (MOTS), dimethoxydimethylsilane (DMOS), trimethoxymethylsilane (TMOS), maleic anhydride (MA), succinimide (SI), n-(benzyloxycarbonyloxy)succinimide (NBSI), vinylene carbonate (VC), vinylethylene carbonate (VEC), 1,3-propanesultone (PS), polydimethylsiloxane (PDMS), maleic anhydride (MA), and succinic anhydride (SA). In a preferred embodiment, the LIB anode active material comprises Si nanostructures or a combination of Si nanostructures and graphite (e.g., graphite foil or powder).

[0144]

[0171] The electrolytes and electrolyte additives of the present invention advantageously provide a suitable SEI on the surface of the Si and graphite structures, which can also self-heal during the charge and discharge cycles of the battery. Without changing the Si structure, the SEI minimizes side reactions between the Si or graphite and the electrolyte while allowing sufficient diffusion of Li ions into the SEI layer, thereby allowing Li ions from the electrolyte solution to penetrate the Si or Si and graphite active material.

[0145]

[0172] In one preferred class of embodiments, the LIB anode comprises an active material of Si and graphite, and an electrolyte comprising EC and DEC, or EC, DEC, and EMC. Preferably, the electrolyte further comprises an additive comprising FEC. Most preferably, the LIB comprises an active material of Si and graphite, and an electrolyte comprising about 90% of a solvent mixture comprising equal proportions of DEC:EC:EMC and about 10% of an additive comprising one or more materials selected from the group consisting of FEC, SA, and DAPC. Most preferably, the electrolyte comprises DEC, EC, EMC, and FEC. For example, the electrolyte may comprise about 90% of a solvent mixture comprising equal proportions of DEC:EC:EMC and about 10% of an additive comprising FEC, FEC, and DAPC, or FEC and SA.

[0146]

[0173] In a preferred embodiment, the LIB includes a Si or Si and graphite active material and an electrolyte. The electrolyte preferably includes one or more additives that provide a self-healing SEI layer on the Si or Si and graphite active material during charge or discharge cycling of the LIB. In a preferred embodiment, the self-healing SEI layer is formed by reducing one or more electrolyte additives on the active material surface during a LIB charge cycle, and the electrolyte additives include FEC, DAPC, MA, SI, NBSI, SA, or a combination thereof. Most preferably, the electrolyte additive includes FEC.

[0147]

[0174] In a preferred embodiment, the SEI layer can be formed as an artificial SEI layer. The artificial SEI layer can be formed in an electrolytic cell prior to the formation of a LIB anode. For example, LIB anode active material nanostructures can be formed using one or more ECD methods of the present invention, and an SEI layer can be formed on the active material nanostructures in the same or a different electrolytic cell by adding one or more SEI precursors and forming the SEI layer by direct ECD onto the active material surface.

[0148]

[0175] In a preferred embodiment, the LIB anode active material composite comprises about 65-95% graphite active material, about 5-45% Si active material, and about 3-6% binder material. In certain embodiments, no binder material is required.

[0149] ECD process

[0176] As described above, the present invention includes a novel, cost-effective method for producing high-quality, high-volume active material nanostructures for use in LIB components and devices, such as silicon- or tin-based nanostructures for use as LIB anode active materials. In particular, the present invention enables a low-temperature, catalyst-free, template-free ECD process for producing discrete active material nanostructures without the need for removal of catalytic materials, template materials, or impurities introduced by the catalyst or template materials. The ECD process of the present invention provides a way to control the physical and chemical properties of active material nanostructures to consistently meet specific requirements over multiple process runs, thereby providing an effective process solution for mass-producing high-quality, high-volume LIB anode active materials. For example, the ECD method of the present invention allows for the formation of highly crystalline active material nanostructures at low temperatures (e.g., room temperature) immediately after deposition onto a desired substrate, without the need for subsequent annealing to achieve crystallinity. In preferred embodiments, active material nanostructures are electrochemically deposited directly onto one or more substrates containing at least one LIB anode active material (e.g., graphite) and / or LIB anode current collector structure (e.g., copper, graphite, or nickel electrodes), thereby improving adhesion between the nanostructures and the substrate and eliminating the need to remove the nanostructures from the ECD-grown substrate for inclusion in the LIB anode. Using techniques available to those skilled in the art, the substrates and the active material nanostructures formed thereon can be formed into LIB anodes, which can be formed into full-cell or half-cell LIBs that use the LIB anode as a rechargeable or disposable energy source. Furthermore, the high quality of the LIB active materials produced by the ECD process of the present invention provides consistency and predictability in the performance of battery systems, thereby allowing for control of changes that occur in these materials and associated battery devices over multiple charging cycles and the various conditions to which they are exposed. These high-quality materials eliminate irreversible, undesirable side effects that contribute to unexpected, detrimental changes in LIBs and cause significant hysteresis in the LIB's operating characteristics.

