HK1138110B - Three-dimensional batteries and methods of manufacturing the same - Google Patents

Description

Three-dimensional battery and method for manufacturing same

CROSS-REFERENCE TO RELATED APPLICATIONS

According to 35 u.s.c.section 119(e), the application claims priority from: (i) U.S. provisional application No.60/884,836, entitled "electrode for three-dimensional lithium battery and method of making the same", filed on 12.1.2007; (ii) U.S. provisional application No.60/884,828, entitled "three-dimensional battery using a skeletal structure and method of manufacturing the same", filed on 12.1.2007; and (iii) U.S. provisional application No.60/884,846, entitled "separator construction for three-dimensional lithium batteries," filed on 12/1/2007; the entire contents of which are incorporated herein by reference.

Background

1. Field of the invention

Implementations consistent with the principles of the invention relate generally to the field of battery technology, and more particularly, to three-dimensional energy storage systems and devices, such as batteries and capacitors, and methods of making the same.

2. Background of the invention

Existing energy storage devices, such as batteries, fuel cells, and electrochemical capacitors, typically have a two-dimensional layered structure (e.g., flat sheet or spirally wound sheet) in which the surface area of each sheet is roughly equal to its geometric area (ignoring porosity and surface roughness).

Fig. 1 shows a cross-sectional view of a prior art energy storage device, such as a lithium ion battery. The battery 15 includes a cathode current collector 10 on which a cathode 11 is mounted. This layer is covered by a separator 12, and an anode current collector 13 and anode 14 assembly are placed over the separator 12. Sometimes this stack is covered with another separator layer (not shown) over anode current collector 13 and wound to fill the can to assemble battery 15. During charging, lithium leaves cathode 11 and enters anode 14 through separator 12 in the form of lithium ions. Depending on the anode used, lithium ions are intercalated (e.g., in a matrix of the anode material rather than being alloyed) or alloyed. During discharge, lithium leaves anode 14, migrates through separator 12 and passes to cathode 11.

Three-dimensional batteries have been proposed in the literature for the purpose of improving the capacity and active material utilization of the batteries. It has been proposed that three-dimensional structures can be used to provide higher surface area and higher energy than two-dimensional, plate-like cell structures. It is beneficial to fabricate three-dimensional energy storage devices because of the increased energy available beyond small geometric areas.

The following references may further help explain the state of the art and are incorporated herein by reference as non-essential subject matter: long e al, "three-dimensional battery junction tree," Chemical Reviews, (2004), 104, 4463-; chang Liu, FOUNDATION OF MEMS, Chapter tenth, pp 1-55 (2006); kanamura et al, "LiCoO for rechargeable lithium batteries₂Electrophoretic (electrophoretic) fabrication of the anode, journal of Power Sources, 97-98(2001) 294-; cabilllero et al. "preparation of LiNi for high voltage lithium ion batteries by electrophoretic deposition_0.5Mn_1.5O₄Thin film electrodes, Journal of Power Sources, 156(2006)583- > 590; wang and Cao, "Li of sol-electrophoretically deposited vanadium pentoxide films⁺Embedded electrochemical/electrochromic properties ", Electrochimica Acta, 51, (2006), 4865-; nishizawa et al, "polypyrrole coated spinel LiMn₂O₄Template synthesis of nanotubes and their performance as cathode active materials for lithium batteries, "Journal of Power Sources, 1923-1927, (1997); shembel et al, "thin layer electrolysis of molybdenum oxysulfide for lithium secondary batteries with liquid polymer electrolyte", 5^thAdvanced Batteries and Accumulators, ABA-2004, lithium polymer electrolytes; and Kobin et al, "Molecular Vapor Deposition," a Molecular coating Vapor Deposition technique to improve MEMS devices, "SEMI technical Symposium: innovations in semiconductor Manufacturing (STS: ISM), SEMICON West 2004, 2004 semiconductor Equipment and Materials International.

It would be desirable to produce a three-dimensional electrochemical energy device that can provide very high energy and energy density while addressing the above considerations or other limitations in the art.

