Rechargeable lithium-ion battery with an anode structure containing a porous zone

Abstract

Battery comprising: a lithium-containing cathode material layer; an anode structure of uniform construction, comprising a non-porous zone and a porous zone, the latter having an upper porous layer with a first thickness and a first porosity, and a lower porous layer arranged below the upper porous layer and forming an interface with the non-porous zone, wherein at least an upper section of the non-porous zone and the entirety of the porous zone are composed of silicon, and wherein the lower porous layer has a second thickness greater than the first thickness and a second porosity greater than the first porosity; and an electrolyte zone arranged between the upper porous layer of the anode structure and the lithium-containing cathode material layer.

Description

BACKGROUNDThe present application relates to a rechargeable battery. More particularly, the present application relates to a high capacity lithium ion rechargeable battery comprising an anode structure constructed from a substrate comprising a porous semiconductor zone having two different porosities and a nonporous semiconductor zone disposed below the porous semiconductor zone.In recent years, demand for electronic devices such as computers, mobile phones, tracking systems, scanners, medical devices, smart watches, power tools, remote systems and sensors, electric vehicles, Internet of Things (IOT), and fitness devices has increased. A disadvantage with such electronic units is the need to integrate a power supply into the unit itself. Typically, a battery is used as a power supply for such electronic units. Batteries must have sufficient capacity to power the electronic unit at least over the duration during which the unit is used. Sufficient battery capacity may result in a power supply that is very heavy and / or large compared to the rest of the electronic unit. Therefore, smaller and lighter power supplies with sufficient energy storage are desired. Such power supplies can be realized in smaller and lighter electronic units in combination with lithium ion materials which function as the charge carrier; since lithium is the lightest and most electropositive charge carrier in the periodic table of the elements, lithium ion batteries and capacitors are considered to be most appropriate for smaller, more energy-density energy storage units.In addition to the demand for light energy storage units that achieve high energy density (high capacity), there is also a demand for faster charging speeds (i.e., for high-speed charging kinetics) in the consumer market. For the next generation of batteries, it would be desirable if the battery could be fully charged in ten minutes or less to meet consumer demands on markets such as electric vehicles, portable telecommunication equipment, IOT and sensors. In the case of electric vehicles, if a load needs to wait for more than ten minutes to charge its vehicle, the battery-powered electric vehicle may present a limit to the user's time-slot and, consequently, its radius of travel. Thus, fast charging speeds for batteries used on the electric vehicle market would help create an existenceable electric vehicle market that could compete with and possibly replace gasoline-powered automobiles.Another disadvantage of conventional batteries is that some of the batteries contain potentially flammable and toxic materials that can escape, which can lead to safety risks and expensive product calls back. As a result, these batteries may become subject to regulations and cause damage to the call of products. The risks of leaks in the batteries may increase due to cracks formed within these batteries. These cracks are most likely caused by internal stresses due to the battery charge / discharge cycles.In addition, and when batteries include a solid electrolyte, there is evidence that battery life is reduced due to formation of dimers within these batteries. The size of the dendrite increases with the life of the battery and is most likely related to the number of charge / discharge cycles. As diesters form within the battery and increase over time, the diesters tend to electrically short the internal components of the battery, resulting in a failure of the battery.With the advent of lithium metal charge-accommodating electrodes that provide stable accommodation of the charge of lithium metal and enable the reversible ionization mechanism of lithium ions to lithium metal and vice versa, persistent full-solid or half-solid lithium ion batteries are achievable for mass production for the consumer market. Lithium metal has a theoretical energy capacity of 3,850 mAh / g, while silicon-based electrode materials harboring lithium have a theoretical capacity of 4,200 mA / g. Both of these materials, which function as an anode, for example, have more than ten times the theoretical capacity of conventional graphite-based anode materials (372 mAh / g). However, these batteries still have the risk of cracking, leaks and precipitation from internal dimers.Thus, there is a need for an improved lithium ion battery for providing an electrical power supply that has reduced charging times, has higher storage capacities, and is safe and rechargeable over many charge / discharge life cycles with reduced risk of cracking, leaks, and failures due to growth of dimers within the battery.SUMMARYLithium ion rechargeable batteries having a high capacity (i.e., a capacity of 100 mAh / g or higher) are provided. In some embodiments, the lithium ion rechargeable batteries of the present application may also have increased life, increased numbers of charge / discharge cycles, decreased charge time (i.e., a fast charge rate), a decrease in volume expansion and / or deformation during the cycles, a decrease in formation of dendrite and crack, and / or decreased battery leakage due to crack formations.The rechargeable lithium ion battery of the present application includes an electrolyte zone disposed between a lithium-containing cathode material layer and an anode structure. The anode structure is of unitary construction (i.e., monolithic structure) and includes a nonporous zone and a porous zone. The porous zone includes an upper porous layer (porous zone 1) having a first thickness and a first porosity and a lower porous layer (porous zone 2) having a second porosity greater than the first porosity and a second thickness greater than the first thickness. The lower porous layer (i.e., porous zone 2) is located below the upper porous layer (i.e., porous zone 1) and interfaces with the nonporous zone. In addition, at least an upper portion of the nonporous zone and the whole of the porous zone are composed of silicon.In another aspect of the present application, there is provided a method of manufacturing the aforementioned anode structure for a lithium ion rechargeable battery. The method includes anodic etching of a substrate including at least a top region comprised of p-doped silicon. In one embodiment, the relative depth, pore structure and surface area of the anode structure comprising porous zones 1 and 2 are controlled by the conditions employed in the process of the present application.Another aspect of the present application shows changes in operation of the anode structure for a rechargeable battery during charge and discharge cycles of the battery. The anode structure and the battery structure of the present application charge in unique ways that exhibit reduced internal stresses and reduced growth of dimers during the life of the battery. Without wishing to be bound by any theory, it is believed that the charging operation of the present application contributes to reduced levels of internal battery stresses and less occurrence of cracks in the anode structure.In yet another aspect of the present application, in combination with the present anode structure, cathode materials are used that contain a particular grain size and density of grain boundaries or a columnar microstructure. The anode structure of the present application can sustainably plate lithium materials obtained from the respective cathode materials of various dimensions and masses. In particular, high capacity battery cells can be easily manufactured because the anode structure of the present application enables perceptible lithium plating during charging and stripping of lithium during discharging.BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGSFIG. 1 is a cross-sectional view of an exemplary lithium ion rechargeable battery according to a first embodiment of the present application. FIG. 2 is a cross-sectional view of another exemplary lithium ion rechargeable battery according to a second embodiment of the present application. FIG. 3 is a cross-sectional view of an exemplary lithium ion rechargeable battery according to a third embodiment of the present application. FIG. 4 is a cross-sectional view of an exemplary lithium ion rechargeable battery according to a fourth embodiment of the present application. FIG. 5 is a cross-sectional view of an exemplary lithium ion rechargeable battery according to a fifth embodiment of the present application. FIGS. 6A to 6B are cross-sectional views of exemplary lithium ion rechargeable batteries according to a sixth embodiment of the present application. FIG. 7A is a schematic illustration of a method of forming the anode structure of the present application starting with a p-type crystalline silicon substrate before anodization and the anode structure after anodization. FIG. 7B is a Transmission Electron Micrograph (TEM) of a porous silicon anode structure showing two separate porous zones after anodization. FIG. 8A is a high resolution transmission electron micrograph (HRTEM) of the porous silicon anode structure illustrating the thickness of the porous zone 1. FIG. 8B is a spectrum of secondary ion mass spectrometry (SIMS) of initial ~30 nm of a silicon anode porous structure corresponding to porous structure 1 and initial ~90 nm of the same silicon anode structure corresponding to porous structure 2. FIGS. 9A through 9F illustrate a flow chart showing the anode structure prior to operative use (FIG. 9A ) and during operative use, wherein a seed layer forms during a charge cycle (FIG. 9B ), lithium plating occurs after further charging (FIG. 9C ), and lithium stripping occurs after discharge (FIG. 9F ), with SEM images of a porous silicon anode structure after 5 cycles when a liquid electrolyte is used (FIG. 9D ) and another SEM image of a porous silicon anode structure after -250 cycles when a liquid electrolyte is used (FIG. 9E ). FIGS. 10A to 10C are SEM images for a full-solid lithium ion battery according to the