WO2015127081A1 - Collecteur de courant pour une batterie plomb-acide - Google Patents

Collecteur de courant pour une batterie plomb-acide Download PDF

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Publication number
WO2015127081A1
WO2015127081A1 PCT/US2015/016622 US2015016622W WO2015127081A1 WO 2015127081 A1 WO2015127081 A1 WO 2015127081A1 US 2015016622 W US2015016622 W US 2015016622W WO 2015127081 A1 WO2015127081 A1 WO 2015127081A1
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WIPO (PCT)
Prior art keywords
silicide
annealing
metal
layers
temperature range
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Application number
PCT/US2015/016622
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English (en)
Inventor
Collin Kwok Leung MUI
Daniel Jason MOOMAW
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Gridtential Energy, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by Gridtential Energy, Inc. filed Critical Gridtential Energy, Inc.
Publication of WO2015127081A1 publication Critical patent/WO2015127081A1/fr
Priority to US15/242,206 priority Critical patent/US10008713B2/en

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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
    • H01M4/82—Multi-step processes for manufacturing carriers for lead-acid accumulators
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/68—Selection of materials for use in lead-acid accumulators
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/029—Bipolar electrodes
    • 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
    • H01M4/14—Electrodes for lead-acid accumulators
    • H01M4/16—Processes of manufacture
    • 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

