30
Ullmann’s Energy:Resources, Processes,Products
Ullmann’s Energy:Resources, Processes,Products
Editor in Chief:
Dr. Barbara Elvers, Hamburg, Germany
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Preface
This handbook features selected articles from the 7th edition of ULLMANN’S Encyclopedia ofIndustrial Chemistry, including newly written articles that have not been published in a printed editionbefore. True to the tradition of the ULLMANN’S Encyclopedia, products and processes are addressedfrom an industrial perspective, including production figures, quality standards and patent protectionissues where appropriate. Safety and environmental aspects which are a key concern for modernprocess industries are likewise considered.
More content on related topics can be found in the complete edition of the ULLMANN’SEncyclopedia.
About ULLMANN’S
ULLMANN’S Encyclopedia is the world’s largest reference in applied chemistry, industrial chemistry,and chemical engineering. In its current edition, the Encyclopedia contains more than 30,000 pages,15,000 tables, 25,000figures, and innumerable literature sources and cross-references, offering a wealthof comprehensive and well-structured information on all facets of industrial chemistry.
1,100 major articles cover the following main areas:
• Agrochemicals• Analytical Techniques• Biochemistry and Biotechnology• Chemical Reactions• Dyes and Pigments• Energy• Environmental Protection and Industrial Safety• Fat, Oil, Food and Feed, Cosmetics• Inorganic Chemicals• Materials• Metals and Alloys• Organic Chemicals• Pharmaceuticals• Polymers and Plastics• Processes and Process Engineering• Renewable Resources• Special Topics
First published in 1914 by Professor Fritz Ullmann in Berlin, the Enzyklopädie der TechnischenChemie (as the German title read) quickly became the standard reference work in industrial chemistry.Generations of chemists have since relied on ULLMANN’S as their prime reference source. Threefurther German editions followed in 1928–1932, 1951–1970, and in 1972–1984. From 1985 to 1996,the 5th edition of ULLMANN’S Encyclopedia of Industrial Chemistry was the first edition to bepublished in English rather than German language. So far, two more complete English editions havebeen published; the 6th edition of 40 volumes in 2002, and the 7th edition in 2011, again comprising 40volumes. In addition, a number of smaller topic-oriented editions have been published.
Since 1997,ULLMANN’SEncyclopedia of IndustrialChemistryhas also been available in electronicformat, first in a CD-ROM edition and, since 2000, in an enhanced online edition. Both electroniceditions feature powerful search and navigation functions as well as regular content updates.
Preface V
Contents
Volume 1 .................................................Symbols and Units ................................... IXConversion Factors .................................. XIAbbreviations ......................................... XIIICountry Codes ...................................... XVIIIPeriodic Table of Elements ..................... XIXPart 1: Energy Resources, Generation
and Storage .......................................... 1Batteries, 1. General .................................. 3Batteries, 2. Primary Batteries ................... 27Batteries, 3. Secondary Batteries ............... 79Batteries, 4. Standards ............................. 147Batteries, 5. Disposal and
Environmental Protection .................. 157Biogas ...................................................... 165Coal ......................................................... 179Coal Liquefaction .................................... 231Coal Pyrolysis .......................................... 317Combustion ............................................. 355Fuel Cells ................................................. 383Gas Production, 1. Introduction ............... 409
Volume 2 .................................................Gas Production, 2. Processes ................... 429Gas Production, 3. Gas Treating .............. 489Heat Storage Media ................................. 547Natural Gas .............................................. 567Nuclear Technology, 1. Fundamentals .... 621Nuclear Technology, 2.
Power Reactors, Survey ..................... 637Nuclear Technology, 3. Fuel Cycle ......... 661Oil and Gas, 1. Introduction .................... 745Oil and Gas, 2. Formation of
Reservoirs .......................................... 761
Oil and Gas, 3. Exploration forOil and Gas ........................................ 771
Oil and Gas, 4. Drilling and Workover .... 799Oil and Gas, 5. Formation Evaluation ..... 829Oil and Gas, 6. Reservoir Performance .... 843Oil and Gas, 7. Production ....................... 881Oil and Gas, 8. Field Processing .............. 945Oil and Gas, 9. Health, Safety,
Environmental and EconomicAspects .............................................. 959
Volume 3 .................................................Oil Refining ............................................. 965Oil Sands ............................................... 1021Oil Shale ................................................ 1073Photoelectricity ...................................... 1103Photovoltaic Cells .................................. 1113Solar Technology ................................... 1157Thermoelectricity ................................... 1217Wind Energy .......................................... 1231Part 2: Fuels .......................................... 1241Automobile Exhaust Control ................. 1243Automotive Fuels .................................. 1261Aviation Turbine Fuels .......................... 1297Heating Oil ............................................ 1313Liquefied Petroleum Gas ....................... 1331Marine Fuels .......................................... 1347Octane Enhancers .................................. 1353Petroleum Coke ..................................... 1373
Author Index ........................................ 1395
Subject Index ....................................... 1401
Contents VII
Symbols and Units
Symbols and units agree with SI standards (for conversion factors see page XI). The following list gives the mostimportant symbols used in the encyclopedia. Articles with many specific units and symbols have a similar list asfront matter.