Disclosure of Invention

Various methods and apparatus related to three-dimensional battery structures and methods of making the same are disclosed and claimed. In certain embodiments, a three-dimensional battery includes a battery enclosure, and a first structural layer within the battery enclosure, wherein the first structural layer has a first surface, and a first plurality of conductive protrusions extending from the first surface. A first plurality of electrodes is within the battery enclosure, wherein the first plurality of electrodes comprises a plurality of cathodes and a plurality of anodes, and wherein the first plurality of electrodes comprises a second plurality of electrodes selected from the first plurality of electrodes, each of the second plurality of electrodes being in contact with an outer surface of one of the first plurality of conductive protrusions.

Other aspects and advantages of the invention will become apparent from the following drawings, detailed description and claims.

Drawings

Some embodiments of the present invention are described with reference to the accompanying drawings.

Fig. 1 is a general cross-sectional view of a prior art two-dimensional energy storage device, such as a lithium ion battery.

Fig. 2 is a schematic illustration of a skeletal structure according to an embodiment of the present invention.

Fig. 3A-3D are schematic illustrations of some shapes that a skeletal structure according to some embodiments of the invention may be assembled.

Fig. 4A-4E are schematic diagrams illustrating a process for fabricating a skeletal structure using a passive ion etching process (reactive ion etch process) according to an embodiment of the present invention.

Fig. 5A-5D are schematic diagrams of a process for fabricating a skeletal structure using a deactivating ion etching process, in accordance with embodiments of the present invention.

Fig. 6A-6C are schematic diagrams of a process for fabricating a skeletal structure using a deactivating ion etching process, in accordance with an embodiment of the present invention.

Fig. 7A-7D are schematic diagrams of processes for fabricating a skeletal structure using electrochemical deposition (electrochemical deposition), chemical deposition, or electrophoretic deposition processes, in accordance with embodiments of the present invention.

Fig. 8A-8E are schematic diagrams of a process for making a skeletal structure using an additive stamping process (additive extrusion), according to an embodiment of the present invention.

Fig. 9A-9C are schematic illustrations of a process for manufacturing a skeletal structure using a sequential deposition and assembly process, in accordance with embodiments of the present invention.

Detailed Description

Certain embodiments of the present invention relate to three-dimensional lithium ion battery structures. Existing energy storage devices, such as batteries, fuel cells, and electrochemical capacitors, typically have a two-dimensional layered structure (e.g., flat sheet or spirally wound sheet) in which the surface area of each sheet is roughly equal to its geometric area (ignoring porosity and surface roughness). The three-dimensional energy storage device may be a device in which the anode, cathode, and/or separator are substantially non-layered. For example, if the electrodes protrude significantly from the substrate to form a non-laminar active cell component, then the surface area of such non-laminar component may be two times larger than the geometric area of the substrate. In some embodiments, the spacing between two constant-Z back-connection plates should be at least greater than the spacing between electrodes in the X-Y plane divided by the square root of 2, assuming mutually orthogonal X, Y, Z directions.

Some embodiments of the present invention relate to the utilization of skeletal structures for the manufacture of three-dimensional energy storage devices, such as batteries, capacitors, and fuel cells. The skeletal structure may be used to provide mechanical stability, electrical connectivity, and a surface of increased unit geometric area. By way of example, the skeletal structure may be fabricated by wire bonding aluminum into a cylindrical shape on a flat substrate, and may be used substantially for cathode or anode material coating of an assembled battery. Examples of skeletal structures formed using various materials, shapes, and methods are described herein, as well as other examples.

Three-dimensional energy storage devices can produce higher stored energy per unit geometric area and recovery rates (retrievals) than conventional devices. The three-dimensional energy storage device may also improve the energy recovery rate for a particular stored energy over a two-dimensional energy storage device, for example by minimizing or reducing the electron and ion transport distance between the anode and cathode. These devices may be more suitable for miniaturization and the geometric area of the devices is limited and/or requires higher energy densities than those obtained with layered devices.

Some embodiments of the invention include a mechanically stable, electrically conductive skeletal structure that ultimately becomes part of the final assembled energy storage device. The framework materials generally do not participate in the efficient electrochemical reactions of the energy storage device and can improve mechanical and electrical strength.

