US20060201801A1 - Electrochemical cell suitable for use in electronic device - Google Patents

Electrochemical cell suitable for use in electronic device Download PDF

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US20060201801A1
US20060201801A1 US10/538,769 US53876903A US2006201801A1 US 20060201801 A1 US20060201801 A1 US 20060201801A1 US 53876903 A US53876903 A US 53876903A US 2006201801 A1 US2006201801 A1 US 2006201801A1
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nickel
electronic device
portable electronic
mesoporous structure
hydroxide
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Philip Bartlett
John Owen
Phillip Nelson
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University of Southampton
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    • 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
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
    • 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
    • H01M10/34—Gastight accumulators
    • H01M10/345—Gastight metal hydride 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • 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
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/32—Nickel oxide or hydroxide 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • 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
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • 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 present invention relates to a novel electrochemical cell, which may be a battery or a supercapacitor or both, and which is suitable for use in portable and other electronic devices, and specifically to such a cell having at least the positive electrode formed of a mesoporous material having a periodic arrangement of substantially uniformly sized pores of cross-section of the order of 10 ⁇ 8 to 10 ⁇ 9 m.
  • battery is used herein in its common meaning of a device that converts the chemical energy contained in its active components directly into electrical energy by means of a redox (oxidation-reduction) reaction.
  • the basic unit of a battery is an electrochemical cell, which will comprise at least a positive electrode, a negative electrode and an electrolyte, the whole contained within a casing. Other components, such as separators, may be included, as is well known in the art.
  • a battery may consist of one or more such cells.
  • the present invention provides an electrochemical cell, which may, for example, be used in a portable electronic device, said cell having a positive electrode, a negative electrode and an electrolyte, characterised in that at least the positive electrode comprises a mesoporous structure having a periodic arrangement of substantially uniformly sized pores of cross-section of the order of 10 ⁇ 8 to 10 ⁇ 9 m.
  • the invention also provides a portable electronic device containing such an electrochemical cell.
  • the invention still further provides an automotive battery comprising a plurality of the electrochemical cells of the present invention.
  • the electrochemical cell of the present invention maybe constructed to function as a battery, as a supercapacitor or as a combined battery/supercapacitor.
  • a supercapacitor having mesoporous positive and negative electrodes operates via the mechanism of proton shuttling between a mesoporous positive electrode, e.g. of Ni(OH) 2 , and a hydrogen absorbing mesoporous negative electrode, e.g. of palladium, as illustrated in the schematic of FIG. 1 .
  • the mechanism is similar to that operating in Ni-MH batteries where the palladium is replaced by another hydrogen absorbing material such as LaNi 5 .
  • portable electronic devices which may include the electrochemical cell of the present invention include: portable computers, including the so-called notebook computers, desktop replacement computers, ultraportable computers etc. (the present invention being of particular value in the smaller versions, such as the ultraportables); mobile telephones; cordless (landline) telephones; PDAs; portable hard disk drives; music players of various sorts, including CD players, cassette players, mini-disk players and other digitally recorded music players, including MP3 and like software-based music players; portable televisions; portable DVD players; portable radios; hybrid devices (i.e. devices serving two or more previously separate functions), such as PDA/mobile telephones, telephone/music players, hard disk storage/music players etc.; and medical devices, such as defibrillators.
  • portable computers including the so-called notebook computers, desktop replacement computers, ultraportable computers etc. (the present invention being of particular value in the smaller versions, such as the ultraportables); mobile telephones; cordless (landline) telephones; PDAs; portable hard disk drives; music players of various sorts,
  • the electrochemical cells of the present invention may also be used in automotive batteries.
  • At least the positive electrode, the cathode, of the electrochemical cell of the present invention is formed of a mesoporous material.
  • the material is preferably a metal, a metal oxide, a metal hydroxide, a metal oxy-hydroxide or a combination of any two or more of these.
  • metals include: nickel; alloys of nickel, including alloys with a transition metal, nickel/cobalt alloys and iron/nickel alloys; cobalt; platinum; palladium; and ruthenium.
  • Such oxides, hydroxides and oxy-hydroxides include: gold oxide; palladium oxide; nickel oxide (NiO); nickel hydroxide (Ni(OH) 2 ); nickel oxy-hydroxide (NiOOH); and ruthenium oxide. Of these, we most prefer nickel and its oxides and hydroxides.
  • conditioning As is well known in the field, certain of these materials require “conditioning” before use. This may be achieved by putting the cell through several cycles of charging and discharging, as is conventional in the art.
  • a typical material requiring such conditioning is nickel, which, as a result of the conditioning, will acquire a surface layer of an oxide.
  • any material may be used having regard to the chemistry of the cell which is to be made.