present application including a structure similar to that illustrated in FIG. 1, wherein the electrolyte zone is a solid material, wherein FIG. 10A is an SEM of the structure before galvanostatic or potentiostatically induced charging or discharging, FIG. 10B is another SEM of the structure after 6 charging and discharging cycles, and FIG. 10C is still another SEM image of the structure after 67 charging and discharging cycles. FIG. 11 is a flow chart illustrating an embodiment for manufacturing the anode structure of the present application.DETAILED DESCRIPTIONThe present application will now be described in more detail with reference to the following description and drawings accompanying the present application. It should be noted that the drawings of the present application are for illustrative purposes only and the drawings are therefore not to scale. It should also be noted that the same and corresponding elements are denoted by the same reference numerals.In the following description, numerous specific details are set forth, including, for example, specific structures, components, materials, dimensions, processing steps, and techniques, in order to provide an understanding of the various embodiments of the present application. However, those skilled in the art will recognize from the present disclosure that there are various alternative embodiments of the present application that may be practiced without providing more specific details. In other instances, well-known structures or processing steps could be used in combination with and / or employing the concepts of the present invention. These structures and steps have not been described in detail in order to avoid obscuring the present application.It will be understood that when an element, such as a layer, zone, or substrate, is referred to as being "on" or "over" another element, it may be directly disposed on the other element or intervening elements may also be present. On the other hand, when an element is referred to as being "directly on" or "directly over" another element, there are no intervening elements present. It will also be understood that when an element is referred to as being "beneath" another element or "beneath" another element, it may be disposed directly beneath the other element or beneath the other element or intervening elements may be present. On the other hand, when an element is referred to as being "directly below" another element or "directly below" another element, there are no intervening elements present.As stated above, lithium ion rechargeable batteries having a high capacity (i.e., a capacity of 100 mAh / g or higher) are provided. In some embodiments, the rechargeable lithium-ion batteries of the present application may also have an increased lifetime and / or a faster charging rate and / or a decrease in volume expansion and / or deformation during the charging / discharging cycles. The rechargeable lithium-ion batteries of the present application include an anode structure designed to increase the capacity and, in some cases, also the charging speed of the battery (as compared to conventional lithium-ion batteries that do not have the anode structure of the present application).In one aspect of the present application, a rechargeable lithium ion battery is provided that includes an anode structure of unitary construction. In particular, the anode structure comprises a non-porous zone and a porous zone having an upper porous layer (porous zone 1) with a first thickness and a first porosity and a lower porous layer (porous zone 2) with a second thickness that is greater than the first thickness and a second porosity that is greater than the first porosity. The lower porous layer (porous zone 2) is located below the upper porous layer (porous zone 1) and forms an interface with the nonporous zone. In the anode structure of the present application, at least an upper portion of the nonporous zone and the entirety of the porous zone (including the porous zones 1 and 2) are made of silicon.Methods of manufacturing the battery, methods of using the battery, structural features of the battery during use, and battery structures with cathodes that enable fast charging speeds are also presented. The anode structure of the present application may be used as an element within various conventional 2-dimensional and 3-dimensional battery configurations.The anode structure of the present application is believed to be stronger than that of the prior art because the porous zone 1 contains on average smaller pore sizes than the porous zone 2. in some embodiments, the anode structure, which together with the porous zone 1 and the porous zone 2 comprises a larger nonporous zone, is mechanically, electrically and chemically made of the same semiconductor material (i.e., the anode structure is of a monolithic construction). Thus, a mechanically stronger anode structure is provided which is continuously connected at the atomic level, particularly for silicon substrates which are crystalline in composition.It is also believed that during the initial lithiating of the anode structure of the present application, an upper portion of the porous zone 2 partially becomes lithium-containing and the lower portion of the porous zone 2 is substantially free of lithium. During this process, a thin seed layer begins to form, the seed layer composition being made up of lithium-rich material and silicon material and thus forming a planar high lithium metal density layer on top of the porous zone 1. This seed layer significantly reduces the migration of lithium ions deeper into the porous zone 2 of the anode structure (and to reduced lithium ion concentrations within the porous zone 2). Thus, the formation of the thin seed layer on / in the porous zone 1 hinders further lithiating of the porous zone 2 and thus minimizes mechanical strain of the entire electrode due to suppression of further lithiating deeper into the porous zone 2 and the nonporous zone.As lithium migrates into the anode structure, the volume zones expand where the lithium combines with the silicon of the anode structure. This volume can extend to as much as 400 percent of the original anode structure volume. Therefore, the anode structure of the present application enables a reduction in volume expansion during the life (the entire charge / discharge cycles) of the rechargeable lithium ion battery, resulting in reduced internal stress during the entire use of the battery.Since lithium combines with silicon in the porous zones 1 and 2, the gaps in these porous zones take up the volume increase in these portions of the anode structure, thereby further reducing the mechanical stresses of charging and discharging.Additionally, as the battery charges / discharges during the battery lifetime, the lithium receives a lithium seed layer in combination with silicon atoms present in the porous zone of the anode structure; this seed layer may be referred to herein as a lithium-containing seed layer. During the formation of the seed layer, a small portion of the lithium (less than 10% of the theoretical capacity) penetrates and penetrates the porous zone 1 and partially penetrates the porous zone 2. This process is relatively slow when not electrochemically induced and the process is faster when galvanostatically or potentiostatically induced. The lithium also forms a thin layer of metallic lithium on top of the porous zone 1 as the lithium accumulates on the previously deposited lithium-containing seed layer on / in the porous zone 1, expands the volume in the porous zone 1, and minimizes further migration of lithium deeper into the anode structure of the present application by physically closing the pores in the porous zone 1 and by the lithium concentration in the seed layer and the metallic layer creating an electrostatic barrier to further penetration of lithium into the anode structure of the present application.The fully formed seed layer minimizes further migration of lithium into the anode structure during subsequent charge / discharge cycles of the battery, thereby reducing cyclic mechanical stresses due to volume expansion and volume reduction during the charge / discharge cycles during a majority of the life of the battery and likewise reducing stresses in the anode structure during the life of the battery.Because the fully formed seed layer inhibits the migration of lithium ions into the anode structure, the following can be observed: (i) lithium ions that move from the cathode and electrolyte zones of the battery toward the anode structure during a charge cycle increase the thickness of the lithium metal layer above the seed layer, and (ii) lithium ions that move from the anode structure from the cathode and electrolyte zones of the battery during a discharge cycle decrease the thickness of a lithium metal layer above the seed layer. However, unlike the prior art, the fully formed seed layer minimizes lithium diffusion during subsequent charge / discharge cycles of the battery. As a result of the anode structure of the present application, the lithium deposits primarily on the seed layer (e.g., by ion plating); in a greatly reduced amount within the porous zone 2; but in no significant amount at all in the nonporous zone of the anode structure. As a result, a very large volume of the anode structure, i.e., the nonporous zone of the anode structure, substantially does not absorb lithium during the charge / discharge cycles and, therefore, does not undergo significant volume expansion and volume reduction that cause cracking and possible leaks observed in batteries that do not contain the anode structure of the present application.It is believed that once formed, the thin seed layer no longer changes significantly during the charge / discharge cycle of the battery. The porosity of the porous zone 1 is chosen such that the volume expansion in the upper porous layer of the anode structure due to chemical connection with lithium during the formation of the seed layer does not cause excessive strain in the porous zone 1.Applicant has experimental evidence that shows that the seed layer forms a smooth planar surface on which addition (removal) of lithium ions during charging (discharging) operating cycles causes a metal lithium metal layer to increase (decrease) in thickness while maintaining a relatively smooth and planar surface during the lifetime of the battery, with a higher likelihood of suppressing the growth of dendrites.Referring now to FIG. 1, there is illustrated an exemplary rechargeable lithium ion battery according to a first embodiment of the present application. The exemplary rechargeable lithium-ion battery illustrated in FIG. 1 includes a battery material