Nickel E Cattaneo and B Riegel, GmbH & Co. KG, Brilon, Germany & 2009
Elsevier B.V. All rights reserved.
Introduction Nickel alloys have been used since centuries for making coins coins,, jewe jewelr lry y, and and hous househ ehold old uten utensil silss due due to thei theirr hardness and relatively high oxidation resistance. Despite the wide wide spread spread of nicke nickell minera minerals, ls, the silvery silvery-wh -white ite metal metal was was first recogniz recognized ed as a new element element in 1751, 1751, when the Swedish mineralogist Axel Frederik Cronstedt discovered in niccolite an impure form of nickel. The name name nicke nickell origin originate atess from from kupfern kupfernick ickel, el, a German German name for niccolite, a copper-red color mineral containing 44% nickel and 56% arsenic. B
General Properties About 0.016% of the earth’s crust is composed of nickel occuring as five stable isotopes. Ni-5 Ni-58: 8:
67:8% Ni-6 Ni-60: 0:
Ni-61:
1:3%
Ni-64 :
26:2%
Ni-62 :
3:7%
1:2%
The The atomic atomic number of nicke nickell is 28 with with the electron electron configuration [Ar]3d84s2. Nicke Nickell has two two allotro allotropic pic crysta crystall structur structures: es: (1) the closed-packed hexagonal a phase and (2) the face-centered cubic b phase phase with a densit density y of 8908 g cm3 and a melting point of 1453 C. Ferromagn erromagneti etism sm is one of the outsta outstandi nding ng physic physical al properties of nickel (T c 358–363 C) also observed for the other transition metals of Group VIII, iron (T c 770 C) and cobalt (T c 1131 C). 1
1
1
1
mine minera rall type type – more more than than 60% of the the world world nick nickel el production derives from sulfidic Ni–Fe–Cu ores and the most important mineral is pentlandite (Fe, Ni) 9S8. Although the nickel production from sulfidic ores still predom predomina inates tes,, an increa increasin singg amount amount is at presen presentt extracted from laterite ores with low nickel contents, such as limonite (oxidic nickeliferous (Fe, Ni)O(OH) n H2O and garnie garnierit ritee (a mixture mixture of Ni–Mg Ni–Mg hydro hydrosili silicat cates). es). Laterit Laterites es are usually usually leached leached to dissol dissolve ve the nickel nickel in low-temperature hydrometallurgical recovery processes. The The choice choice of the leaching leaching proces processs depend dependss on many many facto factors rs (imp (impur urit itie iess in the the matt matte, e, energ energy y pric price, e, and and availability of sulfuric acid). In the case of high-temperature smelting of sulfidic minerals such as (Co,Ni,Fe)3S4 and (Fe,Ni,Cu)S, iron is first oxidi oxidized zed to iron(I iron(III) II) oxide oxide (Fe (Fe2O3) by means means of partial calcination, and then slagged to ironsilicate with silica silica sand sand (SiO (SiO2) added added to the rotation rotation furnace furnace.. The product is a matte of iron(II) sulfide (FeS), nickel sulfide (NiS), (NiS), and copper copper sulfide sulfide (Cu2S). The The iron(I iron(II) I) sulfide sulfide (FeS) portion of the matte is oxidized by air blasting and slagged with silica (SiO2) in a converter. The result is a bessemer matte of nickel subsulfide (Ni3S2) and copper sulfide (Cu2S). The subsequent subsequent processing processing depends depends on the targeted product. Example Example 1: For the produc production tion of the Monel (Ni, Cu) Cu) allo alloy, y, the the Ni3S2/Cu2S bess besseme emerr matt mattee is first first calcinated to remove the sulfur. The oxides, product of the calcinations, are reduced in the following step. The The adva advant ntag agee of the the Mone Monell proc proces esss rests rests upon upon avoiding the expensive nickel–copper separation.