  • suitable materials include: carbon; cadmium; iron; a palladium/nickel alloy; an iron/titanium alloy; palladium; or a mixed metal hydride, for example LaNi 5 H x .
  • These materials are preferably porous, and more preferably mesoporous. Of these, preferred materials are carbon and palladium. Mesoporous palladium is, however, not the preferred negative electrode material for low cost applications, due to its high cost.
  • anode and cathode are Nickel/Palladium, Nickel/Carbon, Nickel/Iron and Nickel/Cadmium, of which Nickel/Carbon is most preferred. Where reference is made to nickel, the oxides and hydroxides thereof are also included.
  • the mesoporous structure of the positive electrode comprises nickel and an oxide, hydroxide or oxy-hydroxide of nickel selected from NiO, Ni(OH) 2 and NiOOH, said nickel oxide or hydroxide forming a surface layer over said nickel and extending over at least the pore surfaces, and the negative electrode comprises nanoparticulate carbon.
  • the positive electrode and the negative electrode each comprise a mesoporous structure having a periodic arrangement of substantially uniformly sized pores of cross-section of the order of 10 ⁇ 8 to 10 ⁇ 9 m.
  • the positive electrode, and the negative electrode if it also is mesoporous, consists of or consists substantially of the mesoporous structure or structures as defined.
  • mesoporous structure By “mesoporous structure”, “mesoporous material” and “mesoporous film” as referred to herein are meant structures, materials and films, respectively, that have been fabricated via a liquid crystal templating process, and that consequently are monolithic in nature, and contain a long range, regular arrangement of pores having a defined topology and a substantially uniform pore size (diameter). Accordingly, the mesoporous structures, materials and films may also be described as nanostructured or having nanoarchitecture.
  • the mesoporous materials used in accordance with the invention are distinct from poorly crystallised materials and from composites with discrete nano-sized solid grains, e.g. conventionally denoted ‘nanomaterials’ that are composed of aggregated nanoparticulates.
  • An advantage of using mesoporous materials, compared with nanomaterials, is that electron transport within the mesoporous material does not encounter grain boundary resistances, affording superior electronic conductivity and removing power losses associated with this phenomenon.
  • the ordered porosity of the mesoporous materials used here provides a continuous and relatively straight, non-tortuous path of flow with uniform diameter, encouraging the rapid and unhindered movement of electrolyte species.
  • conventional nanoparticulate systems have a disordered porosity with voids of varying cross section interconnected by narrower intervoid spaces. As such, substances moving within the pore structure encounter a considerably tortuous path, impeding reaction rates.
  • the mesoporous material is preferably in the form of a film of substantially constant thickness.
  • the mesoporous film thickness is in the range from 0.5 to 5 micrometers.
  • the mesoporous material has a pore diameter within the range from about 1 to 10 nanometres, more preferably within the range from 2.0 to 8.0 nm.
  • the mesoporous material may exhibit pore number densities in the range from 1 ⁇ 10 10 to 1 ⁇ 10 14 pores per cm 2 , preferably from 4 ⁇ 10 11 to 3 ⁇ 10 13 pores per cm 2 , and more preferably from 1 ⁇ 10 12 to 1 ⁇ 10 13 pores per cm 2 .
  • the mesoporous material has pores of substantially uniform size.
  • substantially uniform is meant that at least 75%, for example 80% to 95%, of pores have pore diameters to within 30%, preferably within 10%, and most preferably within 5%, of average pore diameter. More preferably, at least 85%, for example 90% to 95%, of pores have pore diameters to within 30%, preferably within 10%, and most preferably within 5%, of average pore diameter.
  • the pores are preferably cylindrical in cross-section, and preferably are present or extend throughout the mesoporous material.
  • the mesoporous structure has a periodic arrangement of pores having a defined, recognisable topology or architecture, for example cubic, lamellar, oblique, centred rectangular, body-centred orthorhombic, body-centred tetragonal, rhombohedral, hexagonal.
  • the mesoporous structure has a periodic pore arrangement that is hexagonal, in which the electrode is perforated by a hexagonally oriented array of pores that are of uniform diameter and continuous through the thickness of the electrode.
  • the arrangement of pores has a regular pore periodicity, corresponding to the centre-to-centre pore spacing, preferably in the range from 3 to 15 nm, more preferably in the range from 5 to 9 nm.
  • the mesoporous structure having this regular periodicity and substantially uniform pore size should extend over a portion of the electrode of the order of at least 10 times, preferably at least 100 times, the average pore size.
  • the electrode consists of or consists substantially of a structure or structures as defined.
  • pore topologies are not restricted to ideal mathematical topologies, but may include distortions or other modifications of these topologies, provided recognisable architecture or topological order is present in the spatial arrangement of the pores in the film.
