WO2008030215A2 - Procédé et appareil pour des structures carbonées de surface élevée avec une résistance rendue minimale - Google Patents

Procédé et appareil pour des structures carbonées de surface élevée avec une résistance rendue minimale Download PDF

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Publication number
WO2008030215A2
WO2008030215A2 PCT/US2006/027027 US2006027027W WO2008030215A2 WO 2008030215 A2 WO2008030215 A2 WO 2008030215A2 US 2006027027 W US2006027027 W US 2006027027W WO 2008030215 A2 WO2008030215 A2 WO 2008030215A2
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Prior art keywords
carbon
projections
aspect ratio
coating
high aspect
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PCT/US2006/027027
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English (en)
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WO2008030215A3 (fr
Inventor
Chang-Jin Kim
Fardad Chamran
Uichong Brandon Yi
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The Regents Of The University Of California
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Publication of WO2008030215A2 publication Critical patent/WO2008030215A2/fr
Publication of WO2008030215A3 publication Critical patent/WO2008030215A3/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/049—Manufacturing of an active layer by chemical means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/78—Shapes other than plane or cylindrical, e.g. helical
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the field of the invention generally relates to three-dimensional (3D) structures of carbon having a high surface area yet minimize electrical and thermal resistance.
  • the field of the invention also relates to methods of making the same.
  • the methods and devices may be used to form 3D batteries, sensors, and the like.
  • Carbon is increasingly being used in many applications including, for example, electrosynthesis and energy conversion systems. Due to carbon's advantageous electrical, mechanical, and chemical properties, carbon-based electrodes have been extensively utilized in batteries and electrochemical sensors. In typical current applications, two-dimensional (2D) carbon thin-films are used in the device. More recently, 3D architectures of carbon have been introduced and demonstrated in microbatteries to overcome the energy and power deficiencies of conventional 2D thin-film architectures for the application. For example, 3D architectures provide many advantages such as small footprint area and short diffusion lengths in comparison to 2D thin-film devices for powering micro electro mechanical systems (MEMS) and other miniaturized electronic devices. See Hart et al., 3-D Microbatteries, Electrochemistry Communications, 5, 120-123 (2003).
  • MEMS micro electro mechanical systems
  • Lithium-ion microbatteries have increasingly been investigated because of their high energy densities.
  • 3D carbon microelectrodes having height- to-diameter aspect ratios greater than ten (10) have been formed by lithographically patterning a commercial negative photoresist (SU-8) and pyrolyzing it.
  • SU-8 commercial negative photoresist
  • the carbon-based microelectrodes are used as the anode electrode in lithium-ion batteries.
  • the high aspect ratio carbon posts or rods create new problems.
  • a device is formed from an electrically conductive base.
  • a plurality of electrically conductive projections extend away from the base and are conformally coated with a thin film or coating of carbon.
  • the carbon may be formed directly from a conformal chemical deposition process e.g., chemical vapor deposition (CVD), or by conformally coating a polymer, e.g., parylene, first and pyrolyzing the polymer.
  • CVD chemical vapor deposition
  • a three-dimensional battery or sensor having two sets of electrodes formed from one or two electrically conductive bases having a plurality of electrically conductive projections extending away from the base in an interdigitated manner.
  • the electrically conductive projections are coated with a thin film or coating of carbon.
  • the conductive base and the conductive projections may form the current collector.
  • An electrolyte may be interposed between the cathode and the anode.
  • a method in another aspect of the invention, includes the step of providing a mold having a plurality of high aspect ratio apertures or holes formed therein. An electrical conductor is deposited within the plurality of high aspect ratio apertures so as to form a base having a plurality of high aspect ratio projections extending therefrom. The mold is then removed and a polymer or carbon is conformally deposited over the plurality of high aspect ratio projections. The polymer is then pyrolyzed so as to form a carbon coating over the plurality of high aspect ratio projections. In certain embodiments of the invention, the aspect ratio of the projections may be greater than 10:1.