Mineral Deposits The world’s largest deposits are found in Russia (18%), Canada and Cuba (17% each), and New Caledonia in the South Pacific (13%). Significant deposits of sulfide ores are found in Norilsk-Talnakh in Siberia and in Ontario (Sudburry district) in Canada. Othe Otherr wellwell-kn know own n ores ores are are in the the Kola ola Penin eninsu sula la (Petschenga and Montschegorsk) and the Urals (Tscheljabinsk, Jekaterinburg, Orenburg) in Russia. Nickel deposits are also situated in Indonesia, Guatemala, and Australia.
Example Example 2: In the the case case of nick nickel el refin refinin ing g with with the the Mond process, the matte is completely oxidized. 2Ni3 S2 þ 7O2 -6NiO þ 4SO2
½I
1
Nickel oxide is reduced at 700–800 C in the presence of hydrogen NiO þ H2 ðgÞ-NiðsÞ þ H2 OðgÞ
½II
followed by NiðsÞ þ 4COðgÞ-NiðCOÞ4 ðgÞ at 502100 C 1
Extraction and Processing Nickel ores consist of sulfides, arsenides, and oxides. The choice of the extraction process for nickel depends on the
796
½III
1
By heat heatin ingg the the carb carbon onyl yl gas gas up to 180–2 180–200 00 C finely finely divided nickel with 99.90–99.99% purity is obtained NiðCOÞ4 ðgÞ-NiðsÞ þ 4COðgÞ
½IV
Chemistry, Electrochemistry, and Electrochemical Applications | Nickel
797
German chemist Jeremias Benjamin Richter de• The veloped the chemical analytical methods to obtain
Electrowinning Nickel can be recovered from aqueous solutions by electrolysis in the metallurgical process called electrowinning by which the oxidized metals dissolved from the ore are being electrodeposited (reduced) on the negative electrode. This means that a charge transfer reaction takes place from the solid metal toward the positively charged nickel ions in the electrolyte. The electrowinning of nickel is carried out commercially with both sulfate and chloride electrolytes. The main electrochemical reactions are the electrodeposition of nickel on the cathode and the oxygen or chlorine evolution on the anode for the sulfate and chlorine systems, respectively. The anodes for sulfate electrolytes are made of antimonial lead, lead–calcium–tin, or lead– strontium–tin. The direct electrowinning of nickel from the sulfide matte in the previous examples follows schematically the reaction 1 Ni3 S2 -3Ni2þ þ S8 þ 6e 4
• • • • •
½V
During the dissolution of the nickel subsulfide (Ni 3S2) anode, sulfur is being released. The anodic reaction is the oxidation of the sulfur ions at high potential (1.2 V), whereas the Ni 2þ ions go in solution. The sulfur content of the anode has to be higher than 23% to permit the anode dissolution. The anolyte is a sulfate–chloride solution. This procedure is more modern than the standard Hybinette cell electrodeposition and has found increasing application since the end of the 1950s. In the Sherritt-Gordon ammonia pressure-leaching process for sulfidic ores, nickel is recovered from the leach liquor after copper removal and several purification steps. The reduction of the nickel ions in the remaining solution can proceed 1
i. in a high-pressure hydrogen atmosphere at 200 C to produce nickel powder or ii. electrochemically to form cathode nickel. Reduction electrolysis is also used for metal refinement. In this case the main metal, typically nickel, copper, and cobalt is being dissolved anodically and electrodeposited in high purity on the cathode with a relatively low energy consumption. About 30% of the world nickel production derives from electrolysis.
Milestones in Research and Technology of Nickel Swedish chemist Torbern Olof Bergmann was the • The first person to isolate nickel in 1775.