Symbol Unit Physical Quantity
aB activity of substance BAr relative atomic mass (atomic weight)A m2 areacB mol/m3, mol/L (M) concentration of substance BC C/V electric capacitycp, cv J kg�1 K�1 specific heat capacityd cm, m diameterd relative density (ϱ/ϱwater)D m2/s diffusion coefficientD Gy (=J/kg) absorbed dosee C elementary chargeE J energyE V/m electric field strengthE V electromotive forceEA J activation energyf activity coefficientF C/mol Faraday constantF N forceg m/s2 acceleration due to gravityG J Gibbs free energyh m heighth W�s2 Planck constantH J enthalpyI A electric currentI cd luminous intensityk (variable) rate constant of a chemical reactionk J/K Boltzmann constantK (variable) equilibrium constantl m lengthm g, kg, t massMr relative molecular mass (molecular weight)n20
D refractive index (sodium D-line, 20 °C)n mol amount of substanceNA mol�1 Avogadro constant (6.023× 1023 mol�1)P Pa, bar* pressureQ J quantity of heatr m radiusR JK�1 mol�1 gas constantR Ω electric resistanceS J/K entropyt s, min, h, d, month, a timet °C temperatureT K absolute temperatureu m/s velocityU V electric potential
Symbols and Units IX
Symbols and Units (Continued from p. IX)
Symbol Unit Physical Quantity
U J internal energyV m3, L, mL, μL volumew mass fractionW J workxB mole fraction of substance BZ proton number, atomic numberα cubic expansion coefficientα Wm�2K�1 heat-transfer coefficient (heat-transfer number)α degree of dissociation of electrolyte[α] 10�2deg cm2g�1 specific rotationη Pa�s dynamic viscosityθ °C temperatureϰ cp/cvλ Wm�1K�1 thermal conductivityλ nm, m wavelengthμ chemical potentialν Hz, s�1 frequencyν m2/s kinematic viscosity (η/ϱ)π Pa osmotic pressureϱ g/cm3 densityσ N/m surface tensionτ Pa (N/m2) shear stressφ volume fractionχ Pa�1 (m2/N) compressibility
*The official unit of pressure is the pascal (Pa).
X Symbols and Units
Conversion Factors
SI unit Non-SI unit From SI to non-SI multiply by
Masskg pound (avoirdupois) 2.205kg ton (long) 9.842� 10�4
kg ton (short) 1.102� 10�3
Volumem3 cubic inch 6.102� 104
m3 cubic foot 35.315m3 gallon (U.S., liquid) 2.642� 102
m3 gallon (Imperial) 2.200� 102
Temperature�C �F �C� l.8� 32
ForceN dyne 1.0� 105
Energy, WorkJ Btu (int.) 9.480� 10�4
J cal (int.) 2.389� 10�1
J eV 6.242� 1018
J erg 1.0� 107
J kW�h 2.778� 10�7
J kp�m 1.020� 10�1
PressureMPa at 10.20MPa atm 9.869MPa bar 10kPa mbar 10kPa mm Hg 7.502kPa psi 0.145kPa torr 7.502
Powers of Ten
E (exa) 1018 d (deci) 10�1
P (peta) 1015 c (centi) 10�2
T (tera) 1012 m (milli) 10�3
G (giga) 109m (micro) 10�6
M (mega) 106 n (nano) 10�9
k (kilo) 103 p (pico) 10�12
h (hecto) 102 f (femto) 10�15
da (deca) 10 a (atto) 10�18
Conversion Factors XI
Abbreviations
The following is a list of the abbreviations used in the text. Common terms, the names of publicationsand institutions, and legal agreements are included along with their full identities. Other abbreviationswill be defined wherever they first occur in an article. For further abbreviations, see page IX, Symbolsand Units; page XVII, Frequently Cited Companies (Abbreviations), and page XVIII, Country Codesin patent references. The names of periodical publications are abbreviated exactly as done by ChemicalAbstracts Service.
abs. absolutea.c. alternating currentACGIH American Conference of Governmental
Industrial HygienistsACS American Chemical SocietyADI acceptable daily intakeADN accord européen relatif au transport
international des marchandises danger-euses par voie de navigation interieure(European agreement concerning the in-ternational transportation of dangerousgoods by inland waterways)
ADNR ADN par le Rhin (regulation concerningthe transportation of dangerous goods onthe Rhine and all national waterways ofthe countries concerned)
ADP adenosine 5´-diphosphateADR accord européen relatif au transport
international des marchandises danger-euses par route (European agreementconcerning the international transporta-tion of dangerous goods by road)
AEC Atomic Energy Commission (UnitedStates)
a.i. active ingredientAIChE American Institute of Chemical
EngineersAIME American Institute of Mining,
Metallurgical, and Petroleum EngineersANSI American National Standards InstituteAMP adenosine 5´-monophosphateAPhA American Pharmaceutical AssociationAPI American Petroleum InstituteASTM American Society for Testing and
MaterialsATP adenosine 5´-triphosphateBAM Bundesanstalt für Materialprüfung
(Federal Republic of Germany)BAT Biologischer Arbeitsstofftoleranzwert
(biological tolerance value for a work-ing material, established by MAKCommission, see MAK)
Beilstein Beilstein’s Handbook of Organic Chem-istry, Springer, Berlin – Heidelberg –
New YorkBET Brunauer – Emmett – Teller
BGA Bundesgesundheitsamt (FederalRepublic of Germany)
BGB1. Bundesgesetzblatt (Federal Republicof Germany)
BIOS British Intelligence Objectives Subcom-mittee Report (see also FIAT)
BOD biological oxygen demandbp boiling pointB.P. British PharmacopeiaBS British Standardca. circacalcd. calculatedCAS Chemical Abstracts Servicecat. catalyst, catalyzedCEN Comité Européen de Normalisationcf. compareCFR Code of Federal Regulations (United
States)cfu colony forming unitsChap. chapterChemG Chemikaliengesetz (Federal Republic
of Germany)C.I. Colour IndexCIOS Combined Intelligence Objectives Sub-
commitee Report (see also FIAT)CLP Classification, Labelling and PackagingCNS central nervous systemCo. CompanyCOD chemical oxygen demandconc. concentratedconst. constantCorp. Corporationcrit. criticalCSA Chemical Safety Assessment according
to REACHCSR Chemical Safety Report according to
REACHCTFA The Cosmetic, Toiletry and
Fragrance Association (United States)DAB Deutsches Arzneibuch, Deutscher