  • FIG. 1 illustrates a perspective as well as a partial cross-sectional view of a carbon post array having a conductive core (e.g., metal) according to one aspect of the invention.
  • a conductive core e.g., metal
  • FIG. 2 illustrates a cross-sectional view of the microbattery employing an array of carbon posts according to one aspect of the invention.
  • FIG. 3A illustrates a cross-sectional view of a prior art carbon post.
  • FIG. 3B illustrates a cross-sectional view of a metal-cored carbon post according to one aspect of the invention.
  • FIG. 4 illustrates an illustrative process for forming a carbon-coated metal micropost array.
  • FIG. 5A illustrates a scanning electron micrograph (SEM) image of a silicon mold having high aspect apertures formed by anodic etching in HF (5%) during backside illumination.
  • FIG. 5B illustrates a scanning electron micrograph (SEM) image of a nickel- micropost array prior to parylene deposition.
  • FIG. 5C illustrates a scanning electron micrograph (SEM) image of a fabricated carbon-coated nickel micropost array.
  • the nickel posts are 10 ⁇ m in diameter and 170 ⁇ m in height.
  • the carbon coating has a thickness of 1 ⁇ m.
  • FIG. 5D illustrates a scanning electron micrograph (SEM) image of another fabricated carbon-coated nickel micropost array.
  • the nickel posts are 60 ⁇ m in diameter and 400 ⁇ m in height.
  • the carbon coating has a thickness of 3 ⁇ m.
  • FIG. 6 illustrates cyclic voltammetry scan curves (at 1 mV/s) obtained from the carbon-coated nickel micropost array of FIG. 5C.
  • FIG. 7 illustrates a galvanostatic charge-discharge curve (at 0.1 mA/cm 2 ) obtained from the carbon-coated nickel micropost array of FIG. 5C.
  • FIG. 8 illustrates a galvanostatic charge-discharge curve (at 1 mA/cm 2 ) obtained from the carbon-coated nickel micropost array of FIG. 5C.
  • FIG. 9 illustrates a galvanostatic charge-discharge curve (at 0.1 mA/cm 2 ) obtained from the lower aspect ratio carbon-coated nickel micropost array of FIG. 5D.
  • FIGS. 1A and 1 B illustrate perspective and cross-sectional views, respectively, of a device 2 having a three-dimensional array of projections 4 arrayed about base 6.
  • the base 6 as well as an interior portion or core 8 of each projection 4 is formed from an electrically conductive material.
  • the base 6 and the core 8 may also be formed from a thermally conductive material.
  • the base 6 as well as the core 8 of the projections 4 may be made from nickel. Of course, other electrically conductive materials may also be used.
  • Each projection 4 within the array is conformally coated with a thin film 10 or coating of carbon.
  • the array of projections 4 may be formed as posts or rods. It should be understood, however, that the device 2 does not require a specific cross-sectional geometry of the projections 4 in order to function.
  • the cross-sectional geometry of the projections may be circular, oval, polygonal, or the like.
  • the projections 4 forming the array may have relatively large aspect ratios.
  • the aspect ratio is defined as the length or height of an individual projection 4 divided by the width (or diameter in the case of circular projections 4) of the projection 4.
  • the projections 4 may be formed with aspect ratios greater than 10:1.
  • FIG. 1A illustrates an array of projections 4 positioned in an ordered array
  • the invention described herein also contemplates an array of disordered, curved, or even random projections 4 extending away from the base 6.
  • the projections 4 extend away from the base 6 in a generally perpendicular orientation.
  • each projection 4 is covered with a thin film 10 of carbon.
  • the carbon may be formed by first depositing a polymer layer over the exterior of the conductive cores 8 projecting from the base 6. The polymer may be heated at an elevated temperature to transform the polymer into the thin film 10 of carbon.
  • the thickness of the thin film 10 of carbon may be on the order of about 0.1 ⁇ m to about 10 ⁇ m although other thicknesses are contemplated to fall within the scope of the invention.
  • carbon may be directly formed on the conductive cores 8, thereby obviating the need for a separate pyrolysis step.
