AU1013501A

AU1013501A - Amorphous metal/metallic glass electrodes for electrochemical processes

Info

Publication number: AU1013501A
Application number: AU10135/01A
Authority: AU
Inventors: Donald W. Kirk; Steven J. Thorpe
Original assignee: Stuart Energy Systems Corp
Current assignee: Hydrogenics Test Systems Inc
Priority date: 1999-10-26
Filing date: 2000-10-23
Publication date: 2001-05-08
Also published as: NO20020957D0; WO2001031085A3; JP2003513170A; CA2287648A1; CA2287648C; BR0014994A; NO20020957L; WO2001031085A2; ZA200201857B; KR20020037772A; EP1230412A2; CN1382229A; MXPA02002673A

Description

WO 01/31085 PCT/CAOO/01251 5 AMORPHOUS MRTAL/METALLIC GLASS ELECTRODES FOR ELECTROCHEMICAT PROCESSES 10 FIELD OF THF INVENTION This invention relates to an improved electrode material for use in electrochemical processes and particularly an amorphous metal/metallic glass 15 electrode material intended for constituting the active surface of an electrode for use in the electrolysis of aqueous solutions and more particularly in the electrochemical production of oxygen and hydrogen by said electrolysis. BACKGROUND OF THE IENVENTTON 20 In electrolytic cells for the production of hydrogen and oxygen, such as those of the bipolar and unipolar type, an aqueous caustic solution is electrolyzed to produce oxygen at the anode and hydrogen at the cathode with the overall reaction being the decomposition of water to yield hydrogen and oxygen. The products of 25 the electrolysis are maintained separate by use of a membrane/separator. Use of amorphous metals/metallic glasses and nanocrystalline materials, as electrocatalysts for the hydrogen and oxygen evolution reaction are known. The terms "amorphous metal" or "metallic glass" are well understood in the art and define a material which contains no long range structural order but can contain short range structure and 30 chemical ordering. Henceforth, in this specification and claims both terms will be used as being synonymous and are interchangeable. The term "nanocrystalline" refers to a material that possesses a crystallite grain size of the order of a few nanometers; i.e. the crystalline components have a grain size of less than about 10 nanometers. Further, the term "metallic glass" embraces such nanocrystalline 35 materials in this specification and claims. In an electrolysis application, not all of the voltage that is passed through the cell WO 01/31085 PCT/CA0O/01251 2 5 during electrolysis is utilized in the production of hydrogen and oxygen. This loss of efficiency of the cell is often referred to as the cell overpotential required to allow the reaction to proceed at the desired rate and is in excess of the reversible thermodynamic decomposition voltage. This cell overpotential can arise from: (i) reactions occurring at either the cathode or the anode, (ii) a potential drop 10 because of the solution ohmic drop between the two electrodes, or (iii) a potential drop due to the presence of a membrane / separator material placed between the anode and cathode. The latter two efficiencies are fixed by the nature of the cell design while (i) is directly a result of the activity of the electrode material employed in the cell including any activation or pre-treatment steps. Performance of an 15 electrode is then directly related to the overpotential observed at both the anode and cathode through measurement of the Tafel slope and the exchange current density (hereinafter explained). Superior electrode performance for the electrolysis of water may be achieved by the use of addition of metal salts to the electrolyte as "homogeneous" catalysts 20 that function only in the liquid phase. These "homogeneous" catalysts suffer from the difficulty of having to add these additions to an operating cell to be functional, along with the toxicity of the metal salts in powder form and the disposal of electrolyte containing these additions. A desirable alternative would then be a base alloy comprised of Ni, and one or more of these metallic salt constituents which 25 would still provide the same operating characteristics of a low voltage, high current cell behaviour corresponding to the evolution of hydrogen or oxygen while being electrochemically stable in the alkaline solution. United States Patent No. 5,429,725, issued July 04, 1995 to Thorpe, S.J. and Kirk, D.W. describes the improved electrocatalytic behaviour of alloys made by 30 combinations of the two elements Mo and Co in a Ni-base metallic glass. However, there is still a need for higher exchange current densities combined with lower Tafel slopes in the (Cr, V)- containing alloys compared with the Mo-containing alloys and, accordingly, a need for enhanced operating efficiency of electrocatalyst material for alkaline water electrolysis. 35 WO 01/31085 PCT/CAOO/01251 3 5 REFERENCE LIST The present specification refers to the following publications, each of which is expressly incorporated herein by reference. 10 PUBLICATIONS: 1. Lian, K. Kirk, D.W. and Thorpe, S.J., "Electrocatalytic Behaviour of Ni-base Amorphous Alloys", Electrochim. Acta, 36, p. 537-545, (1991) 15 2. Kreysa, G. and Hakansson, "Electrocatalysis by Amorphous Metals of Hydrogen and Oxygen Evolution in Alkaline Solution", J. Electroanal. Chem., 201, p. 61-83, (1986). 3. Podesta, J.J., Piatti, R.C.V., Arvia, A.J., Ekdunge, P., Juttner, K. and Kreysa, G., "The Behaviour of Ni-Co-P base Amorphous Alloys for Water 20 Electrolysis in Strongly Alkaline Solutions Prepared through Electroless Deposition", Int. J. Hydrogen Energy, 17, p. 9 - 22, (1992). 4. Alemu, H. and Juttner, K., "Characterization of the Electrocatalytic Properties of Amorphous Metals for Oxygen and Hydrogen Evolution by Impedance Measurements", Electrochim. Acta., 33, p. 1101-1109, (1988). 25 5. Huot, J.-Y., Trudeau, M., Brossard, L. and Schultz, R. "Electrochemical and Electrocatalytic Behaviour of an Iron Base Amorphous Alloy in Alkaline Solution at 700C", J. Electrochem. Soc., 136, p. 2224-2230, (1989). 6. Vracar, Lj., and Conway, B.E., "Temperature Dependence of Electrocatalytic Behaviour of Some Glassy Transition Metal Alloys for Cathodic Hydrogen 30 Evolution in Water Electrolysis", Int. J. Hydrogen Energy, 15, p. 701-713 (1990). 7. Wilde, B.E., Manohar, M., Chattoraj, I., Diegle, R.B. and Hays, A.K., "The Effect of Amorphous Nickel Phosphorous Alloy Layers on the Absorption of Hydrogen into Steel", Proc. Symp. Corrosion, Electrochemistry and 35 Catalysis of Metallic Glasses, 88-1, Ed. R.B. Diegle and K. Hashimoto, WO 01/31085 PCT/CA00/01251 4 5 Electrochemical Society, Pennington, p. 289-307 (1988). 8. Divisek, J., Schmitz, H. and Balej, "Ni and Mo Coatings as Hydrogen Cathodes", J. Apple. Electrochem., 19, p. 519-530, (1989). 9. Huot, J.-Y. and Brossard, L., "In-situ Activation of Nickel Cathodes by Sodium Molybdate during Alkaline Water Electrolysis at Constant Current", 10 J. Apple. Electrochem., 20, p. 281, (1990). 10. Huot, J.-Y. and Brossard, "In-situ Activation of Nickel Cathodes during Alkaline Water Electrolysis by Dissolved Iron and Molybdenum Species", J. Appl. Electrochem., 21, p. 508, (1991). 11. Raj, I.A. and Vasu, K.I., "Transition Metal-based Hydrogen Electrodes in 15 Alkaline Solution- Electrocatalysis on Nickel-based Binary Alloy Coatings", Int. J. Hydrogen Energy, 20, p. 32, (1990). 