The backbone material can also serve as a high surface area substrate for a high surface area electrochemical device. Since the active materials comprising the device generally have relatively low mechanical stability, mechanical strength can increase the lifetime of the device. Conductivity can increase or maintain the energy density of the device (e.g., by reducing resistivity) while also balancing the current distribution among the electroactive groups.

The skeletal structure may be fabricated in any shape that provides a higher surface area relative to geometric area, such as a column, rod, plate, wave, ring, diamond, spiral, step structure, and the like. The skeletal structure may be made of any material that may be formed, such as metals, semiconductors, organics, ceramics, and glass. The skeletal structure may be used to provide: (i) hardness of active electrodes in energy storage devices, such as anodes and cathodes in lithium ion batteries; (ii) electrical connection of high three-dimensional structures; and (iii) increasing the surface area per geometric area. Desirable materials include semiconductor materials such as silicon and germanium. Carbon-based organic materials may also be used to form the skeletal structure of the three-dimensional structure. Metals such as aluminum, copper, nickel, cobalt, titanium, and tungsten may also be used as the skeletal structure.

In some embodiments, the skeletal structure is made of metal, semiconductor, organic material, ceramic, or glass using subtractive formation techniques (subtractive formation techniques). These materials can be formed by active etching of the substrate with a selective etch mask and a plasma etch process. Alternatively, or in combination, electrochemical etching, stamping, or electrical discharge machining is used to selectively preferentially remove material in areas where such material is not desired.

In other embodiments, the skeletal structure is made of metal, semiconductor, organic material, ceramic, or glass using additive formation technology (additive formation technology). These materials may be formed by sacrificing the template using, for example, conventional lithographic techniques, and depositing the backbone material using techniques such as electrochemical deposition, chemical deposition, electrophoretic deposition, vacuum implantation, template implantation, and the like. In a specific example, the skeletal structure may be assembled directly with the wire bonding. In other examples, the skeletal structure may be formed on a flat panel using conventional lithographic and deposition techniques, and subsequently assembled by "pick and place" and welding or bonding.

In other embodiments, the skeletal structure may be formed using printing techniques, such as three-dimensional printing and inkjet printing, with single or multiple layers of printed skeletal structure to achieve the desired shape and thickness. Alternatively, or in combination, the skeletal material may be assembled in the form of a laminate in which the sacrificial layer is deposited. After the lamination of the plates is substantially complete, the final structure is divided into assembled blocks of predetermined height, and the sacrificial material is removed to provide the skeletal structure.

In the example of a conductive skeletal structure, the active material may be assembled directly on top of and around the skeletal structure by various techniques, such as electrochemical deposition, chemical deposition, co-deposition in organic or inorganic molds, electrophoretic deposition, mechanical injection and compaction, and vacuum fluid deposition.

In the example of a non-conductive skeletal structure, the conductive layer can be deposited by various techniques, such as electrochemical or chemical deposition, vapor vacuum deposition such as Atomic Layer Deposition (ALD) and Chemical Vapor Deposition (CVD), sputter deposition, evaporation, and electrophoretic deposition. These conductive layers may be removed continuously in order to remove the electrical connection between the anode and the cathode. This removal is accomplished using techniques such as sputter etching, ion milling, and lift-off.

Fig. 2 shows an example of a skeletal structure 20 for use in forming a three-dimensional battery. Fig. 2 shows a cross-sectional view of two positive electrodes 21 and two negative electrodes 23. In this embodiment, the skeletal structure 20 includes a non-conductive substrate 24 of a general material, with the conductive material 22 deposited on the substrate 24, and the conductive material 22 removed in areas where the conductive material 22 is not needed for spacing the electrodes 21 and 23. Comparing fig. 2 and fig. 1, it is clear that the surface area of the electrodes 21 and 23 in fig. 2 is higher than that of the electrodes shown in fig. 1, and the product of the length L and the thickness T of the electrodes 21 and 23 is calculated as this area. Notably, the thickness, and thus the relevant properties, such as electrical conductivity, of the various parts (e.g., electrodes and skeletal structure projections) can vary locally (e.g., from electrode to electrode or from projection to projection) depending on the particular embodiment, based on the current that needs to be carried or other relevant properties.