  • hexagonal as used herein encompasses not only materials that exhibit mathematically perfect hexagonal symmetry within the limits of experimental measurement, but also those with significant observable deviations from the ideal state, provided that most channels are surrounded by an average of six nearest-neighbour channels at substantially the same distance.
  • cubic as used herein encompasses not only materials that exhibit mathematically perfect symmetry belonging to cubic space groups within the limits of experimental measurement, but also those with significant observable deviations from the ideal state, provided that most channels are connected to between two and six other channels.
  • the electrolyte in the cell is preferably an aqueous electrolyte, for example an aqueous alkaline electrolyte such as aqueous potassium hydroxide.
  • the mesoporous structure of the positive electrode comprises nickel and an oxide, hydroxide or oxy-hydroxide of nickel selected from NiO, Ni(OH) 2 and NiOOH, said nickel oxide, hydroxide or oxy-hydroxide forming a surface layer over said nickel and extending over at least the pore surfaces, and the negative electrode has a mesoporous structure of carbon or palladium.
  • the positive electrode represents a three-phase composite composed of an interconnected Ni current collector base, coated with Ni(OH) 2 active material which is in contact with the electrolyte.
  • the hydrous structure of the mesoporous Ni positive electrode is retained such that both surface and bulk processes can contribute to the charge capacity of the electrode.
  • the mesoporous materials used as the positive, and optionally the negative, electrodes of the electrochemical cells of the present invention are prepared by a liquid crystal templating method, and preferably are deposited as films on a substrate by electrochemical deposition from a lyotropic liquid crystalline phase. They may also be prepared by electro-less deposition, such as by chemical reduction from a lyotropic liquid crystalline phase.
  • Suitable substrates include gold, copper, silver, aluminium, nickel, rhodium or cobalt, or an alloy containing any of these metals, or phosphorus.
  • the substrate may, if desired, be microporous, with pores of a size preferably in the range from 1 to 20 micrometres.
  • the substrate preferably has a thickness in the range from 2 to 50 micrometres.
  • the substrate preferably is a substrate as above, other than gold, having a layer of gold formed on it by vapour deposition.
  • Suitable methods for depositing mesoporous materials as films onto a substrate by electrochemical deposition and chemical means are known in the art.
  • suitable electrochemical deposition methods are disclosed in EP-A-993,512; Nelson, et al., “ Mesoporous Nickel/Nickel Oxide Electrodes for High Power Applications ”, J. New Mat. Electrochem. Systems, 5, 63-65 (2002); Nelson, et al., “ Mesoporous Nickel/Nickel Oxide—a Nanoarchitectured Electrode ”, Chem. Mater., 2002, 14, 524-529.
  • Suitable chemical reduction methods are disclosed in U.S. Pat. No. 6,203,925.
  • the mesoporous material is formed by electrochemical deposition from a lyotropic liquid crystalline phase.
  • a template is formed by self-assembly from certain long-chain surfactants and water into a desired liquid crystal phase, such as a hexagonal phase.
  • Suitable surfactants include octaethylene glycol monohexadecyl ether (C 16 EO 8 ), which has a long hydrophobic hydrocarbon tail attached to a hydrophilic oligoether head group.
  • aqueous solutions can be stabilised in a desired lyotropic liquid crystal phase, for example a hexagonal phase, consisting of separate hydrophilic and hydrophobic domains, with the aqueous solution being confined to the hydrophilic domain.
  • Dissolved inorganic salts for example nickel acetate
  • Subsequent removal of the surfactant by washing in a suitable solvent, leaves a regular periodic array of pores in the electro-reduced solid, the arrangement of the pores being determined by the lyotropic liquid crystal phase selected.
  • the topology, size, periodicity and other pore characteristics may be varied by appropriate selection of the surfactant, solvent, metal salts, hydrophobic additives, concentrations, temperature, and deposition conditions, as is known in the art.
  • the mesoporous material of which the mesoporous electrode is made is preferably formed by electrodeposition or chemical deposition on a substrate. Since the mesoporous material may lack adequate mechanical strength, it is preferably used as an electrode on a substrate, and, for convenience, this is preferably the same substrate as was used in its preparation.