12. Jaksic, M.M., Johansen, B., and Ristic, M., "Electrocatalytic In-situ Activation of Noble Metals for Hydrogen Evolution" in Hydrogen Energy Progress VIll,T.N. Veziroglu and P.K. Takahashi, Eds., Pergamon Press, 20 NY, p. 461, (1990). SUMMARY OF THE TNVENTION It is an object of this invention to provide an improved electrode having an 25 electrochemically active surface that can be used for the electrolysis of water. It is a further object of this invention to provide an improved electrode that is chemically stable in an alkaline environment for both static and dynamic cycling operations of the cell. It is a further object of the present invention to provide an improved 30 electrode material that is sufficiently active so as to reduce either or both the anodic overpotential for oxygen evolution or the cathodic overpotential for hydrogen evolution. It is a further object to provide an electrode that contains relatively inexpensive elemental constituents compared to the platinum group metals. 35 It is a further object to provide an electrode whose total processing WO 01/31085 PCT/CA0O/01251 5 5 operations necessary to final electrode fabrication are minimized in comparison to conventional electrode materials. It is a further object to provide an electrode which can be operated at elevated temperatures in an alkaline environment to provide enhanced performance since the overpotential required to produce either hydrogen or oxygen is reduced as 10 the operational temperature of the cell is increased. Accordingly, the invention provides in one aspect a metallic glass of use in electrochemical processes, said metallic glass consisting essentially of a material of the general nominal composition (Ni,Co)lo.~ Ax Zt 15 wherein: A is a member selected from the group consisting of IVb, Vb, VIb VIb and VIII of the Periodic Table; Z is a member selected from the group consisting of carbon and a metalloid element selected from group II1a, IVa, Va and VIa of the Periodic Table; and 20 wherein x, t and (I 00-x-t) are atomic percents. Preferably, A is at least one metal selected from the group consisting of Ti, V, Cr, Mn, Fe, Zr, Nb, Mo, Tc, Hg, Ta, and W; and wherein x is selected from about 1 to 20 atomic percent, more preferably x is selected from about 1-5 atomic percent. 25 Preferably, Z is at least one member selected from the group consisting of silicon, phosphorus, carbon, and boron; and wherein t is selected from about 15 to 25 atomic percent, more preferably t is about 20 atomic percent. The metallic glass is most preferably in an elemental and homogenous state but some degree of non-homogeneity in both anionic and cationic form can be 30 tolerated. It will be understood that the general formula defined hereinabove represents a nominal composition and thus allows of some degree of variance from the exact atomic ratios shown. Preferred materials according to the invention have the nominal 35 compositions selected from Ni5oCo25CrB20, NiCo2sV5 B and Ni45Co25Cr5V5 B20 WO 01/31085 PCT/CAO0/01251 6 5 The alloys of the present invention are readily made into self-supporting structures. In a further aspect, the invention provides an electrode of use in an electrochemical cell comprising a metallic glass consisting of a material as hereinabove defined. The electrode may act as an anode, cathode or both as a 10 working electrode. The materials of the invention may constitute a full electrode or a surface coating on a substrate such as a metal or other electrically conductive material. In a yet further aspect, the invention provides an improved process for the electrochemical production of oxygen and hydrogen from an aqueous solution in an 15 electrochemical cell, said process comprising electrolysing said aqueous solution with electrodes, said improvement comprising one or more of said electrodes comprising a metallic glass consisting essentially of a material as hereinabove defined. In the electrolytic production of oxygen and hydrogen, the aqueous solution 20 is alkaline. Surprisingly, the metallic glasses according to the invention do not suffer from the loss of element "A" during use and retain electrolytic activity under severe conditions of use. Thus, we have found that the presence of element "A" in the alloys of the invention, while providing the unexpected advantages hereindescribed, 25 surprisingly, does not result in dissolution of the element "A" under alkaline electrolysis conditions. Thus, the invention provides a metallic glass / amorphous metal electrode material for electrochemical processes produced by rapid solidification (i) having a structure that is either amorphous or nanocrystalline, (ii) containing the principal 30 alloying elements as Ni and Co, (iii) containing alloying additions such as Cr, V, Ti, Mn, Fe and the like in the range of 1 to 20 at. %, and when combined with Ni and Co, represent 0.75 to 0.85 of the atomic fraction of the alloy, and (iv) containing metalloid elements comprised preferably of one or more of the elements C, B, Si and P either singly or in combination to represent 0.15 to 0.25 atomic fraction of the 35 alloy. The electrodes have excellent thermal stability, improved stability in an WO 01/31085 PCT/CAOO/01251 7 5 aqueous electrolyte and can provide improved current efficiency - anodic or cathodic overpotential performance. They are of use in the electrolysis of aqueous electrolyte solutions such as mixtures of caustic (KOH, NaOH) and water in the production of oxygen and hydrogen. The electrodes are comprised of low cost transition metals in combination 10 with metalloid elements in specific ratios to permit the alloy composition to be solidified into an amorphous state. They offer improved current efficiencies via anodic or cathodic overpotential performance and offer improved stability in both static and cyclic exposures. They can be used in concentrated alkaline solutions and at elevated temperatures for improved electrode performance. The electrodes are of 15 use in the electrolysis of alkaline solutions resulting in the production of hydrogen and oxygen via the decomposition of water, and also additional uses in electrodes for fuel cells, electro-organic synthesis or environmental waste treatment. Processing methodology of rapid solidification offers many cost advantages compared to the preparation of conventional Raney Ni type electrodes. The process 20 is a single step process from liquid metal to finished catalyst, which can be fabricated in the form of ribbons or wires for weaving into a mesh grid. The process can also be used to produce sheets, powders, flakes, etc. which can further be consolidated into a desired shape or patterned. By comparison, conventional electrode fabrication involves the production of a billet or rod, wire drawing and 25 annealing operations, weaving to form a wire mesh grid, surface treatment, powder deposition, powder consolidation and an activation step. Table 1 summarizes the results of prior art investigations involving transition metal-metalloid glasses. The performance of an electrocatalyst in Table 1 has been summarized in terms of two principle parameters: (i) the Tafel slope, Pc, and (ii) the 30 logarithm of the exchange current density, log i.. The exchange current density is equivalent to the reversible rate of a reaction at equilibrium at the standard half-cell or redox potential. The Tafel slope refers to the slope of the line representing the relation between overpotential and the rate of a reaction reflected as current density where there exists linearity on a semilogarithmic plot of overpotential and current 35 density.