Apotheker-Verlag, Stuttgartd.c. direct currentdecomp. decompose, decompositionDFG Deutsche Forschungsgemeinschaft
(German Science Foundation)dil. dilute, diluted
Abbreviations XIII
DIN Deutsche Industrienorm (Federal Republicof Germany)
DMF dimethylformamideDNA deoxyribonucleic acidDOE Department of Energy (United States)DOT Department of Transportation –
Materials Transportation Bureau(United States)
DTA differential thermal analysisEC effective concentrationEC European Communityed. editor, edition, editede.g. for exampleemf electromotive forceEmS Emergency ScheduleEN European Standard (European
Community)EPA Environmental Protection Agency
(United States)EPR electron paramagnetic resonanceEq. equationESCA electron spectroscopy for chemical
analysisesp. especiallyESR electron spin resonanceEt ethyl substituent (�C2H5)et al. and othersetc. et ceteraEVO Eisenbahnverkehrsordnung (Federal
Republic of Germany)exp ( . . .) e(. . . ), mathematical exponentFAO Food and Agriculture Organization
(United Nations)FDA Food and Drug Administration
(United States)FD&C Food, Drug and Cosmetic Act
(United States)FHSA Federal Hazardous Substances Act
(United States)FIAT Field Information Agency, Technical
(United States reports on the chemicalindustry in Germany, 1945)
Fig. figurefp freezing pointFriedländer P. Friedländer, Fortschritte der
Teerfarbenfabrikation und verwandterIndustriezweige Vol. 1–25, Springer,Berlin 1888–1942
FT Fourier transform(g) gas, gaseousGC gas chromatographyGefStoffV Gefahrstoffverordnung (regulations in
the Federal Republic of Germany con-cerning hazardous substances)
GGVE Verordnung in der BundesrepublikDeutschland über die Beförderunggefährlicher Güter mit der Eisenbahn
(regulation in the Federal Republic ofGermany concerning the transportationof dangerous goods by rail)
GGVS Verordnung in der BundesrepublikDeutschland über die Beförderunggefährlicher Güter auf der Straße(regulation in the Federal Republic ofGermany concerning the transportationof dangerous goods by road)
GGVSee Verordnung in der BundesrepublikDeutschland über die Beförderunggefährlicher Güter mit Seeschiffen(regulation in the Federal Republic ofGermany concerning the transportationof dangerous goods by sea-goingvessels)
GHS Globally Harmonised System of Chemi-cals (internationally agreed-upon system,created by theUN, designed to replace thevarious classification and labeling stan-dards used in different countries by usingconsistent criteria for classification andlabeling on a global level)
GLC gas-liquid chromatographyGmelin Gmelin’s Handbook of Inorganic
Chemistry, 8th ed., Springer, Berlin –
Heidelberg –New YorkGRAS generally recognized as safeHal halogen substituent (�F, �Cl, �Br, �I)Houben-
WeylMethoden der organischenChemie, 4th ed., Georg Thieme Verlag,Stuttgart
HPLC high performance liquidchromatography
H statement hazard statement in GHSIAEA International Atomic Energy AgencyIARC International Agency for Research on
Cancer, Lyon, FranceIATA-DGR International Air Transport
Association, Dangerous GoodsRegulations
ICAO International Civil AviationOrganization
i.e. that isi.m. intramuscularIMDG International Maritime Dangerous
Goods CodeIMO Inter-Governmental Maritime Consul-
tive Organization (in the past: IMCO)Inst. Institutei.p. intraperitonealIR infraredISO International Organization for
StandardizationIUPAC International Union of Pure and
Applied Chemistryi.v. intravenous
XIV Abbreviations
Kirk-Othmer
Encyclopedia of Chemical Technology,3rd ed., 1991–1998, 5th ed., 2004–2007,John Wiley & Sons, Hoboken
(1) liquidLandolt-
BörnsteinZahlenwerte u. Funktionen aus Physik,Chemie, Astronomie, Geophysik u.Technik, Springer, Heidelberg 1950–1980; Zahlenwerte und Funktionen ausNaturwissenschaften und Technik,Neue Serie, Springer, Heidelberg,since 1961
LC50 lethal concentration for 50 % of the testanimals
LCLo lowest published lethal concentrationLD50 lethal dose for 50 % of the test animalsLDLo lowest published lethal doseln logarithm (base e)LNG liquefied natural gaslog logarithm (base 10)LPG liquefied petroleum gasM mol/LM metal (in chemical formulas)MAK Maximale Arbeitsplatzkonzentration
(maximum concentration at the work-place in the Federal Republic ofGermany); cf. Deutsche Forschungsge-meinschaft (ed.): Maximale Arbeits-platzkonzentrationen (MAK) undBiologische Arbeitsstofftoleranzwerte(BAT), WILEY-VCH Verlag,Weinheim (published annually)
max. maximumMCA Manufacturing Chemists Association
(United States)Me methyl substituent (�CH3)Methodicum
ChimicumMethodicum Chimicum, Georg ThiemeVerlag, Stuttgart
MFAG Medical First Aid Guide for Use inAccidents Involving Dangerous Goods
MIK maximale Immissionskonzentration(maximum immission concentration)
min. minimummp melting pointMS mass spectrum, mass spectrometryNAS National Academy of Sciences (United
States)NASA National Aeronautics and Space
Administration (United States)NBS National Bureau of Standards
(United States)NCTC National Collection of Type Cultures
(United States)NIH National Institutes of Health
(United States)NIOSH National Institute for Occupational
Safety and Health (United States)NMR nuclear magnetic resonance
no. numberNOEL no observed effect levelNRC Nuclear Regulatory Commission
(United States)NRDC National Research Development
Corporation (United States)NSC National Service Center (United States)NSF National Science Foundation
(United States)NTSB National Transportation Safety Board
(United States)OECD Organization for Economic Cooperation
and DevelopmentOSHA Occupational Safety and Health
Administration (United States)p., pp. page, pagesPatty G.D. Clayton, F.E. Clayton (eds.):