  • FIG. 1 represents a schematic drawing showing the flow of protons on charge and discharge to and from a Pd lattice into a NiOOH positive electrode proton sink;
  • FIG. 2 shows a comparison of the cyclic voltammetry of a 1 mm diameter H I Pd disc (—) with that of a 200 ⁇ m H I Ni disc (----) in 6 M KOH at 20 mV s ⁇ 1 ;
  • FIG. 3 shows the charge/discharge behaviour of a 200 ⁇ m H I Ni disc based supercapacitor by cyclic voltammetry at 20 mV s ⁇ 1 separated by 1 cm in 6 M KOH;
  • FIG. 4 shows the flow of charge from the device versus potential during the 20 mV s ⁇ 1 discharge depicted in FIG. 3 ;
  • FIG. 5 shows the potential step charging/discharging of a H I Ni/H I Pd supercapacitor in 6 M KOH composed of a 200 ⁇ m H I Ni disc with a 1 cm 2 H I Pd electrode in 6 M KOH;
  • FIG. 6 shows a comparison of the first fall cycle (—) of a 1 cm 2 H I Ni/1 cm 2 H I Pd supercapacitor incorporating a porous PTFE separator with the 15000 th cycle ( —— ) at 500 mV s ⁇ 1 ;
  • FIG. 7 represents a schematic drawing of the H I electrode structure showing a pore ringed by oxidised active material Ni(OH) 2 which is held in a matrix of a nickel current collector, and further showing the active material occupying 45% of the electrode bulk area;
  • FIG. 8 shows a cyclic voltammogram of nanostructured nickel/nickel hydroxide electrode, as prepared in Example 10;
  • FIG. 9 shows a cyclic voltammogram of high surface area carbon electrode, as prepared in Example 10.
  • FIG. 10 shows a cyclic voltammogram of nickel-carbon supercapacitor, as prepared in Example 10.
  • FIG. 11 shows the potential-charge relationship of the cyclic voltammogram of nickel-carbon supercapacitor of FIG. 10 ;
  • FIG. 12 shows the potential step of the nickel-carbon supercapacitor of FIG. 10 (8 cm 2 , 93.7 mg) pulsed between 0 V and 1.4 V in 6 M KOH at 25° C.;
  • FIG. 13 shows a cyclic voltammogram of a liquid crystal templated iron electrode between ⁇ 0.3 V and ⁇ 1.2 V vs. Hg/HgO in 6 M KOH at 20 mV s ⁇ 1 and 25° C., as prepared in Example 11;
  • FIG. 14 shows the potential-charge relationship of the cyclic voltammogram shown in FIG. 13 ;
  • FIG. 15 shows a cyclic voltammogram of mesoporous nickel versus liquid crystal templated iron in a two electrode set-up between 0 V and 1.4 V in 6 M KOH at 5 mV s ⁇ 1 and 25° C., as prepared in Example 11;
  • FIG. 16 shows the potential-charge relationship of the cyclic voltammogram shown in FIG. 15 .
  • Example 1 The process of Example 1 was carried out using the shorter-chain surfactant C 12 EO 8 in place of C 16 EO 8 .
  • the pore diameters as determined by TEM were found to be 17.5 ⁇ ( ⁇ 2 ⁇ ).
  • Example 1 The process of Example 1 was repeated using a quaternary mixture containing C 16 EO 8 and n-heptane in the molar ratio 2:1. As determined by TEM, the pore diameters were found to be 35 ⁇ ( ⁇ 1.5 ⁇ ).
  • a mixture having normal topology cubic phase (indexing to the Ia3d space group) was prepared from 27 wt % of an aqueous solution of hexachloroplatinic acid (33 wt % with respect to water) and 73 wt % of octaethylene glycol monohexadecyl ether (C 16 EO 8 ). Electrodeposition onto polished gold electrodes was carried out potentiostatically at temperatures between 35° C. and 42° C. using a platinum gauze counterelectrode. The cell potential difference was stepped from +0.6 V versus the standard calomel electrode to ⁇ 0.1 V versus the standard calomel electrode until a charge of 0.8 millicoulombs was passed.
  • a mixture having normal topology hexagonal phase was prepared from 50 wt % of an aqueous solution of 0.2 M nickel (II) sulphate, 0.58 M boric acid, and 50 wt % of octaethylene glycol monohexadecyl ether (C 16 EO 8 ). Electrodeposition onto polished gold electrodes was carried out potentiostatically at 25° C. using a platinum gauze counterelectrode. The cell potential difference was stepped to ⁇ 1.0 V versus the saturated calomel electrode until a charge of 1 coulomb per centimetre squared was passed. After deposition the films were rinsed with copious amounts of deionised water to remove the surfactant.
  • the washed nanostructured deposits were uniform and shiny in appearance.
  • Small angle X-ray diffraction studies of the electrodeposited tin revealed a lattice periodicity of 58 ⁇ , while transmission electron microscopy studies revealed a highly porous structure consisting of cylindrical holes with internal diameters of 34 ⁇ separated by nickel walls 28 ⁇ thick.