WO 01/31085 PCT/CAOO/01251 8 5 Table 1.0: Polarization Data of Ni-Co base Amorphous Metals for HER in Alkaline Solutions Amorphous Solution Temperature -log iB B, Reference Electrode (A/cm2) (mV/decade) Ni5oCo2sSii5Bio 1M KOH 30 5.7 110,178 1 30 6.5 90 2 50 10.6 93 2 70 7.6 127 2 90 7.9 113 2 Surface-treated 1M KOH 30 5.4 91,145 1 NisoCo25Si15Bio 1M KOH 30 5.8 101,144 1 Surface-treated 1M KOH 30 5.4 111,166 1 Co5oNi25P15B1o 1M KOH 30 5.4 124,174 1 Surface-treated 1M KOH 30 5.1 110,173 1 Thermally-treated and 1M KOH 30 4.0 100 3 anodically oxidized 50 3.2 120 3 Nis.sCooP4.5 70 2.8 120 3 90 2.2 100 3 NissCo2OSiioB12 1M KOH 30 5.0 140 2 50 4.7 146 2 70 4.7 155 2 90 4.3 145 2 Co28NiioFe5SinB16 1M KOH 30 4.6 174 2 50 5.5 119 2 70 5.4 120 2 90 5.3 128 2 Ni7oMo2aSi5B5 M KOH 30 4.1 165 2 70 3.8 106 2 90 3.6 276 2 Fe39Ni39Mo2Si12Bs 1M KOH 30 5.0 123 2 50 4.8 150 2 70 4.9 173 2 90 4.9 167 2 Ni7sSisB14 1M KOH 25 6.0 140 4 30 6.1 102 2 50 4.3 150 4 50 4.4 144 2 70 4.9 130 2 75 3.8 125 4 90 4.4 148 2 Anodically oxidized 30% KOH 70 2.9 130 5 Fe4oNi4oB20 1M KOH 30 3.9 174 2 50 3.8 184 2 70 4.3 230 2 90 3.0 188 2 Ni66.Mo23.sB1io 0.5M 25 5.6 120 6 NaOH WO 01/31085 PCT/CAO0/01251 9 Amorphous Solution Temperature -log &BReference Electrode (A/cm2) (mV/decade) Niss.5Mo235Fe10B1o 0.5M 25 5.3 100 6 NaOH Ni56.sMo23sCrioBio 0.5M 25 5.0 135 6 NaOH Ni7oP2oCio coating 1N NaOH 25 6.2-8.4 65-95 7 Ni75CrP20 1M HCl* 30 3.5 - 8 Ni73Cr7P20 IM HCl* 30 3.8 - 8 Ni7OCnoP20 IM HCl* 30 4.0 - 8 5 * not for electrolysis in an alkaline media WO 01/31085 PCT/CAOO/01251 10 5 Table 2: Polarization Data of Ni-Co base Amorphous Metals for HER in Alkaline Solution with Homogeneous Catalyst additions Substrate and Addition [ T 1 1 R of Catalyst (ppm X 10-3) Solution Temperature -log 10Reference (A/cm 2 ) (mV/decade) Substrate Co 7.6M KOH 70 3.9 79 9 Fe 3.9 80 Ni 3.7 95 Pt 4.2 75 Fe addition = 0.014 Substrate Co 7.6M KOH 70 3.4 151 10 Fe 3.1 154 Ni 2.8 182 Pt 3.1 163 Mo addition = 0.024 Fe addition = 0.024 Substrate mild steel 6.OM KOH 80 - 112 11 NiSO4 addition =80 Na2MoO4 addition = 20 Substrate mild steel 6.OM KOH 80 - 112 11 NiSO4 addition =80 Na2MoO4 addition = 20 Substrate mild steel 6.OM KOH 80 - 25 11 NiSO4 addition =80 Na2WO4 addition = 20 Substrate mild steel 6.OM KOH 80 - 50 11 NiSO4 addition =80 ZnSO4 addition = 40 Substrate mild steel 6.OM KOH 80 - 25 11 NiSO4 addition =80 FeSO4 addition = 20 Substrate mild steel 6.OM KOH 80 - 112 11 NiSO4 addition = 80 CoSO4 addition = 20 Substrate mild steel 6.OM KOH 80 - 150 11 NiSO4 addition =80 Cr03 addition = 20 Substrate Pt 5.OM KOH 25 - 80 12 Molybdate addition WO 01/31085 PCT/CAOO/01251 11 5 The electrodes described in Table 1 contain various combinations of the transition metals in combination with (Ni,Co) but none of them incorporate element "A" in addition as described above. The electrodes described in Table 2 derive activity from the presence of the dissolved salts of element "A" as described above when added to the solution phase of the electrolytic cell, but not when incorporated 10 directly into the substrate material. BRIEF DESCRIPTION OF THE DRAWINGS 15 In order that the invention may be better understood, preferred embodiments will now be described by way of example only, with reference to the accompanying drawings, wherein: Fig. 1 is a schematic diagram of an apparatus for making a metallic glass according to the invention; 20 Fig. 2 is a schematic diagram detailing the interior of the vacuum chamber of the apparatus shown in Fig. 1; Fig. 3 is a perspective representation of a boron nitride ceramic crucible of use in the apparatus of Fig. 1; Fig. 4 is a schematic diagram of a three component cell used in the evaluation of the 25 electrochemical activity and stability of the materials according to the invention; Fig. 5 is a diagrammatic representation of the apparatus of use in obtaining electrochemical measurements, and wherein the same numeral denotes like parts. DETAILED DESCRIPTION OF THE PREFERRED 30 EMBODIMENTS OF THE INVENTION The general methods for the preparation and testing of the materials according to the invention followed those described in aforesaid United States Patent No. 5,429,725. 35 EXPERIMENTAL Electrode metallic glass materials were prepared as follows.