• •
•
• • •
nickel with high purity in 1804. Michael Faraday discovered the electrodeposition of nickel in 1832. The German chemist and industrialist Ludwig Mond developed the ‘Mond process’ in 1899 in the United Kingdom for the extraction and refinement of nickel after discovering in 1890 the nickel carbonyl synthesis. Waldmar Jungner patented the nickel–cadmium battery in 1899 in Sweden. In 1901, Thomas. A. Edison patented in the United States the nickel-alkaline accumulator, which started the further development of the nickel–iron system. The Swedish metallurgist Noak Victor Hybinette invented in 1904 the bagged-cathode cell, also called Hybinette cell for the electrowinning of nickel from smelting ores. The cathode and anode compartments of the cell are separated from each other by a filtering diaphragm allowing (especially in the following improved versions of the process) the refinement of nickel from copper and other impurities. The patent for the first nickel-based corrosion-resistant alloy Monel (70% nickel, 30% copper) was granted in 1906 in the United States to Ambrose Monel. The Krupp aktiengesellschaft (AG) in Germany disclosed in 1912 the first corrosion-resistant steel with good mechanical properties, the V2A corrosion-proof alloy, a combination of 70% iron, 7% nickel, 20% chromium, and minor contents of carbon, silicon, and manganese processed with a particular heat treatment. Murray Raney in the United States developed in 1926 the selective leaching process to obtain a finely grained nickel–aluminum alloy from a quenched melt of nickel and aluminum leached in concentrated sodium hydroxide. The ‘Raney nickel’ alloy shows high catalytic activity with a wide application in hydrogenation reactions. Abner Brenner and Grace E. Riddell in the United States developed the autocatalytic electroless plating of nickel in 1944. Sherritt-Gordon’s researchers in Canada introduced in 1950 the ammonia leaching process for treating nickel concentrates (start of the pressure hydro-metallurgical processing). The Finnish metallurgical company Outokumpu introduced in 1959 the flash smelting technology, originally developed for copper, in its Harjavalta plant for the production of nickel (direct Outokumpu nickel).
Nickel Alloys Nickel is the main component of many well-known alloys, for example, corrosion-resistant alloys such as
798
Chemistry, Electrochemistry, and Electrochemical Applications | Nickel
Monel (Ni, Cu), Inconel 600 (Ni, Cr, Fe), Hastelloy (Ni, Mo, Fe), and the already-mentioned stainless steels. Nickel is also present in strong magnetic alloys such as Alnico (Al, Ni, Co), Permalloy (Ni, Fe), and mu-metal (Ni, Fe, Cu, Mo). A very well-known nickel alloy is constantan (Cu 60%, Ni 40%) characterized by a constant resistance over a wide temperature range.
Chemistry of Nickel Nickel is a reactive element that forms compounds in the oxidation state 1, 0, þ 1, þ 3, and þ 4 with oxygen, sulfur, halogens, cyanide, nitrate, ammonia, and carbon. The most stable oxidation state of nickel is þ 2. Typical nickel hydrated salts such as nickel sulfate hydrate (NiSO4 7H2O) and nickel nitrate hexahydrate (Ni(NO3)2 6H2O) are greenish due to the formation of Ni(H2O)62þ complexes. Water-free nickel salts on the contrary are yellow. Nickel hydroxide (Ni(OH) 2) has a low solubility in alkaline solutions and dissolves in acid forming Ni(H2O)6 2þ ions. If ammonia is added to nickel nitrate bromine (Ni(NO3)2), the green color turns blue due to the formation of Ni(NH3)6 2þ, a very soluble complex, which, contrary to Ni(H2O)6 2þ, does not precipitate. Nickel oxyhydroxide (NiO(OH)) is an Ni 3þ black-colored compound that can be synthesized from nickel hydroxide (Ni(OH)2) in the presence of strong oxidants like Br2 in alkaline solutions. In alkaline cells such as Ni–Cd and Ni/Zn, nickel oxyhydroxide forms the positive active mass and is being generated during charging, i.e., the oxidation is driven by the electrochemical potential in concentrated potassium hydroxide solutions following 2NiOðOHÞ þ 2H2 O þ 2e ’2NiðOHÞ2 þ 2HO
U > 0 :49 V
½VI
The higher Ni4þ oxidation state can be obtained by the oxidation of nickel hydroxide with peroxidisulfate to build hydrated nickel dioxide nickel dioxide hydrate (NiO2 n H2O). The already-mentioned nickel carbonyl (Ni(CO) 4) is a well-known example for the zero oxidation state of nickel; it is used primarily as a carrier of carbon monoxide (reaction [IV]) in the synthesis of acrylates (compounds utilized in the manufacture of plastics). Other nickel compounds such as nickel chloride, nickel cyanide, nickel nitrate, nickel phosphate, nickel sulfate, and nickel acetate are currently used in electroplating and plating processes.