  • Nanostructured platinum films were deposited from an hexagonal liquid crystalline phase consisting of 2.0 g H 2 O, 3.0 g C 16 EO8 and 2.0 g hexachloroplatinic acid. Depositions were carried out on 0.2 mm diameter gold disc electrodes at a deposition potential ⁇ 0.1 V vs SCE (stepped from +0.6 V). The charge passed was 6.37 C cm ⁇ 2 . Data were obtained from cyclic voltammetry in 2M sulphuric acid between potential limits ⁇ 0.2 V and +1.2 vs SCE. The Roughness Factor is defined as the surface area determined from electrochemical experiments divided by the geometric surface area of the electrode. The results are shown in Table 2 below: TABLE 2 Effect of temperature on Roughness Factor and double layer capacitance.
  • Nanostructured platinum films were deposited from an hexagonal liquid crystalline phase consisting of 2.0 g H 2 O, 3.0 g C 16 EO 8 and 2.0 g hexachloroplatinic acid. Depositions were carried out on 0.2 mm diameter gold disc electrodes at a deposition potential indicated (stepped from +0.6 V). The charge passed was 6.37 C cm ⁇ 2 . Data were obtained from cyclic voltammetry in 2M sulphuric acid between potential limits ⁇ 0.2 V and +1.2 V vs SCE. The results are shown in Table 3 below: TABLE 3 Effect of deposition potential on Roughness Factor and double layer capacitance. E 2 Roughness Capacitance (V (vs. SCE)) Factor ( ⁇ F cm ⁇ 2 ) +0.1 34 4086 0.0 86 9268 ⁇ 0.1 261 26105 ⁇ 0.2 638 66783 ⁇ 0.3 35 3924 ⁇ 0.4 24 2250
  • Example 1 to 3 show how pore diameter can be controlled by variation of the chain length of the surfactant or by further addition of a hydrophobic hydrocarbon additive. Specifically, a comparison of Example 1 with Example 2 demonstrates that the pore size may be decreased by using a shorter-chain surfactant, whereas comparison of Example 1 with Example 3 shows that the pore size may be increased by the addition of a hydrocarbon additive to the deposition mixture.
  • Example 6 demonstrates how the thickness of the deposited film may be controlled by varying the charge passed during electrodeposition.
  • Examples 7 and 8 show how the temperature and applied potential during electrodeposition affect the surface area and the double layer capacitance of the film. As indicated by the Roughness Factor values, increasing the deposition temperature increases both the surface area and the double layer capacitance of the film. At the same time, the deposition potential may be so selected as to control the surface area and capacitance of the deposited film.
  • Gold discs 200 ⁇ m or 1 mm diameter encased in an epoxy insulator, and thin film gold electrodes (approximately 1 cm 2 ) made by evaporation of gold onto chromium-coated glass microscope slides, were prepared as follows, for subsequent deposition of mesoporous nickel and palladium electrodes:
  • the gold disc electrodes were cleaned by first polishing consecutively on 25 ⁇ m, 1 ⁇ m and 0.3 ⁇ m alumina (obtained from Buehler) embedded microcloths then cycling the electrodes between ⁇ 0.6 V and 1.4 V vs. a saturated mercury sulphate reference electrode (SMSE) at 200 mVs ⁇ 1 for 5 min. in 2 M H 2 SO 4 solution. With each cycle, a monolayer of gold oxide was formed and subsequently removed from the electrode surface.
  • SMSE saturated mercury sulphate reference electrode
  • the evaporated gold electrodes were cleaned in an ultrasonic bath of isopropanol for 60 minutes prior to deposition, then rinsed with de-ionized water and dried under ambient conditions.
  • a mixture having normal topology hexagonal (H I ) phase was prepared from 35 wt % of an aqueous solution of 0.2 M nickel (II) acetate, 0.5 M sodium acetate and 0.2 M boric acid, and 65 wt % of Brij®56 nonionic surfactant (C 16 EO n wherein n ⁇ 10, from Aldrich), and electrodeposition onto polished gold substrate was carried out potentiostatically at 25° C. using a platinum gauze counterelectrode, according to the method disclosed in Nelson et al., Chem. Mater., 2002, 14, 524-529. After deposition the films were washed in copious amounts of isopropanol for 24 hrs to remove the surfactant. A mesoporous nickel film of approximately 1 micrometer thickness and having an hexagonal arrangement of pores was obtained.
  • H I normal topology hexagonal phase
  • a mixture having normal topology hexagonal (H I ) phase was prepared from 35 wt % of an aqueous solution of 0.5 M ammonium tetrachloropalladate (Premion, from Alfa Aesar), and 65 wt % of Brij® 56 nonionic surfactant (C 16 EO n wherein n ⁇ 10 from Aldrich).
  • the presence of the H I liquid crystalline phase in the palladium deposition template solution at 25° C. was confirmed using polarising light microscopy.