  • carbon nanotubes, nanowires, or even porous carbon may be grown or otherwise deposited on the conductive cores 8 using chemical deposition techniques.
  • the base 6 with the arrayed projections 4 may be utilized in a microbattery 50.
  • the design of microbatteries in order to increase the energy density of a three- dimensional electrode for a given footprint area, it is necessary to increase the aspect ratio of the three-dimensional electrodes.
  • the high energy is unattainable at high discharge rates due to excessive ohmic losses.
  • the carbon-based post design of FIG. 3A suffers from significant potential drop along the length of the post.
  • the current design illustrated in FIG. 3B overcomes this limitation. By using an electrically conductive core 8 within the projection 4, potential drops are minimized.
  • the array of projections 4 is integrated within a microbattery 50.
  • the microbattery 50 includes a base 6 and a plurality of projections 4 extending away from a surface thereof.
  • the base 6 and core 8 or inner portions of the projections 4 may be formed from an electrically conductive material.
  • the base 6 and core 8 of each projection 4 may be formed from nickel.
  • the nickel base 6 forms the current collector for the microbattery 50.
  • the exterior surface of the base 6 as well as the outer surface of the core 8 of each projection is covered in a thin film 10 of carbon which forms the anode 12 of the microbattery 50.
  • the nickel core 8 of each projection is electrically connected to the base 6 and effectively extends the current collector into the carbon anode 12.
  • the carbon anode 12 directly communicates with the conductive core 8 without having to go through a long distance inside carbon such as in the design of FIG. 3A. Consequently, the design of FIG. 2 minimizes the overall ohmic potential drops at high discharge rates.
  • a cathode 52 is provided that is coupled to a conductive current collector 54.
  • the current collector 54 may be formed from an electrically conductive material such as a metal or an alloy of multiple metals.
  • the current collector 54 may be formed from aluminum or nickel.
  • the cathode 52 may be formed from lithium cobalt oxide (UCOO 2 ) or other material used for cathodes in lithium ion batteries.
  • an electrolyte 56 is interposed between the carbon anode 12 and the cathode 52.
  • the electrolyte 56 may be formed from polymer-based materials such as poly(ethylene oxide) (PEO).
  • the electrolyte 56 may be formed from inorganic materials such as lithium phosphorus oxynitride (LIPON).
  • the microbattery 50 may be encased in a housing or other cover (not shown in FIG 2).
  • the respective current collectors 6, 54 may be coupled via conductive elements (not shown) to form the terminals or contacts for the microbattery 50.
  • the device 2 having an array of projections 4 like that shown in FIGS. 1A and 1 B may be formed by conformal deposition of a polymer (e.g., parylene) over the array of conductive cores 8.
  • the polymer coating may then be transformed into a carbon thin film 10 or coating by a subsequent heating step in an oxygen free environment to pyrolyze the polymer into carbon.
  • FIG. 4 illustrates an illustrative fabrication process used to prepare a device 2 like the one shown in FIGS.
  • FIG. 4 illustrates a silicon mold having a plurality of high aspect ration apertures 22 formed therein.
  • the apertures may be etched or otherwise formed in the mold 20.
  • DRIE deep reactive ion etching
  • photo-assisted anodic etching may be used to form an array of high-aspect ratio apertures 22.
  • the particulars of these processes may be found in F. Chamran et al, Three Dimensional Electrodes for Microbatteries, Proc. ASME Int. Mechanical Eng. Congress, Anaheim, CA Nov. 2004, CD VoI. 2, IMECE2004-61925, which is incorporated by reference herein.
  • the device 2 having an array of projections 4 like that shown in FIGS. 1A and 1B may be formed by depositing carbon directly using a conformal carbon coating method.
  • Conformal coating of carbon may be obtained typically by a chemical deposition method, such as low-pressure chemical vapor deposition or self- assembled layering.
  • carbon includes a variation of carbonaceous materials, including graphitic carbon, amorphous carbon, porous carbon, carbon nanowires/nanotubes, and the like.