WO 01/31085 PCT/CAOO/01251 12 5 EXAMPLE 1 This Example illustrates the preparation electrodes having a nominal composition: Ni50Co25 Cr 5 B20 A series of processing trials were performed to fabricate amorphous alloy 10 ribbons by the melt-spinning technique. The process was divided into two steps. The first step was termed "pre-melting" where a powder mixture of pure materials, i.e., nickel, cobalt, chromium, and boron, was charged onto a water cooled copper hearth, and melted via the use of vacuum arc melting. The second step employed a boron nitride ceramic crucible, which enabled the pre-melted and crushed button to 15 be remelted and superheated to a temperature higher than 1 1000C in the vacuum chamber. A stream of molten metal was then blown through a thin slit of the ceramic crucible on to the peripheral surface of a massive copper wheel rotating at a high speed. Rapid quenching took place on the cold surface of the wheel, and the solidified deposit was produced in the form of thin ribbons. A concise description 20 of amorphous metal production is given in the following subsections. Apparatus: Melt-Spinner : D-7400 Tubingen, Edmund Bihler, Germany 3.3 x 10- Pascal High Vacuum Chamber Induction Heater : TOCCOTRON 2EG103. The Ohio Crankshaft Co., U.S.A 25 Maximum output 10 kW, 450 kHz Pyrometer : Model ROS-SU, Capintec Institute Inc., U.S.A. Fig. 1 illustrates the experimental apparatus consisting of a melt-spinner shown generally as 10 and an induction heating unit shown generally as 12. The 30 melt-spinner assembly 10 comprised a high vacuum chamber 14, a ribbon collector tube 16, and a controller 18. The vacuum chamber 14 was connected to an argon cylinder 20 that supplied argon gas for purging the chamber 14 and pressurizing a ceramic crucible 22 (Fig. 2) in order to eject a molten mass of liquid material (not shown). The temperature of the molten mass of liquid in ceramic crucible 22 is 35 measured by means of an optical pyrometer 24 attached to a quartz window 26 located above vacuum chamber 14. Induction heater unit 12 was comprised of an induction heater coil 28 (Fig.