[0150]

[0177] It should be understood that any of the materials described herein can be used in the processes of the present invention, including, but not limited to, active material nanostructures, substrate materials, current collector materials, current collector substrate materials, active materials, substrates comprising active materials, binder materials, electrolytes, electrolyte component materials, electrolyte additive materials, SEI materials, LIB anode materials, or other LIB component materials described herein. For brevity, some of these materials will not be individually described in connection with the description of the methods and processes of the present invention. However, it should be understood that all of these materials mentioned herein, and various combinations thereof, can be used as materials in the methods and processes of the present invention.

[0151]

[0178] Generally, a preferred ECD process of the present invention includes an electrolytic cell (EC) for ECD, where the EC is similar to the exemplary EC shown in Figure 44. The EC includes a container 4412, a conductive working electrode (i.e., EC cathode) 4406, an electrochemically stable current electrode (i.e., EC anode) 4407, a reference electrode 4409, a potential voltage source 4408 that provides direct current 4411 through the EC, a potentiostat 4413, and an electroactive supporting electrolyte 4404 that includes one or more precursor materials dissolved in one or more solvent materials. The electrochemical reaction results in the formation of nanostructures 4420 comprising one or more active materials on one or more surfaces of the working electrode 4406.

[0152]

[0179] Reference electrode 4409 preferably comprises a platinum reference electrode, for example a Pt wire.

[0153]

[0180] The current electrode 4407 can comprise Pt, C, Cu, graphite, another conductive material, or any combination of these and other conductive materials. For example, the current electrode can comprise a carbon sheet, carbon foil, carbon paper, Cu foil, Cu foam, Cu sponge, graphite foil, another conductive substrate structure, one or more of these substrate structures, or any combination of these or other conductive substrate structures. In a preferred embodiment, the current electrode comprises carbon paper. In certain embodiments, the counter electrode / current electrode 4408 can comprise a noble metal material that provides a stable counter electrode.

[0154]

[0181] In a preferred embodiment, the working electrode 4406 and the current electrode 4408 are spaced apart by a distance of about 2 cm in the electrolysis cell. As will be appreciated by those skilled in the art, the voltage can be fixed during the ECD process, while the current can vary as the distance between the working and counter electrodes is changed.

[0155]