  • the backside 20b of the mold was etched using reactive ion etching to fully open or expose the apertures 22. This process is followed by thermal oxidation to form a coating of silicon dioxide 23 on the mold 20.
  • the silicon dioxide coating passivates the silicon mold 20 for subsequent passivation steps.
  • a titanium/nickel (Ti/Ni) seed layer 24 having a thickness of 100 A titanium and 1000 A nickel was deposited via evaporation.
  • nickel was electroplated over the seed layer 24.
  • nickel was electroplated at 10mAh/cm 2 to form a sealing layer 26 over the apertures 22 at the top side 20a of the mold 20.
  • step 140 nickel was electroplated inside the apertures 22 of the mold 20 using the just-formed nickel sealing layer 26 as a seed layer. Nickel was electroplated at constant current density of 5 mA/cm 2 . A photoresist layer 28 was deposited on the nickel sealing layer 26 to passivate the top or upper side 20a of the mold 20 from being electroplated during this step.
  • step 150 the silicon dioxide layer 23 and the underlying silicon of the mold 20 were etched away using BOE and XeF2, respectively, to expose the nickel post array 30.
  • the nickel post array 30 is formed with a plurality of electrically conductive core members 8.
  • the nickel post array 30 was conformally deposited with layer 32 parylene-C using chemical vapor deposition at a temperature and pressure of 25 0 C and 25 mTorr, respectively.
  • the layer 32 was pyrolyzed by heating the same in a furnace at a temperature of 1000 0 C under argon gas flow. Ramping of the furnace temperature (both heating and cooling) was set to 1 °C/min. The pyrolysis of the layer 32 of parylene-C transformed the parylene-C into a thin layer 10 of carbon (as seen in FIGS. 1A and 1 B).
  • FIG. 5A illustrates an SEM image of a silicon mold 20 fabricated by anodic etching of n-type silicon in 5% HF during backside illumination.
  • the high aspect ratio apertures 22 are shown penetrating deep within the silicon mold.
  • FIG. 5B illustrates an SEM image of the nickel post array 30 prior to the deposition of parylene-C. This image corresponds to step 150 in FIG. 4.
  • FIG. 5C is an SEM image of the final carbon-coated projections 4.
  • the carbon-coated projections 4 were formed using a anodic-etched silicon mold 20.
  • the nickel posts are 10 ⁇ m in diameter and 170 ⁇ m in height.
  • the thickness of the carbon coating 10 on the exterior of the nickel cores 8 in FIG. 5C was 1 ⁇ m.
  • FIG. 5D is an SEM image of the final carbon-coated projections 4 formed by using a DRIE etched mold 20.
  • a layer 32 of parylene with a thickness of 12 ⁇ m was deposited on the nickel cores 8.
  • the diameter of each core 8 or post of nickel was 60 ⁇ m while the height was 400 ⁇ m.
  • a second, three-dimensional nickel-based array device was constructed in accordance with the fabrication process described above with respect to FIG. 4.
  • the resistivity of parylene-pyrolyzed carbon thin film 10 was measured at 0.015 ⁇ -cm on the flat sample using a four-point probe.
  • Electrochemical measurements were carried out for both the flat sample and the three-dimensional, nickel-based array device.
  • the electrolyte used for both the flat sample and the 3D device was 1 M LiCIO 4 in a 1 :1 volume mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC).
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • a three-electrode system setup was used having a counter electrode, a reference electrode, and a working electrode.
  • the working electrode was either the flat sample or the 3D device.
  • the counter electrode and reference electrode were formed using lithium metal.
  • lithium ion was intercalated at 0.1 mA/cm 2 in a flat sheet of carbonized parylene. The thickness and area of the sample were 1 ⁇ m and 1 cm 2 , respectively.
  • the flat sample was electrically connected using an alligator clip at one corner. The results exhibited reversible intercalation/deintercalation of lithium with an areal capacity of 0.047 mAh/cm 2 .
  • FIG. 5C illustrates the 3D micropost structure shown in FIG. 5C.