stack of an anode current collector 10, an anode structure 12, an electrolyte zone 18, a lithium-containing cathode material layer 20, and a cathode current collector 22. Other orientations for the lithium ion battery are also possible and are not excluded from the present application.In some embodiments, the rechargeable lithium ion battery of the present application may be formed on a base substrate (not shown). If present, the base substrate may comprise any conventional material used as a substrate for a lithium ion battery. In an embodiment, the base substrate may comprise a silicon-containing material and / or any other material having semiconductor properties. The term "silicon-containing material" is used throughout the present application to refer to a material comprising silicon and having semiconducting properties. Examples of silicon-containing materials that can be used as the base substrate for the lithium ion rechargeable battery include silicon (Si), a silicon-germanium alloy (SiGe), or a silicon-based alloy doped with carbon. In an embodiment, the base substrate for the rechargeable lithium ion battery is a bulk semiconductor substrate. By "solid" is meant that the base substrate is entirely constructed from at least one semiconductor material. In one example, the base substrate may be entirely comprised of silicon, which may be monocrystalline. In some embodiments, the bulk semiconductor substrate may include a multilayer semiconductor material stack including at least two different semiconductor materials. In an example, the multilayer semiconductor material stack may include, in any order, a stack of Si and a silicon-germanium alloy. In another embodiment, the multilayer semiconductor material may comprise, in any order, a stack of Si and single or multiple silicon-based alloys, such as silicon germanium or carbon doped silicon-based alloys.In other embodiments, the base substrate for the lithium ion battery may be a current collector, such as aluminum (Al), aluminum alloy, titanium (Ti), tantalum (Ta), tungsten (W), or molybdenum (Mo), copper (Cu), nickel (Ni), platinum (Pt), or any alloys of these materials.In some embodiments, the base substrate may have a non-textured (flat or planar) surface. The term "non-textured surface" refers to a surface which is smooth and has a root mean square surface roughness on the order of less than 100 nm, as measured by profilometry or atomic force microscopy. In yet another embodiment, the base substrate may have a textured surface. In such an embodiment, the surface roughness of the textured substrate may be in a range from a root mean square of 100 nm to a root mean square of 100 μm, also measured by profilometry or atomic force microscopy. Texturing may be performed by forming a plurality of etch masks (e.g., metal, insulator, or polymer) on the surface of a non-textured substrate, etching the non-textured substrate using the plurality of masks as an etch mask, and removing the etch masks from the non-textured surface of the substrate. In some embodiments, the textured surface of the base substrate is constructed from a plurality of three-dimensional features with a large surface area. In some embodiments, a plurality of metallic masks are used, which may be formed by depositing a layer of a metallic material and then annealing. During the tempering, the layer of the metallic material melts and arranges itself spherically, so that the surface of the base substrate is de-wetted.Referring again to FIG. 1, the anode current collector 10 that can be used in the present application includes any metal electrode material for the anode side, such as titanium (Ti), platinum (Pt), nickel (Ni), copper (Cu), aluminum (Al), or titanium nitride (TiN). The anode collector 10 may include a layer of a metallic electrode material for the anode side or a material stack of at least two different metallic electrode materials for the anode side. In one example, the anode current collector 10 comprises a stack of nickel (Ni) and copper (Cu) from bottom to top. The anode current collector 10 may have a thickness of 10 nm to 50 nm. Other thicknesses less than or greater than the above values for thickness may also be used for the anode current collector 10. The anode current collector 10 may be formed by a deposition method including, for example, chemical vapor deposition (CVD), plasma enhanced CVD (PECVD), evaporation, sputtering, plating, or mechanically attaching a metal foil. For improved contact resistance, alloying the metallic electrode material for the anode side with a semiconductor material base is preferred. Alloying can be accomplished by performing a silicide process as is known to those skilled in the art of semiconductor technology.The anode structure 12 is provided to a surface of the anode current collector 10. The anode structure 12 comprises a nonporous zone 14 and a porous zone (16, 17) having two layers having different porosities and thicknesses disposed on the nonporous zone 14. The nonporous zone 14 and the porous zone (16,17) are of uniform construction. In one embodiment, the nonporous zone 14 has a first surface that is in direct physical contact with a surface of the porous zone 2 (i.e., the lower porous zone 16) and a second surface opposite the first surface that is in direct physical contact with the anode current collector 10. The nonporous zone 14 is the largest portion of the anode structure 12 in volume. In some embodiments, the nonporous zone 14 of the anode structure 12 may have a thickness of 5 μm to 700 μm.The porous zone 1 (i.e., the upper porous layer 17) has a first porosity and a first thickness, and the porous zone 2 (i.e., the lower porous layer 16) has a second porosity and a second thickness. To accommodate volume changes during charging and discharging, the porous zone (16,17) is constructed such that the second porosity and the second thickness are greater than the first porosity and the first thickness, respectively. In one embodiment, the second porosity has an average pore opening of greater than 3 nm and the second thickness is 0.1 μm to 20 μm, while the first porosity has an average pore opening of less than 3 nm and the first thickness is 50 nm or less. Without wishing to be bound by any theory, it is believed that the relatively small diameter of the pores contained in the porous zone 1 enables the formation of a planarized lithium-containing seed layer (described in more detail hereinbelow).In the present application, porosity may be a measure of the percentage by volume of pores (void zone in the silicon) divided by the total volume of the porous zone (16,17). Porosity can be measured by techniques well known to those skilled in the art including, for example, SEM, RBS, X-ray diffraction (XRD), nuclear magnetic resonance (NMR), Raman spectroscopy, gas-on-solid adsorption (porosimetry), space-filling mercury porosimetry, density functional theory (DFT), or Brunaauer-Emmett-Teller (BET).It should be noted that the present application avoids a porous zone (16, 17) having a porosity that is 30% or more, which, as in the prior art, tends to be brittle and may form cracks during use, so that failure of the battery may occur.Without wishing to be bound by any theory, it is believed that the porous zone (16, 17) has a porosity such that there is sufficient open space within the porous zone (16, 17) to accommodate the volume expansion (i.e., swelling) and / or deformation of both the porous zone 1 (i.e., the upper porous layer 17) and to a lesser extent the porous zone 2 (i.e., the lower porous layer 16). This is particularly true when forming a lithium-containing seed layer, as described in more detail hereinafter, in the porous zone 1 (i.e., the upper porous layer 17) upon initial operation of a lithium-ion rechargeable battery.The porous zone 2 (i.e., the lower porous layer 16) of the anode structure 12 of the present application has a compressive stress of 0.02 percent to 0.035 percent. Compressive stress may be determined by X-ray diffraction or other optical or spectroscopic techniques.As mentioned above, the porous zone 1 (i.e., the upper porous layer 17), the porous zone 2 (i.e., the lower porous layer 16), and the nonporous zone 14 of the anode structure 12 are of uniform construction. Thus, the nonporous zone 14 and the porous zone (16,17) are electrically, chemically and mechanically part of a same anode structure. In some embodiments, porous zone 1 (i.e., upper porous layer 17), porous zone 2 (lower porous layer 16), and nonporous zone 14 are all constructed of silicon. In this embodiment, the anode structure 12 is produced by efficient method steps. Additionally, and in embodiments where the entire anode structure 12 is made of the same semiconductor material (i.e., Si), there are no mechanical stresses or additional electrical resistances within the anode structure 12 that could be caused by interfaces between dissimilar materials. In one example, the anode structure 12 comprising the nonporous zone 14 and the porous zone (16, 17) has a three-dimensional (3D) lattice frame constructed from a p-type crystalline silicon material. The term "p-type" refers to the addition of impurities to an intrinsic silicon material, thereby creating valence electron vacancies. In a silicon-containing silicon material, examples of p-type dopants, i.e., impurities, include, but are not limited to, boron, aluminum, gallium, and indium.In some embodiments, at least an upper portion of nonporous zone 14 of anode structure 12 that interfaces with porous zone 2 (i.e., lower porous layer 16) and the entire porous zone (16, 17) are constructed of a same material, for example, a p-doped silicon material, while a lower portion of nonporous zone 14 may be constructed of a different semiconductor material than the upper portion of nonporous zone 14 of anode structure 12 that interfaces with porous zone 2 (i.e., lower porous layer 16) and the entire porous zone (16, 17). For example, the bottom portion of nonporous region 14 present below porous region (16,17) may comprise doped silicon having a different dopant concentration than the original p-doped silicon used to provide anode structure 12, or a silicon-germanium alloy containing less than 10 atomic percent germanium.In some embodiments, and due to the simplicity and mikro-mability of monocrystalline material, the silicon material that provides at least an upper portion of the nonporous zone 14 of the anode structure 12 that interfaces with the porous zone 2 (i.e., the lower porous layer 16), as well as the entire porous zone (16, 17), is monocrystalline. In some embodiments, the cost of the process may be reduced and controlled by using lower quality silicon