Definitions

  • the lead acid battery can be considered the earliest type of rechargeable battery, and lead acid chemistry remains the most commonly used battery chemistry.
  • the active materials in a lead acid battery generally include lead dioxide (Pb0 2 ), lead (Pb), and sulfuric acid (H 2 SO 4 ) which also acts as the electrolyte.
  • Pb0 2 and Pb active materials can be pasted and cured onto monopolar lead current collectors to form positive and negative plates, from which an electrochemical cell can be formed with H 2 SO 4 electrolyte.
  • the cells are generally arranged electrically in a parallel configuration such that the voltage of the battery is proportional to the number of cells in the battery pack.
  • bipolar configuration Another configuration for a lead acid battery is a bipolar configuration, in which the cells are generally arranged electrically in series.
  • bipolar plates can be fabricated with positive and negative active materials on opposing sides of a plate. The plates can be stacked such that a negative electrode of one cell serves as a positive electrode of the next cell in series.
  • the bipolar battery plate can include a silicon substrate.
  • a first metal layer can be deposited on a first surface of the rigid silicon substrate, and a different second metal layer can be deposited on a second surface of the rigid silicon substrate opposite the first surface.
  • the first and second metal layers can be annealed to form a first silicide on the first surface and a different second silicide on the second surface of the rigid silicon substrate.
  • annealing of the first and second metal layers to form the first and second silicides can include annealing the silicon wafer using a temperature range sufficient to form both silicide layers contemporaneously.
  • annealing the first and second metal layers can include annealing the first metal layer to form the first silicide using a first annealing temperature range, and separately annealing the second metal layer to form the second silicide using a second annealing temperature range.
  • a peak of the second annealing temperature range can be specified to be lower than temperatures within the first annealing temperature range, such that the first silicide remains stable within the second annealing temperature range.
  • FIG. 2 illustrates generally a section view of an example including a bipolar battery plate, such as can be included as a portion of a bipolar battery assembly.
  • FIGS. 3A and 3B illustrate generally scanning electron micrographs of silicides formed upon silicon, with a nickel silicide (NiSi) layer shown in FIG. 3A and a titanium silicide (TiSi 2 ) layer shown in FIG. 3B.
  • NiSi nickel silicide
  • TiSi 2 titanium silicide
  • FIGS. 4A and 4B illustrate generally glancing incidence x-ray diffraction (XRD) spectra for a nickel silicide (NiSi) layer in FIG. 4A and titanium silicide (TiSi 2 ) in FIG. 4B.
  • XRD x-ray diffraction
  • FIG. 7 illustrates generally examples of techniques, such as methods, that can be used to form silicides on silicon substrates.
  • FIG. 8 illustrates generally a technique, such as method, that can include fabricating a bipolar battery plate including a silicon substrate included as a portion of a current collector, according to an example.
  • FIG. 9 illustrates generally a technique, such as method, that can include fabricating a bipolar battery plate including a silicon substrate included as a portion of a current collector, according to an example.
  • like numerals may describe similar components in different views.
  • Like numerals having different letter suffixes may represent different instances of similar components.
  • the drawings illustrate generally, by way of example, but not by way of limitation, various embodiments discussed in the present document.
  • FIGS. 1A and IB illustrate generally examples of a monopolar battery architecture 102 and a bipolar battery architecture 202.
  • a current collector generally includes an active material of a single polarity (e.g., positive or negative) applied to both (e.g. opposite) sides of the current collector, such as including application of the active material in paste form.
  • a positive-negative pair can be formed such as including the first plate 120A having a first polarity active material and a second plate 120B having an opposite second polarity active material, to form an electrochemical cell in the electrolyte 114, such as shown illustratively in FIG 1A.
  • a single cell voltage can be around 2.
  • a number of cells can be arranged electrically in parallel configuration as a stack 132A. Individual stacks 132A through 132N can be connected in series to assemble a battery pack 102.
  • a first terminal 130A can provide a first polarity
  • a second terminal 130B can provide an opposite second polarity.
  • the first and second terminals can be coupled to the first stack 132A and last stack 132N, respectively, and the stacks can be coupled together serially using a first bus 124A through an "Nth" bus 124N.
  • a battery architecture 202 as shown illustratively in FIG. IB using a bipolar plate configuration, can provide a simpler configuration.
  • Respective positive and negative active materials can be applied, such as through pasting, onto opposite sides of the current collector to form a bipolar plate.
  • FIG. IB illustrates generally an example that can include a battery pack 202 having one or more bipolar battery plates, such as bipolar plates 121A, 121B, and 121C.
  • the bipolar plates 121A, 121B, or 121C can include different silicide layers on opposite sides of the plate assembly, such as shown and described in other examples herein.
  • a first terminal 130A can provide a first polarity
  • a second terminal 130B can provide an opposite second polarity.
  • the bipolar plates can be sandwiched with electrolyte in regions 116A and 116B, for example, to form sealed cells.
  • an electrolyte in region 1 16A can be one or more of fluidically isolated or hermetically sealed so that electrolyte cannot bypass the bipolar plate 121 A to an adjacent region such as the electrolyte region 1 16B, or to suppress or inhibit leakage of electrolyte from the pack 202.