WO 01/31085 PCT/CAOO/01251 13 5 2) in vacuum chamber 14, a 3-stage step-up transformer and a closed-loop water recirculator (not shown) which supplied cooling water through the induction coil during heating. Fig. 2 shows the arrangement of a copper wheel 30 (20 cm in diameter, 3.8 cm in width), ceramic crucible 22 induction coil 28 in high vacuum chamber 14 and 10 ribbon guide 32. A: Premelting The targeted chemical compositions exemplified are collectively expressed as Ni50Co25Cr5B20 Because the compositional range of the alloy is relatively small, careful sample preparation was required to ensure an effective comparison in 15 subsequent electrochemical measurements. In order to achieve the targeted compositions with high accuracy, pure material powders were utilized to fabricate pre-melted buttons first by vacuum arc melting followed by mechanical crushing and remelting using vacuum induction melting. In the exemplified powders each mixture contained 50 atomic % nickel, 25 atomic % Co and 20 atomic % of boron. 20 The remaining 5 atomic % was made up with element A, in this example chromium. In an alternate embodiment of this invention, the boron was added in the form of an intermetallic compound like nickel boride which acted as a melting point depressant and enabled the whole powder mixture to start melting at a relatively low temperature, ca 10350C. 25 A batch of 20 - 50 g of the powder mixture was charged into a quartz crucible (I.D. = 19.05 mm, O.D. = 22.2 mm, height = 130 mm, with round bottom). The quartz crucible was mounted in the vacuum chamber of the melt-spinner and centered in the induction coil. The vacuum chamber was then purged three times with argon and evacuated to ca. 5 x 1 0 4 torr (7 x 10.2 Pa) before heating. The 30 material powder mixture was melted at greater than 1 1000C in the quartz crucible. The weight loss ratio of materials through pre-melting was found to be < 1 weight % for all constituents. B: Melt Spinning 35 The melt spinner used in this work was an experimental sized model WO 01/31085 PCT/CA0O/01251 14 5 manufactured by Edmund Buhler GMBH capable of processing in batch mode 5 100 gram samples of alloy mixtures. The melt-spinner assembly comprised a high vacuum chamber, a ribbon collector tube, and a motor speed controller. The induction heater unit was comprised of an induction heater coil in the vacuum chamber, a 3-stage step-up transformer, and a closed-loop water recirculator, which 10 supplied cooling water through the induction coil during heating. The vacuum chamber was connected to an argon cylinder that supplied gas for purging the chamber and pressurizing the ceramic crucible in order to eject a molten mass of liquid. The temperature of the molten mass of liquid in the ceramic crucible was measured by means of an optical pyrometer that was attached to a quartz window 15 located above the vacuum chamber One or two pre-melted buttons were charged into the BN ceramic crucible. Boron nitride has the advantages of high hardness at elevated temperatures and good oxidation resistance that enabled the molten liquid to be superheated to over 14000C without any chemical reaction with the crucible. 20 The crucible was mounted above the Cu wheel in the vacuum chamber. The chamber was purged and evacuated in the same manner as that described during premelting. The pre-melted button(s) was superheated in the crucible by the induction coil until the liquid temperature reached a stable maximum temperature, which was dependent on the alloy composition. The molten mass of 25 liquid was ejected by argon pressure on to the wheel through a fine slit nozzle (0.5 x 15 mm). Planar amorphous ribbons were formed on the surface of the wheel rotating counterclockwise and driven along the ribbon guides to the collector tube. This particular form of melt spinning is referred to as the planar flow casting technique. From the wheel rotation speed, a quenching rate was estimated to be ca 30 106 oC/sec. One side of the ribbon was free from contact with the wheel and had a shiny appearance (shiny side) compared with the dull appearance for the other side in contact with the wheel (wheel side). To minimize surface imperfections on the dull side due to contact with the wheel, the peripheral surface of the wheel was thoroughly polished with diamond paste and degreased with acetone before each 35 run. Standard experimental parameters of the melt-spinning operation are WO 01/31085 PCT/CAOO/01251 15 5 summarized in Table 3. Table 3: Summary of Operational Parameters of Melt-Spinning Clearance between the bottom most edge of 0.5 mm the crucible and the wheel surface Point of impingement 12 degrees counterclockwise from the top of the wheel Pre-melt button weight 20-50 g Vacuum chamber pressure 7 x 10- Pa or lower Molten ejection pressure 40 kPa Wheel rotation speed 1800-2900 rpm Superheat temperature higher than 11 00CC 10 The alloys of the invention so produced by planar flow casting were submitted to the following further types of evaluation. The first evaluation relates to the actual composition of the alloys produced as poor recoveries during melting can produce substantial deviations 15 between the nominal and actual composition of a given alloy. The second evaluation relates to the structure of the alloys produced as the processing method produces a metastable structure that is amorphous or nanocrystalline in nature. The third evaluation relates to the electrode performance in relation 20 to the overvoltage necessary for hydrogen production for as-melt spun ribbons under conditions related to the electrolysis of an alkaline solution. The fourth evaluation refers to the examination of the surface of the electrode materials used under both constant potential and conditions of potential cycling as described above. 25 The first test was performed in order to obtain reliable information on the elemental composition of the amorphous alloys using inductively coupled plasma spectroscopy (ICP). Although only a very small weight loss, less than 1 WO 01/31085 PCT/CAOO/01251 16 5 weight %, was found during the premelting operation, if the loss was due to a single component, inaccuracies in the targeted compositions would result. Additionally, there was concern about any compositional fluctuation in the longitudinal direction of the amorphous ribbon. For this reason, two positions designated as center and tail were taken from each ribbon and analyzed. ICP is a technique that provides a 10 quantitative analysis of almost all elements with a high level of detectability. The technique requires that the sample to be analyzed be dissolved in an aqueous solution because the sample is introduced to the inductively coupled plasma in the form of an aerosol. Each amorphous ribbon was dissolved into concentrated nitric acid and diluted with water and hydrochloric acid to complete the 15 designated matrix solution which contained 4 weight % HNO 3 and 4 weight % HCL. For experimental error analysis, some standard solutions were prepared with pure material powders. The major elements analyzed were Ni, Co, Cr, V, and B. Expected concentrations of Ni, Co, Cr, V, and B in the standard and sample solutions are summarized in Table 4.