Patty’s Industrial Hygiene andToxicology, 3rd ed., Wiley Interscience,New York
PB Publication Board Report (U.S.report Department of Commerce, Scientific
and Industrial Reports)PEL permitted exposure limitPh phenyl substituent (—C6H5)Ph. Eur. European Pharmacopoeia, Council of
Europe, Strasbourgphr part per hundred rubber (resin)PNS peripheral nervous systemppm parts per millionP statement precautionary statement in GHSq.v. which see (quod vide)REACH Registration, Evaluation, Authorisation
and Restriction of Chemicals (EU regu-lation addressing the production and useof chemical substances, and theirpotential impacts on both human healthand the environment)
ref. refer, referenceresp. respectivelyRf retention factor (TLC)R.H. relative humidityRID réglement international concernant le
transport des marchandises dangereusespar chemin de fer (international conven-tion concerning the transportation ofdangerous goods by rail)
RNA ribonucleic acidR phrase risk phrase according to
(R-Satz) ChemG and GefStoffV (FederalRepublic of Germany)
rpm revolutions per minuteRTECS Registry of Toxic Effects of
Chemical Substances, edited by theNational Institute of Occupational Safetyand Health (United States)
(s) solid
Abbreviations XV
SAE Society of Automotive Engineers(United States)
SAICM Strategic Approach on InternationalChemicals Management (internationalframework to foster the soundmanagement of chemicals)
s.c. subcutaneousSI International System of UnitsSIMS secondary ion mass spectrometryS phrase safety phrase according to
(S-Satz) ChemG and GefStoffV (FederalRepublic of Germany)
STEL Short Term Exposure Limit (see TLV)STP standard temperature and pressure (0°C,
101.325 kPa)Tg glass transition temperatureTA Luft Technische Anleitung zur Reinhaltung
der Luft (clean air regulation in FederalRepublic of Germany)
TA Lärm Technische Anleitung zum Schutzgegen Lärm (low noise regulation inFederal Republic of Germany)
TDLo lowest published toxic doseTHF tetrahydrofuranTLC thin layer chromatographyTLV Threshold Limit Value (TWA
and STEL); published annually bythe American Conference of Govern-mental Industrial Hygienists (ACGIH),Cincinnati, Ohio
TOD total oxygen demandTRK Technische Richtkonzentration
(lowest technically feasible level)TSCA Toxic Substances Control Act
(United States)TÜV Technischer Überwachungsverein
(Technical Control Board of the FederalRepublic of Germany)
TWA Time Weighted AverageUBA Umweltbundesamt (Federal
Environmental Agency)Ullmann Ullmann’s Encyclopedia of Industrial
Chemistry, 6th ed., Wiley-VCH, Wein-heim 2002; Ullmann’s Encyclopedia ofIndustrial Chemistry, 5th ed., VCHVerlagsgesellschaft, Weinheim1985–1996; Ullmanns Encyklopädie
der Technischen Chemie, 4th ed., VerlagChemie, Weinheim 1972–1984; 3rd ed.,Urban und Schwarzenberg, München1951–1970
USAEC United States Atomic EnergyCommission
USAN United States Adopted NamesUSD United States DispensatoryUSDA United States Department of AgricultureU.S.P. United States PharmacopeiaUV ultravioletUVV Unfallverhütungsvorschriften der Ber-
ufsgenossenschaft (workplace safetyregulations in the Federal Republic ofGermany)
VbF Verordnung in der BundesrepublikDeutschland über die Errichtung undden Betrieb von Anlagen zurLagerung, Abfüllung und Beförderungbrennbarer Flüssigkeiten (regulation inthe Federal Republic of Germany con-cerning the construction and operation ofplants for storage, filling, and transpor-tation of flammable liquids; classificationaccording to the flash point ofliquids, in accordance with the classifi-cation in the United States)
VDE Verband Deutscher Elektroingenieure(Federal Republic of Germany)
VDI Verein Deutscher Ingenieure (FederalRepublic of Germany)
vol volumevol. volume (of a series of books)vs. versusWGK Wassergefährdungsklasse (water hazard
class)WHO World Health Organization (United
Nations)Winnacker-
KüchlerChemische Technologie, 4th ed., CarlHanser Verlag, München, 1982-1986;Winnacker-Küchler, ChemischeTechnik: Prozesse und Produkte,Wiley-VCH, Weinheim, 2003–2006
wt weight$ U.S. dollar, unless otherwise stated
XVI Abbreviations
Frequently Cited Companies(Abbreviations)
AirProducts
Air Products and Chemicals
Akzo Algemene Koninklijke ZoutOrganon
Alcoa Aluminum Company of AmericaAllied Allied CorporationAmer. American CyanamidCyanamid CompanyBASF BASF AktiengesellschaftBayer Bayer AGBP British Petroleum CompanyCelanese Celanese CorporationDaicel Daicel Chemical IndustriesDainippon Dainippon Ink and Chemicals Inc.Dow
ChemicalThe Dow Chemical Company
DSM Dutch Staats MijnenDu Pont E.I. du Pont de Nemours & CompanyExxon Exxon CorporationFMC Food Machinery & Chemical
CorporationGAF General Aniline & Film CorporationW.R.
GraceW.R. Grace & Company
Hoechst Hoechst AktiengesellschaftIBM International Business Machines
CorporationICI Imperial Chemical Industries
IFP Institut Français du PétroleINCO International Nickel Company3M Minnesota Mining and
Manufacturing CompanyMitsubishi Mitsubishi Chemical Industries
ChemicalMonsanto Monsanto CompanyNippon Nippon Shokubai Kagaku Kogyo
ShokubaiPCUK Pechiney Ugine KuhlmannPPG Pittsburg Plate Glass IndustriesSearle G.D. Searle & CompanySKF Smith Kline & French LaboratoriesSNAM Societá Nazionale MetandottiSohio Standard Oil of OhioStauffer Stauffer Chemical CompanySumitomo Sumitomo Chemical CompanyToray Toray Industries Inc.UCB Union Chimique BelgeUnion
CarbideUnion Carbide Corporation
UOP Universal Oil Products CompanyVEBA Vereinigte Elektrizitäts- und Bergwerks-
AGWacker Wacker Chemie GmbH
Frequently Cited Companies (Abbreviations) XVII
Country Codes
The following list contains a selection of standard country codes used in the patent references.