  • cells can be disposed in a series configuration. The cells can be aligned to form a stack 131 A.
  • a current collector e.g., a silicon substrate 104 such as included as a portion of the bipolar plate 121A
  • a first bus 124A can connect to a first electrode in each stack 131A through 13 IN
  • a second bus 124B can connect to an opposite electrode in each stack 131 A through 13 IN.
  • the stacks 131 A through 13 IN can each provide serial connections through the bulk of the conductive silicon substrates as shown by the arrows. In this manner, a total number of interconnect buses external to the stack 131 A through 13 IN can be reduced as compared to an architecture using monopolar plates.
  • bipolar stacks 131 A through 13 IN can be connected in parallel for lower voltage applications, such as to assemble a lower voltage battery pack.
  • a single bipolar stack with many cells can form a higher-voltage pack.
  • a bipolar current collector substrate In addition to electrical conduction, a bipolar current collector substrate generally isolates electrolyte between adjacent cells inside the battery, and generally the materials used for the current collector are specified to suppress or inhibit corrosion when immersed or surrounded in the electrolyte (e.g., H 2 SO 4 ) throughout the lifetime of the battery.
  • a current collector substrate can be specified to include a high electronic conductivity but a low ionic conductivity such that it acts as a current collector which also isolates an intercell through-diffusion of electrolyte.
  • the substrate can be specified to resist H 2 SO 4 corrosion, and its surface can be specified to be inert towards passivation in H2SO4. Such passivation can render the current collector non-conductive.
  • the current collector surface is generally specified to have a wider and more stable potential window as compared to the charge and discharge electrochemical reactions of the battery.
  • the cathode and anode surfaces are generally specified to have higher oxygen and hydrogen evolution over- potentials than those on PbC ⁇ and Pb, respectively, and the over-potentials are specified to be relatively stable throughout the lifetime of the battery.
  • the high over-potentials can help to reduce or minimize gas evolution due to water electrolysis side reactions at the electrodes. Such side reactions can lead to one or more of coulombic efficiency reduction, active material loss, capacity fade, or premature failure of the battery.
  • silicon can be used, such as a substrate, for a current collector for a bipolar lead acid battery.
  • silicon wafers are readily available in different sizes and shapes, and are widely used in different industries.
  • Mono-crystalline or poly-crystalline silicon are generally impervious to H2SO4, and can be doped to achieve a specified conductivity.
  • an insulating oxide can form on a silicon surface, a variety surface modification processes can be used to provide desired chemical and electrochemical surface properties.
  • a metal silicide can be formed on a silicon surface by annealing a metal thin film deposited on the surface.
  • a metal silicide generally forms a low resistivity ohmic contact with the silicon, protects the underlying silicon from oxidation or passivation, and extends an electrochemical stability window of the surface.
  • One or more thin films can be deposited onto the substrate to enhance its surface properties towards active material adhesion, such as one or more thin films deposited after silicide formation.
  • FIG. 2 illustrates generally a section view of an example including a bipolar battery plate 121 A, such as can be included as a portion of a bipolar battery assembly 200.
  • the first bipolar battery plate 121 A can include a rigid conductive silicon substrate 104 as a current collector.
  • the silicon substrate 104 can include a circular, clipped, square, or rectangular configuration, such as including a thin wafer.
  • the silicon substrate 104 can include semiconductor grade, solar grade, or metallurgical grade silicon, and the silicon substrate 104 need not be mono-crystalline.
  • the silicon substrate 104 can include one or more dopants or impurities, such as to enhance a bulk conductivity of the substrate 104.
  • the bipolar battery plate 121 A can include one or more of an ohmic contact layer 106A and an adhesion layer 108A located at or near a first surface of the conductive silicon wafer 104.
  • An active material 1 12A can be applied or deposited on the plate 121A, such as including a first polarity, such as supported during or after fabrication by a mechanical support 1 10A.
  • a second ohmic contact layer 106B can be included on a second surface of the conductive silicon wafer 104 opposite the first surface.
  • the second ohmic contact layer 106B can include the same material as the first ohmic contact layer 106A or a different material, such as to provide an electrode for connection to other portions of a battery assembly, to provide a corrosion-resistant layer, or to provide a mirror image configuration having a stack-up similar to the first surface of the conductive silicon wafer 104.
  • a second adhesion layer 108B can also be included.
  • a second active material 1 12B can be included, such as having a polarity opposite the first active material 1 12A.
  • the first and second contact layers 106A and 106B can be formed using one or more techniques described elsewhere herein, such as including sequentially or contemporaneously annealed silicide layers.
  • a first electrolyte region 1 16A can separate the battery plate 121A from an adjacent battery plate 121C, and a second electrolyte region 116B can separate the battery plate 121A from another adjacent battery plate 12 IB.
  • the electrolyte regions 1 16A and 1 16B can include a separator, such as assist in maintaining a specified separation between the battery plates.
  • the electrolyte regions 1 16A and 1 16B are generally fluidically isolated from each other so that conduction occurs serially through a bulk of the conductive silicon substrate 104.