Fig. 3A-3D illustrate some embodiments of three-dimensional structures that can be used with certain embodiments of the present invention and have a cathode and an anode extending from the same backing plate. Fig. 3A shows a three-dimensional assembly with a cylindrical cathode and anode, fig. 3B shows a three-dimensional assembly with a plate-shaped cathode and anode, fig. 3C shows a three-dimensional assembly with a concentric ring-shaped cathode and anode, and fig. 3D shows a three-dimensional assembly with a wave-shaped cathode and anode. Other structures, such as honeycombs and spirals, may also be used with certain embodiments of the invention. In fig. 3A-3D, the cathode 30 and anode 31 protrude from the same backing plate and are periodically alternated. However, in other embodiments, the cathode 30 may protrude from a different backing plate than the anode 31.

Figures 4A-4E illustrate a general process flow diagram for fabricating a skeletal structure using a reduced activity ion etching process, according to some embodiments of the invention. The process involves a substrate 40, the substrate 40 being shaped with a directional plasma source to form a volatile gaseous by-product, thus facilitating removal. A non-limiting example of substrate 40 is a silicon substrate, which may be monocrystalline or polycrystalline in nature. The mask layer 41 is deposited on the substrate 40 by methods such as vacuum deposition, thermal oxidation, surface coating and wet chemical deposition. In the case of silicon as the substrate 40, a thermally grown silicon oxide layer of a certain thickness may be used as the mask layer 41. This layer 41 may be subsequently patterned by standard patterning techniques in order to provide a suitable pattern for further processing to generate the skeleton structure. In an embodiment of the present invention, the mask layer 41 may be covered with a second mask layer 42 suitable for patterning the first mask layer 41 (see fig. 4A-4D). To transfer the pattern of the first masking layer 41 onto the substrate 40, the combination of the substrate 40 and the masking layer 41 is subjected to a directional plasma 43 in a controlled environment (see fig. 4D). The reactive etching process in the presence of a directional plasma source can provide excellent anisotropic etching of the substrate 40 while etching the mask 41 itself at a very low rate. After the reactive etching of the substrate 40 is substantially completed, the mask layer 41 may be removed, leaving a pattern on the substrate, thus forming a skeletal structure (see fig. 4E).

The concepts of the present invention are further explained with reference to the following examples in fig. 4A-4E. Single crystal or polycrystalline silicon may be used as the substrate 40 that may be directionally etched in the presence of the plasma. The first mask layer 41 may be a thermally grown silicon dioxide layer of a certain thickness. Standard photoresists, e.g. AZ4620^TMAnd AZP4620^TM(commercially available from clariant corporation) may be used as the second mask layer 42. This layer 42 can be spin-coated on a silicon dioxide layer and subsequently patterned using standard photolithographic techniques. Using a developing solution, e.g. AZ400K^TMAreas of the photoresist (commercially available from clariant corporation) can be developed. The pattern structure is soaked in HF and NH₃F and water (buffered oxide etch) in which the exposed silicon dioxide surface is dissolved. With compatible organic solvents, e.g. N-methyl-2-pyrrolidineThe ketone optionally removes the remaining photoresist, leaving behind a patterned silicon dioxide layer. To etch the silicon dioxide pattern on the substrate 40, the combination of silicon and patterned silicon dioxide may be subjected to a directional fluorine plasma source. The pattern is transferred to the substrate 40 in the lateral direction without much etch rate difference for etching silicon and silicon dioxide. After the silicon reactive Etch is substantially complete, the mask layer 41 may be etched by immersion in a Buffered Oxide Etch (Buffered Oxide Etch) leaving the patterned substrate 40. In some examples, a stop layer may be added to the bottom of the substrate 40 to facilitate complete etching and insulation of the cathode and anode backbone structures.

In some embodiments, the patterned substrate 40 is conductive, in which case the resulting skeletal structure is ready for further active material processing. In certain other embodiments, the skeletal structure is non-conductive. In this case, further processing by depositing the conductive layer may be performed by various methods.