AT AustriaAU AustraliaBE BelgiumBG BulgariaBR BrazilCA CanadaCH SwitzerlandCS CzechoslovakiaDD German Democratic RepublicDE Federal Republic of Germany
(and Germany before 1949)∗
DK DenmarkES SpainFI FinlandFR FranceGB United KingdomGR GreeceHU HungaryID Indonesia
IL IsraelIT ItalyJP Japan∗
LU LuxembourgMA MoroccoNL Netherlands∗
NO NorwayNZ New ZealandPL PolandPT PortugalSE SwedenSU Soviet UnionUS United States of AmericaYU YugoslaviaZA South AfricaEP European Patent Office∗
WO World Intellectual PropertyOrganization
∗For Europe, Federal Republic of Germany, Japan, and the Netherlands, the type of patent is specified: EP (patent),EP-A (application), DE (patent), DE-OS (Offenlegungsschrift), DE-AS (Auslegeschrift), JP (patent), JP-Kokai(Kokai tokkyo koho), NL (patent), and NL-A (application).
XVIII Country Codes
Periodic Table
Periodic Table XIX
Part 1
Energy Resources, Generation and Storage
Ullmann’s Energy: Resources, Processes, Products 2015 Wiley-VCH Verlag GmbH & Co. KGaA, WeinheimISBN: 978-3-527-33370-7 / DOI: XXX
Batteries, 1. General
DIETRICH BERNDT, (formerly VARTA Batterie AG), Kronberg, Germany
DIETER SPAHRBIER, (formerly VARTA Batterie AG), Kelkheim, Germany
1. Introduction . . . . . . . . . . . . . . . . . . . . . 32. History . . . . . . . . . . . . . . . . . . . . . . . . . 43. Fundamental Laws . . . . . . . . . . . . . . . . 53.1. Equilibrium or Thermodynamic
Parameters . . . . . . . . . . . . . . . . . . . . . . 63.2. Current Flow, Kinetic Parameters . . . . . 73.2.1. Electron Transfer . . . . . . . . . . . . . . . . . . 93.2.2. Tafel Lines. . . . . . . . . . . . . . . . . . . . . . . 103.2.3. Influence of Temperature . . . . . . . . . . . . . 103.3. Heat Effects . . . . . . . . . . . . . . . . . . . . . 113.3.1. Reversible Heat Effect . . . . . . . . . . . . . . . 113.3.2. Current Related Heat Effects
(Joule Effect) . . . . . . . . . . . . . . . . . . . . . 113.3.3. Heat Generation in Total . . . . . . . . . . . . . 123.4. Heating of the Battery . . . . . . . . . . . . . . 124. Battery Properties and Characteristics . . 124.1. Cell and Battery . . . . . . . . . . . . . . . . . . 134.1.1. Active Material . . . . . . . . . . . . . . . . . . . . 134.1.1.1. Change of Volume . . . . . . . . . . . . . . . . . 134.1.1.2. Change of Electrode Structure. . . . . . . . . . 144.1.2. Nonactive Components . . . . . . . . . . . . . . 144.1.2.1. Conducting Components . . . . . . . . . . . . . 14
4.1.2.2. Nonconducting Components . . . . . . . . . . . 154.2. Battery Parameters . . . . . . . . . . . . . . . . 164.2.1. Voltage . . . . . . . . . . . . . . . . . . . . . . . . . 164.2.2. Capacity . . . . . . . . . . . . . . . . . . . . . . . . 164.2.2.1. Secondary Batteries . . . . . . . . . . . . . . . . . 174.2.2.2. Primary Batteries . . . . . . . . . . . . . . . . . . 174.2.3. Energy Content. . . . . . . . . . . . . . . . . . . . 184.2.4. Internal Resistance and Power Output . . . . 194.2.5. Charge Parameters. . . . . . . . . . . . . . . . . . 214.2.6. Self-Discharge . . . . . . . . . . . . . . . . . . . . 214.2.6.1. Mixed Potential . . . . . . . . . . . . . . . . . . . 214.2.6.2. Further Self-Discharge Mechanisms. . . . . . 224.2.6.3. Apparent Self-Discharge . . . . . . . . . . . . . 224.2.6.4. Capacity Loss During Storage. . . . . . . . . . 235. Classification of Battery Systems . . . . . . 235.1. Classification by Electrolyte . . . . . . . . . . 235.2. Classification by Construction . . . . . . . . 235.2.1. External Construction . . . . . . . . . . . . . . . 245.2.2. Internal Construction . . . . . . . . . . . . . . . . 24
References. . . . . . . . . . . . . . . . . . . . . . . 25
1. Introduction
Batteries and fuel cells are electrochemicalenergy converters that directly convert chemicalinto electrical energy. In batteries the energy isgenerally stored within the electrodes. But thereare exceptions, e.g., the air–zinc system, whereone of the reacting substances is continuouslysupplied from outside, or the zinc–bromine sys-tem, where the active material is stored in sepa-rate tanks. Fuel cells receive their chemicalenergy from outside sources (! Fuel Cells).
Batteries can be recharged, if they representreversible systems. This, however, often isrestricted, since not only the system's electro-chemical reactions must be reversible, but alsothe structure of its electrodes. As a consequence,
two basically different battery systems exist, i.e.,primary and secondary batteries:
1. Primary batteries are designed to converttheir chemical energy into electrical energyonly once.
2. Secondary batteries are reversible energyconverters and designed for many cycles,i.e., repeated discharges and charges.