Electrochemical Nickel Plating Electroplating is an electrodeposition process that is used to produce metallic coatings on a substrate by the action
of the electrical current from an external source. Electroplating deposit layers are expected to be fine grained, strongly adhesive, and glassy. This is an essential difference to the relatively coarse grained, mechanically stable, adhesive deposits of high purity required in electrowinning and electrorefinement. The main electrolytes containing Ni2þ ions used in electroplating are nickel sulfate (NiSO4 6H2O), nickel chloride (NiCl2 6H2O), nickel sulfamate (Ni(NH2 SO3)2 4H2O), and the suitable combinations for particular applications. A further main component is boric acid (H3BO3). Other electrolyte components present have specific functions such as (1) neutral salts to increase the conductivity of the bath, (2) additives for reducing the surface tension to avoid porosity, (3) buffer salts to keep the pH of the solution between 3.5 and 4.5, and (4) brighteners to produce grain refining. Nickel electroplating has a very wide range of applications like corrosion protection, nickel alloy film deposition for electronic storage devices, jewelry, and so on. In addition, there are two other processes that involve nickel electrodeposition of great technical relevance at present. These are i. electroless deposition, i.e., nickel deposition on nonconductive materials like plastics without using an external power supply, and ii. electroforming, a process by which pieces are produced (or reproduced) by electrodeposition upon a mandrel or mold that is subsequently separated from the deposit.
Electrochemical Nickel Powder Production In metal powder production by electrodeposition, very different electrochemical reduction conditions are required compared with those used for electroplating, electrowinning, or electrorefining. The electrodeposited metal consists in this process of poorly bonded microparticles, the opposite to the preferred coherent smooth electrodeposit with good substrate adhesion in electroplating. This means that the electrolytic metal powder is formed mainly in a micrometer-sized controlled dendritic morphology, which can spontaneously fall off or can easily be removed mechanically from the electrode. To achieve this powdery deposit, electrodeposition has to be carried out under diffusion control, i.e., in a mass-transport-controlled regime. The most important powders (copper, iron, and nickel) are obtained from aqueous solutions. The morphology of the nickel powder can be modified by introducing suitable additives in the electrolyte. Nickel metal powders are used for sintered and pressed parts, catalysts, conducting pastes, friction
Chemistry, Electrochemistry, and Electrochemical Applications | Nickel
components, and so on. Nickel powder can also be added to the active mass of alkaline cells to enhance the conductivity of the plates. This procedure was first introduced by T. A. Edison in the form of nickel flakes introduced in the positive pocket plates. Edison’s process for electrodepositing nickel flakes was first described in his US 821 626 patent of 1906.
799
concentration define the stability limits, i.e., those denoted with 6 in Figure 1. According to Figure 1, nickel metal would get dissolved in acidic solutions according to Ni-Ni2þ þ 2e
½VII
and in strong alkaline solutions following
Stability of Nickel in Aqueous Solution The Pourbaix diagram for the potential versus pH of the Ni–H2O system at 25 C (Figure 1) shows a common domain for the equilibrium range of nickel and water (lines a and b) for neutral and alkaline solutions. Nickel is considered stable in the regions where it does not go in solution. The lines corresponding to 106 molL1 ion 1
Ni þ 2H2 O-HNiO2 þ 3Hþ þ 2e
½VIII
In the pH window between 9.1 and 12.2, nickel is stable and in equilibrium with the solid phases nickel hydroxide (Ni(OH)2), Ni3O4, and nickel dioxide (NiO2), i.e., a protective layer builds up. At negative potentials below 0.5 V, nickel is immune. The thermodynamic considerations and the choice of reaction mechanisms for
) V ( E
Figure 1 Potential–pH diagram at 25 C for nickel. Reproduced with permission from Pourbaix M (1974) Atlas of electrochemical equilibria in aqueous solutions , 2nd edn. Brussels: NACE international and CEBELCOR. 1
800
Chemistry, Electrochemistry, and Electrochemical Applications | Nickel
concentrated phosphoric acid and aerated or• hot ganic acids.