[0182] The working electrode 4406 can include any of the ECD substrate materials and structures mentioned herein. The working electrode can include one or more conductive substrate materials, or a combination of one or more substrate materials and one or more semiconducting, insulating, and / or non-substrate conductive materials. The working electrode can include one or more metals, Cu, C, graphite, Ni, steel, Al, Pt, Au, Sn, one or more conductive polymers, other conductive materials, one or more binder materials such as CMC, PVDF, PAA, or PAADAA, as well as any composition, mixture, alloy, or combination thereof. In certain embodiments, the working electrode comprises multiple materials, such as Cu and graphite, non-graphitic C and graphite, Ni and graphite, steel and graphite, Al and graphite, Pt and graphite, Cu and C, Cu and Sn, C and Sn, multiple forms of graphite, multiple forms of C, or Cu, non-graphitic C, and graphite, or graphite and one or more binder materials, or any composition, mixture, alloy, or combination thereof. In preferred embodiments, the working electrode comprises one or more LIB active materials or structures and / or one or more LIB current collector materials or structures. Exemplary working electrode structures include one or more of the following:namely, graphite foil or plate, polished graphite foil or plate, graphite flakes or particles, graphite flakes or particles and one or more binder substances such as CMC, PVDF, PAA or PAADAA, graphite flakes or particles coated on graphite foil or plate in combination with one or more binder substances, Cu coated graphite foil, Cu coated graphite foil coated with graphite flakes or particles, graphite flakes or particles coated on Cu coated graphite foil or plate in combination with one or more binder substances, Cu coated graphite foil or plate that has been subjected to a gas treatment, perforated Cu mesh or foam, Cu wire, Cu fiber, Ni coated Cu wire or fiber fiber, patterned Cu wire, Ni-coated patterned Cu wire, carbon sheet, heat-treated carbon sheet, Cu foil or plate coated with graphite flakes or particles, graphite flakes or particles combined with one or more binder materials and coated on a Cu foil or plate, graphite flakes or particles disposed between or surrounded by a porous Cu mesh sheet, graphite flakes or particles disposed between or surrounded by a porous Cu mesh sheet in combination with one or more binder materials, one or more binder materials such as CMC, PVDF, PAA, or PAADAA, and combinations thereof.

[0156]

[0183] In one class of embodiments, the working electrode 4406 comprises a Cu-coated graphite foil or a Cu-coated carbon sheet. Cu is electrochemically deposited onto a carbon sheet or graphite foil substrate to form a working electrode and ECD substrate comprising a Cu-coated graphite foil. For example, Cu can be coated onto a carbon sheet or graphite foil substrate using an EC similar to that shown in FIG. 1A. The Cu coating can include a complete layer of Cu or one or more surface features comprising Cu formed on the underlying substrate. At least one Cu precursor is dissolved in at least one solvent to form an electrolyte solution for depositing Cu onto the graphite foil or carbon sheet substrate. For example, solution 104 can be a solution of non-aqueous n-methyl-n-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide (P 1,4 The solution may contain copper sulfate (CuSO4) precursor dissolved in an ionic liquid solvent, including TFSI (distilled ionized water) or deionized water (DI H2O). [Does DI H2O mean deionized water, deionized water, distilled water, or something else?] For example, the solution may contain P 1,4Less than about 0.03M CuSO4 (e.g., P 1,4 The CuSO4 solution may contain about 0.002-0.02M CuSO4 in TFSI, or less than about 0.15M CuSO4 in DI H2O (e.g., about 0.5-0.1M CuSO4 in DI H2O).

[0157]

[0184] The EC electrolyte solution 104 comprises at least one active material precursor dissolved in at least one solvent. Suitable electrolytes for ECD of Si nanostructures include organic solutions, high-, medium-, and low-temperature molten salts, or room-temperature ionic liquids. Preferred solutions have a wide electrochemical potential window, sufficient conductivity, negligible vapor pressure, and immiscibility with water. As will be appreciated by those skilled in the art, the reduction potential of the material being deposited is preferably lower than the reduction potential of the solvent or other materials in the ionic solution to avoid the solvent or other materials being reduced before the desired material being deposited is reduced. In a preferred embodiment, the solvent is P 1,4 In other embodiments, the solvent may include diluted or deionized water (DI HO), acetonitrile (ACN), or propylene carbonate (PC).

[0158]