The border between both types is blurred,since some primary battery systems permitcharging under certain, but usually limited con-ditions. In general, the efficiency of theirrecharging process is poor and often results inearly failure. The IEC therefore does not recom-mend the charging of any primary system [1, 2].
Ullmann’s Energy: Resources, Processes, Products 2015 Wiley-VCH Verlag GmbH & Co. KGaA, WeinheimISBN: 978-3-527-33370-7 / DOI: 10.1002/14356007.a03_343.pub2
Batteries are of increasing importance in allareas of our daily life. They are fabricated invery large ranges of system, volume, weight,and construction. Batteries may be purchasedas small button cells, that may have volumes ofwell below 1 cm3 to operate a wrist watch, apocket calculator, a hearing aid, or anothersmall electronic device. Other types of batteriespower large electric vehicles including trainsand ships, and may have a volume of the orderof cubic meters and a weight of several tons. Inbetween a huge variety of batteries exists,designed for all kinds of applications. Tomeet all needs of the market, batteries offer alarge range of optimized properties regardingelectric energy, voltage, power output, self-discharge, environmental compatibility, andprice.
The term “direct energy conversion” indicatesthat also nondirect energy conversion systemsexist. A famous example is the combustionengine, which converts chemical into mechani-cal energy via a thermal process (Carnot process)and which may serve for a simplified compari-son. Both systems are characterized by a reduc-ing agent and an oxidizing agent. In the case ofthe combustion engine the reducing agent is thefuel and the oxidizing agent usually atmosphericoxygen. A battery is also characterized by areducing agent (“fuel”) and an oxidizing agent,that serve as energy storage. A well known fuelof this kind is metallic zinc (representing thenegative electrode of, e.g., a flashlight battery),and the corresponding oxidant is manganesedioxide, constituting the positive electrode ofthat battery.
In principle, direct and nondirect chemicalenergy conversion are comparable: In both casesthe reductant is oxidized under consumption ofthe oxidant, the latter being stored inside oroutside the system (e.g., air). However, the directenergy conversion is not restricted by the limitedefficiency of the Carnot process of the combus-tion engine. In the battery the reaction is split upinto one that releases electrons (which meansoxidation), and another one that absorbs elec-trons (which means reduction) (see Fig. 1). Theelectron exchange that is connected with thesereactions, can so be transformed directly into acurrent that flows through the electrical appli-ance (or the charging device).
In principle, a large range of “fuels” and“oxidants” exists for electrochemical energystorage and conversion, each combination repre-senting a new battery system. However, not allcombinations are meaningful. A careful selec-tion has to be made, also with respect to the typeof electrolyte being employed.
2. History
The history of batteries is usually traced back toLUIGI GALVANI (1737–1798), who detected elec-trical phenomena between different metals in hisfamous experiments with frog legs. ALLESSANDRO
VOLTA (1745–1827) built the first primary bat-tery, the so-called Volta pile. The scientificfoundation of electrochemical energy storagewas derived by MICHAEL FARADAY (1791–1867).
The early development of secondarybatteries is connected to names like GASTON
PLANTÉ (1834–1899), CAMILLE ALFONS FAURE
(1840–1898), and HENRY OWEN TUDOR
(1859–1928) in the field of the lead–acid bat-tery, while THOMAS ALVA EDISON (1847–1931)and VALDEMAR JUNGNER (1869–1924) are thetwo important names in connection withnickel–iron and nickel–cadmium batteries.
In the decades following these discoveriesthe lead–acid and the nickel–cadmium system
Figure 1. Electrochemical cell and the split-up of the cellreactionS(N)red and S(P)ox are the reacting components of the nega-tive and the positive electrode, respectively. The shownreactions apply when the battery is discharged.
4 Batteries, 1. General Vol. 1
were constantly improved. Today's motor carswould be unthinkable without their reliable bat-teries. Sealed nickel–cadmium batteries supplythe energy for many of our portable electronicdevices, and valve-regulated lead–acid batterieshave gained a large share of the market forstandby batteries.
In the 1990s new rechargeable systemsappeared on the market. Of special importanceare the nickel–metal hydride and the lithium-ionsystem.
Primary batteries for practical use emerged inthe middle of the 19th century. Special referenceis made to GEORGE LECLANCHÉ, who pioneeredthe 1.5 V manganese dioxide–zinc system withaqueous ammonium chloride as electrolyte. Thissystem was described first by him in 1866 [3]. Itis still produced, technically much moreadvanced by now, of course, but still knownas Leclanché or zinc-carbon battery.
Over the years another 1.5 V system becamemost successful. It is the alkaline version of themanganese dioxide–zinc system, first proposedin 1882. Its development was taken up again byW. S. HERBERT [4, 5] about 70 years later. It took,however, another 20 years before the systembecame commercially available.
Further to be mentioned is the alkaline silveroxide–zinc system. First patents date back to1883–1910 [6]. This 1.5 V battery is an expen-sive system, which, however, exhibits veryfavorable electrochemical properties. To becomesuccessful it needed a market for small batterieswhich opened up in 1975 with the introductionof microelectronics (e.g., wrist watches).
Another primary system that deserves men-tioning is the air–zinc system. H. COHEN [7] wasthe first to develop a practical carbon–zinc ele-ment with aqueous ammonium chloride as elec-trolyte and air as oxidant in 1891. The system isstill in use. Its main application is in the area oflow power output over a long period of time(e.g., electric fence controllers).
Special future promise has the alkaline air–zinc version. C. FÉRY was obviously the first [8]to realize this system in 1925. Owing to furtherdevelopment the alkaline zinc–air element offersthe highest energy density of all currently avail-able battery systems. Since the alkaline air–zincbattery is also an environmentally benign sys-tem, it has replaced the mercuric oxide–zinc
system in important application areas, e.g., hear-ing aids. After activation, however, its storagebehavior is limited, depending on construc-tion (e.g., air access) and environment (e.g.,humidity).