and adjusting the thickness of the silicon and applying simplified crystal growth techniques (as is the case in solar technology).The anode structure 12 of the present application may be formed using the anodic etching process, which is defined in more detail hereinafter (see, for example, FIG. 11 ).The electrolyte that may be present in the electrolyte zone 18 may comprise any conventional electrolyte that may be used in a rechargeable lithium ion battery. The electrolyte may be a liquid electrolyte, a solid electrolyte, a gel electrolyte, a polymer electrolyte, a semi-solid electrolyte, an electrolyte that is originally liquid but then exposed to conditions that convert its phase to a solid or semi-solid phase, or any combination thereof, such as a combination of a liquid electrolyte and a solid electrolyte. In some embodiments, the electrolyte zone 18 is entirely comprised of a solid electrolyte. In other embodiments, the electrolyte zone 18 may comprise a solid electrolyte and a liquid electrolyte. The electrolyte is located between the porous zone 1 (i.e., the upper porous layer 17) and the lithium-containing cathode material layer 20.In some embodiments, the electrolyte zone 18 is a solid state electrolyte constructed from a polymer-based material or an inorganic material. In other embodiments, the electrolyte zone 18 is a solid state electrolyte comprising a material that enables lithium ions to be conducted. Such materials may be electrically insulating and ionically conductive. Examples of materials that may be used as the solid-state electrolyte include, but are not limited to, lithium phosphorus oxynitride (LiPON) or lithium phosphosilicate oxynitride (LiSiPON), thio-LiSiCoN electrolytes (e.g., Li 2 S-P 2 S 5 in any ratio), Li 10 SnP 2 S 12, LiSiCoN-like electrolytes (e.g., Li 10 GeP 2 S 12), Argyrodite electrolytes (e.g., Li 6 PS 5 Br), Garnet electrolytes (e.g., Li 6.55 La 3 Zr 2 Ga 0.15 O 12), NaSiCoN-like electrolytes (e.g., Li 1.3 Al 0.3 Ti 1.7( PO4)3), Li nitride electrolytes (e.g., Li3N), Li hydride electrolytes (e.g. Li 2 NH) or perovskite electrolytes (e.g. Li 0.34 La 0.51 TiO 2.94).In embodiments where a liquid electrolyte is employed in the electrolyte zone 18, a separator, not shown, may be used. A separator may also be used in embodiments where two dissimilar electrolytes are present in the electrolyte zone 18. When a separator is employed, the separator may comprise one or more of a flexible porous material, a gel or sheet constructed from cellulose, cellophane, polyvinyl acetate (PVA), PVA / cellulose blends, polyethylene (PE), polypropylene (PP), or a blend of PE and PP. The separator can also be constructed from inorganic insulating nano / microparticles.In embodiments where a solid electrolyte layer is employed as the electrolyte zone 18, the solid electrolyte may be formed by a deposition process such as sputtering, solution deposition, hot pressing, cold pressing, slurry casting, followed by controlled temperature and pressure conditions, or plating. In one embodiment, the solid state electrolyte is formed by sputtering using any conventional target source material in conjunction with reactive or inert gases. For example, when forming the LiPON electrolyte, the sputtering may be performed in the presence of at least one nitrogen-containing ambient gas. In some embodiments, the nitrogen-containing ambient gas is used neat, i.e., neat. In other embodiments, the nitrogen-containing ambient gas may be diluted with an inert gas, such as helium (He), neon (Ne), argon (Ar), and mixtures thereof. The proportion of nitrogen (N 2) within the nitrogen-containing ambient gas used is typically 10% to 100%, with a nitrogen proportion of 50% to 100% being more typical within the ambient gas.The lithium-containing cathode material layer 20 may include a lithium-containing material, such as a lithium-based composite oxide. Examples of lithium-based composite oxides that can be used as the lithium-containing cathode material layer 20 include, but are not limited to, lithium cobalt oxide (LiCoO 2), lithium nickel oxide (LiNiO 2), lithium manganese oxide (LiMn 2 O 4), lithium vanadium pentoxide (LiV 2 O 5), lithium nickel manganese cobalt (NMC), nickel cobalt aluminum oxide (NCA), The following are also suitable for use in the present invention: any combination of sulfur-based materials with lithium and other structure-supporting elements such as iron or lithium iron phosphate (LiFePO 4). The lithium-containing cathode material layer 20 may have a thickness of 10 nm to 50 μm. Other thicknesses less than or greater than the above-mentioned thickness values may also be used for the lithium-containing cathode material layer 20.In some embodiments, the lithium-containing cathode material layer 20 may be formed by an application method such as sputtering, slurry casting, or plating. In one embodiment, the lithium-containing cathode material layer 20 is formed by sputtering using any conventional precursor source material or combination of precursor source materials. In one example, in forming a lithium-cobalt composite oxide, a lithium precursor source material and a cobalt precursor source material are employed. The sputtering may be carried out in a mixture of an inert gas and oxygen. In such an embodiment, the oxygen content of the inert gas / oxygen mixture may be 0.1 atomic percent to 70 atomic percent, with the remainder of the mixture comprising the inert gas. Examples of inert gases that may be used include argon, helium, neon, nitrogen, or any combination thereof in conjunction with oxygen.In some embodiments, the lithium-containing cathode material layer 20 may be formed by casting slurry, which may include a mixture of electrochemically active [cathode materials, electron conducting materials (e.g., carbon-based materials)], and inactive (binder materials) components. The thickness of such components could range from 5 μm to 500 μm. These slurries may also include an electrolyte component in the mixture together with a lithium-based salt(s).The cathode current collector (i.e., the cathode-side electrode) 22 may include any metallic electrode material for the cathode side, such as titanium (Ti), platinum (Pt), nickel (Ni), aluminum (Al), or titanium nitride (TiN). The cathode current collector 22 may include a single layer of a metallic electrode material for the cathode side or a material stack including at least two different metallic electrode materials for the cathode side. In one example, the cathode current collector 22 includes a stack of titanium (Ti), platinum (Pt), and titanium (Ti) from bottom to top. In an embodiment, the metallic electrode material providing the cathode current collector 22 may be the same as the metallic electrode material providing the anode current collector 10. In another embodiment, the metallic electrode material providing the cathode current collector 22 may be different from the metallic electrode material providing the anode current collector 10. The cathode current collector 22 may have a thickness within the range indicated above for the anode current collector 10. The cathode current collector 22 may be formed by any of the deposition methods set forth above for forming the anode current collector 10. For slurry-based cathode materials, metal foils may be used during the casting process.Referring now to FIG. 2, there is illustrated another exemplary rechargeable lithium ion battery according to a second embodiment of the present application. The exemplary lithium ion battery illustrated in FIG. 2 is similar to the rechargeable lithium ion battery stack illustrated in FIG. 1, except that an additional interfacial material layer 24 is disposed between the porous zone 1 (i.e., the upper porous layer 17) of the anode structure 12 and the electrolyte zone 18. Specifically, the exemplary rechargeable lithium ion battery illustrated in FIG. 2 includes a battery material stack of an anode current collector 10 as defined above, an anode structure 12 as defined above, an additional interfacial material layer 24 as defined in more detail hereinafter, an electrolyte zone 18 as defined above, a lithium-containing cathode material layer 20 as defined above, and a cathode current collector 22 as defined above. The battery material stack shown in FIG. 2 may have different orientations than that shown in FIG. 2. For example, it can be tilted by 180°.An additional interfacial layer 24 (e.g., a dielectric material) is present on the exposed surface of the porous zone 1 (i.e., the upper porous layer 17) of the anode structure 12; the layer 24 may be a single-layer structure or a multi-layer structure. The additional interface material layer 24 may comprise any additional interface material layer, such as a carbon-based material or gold, or a dielectric material oxide, such as aluminum oxide. The additional interface material may be a mixture with any combination of electrically insulating as well as Li ion-conducting components, such as, but not limited to, LiMnO 3, LiMnO 2, Li 4 SiO 4 or Li 3 PO 4. The additional interfacial material layer 24 may have a thickness of 1 nm to 50 nm. The additional interfacial material layer 24 may be formed by a deposition process including, for example, chemical vapor deposition, plasma enhanced chemical vapor deposition, or atomic layer deposition. The additional interfacial material layer 24 may allow for a high level of chemical and physical connections between electrolyte and electrode layers under repeated electrochemical conditioning. The additional interfacial material layer 24 may preserve structural strength for interfacial overlap, thereby allowing high ionic conductivity and reducing the internal resistance of the cell. Additionally, the additional interfacial material layer 24 may provide electrical isolation at the respective interfaces, thereby preventing leaks or shorts of the cell through spatial control of electrically conductive components within the battery. The additional interfacial material layer 24 as described above could be continuous or patterned.Referring now to FIG. 3, there is illustrated another exemplary rechargeable lithium ion battery according to a third embodiment of the present application. The exemplary rechargeable lithium-ion battery illustrated in FIG. 3 is similar to the rechargeable lithium-ion battery stack illustrated in FIG. 1, except that an additional interfacial material layer 26 is disposed between the electrolyte zone 18 and the lithium-containing cathode material layer 20. Specifically, the exemplary rechargeable lithium ion battery illustrated in FIG. 3 includes a battery material stack of an anode current collector 10 as defined above, an anode structure 12 as