  • the first and second active materials 112A and 1 12B can include positive and negative active materials, respectively, such as located (e.g., formed or deposited) on opposite sides of the bipolar plate 121 A as shown illustratively in FIG. 2.
  • Surface modification processes applied to the silicon wafer substrate can be specified to provide a surface compatible with both cathode and anode electrochemistry. However, in some configurations different surface modifications can be used for the two sides of the bipolar substrate.
  • the present inventors have also recognized that it may be beneficial to tailor surface chemical and electrochemical properties for the cathode and anode side of the substrate 104 independently, such as with respective (e.g., different) surface
  • a metal with a higher sintering temperature which is stable to higher temperature, can be deposited onto one side of the silicon substrate 104 and annealed to form a first metal silicide.
  • the second metal can then deposited onto the opposite side of the substrate 104, and the substrate 104 can then be annealed at the lower sintering temperature, at which the first silicide is stable, to form a second silicide.
  • modified silicon current collector substrates can be fabricated with positive and negative active materials, sealed to isolate individual cells, stacked with separators, and filled with electrolytes, such as in a manner in which the cells are in a series configuration as shown illustratively in the bipolar stacks of FIG. 1A and the example of FIG. 2.
  • FIGS. 3A and 3B illustrate generally scanning electron micrographs of silicides formed upon silicon, with a nickel silicide (NiSi) layer shown in FIG. 3A and a titanium silicide (TiSi 2 ) layer shown in FIG. 3B.
  • a bipolar battery plate can be fabricated including a substrate material such as silicon as a base material for the current collector, such as for use in a bipolar lead acid battery.
  • one or more thin film materials can be formed on a rigid conductive silicon substrate, such as to render the substrate surface suitable for use in an environment internal to a lead acid battery.
  • such a current collector e.g., for a bipolar lead acid battery
  • Silicon wafers are generally available in different sizes and shapes. For example, silicon wafers such as for use in photovoltaic applications can be obtained in a square geometry having sides of about 125 or about 156 millimeters. Although silicon wafers can be made extremely pure, metallurgical grade silicon can be produced economically and can be suitable for use as a substrate for a current collector. Silicon is generally impervious to sulfuric acid (H 2 SO 4 ), and can be doped to achieve good electronic conductivity. For example, an electrical resistivity of ⁇ 1 milli-Ohm-centimeter (mQcm) can be provided at least in part using suitable doping.
  • H 2 SO 4 sulfuric acid
  • mQcm milli-Ohm-centimeter
  • a silicon bipolar plate When used as a bipolar current collector in a bipolar lead acid battery, a silicon bipolar plate can provide an intercell electronic connection (e.g., through the silicon substrate) and at the same time such a collector configuration can isolate adjacent cells to inhibit electrolyte diffusion from cell-to-cell.
  • a metal silicide can be formed on one or more surfaces of the substrate to provide an ohmic contact.
  • a metal silicide can be formed by first depositing a metal layer with thickness of about 50 to about 200 nanometers (nm) on the surface. The metal film can then be annealed such that it reacts with the underlying silicon to form a silicide layer on the silicon surface. As silicon is consumed and incorporated into the silicide layer, a resulting silicide is generally thicker than the deposited metal film.
  • Ni nickel
  • Co cobalt
  • Ti titanium
  • Ta tantalum
  • W tungsten
  • Mo molybdenum
  • pM and pS can represent the electrical resistivities of the metal and the metal silicide (in unites of micro- ohm-centimeters), respectively, and where t s / t M can represent a ratio of the silicide film thickness to the original metal film thickness.
  • RTP refers generally to "Rapid Thermal Processing.”
  • about 50 nanometers of nickel can be deposited on a silicon wafer surface by physical vapor deposition (PVD). The nickel film can then be annealed at about 480°C for 2 minutes, such as to obtain a nickel silicide layer with a thickness of about 110 nanometers.
  • a scanning electron micrograph 321A of the Si-NiSi illustrates generally a blurred interface between the two materials, which indicates that iSi 306A forms a good ohmic contact with low contact resistance on the silicon 304 surface.
  • FIGS. 4A and 4B illustrate generally glancing incidence x-ray diffraction (XRD) spectra for a nickel silicide (NiSi) layer in FIG. 4A and titanium silicide (TiSi 2 ) in FIG. 4B. Multiple silicide phases can exist for a metal.
  • XRD glancing incidence x-ray diffraction
  • a desired silicide phase can be obtained by a technique including rapid thermal processing (RTP), in which the annealing process parameters can be controlled precisely.
  • RTP rapid thermal processing
  • Metal silicides formed with RTP generally have high phase purity as illustrated generally in the x-ray diffraction spectra of NiSi in FIG. 4A, and TiSi 2 in FIG. 4B.
  • the NiSi of FIG. 4A can be formed by annealing 50 nm of Ni on silicon at 480°C for 2 minutes, while the TiSi 2 of FIG. 4B can be obtained by annealing 60nm of Ti on silicon at 860°C for 30 seconds.
  • FIGS. 5A, 5B, and 5C illustrate generally various examples of scanning electron micrographs showing a nickel silicide after various durations of exposure to H2SO4.
  • metal silicides are generally stable towards H2SO4 corrosion.
  • scanning electron microscopy experiments illustrate generally that NiSi is stable towards H2SO4 corrosion when exposed to H2SO4 for an extended period of time. Specifically, when NiSi samples are immersed into H2SO4, the thickness of NiSi can remain stable, such as after an exposure duration of 6 months. In addition, no degradation of surface morphology or interface integrity is generally observed in the progression of FIGS. 5A, 5B, and 5C.