Finally there are primary battery systemsusing nonaqueous electrolytes, i.e., lithium bat-teries. Research activities to develop highenergy lithium systems started in about 1960,especially in the USA and soon spread world-wide. Of the many lithium systems developedsince the 1960s, about ten systems haveattained market relevance (see ! Batteries, 2.Primary Batteries, Chap. 3. Batteries with Non-aqueous Electrolyte).
For a more detailed description of the historyof batteries, see, e.g., [9–11].
3. Fundamental Laws
Direct conversion of chemical into electricalenergy requires the split-up of the electrochem-ical reactions into reactions of reductants thatdeliver electrons and reactions of oxidants thataccept electrons. Such a split-up is achieved inthe electrochemical cell, shown in Figure 1. Apositive and a negative electrode are immersed inthe electrolyte and the reacting substances (theactive materials) are usually stored in the electro-des and the electrolyte, if it participates in theoverall reaction.
During discharge, oxidation of S(N)red occursat the negative electrode according to
S�N�red ! S�N�ox � n � e�
while S(P)ox is reduced at the positive electrode:
S�P�ox � n � e� ! S�P�red
Both together form the cell reaction
S�N�red � S�P�ox ! S�N�ox � S�P�red � energy
When the battery is charged, this reaction isreversed and energy has to be supplied to thecell.
The arrangement shown in Figure 1 resem-bles an electrolytic capacitor where also twoelectrodes are separated by the electrolyte.
Vol. 1 Batteries, 1. General 5
However, charging and discharging of such acapacitor involves only charge shifting withinthe double layer at the electrode–electrolyteinterface. Chemical reactions do not occur andthe physical structure of the electrodes is notaffected. For this reason, a nearly unlimitednumber of charge–discharge cycles are possible.Since mass transport does not occur, charge anddischarge of a capacitor occur extremely fast, butthe amount of stored energy per weight or vol-ume is comparatively small.
In batteries, such a double layer also exists,and the large surface area of the active materialgives rise to a high double-layer capacitance thatis observed when impedance measurements aremade. The double-layer capacitance is caused bycharge shifting and is given in the unit Farad, i.e.,As/V. The real battery capacity, however, isbased on chemical reactions and measured asAs or Ah. (Actually, the double-layer capacity isalways involved when a battery is charged ordischarged). Each charge–discharge cyclechanges the physical structure of the electrodes,and these changes inevitably cause an agingprocesses. Thus, with a battery the number ofpossible charge–discharge cycles is inevitablylimited, and performance changes during servicelive are unavoidable.
The cell reaction characterizes each batterysystem and its components that represent thecharged and discharged states determine theamount of energy that can be stored. As aconsequence, the parameters of its cell reactionare of paramount importance for the batterysystem. While for primary batteries onlyreactions are relevant that describe the opencircuit voltage and the discharge behavior, forrechargeable batteries these reactions must bereversible.
In the following, a brief survey is given of themost important rules. For details and derivations,see textbooks of electrochemistry or fundamen-tal books on batteries, e.g., [12–17].
3.1. Equilibrium or ThermodynamicParameters
The laws of thermodynamics generally apply tothe state of equilibrium, which means that allreactions are balanced. In the electrochemicalcell, equilibrium data can only be measured
when no current flows through the cell or itselectrodes. On account of this balance, the ther-modynamic parameters do not depend on thereaction path but only on the difference in energylevels between the final and initial componentsof the system (the products and the reactants ofthe electrochemical reaction). The thermo-dynamic parameters describe the maximallyachievable performance data. As soon as currentflows through the cell, these values are lowered,owing to kinetic parameters.
The main thermodynamic parameters of anelectrochemical reaction are:
1. The enthalpy of reaction ΔH which repre-sents the amount of energy released orabsorbed. ΔH describes the heat that is gen-erated, provided that 100% of the chemicalenergy is converted into heat.
2. The free enthalpy of reaction ΔG, also calledchange of Gibbs free energy ΔG, whichdescribes the (maximum) amount of chemicalenergy that, under equilibrium conditions,can be converted into electrical or mechanicalenergy and vice versa.
3. The entropy of reaction ΔS which character-izes the reversible heat effect T � ΔS (whereT = temperature in kelvins) which describesthe energy loss or gain connected with anychemical or electrochemical process underequilibrium conditions.
Important relations between the three param-eters are:
ΔG � ΔH � T � ΔS or ΔH � ΔG � T � ΔS �1�
The difference between ΔH and ΔG, theproduct T � ΔS, is the aforementioned reversibleheat effect. T � ΔS can be positive or negative. Inthe first case, additional energy is generated bycooling of the environment (Peltier or heat pumpeffect). Otherwise, T � ΔS constitutes an addi-tional heat increment.
The equilibrium voltage Uo is given by
Uo � �ΔG
n � F�2�
where n is the number of exchanged electroniccharges; F the Faraday constant (96 485 As/equivalent; i.e., 26.802 Ah/equivalent); n � F
6 Batteries, 1. General Vol. 1
denotes the amount of electrical charge con-nected with the reaction; and n � F � Uo describesthe generated electrical energy (kJ). Thermo-dynamic quantities like ΔH and ΔG dependon the concentrations (or, more accurately, activ-ities) of the reacting components, as far as thesecomponents are in solution. The correspondingrelation is:
ΔG � ΔGo;s � R � T ��
P
ln��ai�ji �prod �
P
ln��ai�ji �react
� �3�
where ai is the activity of the reacting componenti (approximately its concentration; in mol/cm3);ji is the number of equivalents of this componentthat take part in the reaction; R is the molar gasconstant for an ideal gas (R = 8.3145 JK�1
mol�1); ΔGo,s is the standard free enthalpy valuewhen all activities are unity. The terms “reac” and“prod” designate in the formula reactants andproducts for the forward (spontaneous) reaction.