defined above, an electrolyte zone 18 as defined above, an additional interface material layer 26 as defined in more detail hereinafter, a lithium-containing cathode material layer 20 as defined above, and a cathode current collector 22 as defined above. The battery material stack shown in FIG. 3 may have different orientations than that shown in FIG. 3. For example, it can be tilted by 180°.The additional interfacial material layer 26 may include any of the additional interfacial materials set forth above for the additional interfacial material layer 24. The additional interfacial material layer 26 may have a thickness of 1 nm to 20 nm to minimize the increase in the internal resistance of the cell. The additional interfacial material layer 26 may be formed by a deposition process including, for example, chemical vapor deposition, plasma enhanced chemical vapor deposition, or atomic layer deposition. The additional interfacial material layer 26 may preserve structural strength for interfacial overlap, thereby allowing high ionic conductivity and reducing the internal resistance of the cell. Additionally, the additional interfacial material layer 26 may provide electrical isolation at the respective interfaces, thereby preventing leaks or shorts of the cell through spatial control of electrically conductive components within the battery.Referring now to FIG. 4, there is illustrated another exemplary rechargeable lithium ion battery according to a fourth embodiment of the present application. The exemplary lithium ion rechargeable battery illustrated in FIG. 4 is similar to the lithium ion rechargeable battery stack illustrated in FIG. 1, except that an additional interfacial material layer 24 is disposed between the porous zone 1 (i.e., the upper porous layer 17) of the anode structure 12 and the electrolyte zone 18, and an additional interfacial material layer 26 is disposed between the electrolyte zone 18 and the lithium-containing cathode material layer 20 and another dielectric material layer 26. Specifically, the exemplary rechargeable lithium ion battery illustrated in FIG. 4 includes a battery material stack of an anode current collector 10 as defined above, an anode structure 12 as defined above, an additional interface material layer 24 as defined above, an electrolyte zone 18 as defined above, an interface dielectric material layer 26 as defined above, a lithium-containing cathode material layer 20 as defined above, and a cathode current collector 22 as defined above. The battery material stack shown in FIG. 4 may have different orientations than that shown in FIG. 4. For example, it can be tilted by 180°.Referring now to FIG. 5, there is illustrated an exemplary rechargeable lithium ion battery according to a fifth embodiment of the present application. The example lithium ion rechargeable battery illustrated in FIG. 5 is similar to the lithium ion rechargeable battery stack illustrated in FIG. 1, except that the porous zone (including porous zone 1 and porous zone 2) of anode structure 12 is patterned. The structured porous zone comprising both porous zones 1 and 2 (not individually shown) is characterized in Figure 5 of the present application as element 16P. Specifically, the exemplary lithium ion battery illustrated in FIG. 5 includes a battery material stack of an anode current collector 10 as defined above, an anode structure 12 as defined above, and having a patterned porous zone 16P (including porous zones 1 and 2), an electrolyte zone 18 as defined above, a lithium-containing cathode material layer 20 as defined above, and a cathode current collector 22 as defined above. The battery material stack shown in FIG. 5 may have different orientations than that shown in FIG. 5. For example, it can be tilted by 180°.An additional interfacial material layer 24 may be formed between the patterned porous zone 16P and the electrolyte zone 18 and / or an additional interfacial material layer 26 may be formed between the electrolyte zone 18 and the lithium-containing cathode material layer 20. The structuring of the porous zone (comprising the porous zones 1 and 2) may be performed by conventional structuring techniques, including, for example, lithography and etching, possibly in conjunction with mechanical grinding / polishing and doping. In some embodiments, the structuring of the porous zone (16, 17) may be performed by simple selective doping in silicon, for example by ion implantation, epi or thermal doping. The structured porous zone 16P (collectively comprising porous zones 1 and 2) may provide a means for further enhancing the capacity as well as the kinetic capabilities (performance) of the anode structure 12 of the present application. The structured porous zone 16P (collectively comprising porous zones 1 and 2) may also provide a faster charging rate.Referring now to FIGS. 6A to 6B, there are illustrated exemplary lithium ion rechargeable batteries according to a sixth embodiment of the present application. The exemplary lithium ion rechargeable batteries illustrated in FIGS. 66A and 6B are similar to the lithium ion battery stack illustrated in FIG. 1, except that the porous zone (including the porous zone 1 and the porous zone 2) of the anode structure 12 is patterned and the lithium-containing cathode material layer 20 is also patterned. The patterned porous zone (comprising porous zones 1 and 2) is characterized as element 16P in Figures 6A to 6B of the present application, and the patterned lithium-containing cathode material layer is characterized as element 20P in Figures 6A to 6B of the present application. Specifically, the exemplary lithium ion batteries illustrated in FIGS. 6A through 6B include a battery material stack of an anode current collector 10 as defined above, an anode structure 12 as defined above, and having a patterned porous zone 6P (including porous zones 1 and 2), an electrolyte zone 18 as defined above, a patterned lithium-containing cathode material layer 20P as defined above, and a cathode current collector 22 as defined above. The battery material stacks shown in FIGS. 6A to 6B may have different orientations than those shown in FIGS. 6A to 6B. For example, they can be tilted by 180°.In one embodiment, as shown in FIG. 6A, the components 16P and 20P of the structured battery material stack are facing each other, e.g., the higher zones (lower zones) of each component in the same lateral position of the battery face each other in a non-complementary manner. Alternatively, the components 16P and 20P of the structured battery material stack may be complementary and may fit in shape like a lock and key, as shown in FIG. 6B. In this embodiment, the proximity of the patterned electrodes to each other may be controlled in addition to the thickness of the electrolyte (the electrolyte fills the entire space between the battery components 16P and 20P) by aligning the opposing electrodes in a particular proximity to each other. An additional interfacial material layer 24 may be formed between the patterned zone 16P (collectively comprising porous zones 1 and 2) and the electrolyte zone 18, and / or an additional interfacial material layer 26 may be formed between the electrolyte zone 18 and the patterned lithium-containing cathode material layer 20P.Patterning of the lithium-containing cathode material layer 20P may be accomplished by conventional patterning techniques including, for example, lithography and etching, or by a lift-off process. The patterned lithium-containing cathode material layer 20P may be complementary or non-complementary with respect to the patterned porous zone 16P. The patterned lithium-containing cathode material layer 20P may provide a further increase in capacity as well as kinetic charge / discharge capabilities of the lithium ion battery of the present application. Together, the structured porous zone 16P (collectively comprising porous zones 1 and 2) and structured lithium-containing cathode material layer 20P can provide for maximized battery capacity and possible increase in the charging speed of the battery - as the structural dimensions along with the final specified proximity of the spatial volume between structured porous zone 16P (collectively comprising porous zones 1 and 2) and structured lithium-containing cathode material layer 20P can affect and determine the thickness, density, and other physical properties of electrolyte zone 18, thereby directly affecting ion-electron mobility properties throughout the battery stack.Referring now to FIG. 7A, there is shown a diagram illustrating the overall process of using a p-type crystalline silicon material 50 for the anodic etching process described herein. More particularly, the method begins by providing a p-type crystalline silicon material 50 and then performing an anodic etch, thereby providing an anode structure comprising porous zone 1 (PR1) (i.e., upper porous layer 17) and porous zone 2 (PR2) (i.e., lower porous layer 16) together with an unetched portion of the original p-type crystalline silicon substrate disposed below the two porous zones. The non-etched portion of the original substrate defines the non-porous zone 14 of the silicon substrate. In this drawing, the nonporous zone 14 is also characterized as element 50S; it should be noted that the nonporous 50S has the same properties as the nonporous zone 14 described above.FIG. 7B is a transmission electron micrograph (TEM) (through a cross-sectional view) of an experimentally prepared porous silicon substrate such as that illustrated in FIG. 7A. This TEM image clearly illustrates the two porous zones, PR1(i.e., the upper porous layer 17) and PR2(i.e., the lower porous layer 16) illustrated in Figure 7A, where the porous zone 1 has a thickness on the order of about 30 nm and the porous zone 2 is much thicker than the porous zone 1.FIG. 8A is a high resolution transmission electron micrograph of one embodiment of the porous silicon material referred to herein in FIG. 7A. The scale line in this figure illustrates that the total thickness of the porous zone 1 is about 29 nm. FIG. 8B is a secondary ion mass spectrometry (SIMS) profile of the porous silicon material illustrated in FIG. 8A. This SIMS profile illustrates the relatively low concentrations of the elements carbon, oxygen and fluorine in the first 30 nm of the porous silicon material - which directly correlate with the porous zone 1 (as indicated by the dashed boxes in Figures 8A and 8B connected by a double-sided arrow).Referring now to FIGS. 9A-9F, there is illustrated a sequence of steps as a flow chart depicting a porous silicon electrode (i.e., an anode structure including nonporous zone 50S, porous zone 2 (PR2), and porous zone 1 (PR1)) and