2.0 Passivity
1.5 O / 2 H O 2
1.0 ) V (
E
Nickel is resistant in alkaline solutions of
NiO2
lithium hydroxide, sodium hydroxide, and potas• sium hydroxide up to the boiling point and • ammonia 1%.
Ni2O3
Passivity
o
0.5
0
Ni3O4 Corrosion
Passivity NiO
H +
/ H
Ni 2+
Nickel is not resistant in alkaline solutions of
2
>1% and • ammonia • alkaline hypochlorites. Nickel is also
–0.5 Ni Immunity –1.0 –2 –1 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 pH
Potential–pH diagram for nickel with the practical stability ranges.
to most nonoxidizing salts but not resist• resistant ant to most oxidizing salts, resistant to dry halogen gases 200 C but not • resistant to moist halogens and hydrogen halides, o
Figure 2
nickel in water used to make the diagram in Figure 1 do not include kinetics. For example, the rate for the buildup of protective layers, the influence of the electrolyte circulation, and the detrimental effect of impurity ions or dissolved gases like oxygen are not considered. Fortunately, for many applications the kinetic stability range for nickel is wider than from the pH range expected from Figure 1. The practical stability range for nickel in water demonstrated in Figure 2 confirms nickel’s corrosion in strong acidic solutions, but also shows that it is unexpectedly stable in strongly alkaline solutions even at high anodic potentials. This is due to the buildup of passive layers, a property that explains the successful deployment of nickel electroplated parts for the positive electrodes in alkaline power sources and corrosion protection in general. On the contrary, nickel is usually not stable against substances or environments known to damage protection layers.
Corrosion Properties of Nickel Nickel is resistant in acid solutions to dilute, nonoxidizing acids, • sulfuric acid deaerated ( 80% at room tempera• ture (RT)) and chloric acid deaerated ( 15% at o
o
• •
RT), hydrofluoric acid at RT, and deaerated dilute organic acids and pure phosphoric acid, deaerated at RT.
Nickel is not resistant in acid solutions to acids like nitric acid, sulfuric acid >80% • oxidizing and at high temperature and
•
1
and not resistant to industrial atmospheres that build nonprotective basic nickel sulfate layers (fogging). Fogging is however minimized by a thin coating of chromium (0.003–0.000 7 mm) electroplated over nickel.
The corrosion resistance can be improved by alloying nickel with other metals like copper, chromium, and molybdenum. The enhanced corrosion resistance through alloying is not universal as it suits in most cases the environmental conditions for some particular application. For example, the already-mentioned Monel Ni–Cu alloy is resistant to high velocity (aerated) seawater, where it shows uniform passivation. For this reason it has found application in the naval industry, e.g., to build huge propellers. But, on the contrary, Monel shows pitting (nonuniform local) corrosion in stagnant seawater.