Combination of Equation 2 and Equation 3results in the Nernst Equation:
Uo � Uo;s �R � T
n � F� ln
Π�ai�jreact
Π�ai�jprod
�4�
which is simplified for 25°C (298.2 K) to
Uo � Uo;s �0:0592
n� log
Π�ai�jreact
Π�ai�jprod
�5�
under consideration that
ln�::� � 2:303 log�::�;
R � 8:3145 J K�1mol�1 � 8:3145 WsK�1mol�1
and
F � 96485 As=equiv:
thus
R � T=F � 0:02569 V � equiv: � mol�1�T � 298:16 K�
or
2:303 � R � T=F � 0:0592 V � equiv: � mol�1:
The thermodynamic data also determine thetemperature coefficient of the equilibrium cell
voltage according to:
dUo
dT� �
ΔS
n � F�6�
SingleElectrodePotentials. Thermodynamiccalculations are always based on an electrochem-ical cell reaction and the derived voltage and itstemperature coefficient in fact concern the volt-age difference between two electrodes. The volt-age difference between the electrode and theelectrolyte, the absolutepotential, cannot bedetermined exactly, since potential differencescan only be measured between two electronicconductors [18]. Thus, single electrode potentialalways means the cell voltage between the elec-trode in question and a reference electrode. Toprovide a basis for the electrode-potential scale,the zero point was arbitrarily equated with thepotential of the standard hydrogenelectrode(SHE), a hydrogen electrode under specifiedconditions at 25°C [19].
Hydrogen reference electrodes are not used inbattery practice. They are not only impracticableto handle but also involve some risk of contami-nation of the battery’s electrodes by the noblemetals like platinum or palladium used as elec-trode materials in the hydrogen electrode [20].Therefore, a number of reference electrodesare used instead, e.g., the mercury/mercury(I)sulfate reference electrode (Hg/Hg2SO4) inlead–acid batteries, and the mercury/mercury(II) oxide reference electrode (Hg/HgO) in alka-line solutions (cf., e.g. [21]). In lithium-ionbatteries with organic electrolytes, the electrodepotential is mostly referred to that of the lithiumelectrode.
3.2. Current Flow, Kinetic Parameters
When current flows, the cell reaction must occurat a corresponding rate. This means that electrontransfer has to be forced into the desired direc-tion, and mass transport is required to bring thereacting ions to the electrode surface or carrythem away. To achieve this current flow, addi-tional energy is required. This energy finds itsexpression in overvoltages, i.e., deviationsfrom the equilibrium voltage (sometimesdenoted as “irreversible entropy loss” T � ΔSirr).
Vol. 1 Batteries, 1. General 7
Furthermore, current flow through conductingelements causes ohmic voltage drops. Both meanirreversible energy loss and a corresponding heatgeneration, caused by current flow.
As a result, the voltageU under currentflow i isreduced (on discharge) or increased (secondarycell on charge) compared to the equilibrium valueUo. The difference U � Uo, when measured asdeviation from the cell voltage comprises:
1. The overvoltage, caused by electrochemicalreactions and concentration deviations onaccount of transport phenomena.
2. The ohmic voltage drops, caused by theelectronic as well as the ionic currents inthe conducting parts including the electrolyte.
The sum of all the voltage drops caused by thecurrent flow is called polarization, i.e.,
polarization � overvoltage � ohmic voltage drops �7�
The quantity determined in practice is alwayspolarization. Overvoltage can be determinedseparately only by special electrochemicalmethods.
Usually, the reaction path consists of a numberof reaction steps that precede or follow the actualcharge transfer step as indicated in Figure 2.
The rate of each of these reaction steps isdetermined by kinetic parameters, such as
exchange current density, diffusion coefficients,or transport numbers. The slowest partial step ofthis chain is decisive for the rate of the overallreaction. As a consequence, overvoltages, oreven limitations of the reaction rate, often arenot caused by the electron-transfer step itself, butby preceding or following steps.
Transport of the reacting species is achievedby two mechanisms, diffusion and migration,and, when only one-dimensional transport isassumed, is given by:
N j �ij
n � F� �Dj
@cj@ζ
�i � tjzj � F
�8�
where Nj is the flux of species j in mol/cm2;ij/nF the current equivalent; cj the concentrationof species j in mol/cm3; δcj/δζ the concentrationgradient in mol/cm4; D the diffusion coefficientin cm2/s; t the transference number; zj thevalence number (charges per ion i); and ζ thediffusion direction (cm). Addend 1 describesmass transport by diffusion, which is propor-tional to the (negative) gradient of the concen-tration dcj/dζ that often can be approximated asa linear slope Δc = cj � cj,o where cj is theconcentration of the concerned species at theelectrode surface, while cj,o denotes the corre-sponding concentration in the bulk of theelectrolyte.
Diffusion can limit the reaction rate when themass transport by diffusion precedes the electrontransfer step. If the concentration cj attains thevalue zero at the electrode surface, all the arriv-ing ions or molecules are charged or dischargedimmediately, and further increase of the currentby increased overvoltage is not possible. Thusthe current cannot exceed a certain value, thelimiting current (ilim) that can be derived fromthe first term in Equation 8 with cj = 0.
Addend 2 in Equation 8 describes ion trans-port by migration by the ionic current. Thetransference number t denotes the share of thetotal current that is carried by the correspondingionic species. In a binary electrolyte, dissociatedinto A+ and B�, the transference numbers arerelated by
t� � t� � 1 �9�
Transference numbers depend on the con-centration of the ions and on temperature. In
Figure 2. Course of an electrochemical reaction. Chargetransfer often can only occur with adsorbed species, thenadsorption/desorption steps are included. Furthermore,chemical reactions may precede or follow the electron trans-fer step.
8 Batteries, 1. General Vol. 1