  • the scanning electron micrographs 521 A include NiSi 506A formed on Si 504 (imaged just after deposition) in FIG. 5 A, NiSi 506A formed on Si 504 after exposure to H 2 S0 4 for 1 month in FIG. 5B, and NiSi 506A formed on Si 504 after H 2 S0 4 exposure for 3 months.
  • a surface of a current collector is generally established to be electrochemically stable with respect to the electrochemical reactions of the surrounding battery chemistry (e.g., lead acid chemistry in the example of a lead acid battery). This is because side reactions can occur preferentially on the surface of the current collector, and reaction products can undesirably passivate the current collector surface, such as rendering it electrically insulating. Gas evolution reactions can accelerate active material detachment from the current collector. Such side reactions can contribute to premature efficiency loss, capacity degradation, and eventual failure of the battery.
  • An electrochemical stability window 660 of NiSi 630 and a stability window 650 of TiSi 2 620 can be compared with the window 640 of lead acid chemistry using cyclic voltammetry. The illustrative example of FIG.
  • both NiSi 630 and TiSi2 620 have wider electrochemical stability windows 650 and 660 with respect to the charge-discharge electrochemical reactions of the lead acid battery as compared to the lead window 640.
  • both NiSi 630 and TiSi 2 620 have higher over-potential for oxygen evolution than a lead electrode, and both NiSi 630 and TiSi 2 620 have high over- potential for hydrogen evolution.
  • Experimentally-obtained results generally indicate that TiSi 2 620 has a wider electrochemical stability window 650 than the window 660 of NiSi 630, as shown generally in FIG. 6.
  • FIG. 7 illustrates generally examples of techniques 700A and 700B, such as methods, that can be used to form silicides on silicon substrates.
  • Fabrication of a current collector with the same metal silicide on both sides of the wafer can be performed by depositing a metal species onto both sides of the wafer.
  • the wafer can then be annealed at the appropriate sintering temperature of the metal silicide.
  • an oxidation-resistant surface with high oxidation evolution over-potential can be specified for a contact layer on a positive side of the bipolar plate, and a corrosion-resistant surface with high hydrogen evolution over-potential can be specified at a contact layer on a negative side of the bipolar plate.
  • a "single anneal" or a "double anneal” approach can be used, for example.
  • the two metal silicide materials can have similar formation temperatures.
  • a first metal film can be deposited, such as using a vapor deposition technique.
  • a different second metal film can be deposited, such as using a vapor deposition technique.
  • both metals can be contemporaneously annealed using a temperature range sufficient to form both silicide layers.
  • tantalum disilicide TaSi 2
  • tungsten disilicide WS1 2 which has slow surface oxidation rate
  • These two silicides generally have similar formation temperatures, at about 1000°C, so a "single anneal" approach can be used.
  • about 50 to about 200 nanometers of tantalum can be deposited onto a first surface of a silicon wafer, and about 50 to about 200 nanometers of tungsten deposited onto a second surface opposite the first surface.
  • an order in which the two metals are deposited does not matter in this example.
  • the wafer can then be annealed at a temperature of about 1000°C to form TaSi 2 and WS1 2 contemporaneously.
  • Such a "single anneal" approach can also be used with other metal silicide combinations that have similar formation temperatures.
  • two different metal silicides can be formed using different formation temperatures. For example, at 71 1, a metal with a higher silicide formation temperature can first be deposited onto a first surface of the silicon wafer, then at 721 the wafer can be annealed to form a first metal silicide. At 731, a second metal, which has a lower silicide formation temperature, can be deposited onto a second surface of the wafer opposite the first surface. At 741, the wafer can be annealed again.
  • the first metal silicide is formed at a higher temperature, it can remain stable at the formation temperature of the second metal silicide if a peak temperature of the second annealing operation at 741 is specified to remain below a temperature range of the first annealing operation at 721, or if the thermal processing conditions are otherwise specified to inhibit damage to the first silicide layer formed during the first annealing operation.
  • titanium disilicide TiSi 2 can be formed on the negative side of the bipolar plate, and a nickel silicide NiSi can be formed at the positive side of the bipolar plate.
  • TiSi 2 -NiSi bipolar plate about 50 to about 200 nanometers of titanium (Ti) can be deposited onto one side of the wafer, then the wafer can be annealed from about 800°C to about 900°C to form titanium disilicide (TiSi 2 ). Then, about 50 to about 200 nanometers of nickel Ni can be deposited onto the other side of the wafer, followed by annealing from to about 450°C to about 500°C to form nickel silicide (NiSi). Because TiSi 2 is generally stable in the range from about 450°C to about 500°C, it is not affected by the second annealing operation.
  • lead (Pb) or lead-tin (Pb-Sn) can be deposited onto the negative side of the bipolar plate, whereas lead dioxide (PbC> 2) , tin dioxide (Sn0 2 ), or lead-tin dioxide (Pb x Sni_ x 0 2 ) can deposited onto the positive side of the bipolar plate.
  • an ohmic contact layer can be formed on at least one surface of the conductive silicon wafer.
  • Such an ohmic contact layer can include a silicide.
  • each face of the wafer can include an ohmic contact layer, and the ohmic contact layers on each face need not be the same material or thickness as each other.
  • the ohmic contact layers can include different silicides.
  • One or more other layers e.g., adhesion or barrier layers
  • an arrayed pattern can be formed (such as placed or deposited) on the conductive silicon wafer, such as upon the ohmic contact layer, to provide or enhance mechanical support of the active material pastes.
  • a square or rectangular grid pattern e.g., a scaffold structure