the operation of charge storage across the electrode material when a liquid-based electrolyte is used with a seed layer 52 during charge and discharge cycles, supplemented by SEM images of a porous silicon electrode at 5 cycles (FIG. 9D) and at about 250 cycles (FIG. 9F). In particular, FIG. 9A illustrates a porous silicon electrode as described and illustrated in FIG. 7A prior to its incorporation into an electrochemical energy storage cell. The porous silicon electrode includes the nonporous zone 50S, the porous zone 2 (PR2), and the porous zone 1 (PR1). FIG. 9B is an illustration of the initial lithiating process of the porous silicon electrode when incorporated into a Li-ion electrochemical energy storage cell. While the porous silicon electrode is initially exposed to the lithium ion-containing electrolyte and / or during the initial period of electrochemical lithiating the porous silicon electrode and / or during initial charging of the porous silicon electrode, a planar lithium-containing seed layer 52 is formed. As shown, the lithium-containing seed layer 52 is disposed on top of the porous zone 1 and a portion of the seed layer 52 may extend into an upper portion of the porous zone 2, in some embodiments. The top surface of seed layer 52 is typically flat, i.e., planar. FIG. 9C is a schematic illustration of the planar lithium plating occurring during the charging process. In FIG. 9C, the planar lithium layer that forms during this operation is labeled as the element 54. It should be noted that when the battery reaches the full charge state, the thickness of the plated lithium metal 54 on the seed layer 52 is proportional to the amount of lithium deintercalated from the lithium-containing cathode material layer and transferred from the electrolyte, determined by a working voltage range.FIG. 9D is a scanning electron micrograph of a cross section of a porous silicon electrode demonstrating the plating phenomena illustrated in FIG. 9C; wherein the cross-sectional image of the electrode is taken in the charged state after about 250 charge / discharge cycles. In the charged state, lithium permeation through the porous zone 1 is observed, but only in the upper portion of the porous zone 2, causing some cracks in upper parts of the porous zone 2. FIG. 9E is an illustration of the lithium deplate that occurs during the discharge process, leaving a portion of the irreversibly plated lithium metal 54 on top of the seed layer 52. Due to the discharge, the thickness of the remaining portion of the plated lithium metal 54 is substantially less than the thickness of the planar lithium layer 54 formed during the state of charge, as shown in FIG. 9C. Note that as the battery approaches a sustained discharge state, the thickness of the layer of lithium metal decreases proportionately, as determined by the working voltage range. FIG. 9F is a scanning electron micrograph of a cross section of a porous silicon electrode in the discharge state which has been charged and discharged 5 times, corresponding to FIG. 9E. In one embodiment, the working voltage range is 4.2 V to 3.0 V. In one embodiment, the lithium-containing cathode material layer is a lithium cobalt oxide. The above seed layer formation and lithium metal plating occurring during charging and subsequent deplate of lithium metal occurring during discharging is observed for lithium ion batteries containing a solid electrolyte or liquid electrolyte or any other type of electrolyte mentioned herein.In some embodiments, the rechargeable lithium-ion battery of the present application may be charged and discharged over 200 cycles when a persistent working voltage is used, such as one of those mentioned above. After 200 cycles of charging and discharging, the surface of the plated lithium metal is nominally continuously planar on average.Referring now to FIGS. 10A through 10D, there are shown actual SEM images for a full solid state lithium ion battery according to the present application and including a structure similar to that shown in FIG. 1, wherein the electrolyte zone 18 is a solid state material such as LiPON. The structure also includes the anode structure 12 shown in FIG. 1 or 9A. Specifically, FIG. 10A is an SEM of the structure before galvanostatically or potentiostatically induced charging or discharging, FIG. 10B is another SEM of the structure after 6 charging and discharging cycles, and FIG. 10C is still another SEM image of the structure after 56 charging and discharging cycles.The SEM of FIG. 10A is a cross-sectional SEM image of the full-solid battery before galvanostatic or potentiostatic induction of electrochemical charging or discharging, showing a porous silicon electrode (i.e., an anode structure including the nonporous zone (not shown), the porous zone 2 (PR 2), and a planar porous zone 1 (PR 1)), wherein a solid electrolyte zone 18 is above the porous zone 1 (PR 1). FIG. 10B is a cross-sectional SEM image of the full-solid cell illustrated in FIG. 10A after 6 galvanostatically induced charging and discharging cycles, observing from bottom to top the porous zone 2 (PR 2), a porous zone 1 (PR 1) containing a lithium-containing seed layer 52. In particular, clearly light gray features are observed that originate from the interface of porous zone 1 (PR1) and solid electrolyte zone 18, which features are believed to represent the reaction of air with the lithium-rich material comprising lithium-containing seed layer 52 and / or the plated lithium metal that was on the lithium-containing seed layer 52 that formed during the 6 charge / discharge cycles. FIG. 10C is a cross-sectional SEM image of the full-solid cell illustrated in FIG. 10A after 67 galvanostatically induced charging and discharging cycles, wherein from bottom to top the substantially original porous zone 2 (PR 2), a partially lithiated porous zone 2 (PR 2), a planar formation of lithium metal containing dendritic features mixed with solid electrolyte material are observed in the porous zone 1 (PR 1), and the electrolyte zone 18. As the porous silicon electrode is initially exposed to the lithium ion-containing electrolyte and / or during the initial period of electrochemical lithiating the porous silicon electrode and / or during initial charging of the porous silicon electrode, a planar lithium-containing seed layer 52 is formed. The top surface of the seed layer 52 is typically flat, i.e., planar, as seen in FIGS. 10A and 10B, where PR 1 and the seed layer 52 are in planar, intimate contact with the electrolyte zone 18 prior to cycling. This planar lithium metal-containing seed layer is believed to function as a host or nucleation site for subsequent lithium metal plating / stripping during subsequent charge / discharge cycles. After 6 charge / discharge cycles, the lithium-rich material forming the seed layer and / or the lithium metal plated seed layer is changed from its immobilized planar state after cell destruction and cleavage to obtain the SEM image of Figure 10 - this corresponding lithium metal containing layer now reacts with the ambient air chemistry, thereby forming the light gray features observed to originate / originate from the interface zone PR1 / solid electrolyte zone 18. In Figure 10D, after 56 charge / discharge cycles, a substantially original area of porous zone 2 (PR2) is observed above which a partially lithiated porous zone 2 (PR2) is observed above which an approximately 183 nm planar layer of dendritic-type lithium-rich formations is observed in the area of porous zone 1 (PR1) above which the area of LiPON electrolyte is observed. In particular, planar formation observation of lithium-rich dendritic features in / on the area of porous zone 1 (PR1) which remain stable after cell damage and rupture after 67 charge / discharge cycles, wherein close continuous contact between solid electrolyte zone 18 and the lithium-rich dendritic features in / on the area of porous zone 1 (PR1) illustrates the high effectiveness of the present invention as a stable lithium metal-supplying porous silicon anode in solid state batteries, in addition to liquid electrolyte-containing stable lithium metal-supplying porous silicon anode batteries as illustrated in Figures 9A-9F.In some embodiments and after multiple charge / discharge cycles, in addition to the dendrite formation at the lithium metal / electrolyte interface, unique dendrite formation occurs on / along the (111) silicon crystal planes at the interface of the lower porous layer / upper porous layer.The rechargeable lithium ion batteries illustrated in FIGS. 1-5, 6A, and 6B may have any size and / or shape. An exemplary range includes: 10 μm to less than 1 mm (small), and large is all over 1 mm. In one example, the size of the lithium ion rechargeable batteries may be 100 μm×100 μm×100 μm. In another example, the size of the lithium ion rechargeable batteries may be 50 mm×50 mm×25 mm. In some embodiments where a semiconductor base substrate is present, the rechargeable lithium ion batteries illustrated in FIGS. 1-5, 6A, and 6B may be integrated with semiconductor devices including, for example, transistors, capacitors, diodes, laser diodes, light emitting devices, photovoltaic devices, central processing devices, silicon-based device structures, etc. The battery that powers the semiconductor device could be located on the same side or on the opposite side of the semiconductor substrate.The integration can be performed in two ways: 1) Conventionally, by preparatory patterning, lithography, etching of the semiconductor substrate before anodizing and creating a porous semiconductor zone, or 2) By selective doping, e.g., ion implantation and subsequent thermal annealing, such as furnace or lamp or laser annealing, or selective epitaxial growth, etc. The devices can be placed on the same original semiconductor substrate or can be integrated with the same original semiconductor substrate or can be placed on an adjacent semiconductor substrate within a given working proximity (the same side as the battery or the opposite side of the battery are options).The method of manufacturing the anode structure 12 of the present application will now be described in more detail. The method of the present application provides for 1) the "growth" or production or etching of a porous semiconductor zone associated with a nonporous semiconductor zone (e.g., a monocrystalline silicon material), which can then be integrated into other / with other silicon-based technologies, 2) the successful integration and use of liquid, solid and semi-solid electrolytes and their high functionality in rechargeable batteries (versatile with any electrolyte), and 3) the thickness of the solid electrolyte can be controlled due to