Fig. 5A-5D illustrate schematic diagrams of a subtractive chemical etching process to fabricate a skeletal structure, according to some embodiments. In these embodiments, the substrate 50 is patterned with an electrically insulating mask layer 51 deposited on the substrate 50 by, for example, vacuum deposition, thermal deposition, surface coating, and wet chemical deposition methods. This layer 51 is subsequently patterned by standard patterning techniques, such as lithography, in order to provide a pattern suitable for further processing to produce the skeleton structure. In some embodiments of the present invention, the mask layer 51 is covered with a second mask layer 51 suitable for patterning the first mask layer 51 (see fig. 5A-5B). In this case, the first mask layer 51 is patterned by using the second mask layer 51 as a stencil. The second masking layer 51 is selectively treated with a selective wet or dry process, leaving behind a patterned first masking layer 51 (see fig. 5B). The combination of the substrate 50 and the first masking layer 51 is placed in an electrochemical cell 53 having a counter electrode 54 and a nozzle 55, the nozzle 55 ejecting a solution for electrochemically removing material in the areas exposed to the solution (see fig. 5C). In certain embodiments, the entire workpiece may be immersed in a solution, which may dissolve in the material with which the solution contacts. However, the illustrated process may be substantialIs generally isotropic in the depth directionMay be substantially the same as the amount of material removed on each side in the width directionThe amount of material removed per side of (a) is the same. The soak-tank solution may be used to space the parts soaked therein in the resulting skeletal structureApparent specific widthAnd (3) narrow. A dc power supply 56 may be used to apply sufficient potential to remove material in contact with the solution. The process is substantially complete when a substantially predetermined amount of material is removed, which can be precisely controlled based on the etch rate. In certain other embodiments, the current may be detected and decreased in response to termination of the electrochemical reaction. After the reaction is substantially complete, the workpiece is removed and the mask layer 51 may be removed leaving the patterned substrate 50, thus forming a skeletal structure.

The concepts of the present invention are further explained with reference to the following examples in fig. 5A-5D. One example of a substrate 50 for electrochemical patterning is a copper plate. A copper plate of a predetermined thickness may be used as the substrate 50, and an electrically insulating mask layer 51 (e.g., AZ 4620) may be used^TMOr AZP4620^TM) Patterned and a mask layer 51 is deposited on the substrate 50 by spin coating. This layer 51 may be exposed in the case of a photomask, which blocks light from entering the areas that should be left. The workpiece may be placed in a solution to selectively remove the exposed areas. The combination of the substrate 50 and the first masking layer 51 is placed in an electrochemical cell 53 having a counter electrode 54 (e.g. platinum) and a nozzle 55, the nozzle 55 ejecting an electrochemical etching solution for electrochemically removing metal in the areas exposed to the solution. The 10 wt% sulfuric acid and 1 wt% hydrogen peroxide composition may be sprayed through a nozzle toward the workpiece. A dc power supply 56 may be used to power the substrate 50 an anodic potential is applied to remove copper from the areas of the solution that are in contact with both the copper anode and the platinum cathode, thus forming a local electrochemical cell. After the reaction is substantially complete, the workpiece may be removed, and the mask layer 51 removed with N-methyl-2-pyrrolidone leaving the patterned substrate 51.

Fig. 6A-6C illustrate schematic diagrams of a reduced pressure stamping process (subtractive stamping process) to fabricate skeletal structures according to certain embodiments. The mandrel 60 is prefabricated with a pattern that can be transferred from the desired skeletal pattern, and the mandrel 60 is coated with a thin release layer 61, which layer 61 can be used to facilitate removal of the mandrel 60 after processing. The release layer 61 may be, for example, an organic material that can be vapor deposited uniformly into the three-dimensional part. Such materials have poor adhesion or the additional property of being selectively etched without etching the mandrel 60 or the backbone material. For example, a stainless steel mandrel coated with a thin layer of copper by chemical vapor deposition may be used as a suitable imprinting device for the process where the material used as the moldable material is a thermally curable photoresist (see FIG. 6A). The combination of mandrel 60 and release layer 61 is in contact with a sheet 62 of moldable material on a substrate 63. Pressure is applied to transfer the pattern to the moldable material 62 (see fig. 6B). In the case where the substrate 63 is transparent, the combination is hardened by using temperature or other means, such as photo-curing the moldable material 62. The release layer 61 is removed by suitable means while separating the mandrel 60 and the resulting skeletal structure comprising the molding material and the substrate 64 (see fig. 6C).