[0185] In a preferred embodiment, the EC solution 104 includes a Si precursor including trichlorosilane (SiHCl) and / or silicon tetrachloride (SiCl). In a preferred embodiment, the Si precursor (e.g., SiHCl or SiCl) is 1,4 The Si precursor (e.g., SiHCl or SiCl) is dissolved in an ionic liquid solvent, including TFSI or DI H2O. For example, the ECD method of the present invention can include ECD of Si nanostructures onto a working electrode substrate 215 comprising graphite and / or copper, where the Si precursor (e.g., SiHCl3 or SiCl4) is dissolved in an electrolyte solvent (e.g., P 1,4The SiHCl3 silicon precursor is dissolved in TFSI (Teflon-Teflon-Silicon Dioxide), and Si and chlorine (Cl) precursor ions or Si, Cl, and hydrogen (H) precursor atoms are separated by a redox reaction, resulting in the deposition of Si atoms as discrete nanostructures on the working electrode. During this ECD process, discrete Si nanostructures, such as Si nanowires, are formed on the Cu and / or graphite working electrode substrate. The amount or concentration of the SiHCl3 silicon precursor can be about 0.1M to about 1M, preferably 0.5M to about 1M, about 0.5M to about 0.9M, 0.5M to 1M, or 0.5M to 0.9M. The amount or concentration of the SiCl4 silicon precursor can be about 0.05M to about 0.5M, preferably 0.05M to 0.5M, about 0.05M to about 0.04M, or 0.05M to 0.04M. Most preferably, the active material includes Si and the precursor includes SiHCl3, and solution 104 contains P. 1,4 Most preferably, the solution 104 comprises SiHCl dissolved in a TFSI solvent. 1,4 Most preferably, it contains about 0.6M SiHCl3 dissolved in TFSI.

[0159]

[0186] Although Si is the preferred active material for ECD, other materials, such as those mentioned herein, can also be used. ECD of most metals can be achieved using metal salt precursors dissolved in a suitable solvent material. For example, discrete Sn nanostructures can be formed by ECD using tin chloride (SnCl) precursor dissolved in a suitable solvent material.

[0160]

[0187] In certain embodiments, the EC can include multiple working electrodes and / or multiple precursors. In one exemplary embodiment, Si and Cu are co-deposited onto a graphite foil substrate by ECD, and the EC solution contains a Cu precursor and at least one Si precursor, such as P, dissolved in a solvent. 1,4 Contains CuSO4 and SiHCl3 dissolved in TFSI.

[0161]

[0188] Important factors for controlling the deposition and morphology during ECD of active material nanostructures include deposition voltage, precursor composition, precursor concentration, electrolyte composition, current density, ECD process temperature, and deposition time.

[0162]

[0189] As shown by the various Si nanostructures shown in Figures 6-22, the precursor material and its concentration influence the growth and morphology of Si.

[0163]

[0190] 6A-6B show the resulting Si nanostructures, which exhibit P 1,4 The resulting Si nanostructures were fabricated on graphite foil substrates using an EC solution containing 1 M SiHCl in TFSI. Figures 7A-7B show the resulting Si nanostructures, which exhibited a Pt-based charge at an applied voltage of -2.7 V vs. a Pt reference electrode. 1,4 The resulting Si nanostructures were fabricated on graphite foil substrates using an EC solution containing 1 M SiHCl in TFSI. Figures 8A-8B show the resulting Si nanostructures, which exhibited a Pt-based EC voltage of -3 V vs. a Pt reference electrode. 1,4 The resulting Si nanostructures were fabricated on graphite foil substrates using an EC solution containing 0.9 M SiHCl in TFSI. Figures 9A-9B show the resulting Si nanostructures, which exhibited a Pt-based conductivity at an applied voltage of -3 V vs. a Pt reference electrode. 1,4 The resulting Si nanostructures were fabricated on graphite foil substrates using an EC solution containing 0.7 M SiHCl in TFSI. Figures 10A-10B show the resulting Si nanostructures, which exhibited a Pt-based charge at an applied voltage of -3 V vs. a Pt reference electrode. 1,4 The resulting Si nanostructures were fabricated on graphite foil substrates using an EC solution containing 0.6 M SiHCl in TFSI. Figures 11A-11B show the resulting Si nanostructures, which exhibited a Pt-like charge at an applied voltage of -3 V vs. a Pt reference electrode. 1,4 The resulting Si nanostructures were fabricated on graphite foil substrates using an EC solution containing 0.4 M SiHCl in TFSI. Figures 12A-12C show the resulting Si nanostructures, which exhibited a Pt-based charge transfer at an applied voltage of -3 V vs. a Pt reference electrode. 1,4 The resulting Si nanostructures were fabricated on graphite foil substrates using an EC solution containing 0.2 M SiHCl in TFSI. Figures 13A-13B show the resulting Si nanostructures, which exhibited a Pt-like charge at an applied voltage of -2.8 V vs. a Pt reference electrode. 1,4The resulting Si nanostructures were fabricated on graphite foil substrates using an EC solution containing 0.2 M SiHCl in TFSI. Figures 14A-14C show the resulting Si nanostructures, which exhibited a Pt-like conductivity at an applied voltage of -2.5 V vs. a Pt reference electrode. 1,4 The nanostructures were fabricated on graphite foil substrates using an EC solution containing 0.1 M SiHCl in TFSI. Figures 15A-15B show the resulting Si nanostructures, which exhibited a Pt-like charge at an applied voltage of -3 V vs. a Pt reference electrode. 1,4 The resulting Si nanostructures were fabricated on graphite foil substrates using an EC solution containing 0.05 M SiHCl in TFSI. Figures 16A-16B show the resulting Si nanostructures, which exhibited a Pt-like conductivity at an applied voltage of -2.5 V vs. a Pt reference electrode. 1,4 It was formed on a graphite foil substrate using an EC solution containing 0.05M SiHCl3 in TFSI.