  • the projections illustrated in FIG. 5C had diameters of 10 ⁇ m and were 170 ⁇ m high on a 0.5 cm 2 footprint area.
  • the electrode was cycled at 1 mV/s between 0.01 V and 2 V.
  • FIG. 6 illustrates the cyclic voltammetry scan curves at 1 mV/s. The graph in FIG. 6 shows proper intercalation/deintercalation of lithium within the device.
  • FIG. 7 shows the shows the galvanostatic charge-discharge measurements at 0.1 mA/cm 2 (the first cycle is not shown here due to its irreversible capacity). A lithium capacity of 0.75 mAh/cm 2 was observed at this discharge rate.
  • FIG. 8 illustrates the measured galvanostatic charge-discharge at 1 mA/cm 2 for the same 3D structure. A capacity of 0.16 mAh/cm 2 was observed during this testing.
  • a second 3D device illustrated in FIG. 5D having a lower aspect ratio ( ⁇ 7) was also tested for galvanostatic charge-discharge behavior.
  • FIG. 5D A second 3D device having a lower aspect ratio ( ⁇ 7) was also tested for galvanostatic charge-discharge behavior.
  • the microbattery 50 illustrated in FIG. 2 would eliminate the electric field concentration at the tips of the projections 4. Because of this, the electric field will be more uniform along the projections 4 and a high energy density lithium microbattery 50 may be fabricated.
  • the device 2 described above may be used in other applications beyond batteries.
  • the device 2 may be used to increase the sensitivity of a sensor (not shown).
  • the three-dimensional nature of the architecture allows miniaturization while still maintain a high surface area.
  • the total available carbon surface area can be increased by orders of magnitude for a given footprint. For instance, an effective area of 30 cm 2 is achieved on a 1 cm 2 footprint by fabricating projections 4 (e.g., microposts) with a diameter of 10 ⁇ m, a pitch of 20 ⁇ m, and a height of 400 ⁇ m.
  • projections 4 e.g., microposts

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  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Secondary Cells (AREA)

Abstract

L'invention concerne un dispositif tel que, par exemple, une micro-batterie tridimensionnelle, lequel dispositif comprend un assemblage d'électrodes effilées sur un collecteur de courant. Lorsque les électrodes sont entièrement faites en carbone, la résistance électrique le long des électrodes effilées devient excessive et le système perd de l'efficacité. Cette résistance peut être abaissée en ayant l'âme des électrodes faite d'un bon conducteur électrique tandis que leur surface est revêtue de façon conforme d'un film mince ou revêtement de carbone. Le dispositif conserve une surface totale importante de carbone actif disponible pour des réactions électrochimiques tout en améliorant l'efficacité de collecte du courant par diminution de la résistance électrique le long des électrodes effilées. La demi-cellule peut être incorporée dans une micro-batterie complète pour fournir une densité d'énergie élevée à des vitesses de décharge élevées. Les mêmes avantages peuvent être appliqués pour diminuer une résistance thermique.
PCT/US2006/027027 2005-07-12 2006-07-11 Procédé et appareil pour des structures carbonées de surface élevée avec une résistance rendue minimale WO2008030215A2 (fr)

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JP2011165665A (ja) * 2010-02-05 2011-08-25 Robert Bosch Gmbh 整列したサイクル耐性の構造を有するＬｉバッテリ用のカソード構造体の製造方法
WO2013010628A3 (fr) * 2011-07-15 2013-04-04 Li-Tec Battery Gmbh Batterie de structure poreuse
WO2014028230A1 (fr) * 2012-08-16 2014-02-20 Enovix Corporation Structures d'électrode pour batteries tridimensionnelles
WO2014028853A1 (fr) * 2012-08-16 2014-02-20 The Regents Of The University Of California Micro-batteries 3d à base d'électrolyte à couches minces
GB2505447A (en) * 2012-08-30 2014-03-05 Harrold J Rust Iii Electrode structures for three-dimensional batteries
US8999558B2 (en) 2007-01-12 2015-04-07 Enovix Corporation Three-dimensional batteries and methods of manufacturing the same
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