WO 01/31085 PCT/CAOO/01251 17 5 Table 4: Summary of Expected Concentrations of ICP Samples (ppm) Serial Solute Ni Co Cr or V B No. #1 Blank (1) 0 0 0 0 #2 Standard (2) - metals 10.00 10.00 10.00 0 #3 Standard (3) - metals 100.00 100.00 100.00 #4 Ni 5 4 Co 2CrIB20 center 53.7 24.7 0.9 20.6 #5 Ni 5 4 Co 2 5 CrIB 20 tail 54.0 24.8 1.0 20.1 #6 Standard 54.0 25.0 1.0 20.0 #7 Ni 5 Co 2 5 Cr 5

B

2 0 center 50.6 24.6 5.0 19.9 #8 Ni 5 0 Co 2 5 CrsB 20 tail 49.9 24.6 5.7 19.7 #9 Standard 50.0 25.0 5.0 20.0 #10 Ni 35 Co 25 Cr 2 0

B

2 0 35.6 25.1 20.2 19.1 #11 center 35.7 25.1 20.2 18.9 #12 Nio 3 5 2 sC 2 0

B

2 0 tail 35.0 25.0 20.0 20.0 Standard #13 Ni 50 Co 2 5

V

5

B

2 0 center 50.8 25.3 4.6 19.3 #14 Ni 50 Co 2 5

V

5

B

2 0 tail 50.9 25.3 4.7 19.1 #15 Standard 50.0 25.0 5.0 20.0 #16 Standard B1 0 0 0 10 #17 Standard B2 0 0 0 25 #18 Standard B3 0 0 0 50 #19 Standard B4 0 0 0 100 The second test was performed using the technique of X-ray diffraction in order to confirm the degree of crystallinity of the manufactured 10 ribbons. For comparison, measurements were also carried out on crystallized fragments of the amorphous alloys as well as pure elemental nickel, cobalt, chromium, boron and the intermetallic nickel boride. The amorphous samples were prepared by cutting ribbons into 4 mm x 10 mm rectangular pieces. The samples were then degreased with acetone, methanol and deionized water in sequence. The 15 crystallized fragments had the same bulk composition as the corresponding amorphous alloy and were primarily in the form of brittle plate-like powder. To avoid preferential diffraction due to the plate-like surface of the fragments, the WO 01/31085 PCT/CAOO/01251 18 crystallized amorphous alloy was ground to form a fine powder in an agate mortar and dispersed on a slide glass before measurement. Diffraction patterns were measured on a Siemens D5000 X-ray diffractometer using 50 kV Cu-KE radiation with a Ni filter in the range of 20 to 70 degree-20 at a scan rate of 2 degree-20 per minute. The data was processed by Diffrac AT software. The third test involved determining the electrochemical overpotential for hydrogen evolution by determination of the Tafel slope and exchange current density for the alloys produced above. Working electrodes were prepared from the Ni-Co-Cr-B amorphous alloy ribbons of ca. 20-50 pm thickness and 4 to 15 mm in width. The shiny side of the ribbon was ground, polished, and degreased. The as polished ribbon was cut into approximately 10 mm x 10 mm pieces, and each piece was joined to an insulated copper lead. The joined area, unpolished wheel side, and periphery of the polished side were thoroughly coated three times at 24 hr intervals by Amercoat 90* epoxy resin. This masking coat resists either alkaline or acidic environments. The exposed geometrical surface area of the fabricated electrodes was typically 0.03 ± 0.01 cm 2 . The electrolytic cell shown in Fig. 4 generally as 40 had a three compartment structure consisting of a 300 ml capacity main body formed of Teflon® containing a working electrode 42 of the ribbon of alloy of the invention, a 1/2" Teflon* tube 44 housing a counter electrode 46, and a 1/4" Teflon* PTFE tube filled with mercury-mercuric oxide paste (Hg/HgO) 48. The compartments were separated by electrolyte-permeable membranes 50 in the form of a diaphragm or frit. The counter electrode 46 was a 25 mm x 12.5 mm platinum gauze with a surface 2 area of ca. 4.4 cm . The Hg/HgO paste in aqueous 1 M KOH solution was used as a reference electrode 52. The tip 54 of a Luggin capillary of the reference electrode compartment was placed a distance of ca. 2 mm to the working electrode surface of the alloys of the invention. All potentials quoted herein are referred to the Hg/HgO electrode in 1 M KOH solution at 300C. The electrolyte was aqueous 8 M potassium hydroxide solution prepared with KOH and Type I water that had undergone pre-electrolysis for a minimum of 24 hours to remove any impurities in the KOH. The electrolyte was replaced with fresh electrolyte and was deaerated by WO 01/31085 PCT/CAOO/01251 19 5 argon at a rate of 30 ml/min prior to each experiment. Argon bubbling was continued during the experiment. The solution temperature was controlled at 700C in an 18 L water bath 56 (Fig. 5) with an immersion heater (Polystat Immersion Circulator, Cole-Palmer). The apparatus used for electrochemical measurements comprises 10 water bath 56 in electrical contact with a potentiostat/galvanostat Hokuto Denko HA-501G with a 200 MHz Pentium II personal computer 60, through a GPIB interface 62 and arbitrary function generator (Hokuto Denko HA-105B) 66. The electrocatalytic activity of the amorphous alloys for the hydrogen evolution reaction (HER) was studied by a quasi-steady-state polarization 15 technique. In practice, polarization curves of the amorphous electrodes were measured under quasi-potentiostatic conditions at a very low sweep rate of 2 mV/min. This potential sweep rate was found to be the maximum sweep rate that provided reproducible steady-state measurements. The as-polished working electrode was rinsed ultrasonically with acetone, methanol, and Type I water in 20 sequence prior to testing. The electrode was then placed in the cell with deaerated 1 M KOH solution and held at a potential of -1.3 V vs. Hg/HgO for 3 hours to clean the electrode surface electrochemically. The potential was swept over the range of 0.9 to -1.5 V vs. Hg/HgO for multiple cycles in order to assess the Tafel behaviour of the electrode response. Polarization curves were replicated at least three times for 25 each electrode and analyzed for their reproducibility. The fourth test was performed on amorphous alloy and crystalline surfaces to compare the degree of surface roughening and hence electrode degradation by using optical and scanning electron microscopy prior to and post use as an electrocatalyst in the cell. Optical investigation was achieved using a light 30 stereoscope and light metallograph. Electron imaging was accomplished using a Hitachi S-570 SEM equipped with a Link Analytical 10/85s x-ray analyzer. Nominal imaging conditions were: accelerating voltage - 20kV, beam current 10 A, sample tilt - 150. In the first test a quantitative composition analysis by Inductively 35 Coupled Plasma (ICP) Spectroscopy was performed. The average experimental WO 01/31085 PCT/CAOO/01251 20 5 composition of each amorphous ribbon as determined by the ICP analysis is listed in Table 5. All of the measured compositions of the amorphous ribbons were in good agreement with the targeted compositions. An average magnitude of the deviation of the actual from the nominal composition was < 1 atomic %. Variations of principal element concentrations were also measured at two different longitudinal 10 positions over the ribbon such as center and tail. There was no significant difference in the compositions at different positions. From these data, the amorphous ribbons can be regarded as homogeneous in the longitudinal direction. Table 5: Composition of the Amorphous Ribbons (atomic percentage) 15 Targeted Composition Measured Composition Ni 54 Co 25 CrB 20 Ni 5 3. 7 Co 24