Nickel Compounds in Electrical Storage Devices The application of nickel in electrochemical energy storage systems started with the development of the alkaline accumulators at the end of the nineteenth century. The development of the nickel–cadmium (Ni–Cd) and nickel–iron (Ni–Fe) from the quest for alternative lightweight and robust power sources for powering electrical devices – electricity networks in those days were an exception (in 1901 only 3% of the US population was connected). The rapid evolution of the alkaline systems rested upon previous innovations such as the introduction of the caustic potash electrolyte (KOH) for the zinc–copper oxide by M. F. De Lalande and G. Chaperon in 1883, and the research on nickel chemistry by A. Dunn and F. Hasslacher in the 1880s. Waldmar Jungner in Sweden worked in the 1890s with both the iron and the cadmium electrodes. He developed
808
Chemistry, Electrochemistry, and Electrochemical Applications | Nickel
commercial Ni/Zn cells were carried at Powergenix and US national laboratories. The electrochemistry of zinc will be covered in detail in Nickel-Zinc Battery (Secondary Batteries – Nickel Systems: Nickel–Zinc), Zinc Electrode - Form, Morphology, and Reactivity (Secondary Batteries – Zinc Systems: Zinc Electrodes: Overview). Nickel–Hydrogen Batteries The nickel–hydrogen (Ni/H2) is a sealed secondary battery that combines a fuel cell with a conventional electrode. The fuel-like electrode is the negative and uses hydrogen as the negative active material. The positive electrode is a conventional nickel electrode. The overall reaction for this system is discharge 1 H2 þ NiOOH $ NiðOHÞ2 2 charge
E 0 :
1:36 V
½XIX
A salient feature is that the hydrogen pressure gives an indication of the state of charge and is also proportional to the self-discharge. The oxygen evolved during overcharge is reduced at the hydrogen electrode, which carries noble metal catalysts, a cost factor that has limited the deployment of this system to aerospace applications. This system is distinguished for being very reliable, exhibiting a longer cycle life than other maintenance-free secondary systems; it also resists high-rate overcharging and cell reversal. Nickel–hydrogen showed rapid development in the 1970s, and today one of the main manufacturers is Eagle-Picher in the United States. Sodium–Nickel Chloride ZEBRA Batteries These are high-temperature nickel-based batteries developed in 1985 in South Africa. The name ZEBRA stands for Zeolite Applied to Battery Research Africa. Sodium, the negative electrode, and sodium aluminum tetrachloride (Na[AlCl4]) are molten at the operational temperature (170–400 C) of the cell; sodium aluminum tetrachloride (Na[AlCl4]) is added to the porous nickel chloride to transport Na þ from the surface of the b00 -alumina solid-state electrolyte to the reaction sites at the interior of the positive electrode. The overall cell reaction is 1
impact on operation costs have slowed down its deployment. The thin b-alumina (Al2O3) ceramic is a ‘know how’-sensitive and expensive component of the system that cannot withstand repeated thermal cycling without developing microcracks. MES-DEA socie´te´ anonyme (SA) in Switzerland offers the ZEBRA battery for EV, telecom backup power, and regenerative energy supply (photovoltaic and wind turbines). Alkaline Fuel Cells with Oxygen Gas Diffusion Electrodes of Raney Nickel The Raney nickel alloy was used as an alternative to the silver technology electrodes for making oxygen electrodes for alkaline fuel cells. These highly porous metal electrodes capable of sustaining high current densities owing to their high surface Raney nickel structure were developed by E. Justi and coworkers in Germany in the 1950s. This technology was adopted by VARTA and later adopted and upgraded by Siemens. Lithium Batteries with Li(NiCoAl)O2 Cathodes Lithium nickel dioxide (LiNiO2) has been considered since long an alternative to the more expensive lithium cobalt dioxide (LiCoO2) cathode material for lithium-ion batteries due to its high specific capacity of 200 mAh g1. Lithium nickel dioxide (LiNiO2) belongs to the group of insertion metal oxide electrodes for Li þ ions. Its use, however, was hindered by (1) poor cyclability due to a structural instability, (2) difficulties in synthesizing an electrochemical active form because of its tendency to non-stoichiometry, and (3) poor thermal stability (i.e., exothermic reactions with oxygen liberation). In the past 10 years, the thermal stability and cyclability were notably improved by cationic substitutions in nickel dioxide (NiO2) with cobalt and aluminum. Lithium cells with nickel cobalt aluminum (NCA) cathodes, i.e., Li (Ni0.85Co0.10Al0.05)O2, are considered at present one of the most promising lithium-ion systems for automobile use.