  • Electrodeposition onto polished gold substrate was carried out potentiostatically at 25° C. using a platinum gauze counterelectrode, according to the electrodeposition method disclosed in Bartlett et al., Phys. Chem.
  • the cell consisted of a Pyrex water-jacketed cell connected to a Grant ZD thermostated water bath, mercury/mercury oxide (6 M KOH) reference electrode (Hg/HgO) and a large area Pt gauze counter electrode. All experiments were carried out at 25° C. and potentials in experiments involving a reference electrode are quoted against the Hg/HgO reference.
  • the efficiency of the mesoporous nickel deposition process was quantified by anodic stripping voltammetry. This involved scanning the potential of a mesoporous nickel working electrode between ⁇ 0.45 V and 0.9 V vs. a saturated calomel reference electrode (SCE) in 0.2 M HCl solution at 1 mV s ⁇ 1 .
  • the counter electrode was Pt gauze. The charge associated with the anodic nickel dissolution peak and comparison of this charge with the deposition charge gave a deposition efficiency of 34%.
  • FIG. 2 In order to compare the electrochemical characteristics of mesoporous Ni and mesoporous Pd, the cyclic voltammograms of both of these electrodes in 6 M KOH are overlaid in FIG. 2 .
  • the anodic peak for Ni at 0.38 V vs. Hg/HgO shows oxidation of Ni(OH) 2 to NiOOH via Reaction (1) with subsequent reduction back to Ni(OH) 2 represented by the cathodic peak commencing at 0.4 V.
  • the latter peak represents the proton storage capacity of the electrode, that is, the reversible capacity of the electrode for proton storage. In FIG. 2 , this is 295 mC cm ⁇ 2 .
  • liquid crystal templated mesoporous palladium as prepared in (iii) above, was used.
  • the size of the mesoporous palladium electrode was made significantly larger than the mesoporous nickel electrode such that performance limitations would be due to limitations in the nickel electrode.
  • a two-electrode supercapacitor without a separator was assembled using a 200 ⁇ m diameter mesoporous nickel positive electrode of approximately 1 ⁇ m thickness in conjunction with a 1 cm 2 mesoporous palladium electrode separated by 1 cm in 6 M KOH solution.
  • the deposition charge in synthesis of the mesoporous nickel in this case, as prepared in (ii) above, was ⁇ 1.13 mC, which corresponds to a mass of 0.117 ⁇ g when taking into account a deposition efficiency of 34%.
  • FIG. 3 shows the cyclic voltammogram of the two-electrode supercapacitor cycled in the potential range 0 V to 1.3 V.
  • the device At approximately 1.22 V the device is charged, corresponding to the removal of protons from the Ni(OH) 2 and formation of NiOOH. Discharge occurs as protons from the Pd lattice move into the NiOOH structure reforming Ni(OH) 2 as indicated by the cathodic peak.
  • the discharge current in this 20 mV s ⁇ 1 cycle peaks at 67 mA cm ⁇ 2 and the total charge passed is 257 mC cm ⁇ 2 .
  • the shape of the voltammogram of FIG. 3 more closely resembles that of a battery than a supercapacitor.
  • the majority of the charge on discharge is passed above 1.18 V.
  • FIG. 5 shows a single charge/discharge step sequence. During the anodic spike 800 mC cm ⁇ 2 of charge is passed. Discharge of the device is represented by the large cathodic spike with a maximum amplitude of 50 A cm ⁇ 2 as protons move into the NiOOH.
  • 276 mC cm ⁇ 2 is passed during the discharge step, 222 mC cm ⁇ 2 (7 ⁇ 10 ⁇ 5 C over the 200 ⁇ m diameter or 166 mA.h g ⁇ 1 ) of which is passed in the first 50 ms.
  • a supercapacitor was assembled in a configuration consisting of mesoporous nickel and palladium electrodes, as prepared in (ii) and (iii) above, deposited onto 1 cm 2 evaporated gold substrates, the mesoporous Ni and mesoporous Pd electrodes being separated by a 6 M KOH filled porous PTFE membrane.
  • the cyclability of the nickel-palladium supercapacitor was investigated by continuously cycling the device at 500 mV s ⁇ 1 in the potential range 0 V to 1.2 V. All performance data are quoted in units with respect to the mass or geometric area of the nickel electrode.
  • FIG. 6 compares the first full 4.8 s cycle with the 15000th.
  • the similar form of voltammogram shows that the electrode has not deteriorated significantly during cycling. A shift in peak potentials towards lower values is believed to be due to oxygen ingress, decreasing the average hydrogen content of the palladium electrode and therefore increasing the potential of the negative electrode. An increase in the charge per cycle is believed to be due to thickening of the oxide layer during cycling.