In certain other embodiments, the skeletal structure of the energy storage device may be treated with additional processes. Fig. 7A-7D show schematic diagrams of processes for fabricating a skeletal structure using an electrochemical deposition, chemical deposition process, according to some embodiments. This process can be seen in the LIGA process of the prior art, where germany stands for "lithography, electro-forming and molding" (abermung). In this process, a conductive or non-conductive substrate 70 is used. In the case of a non-conductive substrate, a conductive layer 71 is deposited. A photoresist 72 is applied over the substrate 70 and patterned by standard lithographic techniques using a photomask 73, leaving the photoresist 72 in areas where the backbone material is not deposited (see fig. 7A and 7B). The workpiece placed in the plating bath has a sufficient potential to reduce the metal ions present in the solution to form metal (see fig. 7C). The metal ions are reduced at the conductive surface and do not deposit in the areas where the photoresist 72 is present. When the process is substantially complete, the workpiece including components 70, 72, and 74 is removed from the plating bath and the photoresist 72 is removed leaving the skeletal structure (including components 70 and 74) (see FIG. 7D).

The concepts of the present invention are further explained with reference to the following examples in fig. 7A-7D. In this process, a silicon wafer may be used as the semiconductor substrate 70. Copper may be deposited on silicon using a sputter deposition technique to create conductive layer 71. A positive or negative tone photoresist 72 (e.g., AZ 4620) may be coated on this substrate 70^TMOr AZP4620^TM) Patterned by standard lithographic techniques, leaving photoresist 72 in areas where deposition of the backbone material is not desired. This workpiece may be placed with a platinum counter electrode in a nickel electroplating bath comprising 1M nickel sulphate, 0.2M nickel chloride, 25g/l boric acid and 1g/l sodium saccharin, at a potential sufficient to reduce the nickel ions present in the solution to nickel metal 74. The metal ions are reduced at the conductive surface and do not deposit in the areas where the photoresist 72 is present. When processing is substantially complete, the workpiece including the silicon wafer 70, photoresist 72, and nickel metal 74 may be removed. Subsequently, the photoresist 72 is removed by using N-methyl-2-pyrrolidone, leaving the skeletal structure including the components 70 and 74. The copper metal remaining in the areas where the photoresist 72 is present is removed by a chemical etch comprising 2% sulfuric acid and 1% hydrogen peroxide.

Fig. 8A-8E illustrate a process diagram for manufacturing a skeletal structure with a stamping process, according to some embodiments. The mandrel 80 is prefabricated with a pattern that can be transferred from the desired skeletal pattern, and the mandrel 80 is coated with a thin release layer 81, which layer 81 can be used to facilitate removal of the mandrel 80 after processing (see FIG. 8A). This mandrel 80 also flares out at the edge or top of each opening 85 in order to facilitate the addition of material from which the mold can be made. The release layer 81 may be, for example, an organic material that may be vapor deposited uniformly into the three-dimensional part. Such materials have poor adhesion or the additional property of being selectively etched without etching the mandrel 80 or the backbone material. For example, a stainless steel mandrel coated with a thin layer of copper by chemical vapor deposition may be used as a suitable imprinting device for the process, wherein the material used as the moldable material 82 is a thermally curable photoresist. The combination of the mandrel 80 and the release layer 81 is in contact with the substrate 83 (see fig. 8B). The moldable material 82 protrudes into the opening 85 and fills the opening (see fig. 8C). While any residual material in the opening 85 is purged away (see fig. 8D). In the case where the substrate 83 is transparent, the combination is hardened by using temperature or other means, such as photo-curing the moldable material 82. The release layer 81 is removed by suitable means while separating the mandrel 80 and the resulting skeletal structure comprising the molding material 82 and the substrate 83 (see fig. 8E). Depending on each particular implementation, the release layer 81 may be unnecessary (e.g., if the mandrel/die 80 itself meets the required parameters, otherwise the release layer meets the required parameters). In certain embodiments, the mandrel/die 80 may be released through a solution.