[0164]

[0191] 17A-17B show the resulting Si nanostructures, which exhibit P 1,4 The nanostructures were fabricated on graphite foil substrates using an EC solution containing 0.4 M SiCl in TFSI. Figures 18A-18B show the resulting Si nanostructures, which exhibited a Pt-based charge transfer at an applied voltage of -3 V vs. a Pt reference electrode. 1,4 The nanostructures were fabricated on graphite foil substrates using an EC solution containing 0.4 M SiCl in TFSI. Figures 19A-19C show the resulting Si nanostructures, which exhibited a Pt-like conductivity at an applied voltage of -3 V vs. a Pt reference electrode. 1,4 The resulting Si nanostructures were fabricated on graphite foil substrates using an EC solution containing 0.1 M SiCl in TFSI. Figures 20A-20B show the resulting Si nanostructures, which exhibited a Pt-based charge transfer at an applied voltage of -3.2 V vs. a Pt reference electrode. 1,4 The resulting Si nanostructures were fabricated on graphite foil substrates using an EC solution containing 0.1 M SiCl in TFSI. Figures 21A-21B show the resulting Si nanostructures, which exhibited a Pt-based charge transfer at an applied voltage of -3.1 V vs. a Pt reference electrode. 1,4The nanostructures were fabricated on graphite foil substrates using an EC solution containing 0.05 M SiCl in TFSI. Figures 22A-22B show the resulting Si nanostructures, which exhibited a Pt-like charge at an applied voltage of -3 V vs. a Pt reference electrode. 1,4 It was formed on a graphite foil substrate using an EC solution containing 0.05 M SiCl4 in TFSI. The SiHCl4 precursor is preferred over SiCl4 due to the fact that the SiCl4 precursor makes it more difficult to control the deposition of Si.

[0165]

[0192] As will be appreciated by those skilled in the art, varying the composition or concentration of the precursors can result in changes in the pH of the solution and / or the miscibility of the precursor with the solvent, which in turn affects the mobility of the ions in the deposited material and thus the properties of the electrochemically deposited material. As explained above, the composition or concentration of the precursors can be varied to control the size, shape, morphology, or other properties of the electrochemically deposited nanostructures.

[0166]

[0193] In a preferred embodiment, a potentiostatic voltage is applied to the EC during the ECD process. The applied potentiostatic voltage can be about -2 V to about -3 V relative to a Pt reference electrode. Preferably, the potentiostatic voltage is applied at about -2.4 V to about -2.8 V relative to a Pt reference electrode. These voltage and current ranges are optimized for the specific process embodiment referred to herein. In a preferred embodiment, a current of about 1 mA / cm is applied during the ECD process. 2 ~about 8mA / cm 2 A constant DC current of approximately 0.5 mA / cm is applied to the EC. 2 ~Approx. 1.5mA / cm 2 Preferably, the voltage is applied at 100 mA. In a preferred embodiment, the reaction stops when the measured current drops below about 100 mA. In certain embodiments, the structure and size of the Si deposits can be tuned by varying the deposition potential / current. However, as will be appreciated by those skilled in the art, the applied voltage and current can be varied with the assortment of substrate materials, precursors, electrolytes in the electrolytic cell, etc. Such variations are encompassed by the present invention.