  • the second implication addresses the fact that not only does the mesoporous Ni electrode capacity resist decay, but actually increases with cycling.
  • This effect is rationalized by understanding that in 6 M KOH under potential cycling conditions the amount of Ni(OH) 2 in a Ni electrode can increase with time as more of the Ni base metal is oxidized. In effect this increases the amount of active material in the electrode and hence the capacity.
  • a number of groups have previously shown that the capacity of an electrodeposited Ni electrode may be increased by up to 30 times by application of the appropriate cycling conditions in alkaline solution. Here, such a large increase in capacity is not expected in the present arrangement, since during initial cycling already 45% by mass of the electrode material is utilised.
  • Nickel foil (10 ⁇ m thick) was obtained from Johnson Matthey and was prepared as follows, for subsequent deposition of mesoporous nickel.
  • the nickel foil electrodes (4 cm 2 ) were cleaned in an ultrasonic bath of isopropanol for 15 minutes prior to deposition, and were then rinsed with de-ionized water and dried under ambient conditions.
  • a mixture having normal topology hexagonal (H I ) phase was prepared from 45 wt % of an aqueous solution of 0.2 M nickel (II) acetate, 0.5 M sodium acetate and 0.2 M boric acid, and 55 wt % of Brij 56 (Brij is a trade mark) nonionic surfactant (C 16 EO n wherein n ⁇ 10, from Aldrich)
  • Electrodeposition onto the nickel foil substrate was carried out potentiostatically at ⁇ 0.9 V vs. a saturated calomel electrode and at 25° C. using a platinum gauze counterelectrode, according to the method disclosed by Nelson et al., Chem. Mater., 2002, 14, 524-529. After deposition, the films were washed in copious amounts of isopropanol for 24 hours to remove the surfactant.
  • a mesoporous nickel film of approximately 1 micrometer thickness was obtained.
  • High surface area carbon electrodes were made by mixing 90 wt. % Norit Ultra carbon (1200 m 2 g ⁇ 1 ), 5 wt. % polytetrafluoroethylene (PTFE), 2.5 wt. % acetylene black (100% compressed) and 2.5 wt. % Superior graphite with a pestle and mortar. The paste was then manually rolled into a sheet using a Durston Mini Mill rolling mill (film thickness 50-65 ⁇ m). A layer of gold (0.5 mg cm ⁇ 2 , approximately 100 nm thick) was then evaporated onto the carbon films to improve conductivity of the films. The high surface area carbon electrodes had a capacity of 70-100 F g ⁇ 1 and a mass of 0.45 mg cm ⁇ 2 .
  • FIGS. 8 and 9 In order to compare the electrochemical characteristics of mesoporous Ni and high surface area carbon, cyclic voltammograms of both types of electrode in 6 M KOH are shown in FIGS. 8 and 9 respectively.
  • the anodic peak for Ni at 0.46 V vs. Hg/HgO shows oxidation of Ni(OH) 2 to NiOOH via Reaction (1) with subsequent reduction back to Ni(OH) 2 represented by the cathodic peak at 0.32 V.
  • the presence of Ni(OH) 2 is assumed to be due to oxidation of the underlying nickel during preparation, storage and subsequent cycling or conditioning.
  • the latter peak represents the proton storage capacity of the electrode, that is, the reversible capacity of the electrode for proton storage. In FIG. 9 , this is 104 mC cm ⁇ 2 at 20 mV s ⁇ 1 between 0.6 V and ⁇ 0.5 V vs. Hg/HgO.
  • the electrochemistry of the high surface carbon electrode in 6 M KOH is typical of pure double layer behaviour and does not exhibit any faradaic electrochemistry.
  • the useful potential window of the carbon electrode in 6 M KOH is only limited by the decomposition of the solvent with hydrogen evolution at the negative limit and oxygen evolution at the positive limit. Based on comparison of the voltammetry of mesoporous Ni and high surface area carbon, it may be expected that a charge storage device using these 2 electrodes would have a discharge voltage of approximately 1.4 V since this is approximately the potential difference between the onset of hydrogen evolution at the carbon electrode ( ⁇ 1.0 V vs. Hg/HgO) and the intercalation of H + into NiOOH (0.4 V vs. Hg/HgO).
  • a two-electrode supercapacitor with a separator (Celgard, polypropylene, 25 ⁇ m, 2.75 mg cm ⁇ 2 ) was assembled using a double sided 4 cm 2 (8 cm 2 active area) mesoporous nickel positive electrode (prepared as in (ii) above) with approximately 12 ⁇ m thickness (including 10 ⁇ m thickness of foil current collector) in conjunction with two 4 cm 2 high surface area carbon electrodes (prepared as in (iii) above) on either side of the nickel electrode separated in each case by a 25 ⁇ m Celgard separator in 6 M KOH solution.