  • such a grid can include Pb deposited on the surface of the conductive silicon wafer, such as by electrodeposition.
  • electrodeposition can include use of a mechanical (e.g., contact) mask.
  • the grid can include an acid-resistant polymer material.
  • an array of bumps or mesas can be formed (e.g., placed or deposited) on the current collector, such as by electrodeposition.
  • an array of Sn, Pb-Sn, or In-Sn solder pastes can be applied onto the current collector, such as by pasting, heat pressing, extrusion dispense, or screen printing.
  • the array pattern can adhere naturally onto a Pb adhesion surface (e.g., adhesion layer) of the assembly. While the wafer, grid, and bump pattern configurations shown in FIG. 8 are rectangular, other shapes and symmetries can be used.
  • paste formulations and processing procedures compatible with generally-available lead acid batteries can be used to apply active material paste directly onto the silicon wafer assembly.
  • conductive silicon wafers can be made compatible with such pasting equipment, such as with modifications to adapt such equipment to the size of such wafers.
  • silicon has a high melting point and good thermal conductivity
  • curing temperatures used for generally-available pasting processes can be used to cure active material pastes as a portion of the current collector assembly including the conductive silicon wafer. With higher curing temperatures, a mechanical support including a Pb grid array pattern or a Sn solder bump array can be fused with the active material pastes on the current collector, which can result in strong adhesion and desirable mechanical support.
  • the external grid can be made of H2SO4 resistant plastic such as one or more of acrylonitrile butadiene styrene (“ABS”), low density polyethylene (“LDPE”), polypropylene (“PP”), polyvinylidene fluoride (“PVDF”), or polytetrafluoroethylene (“PTFE”).
  • ABS acrylonitrile butadiene styrene
  • LDPE low density polyethylene
  • PP polypropylene
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • an external grid can be formed of carbon graphite, which can have an advantage of being electrically conductive.
  • the pasted grids can be then sandwiched with the wafer collector, and cured to form a bipolar plate assembly (see, e.g., FIG. 2), such as a bipolar battery plate as described in other examples herein.
  • a conductive silicon wafer can be formed, such as using one or more techniques described elsewhere herein.
  • one or more layers such as an ohmic contact or adhesion layer can be deposited, such as described in other examples elsewhere herein.
  • an "external" mechanical support can be formed, such as can include a grid structure or other shape. As mentioned in examples elsewhere herein, such a mechanical support can be conductive or non-conductive.
  • a paste material can be applied, such as a first polarity active material paste to a first mechanical support, and a second polarity active material paste to a second mechanical support.
  • the first and second pasted mechanical supports can be applied to the conductive silicon wafer.
  • one or more of the pastes can be cured, such as thermally.
  • Battery plate assemblies can be one or more of encased or edge-sealed with mechanical casings.
  • the casings can be made of plastics such as acrylonitrile butadiene styrene (ABS) plastic.
  • the casing can be made from one or more of polypropylene (PP), polyvinyl chloride (PVC), or polytetrafluoroethylene (PTFE).
  • PP polypropylene
  • PVC polyvinyl chloride
  • PTFE polytetrafluoroethylene
  • plastics infused with fullerene particles, nanotubes, or graphene can be used to improve the thermal conductivity of the mechanical casings.
  • the current collectors can be hermetically sealed to the mechanical casing such as using adhesives, or by contact without adhesives.
  • the current collector can be edge-sealed directly onto a casing portion with an acid-resistant epoxy adhesive.
  • a seal ring made of expanded PTFE can be epoxied onto the edge of the silicon current collector, and the sealed current collector can be adhered (e.g., epoxied) to the casing ring.
  • the expanded PTFE seal ring acts can be configured as a shock absorber between the current collector and the casing.
  • current collectors are edges sealed to the casing using
  • Example 1 can include or use subject matter (such as an apparatus, a method, a means for performing acts, or a device readable medium including instructions that, when performed by the device, can cause the device to perform acts), such as can include forming a bipolar battery plate, including depositing a first metal layer on a first surface of a rigid silicon substrate, depositing a different second metal layer on a second surface of the rigid silicon substrate opposite the first surface, and annealing the first and second metal layers to form a first silicide on the first surface and a different second silicide on the second surface of the rigid silicon substrate.
  • subject matter such as an apparatus, a method, a means for performing acts, or a device readable medium including instructions that, when performed by the device, can cause the device to perform acts
  • Example 2 can include, or can optionally be combined with the subject matter of Example 1, to optionally include annealing the first and second metal layers to form the first and second silicides including annealing the silicon wafer using a temperature range sufficient to form both silicide layers contemporaneously
  • Example 3 can include, or can optionally be combined with the subject matter of one or any combination of Examples 1 or 2 to optionally include a first silicide comprising tantalum disilicide, and a second silicide comprising tungsten disilicide.
  • Example 4 can include, or can optionally be combined with the subject matter of Example 1 to optionally include annealing the first and second metal layers including annealing the first metal layer to form the first silicide using a first annealing temperature range and separately annealing the second metal layer to form the second silicide using a second annealing temperature range.