Fig. 9A-9C illustrate a process schematic for fabricating a skeletal structure with a sequential deposition and assembly process, according to some embodiments. During this process, the optional layers of the skeletal material and the sacrificial material are assembled. An example of a group of materials assembled together is a polyethylene terephthalate (PET) sheet 90 having copper foil 91 dispersed therein. Thus, a stacked structure including PET/copper/PET was obtained (see fig. 9A). This layer is cut to the height of the skeleton structureOf a corresponding thickness, are spirally wound inside their shafts and assembled to the base plate 92 with epoxy glue (see fig. 9B). Sacrificial PET is selectively etched away in a selective chemical etching solution comprising sodium hypochlorite (NaOCl). Leaving two wound copper substrates, one serving as a cathode skeleton with intermediate grooves and the other serving as an anode skeleton with intermediate grooves, which accommodate the active material and separator for the electrochemical device (see fig. 9C).

Once available, the skeletal structureThe materials involved in the electrochemical reaction, also referred to as active materials, may be supported on a framework structure. This can be achieved in several different ways. The anode skeleton and the cathode skeleton may be separated from each other, but each motor may be electrically connected to itself. This can be done by electrochemical and electrophoretic deposition techniques as viable options for adding active materials. For example, in the case of lithium ion batteries, the cathode material, e.g. LiCoO₂、LiNi_0.5Mn_1.5O₄、Li(Ni_xCo_yAl_z)O₂、LiFePO₄Or Li₂MnO₄May be electrophoretically deposited on the conductive substrate. V can also be formed by electrophoretic deposition₂O₅And (3) a membrane. The cathode material may also be co-deposited with the polypyrrole matrix. In addition, certain cathode materials for lithium ion batteries, such as molybdenum oxysulfide, can be electrochemically deposited. In certain embodiments, shaping of the cathode comprises electrophoretic deposition of LiCoO₂Thicknesses between 1 micron and 300 microns are known. In certain embodiments, the layer thickness is between 5 and 200 microns, and in certain embodiments, the layer thickness is between 10 and 150 microns. As for the anode material, electrochemical deposition may be used for electroplatable anode material, such as tin, electrophoretic deposition may be used for assembling graphite, and then a carbon cathode may be formed by electrophoretic resistance deposition (electrophoretic deposition) of pyrolysis. Other suitable anode materials may include titanium, silicon, and aluminum. The thickness of the anode formed was the same as described above. Suitable separators may include polyethylene, polypropylene, TiO₂、SiO₂、Al₂O₃And the like.

While some embodiments are described with reference to energy storage devices, it will be appreciated that the skeletal structures described herein may be used in various other types of devices that provide increased surface area per geometric area (or per unit weight or volume). These other types of devices may involve various types of processes during operation, such as heat transfer, chemical reactions, and diffusion.

While the invention has been described with reference to specific embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the true spirit and scope of the invention as defined in the appended claims. In addition, many modifications may be made to adapt a particular situation, material, composition, method, operation or operation to the objective, spirit and scope of the present invention. All such modifications are intended to be within the scope of the claims. In particular, while the disclosed methods have been described herein with reference to particular operations performed in a particular order, it will be understood that these operations may be combined, sub-divided, or rearranged to form equivalent methods without departing from the teachings of the present invention. Accordingly, unless specifically indicated herein, the order and combination of operations do not define the invention.

Claims (32)

1. A three-dimensional battery, comprising:

a battery case;

a first structural layer within the battery case, the structural layer having a first surface;

a first plurality of conductive protrusions extending from the first surface of the first structural layer;

a first plurality of electrodes within the battery case, the first plurality of electrodes including a plurality of cathodes and a plurality of anodes, having a second plurality of electrodes selected from the first plurality of electrodes, each of the second plurality of electrodes being in contact with an outer surface of one of the first plurality of conductive protrusions.

2. The three-dimensional battery of claim 1, wherein the second plurality of electrodes is fewer than the first plurality of electrodes.

3. The three-dimensional battery of claim 2, the second plurality of electrodes consisting of a plurality of anodes.

4. The three-dimensional battery of claim 2, the second plurality of electrodes consisting of a plurality of cathodes.

5. The three-dimensional battery of claim 1, wherein the first plurality of electrodes is the same as the second plurality of electrodes.

6. The three-dimensional battery according to claim 2, further comprising:

a second structural layer within the battery enclosure, the second structural layer having a second surface;

a second plurality of conductive protrusions extending from the second surface of the second structural layer; and

a third plurality of electrodes selected from the first plurality of electrodes, each third plurality of electrodes in contact with an outer surface of one of the second plurality of conductive protrusions.