[0167]

[0194] The voltage and current profiles are important for controlling the morphology of Si during ECD projects. In a preferred embodiment, the ECD process involves applying a constant potential of about -2.5 V to about -3 V for about 3 hours at room temperature. In one exemplary embodiment, the applied potential for ECD of Si can be determined from the reduction peak of Si achieved by using linear sweep voltammetry at a sweep rate of 5 mV / s. Figure 45A shows the current and voltage profiles of 0.5 M SiHCl dissolved in PC solvent at a sweep rate of 5 mV / s, and Figure 45B shows the current and voltage profiles of Si at a constant applied voltage of 5 mV / s. 1,4 Figure 45 shows the current and voltage profiles of 0.5 M SiCl dissolved in TFSI solvent. The reduction potential of Si can be determined from the graphs in Figures 45A and 45B. Figure 46 shows the P 1,4 0.1 M SiHCl34672 dissolved in TFSI, and P at a constant potential of -3 V 1,4 1 shows the current profile of ECD of 0.1 M SiCl44674 dissolved in TFSI.

[0168]

[0195] The ECD methods of the present invention can be carried out at low temperatures, such as room temperature. In preferred embodiments, ECD of nanostructures comprising at least one active material is carried out at about 80° C. or less, about 70° C. or less, about 60° C. or less, about 50° C. or less, about room temperature, or room temperature.

[0169]

[0196] In certain embodiments, the ECD process involves controlling one or more of the potential voltage, current, and precursor and electrolyte concentrations, and temperature to control the size and / or structure of the electrochemically deposited active material.

[0170]

[0197] As will be appreciated by those skilled in the art, the structure and size of the active material nanostructures can be tuned by varying the operating temperature of the ECD process. In a preferred embodiment, the ECD process is carried out at room temperature. In a preferred embodiment, the ECD process is carried out at atmospheric pressure and ambient temperature.

[0171]

[0198] In a preferred embodiment, the reaction is stopped when the measured current drops below about 100 mA. The ECD reaction time can be carried out for a period of about 1 to 3 hours, most preferably about 2 to 3 hours.

[0172]

[0199] In a preferred embodiment, the EC solution 4704 is exposed to one or more forces that create fluid motion during the ECD process. For example, as shown in Figure 47, the EC solution 4704 can be stirred using a magnetic stir plate 4776 and magnets 4778, for example, in an electrolytic cell. In certain embodiments, the fluid motion 4780 of the solution 4704 in the EC provides a uniform distribution of the Si precursor in the solution.

[0173]

[0200] In other embodiments, fluid motion is varied in different regions of the working electrode, resulting in varying Si concentrations or varying Si deposition on the working electrode substrate. For example, different flow rates can be applied to the solution in different regions of the substrate. In yet other embodiments, the fluid flow can be pulsed to provide time-dependent changes in the fluid flow rate of the electrolyte solution. In another class of embodiments (not shown in the figures), the electrolytic cell can include flow paths such that fluid enters the EC vessel at one location and exits the vessel at a different location, thereby causing the fluid to flow through the working electrode substrate.

[0174]

[0201] 48, the electrolytic cell includes a first region 4882 and a second region 4884, where the first region and the second region are separated by a porous separator 4883. Precursor solution 4804 flows freely through separator 4883, allowing one or more active materials to be deposited onto a particulate substrate 4815 (e.g., graphite powder). Separator 4883 can include an insulating material such as a porous ceramic or polymeric insulator, or separator 4883 can include a metallic material such as a porous Cu separator.

[0175]

[0202] In another class of embodiments, a particulate substrate 4915 is disposed within a porous working electrode 4906, as shown in Figure 49. For example, a substrate material comprising graphite powder can be disposed within pockets 4906b of a porous Cu mesh working electrode 4906. Solvated active material ions (e.g., Si ions) are allowed to flow freely through the porous working electrode 4906. For example, this embodiment can be used to form the anode structures described above in Figures 26A-27B and 30A-31D.