  • Example 5 can include, or can optionally be combined with the subject matter of Example 4 to optionally include a peak of the second annealing temperature range lower than temperatures within the first annealing temperature range, wherein the first silicide remains stable within the second annealing temperature range.
  • Example 6 can include, or can optionally be combined with the subject matter of one or any combination of Examples 4 or 5 to optionally include a first silicide comprising titanium silicide, and a second silicide comprising nickel silicide.
  • Example 8 can include, or can optionally be combined with the subject matter of Example 7 to optionally include at least one of the first and second adhesion layers comprising one of a soft metal, a metal alloy, or a metal oxide.
  • Example 9 can include, or can optionally be combined with the subject matter of one or any combination of Examples 7 or 8 to optionally include at least one of the first or second adhesion layers comprising one or more of lead or tin.
  • Example 10 can include, or can optionally be combined with the subject matter of one or any combination of Examples 7 through 9 to optionally include at least one of the first or second adhesion layers comprising a compound including lead and oxygen.
  • Example 11 can include, or can optionally be combined with the subject matter of one or any combination of Examples 7 through 10 to optionally include first and second adhesion layers comprising the same material.
  • Example 12 can include, or can optionally be combined with the subject matter of one or any combination of Examples 7 through 10 to optionally include a first adhesion layer comprising a first material, and a second adhesion layer comprising a different second material.
  • Example 13 can include, or can optionally be combined with the subject matter of one or any combination of Examples 7 through 12 to optionally include first and second adhesion layers specified for compatibility with lead acid battery chemistry.
  • Example 14 can include, or can optionally be combined with the subject matter of one or any combination of Examples 7 through 13 to optionally include applying a first active material having a first conductivity type to the first adhesion layer, and applying a second active material having an opposite second conductivity type to the second adhesion layer.
  • Example 15 can include, or can optionally be combined with the subject matter of one or any combination of Examples 1 through 14 to include, subject matter (such as an apparatus, a method, a means for performing acts, or a machine readable medium including instructions that, when performed by the machine, that can cause the machine to perform acts), such as can include forming a bipolar battery plate, including depositing a first metal layer on a first surface of a rigid silicon substrate, depositing a different second metal layer on a second surface of the rigid silicon substrate opposite the first surface, annealing the first and second metal layers to form a first silicide on the first surface and a different second silicide on the second surface of the rigid silicon substrate, including annealing the silicon wafer using a temperature range sufficient to form both silicide layers contemporaneously, depositing a first adhesion layer on the first silicide, and depositing a second adhesion layer on the second silicide.
  • subject matter such as an apparatus, a method, a means for performing acts, or a machine readable
  • Example 16 can include, or can optionally be combined with the subject matter of Example 15, to optionally include a first silicide comprising tantalum disilicide, and a second silicide comprising tungsten disilicide.
  • Example 17 can include, or can optionally be combined with the subject matter of one or any combination of Examples 15 or 16 to optionally include at least one of the first or second adhesion layers including one or more of lead (Pb) or tin (Sn).
  • Pb lead
  • Sn tin
  • Example 18 a peak of the second annealing temperature range can be lower than temperatures within the first annealing temperature range, and the first silicide remains stable within the second annealing temperature range.
  • Example 19 can include, or can optionally be combined with the subject matter of Example 18, to optionally include a first silicide comprising titanium silicide and a second silicide comprising nickel silicide.
  • Example 20 can include, or can optionally be combined with the subject matter of one or any combination of Examples 18 or 19 to optionally include at least one of the first or second adhesion layers includes one or more of lead or tin.
  • Example 21 can include, or can optionally be combined with any portion or combination of any portions of any one or more of Examples 1 through 20 to include, subject matter that can include means for performing any one or more of the functions of Examples 1 through 20, or a machine-readable medium including instructions that, when performed by a machine, cause the machine to perform any one or more of the functions of Examples 1 through 20.
  • Method examples described herein can be machine or computer-implemented at least in part. Some examples can include a computer-readable medium or machine-readable medium encoded with instructions operable to configure an electronic device to perform methods as described in the above examples.
  • An implementation of such methods can include code, such as microcode, assembly language code, a higher-level language code, or the like. Such code can include computer readable instructions for performing various methods. The code may form portions of computer program products. Further, in an example, the code can be tangibly stored on one or more volatile, non-transitory, or nonvolatile tangible computer-readable media, such as during execution or at other times.
  • Examples of these tangible computer-readable media can include, but are not limited to, hard disks, removable magnetic disks, removable optical disks (e.g., compact disks and digital video disks), magnetic cassettes, memory cards or sticks, random access memories (RAMs), read only memories (ROMs), and the like.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