7. The three-dimensional battery of claim 6, the third plurality of electrodes being comprised of a plurality of anodes.

8. The three-dimensional battery of claim 6, the third plurality of electrodes being comprised of a plurality of cathodes.

9. The three-dimensional battery of claim 1, wherein the first plurality of conductive protrusions surrounds a base material protruding from the first surface of the first structural layer.

10. The three-dimensional battery of claim 9, wherein the base material and the first structural layer comprise the same material.

11. The three-dimensional battery of claim 1, wherein each of the second plurality of electrodes comprises a layer overlying an outer surface of one of the first plurality of conductive protrusions.

12. The three-dimensional battery of claim 1, wherein the first plurality of conductive protrusions comprise ridges that protrude at least 50 microns from the first structural layer and have a thickness of less than 20 microns.

13. The three-dimensional battery of claim 1, wherein the first plurality of conductive protrusions comprise pillars protruding at least 50 microns from the first structural layer.

14. The three-dimensional battery of claim 10, each of the second plurality of electrodes comprising a layer overlying an outer surface of one of the first plurality of conductive protrusions.

15. The three-dimensional battery of claim 10, wherein the first plurality of conductive protrusions comprise ridges extending at least 50 microns from the first structural layer and having a thickness of less than 20 microns.

16. The three-dimensional battery of claim 10, wherein the first plurality of conductive protrusions comprise pillars protruding at least 50 microns from the first structural layer.

17. The three-dimensional battery of claim 13, each of said posts being cylindrical.

18. The three-dimensional battery of claim 16, each of said posts being cylindrical.

19. The three-dimensional battery of claim 6, wherein the second plurality of conductive protrusions are electrically insulated from the third plurality of electrodes.

20. The three-dimensional battery of claim 6, wherein the second plurality of conductive protrusions comprises protrusions protruding at least 50 microns from the first structural layer and having a height of 2.5: 1 to 500: 1 rib with aspect ratio.

21. The three-dimensional battery of claim 1, further comprising a separator between at least one of said cathodes and at least one of said anodes.

22. A method of manufacturing a three-dimensional battery, comprising:

providing a first structural layer having a first surface;

forming a first plurality of conductive protrusions extending from a first surface of the first structural layer;

forming a first plurality of electrodes comprising a plurality of cathodes and a plurality of anodes, wherein each of the first plurality of electrodes is in contact with an outer surface of one of the first plurality of conductive protrusions.

23. The method of claim 22, wherein forming the first plurality of electrodes comprises forming the plurality of cathodes by electrophoretic deposition.

24. The method of claim 22, wherein forming the first plurality of electrodes comprises forming the plurality of anodes by electrophoretic deposition.

25. The method according to claim 22, further comprising:

forming a plurality of non-active skeletal protrusions extending from the first surface of the first structural layer; and wherein forming a first plurality of conductive protrusions comprises forming a conductive layer overlying an outer surface of one of the non-active skeletal protrusions.

26. The method of claim 22, wherein forming the first plurality of electrodes comprises varying a thickness of each of the first plurality of electrodes.

27. The method of claim 25, wherein forming a first plurality of electrodes comprises forming the plurality of cathodes by electrophoretic deposition.

28. The method of claim 25, wherein forming a first plurality of electrodes comprises forming the plurality of anodes by electrophoretic deposition.

29. The method of claim 27, wherein forming a plurality of cathodes comprises electrophoretically depositing LiCoO₂。

30. The method of claim 25, further comprising separating the conductive layer between each of the plurality of non-active skeletal protrusions.

31. The method of claim 27, wherein the step of forming each of said cathodes comprises electrophoretically depositing LiCoO₂Until a thickness of between 1 and 300 microns is formed.

32. The method according to claim 25, further comprising:

providing a second structural layer having a second surface opposite the first surface;

forming a second plurality of conductive protrusions extending from the second surface of the second structural layer and parallel to the first plurality of conductive protrusions; and

forming a second plurality of electrodes, wherein each of the second plurality of electrodes is in contact with an outer surface of one of the second plurality of conductive protrusions.