Nomenclature Symbols and Units
2Na þ NiCl2
discharge $
charge
2NaCl þ Ni
ðE 0 : 2:58V at 300 CÞ ½XX 1
Sodium–nickel chloride batteries were considered promising candidates for HEV applications owing to their high energy density. They are resistant to overcharge abuse and passed successfully many safety tests and crash simulations. The need for a thermal management to keep a relative high temperature (even at rest) and its potential
E E 0 T c k
h
electrode potential standard electrode potential Curie temperature wavelength diffraction angle
Abbreviations and Acronyms AG aktiengesellschaft (corporation)
Chemistry, Electrochemistry, and Electrochemical Applications | Nickel
AGV CVD DAUG EV FNC HEV ICE MH Ni–MH PTFE RT SA SEM ZEBRA
automatic guided vehicles chemical vapor deposition Deutsche Automobil Gesellschaft electric vehicle fiber nickel cadmium hybrid electric vehicle internal combustion engine metal hydride nickel–metal hydride polytetrafluoroethylene room temperature socie´te´anonyme (corporation) scanning electron microscopy Zeolite Applied to Battery Research Africa
See also: Chemistry,
Electrochemistry, and Electrochemical Applications: Hydrogen; Iron; Zinc; Electrochemical Theory: Corrosion; Hydrogen Evolution; Kinetics; Oxygen Evolution; Thermodynamics; Electrolytes: Solid: Sodium Ions; Fuel Cells – Overview: Introduction; Fuels – Hydrogen Storage: Complex Hydrides; History: Primary Batteries; Secondary Batteries; Secondary Batteries – High Temperature Systems: Sodium–Nickel Chloride; Secondary Batteries – Lead–Acid Systems: Electrode Design; Lifetime Determining Processes; Secondary Batteries – Lithium Rechargeable Systems – LithiumIon: Positive Electrode: High-Voltage Materials; Positive Electrode: Nanostructured Transition Metal Oxides; Thermal Runaway; Secondary Batteries – Nickel Systems: Electrodes: Cadmium; Electrodes: Iron; Electrodes: Nickel; Memory Effect; Nickel–Cadmium: Overview; Nickel–Cadmium: Sealed; Nickel–Hydrogen; Nickel–Iron; Nickel–Metal Hydride: Metal Hydrides; Nickel–Metal Hydride: Overview; Nickel–Zinc; Secondary Batteries – Zinc Systems: Zinc Electrodes: Overview; Zinc–Silver.
Further Reading Anderman M and McHenry E (1992) High performance Ni-Cd Cells utilizing fiber structured electrodes (FNC). Proceedings of the 35th IEEE International Power Sources Symposium, p. 149. US: IEEE. Bockris JO’M (1981) Comprehensive Treatise of Electrochemistry, Vol. 3: Electrochemical Conversion and Storage . Plenum Press. Bode H, Dehmelt K, and Witte J (1966) Zur Kenntnis de Nickelhydroxid Elktrode-I. Electrochimica Acta 11: 1079. Brady JA (1990) General Chemistry 5th edn. John Wiley & Sons. Broussely M, et al. (1993) Li/Li NiO2 and Li/Li CoO2 rechargeable systems: Comparative study and performance of practical cells. Journal of Power Sources 43: 209--216. x
x
809
Dai J, Li SFY, Xiao TD, Wang DM, and Reisner DE (2000) Structural stability of aluminium stabilized alpha nickel hydroxide as a positive electrode material for alkaline secondary batteries. Journal of Power Sources 89: 40–45. ¨ rmossy G (1998) Alkaline Haschka F, Wahrtmann W, and Benczu¨r-U batteries for hybrid and electric vehicles. Journal of power Sources 72: 32--36. Hora´ nyi G and Inzelt G (2006) The nickel group in encyclopedia of electrochemistry. In: Bard AJ, Stratmann M, Scholz E and Pickett ChJ (eds.) Inorganic Chemistry , vol. 7A, ch. 18. Weinheim: Wiley VCH. Jindra J (1997) Progress in sealed Ni-Zn cells, 1991–1995. Journal of Power Sources 66: 12--25. Kondo H, et al. (2007) Effects of Mg-substitution in Li(Ni,Co,Al)O2 positive electrode materials on the crystal structure and battery performance. Journal of Power Sources 174: 1131--1136. Kordesch K (1984) Brennstoffbatterien . Springer Verlag. Linden D and Reddy TB (eds.) (2002) Handbook of Batteries , 3rd edn. New York, Chicago, San Francisco: McGraw Hill. ¨ rmo ¨ ssy G, and Scha ¨ dlich G (2000) Alkaline Ohms D, Benczur-U batteries for applications in telecommunication. Proceedings of the Third International Telecommunications Energy Special Conference , p. 111. Dresden, Germany: TELESCON. ¨ rmo¨ssy G, and Scha¨ dlich G (2002) Ohms D, Kohlhase M, Benczu´r-U New developments on high power alkaline batteries for industrial applications. Journal of Power Sources 105: 127--133. Oshitani M, Takayama T, Takashima K, and Tsuji S (1986) A study on the swelling of a sintered nickel hydroxide electrode. Journal of Applied Electrochemistry 16: 403--412. Popov KI and Pavlovic´ MG (1993) Electrodeposition of metal powders with controlled grain size and morphology. In: White RW, Bockris JO’ M, and Conway BE (eds.) Modern Aspects of Electrochemistry , vol. 24, pp. 299–391. New York: Plenum Press. Pourbaix M (1974) Atlas of Electrochemical Equilibria in Aqueous Solutions, 2nd edn. Brussels: NACE international and CEBELCOR. Pourbaix M (1975) Lecons en corrosion Electrochimique , deuxieme edn. Bruxelles: CEBELCOR. Riedel E (1990) Anorganische Chemie . Berlin, New York: Walter de Gruyter & Co (2. Auflage). Ruetschi P, Meli F, and Desilvestro J (1995) Nickel-metal hydride batteries. The preferred batteries of the future? Journal of Power Sources 57: 85--91. Sac Epee N (1999) Self-discharge of the nickel electrode in the presence of hydrogen. Journal of the Electrochemical Society 146: 2376--2381. Sastri MVC (1998) Metal hydrides as hydrogen storage media. In: Sastri MVC (ed.) Metal Hydrides, Fundamentals and Applications , ch. 2, 10. Berlin: Narosa Publishing House, Springer-Verlag. Shukla AK, Venugolapan S, and Hariprakash B (2001) Nickel-based rechargeable batteries. Journal of Power Sources 100: 125--148. ¨ hle J and Schweda E (1990) Einfu¨hrung in das anorganischStra chemische Praktikum. Stuttgart: Hirzel Verlag. (13 Auflage S.). Uhlig H and Winston Revie R (1985) Corrosion and Corrosion Control, 3rd edn. New York: John Wiley & Sons. van Beek JR, Donkersloot HC, and Willems JJG (1985) Rechargeable hydride electrodes for Ni-H 2 batteries based upon stable hydrogenstoring materials. In: Pearce LJ (ed.) Power Sources 10, Proceedings of the 14th International Power Sources Symposium , pp. 317–338. Brighton: International Power Sources Symposium Committee. Varta Batterie AG (ed.) (1978) Gasdichte Nickel-Cadmium Akkumulatoren. Du ¨ sseldorf: VDI Verlag. Willems JJG (1984) Metal hydride electrodes. Philips Journal of Research 39: 1–5. Willems JJG and Buschow KHJ (1987) From permanent magnets to rechargeable hydride electrodes. Journal of the Less Common Metals 129: 13--30. Winnacker K and Ku ¨ chler L (1961) Chemische Technologie. Band 5: Metallurgie. Mu ¨ nchen: Carl Hansen Verlag. Wranglen G (1985) An Introduction to Corrosion and Protection of Metals 1st edn. Berlin: Springer Verlag.