L'invention concerne un appareil et des techniques permettant la fourniture d'une plaque de batterie bipolaire de telle sorte qu'elle puisse être incluse comme partie intégrante d'un ensemble de dispositif de stockage d'énergie, tel qu'une batterie. La plaque de batterie bipolaire peut comprendre un substrat de silicium. Une première couche métallique peut être déposée sur une première surface du substrat de silicium rigide et une seconde couche métallique peut être déposée sur une seconde surface du substrat de silicium rigide qui est opposée à la première surface. Les première et seconde couches métalliques peuvent être recuites pour former un premier siliciure sur la première surface et un second siliciure sur la seconde surface du substrat de silicium rigide.
PCT/US2015/016622 2011-05-11 2015-02-19 Collecteur de courant pour une batterie plomb-acide WO2015127081A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US15/242,206 US10008713B2 (en) 2011-05-11 2016-08-19 Current collector for lead acid battery

Applications Claiming Priority (2)

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US201461941756P 2014-02-19 2014-02-19
US61/941,756 2014-02-19

Related Parent Applications (1)

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US14/477,312 Continuation-In-Part US9570737B2 (en) 2011-05-11 2014-09-04 Wafer-based bipolar battery plate

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107557957A (zh) * 2017-09-14 2018-01-09 清华大学 一种可以刚柔切换的织物材料
US10008713B2 (en) 2011-05-11 2018-06-26 Gridtential Energy, Inc. Current collector for lead acid battery
US10290904B2 (en) 2011-05-11 2019-05-14 Gridtential Energy, Inc. Wafer-based bipolar battery plate
CN112054253A (zh) * 2020-07-30 2020-12-08 济南大学 一种用于修复失效铅酸蓄电池的活化增容剂的制备方法与应用
WO2022265916A1 (fr) * 2021-06-14 2022-12-22 Gridtential Energy, Inc. Collecteur de courant conducteur pour batterie bipolaire

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5837601A (en) * 1996-01-25 1998-11-17 Sony Corporation CMOS semiconductor device having dual-gate electrode construction and method of production of the same
US6500585B1 (en) * 1997-03-12 2002-12-31 Nederlandse Organisatie Voor Toegepastnatuurwetenschappelijk Onderzoerk Tno Method for manufacturing a bipolar plate
US20080090129A1 (en) * 2006-06-12 2008-04-17 Kunz H R Bipolar plate for fuel cell
US7479466B2 (en) * 2006-07-14 2009-01-20 Taiwan Semiconductor Manufacturing Co., Ltd. Method of heating semiconductor wafer to improve wafer flatness
WO2012155082A1 (fr) * 2011-05-11 2012-11-15 Gridtential Energy, Inc. Batterie améliorée et procédé d'assemblage
US8633373B2 (en) * 2008-05-12 2014-01-21 Mtpv Power Corporation Sub-micrometer gap thermophotovoltaic structure (MTPV) and fabrication method therefor

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5837601A (en) * 1996-01-25 1998-11-17 Sony Corporation CMOS semiconductor device having dual-gate electrode construction and method of production of the same
US6500585B1 (en) * 1997-03-12 2002-12-31 Nederlandse Organisatie Voor Toegepastnatuurwetenschappelijk Onderzoerk Tno Method for manufacturing a bipolar plate
US20080090129A1 (en) * 2006-06-12 2008-04-17 Kunz H R Bipolar plate for fuel cell
US7479466B2 (en) * 2006-07-14 2009-01-20 Taiwan Semiconductor Manufacturing Co., Ltd. Method of heating semiconductor wafer to improve wafer flatness
US8633373B2 (en) * 2008-05-12 2014-01-21 Mtpv Power Corporation Sub-micrometer gap thermophotovoltaic structure (MTPV) and fabrication method therefor
WO2012155082A1 (fr) * 2011-05-11 2012-11-15 Gridtential Energy, Inc. Batterie améliorée et procédé d'assemblage

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
OTTAVIANI, G ET AL.: "Reliability and degradation: Mechanisms and interfacial layers in silicide formation.", 1981, pages 105 - 149 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10008713B2 (en) 2011-05-11 2018-06-26 Gridtential Energy, Inc. Current collector for lead acid battery
US10290904B2 (en) 2011-05-11 2019-05-14 Gridtential Energy, Inc. Wafer-based bipolar battery plate
CN107557957A (zh) * 2017-09-14 2018-01-09 清华大学 一种可以刚柔切换的织物材料
CN112054253A (zh) * 2020-07-30 2020-12-08 济南大学 一种用于修复失效铅酸蓄电池的活化增容剂的制备方法与应用
WO2022265916A1 (fr) * 2021-06-14 2022-12-22 Gridtential Energy, Inc. Collecteur de courant conducteur pour batterie bipolaire

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