.

8 Cr B 20

.

1 Ni 50 Co 2 5 Cr 5

B

20 Ni 49

.

9 Co 2 4

.

6 Cr,7 B 1 9 7 Ni 45 Co 25 Cr 10

B

20 Ni451 C249 Cr100 B200 Ni 4 0 Co 25 Cr 15

B

20 Ni 40 3 Co Cr 15 0

B

19 7 Ni 35 Co 25 Cr 2 0

B

20 Ni 35 7 25 1 Crm 189 Ni 5 0 Co 25

V

5

B

20 Ni 5 0.

9 Co 25

.

3

V

4

.

7 B 19.1 In the second test, the structure of the ribbon was assessed using x ray diffraction, as it is an integral part of the electrode performance independent of 20 the exact composition of the electrode material. It is known that a typical X-ray diffraction (XRD) pattern of an amorphous material is a broad spectrum with no prominent sharp peaks relating to crystalline structure. Thus, qualitative confirmation of the amorphous nature of an alloy is demonstrated by a broad band peak in its XRD profile. 25 As additional information, an index, viz. effective crystallite dimension was calculated to evaluate the largest potential size of crystal embryos in the melt-spun ribbons.

WO 01/31085 PCT/CAOO/01251 21 5 The effective crystallite dimension is expressed by the equation: D= 0i9IU Bcoso where D is the effective crystallite dimension in nm and X is wavelength of the Cu K radiation, i.e. 0.1542 nm. B denotes the full width of a given diffraction peak in 10 radians at half the maximum intensity. 0 is the Bragg angle of the peak maximum. The effective crystallite dimension was measured for all the melt-spun ribbons. Results of the calculations are summarized in Table 6. The melt-spun Ni-Co-Cr-B alloys displayed very small values of the effective crystallite dimension determined from their broad band peak width in X-ray diffraction confirming the amorphous 15 nature of the melt spun ribbons. Table 6: Effective Crystallite Dimension Amorphous Peak Apparent Full Width Effective Alloy Maximum Mean of Half the Crystallite Composition Position d-Spacing Maximum Dimension 20 (o) d(A) Intensity D (nm) I__ I_ _B (rad) __ Ni35C025Cr20B20 45.1 1.993 0.138 1.1 Ni50Co25Cr5B20 45.7 2.015 0.126 1.2 514253620 46.3 2.015 0.136 1.1 20 In the third test, the electrocatalytic performance of the various amorphous electrodes was measured and compared to the behaviour of the crystalline elemental constituents. In the potential range of -0.9 to -1.5 V vs. Hg/HgO, the current responses (polarization curves) of crystalline Ni, Co, Cr, and 25 the amorphous Ni-Co-(Cr,V)-B alloys varied from ca. 0.001 to 1000 mA/cm 2 . A linear correlation was found in the potential vs. logarithmic current plot (Tafel plot) which were analyzed to obtain Tafel parameters, DC and i 0 , by a statistical regression method. The Tafel slopes and exchange current densities are summarized in Table 7. 30 WO 01/31085 PCT/CAOO/01251 22 5 Table 7: Tafel Parameters of Electrodes for the HER in IM KOH at 300 C MATERIAL TAFEL PARAMETERS -E* -logi, * Crystalline Ni 1.25-1.56 3.2+0.3 239+14 Co 1.25-1.44 4.0+0.1 178+4 Mo 1.20-1.40 6.6+0.2 90+4 Amorphous Ni 50 Co 25 Cr 5 B 1.01-1.50 3.15 161 Ni 3 5 Co 5 Cr 0