the specular and smooth surface of the starting silicon substrate in the nm regime, which allows good control of battery performance, charging speed, ion mobility, and is compatible with physically deposited electrolytes.In particular, the anode structure 12 of the present application may be fabricated using an anodizing process in which a substrate comprising at least a top zone of a p-type silicon material is dipped into a solution of concentrated HF (49%) while applying an electric current with platinum as the anode and the substrate as the cathode. The anodization process is performed using a constant current source operating at a current density of 0.05 mA / cm 2 to 150 mA / cm 2 where mA is milliamperes. In some examples, the current density is 1 mA / cm 2, 2 mA / cm 2, 5 mA / cm 2, 50 mA / cm 2 or 100 mA / cm 2. In a preferred embodiment, the current density is 1 mA / cm 2 to 10 mA / cm 2. The current density can be applied for 1 second to 5 hours. In some examples, the current density may be applied for 5 seconds, 30 seconds, 20 minutes, 1 hour, or 3 hours. In an embodiment, the current density may be applied for 10 seconds to 1,200 seconds, especially for the doping strength in the range of 10 19 cm 3. The anodization process is typically carried out at a nominal room temperature of 20°C to 30°C or at a temperature slightly higher than room temperature. After the anodizing process, the structure shown in Figure 7B is typically rinsed with deionized water and then dried.In some embodiments, and after anodization, the anode structure 12 may be cut into a desired dimension before being used. In some embodiments, the anode structure 12 may be disposed on and optionally connected to the anode current collector 10 as defined above, and then the various other components of the lithium ion battery may be formed. In other embodiments, the anode structure 12 may be disposed on and optionally connected to the electrolyte zone 18 of a prefabricated battery material stack further comprising a cathode zone comprising a lithium-containing cathode material layer 20 and a cathode current collector 22.Referring now to FIG. 11, there is illustrated a flow chart showing an embodiment for fabricating the anode structure 12 of the present application. In particular, the anode structure 12 comprising the porous zone 1 and the porous zone 2 and the nonporous zone 14 (or 50S) described above can be produced using the process steps illustrated in FIG. 11. In one embodiment, the substrate 12 may be entirely composed of a p-doped crystalline silicon material, while in other embodiments, other silicon materials or germanium (both doped and undoped) may be present below the p-doped silicon material. The method may comprise, in a first step, i.e., step 1 (70), cleaning the p-doped silicon substrate with a mixture of ammonium hydroxide, deionized water, and hydrogen peroxide (5:1:1 v / v) at 60° C. to 80° C. for about 10 minutes. Next, and in step 2 (72), the cleaned p-type silicon substrate is dipped in 49% hydrofluoric acid, and then an electric current is applied thereto to start electrochemical anodization (i.e., anodization etching). In one embodiment, the applied current is a constant current in a range from 1 mA / cm 2 to 10 mA / cm 2. In step 3(74), anodization etching is continued using the following electrochemical anodization conditions: nominal room temperature (20°C to 30°C) and less than or equal to 5 mA / cm 2 for 10 s to 2,000 s. After etching and in step 4(76), the etched silicon substrate is rinsed with deionized water and then dried. By the anodizing method defined in step 3, an upper portion of the substrate containing the p-type silicon is converted into the porous zone 1 and the porous zone 2, and the underlying substrate is not affected by the anodizing method and forms the above-described nonporous zone 14 (or 50S).In each of the above-described embodiments, and as illustrated in FIGS. 1 to 5, 6A, and 6B, the lithium-containing cathode material layer 20 may contain grains having a grain size of less than 100 nm and a grain boundary density of 10 10 cm -2 or more. In some embodiments, the grain size of each grain constituting the lithium-containing cathode material layer 20 is 1 nm to less than 100 nm. In some embodiments, the density of the boundaries may be 10 10 cm -2 to 10 14 cm -2. The term "grain boundary" is defined herein as an interface between two grains of materials. The grain boundaries are present in the lithium-containing cathode material layer 20 in a somewhat random orientation. Some of the grain boundaries may extend entirely through the cathode material such that one end of the grain boundary is at a lowermost surface of the cathode material and another end of the grain boundary is at an uppermost surface of the cathode material. In this embodiment, the grain boundaries are not oriented perpendicular to the top and bottom surfaces of the lithium-containing cathode material layer 20.In each of the above-described embodiments, and as illustrated in FIGS. 1 to 5, 6A, and 6B, the lithium-containing cathode material layer 20 may have a columnar microstructure having columnar grain boundaries. The grain boundaries are oriented perpendicular to the top and bottom surfaces of the lithium-containing cathode material layer 20. In such an embodiment, the lithium-containing cathode material layer 20 includes a plurality of fin-like structures within the cathode material. The lithium-containing cathode material layer 20 having the columnar microstructure has a grain size of less than 100 nm and a columnar grain boundary density of 10 10 cm -2 or more. In some embodiments, the grain size of each grain constituting the lithium-containing cathode material layer 20 is 1 nm to less than 100 nm. In some embodiments, the density of columnar grain boundaries may be 10 10 cm -2 to 10 14 cm -2. In one embodiment, the electrically conductive cathode material is a lithium-containing material as defined above.The presence of a lithium-containing cathode material layer 20 having grains with a grain size of less than 100 nm and a grain boundary density of 10 10 cm -2 or more, or a lithium-containing cathode material layer 20 having the columnar microstructure with the anode structure 12 of the present application, in a material stack of a rechargeable battery, as illustrated for example in FIGS. 1 to 5, 6A and 6B of the present application, enables fast and substantially or fully vertical ion transport, i.e. Li ion transport, which can lead to rapid charging of the batteries.Rechargeable batteries including the anode structure 12 and a lithium-containing cathode material layer 20 including grains having a grain size of less than 100 nm and a grain boundary density of 10 10 cm -2 or more, or a lithium-containing cathode material layer 20 having the columnar microstructure may have a charging speed of 5 C or more, where C is the total battery capacity per hour. In some embodiments, the charging speed of the batteries including the anode structure 12 and a lithium-containing cathode material layer 20 including grains having a grain size of less than 100 nm and a grain boundary density of 10 10 cm -2 or more, or a lithium-containing cathode material layer 20 having the columnar microstructure may be 5 C to 1,000 C or more. In addition, rechargeable batteries including the anode structure 12 and a lithium-containing cathode material layer 20 including grains having a grain size of less than 100 nm and a grain boundary density of 10 10 cm -2 or more, or a lithium-containing cathode material layer 20 having the columnar microstructure may have a capacity of 100 mAh / g of the cathode material or more.The lithium-containing cathode material layer 20 containing grains having a grain size of less than 100 nm and a grain boundary density of 10 10 cm -2 or more, or the lithium-containing cathode material layer 20 having the columnar microstructure can be formed by a sputtering method. In some embodiments, and after sputtering the cathode material, no subsequent anneal is performed; the cathode material sputtered without anneal provides a lithium-containing cathode material layer 20 containing grains having a grain size of less than 100 nm and a grain boundary density of 10 10 cm -2 or more. In other embodiments, and after sputtering the cathode material, an anneal may be performed to provide a lithium-containing cathode material layer 20 having the columnar microstructure. The annealing is performed at temperatures less than 300°C to maintain the charging speed of more than 5C. In one embodiment, sputtering may involve the use of any precursor source material or any combination of precursor source materials. In one example, in forming a lithium-cobalt composite oxide, a lithium precursor source material and a cobalt precursor source material are employed. The sputtering may be carried out in a mixture of an inert gas and oxygen. In such an embodiment, the oxygen content of the inert gas / oxygen mixture may be 0.1 atomic percent to 70 atomic percent, with the remainder of the mixture comprising the inert gas. Examples of inert gases that may be used include argon, helium, neon, nitrogen, or any combination thereof.The lithium-containing cathode material layer 20 containing grains having a grain size of less than 100 nm and a grain boundary density of 10 10 cm -2 or more, or the lithium-containing cathode material layer 20 having the columnar microstructure may have a thickness of 10 nm to 20 μm. Other thicknesses less than or greater than the above-mentioned thickness values may also be used for the lithium-containing cathode material layer 20 containing grains having a grain size of less than 100 nm and a grain boundary density of 10 10 cm -2 or more, or the lithium-containing cathode material layer 20 having the columnar microstructure. A thick lithium-containing cathode material layer 20 containing grains having a grain size of less than 100 nm and a grain boundary density of 10 10 cm -2 or more, or the lithium-containing cathode material layer 20 having the columnar microstructure can provide increased battery capacity because there is a larger area, i.e., more volume, for storing the battery charge.Although the present application has been particularly shown and described with reference to preferred embodiments thereof, it will be understood by those skilled in the art that the foregoing and other changes in form and detail may be made therein without departing from the spirit and scope of the present application. The present application is therefore not intended to be limited to the exact forms and details described and illustrated, but is intended to be determined by the scope of the appended claims.