[0176]

[0203] In another general class of embodiments, the ECD of one or more active material nanostructures on a current collector or active material substrate can be controlled by adjusting the temperature or current of the solution, the substrate and / or the working electrode across different regions of the ECD substrate.

[0177]

[0204] In another general class of embodiments, the active material nanostructures are subjected to one or more prelithiation or prelithiation and delithiation procedures prior to formation of a LIB anode. Such prelithiation or prelithiation and delithiation can be performed in the same EC as that used to deposit the active material nanostructures using an electrolytic cell, e.g., ECD, or in a different EC than the active material deposition EC. In preferred embodiments, the ECD process further includes lithiating the electrochemically deposited nanostructures after the ECD process. In one exemplary embodiment, this process includes providing a solution containing a lithium precursor dissolved in at least one solvent in an electrolytic cell and applying a potential voltage to the electrolytic cell to reduce lithium, where lithium atoms combine with the active material nanostructures (e.g., Si nanostructures), resulting in lithiation of the nanostructures. The nanostructures and substrate material can then be formed into a LIB anode comprising the prelithiated (or prelithiated and delithiated) active material nanostructures. The lithium precursor solution can include at least one lithium salt precursor including lithium hexafluorophosphate (LiPF6) and / or lithium bis(oxatolato)borate (LiBOB).

[0178]

[0205] Illustrative embodiments of the present invention have been presented. The present invention is not limited to these examples. These examples are presented herein for purposes of illustration, not limitation. Alternatives (including equivalents, extensions, variations, deviations, etc., of those described herein) will be apparent to those skilled in the art based on the teachings contained herein. Such alternatives fall within the spirit and scope of the present invention. The above-described invention has been described in some detail for purposes of clarity and understanding, but it will be apparent to those skilled in the art upon reading this disclosure that various changes in form and detail can be made without departing from the true scope of the invention. For example, all of the techniques and devices described above can be used in various combinations. All publications, patents, patent applications, and / or other documents cited in this application are incorporated herein by reference in their entirety for all purposes to the same extent as if each individual publication, patent, patent application, and / or other document was individually indicated to be incorporated by reference for all purposes.

Claims

1. 1. A lithium ion battery (LIB) anode composite structure comprising: a plurality of substrate layers, a bottom one of the plurality of substrate layers comprising a copper (Cu) thin film layer, and other ones of the plurality of substrate layers each comprising a porous substrate comprising graphite particles having an average size of 1 μm to 100 μm, a plurality of discrete active material nanostructures formed on the graphite particles, and a binder; Including, the plurality of discrete active material nanostructures comprise a material that can be lithiated with Li ions; others of the plurality of substrate layers form a three-dimensional composite structure comprising a majority of the thickness of the LIB anode composite structure; the three-dimensional composite structure wherein the size of the graphite particles decreases with distance from the top to the bottom of the other of the plurality of substrate layers, the graphite particles are more densely packed toward the bottom of the other of the plurality of substrate layers, or a combination thereof; The graphite particles and the binder are bonded to each other to form a graphite particle and binder composite structure.

2. 10. The LIB anode composite structure of claim 1, wherein the plurality of discrete active material nanostructures comprises one or more selected from the group consisting of nanowires, nanorods, nanoparticles, and nanotubes.

3. 10. The LIB anode composite structure of claim 1, wherein the plurality of discrete active material nanostructures comprises greater than or equal to 0% and less than 1% oxygen.

4. 10. The LIB anode composite structure of claim 1, wherein the plurality of discrete active material nanostructures comprises greater than or equal to 0% and less than 0.1% oxygen.

5. 10. The LIB anode composite structure of claim 1, wherein the plurality of discrete active material nanostructures exhibits a crystallinity of at least 95%.

6. 10. The LIB anode composite structure of claim 1, wherein the plurality of discrete active material nanostructures exhibits a crystallinity of at least 99%.

7. 10. The LIB anode composite structure of claim 1, further comprising a solid electrolyte interface (SEI) layer formed on the plurality of discrete active material nanostructures.

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