B

0 1.01-1.50 3.58 114 Ni 50 Co 2 5 V B 1.00-1.50 3.96 100 Ni 72 Mo 8 B 0.94-1.55 4.0+0.04 180+2 Ni 7 ?Co 2 Mo 6 B 1.00-1.50 5.1+0.07 142+3 Ni 50 CoMo B 2 0 1.00-1.50 5.1+0.03 148+2 * Potential range (V vs. Hg/HgO), * * Exchange current density (A/cm 2 10 *** Tafel slope (mV/decade), high field Appreciable differences in the current density values were clearly observed as a function of the compositions of the amorphous alloys as shown in Table 7. The following ranking of the electrocatalytic activity was found: 15 Ni 50 Co 25

V

5

B

20 > Ni 35 Co 2 5 Cr 20

B

20 > Ni 50 Co 2 5 Cr 5

B

20 This ranking order does not simply follow the order of magnitude of the Cr/V content in the amorphous alloys, but is particular to the elemental form. The 20 highest electrocatalytic activity of Ni 5 0 Co2 5

V

5

B

20 amongst the amorphous alloys could possibly be attributed to the synergetic effect of Ni-Co-V that may influence the nature of the oxide film formed on this amorphous alloy. The improvement of this invention compared with United States Patent No. 5,429,725 is also evident from Table 7 by comparison of the 25 performance of the amorphous alloys. The invention shows higher exchange current densities combined with lower Tafel slopes in the (Cr,V)-containing alloys WO 01/31085 PCT/CA00/01251 23 5 compared with the Mo-containing alloys; both features contribute to enhanced operating efficiency of the material as an electrocatalyst for alkaline water electrolysis. In the fourth test, in order to obtain additional information on the condition of the electrode surface after multiple cycles of operation, specimens 10 were examined using optical and scanning electron microscopy (SEM). It was found that the potential cycled crystalline Ni, Co and Mo electrodes had thick corrosion product layers. Crystalline Ni electrodes after 200 and 600 cycles showed a growth in the corrosion layer with potential cycling. The crystalline Co electrode showed a sign of crystallization / dissolution reactions by polygon-plate 15 like uniform deposits on the electrode surface. The crystalline Mo electrode showed a severely corroded surface and a remaining skeleton structure that indicated the active dissolution of Mo. All crystalline electrodes showed much higher roughness than their as-polished state. In contrast, potential cycled amorphous electrodes showed very 20 smooth surfaces and no indication of corrosion. Only a slight surface layer (probably Ni oxides) could be seen characterized by a dull transparent film that covered the very smooth surface of the amorphous alloys. No significant difference was found between the amorphous electrodes pre and post cycling. Hence, after exposure to severe potential cycling conditions, the amorphous alloy 25 electrodes were more stable than the crystalline electrodes of the elements Ni, Co or Mo. Although this disclosure had described and illustrated certain preferred embodiments of the invention, it is to be understood that the invention is not restricted to these particular embodiments. Rather, the invention includes all 30 embodiments that are functional or mechanical equivalents of the specific embodiment and features that have been described and illustrated.

Claims

1. A metallic glass of use in electrochemical processes, said metallic glass consisting essentially of a material of the general nominal composition 10 ( Ni,Co)ioo-x-t Ax Zt wherein: A is a member selected from the group consisting of IWb, Vb, VIb VIIb and VII of the Periodic Table; Z is a member selected from the group consisting of carbon and a 15 metalloid element selected from group II1a, IVa, Va and VIa of the Periodic Table; and wherein x, t and (100-x-t) are atomic percents.

2. A metallic glass as claimed in claim 1 wherein A is at least one metal selected from the group consisting of Ti, V, Cr, Mn, Fe, Zr, Nb, Mo, Tc, Hg, Ta, and W; and wherein x is selected from about I to 20 atomic percent. 20

3. A metallic glass as claimed in claim 2 wherein x is selected from about 1 to 5 atomic percent.

4. A metallic glass as claimed in any one of claims I to 3 wherein Z is at least one member selected from the group consisting of silicon, phosphorus, carbon, and boron; and wherein t is selected from about 15 to 25 atomic 25 percent.

5. A metallic glass as claimed in claim 4 wherein t is about 20 atomic percent.

6. A metallic glass as claimed in any one of claims 1 to 5 that is substantially homogeneous. 30

7. A metallic glass as claimed in any one of claims I to 6 wherein said Ni, Co, A and Z are in a substantially elemental state.

8. A metallic glass as claimed in claim I consisting essentially of a material having the nominal composition of Ni 5 0 Co 2 5 Cr 5 B 20

9. A metallic glass as claimed in claim 1 consisting essentially of a material WO 01/31085 PCT/CA00/01251 25 5 having the nominal composition of Ni 5 0 2 Co2 5 5 B 20 .

10. A metallic glass as claimed in claim 1 consisting essentially of a material having the preferred nominal composition of Ni 45 Co 2 5 5 Cr 5 B 2 0

11. An electrode for use in an electrochemical cell comprising a metallic glass consisting essentially of a material as claimed in any one of claims I to 10. 10

12. An electrode as claimed in claim 11 comprising a support and on at least a portion of said support a coating comprising said metallic glass.

13. An electrode as claimed in claim 11 or claim 12 in the form of a self supporting structure.

14. An electrode as claimed in any one of claims 11 to 13 wherein said 15 electrochemical cell is for the electrochemical production of oxygen and hydrogen from an aqueous solution.

15. An improved process for the electrochemical production of oxygen and hydrogen from an aqueous solution in an electrochemical cell, said process comprising electrolysing said aqueous solution with electrodes, said 20 improvement comprising one or more of said electrodes comprising a metallic glass consisting essentially of a material as claimed in any one of claims I to 10.