Claims

A battery comprising: a lithium-containing cathode material layer; an anode structure of unitary construction and comprising a nonporous zone and a porous zone having an upper porous layer having a first thickness and a first porosity and a lower porous layer disposed below the upper porous layer and forming an interface with the nonporous zone, wherein at least an upper portion of the nonporous zone and the entirety of the porous zone are constructed from silicon, and wherein the lower porous layer has a second thickness greater than the first thickness and a second porosity greater than the first porosity; and an electrolyte zone disposed between the upper porous layer of the anode structure and the lithium-containing cathode material layer.The battery of claim 1, wherein the upper porous layer, the lower porous layer and the nonporous zone are entirely comprised of silicon.The battery of claim 2, wherein the silicon is monocrystalline.The battery of claim 1, wherein a bottom portion of the nonporous layer is constructed of doped silicon or a doped silicon-germanium alloy having a germanium content of less than 10 atomic percent.The battery of claim 1, wherein the first porosity of the upper porous layer has an average pore opening of less than 3 nm and wherein the second porosity of the lower porous layer has an average pore opening of more than 3 nm.The battery according to claim 1, wherein the first thickness of the upper porous layer is 50 nm or less.The battery of claim 1, wherein the second thickness of the lower porous layer is 0.1 μm to 20 μm.The battery of claim 1, wherein the nonporous region is constructed of p-doped silicon which is monocrystalline.The battery of claim 1, wherein the nonporous region and the porous regions are entirely made of p-doped silicon.The battery of claim 1, wherein the silicon is p-doped silicon having a p-type dopant concentration in the range of 10 19 cm -3.The battery of claim 1, wherein the silicon is boron doped silicon.The battery of claim 1, further comprising an anode current collector in contact with a surface of the nonporous region of the anode structure.The battery of claim 1, further comprising a cathode current collector electrode in contact with a surface of the lithium-containing cathode material layer.The battery of claim 1, wherein the electrolyte zone is constructed from a solid electrolyte, a liquid electrolyte, a semi-solid electrolyte, an initially liquid then solidifying electrolyte, a gel electrolyte, a polymer containing electrolyte, a composite cathode / electrolyte combination, or any combination thereof.The battery of claim 1, wherein the electrolyte zone is constructed entirely of a solid electrolyte.The battery of claim 1, further comprising an additional interfacial material layer disposed between the upper porous layer of the anode structure and the electrolyte zone.The battery of claim 1, further comprising an additional interfacial material layer disposed between the electrolyte and the lithium-containing cathode material layer.The battery of claim 1, further comprising a first additional interfacial material layer disposed between the upper porous layer of the anode structure and the electrolyte zone, and a second additional interfacial material layer disposed between the electrolyte and the lithium-containing cathode material layer.The battery of claim 1, wherein the porous zone comprising the upper and lower porous layers is patterned.The battery of claim 19, wherein the lithium-containing cathode material layer is patterned.The battery of claim 1, wherein the porous zone is disposed on the top, bottom, or side of any three-dimensional structure.The battery according to claim 1, wherein the lithium-containing cathode material layer is selected from a lithium-containing material containing grains having a grain size of less than 100 nm and a grain boundary density of 10 10 cm -2 or more, or a lithium-containing material having a columnar microstructure.The battery of claim 15, wherein the battery further comprises a seed layer disposed on a surface of the upper porous layer of the anode structure, wherein the seed layer is a planar conformal lithium-containing material.A method of manufacturing an anode structure of a lithium battery, comprising: dipping a substrate comprising at least a top portion comprised of p-doped silicon in concentrated hydrogen fluoride while an anodization structure is used; applying an electric current to the anodization structure; and electrochemically anodizing the substrate, wherein the anodizing provides a structure of uniform construction, and which comprises a nonporous zone and a porous zone having an upper porous layer with a first thickness and a first porosity and a lower porous layer which is disposed below the upper porous layer and forms an interface with the nonporous zone, wherein at least an upper portion of the nonporous zone and the entirety of the porous zone are made of silicon, and wherein the lower porous layer has a second thickness which is greater than the first thickness and a second porosity which is greater than the first porosity.The method of claim 24, further comprising cleaning the substrate prior to dipping.The method of claim 24, further comprising rinsing the structure with deionized water and drying after anodizing.The method of claim 24, wherein an entirety of the substrate is constructed of p-doped silicon.The method of claim 27, wherein the p-doped silicon is monocrystalline.The method of claim 25, wherein the cleaning is performed using a mixture of deionized water, ammonium hydroxide, and hydrogen peroxide (5:1:1 by volume) at a temperature of 60°C to 80°C for a duration in the range of five to thirty minutes, followed by rinsing in deionized water.The process of claim 24, wherein the concentrated hydrogen fluoride is a 49% hydrofluoric acid solution.The method of claim 24, wherein the electric current is a constant current in a range of 1 mA / cm 2 to 10 mA / cm 2.The method of claim 24, wherein anodizing the substrate is performed at a temperature of 20°C to 30°C.The method of claim 32, wherein anodizing the substrate is performed with an electric current less than or equal to 5 mA / cm 2 for 10 seconds to 2,000 seconds.The method of claim 24, wherein the upper porous layer, the lower porous layer and the nonporous zone are all comprised of silicon.The method of claim 34, wherein the silicon is monocrystalline.The method of claim 24, wherein a bottom portion of the nonporous layer is comprised of doped silicon or a doped silicon-germanium alloy having a germanium content of less than 10 atomic percent.The method of claim 24, wherein the first porosity of the upper porous layer has an average pore opening of less than 3 nm and wherein the second porosity of the lower porous layer has an average pore opening of greater than 3 nm.The method of claim 24, wherein the first thickness of the upper porous layer is 50 nm or less.The method of claim 24, wherein the second thickness of the lower porous layer is 0.1 μm to 20 μm.The method of claim 24, wherein the nonporous zone is constructed of p-doped silicon which is monocrystalline.The method of claim 24, wherein the nonporous zone and the porous zones are composed entirely of p-doped silicon.The method of claim 24, wherein the silicon is p-doped silicon having a p-type dopant concentration in the range of 10 19 cm -3.The method of claim 24, wherein the silicon is boron doped silicon.The method of claim 24, further comprising structuring the porous zone comprising the upper and lower porous layers.The method of claim 24, wherein the porous zone is formed on the top, bottom or side of any three-dimensional structure.

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