  • the total mass of the two carbon electrodes was 28.5 mg and the separators was 25.8 mg, therefore the total mass of the dry capacitor was 93.7 mg.
  • FIG. 10 shows the cyclic voltammogram of the two-electrode supercapacitor cycled in the potential range 0 V to 1.5 V after it had become stable. At approximately 1.35 V the device is charged, corresponding to the removal of protons from the Ni(OH) 2 and formation of NiOOH. Discharge occurs as protons move into the NiOOH structure reforming Ni(OH) 2 as indicated by the cathodic peak.
  • the discharge current in this 5 mV s ⁇ 1 cycle peaks at 1.3 mA cm ⁇ 2 and the total reduction charge passed is 133 mC cm ⁇ 2 .
  • the shape of the voltammogram of FIG. 10 more closely resembles that of a battery than a supercapacitor.
  • the majority of the charge on discharge is passed above 0.9 V vs. Hg/HgO.
  • FIG. 12 shows a single charge/discharge step sequence.
  • 105 mC cm ⁇ 2 of charge is passed in 3 seconds.
  • Discharge of the device is represented by the large cathodic spike as protons move into the NiOOH.
  • 95 mC cm ⁇ 2 is passed during the discharge step, 51 mC cm ⁇ 1 of which is passed in the first 100 ms.
  • nickel foil (10 ⁇ m thick, 4 cm 2 ) was obtained from Johnson Matthey and was prepared as follows, for subsequent deposition of mesoporous nickel.
  • nickel foil (Goodfellow, 10 ⁇ m, 2 cm 2 ) was prepared as follows for the subsequent deposition of mesoporous iron.
  • the nickel foil substrates were cleaned in an ultrasound bath of isopropanol for 15 minutes prior to deposition, and then rinsed in de-ionised water and dried under ambient conditions.
  • a mixture having normal topology hexagonal (H I ) phase was prepared from 45 wt % of an aqueous solution of 0.2 M nickel (II) acetate, 0.5 M sodium acetate and 0.2 M boric acid, and 55 wt % of Brij 56 (Brij is a trade mark) nonionic surfactant (C 16 EO n wherein n ⁇ 10, from Aldrich).
  • Electrodeposition onto the nickel foil substrate was carried out potentiostatically at ⁇ 0.9 V vs. a saturated calomel electrode and at 25° C. using a platinum gauze counterelectrode, according to the method disclosed by Nelson et al., Chem. Mater., 2002, 14, 524-529. The total deposition charge was 2.0 C. After deposition, the films were washed in copious amounts of isopropanol for 24 hrs to remove the surfactant.
  • a mixture having normal topology hexagonal (H I ) phase was prepared from a deoxygenated, 40 wt. % of aqueous solution of 0.2 M iron (II) sulphate and 60 wt. % Brij 56 nonionic surfactant (C 16 EO n wherein n ⁇ 10, Aldrich).
  • Electrodeposition onto a nickel foil substrate (2 cm 2 in area) was carried out potentiostatically at ⁇ 0.9 V vs. a saturated calomel electrode and at 25 ° C. using a platinum gauze counterelectrode. After passing 0.2 mAh of charge, the film was removed from the deposition mixture under cathodic protection by attaching the films to zinc foil immediately prior to the films being isolated from the deposition potential. The film, together with the zinc foil, was washed in copious amounts of deoxygenated acetone for 1 hour to remove the surfactant.
  • FIG. 13 A cyclic voltammogram of the iron electrode in 6 M KOH was performed at 20 mV s ⁇ 1 and the result is shown in FIG. 13 .
  • the cathodic charge passed between ⁇ 0.3 V and the interference of hydrogen evolution at ⁇ 1.15V was 25 mC as shown in FIG. 14 .
  • the iron and nickel electrodes prepared as described above were immersed into a 6M solution of KOH.
  • the open circuit potential was measured and found to be 1.1 V.
  • FIG. 15 shows the cyclic voltammogram of the two-electrode supercapacitor.
  • the discharge plotted as a negative current, shows a broad peak around 1.1 V with a peak current of 0.15 mA.
  • the total charge stored was found by integration of the voltammogram in FIG. 16 to be 12 mC.

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US10938032B1 (en) 2019-09-27 2021-03-02 The Regents Of The University Of California Composite graphene energy storage methods, devices, and systems
JP2023059600A (ja) * 2021-10-15 2023-04-27 旭化成株式会社 電極構造体、電解セル、電解槽、電解槽の製造方法
JP7797157B2 (ja) 2021-10-15 2026-01-13 旭化成株式会社 電極構造体、電解セル、電解槽、電解槽の製造方法

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EP1570535A2 (en) 2005-09-07

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